TBR GChem1 Opt

Unit Conversion
a) Dimensional Analysis
b) Density Determination
c) Typical Conversions
Section I Elemental Analysis
a) Mass Percent
Stoichiometry b) Empirical Formulas
c) Molecular Formulas
by Todd Bennett d) Combustion Analysis
t Solution Concentration
M MX(aq) a) Units and Terminology
I
o
U i. Molarity
(g
,a
!
ii.Molality
q iii. Mass Percent (in $olution)
Wavelength iv. Density
b) Dilution
--+ c) Beer's Law
0.20 M MX(aq)
I
2 Balancing Keactions
o
a) Standard Balancing
Wavelength b) Limiting Keagents
Keaction Types
I a) Common Reactions
U -
b) Oxidation States
J!
t1
!l
Wavelength Test.Taking Tips
a) Oeneral Advice
--> b) Mathematical Tricks
i. Addition and Subtraction
ii. Averaging
iii. Multiplication
lv. L,lvtsron
SpeciaLiztng in MCAT Preparation

Stoichiometry Section Goals
Know how to convert one kind of concentration unit into another-
o? The concentration of a solution can be measured in terms of molarity, molality, and density. You
must know the definitions of each unit and how they differ from one another. Atthough the test
does not feature a great deal of math, you should have an idea of how to convert between units.
Understand the difference between empirical and molecular formulas.

Know the difference between the molecular formula (actual ratio of atoms in a molecule) and the
emoirical formula (simplest whole number ratio of the atoms in a molecule). Be familiar with the
expleriments and inforriation needed to determine both of the formulas.
Know the effect of standard conditions.

@v Standard conditions are defined as 1 atm. and 298 K for thermodynamics, but STP (standard
temperature and pressure) is defined as 1 atm. and273 5. Yily..ulculations of gas volume use the
ideal gas assump^tion that at STP, one mole of gas occupies 22.4htets.
..*S Un<lerstand dilution and its effect on concentration of a solute.

w W Dilution involves a reduction in the concentration of a solute in solution by the addition of solvent
( to the mixture. The addition of solvent therefore dilutes the concentration, but does not change the
moles of solute. The equation that you must recall is based on the constant number of solute moles:
Mittltid'Vir,itial = Mfinal'Vfittal.
standard reactions from chemis

The most commonlv recurrjng reactions in general chemistry that you are expected to know include
combustion, single'replace*e"nt, double diiplacement, and protori transfer, to name iust a few. You
must recognize t-hese reactions and have a basic understanding of them.
Recognize the limiting reagent in a reaction and know its effect on the reaction.
The limiting reagent dictates the amount of product that can be formed. and consequently the percent
yield for a Teu.tlott. Using only starting va'lues and the stoichiometric equation, you inust be able
io determine which reacta"nt is ihe limiting reagent in the reaction.
o? Ilnderstand the stoichiometric ratios in combustion reactions.

In the combustion of both hvdrocarbons and carbohydrates, there is a consistent relation between
the number of oxygen moleiules on the reactant side, and the number of water and carbon dioxide
molecules that fo'rtr on the product side. Know each reaction so that you may easily balance the
coefficients.
General Chemistry Stoichiometry Introduction
The perfect spot to start any review of general chemistry is the basics, which
traditionally include stoichiometry and chemical equations. The most
fundamental perspective of a chemical reaction, where bonds are broken so that
new bonds can be formed, is at the atomic and molecular levels. Due to the
minute size of atoms, we can never actually view a chemical reaction (so states
Heisenberg's uncertainty principle). We must therefore rely upon developing
models that can account for changes in all of the atoms and molecules involved
in a chemical reaction or physical process. At the molecular level, we consider
molecules. At the macroscopic level, we consider moles. Stoichiometry allows
us to convert one into the other and to shift between these two perspectives. The
number of molecules is converted into the number of moles using Avogadro's
number (6.022 x 1023). The concept of a mole is based upon the amount of
carbon-12 that is contained in exactly 12.0 grams of carbon, a quantity
determined by knowing the volume of a 12.0-9 carbon sample, the type of
molecular packing in it, and the dimensions of the carbon atom. This task of
quantifying atoms in a mole is similar to guessing the number of peas that are
contained in an aquarium. It is important that you utilize the mole concept to
understand, and later to balance and manipulate, chemical equations.
In the stoichiometry section, we focus on those skills needed to solve ratio
questions. Stoichiometry is most commonly thought of as the mathematical
portion of general chemistry. The MCAT, however, has relatively few
calculations. It is a conceptual test, emphasizing logical thought process rather
than calculations. For some of you, this is great news. But before celebrating too
much, consider where the mathematical aspects of general chemistry fit into a
conceptual exam. The MCAT does involve some math, but it is not too
complicated. Math-related calculations required for MCAT questions involve
making approximations, determining ratios, setting up calculations, and
estimating the effect of errors on results. The initial problems presented in this
section involve slightly more calculations than you should expect to see on the
MCAT. Some of them may look familiar to you from your general chemistry
courses and should stimulate your recall. As the section proceeds, less emphasis
is placed on calculating and estimating, and more emphasis is placed on the art
of quickly determining ratios and approximating values.
The focus of the stoichiometry section is problern-solving, with special attention
to the idiosyncrasies of each type of problem. Definitions of important terms are
presented with sample questions and their solutions. Answer solutions discuss
test strategy and the information needed to obtain the correct answer. Each
problem in the stoichiometry section represents what we might call the "book-
keeping" of reactions in general chemistry, and it offers an ideal opportunity to
begin work on fast math skills as well. As you do each of the questions, learn the
definitions and develop an approach that works well for you. You may want to
consider multiple pathways to arrive at the correct answer. It is important that
vou be able to solve questions in several different ways and to get into the
mindset of the test writers. As you read a passage, think about the questions that
could be asked about it. If a passage gives values for various masses and
volumes, there will probably be a question about density. If it gives values for
moles and solution volume, there will probably be questions on concentration
and dilution. Use your intuition and common sense as much as you can, and
make every effort to develop your test-taking logic.
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General Chemistry Stoichiometry Unit Conversion c
:$$ilffiiii$$ uH
Lr
Dimensional Analysis
Dimensional analysis is a mathematical conversion from one set of units into
another. It involves multiplying a given value by a conversion factor or a series -d
of conversion factors until the value is finally expressed in the desired units. ts
Converting from one set of units to another is a critical skill needed to eliminate C".
incorrect answer choices in the physical sciences section. Be systematic when D
converting between units. The standard measurements that can be expressed in
a variety of units are distance (1 m = 1.094yd,2.54 crn = 1.00 in, and 1.609 km = 5-c
1.00 mile), mass (1.00 kg = 2.205Ib and 453.6 g = 1.00 lb), volume (3.79 L = 1.00 t]
gal and 1.00 L = 1.06 qt), and time (3600 s = 1.00 hr). Always convert units as
they appear in a problem into the units indicated in the answer choices (the so-
called "target units").
Example 1.1
Sprinters can run 100 meters in just under 10 seconds. At what average speed in
miles per hour must a runner travel to cover 100 meters in 10.0 seconds?
A. 3.7 miles/hour
B. 11.2 miles/hour
C. 22.4 miles/hour
D. 36.0 miles/hour
Solution
The first task is to determine the given units and the target units. From there,
convert the given units into the target units. We are given 100 meters in 10
seconds, but the answer choices are expressed in miles per hour. Use the correct
conversion factors, as follows:
tr"-
Given . 100 m * ? x? x? = miles
10.0 s hour
Conversion of distance: 100 m* miles -miles
10.0s m s
fim,r
Conversion o1 1i*". 100 mx s - h "{r"

10.0 s hr hour
Overall:100m* 1km * lmile *3600s= 100x3600 miles c.

10.0 s m 1.609 km L.00 hr 10 x 1000x 1.609 hour
1000
100 x 3600
= x 3600 = 36 miles
1.609 L.609 hour
$o
10 x 1000x 1.609 10 10x
36 < 36 < 36, where 36 = 1g and 36 = 36. So L8 < 36 < 36 ;,;
2 1..609 1, 2 1 t.609 *.11
drn
Only choice C falls within the range of 18 to 36. J,,""
Ir
mrl
A frequent task in chemistry is the conversion between various types of
qu
temperature units, volume units, pressure units, and concentration units.
tue
Chemists, like most scientists, employ the MKS system, so the conversion from
tot
conventional units less commonly used in science to MKS units is routine. :._.
.JllllL
Example 1.2 demonstrates the interconversion between the conventional
Fahrenheit unit and the scientific Celsius unit of temperature.
-
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General Chemistry Stoichiometry Unit Conversion
Example 1.2
At what temperature is the numerical value the same, whether the units are in
Celsius or Fahrenheit?
A. 32"
B. 0'
c. -40'
D. -273"
Solution
The formulas for conversion between Celsius and Fahrenheit are as follows:
T"p= 9 T.c+32 .'. T"6=5 1t"r-sz;

59
Answering the question requires setting T'F = T"C.
T"p= 9 T"c + 32becomes: T=2T +32,soT= 1.8 T +32

55
T = 1.8 T + 32= -0.8 T = 32 :. T = -40'
Density Determination
The density of a material or solution is the mass of the sample divided by the
volume of the sample. Density is a measured quantity, determined
experimentally. Understand the techniques used to measure density. The term
specific graaity refers to the density of a material relative to the density of water,
and may be used in a question in lieu of density. For our purposes, specific
gravity means the same thing as density, but it has no expressed units.
Determining density is a typical example of dimensional analysis.
Example L.3
Exactly 10.07 mL of an unknown non-volatile liquid is poured into an empty
25.41-gram open flask. The combined mass of the unknown non-volatile liquid
and the flask is 34.12 grarns. \A/hat is the density of the unknown liquid?
8.zt g
t- flr 10.07 mL
34.13 8
o.
L0.07 mL
C. g
1.0.07 n
U.- 8.77mL
8.71mL 10.07 g
Solution
The density of the liquid is found by dividing the mass of the liquid by the
volume of the liquid. This results in units of grams per milliliter, which
eliminates choice D. The volume of the liquid is 10.07 mL, so 10.07 should be in
the denominator. This eliminates choice C. The mass of the liquid is the
difference between the final mass of the flask and liquid combined, and the mass
= of the flask (34.12 - 25.41), which is equal to 8.71 grams. This means that the
f numerator should be 8.71. The correct answer is choice B. Incidentally, the
question did not state the reason for using a non-volatile liquid. The liquid must
be non-volatile, to prevent any loss due to evaporation from the open flask. In
1
t.
the event the liquid evaporates away, then the mass you determine is too small,
due to the loss of vapor molecules.
I
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General Chemistry Stoichiometry Unit Conversion {
=
Density questions may on occasion involve a more intricate conversion of units.
For any density question, keep in mind that the target units are mass solution I
divided by volume solution. The mass percent of a solute is mass solute divided
by mass solution. The product of the density and mass percent is mass solute
divided by volume solution. Converting the mass of solute into moles of solute
yields molarity. Example 1.4 shows this.
Example 1.4
\A/hat is the molarity of a3"h NaCl solution with a density of 1,.05 grams/ml?
A. 0.497 M NaCl
B. 0.504 M NaCl
C. 0.539M NaCl
D. 0.724M NaCl
Solution
The first step is to determine the units you are looking for, which in this example
is moles solute per liter solution. You must find both moles solute and liters
solution. The density of the solution is 1.05 grams/ml which means that one j
liter of the solution weighs 1050 g. Three percent (3%) of the solution is sodium
chloride, so the mass of sodium chloride is 0.03 x 1050 g. This is the same as 37o
of 1000 g+3% of 50 g, which is 30 g + 1.5 g = 31.5 g of NaCI per liter solution.
The grams of sodium chloride are converted to moles by dividing by the
molecular weight of NaCl (58.6 grams/mole). The unit factor method is shown I
below: n
.l
3 g NaCl l
1.g5 Ssolution * loooml-* -. mole NaCl .g
mL solution L 100 g solution 58.5 g NaCl 1
3 moles NaCl 3.15 x lOmoles NaCl

= 1.05 x 1000x
100 x 58.5 L solution= 58.6 L solution
On the MCAT, you will not have time to solve for values precisely, so you must
make an approximation. Select the answer that is closest to that approximation.
Q =1, so the value

31.5 > is greater than 0.500 M
58.5 60 2
31.5 < 33 = 11 =5L, so the value is less than 0.550 M
58.6 60 20 100
The value falls between 0.500 M and 0.550 M, so choices A and D are eliminated.
Next you must choose between 0.504 M and 0.539 M. The value is not close
enough to 0.504 M, so you should choose C, and be a wise student! Wise
students are a good thing. Some questions on the MCAT may present
mathematical set-ups, without solving for an exact number.
The physical sciences section of the exam incorporates physics and general
chemistry, so from the beginning of your review, make a conscious effort to
consider physics when working on general chemistry and to consider general
chemistry when working on physics. Determining density is a problem conunon
to both disciplines. Example 1.5 shows an approach to the concept of density
that is more typical of what is found in a physics problem'
Copyright @ by The Berkeley Review 6 The Berkeley Review

General Chemistry Stoichiometry Unit Conversion
Example 1.5
What can be concluded about the density of a metal object which, when placed in
a beaker of water at room temperature, sinks to the bottom?
A. The density of the metal is less than the density of either water or ice.
B. The density of the metal is less than the density of water, but greater than the
density of ice.
C. The density of the metal is greater than the density of water, but less than the
density of ice.
D. The density of the metal is greater than the density of either water or ice.
Solution
When an object floats in a liquid medium, its density is less than that of the
medium surrounding it. The fact that it floats means the buoyant force pushing
upward against it (pmedium.Vobject.g) is greater than gravitation force pushing
downward (weight = mg = pobject.Vobject.g). Thus, an object floats when
Pmedium > Pobject. Because the metal object sinks in water, it must be denser
than water. Ice floats in water, meaning that ice is less dense than water and thus
less dense than the metal object. The density of the metal must be greater than
the density of either water or ice. The correct answer is therefore choice D.
Typical Conversions
In chemistry, conversions between products and reactants are common, so the
mole concept is frequently employed. The mole concept is pertinent in the
interconversion between moles and mass, using either atomic mass (for
elements) or molecular mass (for compounds). These calculations involve using
the unit factor method (also known as dimensional analysis.)
Example 1.5
F{ow many moles of NaHCO3 are contained in 33.6 grams NaHCO3?
A. 0.20 moles NaHCO3
B. 0.40 moles NaHCO3
C. 0.50 moles NaHCO3
D. 0.60 moles NaHCO3
Solution
The first step in determining the number of moles is to determine the molecular
nass of NaHCO3. The mass is 23 + 1. + 12 + 48 = 84 grams. The number of moles
ot NaHCO3 is found by dividing 33.6 by 84, which is less than 0.50. This
eLi.srinates choices C and D. The number is greater than 0.25 (21 over 84) and
nus greater than 0.20, so choice A is eliminated. The only value left is choice B,
-"{0 moles.
3er-ond determining the moles from.grams for the same compound are questions
-,q-herethe moles of products are determined from the grams of reactants. These
:;estions require converting from grams of a given substance to moles of the
;:';en substance, and then expressing the quantity of a final substance in terms of
:ones, grams, or liters. By balancing the reaction, the mass of a selected product
:at is formed in the reaction can be calculated based on the mass of a selected
=a,ctant (which must be the limiting reagent). Examples 1.7 and 1.8 involve
retermining moles, mass, and volume from the given values.
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General Chemistry Stoichiometry Unit Conversion Ge
Example 1.7
Based on the following reaction, how many grams of water would form from
{$!rnu
0.33 moles CaH16O reacting with an unlimited amount of oxygen gas?
lrsin
CaH16O(g) +6O2G) aCO2G) +5H2O(g) i--
r@fl
A. 18.00 grams ffimmn$
B. 24.00 grams - p,mmiii

C. 30.00 grams If,rufle
D. 36.00 grams ryriilllilmnr
ir,mrik,",-'tn*;
Solution Tmm
with an excess of oxygen, the limiting reagent in this reaction is C4H16o. The tfrs ,lit
amount of water formed is determined by the 0.33 moles of CaH1Oo reactant. reldjnt
Using the balanced equation, the ratio of H2O to moles CaHlgO is 5 : 1, so I.667 *lw
moles of water are formed. At 18 grams per mole, this means that fewer than 36 {!mwm
grams but more than27 grams are formed. This makes choice C the best answer. JMIil;
5 *,olujl_ro_ tt qt31 x S6ffi

molesC+Hroo
" 1- mole CalItOO" 1 mole H2O=l3 5*
0.33 18 gH2o = 30 gHzo Tne
" siynlc
n
gxmmfire
Example 1.8
How many liters of Coz(g) result from the complete decomposition of 10.0 grams
of CaCO3(s) to carbon dioxide and calcium oxide at STP?
CaCO3(s) CaO(s) + COz(g) }lq&affi
A. 1.12 liters ---+ fum
B. 2.24liters ".nf;flq
C. 3.36liters nfr&dpdf
D. 4.48liters fu'ilm'
Solution T,&M
You are asked to determine the amount of product from a known quantity of mi mr
reactant. The first step rn problems of this type is to make sure the reaction is ryrnnfll:l
balanced. In this case, it is already balanced. The mole ratio of the two wfirnre
compounds is 1 : 1. The required conversion involves changing from mass ]lmtnm
reactant, to moles reactant, to moles product, and finally to volume product. u
This is one variation of unit conversion via mole ratio calculation. In addition, fuum
there is th" "g-m - m - g" conversion and the "v -m -m - g" conversion. you w'luryfr
need three steps to go from grams reactant to the target (liters product). Units
are important here. The units for the mass of reactant is grams. You need to
multiply mass by moles and dir.'ide by grams. This is the same as dividingby the
MW. The second step is to read the mole ratio from the balanced equation. L:r
this reaction, the mole ratio is 1 : 1 (the units of both numerator and denominator
are moles). The third and final step is to convert from moles product into liters
product (i.e., multiplr' br' liters and divide by moles.) This is done by
multiplying by the molar volume of the product gas, which at STP (standard
temperature and pressure) is 22.-1 Liters.
10 gramsCaCO3 x ,
a1a9? ,. 1 mole CQ *22.4liters COz
-1*ot"
100 gramsCaCO3 l mole CaCO3 l mole CO2
=
1o x Z2.-l
= 2.24liters Co2 fum
100 qwifurd
uMttm
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r(-0ryDilu
I General Chemistry Stoichiometry Elemental Analysis
Elemental analysis determines the atomic composition of an unknown molecule.

It is based on the idea that all molecules of the same substance combine atoms of
that substance in the same way. Lr other words, water always has two hydrogen
atoms and one oxygen atom. Because of this feature of structural uniformity, it is
possible to determine the atomic composition of any molecule. The fundamental
process of elemental analysis involves oxidizing an unknown completely and
collecting the products. The amount of each element that was present in the
unknown compound can be determined from the amount of oxidized product.
These mass values can be converted to mass percent and mole ratio values. In
e
the determination of the empirical formula, the mass percent is converted to a
:.
relative mass value and then a relative mole value. The mass percent of an
7
element within a compound must be determined prior to determining the
)
empirical formula for an unknown compound. An empirical formula, you may
recall, is the simplest whole number ratio of the atoms in a molecule.
Mass Percent (Percent Composition by mass)
) The mass percent of a particular element within a compound is found by
dividing the mass of that element by the mass of the compound and then
converting the fraction to a percentage. This is shown in Equation L.1.
mass percent - mass atoms x 100"h (1.1)

S
mass compound
Mass percent can never exceed 100% for any component element. Determining
the mass percent of an element from the molecular formula is a straightforward
task, although the math may be challenging. Mass percent questions can be
asked in a concepfual or mathematical manner. Mass percent is independent of
the total mass of the sample of compound.
Table 1.1 shows the relative masses of oxygen and carbon from different samples
t of carbon dioxide. This demonstrates the law of multiple proportions. Atoms
S combine in a fixed ratio in terms of mass and moles. Note that the outcome is the
) same in all four trials measuring the ratio of oxygen gas that reacts with a known
S mass of carbon. The experiment involves oxidizing a known amount of carbon
and collecting the product gas. The mass of this product gas is determined, and
the mass of oxygen is assumed to be the difference between the initial and final
I weighed masses of the carbon sample.
S
) Mass Or
Mass Carbon Mass Orygen /Mass C
e
3'53 1. nn =2.6s
n L.33 g 3.53 g / I.JJ
r 2'8'
s 1.07 g 2.87 g / r.0, =2.68
Y
t i.11 g 296 g
''nu / r-rt=2'67
3'39
1.27 g 3.39 g / 't.27 =2'67
Table 1.1
The mass ratio of oxygen to carbon in the four trials avelages out to be2.67 :1',
which is roughly 8 : 3. This means that for the oxidation product of carbon, the
ratio of oxygen to carbon is 8 grams to 3 grams, equivalent to 2 moles to 1 mole.
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General Chemistry Stoichiometry Elemental Analysis j
5r
Example 1.9
How much calcium metal combines with one gram of oxygen to form CaO?
A. 1.00 g Ca
B. 1.25 gCa
C. 7.67 gCa
D. 2.50 g Ca
Solution A,'
From the molecular formula, the mole ratio of calcium to oxygen is 1 : 1. The
atomic mass of calcium (Ca) is 40.08, while the atomic mass of oxygen (O) is *tH
16.00. The mass ratio for the compound is 40.08 to 16.00, which reduces to 2.505 :
1, which rounds to 2.50 to 1. This means that 2.50 grams of calcium combine with
1.00 grams of oxygen to form CaO. Choice D is best.
l\r.i
Example 1.10
What is the mass ratio of iron to oxygen in Fe2O3? -f
i&
A. 1.08 g Fe to 1.00 gO
:
B. 1.63 g Fe to 1.00 gO
C. 2.33 gFe to L.00 gO &1t
D. 3.49 g Fe. to 1.00 gO
Solution
From the molecular formula, the mole ratio of iron to oxygen is 2 : 3. The atomic lhr
mass of iron (Fe) is 55.85, while the atomic mass of oxygen (O) is 16.00. The mass
ratio of iron to oxygen for the compound is 2(55.85) to 3(16.00), which equals
UrE
771,.7 :48.0. This ratio is approximately equal to 116 :50, or 232:100, which
ilm,,.h
reduces to 2.32: 1. Both numbers must be increased proportionally to keep the
ratio the same. Choice C is a ratio of 2.33 to 1, which is the closest of the choices. A"
This means that 2.33 grams of iron combine with 1.00 grams of oxygen to form t,
Fe2O3. Choice C is best. You should note that iron and oxygen can combine to C
make other compounds (with different molecular formulas). One of these n.
compounds is FeO, with a mass ratio of 55.85 to 16.00, which reduces to a ratio of
3.49 : 1.00. The mass ratio (and mole ratio) of an oxide can be used to identify a Solifr
TL.
specific compound. This process is known as combustion analysis. rL.ffi
lftwl,:nI
]:TTMN
Examples 1,.9 and 1.10 demonstrate how mass percent questions can be n'rmn
mathematical. Mass percent questions can also be asked in a conceptual manner,
where the relative mass percentage of a specific element is compared for several
compounds. Examples 1..1.1., 1..1.2, and 1.13 demonstrate some different forms of
this type of question, starting with typical examples and graduating to more
abstract ways of asking for mass percent.
Oilut
L$lrui
Example 1.11 :m0:n
VVhat is the mass percent of oxygen in carbon dioxide? pwmr
A. 27.3% dillnqlllll.r
B. 57.7% .fi@u!u!
c. 62.5%
D. 72.7% tu
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General Chemistry Stoichiometry Elemental Analysis
Solution
The mass of carbon in CO2 is 12 grams, and the mass of oxygen in CO2 is 32
grams. The total mass of CO2 is 44 grams, so the mass percent of oxygen is the
ratio of 32to 44. This ratio reduces to 8 over 11.
MassoercentO=
328o x 100% -32 *'J.00"h =3 x 100%
' 44 gCOz 44 11
Quick Calculation Technique:

Quick calculations require knowing the values of selected fractions. One-
eleventh is equal to 0.091; therefore, eight-elevenths is equal to 8(0.091) = 0.728.
This method gets an exact value and is very fast, if you know how to do it.
8 8x I = 8x =
11= 11
0.091 = 0.728 72.8"h
Narrowing-Down-Choices Technique:
On a multiple-choice exam, you can eliminate answers by narrowing down the
range into which the answer fits. 8 over 11 is less than 9 over 12,but greater than
7 over 10. A range has been established between 9 and !. 9 ou"t 12 is 75"/o,
12 10
and 7 over 10 is70"h, so the correct answer falls betweenT}% and75"/'.
-9 >-8 > T,where 9-=75"/o and,f-=70o/o.So:75"/.>L> 70%
72 1L 10 12 10 11
C:roice D is the best answer.
Example 1.12
lVhat is the mass percent of nitrogen in NHaNO3?
L. 28%
B. 35%
c. 42%
D. 50%
Solution
The total mass of the nitrogen in the compound is 28 g/moIe, because there are
trvo nitrogen atoms in the compound at1"4 g/mole each. The mass of the
compound is 28 + 4 + 48 = 80 g/mole. You must divide 28 by 80 quickly. The
couunon denominator of both is 4. Reducin gby 4yields a fraction of Z.
20
Masspercen,N =,, gNHaNO3

?89T-- x 100% =D* 100"h = J-x fi}%
80 80 20
Quick Calculation Technique:

Quick calculations may involve getting a denominator to some easy-to-use
nurnber, such as 10, 100, or 1000. It is easy to convert a fraction into decimals or
percents when the denominator is either 10, 100, or 1000. For this question, a
denominator of 100 works well. To convert 20 to 1"00, we must multiply by 5.
Multiply both numerator and d.enominatorby 5, to change the fraction -7 ' b E.
20 100
correct.
The percentage is 35%, so choice B is
28=7 =35 =0.35=35%
80 20=7xS
20 x5 100
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General Chemistry Stoichiometry Elemental Analysis Gr
Narrowing-Down-Choices Technique:
Narrowing down the range into which the answer fits can be applied to any Er.a-
multiple-choice math question. 28 over 80 reduces to 7 over 20. The value of 7 '"]-
over 20 is greater than 7 over 21., but less than 8 over 20. A range has been -1[-
established between Z and !. The value of 7 over 21 is 33.3"h, and the value of El
21. 20
8 over 20 is 40"h, so the correct answer falls between33.3% and 40"/o. Only choice m
B fits in this range, so choice B must be the correct answer.
7 <J- < 8,where J*=33.3"h and! =40"/o. So33.3% <f-<+0"/, 5u,riri
21. 20 20 21 20 20 .ir n
: tE:.s
Example 1.13
\A/hich of the following samples yields the MOST moles of sodium cation?
A. 1.0 gNaCl
*l
luil:l:
B. 1.0 g NaBr :lrrtul
C. 1.0 g NaNO3 tri- *
D. 1.0 g Na2CO3
trs
Solution f ]::
r,i[
This question is a subtle way of asking, "Which salt has the greatest mass percent *ninq i{
of sodium?" All choices are 1.0 g of compound, so the most moles of sodium are
found in the compound with the greatest mass percentage of sodium. Choices A,
B, and C have the same number of sodium atoms in the compound (one), so they
each have the same numerator in the mass percent formula. The best choice of ;iiLrLjirlilfr,
those three salts is the lightest compound (resulting in the smallest denominator rsmmI
when calculating mass percent). The lightest compound of the three choices A, ri&
B, and C is the salt with the lightest anion, which is choice A, NaCI. Now the il.
question involves comparing the mass percent of sodium in NaCl to the mass
percent of sodium in Na2CO3, choice D. l
Mass percent Na in NaCl = q-*i- x r00"/. =
o
x 700'/,
-1u g
NaCl
58.5 =.?3
58.5
tillur11]u
f ir {
*:- x 100% - 46 x 100% t -l1Ir
Mass percent Na inNa 2Cos = - 1u 9i
106 gNa2CO3 106 =D xrll"/o ffiffi
53
]firus r
23> 23 , so choice D is the best answer. lItmnil
53 58.5 rng
iMum :
Empirical Formula rumPul

An empirical formula for molecules uses the smallest whole number ratio of the
atoms in a compound. It is the formula that gives the relative numerical values
for each element in the molecule in such a way that the numbers in the ratio {UiWllIrN
cannot be reduced without involving fractions. An empirical formula may or lui & .]ll
may not be the actual formula of the molecule. It is calculated from the mass .ruglmilr
percentage of each element within a compound. You may recall from your r.'m I
general chemistry courses that we start by assuming a 100-gram sampie, so that
the percentages can be changed easily into mass figures. From this point, it is a
matter of converting from mass into moles, using the atomic masses for each
element. The empirical formula is a whole number ratio of these mole values.
Empirical formulas must include whole number quantities as subscripts.
Copyright @ by The Berkeley Review t2 The Berkeley Review !Jm[.iI

Example 1.14
\4/hich of the following is an empirical formula?
A,. C2H6
B. CeHs
C. CaHro
D. C6H6
Solution
-\n empirical formula for a molecule is defined as the formula in which the
:onstituent atoms are in their smallest possible whole number ratio. Choice A,
CtH6, can be reduced to C1H3 (normally written as CH3), so choice A is not an
enpirical formula. Choice C, C4H1g, can be reduced to C2H5, so choice C is not
-. empirical formula. Choice D, C5H6, can be reduced to C1H1 (normally
.'.-iitten as CH), so choice D is not an empirical formula. This eliminates all of the
-:.oices except choice B, C3Hg. The ratio of 3 : 8 cannot be reduced any further,
C3Hg is an empirical formula, making choice B the correct answer. In the case
':
-: C3Hg, the empirical formula and the molecular formula are the same, because
---.e compound is completely saturated with hydrogens' CeHtO has too many
- -,'Jrogens and isnot a possible formula. Organic chemistry rules can help to
-: . = nme on formula questions.
E"r,a-mple 1.15
,',1a: is the empirical formula for a compound that is 72"/o C, I2"/' H, and
i r ::.rcrsed solely of carbon, hydrogen, and oxygen?
4" '::HfO
Ir 'llHt2O
: 'J;l{1-1O
:' --l{1aO C)
:,: lution
: .:
=:.pir-ica1 formula calculations, assume a 100-gram sample of the compound.
.. -.'.--am sample in this case would contain 72 grams C, 12 grams H, and 16
o/
::::^, ,J. The 16 grams of oxygen are determined from the difference between
'i*: :-ai: of carbon plus hydrogen and the 100 grams of sample. Next, you must
r :: ::-l fie grams of each element into the corresponding moles of each element.
'- r
r - ::,:.r glams to moles, divide the mass of the element by its atomic mass' In
:". ::*ie 12 grams of C is equivalent to 6 moles of C, 12 grams of H is equivalent
: -- :.l-es of H, and 16 grams of O is equivalent to l mole of O. This is a
r l:::-*::1-'- easv example, because the ratios turn out to be whole numbers. In
ie rl;r: -,-,'i,r thev don't come out whole, you must divide the mole quantity of
IS .i :i :-::r-er1t in the compound by the lowest mole quantity for any of the
.o , ritr :r i-i l-{orvever, for this example the best answer is choice B. Drawn below
)r ,F i --:"::--i- ia""'out of empirical formula calculations. It is often easier just to plug
>S r, ri:.-i -r i r ar. equation such as this, because you don't have to show your work
1r - ::: l-lC-\T. Do the questions as quickly and carefully as you can/
at .II1 r *:;r-:::"i organization in your path to a solution.
a
fr fl percentage hydrogen O percentage oxygen = CZ2}I]O1f. = COHTZO I
"I 16
-ola. -ass hydt.gen molarmass oxygen 12
5.
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Example 1.16
What is the empirical formula of an oxide that is 60% oxygen by weight?
A. SO lr,e
B. SOz \
C. SzOs s
D. SO3
3
Solution
:riltrj
Here again you should assume a 100-gram sample. A 100-gram sample would
ll:,.
have 60 grams of oxygen and 40 grams of sulfur. The moles of O = 60, and the :1".l]itF
16
moles of S = n-. 60 is more than double 40, so there are more than two oxygen
32 16 32 :r:tt5
:Ul,:,i
A and B. By reducing
atoms per sulfur atom. This eliminates choices
zzto2!,
4'9-
" 1.6 .1fl,5 -
we find that the ratio of oxygen to sulfur is 3 : 1. This makes choice D the best
answer.
$ percentage sulfurO percentage oxygen = S40060 = SZq060 = S103
molar mass sulfur molar mass oxygen 32 16 1'6 1'6
*!t
The test emphasizes ratios, so the more numerical intuition you develop, the _-;
better. To make problem-solving less mathematical, focus on eliminating choices lD0tIrlr
by comparirtg relative ratios. An alternative way to ask an empirical formula trr.lr]ll
question with reduced math is shown in Example 1.1,7. _ lHt
trmfti
mqw
Example 1.17
If a molecule is composed of only two elements (X and Y), and if X and Y
combine in equal mass quantities, and if Y is less than twice as heavy as X, which s[cE[
of the following molecular formulas is NOT possible? ru[
A. XY
B. XYz ihtiu
C. XsYz .,4.
a
D. X3Y
Solution 3
If Y were exactly twice as heavy as X, then equal masses of X and Y would result
Sumu
in exactly twice as many moles of X as Y, a2:1 ratio of X to Y. Because Y is less *- !n
than twice as heavy as X, there are fewer than twice as many moles of X as Y.
TUffm
Thus, the ratio of X : Y must be 2 : l or smaller. This limiting ratio is true of all
the answers except choice D. The wording of this question allows for the
Toe .a
rb .il{s
possibility that the molecular mass of X is equal to or greater than Y.
rimlxnl
F.uls
l'4$;
Molecular Formula
The molecular formula is the actual mole ratio of the elements within the
:ngu0ru
fil!tmn
compound. The molecular formula is found by multiplying the empirical
formula by the whole number ratio (including 1, in some cases) of the molecular "tuluu
mass to the empirical mass. Therefore, conversion from the empirical formula to
the molecular formula requires knowing the molecular mass of the compound. If
:}rn*
the molecular mass is double the empirical mass, then all of the elements in the
empirical formula are doubled to get the molecular formula.
:
Copyright @ by The Berkeley Review t4 The Berkeley Review *"nr
Example 1..L8
What is the molecular formula for a compound that is 82.76% C, has a molecular
mass of 58.1 grams per mole, and is composed solely of carbon and hydrogen?
A. CH2
B. CzHs
C. CsHs
D. C4H1s
Solution
Choice B is eliminated immediately, because a hydrocarbon cannot have an odd
number of hydrogens. For neutral C2H5 to exist, it would have to be a free
radical. Continuing to use organic chemistry logic, choice A is not physically
possible. One carbon requires four bonds to hydrogen atoms to form a stable
molecule (methane). C1H2 would be a carbene (:CH2), which is not stable due to
its lack of an octet. To decide between choices C and D, you must first find the
empirical formula, and then convert that into the molecular formula.
( percentage carbon H percentage hydrogen- C82.76Ht7.24 =Ce .ggHtZ.Z+
molar mass carbon molar mass hydrogen 72 1
empirical formula: C#+# = CtHtTs = C1H2.5 = C2Hs
An empirical formula of C2H5 when multiplied by a whole number cannot yield

C3Hg, so choice C is eliminated. This leaves only choice D. The correct ratio of
molecular mass to empirical mass confirms that choice D is the best answer. The
molecular formula is found using the molecular mass of 58.1 grams per mole.
The empirical mass is 2(12) + 5 = 29. This value is only half of the molecular
mass, so the formula must be doubled to yield C+HfO. This question could have
been solved in seconds by seeing that only choice D has a molecular mass of 58.
Example L.L9
-{n unknown stable gas is composed of 13.10% H, 52.23"h C, and the remainder
O. A 0.10-mole sample weighs 4.61 grams. \Alhat is the molecular formula for
dre compound?
A. C2H6O
B. C3H3O
C. C3HeO
D. CaHsO
Solution
-{ stable compor.rnd made of carbon, hydrogen, and oxygen cannot have an odd
rumber of hydrogens, so choice C is eliminated. Neutral C3H9O would have to
:e a free radical. The remaining choices obey the octet rule. The molecular mass
-16.1, so choice A is the correct answer. That is the method you should use on a
=
=tultiple-choice exam. Now let's confirm that by using
the molecular formula.
iirst you must assume a 100-gram sample, resulting in 13.10 g}{,52.23 g C, and
34.67 g O. Next, the numbers are converted into moles, and then the values are
=duced to a whole number ratio. The calculation of the empirical formula is
=hown below, where a formula arrangement is used to help keep track of the
;alues,
Cq?23fiEJq 094"62- = Ca.aHtg.t oz: =C+.+Huto?z =C2H'6o1
12 7 1.6 2.2 2.2 2.2
The empirical mass is 2(12) + 6 + 1,6 = 45. This value is equal to the molecular
:lass, so the empirical formula is the molecular formula.
Copyright @by The Berkeley Review l5 Exclusive MCAT Preparation

General Chemistry Stoichiometry Elemental Analysis G
Combustion Analysis (an Experimental Procedure)

Combustion analysis entails determining the mass percent of each component
s
element in an unknown compound. It is accomplished by oxidizing the lLr
unknown with excess oxygen (to ensure complete combustion), followed by the )--.
separation and collection of all of the oxidized products. This is an experimental :;
procedure, which makes it a likely topic on a conceptual exam such as the ::
MCAT. When a hydrocarbon is oxidized, carbon dioxide and water are formed.
Carbon dioxide and water can be separated using various methods. One method ]1:
involves passing the CO2 gas and H2O vapor across a hydroscopic salt of known l-l
mass. The hydroscopic salt absorbs the water, and thus increases in mass. ::
The hydroscopic salt must not react with carbon dioxide. A good choice for the ::
hydroscopic salt is either calcium chloride or magnesium sulfate (both of which lr
i..
you should have used as drying agents in your organic chemistry lab). Once the J
water is absorbed, the remaining gas is passed across a sample of KOH of known hfi,r
mass. KOH is a base that reacts with acidic carbon dioxide to form potassium fr.
'lt
tilt.
bicarbonate (KHCQ). The potassium hydroxide salt absorbs the carbon dioxide, s;:
and thus increases in mass. Knowing the masses of CO2 and H2O, we can ;g'
'.
determine the masses of carbon and hydrogen by multiplying the mass percent iI
of each element by the mass of its respective oxide product that was collected.
Upon dividing these numbers by the mass of the original sample, the mass :
percent of hydrogen and carbon in the original sample is determined.
-,"T-
The carbon dioxide and water can be separated and collected using a different
method than passing the gases over salts that bind the products. By lowering the ,4-
temperature, carbon dioxide and water can be converted to their solid states. U'
Because solids do not flow, they can be collected easily. The math is the same, c.
once the quantity of each product has been established.
Figure 1-1 shows a typical apparatus used in a combustion analysis. The oxygen
tank serves to provide excess oxygen to the system constantly. The pressure $rur
valve is a one-way valve designed so that oxygen can flow into the sample iMr&L:
chamber, but no gases can flow back. The resistor in the base of the sample !trill;
chamber provides heat to initiate the oxidation. The tube to the right of the mffi
sarnple chamber is connected to a vacuum, to generate a low pressure. Once the
reaction is complete, Valve #3 is closed so that no gases are lost to the
environment, and Valve #1 is opened. Gases flow into the region above the
magnesium sulfate. Magnesium sulfate absorbs moisture from the gases. After a
time, Valve #2 is opened so that gases flow into the region above sodium u
hydroxide. Sodium hydroxide absorbs carbon dioxide gas. Oxygen gas is then
used to flush any remaining gas in the sample chamber through the system' TInI
md
ilro
h,w
Pressure
valve
Valve #1 Valve #2 Valve #3 ,0rfic
M5
'tdr
MgSO+(s) NaOH(s) m{m
wt
flm
M
lflm'
Variable voltage
f$filr
Figure 1-1 Wt
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rfl-im
General Chemistry Stoichiometry Solution Concentration
t
#ffiilffffirfiffixiiffi$ffi$ffsr#
e Units and Terminolgy
Solutions are mixfures formed by the addition of a solute to a solvent. A solution
I may contain several different solutes. The amount of solute is measured relative
e to the amount of solvent, which results in a certain concentration for the solution.
t. Concentration units include molarity (moles solute per liter of solution), molality
1 (moles solute per kilogram of solvent), mass percent (mass solute per mass of
n solution), and density (mass solution per volume solution). The concentration of
a solute can be changed by changing the amount of solvent. Addition of solvent
e to solution is referred to as dilution and results in a lower concentration by any
h measurement. Paramount to solving problems involving concentrations and
e dilution is an understanding of the different units'
n
Molarity
n
\{olarity (M) is the concentration of a fluid solution defined as the moles of a
solute per volume of solution, where the volume is measured in liters (L). To
m
Cetermine the molarity of a solution, the moles of solute are divided by the liters
rt of solution.
i.
;S
Erample 1.20
rt "r\hat is the molarity of 500.0 mL of solution containing 20.0 grams of CaCO3(s)?
re
-{. 0.15 M CaCO3(aq)
S. B. 0.20 M CaCO3(aq)
C. 0.33 M CaCO3(aq)
D. 0.40 M CaCO3(aq)
n
re Solution
le \tolarity is defined as moles of solute per liter of solution. In this question, you
le ru.rst convert from grams CaCO3 into moles CaCO3 by dividingby the molecular r,i
re :iass of CaCO3, and then dividing this value by the liters of solution: f*,'-.-
',t- ."t. "'
IE
2o grams CaCQ e'$
te = o.2o moles CaCo3
te 100 Srams/
/mole
'a
-.10 moles CaCOg
m =0.20 M CaCO3 =0.40 M CaC03 = 0.40 M CaCO3, choice D
)n -r.50 L solution 0.50 1
laese questions can be trickier if the units are milligrams, milliliters, or

:jlimolar. The question uses similar math, but there are more oppoltunities to
:::ke an error. A common error to avoid is the "factor of a thousand" error. To
:e.ome more conscious of possible trick questions, ask yourself: "If I were
-u-nting this test question, what would I ask?" If you consider questions from the
:.*t rr.riter's point of view, the tricks become more apparent.
\folality
}-{rlality (m) is the concentration of a fluid solution defined as the moles of a
.-.-ute per kilogram of solvent. The molality of a solution does not change with
:.nperature, so it is often used to determine a change in the solution's
:::lperature when the change depends on concentration. Notable examples of
::s include boiling-point elevation and freezing-point depression. To determine
:,e nnolality of a solution, the moles of solute are divided by the kilograms of the
::1.;ent.
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General Chemistry Stoichiometry Solution Concentration G
IfE
Example L.21 Tb
\A/hat is the molality of a solution made by adding 7.46 gKCl to 25a g of water? pEr
A. 0.20 m KCI(aq) dc!
B. 0.33 m KCI(aq) tu
C. 0.40 m KCI(aq) tu
D. 0.50 m KCI(aq) trm
&
Solution
Molality is defined as moles of solute per kilogram of solvent. In this question, r
you must convert from grams KCI into moles KCl by dividing by the molecular m
mass of KCl, and then dividing this value by the kilograms of solvent: tu
7.46 grarnsKCl
d
= 0.10 moles KCI foa
74.6gIamsl/mole rffi
0.10 moles KCI -0.10 m KCI =0.40 m KCI = 0.40 m KCl, choice C
0.25 kgH2O 0.25 L
m
mlfl
Mass Percent (in Solution)
Mass percent is the concentration of a fluid solution defined as the mass of solute
h
per mass of solution multiplied by one hundred percent. The mass percent of a
{m
solution remains constant as temperature changes. To determine the mass ry
percent of a solution, the mass of solute is divided by ihe mass of the solution [F
(where both are measured in grams). Mass percent is a unitless value, because
mass is divided by mass.
#
tu
tu
Example 1.22
What is the mass percent of a 1.0 m NaCl(aq) solution?
A. 5.53% NaCl by mass
B. 5.85% NaCl by mass
C. 6.22%NaCIby mass
D. 9.50% NaCl by mass
Solution
Mass percent is defined as grams of solute per grams of solution. In this
question, you must convert from moles NaCl into grams NaCl by multiplying by
the molecular mass of NaCl, and then dividing this value by the total mass of
solution. The total mass of solution is the sum of the mass of solute and the mass
of solvent. It is easy to forget to consider the mass of solute in the total mass,
which leads to the incorrect answer choice B.
1.0 moles NaCl(aq) x 58.5 8/-ole = 58.5 g NaCl
Total mass solution = 58.5 g NaCl + 1000 g H2O = 1058.5 g solution
58'5 g NaCl 58.5 < 58.5 = 5.85%
Mass % NaCl = 1058.5 g solution
, where
1058.5 1000
Only choice A is less than 5.85%, so choice A is the best answer. Sometimes
questions that would normally require a calculator for a precise answer can be
determined well enough without one to answer a multiple-choice test question.
Copyright @ by The Berkeley Review la The Berkeley Review

General Chemistry Stoichiometry Sotution Concentration
Density
Density (p) is the concentration of a fluid solution defined as the mass of solution
per volume of solution. The density of a solution varies with temperature. The
density of a solution is uniform throughout, so a small sample of the solution has
the same density as the entire solution. To determine the density of a solution,
the mass of a sample of the solution is divided by the volume of the sample
(usually measured in milliliters). Examples 1.3 and 1.5 addressed the topic of
density.
Dilution
Dilution involves the addition of solvent to a solution, thus resulting in an
increase in the volume of the solution and a decrease in the concentration of the
solute in solution. Equation 1.2 below describes simple dilution where a solvent
js added to solution. Determining the concentration when two solutions are
mixed requires more work than simple dilution.
Mir,itiul'Vinitiil = Mfinal'Vfinut (1.2)
I*then working with ditution questions, be aware of a common twist that the
ititers can employ. Their question may ask for aolume added tathet than asking
ior the final total volume. Percent dilution may also be discussed. Multiple
:ontainers are used in standard dilution procedure, so rinsing ensures that the
;.rn-rcentration of solution on the walls of the new containers are equilibrated with
i,e contents they will hold. You may recall filting a volumetric pipette with a
o:lution in general chemistry lab, then draining the pipette before filling it with
::e sample to be transferred. This is done to ensure that any residual liquid in
:te pipette has the same concentration as the solution being transferred and that
=.i- rvater in the pipette is rinsed away.
Lrample 1.23
r'*:"at is the molarity of a solution made by mixing 200 mL pure water with 100
:10.75 M KCI(aq)?
-q- 0.25 M KCI(aq)
ts 0.50 M KCI(aq)
C 1.50 M KCI(aq)
s
D. 1.25 M KCI(aq)
v i,ol,ution
rf
],.-;;L15e water has been added to the solution, the concentration must decrease,
;S
jloices C and D are eliminated. Solving this question involves using Equation
i, ':- :o determine the effect of dilution on the molarity. The initial molarity
-
l,{-.rut) is 0.75 M, the initial volume (Vmiti"t) is 100 mL, and the final volume
-'-_:r-xj is
300 mL. The question requires solving for the final molaritl (Mfi"ail.
Mitiud'Vir',itial = Mfinal'Vfinal 0'75 M'1-00 mL = M1i1n1'300 mL
"'
Mittitiul'Vinitiut M.100 mL
l.{:.rl = .'. Mfinal =-0.75300 mL = o.?s M(r) = 0.25 M
Vfinal
lk inat molarity is 0.25 M, so choice A is the best answer. Because the moiarity
l* je;reased by a factor of three, the dilution process in this example is referred
u as a threefold dilution. That is, when two parts solvent are added to one part
;:r.::.on. the volume is tripled and the dilution is threefold. This terminology
m,* ; be unJamiliar at first, but in a short time it should make sense'
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General Qhemistry Stoichiometry Solution Concentration e
Example L.24
How many milliliters of water are needed to dilute 80 mL 5.00 M KNO3(aq) to
h
Wht
1.00 M?
KCT
A. 160 mL H2O
B. 320 mL
lL1
H2O Lt
C. 400 mL H2O rc.l
D. 480 mL H2O
D. I
Solution n
Again, Equation 1.2 should be employed to calculate the change in concentration
of a solution after dilution from the addition of solvent. First we must solve for
tu
@
the final volume. You are provided with values for M;r.,i1i61, Mfinat, and Vini1ix1,
so you can manipulate the equation to solve for V1ir.,21.
ffir
@
Vfinal -Minitial'vinitial =5.00Mx8OmL = 5x g0mL = 400ml

M
Mfinal 1.00 M
mr||
The question asks how much water is added, not the final volume. The volume
added is the difference between the initial volume (80 mL) and the final volume
(a00 mL). The difference between the two values is 320 mL, so 320 mL of water ffiffi
must be added to 80 mL of 5.00 M KNO3(aq) to dilute it from 5.00 M KNO3(aq) to drurtll
1.00 M KNO3(aq). Choice B is the best answer. r-
h
Example 1.25 rfr
Which dilution converts 6.00 M HCl(aq) to 0.30 M HC(aq)? ryl
A. 11 parts water to 1 part 6.00 M HCI(aq) dXn
B. 19 parts water to 1 part 6.00 M HCl(aq) n0
C. 20 parts water to L part 6.00 M HCl(aq)
D. 27 parts water to 1. part 6.00 M HCI(aq) nfl
Solution
Hydrochloric acid goes from 6.00 M to 0.30 M, which is a twenty fold dilution.
This means that the final volume is twenty (20) times the initial volume. when
dealing with answer choices that present the dilution in terms of parts, the ratio
is volume of solvent added to volume of original solution. For the final volume
to be twenty times greater than the initial volume, nineteen parts must be added.
Vfinal y
=Mittitiul =9.00 =20 :.vfinal = 20 (vini1i21)
Vinitiul Mfinal=r Vir,itiul
-Yfinat 0.30 M
Vadded = Vfinal - Vi.,itial = 20 Vi61i21 - Vi.,itiul = 19 (V6i1i31)
The ratio of the volume added to the volume of solution initially present is 19 : 1,
so the best answer is choice B. A part can be any set volume. A20 :1 dilution
would result in a final volume that is 21 times the initial volume, so the final
concentration would be less than 0.30 M.
A solution can be diluted by adding solvent or another solution to it. The

addition of pure solvent is known as a simple dilution. Mixing two solutions is
more complicated than a simple dilution where pure solvent is added, because
solute from both initial solutions must be considered. The final concentration lies
somewhere between the two initial concentration values before mixing. The final
concentration is a weighted average of the initial concentrations.
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I General Chemistry Stoichiometry Solution Concentration
Example 1.26
What is the final concentration of Cl- ions after mixing equal volumes of 0.20 M
KCI(aq) with 0.40 M CaCl2(aq)?
A. 0.20 M Cl-(aq)
B. 0.30 M Cl-(aq)
C. 0.40 M Cl-(aq)
D. 0.50 M Cl-(aq)
Solution
n The salt KCI yields one chloride ion when it dissociates in water, so the chloride
r concentration is 0.20 M. The salt CaCl2 yields two chloride ions when it
I, dissociates in water, so the chloride concentration is 0.80 M. The final
concentration equals the total Cl- ions from both solutions divided by the new
total volume. Because equal volumes are mixed, the final concentration will be
an average of the two initial concentrations.
.e
0.20 M Cl- + 0.80 MCI- = 1.00 M Cf = 0.50 MCI-
L
22
:r I{ the volumes are not equal, then a weighted average yields the final
to concentration. For this example, choice D is the best answer.
Example L.27
lVhat is the concentration of K+ ions in solution after 25.0 mL of 0.L0 M
K2SOa(aq) is added to 50.0 mL of 0.40 M KOH(aq)?
A. 0.25 M K+(aq)
B. 0.30 M K+(uq)
C. 0.33 M K+(aq)
D. 0.50 M K+(aq)
Solution
n. The salt KOH yields one potassium ion when it dissociates in water, so the K+
tn concentration is 0.40 M. The salt K2SOa yields two potassium ions when it
io diq,s6sislss in water, so the K+ concentration is 0.20 M. The final concentration
ne equals the total K+ ions from both solutions divided by the new total volume.
i. tseca,tse unequal volumes are mixed, the final concentration is a weighted
a\rerage of the two initial concentrations. The mixture involves 25 mL 0.20 M K+
n'ith 50 mL 0.40 M K+, so the final concentration must fall between 0.20 M and
0.40 M. This eliminates choice D. If the two volumes were equal, the final
concentration would be 0.30 M K+, the average of the two concentrations' But
because there is more of the more concentrated solution, the final concentration is
t, greater than 0.30 M, so choices A and B are eliminated. Only choice C remains.
on 25mLx0.20MK+ *50ml-x0.40MK+ (0.20MKl *L
75mL =13
10.+oMK+)
ral 75rnL 3
+.8- Vtf* =1MK* = 0.33 MK+,choiceC
=Z333
he
iis Beerts Law
15e When electromagnetic radiation is passed through a solution, the solute may
Lies absorb some of the light. The light absorbed is in a specific wavelength range/
nal and the intensity of the absorbance varies with the concentration of solute. A
generic absorbance spectrum for a hypothetical solute is shown in Figure 1.-2.
ew Copyright @ by The Berkeley Review 2l Exclusive IICAT Preparation

General Chemistry Stoichiometry Solution Concentration (fr
ffi
gh
c,)
[,dr
WDfr
c) fur
(6 ffi
OJ
M
lrimi
I*u* Wavelength (nm) M
ilffillllt
Figure 1-2 qtr
Because the absorbance of lighi varies with concentration, absorbance can be
used to determine the concentration of a solute. This is the essence of Beer's law.
Beer's law is expressed in Equation 1.3, where e is a constant for the solute at
l,rrru* (the wavelength of greatest absorbance), C is the solute concentration (C =
[Solute]), and I is the width of the cuvette (length of the pathway through which
the light passes).
m
Absorbance = Cl (1.3)
The key feature of this equation is its expression of the principle that absorbance
is proportional to concentration. By knowing the absorbance for solutions of
known concentration, the concentration of an unknown solution can be
determined by comparing its absorbance value to the known values.
Example 1.28
For 100 mL of a solution with an absorbance of 0.511, what amount of water must
be added to reduce the absorbance to 0.100?
A. 389 mL H2O
B. 411 mL H2O
C. 488 mL H2O
D. 511mL H2O
Solution
For this question, a hybrid of Equations 1.2 and 1.3 should be employed to
determine the volume that must be added to dilute the solution. Because
absorbance is directly proportional to concentration, Equation 1.2 can be re-
written as follows:
Absinili6l.Vinitial = Abs661'Vii1a1
First, we must solve for the final volume. You are provided with values for
Absi1i1ix1, Abs1i1n1, and Vi61ia1, so you can solve for V6nn1.
Absinilinl'Vit iUut 0.511 x 100 mL - 5.11 x 100 mL - (1 1 mT
Vfinal - -
Abs1i61 0.100 1
The question asks for how much water is added, which is the difference between
the initial volume (100 mL) and the final volume (511 mL). The difference
between the two values is 41,1, mL; therefore, 4L1 mL of water must be added.
The best answer is choice B.

n General Chemistry Stoichiometry Balancing Reactions
B"ffififf RHHruffi$ffigiii
Standard Balancing
Let us briefly address the process of balancing chemical reactions. Reactions are
lvritten from reactants to products. Because of the law of conservation of matter,
the number of atoms must be identical on each side of the reaction. The two
sides of the reaction are separated by an arrow drawn from left to right.
C5H12(l)+Oz(g) COz(g)+H2O(g)
There are carbon atoms, hydrogen atoms, and oxygen atoms on both sides of the
reaction. To balance the reaction, keep track of the atoms on each side of the
reaction. Start with the compound whose atoms are least present in the reaction
(carbon and hydrogen are present in only two compounds each, so we start with
CSHTZ). Starting with one CSHIZ, the atoms must be balanced step by step:
re 1C5H12(l) + Oz(S) ---l> COz(g) + H2O(g)
5C ?C
lt 72H ?H
?o ?o
h
Balance carbon atoms by multiplying CO2 by five:
1C5H12[) + Oz(g) 5 CO2(g) + H2O(g)
3)
5C --> 5C
:e
72F{ ?H
rf ?O 10+?O
)e Balance hydrogen atoms by multiply H2O by six:
1 C5H12(l) + Oz(g) ---r> 5 CO2(g) + 6 H2O(g)
5C 5C
t2H 12H
St ?o 1"60
Balance oxygen atoms by multiply 02 by eight:
1 C5H12[) +8O2(g) 5CO2G)+6H2O(g)
5C
--+ 5C
12}{ 12H
160 160
to
SE
Example 1.29
iVhat are the correct coefficients needed to balance the following reaction?
e-
: Co(OH)3(s) + H2SOa(ae) ------+ Co2(SOa)3(aq) + H2O(l)
-{. ).e,. 1 6
.8. 3:2: 1 J
C. 2:3: 1 J
D. 3:2: 1 6
Solution
en Balancing equations requires that you keep track of each atom. In this case,
,ce
because of cobalt, the ratio of Co(OH)3(s) to Co2(SOa)s(aq) must be 2 : 1, which
:d. eLiminates choices B and D. The correct answer is found using water. Two moles
of Co(OH)3(s) and three moles of H2SOa(aq) have a total of tn 12 H atoms and 1,8
O atoms, making choice A the best answer.
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General Chemistry Stoichiometry Balancing Reactions Gt
Balanced equations can be used to determine the amount of a product from a :
given amount of reactant. As we saw in Example 1.2, balanced equations can be
used to determine how much product is formed from a given mass of a reactant.
We refer to these questions as gram-to-mole-to-mole-to-gram conversions, where
the overall conversion process is from grams reactant to grams product.
Example 1.30
How many grams of water are formed when 25.0 grams of pentane (CSHrz)
reacts with oxygen?
A. 18.8 g H2O
B. 25.0 g H2O
Sirnrinrlnt
C. 37.5 g H2O
rar jfunm
D. 75.0 B F{zO
:m.il:
ruue.ls
Solution
Step 1: Convert grams reactant to moles reactant by dividing by molecular mass
of the reactant:
*,c t,
TIt] IES
grams reactant mole reactant ,{/rlry

= moles reactant "[*-i
" grams reactant i])n.lNmmt
Step 2: Convert moles reactant to moles product using the coefficient ratio from
,umubfrMie
the balanced reaction:
lmulrirT llxl'r
moles Product
moles reactant t = moles product
moles reactant
step 3: Convert moles product to grams product by multiplying by molecular Uirryry
mass of the product:
-flMrtnmr I
liL rh
. grams oroduct gfZrfitS product

motes product X *- =
moles product
m, lm-
The overall conversion is as shown below: n Tnrr
18 g-Hzo
,c im
25.0 gC5H1z
- ,.T4S#1Z* mgle-I{z-o
6
* =27.s BHzo M[. lhm
72 gCSHTZ CSFITZ l mole H2O
L mole
The ratio of water to pentane comes from the balanced oxidation reaction. The $ntluiiuun
product of 6 x 18 is 108, which is greater than 72. This means that the original '!ilMm mu,
25.0 grams is multiplied by a number greater than 1, which in tum means that fuitrmL,
the final number is greater than 25.0 g. This eliminates choices A and B. 108 over rf|nqffii1lmn
72 is less than two, so the final value is less than 50.0 grams, so choice D is snnwUs :
eliminated. The only answer that remains is choice C,37.5 g. gpflmimHndlTW
Etmmmnffil
1frlrtr'-*rnrll
Limiting Reagents
Determining the limiting reagent in a reaction requires comparing the number of
moles of each of the reactants. The limiting reagent is the reactant that is @ipm
exhausted first, not necessarily the reactant with the lowest number of moles.
when the limiting reagent is completely consumed, the reaction stops, regardless uuu @ mrnrl
of the amount of the other reactant. To determine the limiting reagent, the m
Mmmwr *nn*
amount of all reactants and the mole ratio of the reactants must be known. If the
ratio of the moles of Reactant A to Reactant B is greater than the ratio of Reactant ndhusfi s
A to Reactant B from the balanced equation, then Reactant B is the limiting m ittrre
reagent. If the ratio of the moles of Reactant A to Reactant B is less than the ratio
of Reactant A to Reactant B from the balanced equation, then Reactant A is the
limiting reagent.

General Chemistry Stoichiometry Balancing Reactions
Example 1.3L
Assuming that the following reaction between oxygen and hydrogen goes to
completion, which statement is true if 10.0 grams of hydrogen are mixed with
64.0 grams of oxygen?
{' ,,u i
1;',,
2HzG) + Oz(g) --+ 2 H2O(t)
A. The limiting reagent is oxygen.
B. 74.0 grams of water will form.
C. 3.0 moles of hydrogen will be left over following the reaction
D. 68.0 grams of water will form.
Solution
Lr limiting reagent reactions, you must decide which reactant is depleted first.
Limiting reagent questions often look like ordinary stoichiometric questions. The
rule is simple: If they give you quantities for all reactants, it is probably a limiting
reagent problem. In this question, you are given quantities for both hydrogen
and oxygen. 10 grams of H is equal to 5 moles of }{2, and 64grams of oxygen is 2
rtoles of 02 (remember your diatomic elements!) From the balanced equation,
ir-e learn that twice as many moles of hydrogen as oxygen are needed. The
number of moles indicates there is a 5 :2 ratio of hydrogen to oxygen, which is
greater than a 2 : 1 reaction ratio, so oxygen is depleted first. The correct choice is
answer A. The question gives you opposing choices in A and B. One of these
:-,vo choices must be true. The correct choice is A.
Exarnple 1".32
l\-hat is the limiting reagent when 22.0 grams C3Hg are mixed with 48.0 grams
'l?
C3H3(l) + Oz(s) COz(g) + H2O(g)
-{.. Oxygen is the limiting reagent.
ts. Propane is the limiting reagent.
C. Water is the limiting reagent.
D. There is no limiting reagent.
.e Solution
il },is question is more difficult than the previous question, but you are still
rt :eciding which reactant is depleted first. Because the limiting reagent is a
)r =actant, choice C (a product) is eliminated. To solve the question, stick to this
is
'::nple rule: Compare the actual ratio of the two reactants to the balanced
*:'.ration ratio of the two reactants. In this question, you are given unequal mass
:-uantities of C3Hg and 02 and a mole ratio that is not l. : 1. Good luck.
i-:rnember, the first step is to balance the reaction.
t,
:.
1 C3H3[) +5 O2(g) 3CO2(g) +4H2O(g) l_
rf --
is grams of C3Hg is 22 moles of C3H6, -->which is 0.50 moles CSHg. 48 grams of 02 I
44
,C
. 49 moles of 02 (remember your diatomic elements!), which is L.50 moles of.C,2.
\]
SS
t2
1e ::.rm the balanced equation, we see that we need 5 moles of 02 for L mole of
1e *,.1{3. The number of moles indicates there is a 1.50 : 0.50 ratio of 02 to C3H8, ,
nt i,-:.ich is less than 5 : 1. This means that oxygen (O2) is depleted first. Oxygen
18 r- is the limiting reagent, so choice A is the best answer.
io
he
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'rg
General Qhemistry Stoichiometry Reaction Types
C.ffin!
A:'rrm
Common Reactions Tfue m
There are some reaction types that are standard reactions in inorganic chemistry' rcndfo
Included among the common reaction types are the following five: 1) 'ryN
precipitation ,"uition, (also known as double-displacement reactions), 2) acid-
tase reactions (also known asneutralization reactions), 3) composition reactions,
4) decomposition reactions, and 5) oxidation-reduction reactions (electron-
transfer reactions). Oxidation-reduction reactions can be categorized as either
fr{rrfi'rlr]Wr
*|'lriwn
single replacement or combustion. Each reaction type will be addressed in more
aetiit in later sections, so let us consider each type of reaction in minimal detail
in this section. h
,dhdho
Precipitation Reactions offi
A reaction that involves two aqueous salts being added together to form [hilffi
spectator ions and a solid salt precipitate that drops out of solution is known as a dhn
precipitation reaction. It may iho 6e referred to as a double-displacement reaction,
although that term is not as useful in describing the chemistry' Drawn below is a
sample precipitation reaction:
mriih
Na2CrO4(aq) + Sr(NO3)2(aq) + 2NaNO3(aq) + SrCrO4(s) {e
rmq'nffiht
Aqueous Salt Aqueous Salt Ions Precipitate
Precipitation reactions can be recognized by the solid salt 9"-q" product side_of
the equation. Recognition of the type of reaction is useful for predicting_the
product. Recogniziig a precipitate is highly bene{icial in identifying a d91ble-
-
displacement ieaction. The following solubitity rules can be helpful in
identifying the likelihood of a precipitate's forrning:
1. Most salts containing alkali metal cations (Li+, Na+, K+, Cs+,
Rb+) and ammonium (NH+*) are water-soluble'
2. Most nitrate (NOa-) salts are water-soluble'
3. Most salts containing halide anions (CI-, Br-, I-) are water-soluble
(with heavy metal eiceptions such as Ag+ and Pbz+)'
4. Most salts containing sulfate anions (SO+2-) are water-soluble
(with exceptions such-as BaZ+,Pb2-,lH82*, and Caz+)'
5. Most hydroxide anion (oH-) salts are only slightly water-soluble.
KOH ind NaOH are substantially soluble, while Ca(OH)2,
Sr(OH)2, and Ba(OH)2 are fairly soluble in water'
6. Most carbonate anion (COg2-), chromate anion (CrO42-)'
phosphate anion (po43-),'and sulfide anion (t-) salts are only
slightly water-soluble.
Acid-Base Reactions
A reaction between an acid (a proton donor) and a base (a proton acceptor) forms
a neutral salt and water. Foi now, recognize that proton donors (acids) must
have a proton on an acid (H-Acid). Acids to recognize are-{!1, HBr' HI' HNO3'
H2SO4-,and NH4+. Bases to recognize are NaOH, KOH, LiOH, and CaCO3'
HCIOa(aq) + LiOH(aq) + LiClOa(aq) + H2O(l)
Acid Base Salt Water
Acid-base reactions can be recognized by the formation of a salt and water on the
prod.uct side of the equation. Aqn"ont acid-base reactions can be identified
by
ihe transfer of an H fiom the acid to the hydroxide of the base on the reactant
side of the equation.
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s General Chemistry Stoichiometry Reaction Types
Composition Reactions
A composition reaction involves the combining of reactants to form a product.
The number of reactants exceeds the number of products in a composition
reaction. Entropy decreases and more bonds are formed than are broken in
composition reactions.
PCl3(s) + Cl2(g) + PCl5(g)
'
)t
2 Reactants 1 Product
t-
r Composition reactions may fall into other reaction categories as well. In the
e with Cl2,PClg is oxidized and Cl2 is reduced.
sanrple reaction, when PCl3 reacts
il
Decomposition Reactions
-{. 'C.ecomposition reaction is the opposite of a composition reaction. It involves
:eactants decomposing to form multiple products. The number of reactants is
n :es-s than the number of products in a decomposition reaction. Entropy increases
a lnd more bonds are broken than are formed in decomposition reactions.
1,
CaSO3(g) ----+ SOz(g) + CaO(s)
a
L Reactant 2 Products
-;ie composition reactions, decomposition reactions can also fall into other
::action categories as well.
rf ,Crildation-Reduction Reactions
re "u:: oxidation-reduction reaction involves the transfer of electrons from one atom
3- lr: another. Loss of electrons is defined as oxidation, while gain of electrons is
n :e:-raed as reduction (LeoGer). The atom (or compound) losing electrons is
:n:.:rsing reduction, so it is referred to as the reductant (reducing agent), while the
t:om (or compound) gaining electrons is causing oxidation, so it is referred to as
:"e oxidant (oxidizing agent). The oxidation states must change in an oxidation-
:eCuction reaction. A sample reaction (below) shows how magnesium is losing
:-ectrons (thus being oxidized and having an increase in oxidation state) to
-omine (which is being reduced and having a decrease in oxidation state):
Mg(r) + Br2[) ------> MgBr2(s)
Reductant Oxidant Salt
Combustion Reactions
ilombustion reactions are a special case of oxidation-reduction reactions, where
ne oxidizing agent is oxygen gas, and the products are oxides. Typical examples
lf combustion reactions include the oxidation of organic compounds, such as
:r-fuocarbons and carbohydrates, into carbon dioxide and water.
1C3H3(aq) +5O2(s) 3CO2(s) +4 H2O(l)
Hydrocarbon Oxygen Carbon dioxide Water
15
st Combustion reactions of both hydrocarbons and monosaccharides balance in a
t^
'5t :redictable manner, as shown below:
Hvdrocarbon Combustion
C*H, +,. * o2(g) -------> x Co2(g) *I-uzo(g)

l)
he
ry Monosaccharide Combustion
nt C1H21O1 + xO2(g) + xCO2(g) + xH2O(g)
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General Chemistry Stoichiometry Reaction Types
=
Example 1.33 ru
The following reaction is an example of which type of reaction? Gtn
MgCl2(aq) + AgNO3(aq) Mg(NO3)2(aq) + AgCl(s) M:
A. Cation-crossover M
B. Oxidation-reduction -- {mnllmq
C. Neutralization l;i@[
D. Double-displacement firmfiff m
rildlffiil
Solution TM
Of the generic reactions with which you are familiar, there are typical features to milfu
note. In this example, you have two salts undergoing an exchange reaction to
llh{ilqi*
yield a precipitate. This makes it a precipitation reaction. No proton was
transferred (eliminating neutralization), and no oxidation states changed [[ml
(eliminating oxidation-reduction). Cation-crossover is a fabricated name, so M
choice A is eliminated. Choice D, double-displacement, is another name for a {oafdhi
precipitation reaction. In double-displacement reactions, you have two salts *ro[h,
undergoing a reaction where they exchange counterions, and one of the new
combinations forms a precipitate. This is shown in a generic fashion below: hffi
mrmmn
MX(aq) + NY(aq) --------+ MY(aq) + NX(s) lrrr'lfrir!
Oxidation States
Assigning an oxidation state to an atom is a matter of distributing electrons
within a bond based on which atom is more electronegative. The oxidation state
of an atom can be determined by assigning it a value of positive one (+1) for
every bond it forms with a more electronegative atom and assigning it a value of
negative one (-1) for every bond it forms with a less electronegative atom. The
oxidation state is a sum of all these bonding values. In general chemistry, it is
often easiest to say oxygen is -2 (except in molecular oxygen and peroxides),
hydrogen is +1 (except in molecular hydrogen and hydrides), and halides are -1
(except when they are a central atom in an oxyacid). The sum of the oxidation
states of the elements in the compound must equal the overall charge, so the
oxidation state of any remaining atom can be determined by finding the
difference between its charge and the sum of the known oxidation states.
Example L.34
What is the oxidation state of manganese in KMnO4?
A. +1
B. +3
c. +5
D. +7
Solution
To simplify this example, we will consider that O = -2, arrd alkali metals = +1. In
this case, K = *1, and there are 4 Os valued at -2 each, for a net oxidation state of
-8. Summing oxygen and potassium yields a total of -7. This means that for the
molecule to be neutral, the Mn (the only atom remaining) must cancel out that -7
by being +7. In other words, the sum of the oxidation states equals the
molecule's formal charge (zero). So in this case, the oxidation state of manganese
is +7. The correct rnswer is choice D.
Copyright @by The Berkeley Review 2A The Berkeley Review

General Chemistry Stoichiometry Test-Taking Tips
I eneral Advice
-:: stoichiometry section of this review course is best learned by trial and error
: - .-',x?rnples (i.e., practice with many problems.) For the most part, to be
----:essful in stoichiometry requires being fast at math and being able to see
-:-::Lediately what a question is asking for. These are skills that are acquired and
- ,: :lecessarily memorized. Keep in mind that on a multiple-choice exam, the
::-: has been done for you, so all you need to do is approximate the answer.
'- =:e is no universal shortcut that works in every situation, but finding a range
o :::n which only one answer choice fits is a good approach to most questions.
o
-.::lion will also prove useful on the MCAT. Traditional testing at major
S
d -:.','ersities genera\ rewards memorization over intuitive skills, but preparing

io : -:e MCAT forces you to hone your analytical and intuitive skills as you recall
a
-:::.:n facts from memory. You should try to emphasize this thought process
tS
'':.',' and regularly throughout your review studies.
- ::.e examples above, several topics and styles of questions were presented.
;,=: - :e I'ou move on to the practice questions in the passages, make sure that you
:=rstand the basic principle of each topic and the math typically used to
-.::,'.'cr these questions. Math tricks may prove helpful, even for the
conceptual
. ,-...ions in stoichiometry. Keep in mind that you are not graded for showing
- :: rvork on the MCAT, so don't solve every problem to the last decimal place.
NS ': ?.--,.-ze each question only well enough to eliminate three wrong answers. Be
,te :::ise and efficient rn your problem-solving, not exhaustive. Generally, the
or - = -:rons ask you to decide which fraction (or ratio) is larger. This can be done
of ,.---.'by converting all the fractions to values over the same denominator, and
he "-:',g for an answer choice that falls within a range. Keep it simple.
is
s), 'i:.:hematical Tips and Shortcuts
-7 - --e the MCAT does not require elaborate calculations, you still must be able to
on , .. -"'''ith ratios and percentages. Do not use a calculator when practicing for the
he - -T. The following strategies are useful ways to calculate a value quickly and
he : ::ir approximation without tables or a calculator:
. : lition and Subtraction
:: -:,-ng numbers and adding common terms is a useful way to make addition
- : subtraction easier. To split a number, consider how you would round it, and
.' .: split it into the rounded number and the difference between the original and
' -,.led numbers. 193 rounds up to 200, so 193 canbe thought of as 200 - 7. 826
-- js down to 800, so think of 826 as 800 + 26. Adding and subtracting
';
- -rrS Linking like terms. Thus, adding 193 to 826 canbe thought of as:
+826=200- 7+ 800 +26= 200 + 800 +26-7 = 1000 +19 =1019

793
- , ::action is done in a similar way. 826 - 193 can be thought of as:
ln
826 - 193 = 800 + 26 - 200 + 7 = 800 - 200 +26 + 7 = 600 + 33 = 633
eof
the -.. approach may seem awkward at first, but it is effective and easy when
rt-7 ::-:g and/or subtracting several numbers at once. For instance, consider
the : ::g 213 to 681., then subtracting 411.
IESC
l-3 + 681 - 477 =200 + 13 + 700 - 19 - 400- 11 = 200 +7A0 -400 +13 - 79 - 77
=500-17=483
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General Chemistry Stoichiometry Test-Taking Tips
Averaging Terms
Averaging terms involves estimating a mean value, and then keeping a running
tally of the differences between the actual values and the estimated average. To
find the average difference, the running tally is divided by the number of values
being averaged. For instance, the average of 25, 33,21",28, and 30 can be thought
of as being around 28 (the median value), so the actual average is 28 + /- the
average difference:
The total difference is -3 + 5 -7 +0 +2 = -3

\vVhen the total difference is divided by 5, it yields an average difference of - 0.6
The average of the five values is thus 28 - 0.6 = 27.4
Multiplication
Multiplication can also be made easier by splitting numbers as you would round
them. For instance, 97 is 100 - 3. Only one number need be split in
multiplication. Thus, multiplying 97 by 121. can be thought of as:
97 x121. =(100 -3)x121, =(100 x121)- (3x121) =12,100-363
12,100 - 363 = 1,1,,700 + 400 - 363 = 7L,700 + 37 = 1L,737
Division
If you memorize the following set of fraction-to-decimal conversions, then
problems involving division will be far easier:
L = 0.200,L = 0.L66,L = 0.I4g,L = O.IZS,I = 0.111,-1* = 0.091,*1- = 0.083 5{r
567891.772
Memorizing these decimal values can be useful in several ways. For instance, the 1r
decimal equivalent of the fraction 18 / 66 can be found in the following manner:

18 = 3 = 3x! = 3x (0.091) = 0.273
66 1,1. 11 tl
Knowing these decimal values is also useful for estimating in decimal terms
fractions that are just less than 1. For instance, the decimal equivalent of the
fraction 11./12 can be found in the following manner:
m
77 =12-1 =72 __L- = 1_ 1 - 1_ 0.0g3 = 0.917
12 12 12 12 72
These decimal values are also useful in deciding what to multiply a denominator
by to convert it to some number close to 10, 100, or 1000. For instance, the
numerator and denominator of the fraction 47 / 742 should be multiplie d by 7 ,
because 0.143 = 1,/7 so7 x1.43 is nearly 1000 (actually, it's 1001). The decimal
equivalent of the fraction 47 /1.42 can be found in the following manner:
47 -g2g -329 + ahttle =0.32g +alittle

742=7x47
7 x142 994 1000
Iq
Copyright @ by The Berkeley Review 30 The Berkeley Revierr
fs
rg
.o
3S
Stoichiometry
Passages
ht
1e
l2 Passages
IOO Questions
nd
in
)83 Suggested Stoichiometry Passage Schedule:

the I: After reading this section and attending lecture: Passages I - III & VI - VIII
Qrade passages immediately after completion and log your mistakes.
II: Following Task I: Passages IV V & IX, (2O questions in 26 minutes)
nns Time yourself accurately, grade your answers, and review mistakes.
the
{II: Review: Passages X - XII & Questions 87 - IOO
Focus on reviewing the concepts. Do not worry about timing.
ator
the
)y 7,
imal
I. Density ExPeriment (r -7)
II. CombustionAnalYsis (8 - 15)
III. Empirical Formula Determination (14 - 20)
IV. Molar Volume of a Cas (2r - 26)
V. Elemental AnalYsis (27 - 33)
VI. Dilution DxPeriment (34 - 40)
VII. Solution Concentrations and Dilution (4r - 47)
VIII. Beer's Plot and Light Absorption (48 - 54)
IX. Beer's Law DxPeriment (55 - 6l)
X. Reaction lYPes (62 - 68)
XI. Calcium-Containing Bases (6e - 78)
XII. Industrial Chemicals (7e - 86)
Questions Not Based on a Descriptive Passage (87 - loo)
Stoichiometry Scoring Scale

Raw Score MCAT Score
84 - 100 15 - 15
66-83 lo- l2
47 -65 7 -9
34-46 4-6
L-33 l-5
oassage | (Questions 1 - 7) 3. What would be the volume of a 20.0-gram picce of
'7 unknown Solid #1?
A student fills a 50-mL graduated cylinder exactly
A. 13.3 mL
-.,fway with water, adds a previously weighed sample of an
- .l,nown solid, and records the new water level indicated by
B. 15.0 mL
-: markings on the side of the graduated cylinder. After C. 25.0 mL
'' : rrding the volume, she removes the unknown solid and D. 30.0 mL
.r:s water to the cylinder to raise the volume back to
:-.:rsely 25 mL, replacing any water that may have adhered
::e solid. This procedure is repeated for a total of five 4. How many of the unknown solids can float on Liquid
- - r,:.rwn solids, and it is discovered that each of the solids #7?
- ,:-: to
the bottom of the graduated cylinder. Table 1 shows
- l"la for all five trials. A. 0
' B. I
Lnknown Mass Volume Reading
c.2
D.3
I 9.63 s 31.42 mL
2 12.38 s 31 19 mL
3 14.85 s 29.95 mL
4 8.22 s 28.00 mL 5 . Which of the following sequences does NOT accurately
26.41mL reflect the relative densities of the unknown liquids?
5 5.64 s
Table I A. Liquid #7 > Liquid # 6 > Liquid #8
Liquid #8 > Liquid # 6 > Liquid #9
"--B:
--c": Liquid #7 > Liquid # 8 > Liquid #9
- ,::ond experiment is conducted with liquids, using a
--.- Liquid #7 > Liquid # 8 > Liquid #6
,,olumetric cylinder (one that holds exactly 10.00
- ,,..rrion) that weighs 42.61 grams when empty. In
?-{
a .-,
4'^^
:::::.:e trials, unknown liquids are poured into the s''''l- '
'::: :'.:ctly to the 10.00-mL mark on the cylinder each
6 , How would the results in Experiment 2 differ from the
-.- : :r're combined mass of the cylinder and the liquid is if a heavier graduated cylinder had been
actual results,
, ,: - . .ble 2 shows the results of the second experiment.
used?
: lr-noq'n Mass of Cylinder with Liquid A. Both the mass of the cylinder with the liquid and
the density of the liquid would increase.
51.33 e B. The mass of the cylinder with the liquid would
58.72 s, increase, while the density of the liquid would
53.21 s. decrease.
49.03 s p. The mass of the cylinder with the liquid would
/' increase, while the density of the liquid would
Table 2
remain the same.
,-.: ali of the unknown liquids are immiscible ,E'. The mass of the cylinder with the liquid would
- ,: :-ssolve) in water, how many of the unknown decrease, while the density of the liquid would
, :.: :loat on water? increase.
t-"t\
7 . Which of the following is NOT a unit of density?

,-s
,K.
'mL =
B. !i
cm-
-.:;.: unknown solids is the DENSEST?
ks
c. -L
,..D. ++
tn
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Passage ll (Questions B - 13) 9. The properties of sodium hydroxide should
being:
Elemental analysis is often a preliminary study in
structural analysis. A sample compound is placed into a A. hydrophobic and semi-reactive with CO2.
chamber with a positive pressure of oxygen gas flowing in. and highly reactive with CO2.
.h-l"Vdrophobic
The chamber has an ignition coil that is heated by a cunent. (-E. hydroscopic and semi-reactive with CO2.
As the reaction proceeds, the pressure in the chamber builds D. hydroscopic and highly reactive with CO2.
up. After a short time, Valve #l is opened to allow the
product gas mixture from the reaction to flow into an
evacuated tube containing some magnesium sulfate, which
absorbs water vapor from the product gas mixture. Then
Yalve #2 is opened, allowing the gas to flow into a second
evacuated tube containing some sodium hydroxide, which 10. Why is the oxygen tank attached to a pressure valve?
absorbs carbon dioxide from the product gas mixture.. The A. It absorbs excess oxygen.
apparatus is shown in Figure l. The oxygen tank provides
B. It helps cool the reaction chamber.
oxygen in excess throughout the process. Valve #3 is
C. It ensures that oxygen gas is in excess.
connected to a line that can either evacuate the system or
supply nitrogen to the system.
D. It ensures that oxygen is limiting.
Valve #1 Valve #2 Valve #3
11. Which of the four unknown compounds is

likely to contain oxygen?
a(s) NaOH(s) A. Compoundl
B. Compoundtr
C. Compound Itr
D. Compound IV
Figure 1
Four different samples are analyzed. The sample mass of
each unknown substance is approximately two grams. Table
I shows the sample mass placed into the reaction chamber,
and the initial and final masses of magnesium sulfate and
12. Why are the U-tubes containing the two salts
:odium hydroxide in the side tubes.
in the order that they are?
Unknown Sample Mass MgSO4 Tube

A. To ensure that water is absorbed before the
NaOH Tube interact with the NaOH chamber
I 2.011 g
Init: 40.00 g Init: 30.00 g B. To ensure that carbon dioxide is absorbed be
Fin: 41.21 g Finl. 32.94 E gases interact with the NaOH chamber
tr 1.995 g
Inir: 40.01 g Init: 30.00 g C. To enhance the reaction between water and
Fin: 41.26 g Fin: 34.39 s dioxide
Init: 40.00 g Init: 30.00 g
D. To absorb any excess oxygen gas before it
m 2.003 g with NaOH
Fin: 42.00 e Fin: 34.89 s
IV Init: 40.00 g Init: 30.00 g
2.001 g
Fin: 41.75 e Fin: 35.99 e
Table I
8. The relative mass percent of carbon in the four 13. What solid is being formed in the second tube
product gas mixture interacts with the salt?
compounds is BEST described by which of the
following? A. Magnesium bicarbonate
A. I>II>III>IV B. Magnesium carbonate
B. I>III>II>IV C. Sodium bicarbonate
C. IV>II>III>I D. Sodiumcarbonate
D. IV>III>II>I
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J includ rassage lll (Questions 14 - 20) 15. The percentage of carbon by mass in the unknown
compound can be calculated as:
Exactly 10.0 grams of an unknown organic compound is
into a flask. The compound is then exposed to excess
-rred A. 23.79 x 12 x 10 x l00Vo
" '.'.sen gas to oxidize it to CO2 gas and H2O gas. The 44
' -lized vapor flows through a tube filled first with copper B. 23.19 x4Lx10x 100Vo
.le to ensure complete oxidation. The vapor then flows t2
': ugh 100.00 grams of powdered anhydrous sodium sulfate, C.23.79xf2xJ_xtoovo
-,:h binds water vapor to form 112.16 grams of hydrated 44 10
. . The vapor continues to flow through 100.00 grams of D. Z3.jg *44* f_x t00%o
' , :ered anhydrous sodium hydroxide, which binds
carbon
12 10
-Je vapor to form 123.19 grams of bicarbonate salt.

alve?
The unknown compound contains only oxygen, carbon,
'
- -r'drogen. The mass percent of carbon in the compound 16. What can be said abour rhe boiling point (b.p.) and
,':ermined to be greater than 50%. In a subsequent melting point (m.p.) of the unknown compound relative
r.:-ment, the compound is found to have a molecular mass to ambient temperature (T)?
--- '. here between 70 and 80 grams per mole. When the
. ;ontaining the unknown compound is left uncapped,
A. m.p. > T2, and b.p. > T"
. .:ents slowly evaporate. B. *.p. > T2, and b.p. < Ta
C. m.p. < T2, and b.p. < Tu
- ie information from the combustion reaction can be D. m.p. < Ta, and b.p. > Tu
- .::ed into mass percent for both carbon and hydrogen.
LEAS' : - rltiplying the grams of CO2 times the mass of one
. arom and dividing by the mass of carbon dioxide, the
. .: the carbon in the original sample can be determined. 17. Which of the following formulas CANNOT be a
: -;SS of hydrogen in the original sample can be found in molecular formula?
'-:_ar manner.
. :. , rhe grams ofThese two mathematical procedures A. C2H4O
product molecules into the grams of
' ::rm. The final numbers are the grams of carbon and B. C2H5O
' .-3n. respectively, in the unknown compound. To C. C3H6O
D. CaH3O2
-. re the mass percent, the mass of the atom is divided
'; rt?SS of the sample. The mass percent of oxygen in
--, towll compound is determined by difference.
-: information from the 18. How many moles of water are formed from the
|]rang3 , mass percents of the
combustion of 10.0 grams of the unknown compound?
: .-nt atoms can be used to determine the empirical
le gasi - . iormula of the lowest coefficients) for the unknown A. 0.31 moles H2O(i)
: -.:d. To determine the molecular formula from the B. 0.69 moles H2O(l)
:tbre
- -.- formula, the compound's
molecular weight must be C. 1.10 moles H2O(l)
rL
' For compounds containing only carbon, hydrogen, D. 1.38 moles H2O(t)
I carb;lr
.-en, the molecular formula must always have an even
',: rl hydrogens. Molecular formulas with an odd
' ,: :i carbons and oxygens, however, are possible.
t reaif 19. What is the empirical formula for the unknown
i r.0 grams of the unknown compound described in compound?
-': -:assage were oxidized, what would be observed? A. C3H6O2
.. . The moles of CO2 would double, while the B. CaHsO2
percentage of carbon in the sampie would remain C. CaH16O
:he same. D. C3H19O
Iter lk ! , The moles of CO2 would double, and the
fercentage of carbon in the sample would also
touble. 2 0. What is the mass percent of carbon in C5H2O2?
The moles of CO2 would remain the same, and the
:ercentage of carbon in the sample would also
A. 26.4Vo
.:main the same.
B. 51.1Vo
i The moles of CO2 would remain the same, while
C. 60.8Vo
D. 68.2Vo
::'te percentage of carbon in the sample would
:oub1e.
).{G{i
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Passage lV (Questions 21 - 26) 21. What is the mass percent of carbon in CO2 gas? r. sr
A researcher completely oxidizes exactly 1.00 grams of
A. 25.0Vo ry
B. 21.3Vo ftD
an unknown liquid hydrocarbon in a containment vessel to
c. 3l.4vo m
yield carbon dioxide and water vapor. The two gases thus
formed are collected and analyzed for quantity. The water
D. 35.0Vo rL-
vapor is collected by passing the gas through a tube
containing anhydrous calcium chloride. The carbon dioxide
gas is collected by passing the remaining gas through a tube
n,
22. How can the molecular weight of this unknown liqu
containing anhydrous sodium hydroxide. The mass of the be determined?
carbon dioxide gas thus collected is 3.045 grams at STP.
The carbon dioxide gas is regenerated upon heating the ^ 22.41
grams 0-
2.32 mole
sodium carbonate and this gas is found to occupy a volume of
1.55 liters at STP. The experimental apparatus is shown in
D 24.96 grams
2.32 mole
Figure 1.
grams
C . (2.32 x 22.41)
mole
co,. H,o. and -Jq Jt-t fg*
"*"!rr5r"","-ffi D. (2.32 x24'961Erams
mole
CaClz(s) NaOH(s)
23 . If the mass percent of carbon in the unknown compou
Figure 1 is found to be 82.9Vo, what is the empirical formula
In a second experiment, the researcher places a 5.0-mL the unknown hydrocarbon?
aliquot of the unknown liquid into a capped 1.00-liter flask. A. CH2
The cap has a tiny hole in the top, and the empty flask with B. C2H5
cap weighs exactly 120.00 grams. The compound is heated C. CH3
until it reaches a gentle boil. The vapor escapes through the D. C2H7
tiny pore in the cap. The liquid continues boiling at 31"C,
until none of it remains visible in the flask. The heat source
is removed from the flask, and the contents are allowed to
cool back to ambient temperature. As the flask cools, the 2 4. Using the data from the first experiment, how can
vapor in it condenses into a small pool of liquid at the base mass percent of carbon in the unknown compound
of the flask. determined?
The flask and cap are then massed with the condensed 6. 1.55 x 12.011 x t00Vo
liquid present. The entire system is found to have a mass of 22.41 x 1.00
exactly 122.32 grams. This means that the mass of the g, 1.55 x22.41 x l2.0ll x l1OVo
liquid is 2.32 grams. It is assumed that at the moment when 1.00
the heat source was removed, the flask was completely filled g. 22.41 x l2.Oll x t1OVo
with vapor from the liquid and that all of the air originally in 1.55 x 1.00
the flask was displaced. Table 1 lists the molar volume for p, 22.41x1.00 xI11Vo
an ideal gas at selected temperatures. 1.55 x 12.011
Temperature (K) Molar Volume

2"t3 22.4r L 2 5. How many moles of CO2 gas were formed in the
288 23.64 L experiment?
298 24.46 L
24.96 L
A. 1.55 -o1",96,
304 22.41
3t3 25.69 L
B. 1.55
-o1", gg,
323 26.5r L 23.64
Table C. 22.41 gg,
1.55 ô6"
D. 1.00 moles CO2
22.41 x 1.55
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l: . If in the second experiment the organic vapor had not Passage V (Questions 27 - 33)
fully displaced all of the air from the flask by the time
the heat was removed from the flask, how would the The empirical formula for a compound can be determined
results have been affected? using the technique of elemental analysis. For hydrocarbons
\. and carbohydrates, the process involves trapping and
The mass of unknown liquid collected would be too
removing water vapor and carbon dioxide gas and then
great, so the calculated molecular mass would be
quantifying the amounts collected. The products can be
too high.
trapped in many different ways. In this experiment, the
B . The mass of unknown liquid collected would be too
n liquii trapping of the gases is accomplished by passing the product
small, so the calculated molecular mass would be
gas through a series of low-temperature gas traps. By
too high.
lowering the temperature, the gas can be converted into
C , The mass of unknown liquid collected would be too
solids, which cannot flow and thus are easily collected at the
great, so the calculated molecular mass would be
bases of their respective temperature traps. The system is
too low.
evacuated completely and then flushed with nitrogen gas to
D . The mass of unknown liquid collected would be too
remove any remaining air. The vapor from the reaction
small, so the calculated molecular mass would be
vessel is then allowed to enter one trap at a time. The gas
too low.
remains isolated in the region ofeach trap for a short interval,
to allow any gases to form a solid or freeze into a liquid. The
apparatus is shown in Figure 1.
)mpoun; +Vacuum
rmula o.
Reaction
vessel
Gas Gas Gas

trap I trap II trap III
Oil bubbler
Figure I
It is important to allow the excess oxygen gas to flow
i can thlt out of the system. To accomplish this, the line is fitted with
round hr. a one-way oil bubbler. The oil bubbler maintains the closed
system by not allowing air to flow into the system, while
allowing the pressure to equilibrate with the environment
through venting.
27 . At what temperature should the first trap be held in

order to collect water vapor?
A. 25"C (standard temperature)
B. 0"C (melting point of ice)
C. -33"C (boiling point ofFreon refrigerant)
D. -196"C (boiling point ofliquid nitrogen)
nthefu 28. The temperatures of the successive traps (i.e., Trap I,

Trap II, and Trap III) should be set in what manner?
A. The temperatures should gradually increase, so that
each gas is selectively removed one trap at a time.
B. The temperatures should gradually increase, so that
each gas can be trapped into all three traps,
allowing one to determine the moles by difference.
C. The temperatures should gradually decrease, so that
each gas is selectively removed one trap at a time.
D. The temperatures should gradually decrease, so that
each gas can be trapped into all three traps,
allowing one to determine the moles by difference.
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29. What additional piece of information is necessary to 33. Which of the following is NOT associated with
determine the molecular formula for the experimental increasing mass percent of carbon in a hydrocarbon?
compound? I. An increase in the mass of carbon per gram of
A. The volume of CO2 collected compound
B. The volume of the water collected tr. An increase in the mass of water formed
C. The volume of the hydrocarbon before the reaction oxidation of one gram of the compound
was carried out trI. An increase in the mass of hydrogen per gram
D . The molecular mass of the hydrocarbon the compound
A. II only
B. Itr only
C. Iandtronly
D. II and Itr only
3 0. If an unknown compound were combusted in the
presence of excess oxygen, what by-product of the
combustion would be collected to determine the
percentage of sulfur within that compound?
A. SO2
B. CS2
C. H2S
D. Ss
31. The mass percent of oxygen within a compound cannot

be determined directly using elemental analysis. Which
of the following is NOT an explanation for this?
A. Oxygen gas does not exist in the solid phase at any
temperature.
B . When a carbohydrate is oxidized, the oxygen of the
unknown carbohydrate can be found in both water
and carbon dioxide.
C . The procedure requires adding excess oxygen, so the
oxygen atoms from the carbohydrate cannot be
distinguished from the oxygen reactant.
D. Oxygen in the carbohydrate, being fully reduced,
does not react with oxygen gas.
3 2. Why is the bubbler filled with mineral oil?

A. The oil traps out any unreacted organic vapor.
B. The oil can transfer heat to warm the gas rapidly.
C. The oil prevents back-flow of gas from the outside
environment.
D. The oil filters out any liquid products from the
reaction.
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ith ar ::ssage Vl (Questions 34 - 40) 36. What is the final Cl- concentration after you mix 50.00
r? mL 0.25 M HCI with 25.00 mL 0.50 M NaOH?
of the f ilution reduces the concentration of a solute by adding
A. 0.33 M
:
solvent to the solution. The addition of solvent
B. 0.25 M
.-:ises the volume of solution while having no effect on
upot c. 0.17 M
--.:les of solute. Molarity is defined as moles solute per D. 0.15 M
i- : rlution, so the denominator is increased by the addition
:am o' .'.ent. while the numerator is unaffected. To determine
: , .:Jentration, use:
M;Vi = \'t1Y,
Equation 1 3 7. Why in step III is water passed through the volumetric
-
=:: Mi is the initial molarity, V1 is the initial volume, pipette?
I . the final molarity, and V1 is the final volume. A . To ensure complete transfer of solution
- ..rtion can be described by the relative concentration of B . To measure the volume of the water added
- ..r1 and final solutions. For instance, a fifty percent C. To cool the volumetric pipette
. = involves a reduction of the molarity by fifty percent. D . To warm the water prior to mixing
' ruld result from doubling the volume of the solution,
:,:1by mixing one part solvent with one part solution.
-. .olution is diluted as a solvent is added to it in a
"-;iric flask, until the desired volume is reached. To
--- --omplete transfer of the solute, the original flask is 38. Which of the following mixtures results in a 10-fold
' : rsed with the new solvent, and then the contents are
.; dilution?
. , rto the volumetric flask. The laboratory instructions
. .--old dilution are: A. 9 parts solvent with 1 part solution
B. 10 parts solvent with I part solution
, , a volumetric pipette with a sample of solution C. 10Vo solvent with90Vo solution
': r a beaker and then discard the solution. Repeat this D . 91% solvent with 9Vo solution
:::-'edure two additional times to equilibrate the
, ..:entration of the solution on the walls of the pipette
.1 the concentration ofthe solution in the beaker.
- . :t-s the treated volumetric pipette, transfer ten

- .iliters of solution to a 100-mL volumetric flask. 3 9. Addition of water to an aqueous salt solution would do
: ..e pure water through the pipette and into the all of the following EXCEPT:
-imetric flask until the flask is roughly eighty
:: rent full.
A. lower the molality.
B. lower the molarity.
::. ihe pipette aside, and continue to add water to the C. increase the density.
'-,i: until the base of the meniscus is flush with the D. increase the mass percent ofsolvent.
' -nL line on the volumetric flask.
- '--.:h of the following solutions has the GREATEST
- ..rity'?
\, . j7c by mass KBr in water
40. Which of the following would MOST dilute 0.10 M
:" ':Vc by mass KCI in water LiCl(aq)?
- . jVc by mass NaBr in water
l '-c bv mass NaCl in water A. The addition of 100 mL HzO(l) to 25 mL 0.10 M
LiCl(aq)
B. The addition of 200 mL H2O(l) to 60 mL 0.10 M
LiCl(aq)
- rr-rrlvert 300 milliliters of 0.150 M solution to a C. The addition of 50 mL H2O(l) to 15 mL 0.10 M
-:ion with a concentration of 0.0075 M, how much LiCl(aq)
. :: must be added? D. The addition of 150 mL H2O(l) to 50 mL 0.10 M
., , 6,00 liters LiCl(aq)
:l . -<,70 liters
- :,30 liters
I : 10 liters
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Passage Vll (Questions 41 - 47) 42. When 1.0 grams of a salt are dissolved into 100 mL
water, the volume of the solution is greater than 1 45. F{oqm
There are many ways in which the concentration of a mL but less than 101 mL. What can be said about I _lrl n
solution can be expressed, including: concentration of the solution? -{. I
Molarity: The concentration of a solution as measured in A. The molality of the solution is greater than fr. :
moles solute per liter solution. molarity of the solution; the density of the sol C.:
moles solute is greater than that of pure water. m.5
N/r
- B. The molarity of the solution is greater than
lit"rs sotution
molality of the solution; the density of the sol
Molality: The concentration of a solution as measured in is greater than that of pure water.
moles solute per kilogram solvent. C . The molality of the solution is greater than
moles solute molarity of the solution; the density of the soluti
T,m m
kilogram tof is less than that of pure water.
""r,t D. w,-@
The molarity of the solution is greater than ilmm"J
Percent solution: The percent of solute in a solution by molality of the solution; the density of the so
mass or moles.
w&r
is less than that of pure water.
mass solute J[- U
7o Solution by mass - x l00Vo
mass solution
moles solute
l- il.
7o Solution by moles = x IOOVo
total moles in solution 4 3. An organic compound with a density that is less
c- il.
1.00 g/ml- is added to an organic liquid, also w
Density: The mass of the solution divided by the volume density that is less than 1.00 g/ml.. What can be
of the solution. about the concentration of the solution? D-[
^
n - mass solution A. The molality of the solution is greater than
uolur. rolr'rl'ion molarity of the solution; the density of the sol
is greater than that ofpure organic liquid.
The concentration of a solution can be expressed in any
B. The molarity of the solution is greater than
of these units, which can be converted into one another as
molality of the solution; the density of the so
long as the molecular mass of the solute and solvent are
is greater than that ofpure organic liquid.
ffiim,
known. For instance, when the percent solution by mass is
C. The molality of the solution is greater than
rffi
multiplied by the density, the result is mass of solute per
molarity of the solution; the relative densiti
volume of solution. When the mass of solute is converted
the solution and the organic liquid cannot
into the moles of solute (which requires knowing the
determined without more information.
molecular mass), the molarity can be determined. The
D. The molarity of the solution is greater than
percent solution by mass can be converted into molality by
molality of the solution; the relative densiti
subtracting the mass of solute from the mass of solution to
the solution and the organic liquid cannot
find the mass of solvent. That determines the denominator.
determined without more information.
To get the numerator, the mass of solute is converted into
moles solute, and solving for the molality becomes a simple
division problem.
Adding solvent to a solution dilutes the solution and
thus reduces the concentration of the solute in the solution. 44. Given that a solute is denser than the solvent
which it dissolves, what is TRUE of the concen
Addition of solvent to the solution decreases all of the above
measurements of different solutions made up so
measurements of concentration, with the exception of the
the two components?
density. The density change of a solution depends on the
relative density of the solvent and solution. A. The solution with the greatest density also
greatest molarity and molality.
4 1. Adding water to an aqueous solution of known B. The solution with the greatest density also
greatest molarity, but the molality is the
concentration alwavs decreases all of the following
EXCEPT: all of the solutions.
C . The solution with the greatest density also
A. density. lowest molarity and molality.
B. molarity. D. The solution with the greatest density also
C. molality. lowest molarity, but the molality is the sa
D. mass percent of the solute. all of the solutions.
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mL
an 10f
o-
r5. How many milliliters of pure water must be added to Passage Vlll (Questions 48 - 54)
100 mL 0.25 M KBr to dilute it to 0.10 M?
out thr The absorbance of visible light by colored aqueous
.{. 100 solutions is directly proportional to the concentration of
ran the B. 150 solute in the solution. Based on this fact, the concentration
olutior c. 250 of a solution can be determined by monitoring the absorbance
D. 500
at one wavelength of light. For best results, the detector
ran the should be focused on the wavelength of highest absorbance
olutior (known as l".u*;. The relationship between absorbance and
solute concentration is expressed as
ran tht
Absorbance = e[C]l
;olutior To achieve the same chloride ion concentration as 1.0
Equation L
:rams NaCl(s) dissolved into 100 mL solution, how
ran the nany grams of MgCl2(s) must be added to enough where E is the molar absorbtivity constant of the solute, [C]
;olutior '.', ater
to make 100 mL of solution? is the concentration of solute, and 1 is the path length of the
light passing in through the cuvette.
\. 1.0 x 1 x 58'4 gMgCl2(s)
2 94.9 A student measures the absorbance for a series of standard
B. 1.0 x2x 58'4 g MgCl2(s) solutions. Once enough data points are collected, the
94.9 molarity of another solution using the same solute in an
:ss tha: C, 1.0 x1 x94'9 gMgCl2(s) unknown concentration is analyzed by comparing its
with r 2 58.4 " properties with the experimental data. The molar
be saii
D. 1.0 x 2 x94'9 g" MgCl2ts) absorbtivity constant and cuvette path length remain constant
-58.4 throughout all the frials, so any difference in absorbance
han th between the unknown and the reference compounds can be
soluticrr attributed to differences in solute concentration. Figure 1 is a
graph ofthe student's data collected for the standard solutions.
han tbt
solutiolt
l:r'en two compounds, Compound A and Compound B,
.,:d the fact that B has a higher molecular mass than A,
han th : -t A is denser than B, which of the following mixtures
;ities o; .'. ruld have the greatest mole fraction of A?
lnot br(
{. The mixture of 1.0 grams Compound A with 1.0
han thr grams Compound B
sities m
3. The mixture of 1.0 moles Compound A with 1.0
nnot nr
moles Compound B
The mixture of 1.0 mL Compound A with 1.0 mL Concentration (in molaritY)
Compound B
D, The mixture of 1.0 x 1023 molecules Compound A Figure 1
',vith 1.0 x 1023 molecules Compound B Table I lists the same data summarized graphically above.
ent l!r!o Molarity Absorbance

:ntrati'nc 0.10 0.093
,o1e1r' d o.20 0.1 88
0.30 0.218
r has 0.40 0.363
0.50 0.456
r has 0.60 0.560
;ame 0.70 0.636
r has Table 1
r has 4 8. If the concentration of a solute were doubled, what

!ame would happen to the absorbance of the solution?
A. It would increase by a factor of four.
B. It would double.
C. It would be cut in half.
D. It would decrease by a factor of four.
:.:ht O by The Berkeley Review@ 4t GO ON TO THE NBXT PAGE

4 9. How could the plateau of the following curve be 53. What are the units of e?
explained? A. M.cm
B. M.cm-l
e C. cm.M-l
()
X p. 1
+i M.cm
C)
O
!
a
.o
54. Which of the following relationships may be TRUE?
Solute added to solution L As the molarity increases, the absorbance inc
A. The solvation catalyst in solution has become II. If Compound X has a lower molar absorbti
saturated. constant (e) than Compound Y, then to have
B. The reverse reaction is favored at higher solute absorbance readings for separate solutions of
concentration. and Y(aq), the concentration of Y must be g
C. As more solute is added to the solution, the solute than the concentration of X.
that is already dissolved begins to repel the solvent. III. Absorbance = e[C]l at all ], where absorbance
D . A maximum solute concentration has been reached, light can occur.
because no more solute molecules can dissolve into A. I only
solution. B. II only
C. I and III only
D. tr and Itr only
50. Adding 50 mL of pure water to a 10.0-mL sample of

aqueous salt solution with an absorbance of 0.518
would yield a new absorbance of:
A. 0.518.
B. 0.104.
c. 0.086.
D. 0.259.
5 L. The concentration can be found according to which of

the following equations?
A. tcl =Abs
e.l
B. tcl =
t'l
Abs
C' tcl-Abs'l
e
D' tcl - Abs'e

I
5 2. According to the data from the experiment, what is the

concentration of an unknown solution, if it has an
absorbance of 0.242?
A. 0.197 M
B. 0.240 M
c. 0.258 M
D. 0.289 M

rassage lX (Questions 55 - 61) 5 7. Which solution has the GREATEST concentration?
A. Compound M solution, with an absorbance 0.400
-\n experiment to ascertain the effects of solution
B. Compound Q solution, with an absorbance 0.250
" ::ntration on the absorbance of visible light studies
C. Compound T solution, with an absorbance 0.500
-:rons of varying concentration for three different D. 0.10 M KCl(aq)
. -:.runds. The solutions are analyzed in cuvettes using a
- -\-IS spectrometer set at fixed values specific for each
-:rund. The goal is to maximize the absorbance, so the
, - of maximum absorbance is used for each
;.ength 5 8. Which graph accurately shows absorbance as a function
of concentration for Compounds M, Q, and T?
-:'rund. For Compound M, the spectrometer was set at
UE? :n: for Compound Q, the spectrometer was set at 413
reases. .:ld for Compound T, the spectrometer was set at 691
'btiviq Table 1 shows concentration and corresponding
. r: ance for each solution.
e equal ":
f X(aq
Trial Contents Absorbance
greatel
0.10 M Compound M 0.362 Concentration Concentration
rnce clj iI 0.10 M Comoound O 0.299
Itr 0.10 M Compound T 0.511
n' 0.06 M Compound M 0.211
0.06 M Comoound O 0.1 80
\l 0.06 M Compound T 0.307
\TI 0.03 M Compound M 0.109
\]tr 0.03 M Compound Q 0.090 Concentration Concentration
x 0.03 M Comoound T 0.r53
Table 1 5 9. What can be expected for other solutions?

-:e absorbance of each solution was compared to the I. 0.05 M Compound M has an absorbance of A =
: :nce of a sample of distilled water, which remained in l, = 561 nm.
0.181 at
- ; ln the spectrometer for the duration of the study. II. A solution of Compound Q with an absorbance of
,--se all three compounds have absorbance bands in the A = 0.225 at ?t, = 413 nm has a concentration of
-.: range, they are all observed to have a distinct color 0.075 M.
:1 .nev are exposed to white light. The absorbed color is m. 0.11 M Compound T has an absorbance of A =
- ::plementary color of the observed color. The visible 0.611 at l, = 710 nm.
-:l:n ranges from a wavelength of 400 nm to 700 nm. A. I only
'i-hy is the spectrophotometer set at 561 nm for the B. I and II only
:ral involving Compound M? C. I and III only
A , 561 nm is the average wavelength of absorbance for

D. II and III only
the complementary color of what is absorbed.
B , 561 nm is the average wavelength of absorbance for
6 0. To form a solution of Compound T with an absorbance
the color that is absorbed.
of 0.250 atlv = 697 nm, what must be done?
C . 561 nm is the wavelength of maximum absorbance
A. Mix 10.0 mL 0.10 M T with 5.0 mL H2O
for the complementary color of what is absorbed.
D . 561 nm is the wavelength of maximum absorbance B. Mix 20.0 mL 0.10 M T with 20.0 mL H2O
for the color that is absorbed. C. Mix 19.0 mL 0.10 M T with 20.0 mLH2O
D. Mix 10.0 mL 0.10 M T with 9.0 mL H2O
How can a compound's molar absorbtivity constant be
: L,tained, if absorbance varies with cuvette length?
61. What are the observed colors for each solution?
{. e = Abs.[Compound].1
A. M: green; Q: violet; T: red
R c- Abs
B. M: red; Q: violet; T: green
[Compound].1
C. M: green; Q: yellow; T: red
r.- c - [Compoundl'l
D. M: red; Q: yellow; T: green
Abs
D. e=Abs
1
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Passage X (Questions 62 - 68) 6 3. A precipitate is LEAST likely to occur as a result of
Stoichiometric reactions can be classified into six

A. combustion reaction.
categories:
B. decomposition reaction.
C. single-replacement reaction.
Combination Reaction: Occurs with the combination D. metathesis reaction.
ofreactants to form one product.
PBr3(l) + Br2O '+ PBr5(s)
Decomposition Reaction: Occurs with the 64. What is the precipitate formed when aqueous sod
decomposition of one reactant to form two products. iodide reacts with aqueous calcium nitrate?
CaCO3(s) + CaO(s) + COzG) A. CaI
B. NaNO3
Single-Replacement Reaction: Occurs with the C. CaI2
exchange of either the cations or the anions in a salt, but not D. Na2NO3
both. A single-replacement reaction is also referred to as an
o xidation- re ductio n r eac tion.
3 Mg(l) +2 ScBr:(g) -* 2 Sc(s) + 3 MgBr2(s)

6 5. What is the gas formed when magnesium
Metathesis Reaction: Occurs when two cations neated with hydrobromic acid?
exchange their anions. At least one precipitate falls out of A. Hydrogen gas (H)
solution. A metathesis reaction is also referred to as a B. Hydrogen gas (H2)
doub le -dis plac eme nt r e action. C. Carbon dioxide gas (CO2)
AgNO3(aq) + KCI(aq) KNO3(aq) + AgCl(s)
D. Magnesium bromide gas (MgBr2)
->
Combustion Reaction: Occurs with the addition of
oxygen to a reactant to form oxidized products, (usually
carbon dioxide and water, when dealing with hydrocarbons and 6 6. What type of reaction is LEAST likely to form
carbohydrates). dioxide gas?
I C3Hs(g) + 5 O2(g) "+ 3 COzG) + 4H2O(r) A. Combustion reaction
B. Metathesis reaction
Neutralization Reaction: Occurs with the reaction of an C. Decomposition reaction
acid with a base to form water and a salt. D. Neutralization reaction
HNO3(aq)+KOH(s) + KNO3(aq)+H2O(l)
Each reaction is unique from a stoichiometric

perspective. When a solid is formed by the reaction of ions 6 7. How should the following reaction be classified?
(in the metathesis example above), it is referred to as a CaBrz(l) + Cl2(g) + CaCl2(s) + Br2(l)
precipitate. Gases can also be formed from reactions. The
neutralization of sodium bicarbonate (NaHCO:) yields carbon A. Combination reaction
dioxide gas. It is possible to categorize all inorganic
B. Decompositionreaction
C. Single-replacement reaction
chemistry reactions by reaction type.
D. Metathesis reaction
6 2. How should the following reaction be classified?
Ba(NO3)2(aq) + K2SO4(aq) +
2 KNO3(aq) + BaSOa(s) 68. What type of reaction is MOST likely to ha
A. Combination reaction negative value for the change in entropy (AS)?
B. Decompositionreaction A. Combination reaction
C. Single-replacement reaction B. Decompositionreaction
D. Metathesis reaction C. Single-replacement reaction
D. Combustion reaction

're'urs$,age Xl (Questions 69 - 78) 7 1. The mass percent of calcium is LEAST in which of the
following molecules?
'';ium carbonate is found in many everyday products,
- A. CaO(s)
r '- ., narble, chalk, and antacids. Commercially, it can be
rrLr
B. Ca(OH)z(s)
| : :rid as either calcium oxide or calcium carbonate. C. CaCO3(s)
r,,. , -:r oxide converts to calcium carbonate upon exposure
D. CaCl2(g)
r dioxide under high pressure. At room temperature,
-r":i- n
r,,. -:, ;arbonate is relatively insoluble in water. The
ri "- ,-." of calcium carbonate increases as the pH of the
luilir -u . -! solution decreases, because calcium carbonate is 7 2. If 10.00 grams of Ca(OH)z(s) produces 5.00 grams of
rlrii, , R.eaction I can be combined with Reaction II to CaCO:(s), what is the percent yield for the reaction?
r rr' :* :alcium oxide into calcium carbonate in water.
A. 31Vo
CaO(s) + HzO(l) + Ca(OH)z(aq) B. 68Vo
Reaction I C. 14Vo
D. l00Vo
-: DH)2(aq) + CO2@) -+ CaCO:(s) + HzO(l)

Reaction II
:
OH)2 and CaCO3 both readily form a relatively
,
7 3. What is the mass percent of calcium in CaO?
m -:-e white solid precipitate in water. Because of this (Ca = 40 g/mole O = 16 g/mole)
. ':.;bility, the products of both Reaction I and Reaction A. 28.6Vo
- :: :;.sv to isolate from solution. Fortunately, calcium B. 50.0vo
r"', *-. r -;e is more soluble in water than is calcium carbonate, c. 66.1Vo
,ur" ":. :trlows for the selective precipitation of calcium D. 7l.4%o
rlr- . - r:e in Reaction II. Because of this, industrial processes
,,' ,,,.ating calcium carbonate are primarily water-based.
, , -:r carbonate can also be formed according to the
'r ;',.-,S equilibrium reaction: 74 . 28.0 grams of CaO(s) when reacted with 10.00 grams of
H2O(1) would yield which of the following?
CaO(s) + CO2(g): CaCO3(s)
(Ca= 40 g/mole O = 16 g/mole H = 1 g/mole)
Reaction III A. 37.00 grams Ca(OH)2 with leftover water
,il I Ja OH)2 is considered to be which of the following?
B. 37.50 grams Ca(OH)2 with leftover CaO
C. Exactly 38.00 grams Ca(OH)2 with no leftover
\, An amphoteric salt D. Exactly 42.60 grams Ca(OH)2 with no leftover
B. A non-metal hydroxide
C. An Arrhenius acid
D, An Arrhenius base
75. Which of the following is required to neutralize 5.00
mL of 0.20 M CaCO3(aq)?
A. 10.0 mL 0.10 N NaOH(aq)
B. 10.0 mL 0.10 N HNO:(aq)
- 'i''hich of the following molecules are NOT held C. 10.0 mL 0.30 N HrPO+(aq)
::gether by ionic bonds? D. 10.0 mL 0.20 N HCI(aq)
r. cot2-
II. COz
7 6. What is the final concentration of Ca(OH)z(aq) after
I. CaO 50.0 mL of pure water are added to 5.0 mL of 0.50 M
A. I only Ca(OH)2(aq)?
B, tronly A. 0.055 M Ca(OH)z(aq)
C . III only B. 0.050 M Ca(OH)z(aq)
D , I and II only C. 0.046 M Ca(OH)z(aq)
D. 0.025 M Ca(OH)2(aq)
- ::.. right @ by The Berkeley Review@ 45 GO ON TO THE NEXT PAGE

77 . If 20.0 mL of 0.20 M CaCl2(aq)
were mixed with 30.0 Passage Xll (Questions 79 - 86) f0" fr]
mL of 0.30 M CaCO3(aq), what would the final Ca2+ tmn
concentration be? Every year, a substantial amount of the countless tons of
chemicals produced worldwide is used in the manufacture of
A.
A. 0.233 M Ca2+1aq; E.
B. fertilizers and plastics. Described below, according to a
0.250 M Ca2+1aq;
common element each one contains, are some of the typical
c.
C. 0.260 M Ca2+1aq; n"
D. chemical fertilizers used in America.
0.267 M Ca2+1aq;
Potassium:
Salts containing potassium are referred to as potash.
most common forms are K2SO4, 2 MgSOa.K2SO4, and rm
KCl. The amount of potassium per gram of salt is importan
78. If 50.0 grams of CaCO3(s) are completely neutralized to know when determining the quantity of fertilizer needed
Jt-
with HCl, how many liters of COZ(g) form at STp, a job. The compound richest in potassium (by mass per<
:-
knowing that one CaCO3 yields one CO2? is potassium oxide, K2O. The potassium conteni of c-
D.
A. 4.48L potash is expressed as a fraction of the potassium i
B. 10.00 L potassium oxide (K2O).
c. 1t.20L
D. 13.56 L Nitrogen:
Salts containing nitrogen are very useful as fertilizers. ilh
most common forms are NH4NO3, (NHa)2S04, u ryd
NHaH2POa. A very common organic fertilizer containi
nitrogen is urea, H2NCONH2, which is made from am
il-
and carbon dioxide. Ammonium sulfate is also made f
ammonia by combining Reaction I with Reaction II: l-
2 NH3(aq) + COzG) + H2O(l) ----+ (NHa)2CO3(aq)
c-
Reaction I
(NHa)2CO3(aq) + CaSO4(aO L-
-->
(NHa)2SOa(aq) + CaCO3(s)
Reaction II
Phosphorus:
Salts containing phosphorus are also very useful
fertilizers. The most common form is Ca(H2pOa
Calcium bisdihydrogenphosphate is produced by Reaction
2 Ca5(POa)3F(t + 7 H2SOa(aq) I
{
3 Ca(H2POa)2@q) + 7 CaSO4(aq) + 2 HF(e)
-.; (
Reaction III I
Fluoroapetite (Ca5(POa)3F) is added as the limit
reagent in Reaction III. This is done to maximize the
yield of phosphorus in the reaction. Industrially, the
yield of a reaction and the mass percent of its product
critical in terms of profit margin for the fertilizer producer.
I
79. Which of the following compounds has t U
GREATEST amount of potassium per gram? ,[
A. K2O il
B. K2SO4 I
C. KCI
D. KNO3
Copyright @ by The Berkeley Review@ 46 GO ON TO THE NEXT PA

$ l"t. Which of the following compounds has the LOWEST 85. From which of the following reactions is it EASIEST
mass percent of nitrogen? to isolate the desired product?
tons of
^{. H2NCONH2 A. A reaction yielding the product as a precipitate
rture of B. NHaNO3 B. A reaction yielding the product as a liquid
rg to C. (NHa)2SOa C. A reaction yielding the product as a gas
D. NHaH2POa D. A reaction yielding the product as an aqueous solute
l.
t4, a \\hat is the mass percent of nitrogen in urea? 86. Which of the following relationships must be TRUE?
A..23.3VoN I. pKal(H3pOa) is less than PKa(HF)
ded B.3l.9VoN tr. pKa2(H3pOa) is less than PKa2(HzSO+)
erce C . 46.6V0 N
of D. 66.'7VoN m. pKa(HF) is less than PKal(H2SOa)
ium
A. I only
B. II only
C. Iandtronly
rS.
frhy is Ca5(POa)3F the limiting reagent in the D. IIandItronly
;1 nthesis of Ca(H2POa)2?
4,
tarru -\. It prevents leftover Ca5(POa)3F from being
rvasted, so that P-containing compounds are
conserved.
ts " It allows leftover Ca5@Oa)3F to be wasted, so that
P-containing compounds are conserved.
):(ac f
C. It prevents leftover Ca5(POa)3F from being
rvasted, so that P-containing compounds are not
conserved.
D . It allows leftover Ca5(POa)3F to be wasted, so that
P-containing compounds are not conserved.
)03(sr
:ful
L i l,:r.0 grams of (NH+)zCO: are used in Reaction II to
,o4 :':';in 10.0 grams of (NH+)ZSO+, then what is the
lon
rtr:ent yield for the reaction?
s . Less than 50Vo
M . Greater than 50Vo, but less than 7 5Vo
ll . Greater than75%, but less than l00%o
D ., Greater than loj%o
T:e rrolarity of potassium is GREATEST for which of

:lliowing solutions?
tlrc
4., -0.0 g KCt in enough water to form 100 mL of

>olution
il. 10.0 g K2SO4 in enough water to form 100 mL of
solution
1: 10.0 g K2CO3 in enough water to form 100 mL of
roiution
Dt. 111.0 g KNO3 in enough water to form 100 mL of
solution
",,,, nnnr:git O by The Berkeley Review@ 47 GO ON TO THE NEXT PAGE

92. For the following reaction, calculate the mass
Questions 87 - 100 are NOT based Mg2P2O7(s) that is formed from the decomposition
on a descriptive passage
2.0 grams MgNHaPOa(s).
MgNHaPOa(s) -+ Mg2PzOz(s) + 2 NH3(g) +
8 7. If 25 grams of oxygen are combined with 20 grams of
A. 0.8 grams
propane gas, which of the following statements would
be TRUE after the compound is ignited?
B. 1.7 grams
C. 2.2 grams
A. 45.0 grams of carbon dioxide forms. D. 2.8 grams
B. 38.0 grams of water vapor forms.
C. Oxygen is the limiting reagent.
D. Propane is the limiting reagent.
9 3. A compound containing 50Vo by weight of Element
(atomic weight = 40) and SOVo by weight of Element
88. The hemoglobin in red blood corpuscles of most (atomic weight = 80) is one in which:
mammals contains approximately 0.33V0 iron by A. the molecular formula isXZorZX.
weight. If osmotic pressure measurements show that B. the simplest formula isXZorZX.
the molecular weight is 68,000 for hemoglobin, how C. the simplest formula is XZ2 or Z2X.
many iron atoms must be present in each molecule of D. the simplest formula is X2Z or ZX2.
hemoglobin?
A. 1
8.4
c.224
D. 400 94, 11.89 grams of hot iron are exposed to a
stream of pure oxygen for ten minutes. At the end
this time, the completely oxidized sample weighs 1
grams. The empirical formula for the compound
89. 9.00 grams of a sugar are burned in a containment formed is MOST accurately written as:
vessel, and all the COz is collected. The volume A. Fe3O2.
occupied by the CO2 at STP is 6.72 liters. If the B. FeO.
molecular weight of the sugar is 180 g/mole, what is C. Fe2O3.
the ratio of 02 to CO2 in the balanced equation? D. FeO3.
A. 3:3
B. 3:6
C. 6:3
D. 6:6
95. A stable compound consisting of 53.4Vo C, ll.0%o
and the remainder O has a molecular weight of
grams/mole. The molecular formula for the
9 0. What is the molecular formula for an unknown gas with is:
the empirical formula C2H3O, if 1.00 grams of the A. C5H6O2.
unknown gas occupies 26OmL at STP? B. C3H6O3.
A. C2H3O C. C4H26O.
B. CaH6O2 D. C4H16O2.
C. C6H9O3
D. CsHl2Oa
96. In reducing CrO42-(aq) to Cr2O3(s), how does

91. What volume of O2G) is produced from 1.0 g BaO oxidation state of chromium change?
upon its decomposition to Ba(s) and OZ(g) at STP? A. From +6 to +3
A. 0.074 L B. From +4 to +3
B. 0.100 L C. From +3 to +4
c. 0.148 L D. From +3 to +6
D. 0.166 L
Copyright @ by The Berkeley Review@ 4A GO ON TO THE NEXT P

-\n unknown metal is found to combine with oxygen in
a 2 : 3 ratio in the molecular formula. The metal oxide
rs approximately 53Vo metal by mass, and the remainder
rs oxygen. What is the MOST probable identity of the
netal?
.\. Calcium
B, Iron
C. Chromium
D. Aluminum
thich of
the following organic compounds has the
;REATEST mass percent of carbon?
\. Acetic acid (CH3CO2H)
B. Ethanol (CH:CHzOH)
C. Methyl acetate (CH3CO2CH3)
D. Glucose (C6H12O6)
fl
nd -,i
l! hen one gram of each of the following organic
16.
- nrpounds is burned (oxidized), which one yields the
:REATEST amount of carbon dioxide (by mass or
-":ies)?
\ , Acetic acid (CH3CO2H)
B. Ethanol (CHTCHzOH)
tl , Methyl acetate (CH:COZCH:)
D, Glucose (COH1ZOO)
1t
)f l,r'-hat is the mass percentage of chlorine rn
\1g(ClOa)2?
.\. 7t.0vo
B. 40.6Vo 1.8 2.D 3.A 4. B 5.A 6.C
C . 31.8Vo 1.D 8D 9.B 10.C 11.D 12.A
D. 15.9Vo 13. C 14. A 15. C 16. D 17. B 18. B
19. C 20. B 21. B 22. D 23. B 24. A
25. A 26. D 27. C 28. C 29. D 30. A
31. A 32. C 33. D 34. D 35. B 36. C
37. A 38. A 39. C 40. A 4r. A 42. A
43. C 44. A 45. B 46. C 47. C 48. B
49. D 50. C 51. A 52. C 53. D 54. C
55. D 56. B 57. A 58. D 59. B 60. c
61. D 62. D 63. A 64. C 65. C 66. B
67. C 68. A 69. D 70. D 1r. D 12. A
73. D 14. A 15. D 16. C 11. C 18. C
79. A 80. D 81. C 82. A 83. B 84. C
85. A 86. A 87. C 88. B 89. D 90. B
91. A 92. B 93. D 94. C 95. D 96. B
97. D 98. B 99. B 100. C
;;:i,ght @ by The Berkeley Review@ 49 YOU ARE DONE.

Stoichiometry Passage Answers
1' Choice B is correct. In order for a liquid to float on water, the liquid must be
both immiscible in water and less
dense than water. All of the liquids are assumed to be immisciLle in water, accord.ing to the question,
so the
only stipulation that remains to be considered is the density of each liquid. The
densiiy of watir is defined as
1'00 grams per milliliter. We know that the mass of the empty volumetric
cylinder is 42.6r grams and its
capacity is 10'00 mL. For the density o1,u"y liquid to be less thin 1.00, a 10.00-mL
sample of the liquid must
have a mass of l1s; t\n 1o.00 grams. This *"un, that when 10.00 mL of a
liquid is added to the volumetric
cylinder, the liquid and cylinder must have a combined mass of less than 52.61 grams.
If the combined mass is
less than that, then the density of the solid must be less than 1.00. According
to tubl" 1, unknown Liquid #6
(with a combined mass with the volumetric cylinder of 51.33 grams) and unkriown
Liquid #9 (with a combined
mass with the volumetric cylinder of 49.03 grams) are the or,!, t*o' lrr,known
liquids with combined. masses of Wl
less than 52.67 gtams. Only Liquid #6 and Liquid #9 can float on water.
The best answer is therefore choice B. [u
M
2' Choice D is correct. This question requires evaluating the density for unknown
Solids #2, #3, #4, and #5. !@
Density is defined mass per volume. In this case, the'volume of ihe solid is obtained by taking
-as the volume ds
reading from the chart for each unknown ald subtracting 25.00 mL for the volume of the water iready in
the
cylinder' This method of measurement is known as thei'volume by displacement
table shows the values of mass, volume, and density obtained for each
technique.', The following c
solid: ffi
Unlcrown Mass (e) Volume (mL) il,
Densitv
@
2 12.38 31.19-25.00=6.79 72.38g
=2.00
g
6.19mL mL 0
3 14.85 29.95-25.00=4.95 1'4.859
=3.00
g od
4.95mL mL dc
L@ll
4 8.22 28.00-25.00=3.00 8.229 _rrn g
ffift
3.00 mL mL u[r
5 5.64 26.47-25.00=1.41 5.649
=4.00
g @
1.41mL mL tifi
The unknown solid with the greatest density is unknown Solid #5. The
numbers could have been compared to one another to obtain the relative
correct answer is thus choice D. The
values.
3' Choice A is correct.- The density of unknown Solid #1 must be determined first.
It is found by dividing its mass
by its volume (found by difference):
9.639 9.639 j.5o g rdm

'p = 37.42 - 25.00 mL- 6.42mL=
mL rffi&c
Because the density t: 1q0 grams per milliliter, a20.0-gtam piece of the solid must have a volume of 13.3 mL, @
because 20'0 grams divided by 13.3 mL is equat to r.s-o gru*, per milliliter.
The correct answer is choice A.
Choices C and D should have been eliminated immediailly, because when the
volume of an object is greater
or.the object is less jl1" 09: soud #1 sinks when placed into waier, indi"cating
:lii,T:
that Tjl:j$ t:l:"',1,t
its density is greater than that of water, which is 1
1.00 grams per milliliter. Distinguishing between
choice A and choice B requires looking more closely at the ratios.
4' Choice B is correct. In order for a solid to float on unknown Liquid #7, it must have a density less than that
liquid. The density for unknown Liquid #7 is:
58.72-42.619 _ 1.6.11g
, _ 10.00 = L611
g
mL 10.00 mL mL
only Solid #1, with a density of only 1.50 grams per milliliter, has a density less than 1.611
milliliter. The best answer is choice B. The teGtirre densities of Liquid #7 andsoiia +r are shown grams
below:
pliquido, =
#*. =
#k,psoria+r =
##,= ##, - #k, ##
Copyright O by The Berkeley Review@ 50 Section I Detaited
Choice A is correct. The following table shows how to solve for the densities of the four liquids:
u Unlmown
6
Mass (s)
51.33 - 42.61- = 8.72

Volume (mL)
10.00
Densitv ( I
.-mr-
8.729
)
E
I less
o the
i
10.00 mL=o.gr2mL
1.6.71.9 g
:d as 7 58.72 - 42.67 = L6.77 10.00 =L67I
d its 10.00 mL mL
must 1o.6og I
8 53.2L - 42.67 = 10.60 10.00
retric 10.00 mL=1.060mL
rss is
9 6A29
rd #6 49.03 - 42.61. = 6.42 10.00 =0.642 E
,ined
10.00mL mL
es of ":om the calculations, the relative densities in descending order are: Liquid #7 > Liquid #8 > Liquid #6 >
B. -rquid #9. The answer choice that does not follow this pattem is choice A: Liquid #7 > Liquid #6 > Liquid #8.
-lhis
question could also have been solved by comparing the masses in the chart for the cylinder and liquid
r #5. :-.nbined. All of the liquids have the same volume (10.00 mL) and were in the same cylinder, so the same mass
iume -o subtracted from each in determining the liquid's mass. This would have saved much time.
n the
rving [hoice C is correct. If the mass of the cylinder were heavier than 42.61, grams, then the reading for the mass of
:-.e liquid and cylinder combined would be greater than it was in Experiment 2. However, the mass of liquid in
: ired volume is the same, so its density does not change. No matter what container is chosen to hold it, the
:=nsity of a liquid is an invariant property of that liquid. This is best reflected in answer choice C.
Chroice D is correct. Density is defined as a measure of mass per volume. The units for density should therefore
:=lect a mass unit divided by a volume unit. In answer choice A, the mass is measured in grams and the volume
--. reasured in milliliters, which makes choice A acceptable. In answer choice B, the mass is measured in
, -:-rces and the volume is measured in centimeters cubed, which makes choice B acceptable. You should recall
--:t a milliliter is a centimeter cubed. In answer choice C, the mass is measured in kilograms and the volume is
:=asured in liters, which makes choice C acceptable. In answer choice D, the weight (and not necessarily the
* '.s) is measured in pounds and is divided by an area (dimension squared) and not by volume. Choice D is thus
: :..easure of pressure, not density. The correct answer is choice D.
-hoice D is correct. Given that all of the samples were of nearly equal mass (between 1,.995 g and 2.011 g), the
:.::est mass percent of carbon is in the compound that has the greatest mass of carbon. The compound with the
;:=":est mass of carbon produces the greatest mass of carbon dioxide gas. This means that the easiest way to
. -' e this question is to compare the amount of carbon dioxide collected for each sample, as listed in column 4
:-= \aOH tube column) in Table 1. From the data in the NaOH tube column, the greatest mass of CO2 is
" *=;ted from Compound IV (35.99 - 30.00 = 5.99), eliminating choices A and B. Because a greater mass of CO2 is
I mn* r - .,::.rcd by oxidizing Compound III than by oxidizing Compound II, choice D is the best answer.
ce A.
:ea
ll: ::ce B is correct. The role of the sodium hydroxide salt is to bind CO2, not to bind H2O. This means that the
atinq r,.: =:rould be both hydrophobic (non-water-binding) and reactive with carbon dioxide, making choice B the
" "x r rrlswr. The term "hydroscopic" refers to a compound with a high affinity for binding water.
-,: : irce C is correct. The pressure valve is designed to allow oxygen gas to flow from the tank into the system
r. tl:d ' -:: a threshold pressure is maintained. The oxygen partial pressure can be controlled and maintained at a
::- .evel. The oxygen tank is left open with a positive pressure of oxygen to ensure that oxygen gas is
: --:.ual1y flowing into the system, so choice A is eliminated. Nothing was mentioned about the temperature of
-" : :',,\'gen gas, so choice B is eliminated. Oxygen gas is always present, so it is in excess and is not a limiting
'', r i:r:t. This eliminates choice D and makes choice C the correct answer.
l.- : ice D is correct. The greatest mass percent of carbon is found in the compound with the smallest number of
' ;:r atoms in its formula. Thus, the compound least likely to contain oxygen is the one that produces the most
" - :pon combustion. That is Compound IV. In additionr pure carbon when oxidized yields 7.33 g CO2.
- : ::.-r-rnd IV yields 6.00 grams CO2, so it is close enough to pure carbon to assume no oxygen is in it, choice D.
ri * ri: 3 by The Berkeley Review@ 5l Section I Detailed Explanations
12. Choice A is correct. When the first valve is opened, the gas is exposed to magnesium sulfate, which binds water,
!8.. (
but not carbon dioxide. This means that water is bound first, leaving an atirosphere of excess oxygen gas and
l
carbon dioxide. This is important, because the sodium hydroxide compound can bittd both carbon iioxide and
lt
water. Using magnesium sulfate first to remove the water vapor ensures that all water is removed. from the gas
when the second valve is opened, exposing the gas to the sodirm hydroxide salt. Any increase in the mass oJ
:
tr
magnesium sulfate is due to the binding of water. Any increase in the mass of sodium hydroxide is due to the
binding of carbon dioxide. If the gases were first exposed to sodium hydroxide, the increase in mass would be due
to both water and carbon dioxide. Choice A is the best answer. Excesi oxygen leaves the system as a free gas. fl
di
13. Choice C is correct. The solid formed in the second tube results from the reaction of sodium hydroxide (NaOH
with carbon dioxide (COil, so it must be a sodium salt. This eliminates choice C. The following reactior
confirms that the best answer of the given choices is sodium bicarbonate, choice C:
NaOH(s) + CO2(g) _-+ NaHCO3(s)
c
74- Choice A is correct. If 20.0 grams of the unknown were oxidized, instead of 10.0 grams, then the amount
carbon dioxide and water formed as products would double. This eliminates choices L and D. The mass percr
of carbon should remain the same, because the mass of carbon dioxide formed and the mass of the compound bo
c
ffi
doubled. The best answer is choice A. The mass percent of carbon is constant, because the formula is cbnstant. eI
,ffi
1,5. Choice C is correct. To determine the mass percent of carbon in the unknown compound, the grams of carbon
carbon dioxide (COz) are divided by the total number of grams of original compound. Tie mass of carb
dioxide formed is found by subtracting 100.00 grams of original sodium hydroxide from the 1zg.7g grams
bicarbonate salt. The difference is the mass of carbon dioxide that binds the salt.
72gC
23.79 gramsCo2 x
,r"*"t-#q x100% =23.79x]2xLxfi)%
44 10
This makes choice C the best answer.
16. Choice D is correct. In the first sentence of the passage, we read that the unknown organic compound is por
into a flask. The term "poured" implies that the compound flows, which makes it a-fluid. ThL fact thai it
be poured into a flask means that it is flowing down, which defines it more specifically as a liquid.
compound is a liquid at ambient temperature (room temperature). This means that the melting point it
than ambient temperature, because at room temperature ii has already melted into a liquid. rhe"boiling poi
is greater than ambient temperature, because at room temperature it has not yet boiled- into a gur. eeJrrse
readily evaporates, the boiling point may be close to ambient temperature; bui because it is a liquid at ambi
temperature, the boiling point must be greater than ambient temperature. The best answer is choice D.
17. Choice B is correct. As stated at the end of the passage, the molecular formula for a compound with jt
hydrogen, oxygen, and carbon cannlt have an odd number of hydrogens. An odd number of hydrogens results
an odd number of bonding electrons (electrons present in bonds). Considering that there are two electrons
I
bond, an odd number of bonding electrons results in only half of a bond somewhere in the compound (whl
equates to a single electron, or free radical.) A half-bond is not stable (possible to isolate physically), so cho
B,-with five hydrogens in the formula, is not possible. Knowledge from organic chemistry .un prorru useful
solving general chemistry questions. You must incorporate informition from many sources to excel at this
18. Choice B is correct. Thgre are 1'2.76 grams of water produced from the oxidation of 10.0 grams of the 1nkno*
This can be determined by subtracting 100.00 grams for the mass of the anhydrous sodium sulfate from the fir
mass of 772.76 grams for the hydrated sodium sulfate salt. The moles of waier formed are greater than 0.5 n
because 12.16 grams divided by 18 is greater than 9 grams divided by 18. The moles of waler formed is less
1.0 moles, because 72.1'6 grams divided by 18 is less than 18 grams divided by 18. The best answer is there
choice B.
9g 12.769 \-
,\ -----, 18g
0.5moles = = 1.QmOleS
.,s8l
/mole lssl
-" /mole ---_l_
-"
:msl/mole
Copyright @ by The Berkeley Review@ 52 Section I Detailed Expl

,tr, Choice C is correct. The question asks for the empirical formula, but because information is given about the
1d molecular mass, you may wish to consider the molecular formula first, then eliminate choices based on that
:td information. According the passage, the molecular mass has a value between 70 and 80 grams per mole, so
;as choice B (MW = 48 + 8 + 32 = 88) and choice D (MW = 96 + 10 + 16 = 122) are eliminated. The only choices with a
o{ mass in the range of 70 grams to 80 grams are choice A (which has a mass of 74 grams per mole) and choice C
he
(which also has a mass of 74 grams per mole). Choice A is 36 percent carbon, while choice C is 4& percent
ue ' 74 74'
carbon. The mass percent of carbon is greater than fifty percent, so choice A is eliminated, leaving choice C as
the best answer. The exact numerical value for the mass percent of carbon can be approximated as follows:
72gC
23.79 gramsCo2
- x
MgCOz L x J- x 100"/' 23.79 x 12 ..
x 100% = 23.79 x =-r( IoO"k=23'79x3 xlp"h
10J grrt* 4410 44x10 11x10
""1*"*"
=71..37 x 111"h,where 7L.37 x rc1% > S0%
110 110
Choice C is both the molecular formula and the empirical formula.
of
nt Choice B is correct. The mass percent of carbon in C5H12O2 is found by dividing the mass of five carbon atoms
rth (60 amu) by the molecular mass of C5H12O2 $O + 12 + 32 = 104 amu). The value determined when 60 is divided
by 704 is less than60"/o, because it is less than 60 divided by 100. The best choice for a value close to, but less
than, 60% is choice 8,57.7"/o. You really should choose answer choice B, if you know what's best for you.
in 5 x 12
- 60 < 60 60oh
ffi+12+32 = 704 100 =
fn mass percent of carbon
of
:: Choice B is correct. The mass percent of carbon in carbon dioxide is the mass of carbon (12.011) divided by the
massof carbondioxide (44.009)x100%. Thefraction12 reducesto 3
44 11=3*a-=3x0.091
11
=0.273x1,00%=27.3"/o.
To make math easier, you should memorize the following set of fraction-to-decimal conversions. A
demonstration of how these fractions are useful is found on page 30.
3d 1= 0.333,L= 0.250,L=0.200,L= 0.1.66,L= 0.143,1 = 0.125,1 = 0.100,! = 0.091,! = 0.091,! = 0.083

arl 3456789 10 11 72
he This trick works well, once learned. It may seem awkward at first, but try it. The correct answer is choice B.
ss
nt :" Choice D is correct. The second experiment was conducted to determine the molecular mass of the unknown
rt Liquid. At 304 K, the boiling point of the liquid (and thus, the temperature of the gas), the volume of gas is
nt exactly 1".00 liters, assuming that the flask is completely filled with vapor from the liquid. Molar volume at
this temperature is 24.96literc per mole. At 304 K, the gas has a density of 2.32 grams per liter. \Alhen this
value is multiplied by molar volume at 304 K the liters cancel out and the remaining units are grams per mole.
$t The molecular mass is 2.32 g/L x 24.96 L/mole = 2.32 x 24.96 g/mole = 58 g/mole. The best answer is choice D.
in You should always consider units when looking at math questions. The question asks for a molecular weight,
'r rvhich has units of grams per mole. The numbers in the answer choices arc 2.32 (which is in grams per liter),
ch 22.41 (which is in liters per mole), and 24.96 (which is in liters per mole.) To get the target units, grams per
ce liter are multiplied by liters per mole, choices C or D. Choice D has the correct molar volume of the unknown
i-n liquid at 304 K.
t"
:i: Choice B is correct. You know the molecular mass of the unknown compound (58 grams per mole) and the mass
:n- percent (82.9%), so you can make an intuitive determination of the molecular formula. The mass of carbon in the
ral compound must equal either 12, 24, 36, or 48 (multiples of 12). Given that 82.9% of 58 is closest to 48 of the
X multiples of. 12, it can be assumed that the molecule has four carbons. This leaves ten hydrogens (to round out
a.m the 10 grams in 58 grams per mole not accounted for by the four carbons); so the molecular formula is C4H19,
ire rvhich has an empirical formula of C2H5. AII of this intuition should lead you to pick B.
if you want to solve for the empirical formula
exactly, here is the math using the compact formula, where a
100-gram sample is assumed. Do lengthy math calculations only if they are absolutely necessary.
Cl2gFltz.t = C6.gHl7] = C6.eH17.1 = C1H2.5 = C2H5
1.2 1 6.9 5.9
5.' Section I Detailed Explanations
24. Choice A is correct. The mass percent of carbon in the unknown compound must be less than 100%. This
automaticallr' elimrnates choices B, C, and D. If you didn't notice thatlact, then the problem can be solved
knort'ing that the mass of carbon in the CO2 is equal to the mass of carbon in the unknown The mass of
carbon rn CO2 n.ill be the moles of CO2 0.55/22.41) multiplied by the mass of carbon"omporrnd.
(12:011). When this is
dir ided b'r- the mass of the sample (1.00), the result is answer choice A.
25. Choice A is correct. The key fact in the passage is that the 3.045 grams of carbon dioxide gas formed occupies
1.55L at STP. The question asks for moles of carbon dioxide, so the liters must be converted to moles. The
.-?"Lut:i9tt is given in the chart as 22.4liters per mole. To convert to moles, either the 3.045 CO2 grams must be
divided by the molecular mass of 44 grams per mole, or the 1.55 liters CO2 must be divided Uy in" 22.41liters
per mole. The second option is answer choice A, so pick that. If you wish to get an exact value for the moles, you
must get the denominator close to 100. This can be done by scaling the numerator and the denominator (i.e.,
adding a value to each that is equivalent to multiplying both by the same value).
1.55 x 4
- 89.6
6.20 = 6.20 + 0.775
= 9!!5_- = 0.069 moles CO2 .&a {
22.4x 4 89.6 + 11.2 100.8 I
This is fairly precise, but unnecessary on the MCAT. The addition of 0.775 to the numerator and addition of 1.1..2 I
to the denominator accomplish the goal of making the denominator close to 100 while scaling proportionally. .1ll
$
26. Choice D is correct. If the organic vapor had not displaced all of the air in the flask at the time the heat was ,g
removed, then the flask would not have been filled with pure organic vapor at that time (as was assumed). il
The actual amount of organic vapor in the flask would be less thin the aisumed value (10b%), so the actual (
amount of liquid collected would be too low. If the measured mass of the liquid is too small, ttren the value in
the numerator is too small for the calculation of the molecular mass, so the caiculated molecular mass is too low C
as well. Pick D to feel that happy sensation of correctness. flli
T
illq
fur
27. Choice C is correct. Water must be frozen out of solution, so the temperature of the trap should be less than the ffi
freezing point of water (0'C). This eliminates choices A and B. Th; temperature of the trap cannot be lower
0e
than the sublimation point of carbon dioxide, however; otherwise, the car6on dioxide gur
-ontd sotidify in the
trap along with the water vapor. The trap's temperature must be greater than the sub-limation point oicarbon
(m
dioxid,e, but that temperature is neither given in the passage nor is it common knowledge, unless yo, happen to
own the Jeopardy@ Chemistry game. To play it safe, choose a temperature just less i-han the boiling pornt of
water. The value closest to 0"C without exceeding 0'C is -33"C. The best answer is therefore choice C. (s
ffih
28. Choice C is correct. The successive traps should be aligned in a manner to isolate each gas separately. T uo
moles are not determined by difference, so choices B and D are eliminated. The trick here is determining t
relative temperature sequence. If the traps were set first to isolate carbon dioxide by deposition (convertin
from gas into solid), then water vapor would freeze out along with the carbon dioxide gas, and thus th
compounds would not be separated. By freezing water vapor first, the carbon dioxide puss to a later tr
where it can in turn be isolated free of water. Because the freezing point of water is O"C"u.and the sublimati
point of carbon dioxide is -78"C, the temperatures of successive traps should gradually decrease. Choose C.
29. Choice D is correct. To determine the molecular formula from the empirical formula, the molecular mass of
compound must be known. This fact makes choice D the best answer. The volume of the products and redctanl
is dependent on the mole ratio in the reaction, but not exclusively on the molecular formula. The volume ma
change depending on other conditions, such as temperature. This eliminates choices A, B, and C. pick D
Determination of the molecular formula from the empirical formula involves comparing the empirical mass
the molecular mass. If the empirical mass is equal to the molecular mass, then the empirical ?ormula is I
molecular formula. Choose D for the satisfaction of knowing you got this correct.
30. Choice A is correct. Combustion analysis involves oxidizing compounds and collecting their oxide gases. I
gas can be oxidized like carbon (given that carbon and sulfur are roughly equivalent in electronegutirrity;.
means that sulfur oxide can be collected and analyzed like the oxide of carbon. The oxide oisulfur that
formed is uncertain, but the only answer choice showing oxidized sulfur is choice A, where sulfur carries
positive four (+4) oxidation state. Sulfur can also be oxidized into sulfur trioxide (SOS), but that is not listed
a choice.
Copyright O by The Berkeley Review@ 54 Section I Detailed
this Choice A is correct. If oxygen gas were trapped out from the gas mixture, there would be no way to know
ved whether the oxygen gas collected was from the original hydrocarbon, or from the excess oxygen gas needed to
;s of ensure the complete combustion. This makes choice C valid. It is true that oxygen from the carbohydrate is
is is found in both the carbon dioxide product and the water product; thus, the oxygen from the compound cannot be
isolated. This makes choice B valid.
Oxygen in the carbohydrate is fully reduced (has a negative two (-2) oxidation state when bonded to carbon and
pies
hydrogen). When looking at complete combustion reactions, remember that oxygen atoms from the compound do
The
not react with oxygen gas at all. This makes choice D valid. Oxygen gas has a sublimation point around -180"C
;t be
(so oxygen gas undergoes deposition when the temperature drops below -180"C); thus, oxygen gas can be
iters
collected out of the air using a liquid nitrogen trap. Nitrogen liquid has a boiling point of -796'C, so the
you
temperature of the trap must be -196'C. The best choice is therefore choice A, because oxygen can exist as a
(i.e',
solid. The correct answer was a double negative.
Choice C is correct. As stated in the passage, the bubbler vents any pressure buildup within the system while
keeping the system closed. The bubbler is a one-way valve that allows gas to effuse from the system, but does
11.2
not let gas infuse from the environment. The oil in the bubbler is intended to interact only with the gas, so no
,y.
unreacted organic vapor should dissolve into the oil. Choice A is a valid possibility in the reaction (a true
statement), but it is not relevant to the goals of the experiment. Answer choices like choice A are difficult to
was eliminate sometimes. The oil in the bubbler is not serving as an oil bath, so choice B is eliminated. The bubbler
red). keeps the system closed by preventing infusion of gaseous compounds from the outside. The best answer is choice
:tual C. Liquids cannot flow into the oil in the bubbler, so choice D is eliminated.
re in
low Choice D is correct. An increase in the mass percent of carbon is defined as an increase in the amount of carbon
per gram of the compound, so statement I is valid.
q The amount of water formed depends on the number of hydrogens in the compound, which depends on the mass
percent of hydrogen. As the mass percent of carbon within a hydrocarbon increases, the mass percent of
hydrogen in the hydrocarbon decreases. This reduces the amount of water formed from one gram of compound, so
r the it is not true that the mass of water formed increases upon oxidation. The decrease in mass percent of hydrogen
)wer reduces the mass of hydrogen formed per gram of compound. This means that neither statements II nor III is
n the associated with an increasing mass percent of carbon within a hydrocarbon. Choice D is the best answer.
rbon
en to
nt of
Choice D is correct. The four salts listed as choices are all present in the same mass quantity in solution (4"/o of
their respective solution.) All of the solutions have 96o/o water solvent, so the salt with the greatest number of
The moles has the highest molarity. Given that all of the salts have an equal mass, the greatest number of moles
g the belongs to the salt with the lowest molecular weight. Sodium (Na) is lighter than potassium (K), and chlorine
rting (Cl) is lighter than bromine (Br), so NaCl is the lightest salt of the choices. Pick D, and feel fresh.
s the
: trap Choice B is correct. The trick here lies in the wording: "...how much water must be added?" This question
ation requires that you use the dilution equation, Mi.,itiulVi.,itial = MfinalVfinat, where M is molarity and V is volume.
0.15 Mx 300 mL = 0.0075 Mx V6nu1 .'. Vfinal =

0.15M x 300mL 15 3ooml - 15 J-x 4 x 3ooml
rf the 0.0075 M 0.75
:tants = 15 x 4 x 100mL = 6000 mL = 6.0 L
) may
This value is V;inn1, not the answer to the question (volume of water added)! To finish with 6.0 liters of
ck D.
solution from an original volume of 0.3 liters, 5.7 liters must be added. Choice B is the correct answer.
ass to
is the
Choice C is correct. As far as chloride ion concentration is concerned, it doesn't matter whether you add pure
water or NaOH(aq) to the HCI(aq) solution, because Cl- is just a spectator ion in the acid-base reaction. Neither
NaOH(aq) nor pure water increases the moles of chloride anion in the solution. Solve the question by using the
iulfur dilution equation, MiîtiulVi.ritial = MfinalVfinal, where M is molarity and V is volume:
This
hat is 0.25M x 50mL
0.25M x 50mL = Mfinal x75mL.'. Mfittul = - 50 x 0.25M = Z x 0.25M = 0.167M
ries a 75mL 75 3
ted as
The final molarity is 0.1,67 M, which makes choice C,0.77M, the best answer.
ftions - rpvright O by The Berkeley Review@ DD Section I Detailed Explanations

37. Choice A is correct. Pure water is passed through the volumetric pipette to flush any residue out of the &c
volumetric pipette. Not all of the contents of the pipette may come free because of the adhesion of water to the el
glass, so rinsing ensures that the residual solution in the pipette is forced from the pipette into the new sa
solution. The rinsing is not quantitative, so it does not measure a volume. This eliminates choice B. No lXhr
temperature is mentioned, so the water used to rinse the pipette is not responsible for heating or cooling ilm
anything. This eliminates choices C and D. The best answer is choice A. kil
dtr
38. Choice A is correct. A ten-fold dilution is defined as a dilution that results in a final concentration of a solution
that is ten percent of its original concentration. For this to occur, the final volume of the solution must be ten q
times the initial volume. The final volume is the sum of the initial volume and the added volume, so t u6
following math can be applied: lc0!!

q{
Vfinal = Vititiul + Vadded and Vfinal = 10Vini1in1, so 10Vitli1iul = Vinitial + Vadded
gVi.,itial = Vadded, so 1 part solution is mixed with 9 parts solvent. g
Ten parts solvent mixed with one part solution yields a final volume that is eleven times larger; thus, the fi MJ
concentration would be one-eleventh, which is less than ten percent. This eliminates choice B. Choice C is
iI
reverse of a ten-fold dilution. Choice C is a dilution to ninety percent of the original concentration. Choice D
the same as choice B. Pick choice A to feel that jovial tingle of correctness.
mm
39. Choice C is correct. The addition of water to an aqueous salt solution increases the mass of the solvent wit
,d
changing the moles of solute, so the molality decreases (given that the denominator increases.) This ma (n
choice A valid. Addition of water to an aqueous salt solution increases the volume of the solution wi
changing the moles of solute, so the molarity decreases (given that the denominator increases.) This ma
m
choice B valid. The salt solution is denser than the pure water, so the addition of water (a less dense soluti
m
@0[
to the salt solution decreases the density of the solution, making choice C invalid. Addition of water to onfu
aqueous salt solution increases the mass of the solvent without changing the mass of solute, so the mass
mm
of solvent increases. This makes choice D valid. The correct answer is choice C.
frM'
,upr
40. Choice A is correct. The greatest dilution results from the greatest relative addition of solvent. The grea
mmq!
dilution involves the greatest ratio of solvent added to initial solution present, and it does not depend on
total volume of the initial or final solution. The ratio of solvent added to the initial volume of solution
frc
choice A is 100 : 25, which reduces to 4 : 1. The ratio of solvent added to the initial volume of solution in cho
B is 200 : 60, which reduces to 10 : 3. The ratio of solvent added to the initial volume of solution in choice C is
: 1"5, which reduces to 10 : 3. The ratio of solvent added to the initial volume of solution in choice D is 150 :
which reduces to 3 : 1. The greatest ratio of solvent added to initial volume of solution is found in choice A,
best answer.
4't. Choice A is correct. if the density of the solution is less than the density of water, then the addition of w
to the solution may actually increase the density of the solution. The molarity and the molality of the solu
always decrease as solvent is added, because the denominator in both molarity and molality increase w
the numerator remains the same. As solvent is added to the solution, the mass percent of solute in solu
decreases, because the mass of solute in solution remains constant while the mass of solution is increasing.
the density does not always decrease upon the addition of water to an aqueous solution; thus, the best answer
choice A. ln rare cases where the aqueous solution has a density of less than 1.00, the density increases
water is added.
42. Choice A is correct. Calculating the molarity and the molality of the solution involves the moles of salt in
numerator. The numerator is the same in both the molarity and molality, so the difference between the
values depends solely on the denominator. The mass of water is 0.100 kg, while the volume of solution
greater than 0.100 liters. This means that the denominator in the molarity calculation is greater than
denominator in the molality calculation. The larger the denominator, the smaller the value. This means
the molality is greater than the molarity, which eliminates choices B and D. The density of pure water is 1
grams per mL. The density of the aqueous salt solution is the mass (L01 grams due to salt and water) divided
the volume. The volume of the solution is less than 101 mL, so the density of the solution is greater than 1
(given that the numerator is 101 and the denominator is less than 101). The density of the solution is g
than the density of water, so the best answer is choice A.
Copyright @ by The Berkeley Review@ 56 Section I Detaited Explanat

t of the Choice C is correct. Because the density of the solvent is less than 1.0 grams per mL, the volume in liters
rr to the exceeds the mass in kilograms for the solvent. When comparing molality and mblarity, both values have the
he new same numerator' You are looking for the value with the smaller denominator. The mass of solvent is less than
B. No the volume of solution, so molality is greater than molarity. This eliminates choices B and D. The density is
cooling the mass of the solution divided by the volume of the solution. The density values are less than 1, but are not
known specifically. In addition, there is no information about the mixing process. The density cannot be
determined without information about the density of the components. The beifanswer is choice C.
;olution
t be ten Choice A is correct. All of the solutions are made up of one solute and solvent, but in different ratios. The solute
, so the is denser than the solvent, so it can be concluded that the solution with the greatest density has the highest
concentration of solute. As solute concentration is reduced, the density is also reduced. Increas-ing the amount of
solute relative to solvent increases both molality and molarity. The best answer is choice A.
4f Choice B is correct. This questions requires the use of the dilution equation, Mi.,itiulVi.ritial = MfinalVfinal,
he final n'here M is the molarity and V is the volume. Plugging the given values into the equation yields:
C is the
fce D is 0.25Mx100mL=0.10Mxv6i1a1 .'.Vfi.ut-0'25Mx100mL-0!25x100mL=2.5x100ml=250mL
0.10 M 0.10
The final volume (Vmat) is 250 mL, but Vfinal is not tlne answer. The question asks for the volume of water
added' To start with 100 mL of solution and finish with 250 mL of solution, 150 mL of water must be added.
wit
;ma r14*r..
Choice C is correct. The units of molarity are moles solute per liter solution. Because both solutions have the
wl
same final volume (100 mL), the question reduces to asking how many grams of MgCl2 yield the same number of
;ma
rtoles of Cl- as 1.0 grams NaCl. There are two chlorides per magnesium chloride molecule, so only half the
olu
number of moles of MgCt2 as moles of NaCl is required. This accounts for the factor of one-half in the
er to
;alculation. The grams of NaCl must be converted into moles of NaCl, which in turn are converted into grams of
pe
\lgcl2 after accounting for the mole ratio of the two salts This calculation requires knowing the molecular mass
:or both salts. Because the magnesium chloride is heavier than sodium chloride, intuition tells us that more
*rams of the magnesium chloride are needed to form a mole quantity equal to that for the sodium chloride.
$e ilhis means that in the calculation, the molecular mass ratio term should be greater than 1, making choice C
lon he best answer. The unit factor method solution is as follows:
ution
n
l.0gramsNaCl x lmoleNaCl r lMgClz r 94'9gramsMgClz 1.0 x t x94.g qramsMec6
eCis 58.4 grams NaCl 2 NaCl l mole MgCl2 = Z 58.44 o
150 :
lhe final answer is less than 1.0 grams MgCl2.
:C A,
4fr Choice C is correct. The mole fraction of a compound in a solution is found by dividing the moles of the given
-ompound by the total moles of the solution. Choice B has a mole fraction of 0.50 for both Compound A and
Compound B, because there is one mole of each compound, and the total number of moles is two. In an equal-
rass mixfure (one gram each), the greater number of moles is present in the compound with the lower molecular
ofw
=ass. Compound A is lighter than Compound B; therefore, in equal masses of Compound A and Compound B,
soluti --:,ere are more moles of Compound A than Compound B. The
;e wh mole fraction of Compound A is therefore greater
--:nn 0.50 in choice A. This eliminates choice B. For an equal volume
soluti solution (in choice C there is one mL each),
--:e relative masses can be determined by the densities. Because Compound A is denser than
lg Compound B, equal
'b' '.'olumes of Compound A and Compound B result in the mass of Compound A being greater
nswer than the mass of
iompound B. The mass percent of Compound A is greater than 50%, as it is in answer choice A; thus, choice C
ES
:esults in an even larger mole fraction of Compound A than in the equal mass solution of choice A. The equal-
rolecules solution (choice D) has the same mole fraction as the equal-mole solution (0.50 for each). Because
::oice B and choice D are the same answer, they are both eliminated. The greatest mole fraction of Compound
rlt in
-:";s found in the equal-volume solution, choice C.
the
lution
than
)ans
Choice B is correct. According to the absorbance equation (and the data and the graph), when the concentration
:ris1 -: I solute is doubled, the absorbance of the solution containing it doubles. This occurs because twice as many
vided
han 1 =-olecules are present to absorb light. The best answer is choice B. Choices C and D should have been
:-rminated immediately, because the absorbance increases as the concentration of solute increases. Choice A is
s grea
'*-:minated, because the absorbance does not increase as the square of an increase in molarity.
::sit O by The Berkeley Review@ 5t Section I Detailed Explanations

49. Choice D is correct. At low concentrations, the relationship between concentration and absorbance is linear, as (
predicted from the absorbance equation. At higher concentrations, deviation begins to occur, until the
absorbance reaches a maximum. There is no reaction occurring, so choice B can be eliminated. No solute would e
dissolve into the solvent if the two repelled one another, so choice C can also be eliminated. Choice A mav ,tut
sound tempting, if you are blindly choosing an amount on the basis of words you recall from biochemistry. The fld
saturation of the solvation catalyst sounds like a good answer (especially considering that Michaelis-Menten
kinetics shows a similar graph when saturation of some sort occurs). The problem here is that "saturation oi c
solvation catalyst" means nothing, as there is no solvation catalyst. Also, catalysts affect the rate (not the r@m
concentration) of reactants, products, solutes, or other components of a solution. Choice A should be elimjnated" tu
Once water (the solvent) has interacted with as much solute as it can, no more solute can dissolve into solution tu
The molarity reaches a maximum, so the absorbance reaches a maximum. The graph would be a line that WM
ends at the saturated concentration. The best answer is choice D. ffi
50. Choice C is correct. The addition of 50 mL of water to 10 mL of solution results in a dilution to one-sixth of 0
original concentration value. The absorbance of light should also be reduced by a factor of one-sixth. One-six M
of 0.518 is a value less than 0.100, so the only possible answer choice is choice C. ro@
t@q
51. Choice A is correct. Dividing the equation Absorbance = s[C]l by e and I isolates the value of solu dh
concentration (tC]). The result is that choice A is the best answer. This question may have seemed too simple t {@[ls
you. On occasion, there are some simple questions about the MCAT, so don't try to find tricks that aren't there. tul
dM
52. Choice C is correct. From the data in Table 1, we know that the absorbance of a solution with a concentration dtu
0.20M is 0.188, while the absorbance of a solution with a concentration of 0.30 M is 0.278. If the absorbance ,d&m
the unknown solution is 0.242, then the molarity of the solution must lie between 0.20 M and 0.30 M. ffi@
average of 0.20 M and 0.30 M is 0.25 M, and the average of 0.188 and 0.278 is 0.233, so the absorbance for a 0
M solution should be roughly 0.233. Because 0.242 is slightly greater than 0.233, an absorbance value of 0.242 OL
associated with a concentration value that is slightly greater than 0.250 M. The best answer is choice C. rOfftll[
,W
53. Choice D is correct. Isolating the value for e in the absorbance equation yields absorbance divided ll0)illl[lm
(concentration.pathlength). Absorbance is unitless, while concentration is in molarity, and pathlength is ,n0
some fraction of meters (like centimeters). The units of e therefore must involve inverse molarity times ffim
centimeters. The best answer is choice D.
54. Choice C is correct. As solute concentration (molarity) increases, the absorbance increases. This ma
statement I valid. At this point, the answer choices narrow to either choice A or choice C. If you are strap
for time, just look at statement III. Beer's law applies at all wavelengths (I*u* is chosen because it is
greatest value, and thus is the easiest wavelength at which to obtain an accurate measure of absorb
Because statement III is valid, choice C is the best answer. The absorbance depends on both the m
absorbtivity constant and solute concentration, so if Compound X has a lower constant than Compound Y,
the solution with Compound X must be more concentrated than the solution with Compound Y, in order to ha
an equal absorbance. This makes statement II invalid. The best answer is choice C.
55. Choice D is correct. The spectrophotometer measures the absorbance of light, so the wavelength set
corresponds to an absorbed color, not a complementary color. This eliminates choices A and C, both of w
refer to the reflected (or complementary) color. To obtain the most accurate value, the spectrophotometer is
at the wavelength corresponding to maximum absorbance. This makes choice D the best answer. Choice B
coincidentally correct in some cases, where the absorbance band is symmetric. This does not make choice
better answer than choice D, but it does raise an important point: Remember that the test writers reward r
for choosing the best answer, not just a correct answer.
55. Choice B is correct. The question states that the absorbance varies with cuvette length. From the passage.
know that absorbance varies with the concentration of solute in the solution. It makes sense that
absorbance depends on the molar absorbtivity constant (e), so the Beer's law relationship of Abs. = e.[C].1 car
deduced. Dividing both sides of ihe equation by [Compound].I yields choice B. From the term ''
absorbtivity," it can be inferred that absorbance is in the numerator and molarity in the denominator, r.r-1
makes choice B the only possible answer. Units may not always be the best route to the correct answer.
Copl'right O by The Berkeley Review@ 58 Section I Detailed Explanat

Choice A is correct. This question requires converting absorbance to concentration. -{ 0.10 \1 soluion oi
the Compound M has an absorb-an ce of 0.362, so if the absorbance is 0.400, the molarity is greater than 0.10 \1. This
ruld eliminates choice D. Compound e with an absorbance of 0.250 is less that 0.10 M (where the absorbance is
:na)' ).299), so choice B is eliminated. Compound T with an absorbance of 0.500 is less that 0.10 M (r.t'here the
The absorbance is 0.511), meaning choice C is eliminated, leaving choice A as the best answer.
nter,
,n oi Choice D is correct. From the data in Table 1, we see that Compound T has the greatest absorbance of the three
i the :ompounds, so choices A and B are eliminated. The absorbance values for Compound M at a concentration equal
ated :r that of the other compounds are closer to the values of Compound Q than Compound T. That means that the
.tion :etter graph is choice D. This is a question where it easy to make a mistake by choosing answer choice C
t jus: ,., rthoul examining the other choices more closely. A brief survey of former students
showed that roughly one-
::ird of you will make a careless mistake on this question and choose C.
Choice B is correct. Compound M has an absorbance of 0.217 at56L nm when the concentration is 0.06 M.
--:erefore, when the concentration is reduced to 0.05 M (a value that is aboutt7"h less), the absorbance should
,= :educed to a value that is five-sixths of 0.277, which is roughly 0.181. Statement I is valid. A solution of
- -:i,pound e with an absorbance of 0.225 at 41.3 nm
must have a concentration between 0.06 M (where the
,-.-.rbur,." is 0.1g0) and 0.10 M (where the absorbance is 0.299). Because 0.225 is a little closer to 0.180 than
makes statement II valid, and
-:i. the concentration should be a little closer to 0.C6 M than 0.10 M, whichnm, 0.10 M Compound T has an
: -:(es choice B the only possible choice. Statement III is invalid, because at 697
::.-,:bance of 0.511. fhi, -uun, that at the same wavelength, with a molarity of 0.1'1 M, the absorbance is
]lon ! , : *: 0.56+. Given that the wavelength is not 697 nm (the wavelength where maximum absorbance is
-Lfc :.=:r-ed), the absorbance is actually lJss. This makes statement IIi invalid, agreeing with the selection of
I - ,:e B. pick B to gain the prestige, i onor, and pride that goes with knowing you got another question right'
- .t ^;
- - :,-ce C is correct. Compound T has an absorbance of 0.511 when it has a concentration of 0'10 M. An absorbance
just less than 0.05 M (half of 0'10
-rl is just less than half of the 0.511 value, so the concentration mustof be
Compound T that is just less than
he question is then, "Which solution results in a concentration
led :l.l: The starting solutions are all 0.10 M Compound T; so to achieve a solution that is just under 0'05 M, the
:*- . -:.: of water adied should be just a tiny amount greater than the amount of Compound T solution.
:h i= This is
"- : r-.'l tvith choice C. The absorbance for each choice is listed below:
/ ts (0.511) ,1 / z (0.511) > 0.25; therefore, choice A has too high

Choice A, 70 an absorbance'
Choice Bt 20 / so (0.511) =1/z(0.511) > 0.25; therefore, choice B has too high an absorbance.
Choice ct 79 / gs (0.511) .1 / z(0.511) t.19 / zs (0.511) may equal 0.25; therefore, choice C is good.
Jhoice D, 10 / tg (0.511) ,7 / z (0.511) > 0.25; therefore, choice D has too high an absorbance.
. _ *= of ,9 / gg(0.5i1) should be close enough to 0.250 to convince you to choose C.
. : :: D is correct. Although colors were not reviewed in this section, it is a topic that frequently is discussed
' : ,,:n the absorbarr.u oT Hght. One of the goals of these review passages is to expose you to this kind of
:- . .= i material. In each ,uJtion, there are sJme questions on topics that have yet to be discussed' Such is
,:,: :..re. The color observed for the solution is ihe complementary color of what is absorbed. The visible
, .'-:: . from roughly 200+ nm to 400 nm. Red light is the least energetic of vi-sible light, so red light has a
. , : , -,-,,,elength of"approximately 700 nm. Violet lignt t the most energetic of visible light, so violet light
, , - : rr:-,r' l.ivelengih of approximatety 400 nm. Compound Q absorbs tight with a wavelength of maximum
'.:rct , - : :-- :: i,.,u") of Zf g ,-rrr,. -Thi, corresponds to violei light, so the color observed for the solution is yellow
:-:-ementary color of violet). This eliminates choices A and B. Compound T absorbs light with a
- : r l--r of maximum absorbance (l-u*) of 697 nm. This corresponds to red light, so the color observed for
, -:.,.. rs green (the complimerrtary color of red). This eliminites choice C, and makes choice D thebest
r, 'r,: : should be able to answer this with the background knowledge that 400 nm is at the violet end of
L r = s;1ectrum, 700 nm is at the red end of the visible spectrum, and a working knowledge of
' : ,:.li -^rrrs. Compound M is irrelevant in solving this queition. Appearing red (reflecting red light)
LUIL
nr :-:: -een light (the complementary coior of red) *as absorbed. Green light is in the middle of the
. ::,::::.irn, so It could have a warrelength of 561 nm. There is no reason for you to know the exact l" values
, - . - -: but you must be able to deduce the best answer to this question. Absorbed light, reflected light,
i,r,,- ^ . - : r i r^r-,- col,ors, the color wheel, and the visible spectrum will all be addressed in the
next chapter'
tana ,: - Berkeley Review@ 59 Section I Detailed ExPlanations

g
c[E
62. Choice D is correct. It is not a combination reaction, because no compounds combined to form a single compou A$
so choiceA is eliminated. It is not a decomposition reaction, because no comPound broke apart to form multi mm
w
compounds, so choice B is eliminated. It is not a single-replacement reaction, because no metal compound
,dM
the barium cation (Ba2t) and the potassium cation (K

formed or consumed, so choice C is eliminated. Becairse frm
have exchanged their respective anions in this reaction, the reaction is classified as a metathesis reac fld
(known also is a double-displacement reaction). The best answer is choice D. By picking choice D, you can ffim
iatisfied knowing you picked a correct answer. Go ahead, feel good! tm
'@
the flask
53. Choice A is correct. A precipitate is a solid that forms from solution and deposits on the bottom of m
a reaction proceeds. The reaction least likely to form a precipitate is the reaction that is least likely to form
forms water liquid and carbon dioxide gas, but does not fc
solid product. In choice A, the combustion reaction
In reaction, a solid can
a solid of any kind. For this reason, choice A is the best choice. a decomposition
formed, as in the example offered in the passage. In the single-replacement and metathesis reactions, salts 0
formed as products, so precipitates are both likely and probable' &
@
64. Choice C is correct. The reaction of aqueous sodium iodide (Nal(aq)) with aqueous calcium nitr h
(Ca(NOg)z(aq)) is a double-displacement (metathesis) reaction, so the precipitate formed in the reaction m f,
be one oJ tt t*o possible product salts. Calcium is a dication (carries a +2 charge), so choice A is elimina
because the "calcium salt is not neutral when bonded to only one iodide anion. Sodium and nitrate are
t ffi
highly soluble in water, so neither sodium nor nitrate is found in the precipitates. Both choice B and choice
are therefore eliminated. The best choice is answer C. The reaction is given below: u[
2 Nal(aq) + 1 Ca(NO3)2(aq) .+ 2NaNO3(aq) + 1 CaI2(s)
(MgCO3) i
65. Choice C is correct. The reaction of aqueous hydrobromic acid (HBr) with magnesium carbonate
neutralization reaction. It is stated in the purrug" that carbonates, when neutralized, yield carbon diox
gas. The best choice is answer C. The reaction is drawn below:
2HBr(aq) + 1 MgCO3(s) + L H2CO3(aq) + 1MgBr2(s)
1H2CO3(aq) -+ 1H2O(aq) + I COzG)

2 HBr(aq) + 1MgCO3(s) -+ 1H2O(aq) + 1 CO2(g) + 1MgBr2(s)
you should recall that baking soda (sodium bicarbonate) effervesces when an acid is added. The bubbles
form are carbon dioxide guri Uydtogen gas cannot exist as H (molecular hydrogen is a diatomic gas),
magnesium bromide is an"ionic titt 1*li"tt-is definitely not a gas at room temperature), meaning that
choi
and D should be discarded immediately. To eliminate choice B, you had to recognize that magnt
carbonate is a base, and not a reducing aglnt. _Magnesium metal is rich in electrons, so it would
make a s
of HBr Mg(s) would yield H2(g) by way
reducing agent, but not magnesium .utiot (Mg2*). The addition to
oxidation-reduction reaction'
so choice A is elimi
66. Choice B is correct. Carbon dioxide gas is a common product in combustion reactions,
The example reaction for decomposiiion shows calcium carbonate (CaCO3) decomposing to form:4ttlT
reaction is possible with calcium sulfite (CaS(
an4 carbon dioxide. Choice C is thus eliminated. The same
of calcium sulfite. The passage states that
so sulfur dioxide can be formed in the decomposition reaction
neutralization of sodium bicarbonate (NaHCO3) forms carbon dioxide gas; therefore, choice D is elimi
cations are interchanged, but no
The only choice left is answer choice B, the metathesis reaction, where
r
dioxide gas is formed. If the anion begins as carbonate, it finishes as carbonate, and not carbon dioxide'
67. Choice C is correct. In the reaction, the chlorine gas is reduced to chloride anion and exchanged for the b
'The
anion, which is oxidized into bromine liquid. product is not the result of coupling (combining)
reactants, so it is not a combination reactiin. This eliminates choice A. The products are
not the result <
reaction. That eliminates choice B'
breakdown (decomposition) of a reactant, so it is not a decomposition
reaction, m
anion in the salt is exchanged, while the cation is not. This describes a single-replacement
cannot be a metathesis reaction,
choice C is valid. Because the cation remains the same, the reaction
eliminates choice D. The best answer is choice C'
Copyright @ by The Berkeley Review@ 6() Section I Detailed Ex

il
rnd,
i58. Choice A is correct. A negative value for AS results when the reaction gains order (or loses randomness). Ir, u
combination reaction, the number of molecules decreases from reactant to product, which is an increase in order.
As such, a combination reaction is likely to have a negative value for AS. This makes choice A the best answer.
dple In a decomposition reaction, the number of molecules increases from reactant to product, which is an increase in
was disorder. A decomposition reaction is likely to have a positive value for AS. This eliminates choice B.
(K*) In a single-replacement reaction, the number of molecules remains the same on each side of the reaction. Both
:tion sides of the equation have a precipitate and a solute, which leads to no conclusion about the change in order for
L feel the system. A single-replacement reaction can have either a positive or negative value for AS. Although a
single-replacement reaction may have a negative AS, choice C is not as good an answer as choice A. In a
combustion reaction, there is an increased number of molecules from reactants to products. The products are
sk as gases, so there is a large positive value for AS. This eliminates choice D.
rrn a
form
ur be
s are Choice D is correct. Ca(OH)2 yields a hydroxide anion (OH-) when added to water, which makes Ca(OH)2 an
Arrhenius base. Ca(OH)2 cannot donate a proton, so it is not an Arrhenius acid. This eliminates choice C.
Choice A is also eliminated, because it cannot be an amphoteric species, unless it can act as both an acid and a
itrate base. Calcium is a metal, so Ca(OH)2 is a metal hydroxide, not a non-metal hydroxide. Choice B is
must eliminated. The correct answer is choice D.
rated,
rboth Choice D is correct. Although COtz- is charged and thus an ion, the anion itself is held together by covalent
rice D bonds (three o-bonds and a resonating r-bond). Carbon dioxide is held together by covalent bonds between the
central carbon and the two adjoining oxygens atoms. Only CaO (III) has an ionic bond, and it is considered to be
partially ionic. Calcium carries a +2 charge, and oxygen carries a -2 charge. This makes D the correct choice.
The structures and bonds are shown below:
o
Ionicbond
ooL-t)
tJ c# 02-
";K" -
Choice D is correct. All of the compounds contain only one calcium per molecule, so the smallest mass percent of
calcium is found in the compound with the greatest molecular mass. The mass percent is found by dividing the
mass of calcium by the mass of the compound. The molecular mass for CaO is 56 grams per mole; for Ca(OH)2 it
is 74 grams per mole; for CaCO3 it is 100 grams per mole; and for CaCl2 it is 111 grams per mole. The heaviest
ES compound is CaCl2 (choice D), meaning choice D has the greatest denominator and therefore the smallest mass
s), percent of calcium. This makes choice D the best answer.
rices
1es1 Choice A is correct. To calculate the percent yield, the actual yield (in moles) is divided by the theoretical
vield (in moles). The actual yield in moles is 5 9/100 g.moles-r, while the theoretical yield in moles is 10 g/74
ry of B.moles-l. The percent yield is found as follows:
6o
una
no
percentyield =*ffl91 x 100% =
fr|fr- x1N./, =
#, x 100% =
ffi x 100% = 37"h
,4 g-,"I"t
that
The percent yield is 37"/o, which makes choice A the correct answer.
)ca
Choice D is correct. The mass percent of calcium in calcium oxide is the mass of calcium (40 grams per mole)
divided by the mass of calcium oxide (56 grams per mole) and multiplied by 100%. 40 / 56 x I00"/" is greater than
50%, which eliminates choices A and B, and is greater than 66.7"/o, which eliminates choice C. Only choice D
is greater than66.7"h, so choice D must be the correct answer.
I) of
[t of 408
:B. Rangemethod:
-56g603 x 100% > 40 x 100% =Z x 700% = 66.7%
trrw 4!3 xl= 5 x 0.143 = 0.775

Calculationmethod: =5 =5 = 77.5oh
ffig77
I n:-'right @ by The Berkeley Review@ 6l Section I Detailed Explanations
74. Choice A is correct. Because matter can be neither created nor destroyed, the total mass of reactants must equal
the total mass of the products. There are 38.0 grams of reactants, so choice D is eliminated for having more
than 38.0 grams of products. The question from here becomes a limiting reagent problem. We must decide
whether there is leftover water (is CaO the limiting reagent?), leftover calcium oxide (is water the limiting
reagent?), or an exact mixture (there is no leftover and thus no limiting reagent.) The moles of CaO equal2S/56
(which is one-half) and the moles of H2O equal 10/18 (which is greater than one-half.) Because the calcium
oxide reacts with the water in a one-to-one ratio, there is leftover water. This means CaO is the limiti
reagent in the reaction, so the reaction does result in leftover H2O. The only choice with leftover water is A.
75. Choice D is correct. The N in the answer choices stands for normslitq, which is the molarity of the proto
that can be generated by the acid. Normality is the molarity of an acid times the equivalents of hydroni
per molecule. CaCO3(aq) reacts according to the equations shown below. A 2 : 1- ratio is needed to reach
neutralization.
CaCO3(aq) + 2 H+(aq) ------> H2CO3(aq) + Ca2+1aq; H2CO3(aq) -* H2O(1) + CO2(g)
5 mL x 0.2 moles/liter = 1 mmole CaCO3, so 2 mmoles of a strong acid (which yield H+) are needed to
equivalence. Choice A is a strong base, so eliminate it. Choice B yields only 1 mmole of H+, and choice C yie
3 mmole of FI+, so eliminate both choices B and C. Choice D yields the 2 mmole of H+ that are needed. The
answer is choice D. For a monoprotic acid, normality and molarity are the same. However, for a diprotic
the normality is double the molariiy; and for a triprotic acid, the normality is triple the molarity.
76. Choice C is correct. This is a case where Equation 1.2 in the text, Mi'riliulVinitial = MfinalVfinal, rrust be used.
0.500Mx5.0mL=Mfinatx55.0mL.'.Mfir.,ut=5/55x0.50.'.Mii'ul=1/ttx0.50<t/tO*0.50=0.050
The final molarity is therefore less than 0.05 M. Without pounding numbers, you should see that choice C
the best choice (the choice just less than 0.050 M). Choice D is too far below 0.050 M to be reasonable. Do
(
solve math questions exactly, but find a range into which only one answer choice fits. In this case, the range m
from just less than 0.050 (maybe 0.040 or so) to 0.050. OnIy choice C fits into that range. ffi
M
77. Choice C is correct. The final concentration can be determined by taking a weighted average of
concentrations for the two initial solutions before they are mixed. A quick observation you should apply to
m
question is that if the mixture were a fifty-fifty mixture by volume (the mixture of equal volume soluti
fr
then the final concentration would lie exactly between (be the mean value of) the two values. In
,h
,ilr
particular question, the mean value would be 0.250 M. Because there is an excess of the higher-concentra
ffiM
solution (30 mL at 0.30 M, with only 20 mL at 0.20 M), the answer should be closer to 0.30 M than 0.20 M (
it greater than 0.250 M). This eliminates choices A and B. The exact value can be solved for as follows: ffi
WA
Total moles = (20 mL x 0.20 M) + (30 mL x 0.30 M)
= 4+9 - 13 = 0.26, choice C.
Total volume 50mL 50 50
78. Choice C is correct. 50 grams CaCO3(s) is equal to 0.50 moles CaCO3(s), because the molecular mass of C
is 100 grams per mole. Because there is only one carbon in CaCO3(s), 0.50 moles CaCO3(s) yield 0.50 moles
CO2. 0.50 moles of CO2 at STP occupies a volume of: 0.50 moles x 22.4liters/mol" =1 / 2x22.4 = 11,.2L. Pick C. utu
(lm
ilrildl
lWftl
79- Choice A is correct. The greatest amount of potassium per gram of compound is found in the compound with
ffi
greatest mass percent of potassium. The greatest mass percent of potassium is found in K2O, as was menti
the passage. This means that the best choice is answer A. The mass percents for the four salts are as follows: tu
M
K2(): 2x39.7
=78.2 _39.7
(2x39.1) + 76 94.2 47.7
K2SOa: 2x39.'l
(2x39.1) +32+$x16)
78.2
174.2
=39.1
87.1
W
nfu
1ftu
661. 39.1 =39.L KNO3: 39'I - 39.7
39.1 + 35.5 74.6 39.7 + 74 + (3 x 16) 101.1 m&m'u
rfu
The relative mass percents when comparing the four values are' 39.1 > 39.1 > 39.1 > 39.L ildAilii
The greatest mass percent of the choices is found with K2o (choice A).
47 '1' 74'6 97 '1 101'1 t@@
sMs
4Wm-
Copyright @ by The Berkeley Review@ 62 Section I Detailed Explana
Choice D is correct. The compounds in choices A, B, and C all have two nitrogen atoms per compound, while the
)re compound in choice D has only one nitrogen atom in the compound. The lowest *u5 p"r""niof nitrogen is in
l-
choice D, because the four compounds are roughly comparableln molecular mass, but they have differeri-urr",
ni-
of nitrogen. The mass percents for the four choices are shown below:
A. H2NCoNH2 + 28gN * 2a - -7 < L

609 H2NCONH2 60 15 2
28gN _?a _ 7_ 35%
B. NHaNO3
1E
= B0g NHaNO3 80 20
C. (NHa)zSo+
28gN _28_ 7_
= 132g (NHa)2SOa 732 JJ
21*"/"
14g N 14 <
D. NH4HzPOa .+ - 14"/.
1159 NHaH2PO4 115
.L
iL.
i- 28- 28 >29 > 28 (= 14)
60 80 132 230 1ls
Choice C is correct. The mass percent of nitrogen in urea is just less than 50%:
28gN 8_7 -1
Mass percent urea =
609 H2NCONH2 60152
lhe only answer choice that is just less than 50% is choice C.
Choice A is correct. According to the passage, the phosphorus content of the compound is critical, so no
:nosphorus should be wasted in unreacted reactant. This can be prevented by adding the reactants in a ratio
::-at avoids the presence of any leftover phosphorus-containing reactant. The goal is to conserve the
:iosphorus-containing compound, which makes choice A the best answer.
Choice B is correct. The percent yield for a reaction is defined as the actual quantity of product isolated from
-:-e reaction mixture, divided by the
theoretical quantity of product that should form, as determined from the
-:miting reagent of the reaction. According to the balanced equation, for every one mole of (NHa)2CO3 that
:eacts, one mole of (NHa)2SO4 forms. This means that 10 grams of (NHa)2CO3 (which is 1,0/96 moles
\Ha)2CO3) should produce 1,0 /96 moles of (NHa)2SO4, which is (10 /96 x 732) grams (NHa)2SOa. Dividing
::-e mass of (NHa)2SO4 obtained (10 grams) by the theoretical mass of (NHa)2SOa that should have formed
-3 75 grams) determines the percent yield. The calculation of the yield is shown below:
Theoretical*urr, 10 x13Z=1320 = 330 - 110 > 104 +6 = 133 =13.75

9696248884
Rangeforthepercentyield:50%<5 =10 <10'00 <3 = \0 =75"/o
7 74 73.75 4 73.33
-:.e value for the percent yield lies somewhere between 50% and 75"/", which makes choice B the best answer.
Choice C is correct. All of the choices have the same volume (100 mL) and the same mass of salt, so the greatest
::larity of potassium is present in the solution with the greatest number of moles of potassium in solution.
i -ence, the greatest molarity results from using the compound with the greatest *uss pet""nt of potassium,
;:jch corresponds to the salt with the lowest molecular mass. Choice D iJ ehminated, because NOj is heavier
:-;n Cl, so KCI has a lower molecular mass than KNO3, and thus a greater mass percent of potassium than in
:'.\O3. Choice B is eliminated, because SO4 is heavier than CO3, so K2CO3 has i lower molecular mass than
r '-SO4, and thus a greater mass percent of potassium than K2SOa. The question boils down to determining
the
:=-afive mass percents of potassium in KCI and K2CO3. The molecular mass of KCI is74.5 grams per mole, and
*-: molecular mass of K2CO3 is 138.2 grams per mole. Potassium carbonate (K2CO3) yields two pbtassium ions
:'.: molecule, so to have the same mass percent of potassium as KCl, its molecular mass would have to be double
:*'a: of KCI (which equals 149 grams per mole.) Because K2CO3 is less than twice as massive as KCl, the
:=-alive denominator is smaller when calculating the mass percent of K2CO3 than when calculating the mass
:':,:cent of KCl. The greatest mass percent of potassium, and thus the most grams of potassium in a 10.0-gram
;r-l sample, is found in K2CO3. This means that the highest concentration of potissium is present in the
:. -ieous K2CO3 solution, so choose answer choice C for best results.
,,: :-::.t O by The Berkeley Review@ 63 Section I Detaited Dxplanations
85. Choice A is correct. It is easiest to isolate a solid (precipitate) from solution, because the solid can be filtered
from solution rather easily. Equally, a liquid and gas can flow, while a solid cannot, so removing liquid and gas
to leave solid behind is easy. This is the crux of many lab techniques. A liquid must be distilled away from
solution, a solute must be either distilled, extracted, or removed by chromatography, and a gas must be
collected in a gas-trap free of air. The best answer is thus choice A. )
86. Choice A is correct. This is another case where the question focuses on a topic we have yet to discuss. There are I
a few things you should recall. First, the lower the pKu value is, the stronger the acid is. Second, when the pH
of the solution exceeds the pKu of an acid, that site exists predominantly in the deprotonated state; Statement
III can immediately be eliminated, because the first proton of sulfuric acid is strong, meaning it has a very low
(negative) pKu value associated with it. From the products of the last equation in the passage, it can be seen
that H2POa-,5C.42-, and HF all simultaneously exist in solution. Sulfuric acid has lost both of its protons,
phosphoric acid has lost its first proton, and hydrofluoric acid has yet to lose a proton. The first proton of
phosphoric acid is lost more readily than the proton of HF, which means that pKnl of H3PO4 is lower than
the pKu value of HF. Statement I is thus true. Because the second proton of sulfuric acid has been lost, while
the second proton of phosphoric acid has not been lost, the second proton of sulfuric acid is more acidic than the
second proton of phosphoric acid. The result numerically is that pKu2 of H2SOa is less than pKn2 of H3PO4.
Statement II is thus false. Only statement I is true, so the best answer is choice A.
87. Choice C is correct. This is a limiting reagent question. The balanced equation for the reaction is as follows:
1C3H3(g) +5 O2(g) + 3CO2(g) +4H2O(g)
There are 25/32 moles O2(g) and 20/44 moles CSHS(g) as reactants. According to the mole ratio from
balanced equation, the moles of O2(g) must be five times that of CSHA(g). The moles of O2(g) needed to re
with 20 / 44 moles of C3Hg(g) is 1,00 / 44. The value of 25 / 32 is less than 1, so there is less than one mole of 02
present. The value of 700 / 44 is greater than 2, so more than two moles of O2(g) are needed. This means
oxygen (OZ(S)) is depleted before CSHS(g), making O2(g) the limiting reagent and choice C the best answer.
88. Choice B is correct. If you know this answer from your biology classes, trust your knowledge and don't w
time doing the calculation. You should know that hemoglobin contains four iron atoms. That is the point
this question. The math is time-consuming, so save time wherever you can. If you didn't know that fact
hemoglobin, then doing the math was necessary. The mass of iron in hemoglobin is the mass percent of i
times the totalmass of hemoglobin. 0.33% x 68,000 =.0033x68,000 = 3.3x 68=204+20.4=224.4 gramsFe.
number of irons is therefore 224.4/55.8, which makes 4 (choice B) the best answer choice.
89. Choice D is correct. The first method which probably comes to your mind is the method learned from
chemistry classes. In this method, the 9 grams of carbohydrate are converted to 0.050 moles of carbohydrate
dividing by the molecular mass of 180. The 6.72Liters of carbon dioxide at STP are then divided by 22.41i
per mole to yield 0.30 moles CO2. The ratio of CO2 to 02 in the combustion of a monosaccharide is 1 :
Therefore, 0.30 moles of oxygen reacted as well, and thus the mole ratio of carbohydrate to 02 to CO2 is
0.30 : 0.30, which equals L :6: 6. This is a long-winded, but valid, solution. A shorter method is as follows:
In the combustion of a monosaccharide, the mole ratio of oxygen reactant to carbon dioxide to water is always
1 : L. A monosaccharide has the molecular formula C1H21O., so it has a molecular mass of 30n (12n + 2n + 1
grams per mole. For a molecular mass of L80 grams per mole, the value of n is 6, so the formula for
monosaccharide is C6H12O6. The mole ratio of O2to CO2 is therefore 6 : 6. Pick D and feel relaxed.
90. Choice B is correct. Choices A and C are eliminated, because they cannot be a molecular formula.
compound with just carbon, oxygen, and hydrogen, the number of hydrogens must be an even number. With
odd number of hydrogens, the bonding does not work out. To decide between choices B and D, you must
the molecular mass of the compound, by dividing the mass by the volume and then multiplying this value
the molar volume:
1 gram * 22.4 literc _ 22.4 grams
- 22.4 grams
x g9.6grams
mole=
= 4 22.4{ams
0.26 liters L mole 0.26 moles 0.25 moles mole
Only CaH6O2 has a molecular mass just under 90 g/rnole, so choice B is the best answer.
Copyright @ by The Berkeley Review@ 64 Section I Detailed

Choice A is correct. This is a question testing your knowledge of the irnit factor method. Barium oxide (BaO)
can form barium metal and oxygen gas (O2) upon decomposition. These are the only two products possible from
the decomposition of barium oxide. Hence, for every two moles of BaO, one mole of 02 forms. To solve this
problem, the 1.0 grams of BaO must be converted to moles, and the moles of BaO in the 1.O-gram sample must be
multiplied by one-half. This gives the moles of 02 formed. Multiplying the moles of O2by 2Z.4literc per mole
(the volume for one mole of gas at standard temperature and pressure), gives liters of oxygen gas produced by
decomposition:
1.0 grams BaO x 1 mole BaO ,. 1*ll"=O2, * 22.4Iiters - 22.4 = 22.4 < 1
153 grams BaO 2 moles BaO 1 mole 153 x 2 306 10
Only choice A is less than 0.1 liters, so pick choice A and make yourself one point wiser.
Choice B is correct. To determine the grams of product, the conversion must go through moles. This question is a
standard grams reactant-to-moles reactant-to-moles product-to-grams product conversion.
2.0 grams MgNHaPOa TM9ZPZOZ
, ,222.6.eYgzl_zo_-r = ?-: ?rr9 = HsMszpze
13Zs8ran.sl 2 MgNHaPOa l mole Mg2P2O7 737.3 x 2 1.37.3 -
/mole
22 222.6 s1
137.3
The mass of Mg2P2O7(s) is greater than 1, but less than 2. The only answer that falls between 1 and 2 is answer
,hoice B.
Choice D is correct. We know nothing of the molecular mass, so any formula we determine is the empirical
:ormula (simplest formula). This eliminates choice A. Because the elemental mass of. Z is twice the elemental
:rass of X, a compound with equal mass quantities of X and Z contains twice as many moles of X as moles of Z.
llre mole ratio of X to Z is therefore 2 : 1; thus, the empirical formula is either X2Z1 or 21X2. Pick choice D to
:eei correct.
Choice C is correct. The math here is beyond the MCAT level, but the point of such a question is to encourage
.'iru to use intuition and simplify the question. You can always eliminate some of the answer choices, and at
-east narrow your guess from random choice to a fifty-fifty chance of success. This question is simplified by
,.rowing the possible oxidation states of iron. From your experience with hemoglobin, you know that iron has a
:ridation state of either +2 or +3, and that oxygen has an oxidation state of -2 when it is coupled with a metal.
' oxygen has an oxidation state of -2, then iron cannot have an oxidation state of +2 or +3 in either Fe3O2 or
-eO3. Choices A and D are eliminated based on outside knowledge. This problem can now be solved using your
:rathematical intuition. In the iron oxide sample, there are 11.89 grams of iron and 5.10 grams of oxygen (found
iul :-,'subtracting 11.89 from 16.99). The molecular weight of iron (Fe) is 55.85 grams per mole, and the molecular
16' ,';eight of oxygen (O) is 16.0 grams per mole. An empirical formula is based on mole ratios, so the elemental
si ::.asses must be converted into mole quantities. 5.1 over 16 is just less than one-third, so there are roughly 0.30
;." :,.rles of oxygen in the iron oxide. 11.89 over 55.85 is just over one-fifth, so there is roughly 0.20 moles of iron in
::.e iron oxide. There are more moles of oxygen than iron, which eliminates choice B (FeO has equal moles of
,:rn and oxygen) and leaves choice C as the correct answer by default. Minimize doing math by using your
::ckground knowledge and logic.
05.10 - Fer*O1
Fe11.se - Fe0.2* OO.SS- = Fe2O3
55.85 16.0 5 3
tliir Choice D is correct. It is not possible to have 26 hydrogens and only 4 carbons in a stable compound. You may
in hydrocarbon or carbohydrate is 2n +
=tall from organic chemistry that the maximum number of hydrogens a
I -,r-here n is the number of carbons in the compound. This eliminates choice C. Perhaps it is easiest to solve
-:r: question by first determining the number of carbons in the molecule. The mass percent of carbon in the
:-"riecule is 53.4"/o. When this percentage is multiplied by 90 grams/mole, it tells us that just over half the mass
-. carbon. Carbon has a mass of 12 grams per mole, so the value must be a multiple of L2. The mass due to carbon
*. 48 grams, which is the mass of four carbon atoms. The molecular formula therefore contains four carbons,
:-:ninating choices A and B. The only choice left is answer D, which does in fact have roughly 11% hydrogen.
a-ran, the goal in preparing for your exam is to be able to solve these questions quickly and using as much
::-ution as possible. You are not rewarded only for being thorough; you are also rewarded for being fast. Take
-: dcal short cuts whenever they present themselves. Do not blindly repeat the calculation techniques you
-:::ned in your general chemistry courses.
,, r: ,::it @ by The Berkeley Review@ 65 Section I Detailed Explanations
96. Choice A is correct. Because this is a reduction reaction, the oxidation state must decrease, which elimina
choices C and D. By assuming oxygen has a -2 oxidation state, it is possible to reduce this problem to sim
algebra. In the teactant, the sum of the oxidation states for the four oxygen atoms is -8. hr order for the ove
charge on CrO42-(aq) to be -2, the chromium must have an oxidation staie of +6. The sum of +6 and -8 is the i
charge of -2. In the product Cr2O3(s), each chromium must be +3 to cancel out the three oxygen atoms (at
each) to make the overall molecule neutral. For this reason, choice A is the best answer.
97. Choice D is correct. The metal combines in a 2 :3 ratio with oxygen to form an oxide that is 53% metal by
Assuming a 100-gram sample implies that there are 53 grams of metal and 47 grams of oxygen in the 100-gr
sample of the metal oxide. This means that the ratio of (53 divided by the molecular mass of the
metal) to (47 divided by the molecular mass of oxygen/ which is 16) is equal to 2 : 3. This can be solved
hand or by intuition. Rather than solve the math exactly, it is a good idea to plug the values for all
answer choices into the setup, and get a rough estimate:
53 g metal go -2:i +Given that4zis roughly 3, 53 g metal mustbe about2
. 47
MW"r"."l *81 ,
/mole
76 MWmqhl
The molecular masses of the four answer choices are 40.0, 55.9,52.0, and 273 respectively. 47 dividedby 16
slightly less than 3, so 53 divided by the molecular mass of the metal must be slightly less than 2.
eliminates the first three choices (40.0, 55.9, and 52.0), leavin g 27 .0 (aluminum) as the best answer. The
answer is choice D. You could also have eliminated choice A from knowing that calcium cannot achieve a
oxidation state (or charge), so calcium cannot combine with oxygen ina2:3 ratio.
98. Choice B is correct. The mass percent of carbon is the mass of carbon in each compound, divided by the
mass of each compound, multiplied by L00%. For each compound, the mass percent can be determined as
Acetic agicL: 24 b x 100%

x lCf,,h Ethanol: Methyl acetate: 35 x fiO% Glucose: 72 x
60 46 74 180
24-n_L 24,?3_]. %,37_7 72-90_7
6060246462747421801802
Of the choices, only choice B (ethanol) has a fraction greater than one-half. This implies that the grea
mass percent of carbon is found in ethanol. The best answer is therefore choice B.
99. Choice B is correct. The MCAT test writers can ask about the same concept in many ways. It is more im
that you walk away from this questi.on knowing the concept than it is getting the question correct. The
carbon dioxide results from the compound with the greatest mass percent of carbon, as long as there are
masses of each sample present initially. There was one gram of each compound initially, before oxidatiorL
our only concern is with the mass percent of carbon. The greatest mass percent of carbon is found in eth
the greatest amount of carbon dioxide results from the oxidation of ethanol. The best answer is choice B.
100. Choice C is correct. Because there are two Cl in the Mg(ClOa)2 molecule, the mass percent of chlorine is
mass of two Cl over the mass of Mg(ClOa)2.
Mass chlorine = ?vi55 =71=71
Masscompound 128 223.3
243+(2x35.5)+(8x16) 243 + 71, +
7L > 7L > 71 ,whereTl =L=13-3%,and fI -1-25%.Sog3.g%> 71 >ZS%
213 223.3 284 213 3 284 4 223.3
The mass percent is a little less than 33.3"/', so choices A and B are eliminated. The value is just a little
than 33.3%, because the denominator (223.3) is just a little greater than 213. The best answer is the choice
is slightly less than 33.3o/o, which is 31..8"h, choice C. Choice D can be eliminated, because it is less than
Copyright @ by The Berkeley Review@ 66 Section I Detailed Dx

Atomic Structure
a) Subatomic Particles
b) Isotopes
c) Average Atomic Mass
d) Classical E,xperiments and Machinery
i. Thomson E,xperiment
Section II ii. Mass Spectroscopy
iii. Millikan Oil Drop Experiment
iv. Rutherford Experiment
e) Heisen berg's UncertainLy Principle
Atomic Model
Atomic 0
g) Hydrogen trnergy Levels
Theory Electronic Structure

a) Electronic Theory
by Todd Bennett b) Effective Nuclear Charge
c) Electronic Spin Pairing
d) Spin Pairing and Magnetism
e) Electronic Density and Orbitals
Filter
f) Collective Orbital View o[ Energy Levels
gl Electronic_Configuration
Photographic
plate
h) Quantum Numbers
Prism
Periodic Trends
- tr3s
a) The Periodic Table
b) Ceneral Elemental Periodic Trends
i. Atomic Radius
ii. lonization Energy
iii. Electron AttiniLy
iv. trlectronegativily
c) Periodic Families (Groups)
Light Absorption and Emission

a) Excitation and Relaxation
b) Atomic Spectrum of Hydrogen
c) Electromagetic Spectrum
d) Visible Spectrum and Colors
iii. Emitted Color
iv. Reflected Color and the Color Wheel
e) Fluorescence
f) PhotoelectricE,ffect
Nuclear Chemistry
al Nuclear Particles
b) Nuclear Decay and Capture
c) Half-Life
PEBITruEY
l)n.n-v.r.E-'w'
Specidrrztng in MCAT Preparation
Atomic Stnrcture Section Goals
ov Be familiar with the location, mass, and charge of sub-atomic particles.
An atom, from the chemist's perspective, is composed of a nucleus made up of protons and neutrons,
surrounded by orbiting elections. You must know the Bohr model and the properties of each particle
with regard to its charge, mass, and effect on the atom. For instance, additiohal electrons result in
the formation of an anibn, while a decrease in electrons results in the formation of a cation.
av Be familiar with energy levels and energy transitions.

The electrons orbit in distinct, quantized levels. There is a base (lowest-energy) level, and excited
states above that to which electrons jump when energy is added to the atomil system. Energy is
absorbed when an electron is elevated from the ground state to an excited state. Ehergy, in the frirm
of a photon, is released when an electron drops"to the ground state from an excited siite.
Understand electronic configurations.

Electrons fill the orbitals according to a defined sequence, described by the Aufbau principle. The
keys facts to recall about the prindiple are that ther-e are two electrons-per orbital, and there is one
s-orbital per level, three p-orbitals per level, five d-orbitals per level, and seven f-orbitals per level.
The filling order has exceptions in the transition metals, lanthanides, and actinides. There are
exceptions that allow for half-filled shell stability, as is seen with chromium.
Understand qgantum numbers.

@? Quantum numbers are used to define the orientation and location of an electron. There are four
quantum numbers: n, Im1, and ms. You must be familiar with the quantum numbers and how to
determine them for a given electron within an atom.
Be familiar with periodic trends.

"v Knowing the periodic trends for the main-group elements is essential. The trends that you must be
familiar with ihclude ionization energy, atomic radius, electron affinity, and electronegativity (although
electronegativity of the noble gases need not be committed to memory). [t is important that you be
familiar with eath basic trend and the reason for that trend. Be able tb explain
t ahyr deviations from
standard periodic behavior.
Understand isotopes, average atomic mass, and isotopic labeling.

'3 Isotopes are atoms with the same number of protons, but a different number of neutrons in their
nuclei. For some elements, there are several isotopes. The elemental mass (average atomic mass)
found in the periodic table is a weighted average of all of the isotopes of that given element. [sotopes
are chemically equivalent, so they are hard to detect without using a mass spectrometer. lsotopes,
because of th'eir ihemical similaiity, are substituted for one another in som-e reactions to servb as
1abe1s.
Understand nuctear decav and half-life associated with first-order decay.

It is essential that you understand the breakdown and buildup of nuclei through the gain and loss
of nuclear particles. It is also important to be able to determine the concentralion oFa species by
combining'the initial concentratibn with half-life information. The half-life is the period of tim-e
required for half of a given sample to decay to some product. Most examples will involve determining
the concentration at a given time for a reaction (or process) that follows fjrst-order decay kinetics-.
General Chemistry Atomic Theory Introduction
l:rm the work of Thomson, Millikan, Rutherford, Bohr, Pauling, and others, we
::','e a modern view of the atom and its fundamental structure. The core of the
:::rL by this view is a nucleus composed of protons and neutrons held together
:', an unbelievably strong force. The details of the nucleus are not well
..- Jerstood, but using a simplistic model, the majority of the mass and all of the
: :.:live charge of the atom is found at the core. The nucleus is surrounded by
::::ling electrons that stay in distinct orbits, no two of which are exactly the
;.:,e (Hund's rule). Coulomb's law explains the mutual attraction of the orbiting
:-n::rons and the nucleus. Electron energy levels are based on Coulomb's law,
:-:'ough quantum mechanics is invoked to explain the overall behavior of the
::::ing electron. The closer an electron is on average to the nucleus, the more
:l:'.lv it is held, and the greater the energy required to remove that electron
.:::r the atom. The space in which an electron is believed to orbit is referred to
:; zn orbital Each orbital is distinct from all other orbitals, and electrons have the
:::-rn of spinning clockwise or counterclockwise as they occupy the orbital.
-l---,- two electrons may occupy each orbital at the same time, and they must
"-:'"'e opposite spins to do so. These distinct orbitals are quantized energy levels
'':.re the electrons are said to reside. This fundamental idea is the basis of all
.::::ic theory.
r: ::lic behavior andelectronic configurations are explained by the concept of
r.':"::onic bookkeeping. The ease or difficulty of gaining, removing, or sharing
i: :iectron are determined by the location of the electron. An electronic
. ::::quration is an account of all of the electrons in an atom. Quantum numbers
, -. specific for each individual electron. Questions about electronic
.:::guration and quantum numbers on the MCAT should be some of the
,-::ler questions you see, so be sure to get them correct, as they are worth the
i:. amount of points as the more difficult topics. Understanding the
1 :'E:nents and applications associated with the absorption and emission of
- r-: LS critical to performing well on the MCAT. Absorption spectroscoPy,
.:*rs. drld fluorescent tubes are jusi a few examples of devices thatutilize light
'i" i: ','ou are expected to understand for the MCAT.
I : -.iiiv important as understanding the structure of an atom and the energetics

:. orbiting electrons is seeing the effect the structure has on the reactivity of
:1 : ::om. There are distinct trends in atomic radius, ionization energy, electron
*::.-,::n-, and electronegativity that can be traced back to the filling of electrons in
'I'E rif,rr. Knowing the reasoning behind the periodic trends is more important
i';,- nemorizing the direction of each trend and notable exceptions to the trend.
-'= -ast of the topics that fits under the heading of atomic structure is nuclear
'::,*::-rstry. This section should be one of the easier sections, as scientists do not
:e:stand the topic in enough detail to expect you to have a deep
.:.i:
.*::=:standing of it. Nuclear chemistry is made easy by knowing the particles
*- - re processes of decay and capture, and your ability to do algebra. Know the
,il::,:itions of isotopes, nuclear decay, nuclear capture, nuclear particles, and
-* ---rre. This chapter starts with an elementary look at subatomic particles and
l:i:-es with an overview of the atom, the energy states of its particles, and
: between energy levels.
":*o:tions
69 Exclusive MCAT Preparation

General Chemistry Atomic Theory Atomic Structure
Subatomic Particles
Our most fundamental view of matter is that atoms are composed of three sub-
atomic particles. These particles are the proton, neutrory and electron. Each sub-
atomic particle is unique in its properties and position. A proton and neutron are
comparable in mass, while an electron is roughly 1/ ;3OO of the mass of a proton.
The proton and electron carry the same magnitude of charge, but with opposite
sign. Physical properties associated with each particle are listed in Table 2.1
Particle Mass (kg) Mass (amu) Charge (C) Charge (e)

Electron 9.11 x 10-31 5.49 xt0-4 -1.602* 10-19 -1
Neutron I.67 x 10-27 1..0087 0 0

Proton I.67 x t0-27 I.0073 I.602 x 1O-19 +1
Table 2.1
The nucleus is made up of neutrons and protons. Mass and charge are the two
measurements repeatedly used to describe subatomic particles and whole atoms.
By convention, the mass of an atom is said to be due only to the protons and
neutrons, because the electrons are essentially massless. An atom normally
carries a neutral charge, unless it has lost or gained electrons. In a neutral atom,
the number of protons equals the number of electrons. A convenient shorthand
notation is used to describe every element. There is the mass number (A) used to
describe the number of protons and neutrons in an atom. There is also the
atomic number (Z) used to describe the number of protons in an atom (and thus
the number of electrons in a neutral atom). The notation used to represent each
atom is shown in Figure 2-1.
number lemental Symbol The A number tells us that the combined

\ number of neutrons and protons is L95.
,/ TheZnumber tells us that the number of
195
78 t protons is 78. Combining these facts
.r'
number platinum-195
tells us that there are 'J,17 neutrons and
78 protons in this atom.
Figure 2-1
Isotopes
Isotopes are atoms of the same element that contain a different number
neutrons but the same number of protons within their nuclei. Isotopes, h
the same number of protons, are chemically similar but have different a
masses. Isotopes react the same way chemically and thus can be distingu
only by mass separation techniques (such as mass spectroscopy). Isotopes
often used as markers in chemical labeling experiments and as tags in
magnetic spectroscopy studies. An isotope can be traced from the source (
it is added) to the endpoint in a physiological system, a biochemical pathway,
a reaction mechanism. Typical examples of isotopes include 1H (standa
hydrogen), 2H (deuterium), and 3H ltrltrum;. Common isotopes used in
studies include deuterium, tritium, carbon-13, carbon-14, phosphorus-32,
iodine-121. These isotopes can be monitored either by the radioactive decay
emit or by nuclear magnetic resonance imaging (known as NMR spectroscopy).
Copyright @ by The Berkeley Review 70 The Berkeley

ure General Chemistry Atomic Theory Atomic Structure
Example 2.1
:low do the subatomic particles n261'l and27 Aldiffer?
ub-
ub- -\. The two are isotopes with a different number of neutrons.
are
B. The two are isotopes with a different number of protons.
:on.
C. The two are ions with a different number of electrons.
D, The two are ions with a different number of protons.
site
Solution
Secause the symbol is Al, the atomic number is always 13, implying that there
-e protons. This eliminates choices B and D. In either case there is no charge,
13
. r there are thirteen electrons present and the species is not an ion. This
=iminates choice C and leaves chbice A as the "orreit answer. In26Al, there are
,l neutrons (because 13 and L3 sum to 26), while in 27 Al, therc are 14 neutrons
recause 1,4 and 13 sum to 27). In26Al, there are 13 neutrons, 13 protons, and 13
-,ectrons, while in 27 Al, therc are L4 neutrons, 13 protons, and 13 electrons. The
.,','o differ by one neutron, making them isotopes. Choice A is good.
lVO
ms. Example 2.2
md ',hat symbol represents the neutral atom with fifteen electrons and sixteen
ily ,.-utrOnS?
)m/
md
+ i4Ga
lto E. i8P
the :. ?4p
lUS D ?;S
lch
: llution
:=;ause there are fifteen electrons, there are also fifteen protons in the neutral
:d r::n. This makes the atomic number 15, which is associated with the element
;.
- -.:sphorus, and eliminates choices A and D. The mass is 31 (15 protons and 16
f -.-:trons), so the symbol is ?1P, choice C.
:tS
rd
::.ample 2.3
:rch of the following is an isotope of element 35 containing 44 neutrons?
{", 31Br-
3 79gt
of : SlBr
rng
l ;9Kr
nic
5,r'np1i61
red
are
1,.: atomic number of bromine is 35, regardless of which isotope is being
ear
: :served. Because the element in this question is bromine, choice D is eliminated
ere -::rediately. When the 35 protons of bromine are coupled with 44 neutrons, the
or ::.s of the bromine isotope is 79 amu. The answer which shows a mass of 79
rrd i:.-r is choice B. Choice A is an anion, which is formed upon the addition of an
ing '- -=:iron.
nd
le)-
).
EH
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General Chemistry Atomic Theory Atornic Structure
Average Atomic Mass

The average atomic mass of an element is a weighted average of the masses of all
of the isotopes, an ave_rage that takes into account abundance. The reference for
all isotopic masses is rzC, whichîs assigned a mass of 12.000 amu. All isotopic
masses are measured relative to rzC.
Example 2.4
it is found that
IrVhen a sample of magnesium is subjected to mass spectroscoplr,
there are three detectable isotopes. What is the average atomic mass of
magnesiqm, given that the relative isotopic abundance is796/o2nMg,70"h25Mg,
and11"/"26vtgz
A. 23.71.8 /
B. ôl"
24.318 f oroL
C. 25.838 /
D. 26.928
ô1"
/
ôte
Solution
The math associated with this question is time-consuming, so before diving into
it, review the answers to see what can be eliminated. The average mass has to
fall within the range between the lightest and heaviest isotopes. In other words,
the average is in the middle somewhere. This eliminates choices A and D. The
most abundant isotope is24Mg, so the average atomic mass should be close to 24
grams per mole. Because the heavier isotopes are 21"/" the total mass of the
sample, the average atomic mass is a little more than 0.21 grams above 24. The
best answer is choice B. The mathematical solution is shown below, but in
preparation for this exam, use rigorous math only to confirm infuitively obvious
answers.
Average atomic mass = 79%(24) + 10%(25) + 11"/.(26)
= (0.79 x24) + (0.10 x 25) + (0.11x26)
= (0.79 x 24) + (0.10 x Qa + \) + (0.11 x (24 + 2)
= (0.79 x24) + (0.10 x 2a) + (0.10 x 1) + (0.11 x24) + (0.11 x 2)
= (0.79 x 24) + (0.10 x 2\ + (0.11 x 24) + (0.10 x 1) + (0.11 x 2)
= (1.00 x24) + (0.10 x 1) + (0.11 x2)=24 + 0.10 +0.22=24.32
The math is shown in an intuitive, step-wise fashion that does not require a
calculator. The number used as the center point, 24, was chosen knowing that
the average value was around 24.
Classical Experiments and Machinery

Classical experiments in chemistry are studies that determined the fundamen
features of matter. These experiments are important, because they define
nature of matter and the smallest units of matter. Of interest when looking
matter are charge, mass, location, and composition. There are three classi
experiments: the Thomson experiment (used to determine the sign of c
the Millikan oil drop experiment (used to determine the magnitude of
and the Rutherford experiment (used to determine the location of
particles). The experiments as listed here are modified from their original
to emphasize the rationale, rather than the procedure. Of equal signifi
today is the mass spectrometer (used to determine the charge to mass ratio for
particle), which was developed to support the classical experiments.
Copyright @by The Berkeley Review 72 The Berkeley

Thomson Experiment
The Thomson experiment determined the existence of
opposite charges in an
aiom andthat charge is.a fixed quantity. Thomson deflected
a stream oicharged
:articles (electrons) using an eitet.rai electric field (the plates of
a capacitlr).
lecause the stream of particles bent in a uniform rasruon, Thomson
-:'at there was a consistent concluded
charge-to-mass ratio for the particles.
a -tcedure and Apparatus
-- the Thomson experiment, a beam of electrons was generated travering left to
:-iht, as shown in Figure 2-2. Thomson observed ihut *h"r, he appiied an
.-:ctric field (a positively,charged plate on one side and a negatively charged
:-iie on the other) to an electron beam, he could deflect it by in exact amount,
:=rending on the strength of the field (charge on the plates) ind the mass
of the
.-::tron. Reversing the plates of the externufri"la gets the opposite deflection.
No applied electric field
Electric field on
Figure 2-2
, ,":s and Conclusions
:" ::r-ise the direction of the deflection changed when the orientation of
- ::
the field
red, Thomson concluded that there must be two types of charge that oppose
- . :nother.
Because the arc of the deflection was consiant, Thomson corrci rd"d
:' .: =lectrons have a fixed charge-to-mass ratio, measured tobe 1]6
x1,08 C/ g.
.:,.:::d Thomson Experiment (in MCAT testing style)

--::
is presented is an adaptation of the rho-son experiment, with changes
,, ;" j on current knowledge.
The simplified apparatus has un accelerating fiild
" : shown), which accelerates particles to the left, a doubre filter to ulsrrr"
: :r:rn linear, perpendicular trajectory, and an electric field perpendicular to
. ','.ctor of entry. Charged particles are deflected according to their sign of
' :--:e. Four particles are considered.
Their pathways are shown ln Figure I-3.
++++++++++++++++
Particle accelerated
trom left to right II
il
Double *r"rll
Figure 2-3
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Pathway I is attributed to an electron beam, while Pathways II, III, and fV are not
identified. The MCAT test writers are more interested in ascertaining your
intuitive understanding of problems than your superficial knowledge of facts.
Questions are likely to introduce obscure particles and test you on their
properties, which must be derived from the experiment. Consider the following
question based on the data in Figure 2-3.
Example 2.5
Pathway II is taken by which of the following?
A. A positron
B. A neutrino
C. A gamma ray
D. A muon
Solution
The particle following Pathway II must be negatively charged, based on the
direction of its deflection. It deflects in the same direction as the electron.
Although some of the particles in the answer choices may seem unfamiliar, the
question still can be answered. Based on the name, you should deduce that a
positron is positively charged. This eliminates choice A. A positron is an anti-
electron, in that it has the same mass as an electron, but the opposite charge.
Based on the name, you should deduce that a neutrino is neutrally charged. This
eliminates choice B. A neutrino is essentially massless and carries no charge.
They are difficult to detect. Detection of neutrinos is done through collision and
scintillation. Choice C is eliminated, because a gamma ray is a photon. A photon
does not bend in an electric field. Photons may be refracted, but that requires a
change in medium. The only choice left is a muon, choice D. In all likelihood
you do not know what a muon is. This question is not testing your knowledge of
particles; it is testing your reasoning abilities. A muon traces a different pathway
than the electron, because it is about 200 times as massive as an electron.

\[ass Spectroscopy
-- irass spectrometer is designed to measure the charge-to-mass ratio for a
-:rrged particle. This is accomplished by sending a particle into a perpendicular
:::rretic field and observing the degree to which it curves. The degree of arcing
:::jus of curvature) for a particle can vary with mass, initial velocity, magnitude
.: iarge, and the strength of the magnetic field. As momentum increases (either
:.:is or initial velocity), the particle deflects less, so the radius of curvature
i- ::eases. As the charge magnitude increases, the force causing deflection
r:::eases, so the particle deflects more, causing the radius of curvature to
:,:":ease. By comparing the curvature for an atomic or molecular ion to a known
*:iard, the mass of the unknown ion can be determined. The mass
,:"::rometer is used in general chemistry to determine isotopic abundance.
;;,:.:trl that isotopes are the same element with a different number of neutrons. In
:r":ic chemistry, the mass spectrometer is used to determine molecular mass
"::: fragmentation behavior to help elucidate the structure of an unknown
:,:.:ound. Figure 2-4 shows a basic schematic design for a mass spectrometer.
:= that mass spectrometers may have a velocity selector situated earlier in the
: i:: ,\-ay than the deflecting region.
xxx
XX 12) r"l
Figure 2-4
"' i;:ir and Apparatus
l'r',r :-.a-rs spectrometer embodies a simple concept. Force depends on mass, so
''|*:r ll1 equal force is applied to different masses, they accelerate at different
'r *s llhe mass spectrometer takes advantage of this by accelerating charged
: r*- -'r'q in motion using a magnetic field. The procedure is as follows:
O -{n element or molecule is ionized using high-energy electron

rmpact. The ionized particle is accelerated from the cathode plate.
The electric field strength is adjustable, so the velocity of the particle
can be set to any desired value.
A The particle passes through the double filter to ensure a uniform

perpendicular beam.
'6 The particle is deflected in a counterclockwise, radial fashion by the

aerpendicular magnetic field oriented into the page.
S The radius is measured using a detector, where the detector simply
detects collisions. The mass-to-charge ratio is calculated from the
radius of the arc.
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General Chemistry Atomic Theory Atomic Structure (
Example 2.6
\A/hich of the changes to the system would increase the radius of curvature in the
mass spectrometer?
A. Using a doubly ionized rather than singly ionized element
B. Using an isotope with fewer neutrons
C. Increasing the accelerating voltage
D. Increasing the magnetic field
Solution
The trick here is translating what the answer choices mean in terms of the
physics of the apparatus. Using a doubly ionized element (+2 cation) rather than
a singly ionized element (+1 cation) results in a greater q value, so a greater
degree of deflection is observed. This reduces the radius of curvature (r), so
choice A is invalid. Using an isotope with fewer neutrons results in a reduced
value for mass, so a greater degree of deflection is observed. This reduces the
radius of curvature (r), so choice B is invalid. Increasing the accelerating voltage
results in a greater velocity, so a lessened degree of deflection is observed. This
increases the radius of curvature (r), so choice C is the best answer. Increasing
the magnetic field results in a greater force, so a greater degree of deflection is
observed. This reduces the radius of curvature (r), so choice D is invalid. This
question can be answered from a conceptual perspective or based on the
relationship of variables described in a formula, with equal success. Whether
you use equations or intuition is a matter of personal preference and timing.
The mass spectrometer can be used to determine the charge-to-mass ratio for the
electron and the proton. The mass of a neutron is obtained by looking at the
mass difference between known isotopes. For instance, the mass difference
between 1H* (a proton) and 2H+ (deuteiium ion) is the mass of one neutron. The
mass spectrometer can also be used to determine the isotopic abundance for the
component atoms of each element. Common isotopes that should be memorized
include: 12C lthe most abundant isotope of carbon), 13C (used in carbon NMR).
14C (used in carbon dating, because it undergoes decay), iH
1ttr" most abund.ant
isotope of hydrogen),2H (deuterium, used in proton NMR solvents), 3H (tritium,
used in radio{abeling experiments), 235t (used in nuclear fission), ut't4 238g 16.
most abundant isotope of uranium).
Millikan Oil Drop Experiment

The Millikan oil drop experiment is a difficult experiment to perform. Its aim L.
to suspend a charged oil drop in an electric field. To do this, an electron must be
added to the oil drop or the oil drop must be ionized by impact, before it is
placed into the electric field. We wiil consider adding the electron here. This
cannot be accomplished easily, given that the oil drop is neutral and has no
affinity for the negatively charged electron. Falling oil drops pass through a
beam of electrons where some oil drops are penetrated at random by an electron.
Ideally, the electron penetrates the core of the oil drop and comes to rest, due to
the viscosity of the oil. The suspension of an electron in the oil drop produces a
charged oil drop. Enough charged oil drops continue to fall, one of whi&
eventually passes through a pore in the upper plate of a capacitor. The twcr
plates of the capacitor are separated, but both lie within the walls of a glass
cylinder. Figure 2-5 is a basic schematic of the apparatus used in the Millikan oil
drop experiment.

l
lqr
I
i'.*
oil drop*o . I
If suspended, q E=-mB
e mg
.'. O=
n 'E
rr
o
c Figure 2-5
e
. -:cedure and Apparatus
e
-:. ihe Millikan experiment, a fine mist of oil droplets is allowed to fall through a
:r-L\- por in the upper capacitor plate into a region where a uniform electric field
-s
g
5
5 =r:sts. The oil droplets fall because of gravity, so Millikan set out to apply a force
-:.at could stop the droplets from falling. If the droplets are suspended, then the
5
-: ice applied equals the gravitational force (a known quantity thai is dependent
e
,:- the mass of the falling object). The applied force is formed by charging the oil
r
::rplets by exposure to either an electron beam or an x-ray beam (only one of the
:eams is applied in different trials of the experiment). An electric field is applied
: - suspend the charged droplets. The uncharged oil drops fall unaffected by the
e
=:id. Despite the difficulty of this experiment, Millikan obtained enough valid
:n:a so that an average measurement was put forth and accepted by the scientific
: -,nmunity at large.
O The falling oil drop gains a charge by engulfing an electron as it falls.

I On rare occasions, the falling oil drop both gains an electron and
passes through the pore in the upper plate. The electric field
t strength is adjustable, so that the oil droplet can be suspended.
O If the particle is suspended (or falting at a constant velocity), then the
net force is zero, so mg = - qE. Because we know g/ we can set the
electric field strength (thus we know E); and because we can
determine the average mass of an oil drop (we know an average m),
we can solve for q, the charge of the electron.
;: ::tlts and Conclusions

l:-. charge of an electron has a fixed numerical value that is the same for all
=-=cirons. The value for this fundamental unit of charge is 1'6 x 10-19 C. The
-:.erge of a proton is found to have the same magnitude, but opposite sign of the
.-i:tron. When a proton is combined with an electron, there is no net charge.
l]:e Millikan oil drop experiment was difficult to carry out, so even after many
::.s, there were only two significant figures in the final number.
lLe Thomson experiment, the Millikan oil drop experiment, and the use of the
: lss spectrometer generally address questions about the subatomic particles in
:=:irs of what they are. Tlne where they are questions are answered by interactions
' -:h incident light and particle beams. The Rutherford experiment is the most
-.:=r-iJicant location experiment we will consider.
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Rutherford Experiment
The Rutherford experiment determined that atoms have dense nuclei with nearly
all of the atomic mass centtally concentrated, and that metals have uniformly
spaced atoms in their microscopic composition. The Rutherford experiment
relies upon a technique that can be employed to find a ball in the bushes in the
dark. "what does finding a ball in the bushes at night have to do with the
MCAT?" you may ask. well, when a ball is lost in the bushes, it is easier to find
its location by looking for its shadow than by hunting for the ball itself. By
shining light through the bushes and observing the shadow cast against the
background of a wall, a circular shadow can give hints as to the location of the
spherical ball. Depth in the bushes can be obtained by first moving the flashlight
closer to the bushes, then moving it farther away. The size of the shadow varies
with position of the light source, so the relative position of the ball to the light
source is determined from shadow dimensions. In essence, the ball can be
located and its dimensions can be found without ever seeing the ball. This same
principle was used by Rutherford to find subatomic particles. A subatomic
particle is smaller than a ball, so a light source of significantly shorter wavelength
must be employed. In this example, we use x-rays as the light source. In the
analogy, the bushes had to be thin for the light to pass through them, so a thin
strip of gold foil is used for the study. Rather than looking for a shadow on the
wall, the experiment uses photographic paper to collect the x-rays that pass
through. Figure 2-6 shows the basic design of the experiment.
Lead reaction vessel

X-ray beam
Photographic plate
or
Luminescing screen
X-ray source
Lead filter
Figure 2-6
Procedure and Apparatus

An incident beam (x-rays, alpha particles or electrons may be used) is focused
and aimed at a thin slice of gold metal, thin enough that the beam is able to
penetrate and pass through the gold foil. Gold is chosen, because it has a large
nucleus. If alpha particles are used, a luminescent screen is placed around the
gold foil to detect where the particles pass through the foil and strike the
luminescent screen (which glows when struck by an alpha particle). If x-rays are
used, a photographic plate is placed around the gold foil to detect where the
photons pass through the foil and strike the film. In the alpha-particle version of
the experiment, some particles are deflected by the gold sample, resulting in
parts of the luminescing screen never illuminating.
Results and Conclusions

Because the incident beam mostly passes straight through the sample, with
deflection being observed in only a few cases, it is concluded that the atom is
made up predominantly of empty space. The mass associated with the atom
occupies very little space and is not spread uniformly through the material.
Atoms are composed of a nucleus holding the mass (the protons and neutrons.)
This dense nucleus carries all of the mass besides that of the electrons. But given
that the electrons are of such low mass, it is not possible to discern their
whereabouts from the Rutherford experiment.
Copyright @by The Berkeley Review 7A The Berkeley Review

e General Chemistry Atomic Theory Atomic Sh:ucture
The Rutherford experiment disproved the diffuse particle model (referred to as

the plum pudding model) In the version of this experiment using the x-ray beam,
v
the photographic screen displayed the output shown inFigure2-7.
v
rt
re aaaaa
re aaaaa
d
aaaaa
iy
IE
aaaaa
le aaaaa
ht
ES
Figure2'7
ht
)e lark spots represent areas where no x-rays struck the film. In essence, the spots
1e ::e the shadows of the sub-atomic particles. Based on the distribution of the dark
is not evenly distributed in the gold
':ots, it is concluded that the mass of gold
Lic
th , ,,1, but is in fact found in concentric, dense nuclei. Because the nuclei (spots) are
he
='.'enly spaced, the gold atoms must be arranged in a
lattice structure. This is
Lin ::ause the shadow pattern on the film mimics the distribution of particles in the
he :..lerial. Gold is chosen because it is malleable and it has a massive nucleus,
ISS ::s it diffracts x-rays more readily than lighter elements, like aluminum. This is
, :,1,- x-rays in medical imaging show bones and teeth (rich in calcium nuclei)
::-:.er than tissue (rich in the light carbon, oxygen, and nitrogen nuclei). In order
"-. ztalyze blood using x-rays, a heavy salt must be added to the solution, often
::i:'rnr iodide.
I.l anple 2.7

::t hypothesis did the Rutherford experiment support?
L -{toms combine in definite proportions'
i -\toms contain subatomic particles.
- l:otons and electrons carry opposite charges.
l, Sriids are made of atoms with a dense nucleus and vast empty space
:etlveen nuclei.
sed
:to
: : -ubion
rge
,--::e A is Dalton's law of definite proportions. Choice B is particle theory.
the
,-' : r:e C is the Thomson experiment, conducted by observing the deflection of
the
are
-.: :Eam in a cathode ray tube when an external electric field is applied. The
i --* e:ford experiment involves the bombardment of a thin piece of metal foil
the
nof
: t:ther high-energy photons (x-rays) or a beam of electrons (Rutherford did
. ._: ::1 sepaiate experiments.) The photons pass through and strike an
qin
. -- -:.ating screen, which forms a shadow pattern indicative of the material's
- ::. Voit of the beam passes through, with a minimal amount being either
',, or diffracted. The conclusion is that the material is essentially empty
"::ed
,;::-= ',r-ith a few dense nuclei scattered throughout the material. The spots on
,, ith
:".. :.::een are uniformly spaced, so the nuclei must also be evenly spaced within
vr L.
l'" : .-.:nent. This makes choice D the best answer.
tonl
riaL.
ln-<. -", .-:ation of the electrons is not determined by Rutherford experiment.
1\-en
-'^ ^; - . .:. : : :, *rs are too small and moving too fast to locate precisely. This is described
J IE..
'- ---='-senberg's uncertainty principle.
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t"teu'
General Chemistry Atomic Theory 61qmic Structure
Heisenberg's Uncertainty Principle

The Heisenberg uncertainty principle quantifies the idea that it is not possible
simultaneously to identify a particle's position (where something is) and velocity
(how fast and where it's going). Equation 2.1 is the mathematical version of ttre
Heisenberg uncertainty principle, where Ax is the uncertainty in position and
A(mv) is the uncertainty in momentum.
Ax.A(mv) ,h / nn (2.1])
The basic premise here is that you can know either where something is, or how
fast it is going, but not both at the same time. Think of using a camera to focus
on a moving ball. If your aperture is small and the shutter speed is fast, then the
picture of the ball shows you where it is, but you don't know where and how fast
it's going. If your aperture is large and the shutter speed is slow, then the picture
of the ball is a streak that shows you where and how fast it's going, but you don't
know exactly where the ball is. Because we cannot locate an electron's precise
position, we settle for a view where the electron is observed over time. This
results in orbitals as a model for the orbiting electron.
Atomic Model
The Bohr model presents a simplified picture that explains the quantization of
light and the reproducibility of spectra. The basic premise is that electrons
occupy specific circular orbits about the nucleus, and thus the electrons have
specific energy levels (associated with each orbit). Electrons can exist only in
specified orbits (electronic shells), so each energy level of an atom is quantized.
Figure 2-8 shows this:
n=4
n=3
tt=2
Lq-t
r:_r
Lz-t
n=1
Electronic energy levels Electronic shells
Figure 2-8
The energy levels are spaced accord.ing to the energetics of transition between the
levels. More energy is required to carry out transitions when the electron is
nearest to the nucleus. The electrons are situated in various energy levels
(known more accurately as orbitals). These are quantized states that electrons
occupy. Principle energy levels are numbered 1 to -, where n = 1 is the lowest
electronic energy level. Energy must be absorbed by the atom for an electron to
elevate to a higher energy level. This is referred to as both excitation of. an
electron and absorption of energy. Conversely, energy is emitted when an
electron drops from a higher energy level (excited state) to the lowest energy
level (ground state). A good analogy to electrons climbing energy levels is a
Copyright @ by The Berkeley Review ao The Berkeley Revieu

:ocket ship escaping Earth's gravitational pull. it takes less energy to increase
liqtance as the rocket ship pulls farther away from the Earth. Likewise, it takes
-ess energy for an electron to increase energy levels as the electrons increase to
::gher energy levels (farther from the nucleus). For instance, it requires more
.lergy for an electron to go from the n = 2 level to the n = 3 level, than for the
.,ectron to go from the n = 3 level to the n = 4 level in any atom. This is why the
::'rergy levels for electron states are drawn closer and closer as the principle
::rantum number (n) increases in Figure 2-8. This picture becomes a little more
- rmplicated if the rotational energy levels associated with an atom
are combined
;";ith the electronic energy levels. At the level of understanding needed for
"_:.swering
MCAT questions, we ignore the rotational energy levels when we
-:"ok at electronic energy levels. We shall consider only the principal energy level
,",'hen considering electrons. Equation 2.2 is used to determine the energy of an
=-ectron in its principal energy level.
zn2mzlea (2.2\
',2h2
: = energy (principal energy level) m = mass of an electron (9.11 * 10-31
\A)
r = nuclear charge e = the charge of an electron (1'.6. x 10-rv C)
: = the electronic energy level h = Plank's ionstant (6.63 x 19-34 J'sec)
-:.e mass of an electron, m, the charge of an electron, e, and Planck's constant, h,

::e all constants, so when Equation 2.2 is considered as a proportionality, it
:,:omes Equation 2.3.
o2
EnL (2.3)
*
Lrample 2.8
.-_::ording to Figure 2-8, how would the photon from an n = 4 to n = 2 transition
-,:lpare to the photon from drr = 2 to n = 1 transition?
\. Then = 4 ton = 2 transition is twice as energetic asthen = 2ton = 1
transition.
E. The n = 4 to n = 2 transition is more than twice as energetic as then = 2 ton =
1 transition.
The n = 2 ton = L transition is twice as energetic as the n = 4 ton=2
lransition.
l. The n = 2 to n = 1 transition is more than twice as energetic as the n =4ton=
? transition.
S nlution
li.e distance between the n = 4 and n = 2 levels is less than the distance between
= 2 and n = 1, so transition energy is greater from the n = 2 level to the n = 1
.=.,'e1. The photon released from an n = 2 level to n = 1 level transition has more
::.ergy than the photon released from an n = 4 level to n = 2level transition. This
:-:n-inates choices A and B. The transition energy from the n = 2level to the n =
- -evel is more than twice the transition energy from n = - to n = 2, so it is
:=initely more than twice the energy of the n = 4 level to n = 2 level transition.
-:roice D is the best answer. This energy difference is shown in Figure
2-8. On
-*-,e MCAT, you should assume that the diagrams are drawn to scale, unless
: -:.erwise noted in the question or passage.
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The energy required to excite an electron from a lower level (orbital) to a higher
level is often in the ultraviolet (UV) to visible range of electromagnetic radiat"ion,
so the energy given off as the electron drops back down to the lower level (orbit)
is emitted as light energy. This is the basic principle behind spectroscopy.
Lower energy levels have less absolute energy and thus are more stible states in
which an electron can exist. The smaller the gap between energy levels, the less
energy that is given off, and therefore the longer the wavelengin of hght that is
emitted. One formula is important for understanding the relationship between
the speed of light, the frequency and wavelength of light, and light energy. The
energy of a photon and its wavelength of light are inversely propo*ional.
Equation 2.4 sums this up, where E is the energy of the photon, v is frequency, c
is speed of the wave, and l, is wavelength.
E - hv =hc (2.4)
)"
Hydrogen Energy Levels

Hydrogen is the simplest atom to study, because it has only one electron and one
proton. Much of our atomic theory is extrapolated from what we know about
hydrogen. Because energy is quantized and the energy of the electron depends
on features of the hydrogen atom, the energy levels can be calculated. Equation
2.5 represents the energy of the different levels of hydrogen.
E- -2.178xrr"(#) (2.s)
Energy levels are defined as being negative relative to a free electron. If the
electron is in the 11 = @ energy level, then E = 0, and the electron is free from a
nucleus. Considering that photons are absorbed and emitted when electrons
change energy levels, the more useful application of the energy equation involves
transition energy. Equations 2.6 and2.7 show the relationship between transition
energy and the corresponding wavelength of the photon involved.
AE = E6ru1 - Einitiul ... AE = -2.77gx10-18/--L

L.LIV LW - 1 \ (2.6)
(;il il;J
r -hc (2.7)
AE
The ionization energy of hydrogen from its ground state (from the n = L level) is
1312 kl/mole. Because of the squaring of the principle energy level, the
ionization of an electron in hydrogen from the n = 2 level is one-fourth of that
value (328 kJlmole). The transition energy from the n = 1 level to n = 2level is
the difference between the two values,984 kjlmole.

General Chemistry Atomic Theory Electronic Structure
EIe fffiHi'iffiG- #ffiH

I-lectronic Theory
:, atoms, the electrons orbit in distinct shells. Not all shells can hold the same
:.-::rber of electrons. Shells farther from the nucleus have a greater radius, and
-:us a greater capacity to hold electrons. Equation 2.8 gives the maximum
.,::.1pancy of electrons in a shell, where n is the principle quanfum number.
Number of electrons in shell = 2 (n)2 (2.8)
: -:.re 2-9 shows electrons of the lithium atom in their respective shells. The first
i- .-l holds two electrons, so the third electron must occupy the second shell. The
'-:': shell is the core shell, while the outermost shell is the aalence shell-
2"0 energY level--+

valence ,h"ll (electron occupancy up to 8) /
1st energY level

Core shell
(electron occupancy of 2)
Nucleus: made up of both

neutrons and protons
Figure 2-9
i:ective Nuclear Charge (Nuclear Attraction)

l:irLing electrons are held in their orbits by an attractive electrostatic force to the
- -;leus. In addition to nuclear attraction, electrons are also repelled by other
:-::hons. The net force is responsible for holding the valence electrons in place.
l: t net charge exerted upon the valence electrons is referred to as the effectiae
-:y charge. The effective nuclear charge accounts for attraction to the nucleus,
' :."..
--: ision from core electrons, and minimal repulsion by other valence electrons.
' :en approximating the effective nuclear charge (Zefil, the nuclear charge is
r::ed to the core electron charge (a negative term). Figure 2-10 shows effective
- - -iear charge increasing while moving left to right across the periodic table.
@
i-.ucleus: +3; core electrons -2
@
nucleus: +4;core electrons -2
.7
... Leff
7 _,1TL
- " "ett,-=+)
- '-
Figure 2-10
:.en we move from left to right in the periodic table, the nucleus of each
,-::eeding atom adds a proton and the valence shell adds an electron' The effect
:: -i.e extra valence electron is not as significant as the effect of the additional
'::,:on. As a result, the effective nuclear charge increases as the periodic table is
i'::::ned from left to right.
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General Chemistry Atomic Theory Dlectronic Structure
Each electron in an element travels a unique pathway, dictated by several

principles. Electrons are difficult to track, so we have theories to explain
electronic behavior, but they are just models to explain observed behavior.
According to the Heisenberg uncertainty principle we cannot see an electron, but
we can study its pathway over time. Charged particles in motion create
magnetic fields, so by studying the magnetic field generated by a moving
electron, it is possible to learn about the pathway and position of the moving
electron. This is why two of the four quantum numbers associated with an
electron refer to magnetism that results from a moving electron. We shall blend
the many ideas about the electron that have evolved over time, starting with the
most simplistic model, the Bohr model.
Electron Spin Pairing

Electrons fill orbitals in a pre-determined sequence, filling evenly into orbitals of
equal energy with like spin (all orbitals get a single electron, said to be "spin up"),
before placing a second electron with opposite spin into each orbital. The
physical reality is that electrons may spin either clockwise or counterclockwise
about their axis. spinning charged particles generate magnetic moments, so the
two opposite spins produce opposite magnetic fields. The magnetic fields
generated by electrons revolving about their axis are referred to as either spin up
(implying that the spin produces a magnetic field vector oriented upward) or
spin down. By convention, electrons are said to fill orbitals spin up first, before
filling spin down. Figure 2-11 shows the electron filling of lithium-7 and
beryllium-9, where arrows represent electrons, and the orientation of the arrow
implies spin.
1s
it is paramagnetic.
1s
it is diamagnetic.
Figure 2-L1
The shells represent energy levels an electron can occupy, while orbitals
represent the region in which the electron is likely to be found. An s-orbital has
spherical electron density. The difference between the 1s and 2s orbitals lies in
their dimensions. The 1s has a smaller radius and has no nodal shells (regions
where the electron has zero probability of existing.)
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lrre General Chemistry Atomic Theory Electronic Strrctrre
-'ral Spin Pairing and Magnetism

ain Aparamagnetic species is defined as an atom or molecule that contains at least one
ior. r.rnpaired electron. In organic chemistry, paramagnetic compounds are referred
but lo as radicals. An unpaired electron is an electron that has no second electron
:ate spin paired with it. By convention, the first electron into an orbital is said to
ing enter in a spin up fashion, thus an unpaired electron is a spin up electron in an
ing orbital that has no spin down electron. Because the electron is unpaired, it is
an susceptible to magnetic fields. If an external magnetic field is applied to a
end paramagnetic species, the electron spins align with the field. This induces a
the nagnetic moment into the compound, thus making it magnetic. This is to say
:hat paramagnetic species can have magnetism induced into them.
.\ diamagnetic species is defined as an atom or molecule that contains no unpaired

sof electrons. Al1 electrons in the atom or molecule are spin-paired, meaning that
P"), er.ery electron that is spin up will have a spin down electron sharing its orbital.
The Bv convention, the first electron into an orbital is said to enter in a spin up
r'ise iashion, so the second electron is a spin ilown electron. Because all of the
the electrons are spin-paired, diamagnetic compounds are not susceptible to
,"1ds :ragnetic fields. If a magnetic field is applied to a diamagnetic species, half of the
4up electron spins align with the field, forcing the other half to align against the field.
)or \o magnetic moment is induced into the compound. This is to say that
fore ,:-iamagnetic species cannot have magnetism induced into them.
and
row Electron Density and Orbitals
-\tomic orbitals are three-dimensional pictorial representations of the region
-,,.'here an electron is likely to be found. Because we observe electrons over time,
-,",'e look at where the electron usually is, and draw a probability map of the
:lectron distribution. It's like look at a spinning fan. You cannot see each blade
a= they turn, but you can see over time the area where they spin' Figute 2-\2
:epresents the electron density of an electron in an s-orbital over time, the orbital
:epresentation, and the probability map based on distance from the nucleus.
' ':i.1 '

. l"r '." '
-o
[<
H
Electron Orbital
density map representation
df.o- nrrclerrs
Figure 2-12
lhe electron density map shows that electrons are found most often near the
:.ucleus. This is also represented by the graph of the probability of finding an
ritals :rectron as a function of its distance from the nucleus. The orbital representation
-. tvpically used by chemists to depict the s-orbital. The size of the
sphere varies
I has
,,-ith the electron density map, depending on the atom. The shape of an orbital is
es in
:efined by the distribution of electrons about the nucleus. Ninety-five percent of
;ions -:.e time, the electron can be found within the boundaries of the orbital. We will
-:,ok at the s-, p-, and d-orbitals in substantial detail, while f-orbitals will be
:onsidered, but in minimal detail. Most common elements do not have electrons
,':cupying the f-orbitals.
vrew
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S-orbitals
S-orbitals result from spherical distribution of the electrons about the nucleus.
Figure 2-13 shows three different s-orbitals, where the principle quantum
number represents the energy level and the average distance from the nucleus.
@
1s 2s
Figure 2-13
P-orbitals
P-orbitals result from barbell-like distribution of the electrons about the nucleus.
Figure 2-14 shows the three different p-orbitals, each oriented about a different
axis. Electrons are not found at the nucleus in p-orbitals. Absence of electron
density at any point is referred to as a node. P-orbitals have one node at the
nucleus that is part of a nodal plane between the two lobes.
P* P, Py
Figure 2-14
D-orbitals
D-orbitals result from double barbell-like distribution of the electrons about the
nucleus. Figure 2-15 shows the five different d-orbitals, each oriented differently.
D-orbitals have two nodal planes, and electrons are not found at the nucleus.
d"" dry dr"

Irl dxz, d*r, and drr, lobes lie between the axes
d"z -rz
rz and drz,lobes lie on the axis

In d*z _
Figure 2-15
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I-orbitals
l-:rbitals result from triple barbell-like distribution of the electrons about the
. ::leus. There are the seven different f-orbitals, each oriented about a different
:-ane or axis. Electrons are not found at the nucleus. F-orbitals have three nodal
: -anes. Little chemistry is carried out with the f-orbitals, so they are unconunon.
Ll.cllective Orbital View of Energy Levels

l':bitals result from probability calculations, where energetics is considered.
l:rierent orbitals are associated with different energies. Conceptually, we use
,::itals to show the energy and most frequent location of an electron. Figure 2-
-: .hows orbitals with relative size emphasized, from lowest energy levels to the
--iher energy levels. Levels are spaced according to energetics. Arrows
:.:resent electrons and their spin orientation. Because there are twelve electrons
:: r\vn, the element represented is magnesium.
w T
ap,.D@
,*# ro-ffi ,o*ffi 3d.'rm r.rE
3p*C>@ t rC@ Bp,
I
*@
_lr
2p*O@
lJ_
2Pr8
_ll_
,r"
8
3w
The upward single-headed The downward single-headed
arrow represents an electron in arrow represents an electron in
the 1s orbital with its magnetic / I the ls orbital with its magnetic
spin orientation up. I i spin orientation down.
f@
Figure 2-16
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Electrons within an element fill the energy levels starting from the lowest energy.
This means that the electrons within an element follow a specific filling order.
There are some rules to consider when looking at electronic configurations.
Pauli's exclusion principle: No two electrons can have the same set of quantum
numbers (n, l,rry,rnr).
Hund's rule: Electtons completely fill lower energy levels before starting to fill
higher energy levels. kr a degenerate set of orbitals, electrons singly occupy each
orbital before a second electron pairs up within the same orbital. Figure 2-17
demonstrates Hund's rule.
1t
Not allowed, because electrons fill Allowed, because electrons have filled
different orbitals before pairing up. each orbital singly without pairing.
Figwe2-17
Aufbau principle: Electrons are added one by one to the shells, starting with the
lowest energy level, and then into sequentially increasing energy levels. The
numbers in Figure 2-18 represent the sequence of addition for the electrons.
,,J_f J A
I Il"
"ôl
llu
.ol I
Figure 2-18
Electronic Configuration
Electronic configurations are shorthand notation for the electrons present in an
atom and their energy levels. Electrons fill according to a set pattern, one that is
derived from the Aufbau principle chart shown in Figure 2-19. By drawing the
table and then sequentially following the arrows, the orbital filling sequence is
generated. Couple this information with the orbital occupancy, and electronic
configurations are seen to be systematic. For instance, the first line shows that
the 1s level fills first, to an occupancy of two electrons. The next arrow crosses
through the 2s level, so the 2s orbital is filled next. From here the third arrow
shows that the 2p level followed then by the 3s level are filled. It continues down
the chart. The first break from numerical sequencing comes when the 4s level is
filled before the 3d level, despite the fact that the perimeter of the 3d level is
closer to the nucleus than the perimeter of the 4s orbital. The reason for the
apparent discrepancy is that the energy of the level is based on an average
position of the electron, not the extreme position. Ionizing electrons are not
removed from the atom in reverse order, however. Outer shell electrons are
always removed first when forming cations. Figure 2.8 shows only the first five
arrows, but the pattern continues. You should also be able to deduce the
electronic configurations for neutral atoms, cations, anions, excited states, and
any exceptions to the rules.
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Fills the 1s orbital to: 1s2
2: Fills the 2s orbital to; 2s2
3: Fills the 2p then 3s orbitals to: 2p63s2

4f 4: Fills the 3p then 4s orbitals to: 3p64s2
5f 59 5: Fills the 3d,,4p then 5s orbitals to: 3d104p65s2
Figure 2-19
-rEure 2-19 shows that the electrons fill according the orbitals listed by the
-quential arrows. It works by following the arrows sequentially. Arrow 1 goes
-iough 1s, so the Ls orbital is filled first. Arrow 2 goes through 2s, so the 2s
:rrital is filled next. Arrow 3 goes first through 2p, then through 3s, so the 2p
:r:ital is filled after the 2s orbital, followed by the filling of the 3s orbital. The
:rocess is repeated arrow after arrow until all of the electrons have been
::counted for. Althougli. g-, h-, and j-orbitals exist in theory, the periodic table
:-rntains no elements that have electrons in either g-, h-, or j-orbitals.
fxample 2.9
ll"e electronic configuration for manganese is which of the following?
.c". rs2zs2zp6 g"2916 96.7
E 7s22s22p6 gt2g16 965
rl 7s2 2s2 2p6 9"2 g16 4"2 g 65
D. 7s2 2s2 2p6 9"2 g16 4"2 36,7
5,u-lution
l'{anganese (Mn) is element number 25, so a neutral manganese atom must
::ntain 25 electrons. This eliminates choice B (only 23 electrons) and choice D
::rtaining 27 electrons). Because the 4s orbital is filled before the 3d orbital,
: ':,ice A is eliminated. This leaves only choice C.
srample 2.10
':. element in which column of the periodic table is diamagnetic?
\ Column 1 (alkali metals)
:r Column 2 (alkaline earth metals)
: Column 7 (halogens)
iqlution
-- ;iamagnetic compound has all of its electrons spin-paired. This means that
r,t:e must be an even number of electrons in the element. Based on the even
r ':lber constraint, choices A and D are eliminated. Column 6 elements (the
:,ilcogens) have a valence electronic configuration of ns2np4, which results in
*,',
: p-orbitals having only one electron each. This means that chalcogens are
;
'::magnetic, eliminating choice C. This means that the alkaline earth metals in
::r--unn 2 are diamagnetic, with a valance electronic configuration of ns2. The
l---r;a,line earth metals and the noble gases are diamagnetic. The best answer is
: ::ce B.
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General Chemistry Atomic Theory Electronic Structure (
Electronic configurations may include abbreviations based on filled core shells. a

A filled core is represented by the, noble gas that contains those same electrons. I
For example, aluririnum (Al) is k22s22p61s23p1, which is equivalent to drawing IMT
it as [Ne]3s2gp1. Thir shorthand is typical, In addition, you must be aware of Ilr

some common exceptions to the Aufbau principle. Half-filled d-shell and filled dmr
d-shell stability results when a single electron is elevated from a lower energy fiu
level that is paired (usually the s-orbital) to yield even distribution of electrons in tdtt
the d-level. Half-filled d-shell stability is seen with chromium, molybdenum, tru[
and tungsten. Filled d-shell stability is seen with copper, silver, gold, and some s*s
say platinum. Figure 2-20 shows the electronic configurations for chromium and mr-t
copper, exceptions to the Aufbau filling order. $uill
dss
Half-filled d-shell stability in chromium: [Ar]4s13d5 rather than [Ar]4s23d4 qru [t
mrrl
Filled d-shell stability in copper: [Ar]4s1gd10 rather than [Ar]4s23d9 t*
tu
Figure 2-20
Elements in the same column of the periodic table have similar valence shells and N
electronic configurations, with the notable difference being the shell number. For
instance, Wa is iNe]gs1 and potassium is [Ar]4s1. This means that alkali metals li
are s1 metals, and exhibit similar chemical behavior, given their common L_
tendency to lose one electron. Blocks in the periodic table are named after the
last electron in the electronic configuration. Alkali metals fall into the s-block by rli
virtue of their last electron in an s-orbital. So far, we have viewed ground state l
electronic configurations. Ground state electronic configurations occur when the

electrons occupy the orbitals in the exact predicted order, starting from least
energetic and filling orbitals that are progressively of higher energy. An excited
state electronic configuration occurs when any electron absorbs energy and l
moves to a higher energy level than it normally occupies in the ground state.
The absorption and emission of energy, usually in the form of a photon, is
associated with the excitation and relaxation of an electron, as it moves between L
the ground and excited states.
Example 2.11
\A/hich electronic configuration represents an excited state?
A. Fi 7s22s22D6
B. 19. 1r22r2jo3
C. He: 1s2
D. Li:1.s22p1
Solution
An excited state electronic configuration does not follow energetic sequence. Ar.
excited state has at least one electron in an energy level higher than what i:
drawn as standard for the ground state. Be sure not to confuse an ion (eithe:
cation or anion) with an excited state. A cation is an atom that has a deficit of al
least one electron and thus carries a positive charge. An anion is an atom thai
has an excess of at least one electron and thus carries a negative charge. In thl'
question, choice A is a fluorine anion (it contains an extra electron), and choices E
and C are normal. For Li, it should have 1s22s1 as a ground state. The electron -
configuration given in the answer choice has the last electron in a 2p-orbitar
which is of higher energy than the ground state 2s. This makes choice D th.
correct answer, because it is an excited state.
Copyright O by The Berkeley Review 90 The Berkeley Revier ffi,[lL'''::,.{

Quantum Numbers
Quantum numbers are a set of four numbers that uniquely describe an electron
;r-ithin an atom. Four factors describe an electron: the shell, the orbital, the
rrientation of the orbital, and the alignment of the magnetic field resulting from
ie precessing electron. These terms translate into the quantum numbers. A
:undamental rule with quantum numbers is that no two electrons can have the
same set of quantum numbers (this is the Pauli exclusion principle). Quantum
:.umbers are used to describe the motion and location of each electron in an
=Lement. Quantum numbers describe the shape of an electron's cloud, the
romentum of the electron, the orientation of the electron density, and the
::tation of the electron about its axis. There are four quantum numbers used to
:escribe an electron; n, l, rr.1, and ms. There are also rules that must be followed
'','ren assigning quantum numbers to an element. Each number has its specific
:.ridelines, which often depend on the other quantum numbers. Table 2.2 lists
':e rules for assigning quantum numbers.
Quantum # Rules
Principle (n): Describes the shell (average radius of the
n electron from the nucleus and its energy level) in which the
electron resides. It can be any integer greater than zero.
Angular Momentum (l): Describes the orbital (shape of the
I electron cloud formed by the orbiting electron) in which the
electron resides. It must be less than the value of n. It can be
a positive value or zero.
Magnetic (m): Describes the orientation of the orbital about a
m1 plane or axis. It can be any value in the range from negative I
to positive l, including zero.
Spin (mr):Describes the rotation (counterclockwise or
ms clockwise) of the electron about its axis. It can be either
positive or negative one-half (spin up or spin down).
Table2.2
:: -e 2.3 shows the correlation of quantum numbers to electrons within an atom.
I m1 ms orbital
total Description
electrons
0 0 +1 1s 2 tst tsJ
)
0 0 a1 2s 2 zsI zsl
)
1 +1, 0 t1) 2p 6 2p*I 2puI 2prl 2p*!Zpul2prl
:i0 I
0 +1 3s 2 gs'l gsJ
2
1 +1,0 +1 3p 6 3p*'l 3put 3pr'l 3p*J 3puJ 3prJ
)
-0 0 +1 4s 2 +st +sJ
2
a1 3dxyt 3dxzI 3dyzI 3dx2_yzI 3dz2I
2 1-.) +1, 0 3d 10
2 3d*.rJ gdxz! 3dvzl 3dx2 - v2I gdz2!
Table 2.3
9l Exclusive MCAT Preparation

General Chemistry Atomic Theory Electronic Structure (
When assigning quantum numbers to an electron, you must keep in mind that m
"no two electrons orbiting the nucleus of the same element have the same set of F
quantum numbers." To assign quantum numbers, you must first describe the e!
electron in words. Consider an electron in the third shell. There are eighteen tu
electrons held in the third shell, so we need to be more specific. An electron in W
the third shell can be in either an s-orbital, a p-orbital, or a d-orbital. For sake of M
argument, let's consider a p-orbital. There are three p-orbitals, each capable of
holding two electrons, so there are six electrons that can be found in the 3p level.
We need to be more specific. Each p-orbital has a different orientation in space
(p* along the x-axis, pu along the y-axis, and p" along the z-axis). For sake of
argument, let's considei the p-orbital aligned on the x-axis. This is the p*-orbital.
Two electrons can be found within a 3p*-orbital, one with a magnetic spin
moment upward and the other with a magnetic spin moment downward. By
describing the electron as spin up, the electron is unique. There is only one
electron that can be spin up within a 3p*-orbital. It took four terms to narrow it
down to a unique electron, hence there are four quantum numbers. Let's lM
consider that same electron: rfun
A 3p*-spin up electron has the following description in words and therefore
these corresponding quanfum numbers: nMm
mt
shell
Third therefore, the principle quantum number (n) is 3 ,flfiq
P-orbital therefore, the angular momentum quantum number (/) is 1
ml@
X-axis orientation therefore, the magnetic quantum number (m) is -1 W:
Spin up therefore, the magnetic spin quantum number (ms) is + 1 rdh'd
2 W
The quanfum numbers for the electron are: n - 3, I = 1, m1- -L, and ms = + 1. The
2
skill you must (re)develop is getting the four numbers quickly. Determining n
and I is relatively easy. The n-value is the shell number, so it is pretty much a
given. The l-value is the orbital. Orbitals increase from s to p to d to f, and so on,
and the l-values increase from 0 to 1 to 2 to 3 and so on. An l-value of 0
corresponds to an s-orbital, an l-value of 1 corresponds to a p-orbital, and so
forth. The challenging part is finding the m7 and ms values. In all likelihood,
you have no idea why x-axis orientation leads to the conclusion that ml = -1.
That's just the way they do it. Just as x comes before y and z in the alphabet, -1
comes before 0 and +1 numerically. To get the m7 and ms values, you must drarn'
out the energy levels. The assignment of m7 values for the p-orbitals is shown in
Fig:re2-21,.
Px Py Pz
ml= -1 ml=0 ml= +1
Figure 2-2L
Chemistry convention tells us to number the different orbitals from -l to +'

sequentially. The middle orbital always has an m7 value of 0. This is true for a1l
orbitals. The assignment of m7 values for the d-orbitals is shown tnFigwe2-22.
dxy d*, dyt d*z -rz d12

ml= -2 ml=-1 ml=0 m7-+L ml= +2.
Figure 2-22
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Flectrons are filled into orbitals one at a time from left to right, with spin up
qoing in first, followed by spin down once each degenerate orbital has one
:iectron. Filling spin up first is a convention and does not represent the physical
reality of electrons. When an electron is spin up in an orbital, it has a spin
:uantum number (mr) of +1 12. tNhen an electronis spin down in an orbital, it
:.as ms = -1 /2. For the 3p* spin up electron, the filling is shown in Figure 2-23.
Px Py Pz
ml= -L ml=0 ml= +'1,
Figure 2-23
lLe electron falls into the first p-orbital, so m7 is -1. The electron is spin up, so ms
..i -- /2-
, : be able to apply these quantum numbers, keep in mind that each electron
--iin an element has a unique set of quantum numbers. An electron can be
:=-cribed in terms of words (such as an electron in the second energy level in a
:--:bital with x-orientation and spin up is a 2p" t) or in terms of numbers (n = 2,
= 1. r1l = -1, rns = +1 /2). Quantum numbers follow arbitrary guidelines. For
:-i:ance, the electron in a p-orbital oriented on the z-axis in the third shell with
: -:. up has the quantum numbers n = 3 (for the third shell), I = 1 (because the
: rirofl is in a p-orbital), trrt= +l(for the z-axis), and me = +1 / 2(for spin up).
:r-ample 2.12
'* --Ithe following are true of an electron EXCEPT:
'- tiecttons in a lower energy level can absorb energy and elevate to a higher
:r'rergy.
: :ractly the same amount of energy is emitted when an electron relaxes
:etrveen the same states.
." ::.ere are many energy absorptions possible, but they are always of a
: :ecisely known energy.
- ..r. electron in the n = 1 energy level can be found at an infinite number of
:
stances from the nucleus.
: : . "tf,ion
-: :r.odel of atoms is a positive concentric nucleus surrounded by orbiting
: . r r,fls. These electrons may occupy only specific orbits, which have distinct
' :i:s and pathways. According to this description, electrons in a lower
-.::,'level can absorb energy and elevate to a higher energy, so choice A is
. -: and thus eliminated. According to this description, exactly the same
r: . -:.t of energy is emitted when an electron relaxes between the same states, so
:= B is valid and thus eliminated. According to this description, there are
-.---, possible energy absorptions possible, but they are always of an exact
" ,::I,'. so choice C is valid and thus eliminated. According to this description,
,;' =-:::ron in the n = L energy level is found at only one distance from the
.- '-i, not at an infinite number of distances. This makes choice D invalid, and
=
''" -.:: --i. best answer.
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General Chemistry Atomic Theory Periodic Trends
PeriodicTrendS''''.''..'::..::'::'::''
The Periodic Table
The periodic table is organized according to valence electrons. Figure 2-24 shows
:
the shell of the periodic table. The blocks are named after the last electron that
1
fills each respective atom in that section of the periodic chart. For instance, an
element in the D-block has its last electron (a valence electron) in a d-orbital.
Understanding the blocks helps to understand the periodic trends. The S-block :
comprises only metals. The D-block houses the transition metals, where periodic
$
behavior is not necessarily an obvious trend. The P-block includes metals and
metalloids in its left side and non-metals in its right side. 5
Sr
TT
ltu
ltltl s
'-Ez17r"r'
lrlal
+--+--+--+--+-- :
i i lDntrict<i
--T--i--t--i-'l; i : lP block
--+--f--+--t--+--
:
Fr
ltltl
Itltl s{frr
--+--+--+--+--+--
llttt lfu'ui
ttttt
i:[ilm
lmul
:iil0il
Tlh'
ttllltttttttt ,,b
tttrttltttttt
--+--+--+--+--+--
llltltltltttl
S:btoak --+--+--+--+--+-- lffi
i:il"*'
l!ltltltltltt
o
Figure2-24
General Elemental Periodic Trends
Periodic trends refer to any chemical behavior that can be matched to a trend
within the periodic table. All chemical properties depend on the valence
electrons, so periodic trends ultimately grow out of valence electron trends. Anr-
feature of an atom that affects how tightly a valence electron is held contributes
to periodic trends. The two major factors are the effective nuclear charge and the
valence shell, both of which support periodic trends. They are listed below:
O As you move from left to right across a period in the periodic table, the
ffimmm
effective nuclear charge increases.
ftiilfifinuL:
@ As you descend a family in the periodic table, the valence shell increases/ sc
the distance of the valence electron from the nucleus of the atom increases. i&1
m:
The effective nuclear charge (2"1) is the net charge exerted upon the outermos: t
rq,,
electrons (valence electrons). This value is empirically determined and takes inti 0m:
account attraction due to the protons, shielding due to the neutrons, ani
repulsion due to the core electrons. It is generally approximated as the proto: S@fiulrfir
charge minus the electron repulsion. The effective nuclear charge affects horr' Tffiinm e
tightly the electrons are held, which affects the ionization energy, the electro: ltrlllur{ultti
affinity, and the atomic radius. The effective nuclear charge increases across : tthm p'*
row in the periodic table. Although we generally approximate the effectir': lll[l0im,.ximr
nuclear charge, it can be derived from the ionization energy. This procedur:
assumes that ionization energy is purely related to the effective nuclear charge
and fails to account for shell stability, particularly filled-octet stability.
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General Chemistry Atomic Theory Periodic Tfends
Exarnple 2.13
r\tLich of the following atoms has the GREATEST effective nuclear charge?
-A.. Carbon
B. Fluorine
C. Sodium
D. Sulfur
Solution
:lfective nuclear charge increases from left to right in the periodic table, so the
.lement in the column that is farthest to the right has the greatest effective
:,uclear charge. Fluorine is to the right of carbon within the same period, so it
:,as a greater effective nuclear charge (2s16). Choice A is eliminated. Sodium is in
re first column of the periodic table, so it has the smallest effective nuclear
:rarge. Choice C is eliminated. The correct answer is choice B.
: =riodic trends depend on both the effective nuclear charge (affecting the
'::ength with which valence electrons are held) and the valence shell (affecting
-.:.e distance between electrons and the nucleus.) Periodic trends as we move
i"-nl left to right across a row of the periodic table (period) are attributed to
:.;reasing effective nuclear charge. Periodic trends as we move up through a
::-urrm of the periodic table (family) are attributed to decreasing valence shells.
l}le net result of these two effects is represented by the bold arrow shown in
::rure 2-24. As we move along the pathway of the bold arrow, the following
atomic trends are observed:
=:reral
@ The atomic size decreases (the radius of the atom is defined as the distance
rrom the center of the nucleus to the exterior of the valence electron cloud).
'g The ionization energy increases (the energy required to remove the
outermost electron from the atom).
,0 The electron affinity increases (the energetics associated with an atom
gaining an electron).
{D The electronegativity increases (the tendency to share an electron with
aaother atom within a bond).
iuanple 2.14
',::ch sequence accurately lists increasing ionization energy of the atoms?
4- Br>F>Cl>Te
3 O>S>P>Br
l- Br<FcCl<Te
I O<S<P<Br
i'c,lution
1'e appearance of fluorine in the middle of a trend should get your attention as a
,';-'--B orSWer, eliminating choices A and C. Oxygen is directly above sulfur in
rt periodic table, so oxygen has a greater ionization energy than sulfur. The
::ect answer is choice B.
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@neral Chemistry Atomic Theory Periodic Trends
None of the trends is uniform or perfect. The effective nuclear charge does not
uniformly increase when we scan across a period. There are deviations in some
trends. One of the more common deviations is seen with electron affinity and
ionization energy/ due to half-filled stability and filled-shell stability. For
instance, nitrogen has a greater ionization energy than oxygen, because upon
ionization, nitrogen loses its half-filled p-shell. On the contrary, oxygen gains
half-filled stability upon being ionized. The test writers may not prey on these
exceptions, but ihey certainly can emphasize the conceptual aspects by looking at
the factors that affect periodicity. For instance, rather than ask about atomic
radius, they may ask about ionic radius.
As a general rule, cations are smaller than neutral atoms, because the loss of
electrons allows the atom to compact more tightly, given the diminished
repulsion associated with the missing electrons. As a general rule, anions are
larger than neutral atoms, because the gain of electrons causes the atom to
expand, given the enhanced repulsion associated with the additional electrons.
Valance electrons account for the size of anions, neutral atoms, and cations.
Extra electrons repel and thus increase the atomic size of an aniory while a loss of
electrons results in less repulsion and a smaller radius for a cation.
Example 2.15
\zVhen strontium (Sr) becomes an ion, what is observed?
A. It forms a +L cation that is smaller than Sr.
B. It forms a +1 cation that is larger than Sr.
C. It forms a +2 cation that is smaller than Sr.
D. It forms a +2 cation that is larger than Sr,
Solution
Choice C is correct. Strontium (Sr) is found in the second column of the peri
table. Alkaline earth metals lose two electrons to gain octet stability. As
strontium carries a +2 charge, so choices A and B are eliminated. Cations
smaller than neutral species, because there are fewer electrons and thus
repulsion. This makes choice C the best answer.
Example 2.15
Which of the following ions is the LARGEST?
A. CT
B. Na+
c. K+
D. Br-
Solution
Within a period, anions are larger than cations, so chloride (Cl-) is larger
sodium cation, and bromide (Br-) is larger than potassium cation. This elimi
choices B and C. Because Br is lower in the periodic table than Cl, Br is larger
a neutral atom than Cl. This same trend holds true, if both Br and Cl pick up
same number of electrons. In this case, both bromide and chloride picked up
electron each, so bromide, with its electrons in a higher valence shell, is
than chloride. The answer is choice D.
Copyright O by The Berkeley Review 96 The Berkeley

:nds General Chemistry Atomic Theory Periodic Trends
; not Atomic Radius

ome lhe atomic radius is the distance from the center of the nucleus to the edge of the
and '.'alence cloud of electrons.
However, most of the empirical measurements of
For ::omic radii that exist are not from electron density maps, but instead are
lpon ietermined by dividing bond distances between like atoms in half. Because of
;ains :''"'erlapping electron clouds, this method does not generate a true atomic radius,
hese :ut rather a covalent bonding radius. However, it does lead to internally
rg at :-rnsistent values. Atomic radii are measured in units of picometers. The radius
rmic :: an atom decreases as a family in the periodic table is ascended, because the
:::.mber of electronic shells decreases. The radius of an atom decreases as a
:eriod in the periodic table is scanned from left to right, because the effective
ss of :--rclear charge increases. The trend is fairly uniform from left to right, with no
shed ::<Linct exceptions due to half-filled stability.
s are
mto .,rure 2-25 lists the atomic radii of the first twenty elements. As a general
rons. ::servation, within a period, atomic radius decreases as the atomic number
ions. :areases.
,ss of
7.6
1.5
1.4
1f
iodic
iuch, 1.2
s are
1
; less
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
than 0.2
nates
0.1
ter as
p the
P one 7 B 710 1.1 12 13 14
arger Atomic Number
Figure 2-25
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The sudden increase in size from He to Li, Ne to Na, and Ar to K is attributed to

the expanded valance shell associated with the additional electron. For instance,
the electronic configuration of Ar is k22s22p69s23p6, while K is
k22s22p6gs2g?64s1. The fourth shell (n = 4 quantum level) has a larger radius,
so the potassium atom is larger than the arSon atom. Table 2-25 terminates at
element 20, because from element 2'J. to 30 the radius stays roughly equal, since
the electrons are being added to the third quantum level (3d orbitals). This does
not affect the radius of the electron shell drastically. The transition metals have
very similar atomic radii, although they are not exactly equal'
The trend is consistent through the elements listed, with the exception of helium
and hydrogen. The larger atomic radius of helium when compared to hydrogen
goes against the discussed trend in effective nuclear charge. The best explanation
for this deviation involves both the shielding effect of the two neutrons in the
helium nucleus and the electron repulsion experienced by electrons in the first
quantum level where they are closer together than in any other quantum shell.
In other words, the electrons in the n = 1 level repel one another more than
electrons in the tt = 2 level, because they have the smallest interelectronic
distance. This repulsion forces the electrons away from one another, resulting in
a greater area being occupied by the orbiting electrons. Keep in mind that the
electrons, not protons ot neutrons, define the radius of an atom. The atomic radii
of atoms may be used to predict the bond length within molecules. The smaller
the atomic radius of the atom, the shorter the bond it forms when sharing
electrons with another atom. Shorter bonds are stronger bonds, so there exists a
correlation between an element's location in the periodic table and the strength of
the bonds that element can form.
Example 2.17
Which of the following elements has the LARGEST atomic radius?
A.O
B.F
C. Ne
D. Na
Solution
This is just a simple case of reading from the periodic table' The element in the
lowest and furthest left position is sodium, Na, so choice D is the best answer.

General Chemistry Atomic Theory Periodic Ttends
Ionization Energy
Ionization is the process of losing an electron from the valence shell. \Atrhen an
atom is ionized, it becomes a cation. The energy required to remove the outer-
most electron from the valence shell is known as the ionization energy. A generic
reaction for ionization is shown below, where E represents any element.
E(g) + E+(g)+e-
The energy required to carry out ionization depends on the attraction of the
electron to the nucleus, its distance from the nucleus, and the stability of its
electronic configuration. Because several factors influence ionization energy, it is
ioo difficult to calculate, and thus it is generally evaluated in a qualitative sense.
figure 2-26 lists the ionization energies of the first twenty elements in the
:eriodic table. Within a row in the periodic table, ionization energy increases as
re atomic number increases. This is a general trend, but with some exceptions.
2500
2400
2300
2200
1100
r000
_ icO
- ?.10
- i..rO
7 8 91.0 1.1 1273 14 15 t6 t7 18 t9 20

Atomic Number
Figure 2-26
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Ionization energy for an element generally increases as you move left to right in
I
the periodic table. Notable exceptions occur when there is half-filled stability of n!
the energy level and when there is an s2-shell. Ionization energy for an element i1{;
increases as you ascend a column in the periodic table, with the element higher M
up the column having the greater ionization energy. This is because as the
number of electronic shells decreases, the proximity of an electron to the nucleus
,L
increases, and thus the attraction to the nucleus increases. The sudden decrease
in ionization energy from He to Li, Ne to Na, and Ar to K is attributed to the
il
expanded valance shell (and thus reduced attraction) associated with the
adbitional electron. For instance, the electronic configuration of Ne is 1s22s22p6,
c.
n_
while for Na it is 1s22s22p63s1. The third shell (n = 3 quantum level) has a larger
radius, so the sodium atom can more easily lose an electron than the neon atom
(with its outermost electron being more attracted by the nucleus). As with sd
Immr
atomic radius, from element 21 to element 30 the ionization energy remains
,iml
roughly equal, because the electrons are being removed from the same 4s-orbital.
Umhil
The effective nuclear charge on the 4s-electrons does not change drastically. The
exceptions in the transition metals are also due to half-filled and filled d-shell wc!
@h
stability.
N
,r!ffi
Ionization energy may be used to predict the oxidation and reduction potentials
of an atom. The easier it is to ionize an atom, the easier it is to oxidize that atom
by one electron. This leads to a larger (more positive) value for the oxidation -h
potential. A low ionization energy for an atom correlates to a smaller (or more mm
negative) value for the reduction potential of the cation that is formed. ittti@
,dli"
Example 2.18
\Alhy is the ionization energy of beryllium greater than the ionization energy oi
lithium?
A. Be has a larger principal quantum number than Li.
B. Li has a greater density than Be.
C. Be has a larger effective nuclear charge than Li.
D. Li has a bigger proton count than Be.
Solution
Both beryllium and lithium have their last electron (the electron lost upon
ionization) in a 2s-orbital. This eliminates choice A, because the principle
quantum number (valence shell) is the same for both. Lithium is less massive
and larger than beryllium, so it is less dense. This eliminates choice B. Lithiu:r
has three protons, while beryllium has four, so choice D is a false statement,
Only choice C remains. The difference between lithium and beryllium lies in the
effective nuclear charge. The beryllium nucleus has four protons, while the
lithium nucleus has only three protons. The greater number of protons increases
the attractive pull on the electron. Because the pull is greater, the effectir-e
nuclear charge is greater. The greater the effective nuclear charge, the greater the
ionization energyi therefore beryllium has a greater ionization energy thar
lithium, because it has a greater effective nuclear charge than lithium.
The MCAT test writers design questions to encompass logical analysis. To test a
concept and generate the illusion of unfamiliarity, they can make subtle change=
to a question. The second ionization energy can be tested in a questior:.
Consider the periodic trends for elements, but remember that when you evaluale
ions, reading from the periodic table does not always give the right answer.
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General Chemistry Atomic Theory Periodic Ttends
Example 2.19
:{ow does the ionization energy of sodium compare to the ionization energy of
nagnesium?
1. Na has a greater ionization energy, because it has the greater effective
nuclear charge.
B. Mg has a greater ionization energy, because it has the greater effective
nuclear charge.
C. Na has a greater ionization energy, because it has the greater electronic shell.
D. Mg has a greater ionization energy, because it has the greater electronic shell.
S olution
.:.:s is just a simple case of reading from the periodic table. Both magnesium
:--.1 sodium are in the same period (third), so they have the same valence shell.
':-s eliminates choices C and D. The element that is furthest to the right in the
:=::.odic table is magnesium, so magnesium has the greater ionization energy.
-:.oice B is the best answer, because Na and Mg are in the same row of the
:'=::odic table, where effective nuclear charge is the reasoning behind periodic
: -::erences.
lnmple 2.20
-,:-,.'- does the second ionization energy of sodium compare to the second
::zation energy of magnesium?
I-. \a has a greater second ionization energy, because it has the greater effective
:,uclear charge.
\1g has a greater second ionization energy, because it has the greater
.if ective nuclear charge.
\a has a greater second ionization energy, because it has the smaller
.lecfronic shell.
- \lg has a greater second ionization energy, because it has the smaller
:lecfronic shell.
:.:,ution
-". second ionization energy is the energy associated with losing the second
, :-::orr, which takes the element from +L to +2. For sodium, an octet is obtained
" .:sLng the first electron, thus the second electron lost drastically destabilizes
."
= =lectron cloud. This makes the second ionization energy very high. For
:: =.esium, an octet is obtained by losing the first and second electrons, thus the
,,'-,:,d electron lost stabilizes the electron cloud. This makes the second
: -ation energy very low for magnesium, eliminating choices B and D. Because
' . ::e talking about shell stability, the best (albeit not perfect) answer is choice
Na+ -------+ Na2+ Mg* Mg2*

622"22O6 1"21s22ps 1"22"22'.69s1
-> 1s22s22p0
*'"
. .-ectronic configurations show that sodium loses octet stability upon its
, .: i ionization, while magnesium gains octet stability upon its second
"-.ion.
..king about the second ionization energy, the concept rather than the
:::ization of periodic trends is tested.
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General Chemistry Atomic Theory Periodic Tfends
Electron Affinity
Electron affinity measures the tendency of an element to gain an electron. It is a
measurement of the energy absorbed or released when an electron is added into
the valence shell. Electron affinity can be either negative or positive, meaning
that gaining an electron can be either exothermic oiendotherrnic. The generii
reaction for electron affinity is shown below, where E represents any elemfnt:
E(g) + e- E-(s)
--+
Figure 2-27lists the electron affinity for the first twenty elements in the periodic
table. Within a row in the periodic table, electron affinity correlates with atomic
number, but there are some extreme spikes in the trend.
CJ
J(
x
o
ti
U
CJ
I!
-100
-725
-150
-175
-200
-225
-250
-275
7 8910ltL213
Atomic Number
Figure 2-27
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General Chemistry Atomic Theory Periodic lfends
The biggest deviations are attributed to the stability associated with a filled s-
shell. The graph may seem confusing at first, because the lowest numbers have
'Jre greatest electron affinity. The numbers listed are energy released upon
:aining an electron, so a negative number refers to an element with a high
rlectron affinity. The sudden increase in electron affinity (energy released upon
an electron) from Be to B, Mg to Al, and Ca to Ga is attributed to the
=aining
-rstability of one electron in the p-level. For instance, upol gainilS 1n electron,
:re electionic configuration of Mg goes from 1s22s22p63s2 to 1's22s22p63s23p1,
.'hich creates a new energy level, and is unfavorable. Upon gain{g a-n electron,
--.e electronic configuration of Na goes fromLs22s2zp6ZJ
to 1's22s22P63s2, which
i-Js the s-shell and generates stability. From element 21 to element 30, electron
::f,nity is erratic, because the d-shell stabitity is changing. No trend for electron
-:inity is evident in the transition metals.
-:ke ionization energy, the energy associated with electron affinity depends on
re attraction of an electron to the nucleus, its distance from the nucleus, and the
-:ability of its electronic configuration. Because several factors influence electron
.--irLity, the trend across a period is erratic. In general, an element releases more
::.ergy upon gaining an electron as you move left to right in the periodic table.
-r:astic exceptions occur when there is half-filled stability of the energy level and
:-en there is an s2-shell. In general, an element also releases more energy upon
:,iing an electron as you ascend a column in the periodic table. This is because
,, the number of electronic shells decreases, the new electron is closer to the
- ::leus, and thus the attraction to the nucleus increases.
-:r.ample 2.21
-:.t electron affinity of an element is MOST similar to which of the following
::-:erties?
l" Electronegativity
l lonization energy
: Cxidation potential
l, Reduction potential
: : Xution
-- electron affinity for an element measures the energy associated with the gain
=
: re electron. Choices B and C are out, because both of them deal with losing
.: =-ectron. Electronegativity is not the best choice, because it deals with the
r" r:ng of electrons in a bond, not the gaining of an electron. The best answer is
:.r" : -;e D, reduction potential, because reduction is the gain of an electron. An
, s:..flt with a high reduction potential has a high electron affinity.
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:
Wm
Electronegativity
Electronegativity is a measure of an atom's tendency to gain and retain an fu@
electron from a neighboring atom within a bond. It is formally defined as the tu

ability of an atom to attract towards itself the electrons in a chemical bond. &
Electronegativity is related to both ionization energy and electron affinity. This
is to say that the electronegativity of an atom depends on both the electron
affinity and ionization energy of that atom. Linus Pauling generated a method to
measure electronegativity, and created a scale, referred to as the Pauling scale.
Electronegativity is measured on a relative scale, with the values measured from
the electron distribution within a bond. The standards are 0.9 for sodium and 4.0
for fluorine, and all other values are based on dipole moments associated with
bonds to these atoms.
The electronegativity of an atom increases as the periodic table is ascended,

because as the number of electronic shells decreases, causing the attraction to the 1-
nucleus to increase. The electronegativity of an atom increases as the periodic mr

table is scanned from left to right, because the effective nuclear charge increases. m
The trend in electronegativity is very clean, showing no exceptions. Figure 2-28
reflects these trends.
/t"
l"
o,
4.0 m
3.8
fid
3.6 mm
3.4 dW
4!1h
3.2
rfu
3.0 rilitu
2.8
@'r
,ffi
2.6
h
b z.+ &
'E ))
(d -'-
bo
20
H
!U 1.8
E 1.6
1..4
1.2
1.0
0.8
0.6
0.4
0.2
1. 2 3 4 5 6 7 I 910 11 12 1,3 14 15 16 17 1.8 19

Atomic Number
Figure 2-28
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General Chemistry Atomic Theory Periodic Tlends
\Alhen the electronegativity values of the two atoms within a bond are close, the
bond is covalent. When the electronegativity difference exceeds 2.0, then the
bond is ionic. Figurc 2-29 represents the electron clouds and shows the relative
electronegativity of the atoms involved in an ionic bond and a covalent bond.
Unequal sharing Relatively equal sharing

(AEneg =2.1, :. the bond is ionic) (AEneg = 1.0, .'. the bond is covalent)
Figare 2-29
Example2.22
:lectronegativity difference between bonded atoms is BEST determined by:
.\. measuring the bond length.
B, measuring the dipole moment.
C. calculating the difference in electron affinity between the two elements.
D. calculating the difference in ionization energy between the two elements.
Solution
iecause electronegativity measures the tendency to share an electron, and the
' pole moment represents the degree of sharing between two atoms in a bond,
-.e best answer is choice B. Electronegativity is related to both electron affinity
.:-C ionization energy, so electronegativity can be estimated knowing both
,:-ization energy and electron affinity, but not just one of them. Choices C and
I are eliminated, because you need both to approximate the electronegativity
::-'ierence. Choice A is eliminated, because bond length dictates bond strength,
: -t not necessarily the relative electronegativity. This question may
'âllenging, because the terms are interconnected.
seem
:'tample 2.23
l-.e lrend in electronegativity increases with which of the following?
r. Ionization energy
I -{tomic radius
- -\tomic number
l, Number of valence electrons
::lution
-- . question is close to verbatim in reproducing a question from a recent MCAT
: :3. Electronegativity follows a cleanly predictable trend, so choice A is
, -::unated, because ionization energy follows an erratic trend. Electronegativity
r- :reases as atomic radius decreases, so choice B is eliminated. Increasing atomic
'-::.ber sounds tempting; but when a new shell is formed, electronegativity
-:s, while atomic number increases. This can be seen in going from fluorine to
:.--
";-:. to sodium. This eliminates choice C. As the number of valence electrons
-" :::ases, we are moving from left to right across a period of the periodic table.
-- ::easing valence electrons does not affect shells. From left to right in a period,
.":::onegativity increases. This makes choice D the best answer.
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General Chemistry Atomic Theory Periodic ltends
Periodic Families (Groups)

Columns in the periodic table (families) contain elements that have the same
valence electron count and thus show similar chemical reactivity. They are
referred to as groups of elements. some of the groups you should know aie the
alkali metals (first column of H through Fr), the alkaline earth metals (second
column of Be through Ra), the chalcogens (sixth column of o through po), the
halogens (the seventh column of F through At), and the noble gases (last column
of He through Rn). The last column of elements is observed to be generally non-
reactive. They are the inert gases. we shall address the general properties of
each group, without emphasizing trivia. The MCAT test-writers often mislead
you with trivial information in the passage. It is up to you to recognize the trivia.
Alkali Metals (Group I)

Alkali earth metals are in the first column of the periodic table. Included are
lithium, sodium, potassium, rubidium, cesium, francium, and to some extent
hydrogen. Hydrogen can act as both a halogen and an alkali metal. The
couunon feature is that their valence shell is ns1, where n is any integer greater
than one. As neutral elements, they are strong reducing agents, because they
readily lose an electron to become a +1 cation with a filled octet. They are some
of the strongest reducing agents (most favorably oxidized). They react with any
compound or element that has a high electron affinity. Their reactivity increases
as you descend the column, mostly because it is easier to lose an s-electron from a
shell that is further out (greater n quantum number). Their cation form is very
soluble in water with almost any anion.
All alkali
metals react favorably with water to form the metal hydroxide and
hydrogen gas. Reaction 2.1 is the generic reaction:
2M(s) + 2H2O(g) 2MOH(aq) + Hz(g)

---+
Reaction 2.1
The oxides they form are variable with the metal. Lithium forms an oxide (MzO),
sodium forms a peroxide (MzOz), and potassium, rubidium, and cesium f
superoxides (MOz). Reactions 2.2, 2.3, 2.4, 2.5, and 2.6 show the oxidati
reactions of the alkali metals:
4 Li(s) + Q(g) 2Li2O(s)

-----+
Reaction 2.2
2 Na(s) + Oz(g) Na2O2(s)

----+
Reaction 2.3
K(s) + Oz(g) + KO2(s)
Reaction 2.4
Rb(s) + Oz(g) + RbO2(s)
Reaction 2.5
Cs(s) + Oz(g) + CsO2(s)
Reaction 2.6
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General Chemistry Atomic Theory Periodic lfends
Besides reacting with oxygen, alkali metals are oxidized by halogens, nitrogen,
nd hydrogen. Reactions 2.7,2.8, and2.9 are a sampling of these reactions.
6l,i(s) + Nz(g) 2Li3N(s)

Reaction 2.7
2 Na(s) + HzG) 2 NaH(s)

-->2.8
Reaction
2Cs(s) + Br2[) 2CsBr(s)

Reaction 2.9
Lxample 2.24
',l:rat happens to sodium metal when it is added to water?
{.. It is oxidized to yield sodium hydroxide, which is insoluble in water.
B It is oxidized to yield sodium hydroxide, which is soluble in water.
:. It is reduced to yield sodium hydride, which is insoluble in water.
D" It is reduced to yield sodium hydride, which is soluble in water.
r'olution
--: shown generically in Reaction 2.1, a metal hydroxide is formed upon addition
-: an alkali metal to water. Because sodium is going from neutral to +1 when
-,sng an electron to oxygen, sodium is oxidized. This eliminates choices C and
-- You may recall from your acid-base chemistry experience that sodium
:roxide is a strong base, and it readily dissociates in water. This makes NaOH
.
.:",. soluble in water. The best answer is choice B.
4,&aline Earth Metals (Group II)

*;aline earth metals are metals from the second column of the periodic table.
*-:,uded are beryllium, magnesium, calcium, strontium, and barium. Most
:,::-.-llium complexes are covalent in nature. The common feature is that their
:-'nce shell is'.rr2, where n is any integer greater than one. As neutral elements,
:':,.- are strong reducing agents, because they readily lose two electrons to
: tr": rme a +2 cation with a filled octet. However, they are not as reactive as alkali
: =:als. Like alkali metals, they are strong reducing agents. They too react with
L:',- compound or element that has a high electron affinity. Their reactivity
i: ::eases as you descend the column, because the first and second ionization
,:=:gies both decrease. Their cation form is not as soluble in water as are the
.-" rli metals, primarily due to their +2 charge and smaller radius.
--.ratrine earth metals, except beryllium, react favorably with water to form a
::::a1 hydroxide and hydrogen gas. Reaction2.l0 is the generic reaction:
M(s) + 2 H2O(g) ------'> M(oH)2(aq) + HzG)

Reaction 2.10
-:: alkaline earth metals all form oxides (MO) when oxidized by oxygen gas.
-:= generic reaction is shown in Reaction 2.11.
2M(s)+Oz(g)+2MO(s)
Reaction 2.1L
t07 Dxclusive IICAT Preparation

General Chemistry Atomic Theory Periodic T?ends
Besides reacting with oxygen, alkaline earth metals can also be oxidized by
halogens, nitrogen, and hydrogen. Reactions 2.I2, 2.I9,2.I4, and 2.1.5 arc a
random sampling of these reactions:
Mg(s) + 2 HCI(aq) ----+ MgCl2(aq) + Hz(g)

Reaction 2.L2
3 Sr(s) + 2 N2(g) ---'- 2 Sr3N2(s)
Reaction 2.13
T
Be(s)+Hz(g)+ BeH2(s)
Reaction 2.L4
0
Ba(s) + I2(g) -+ BaI2(s)

x
Reaction 2.15 "I
it
Chalcogens (Group VI) lil
Chalcogens are metalloids and non-metals from the sixth column of the periodic
rH
table. Included are oxygen, sulfur, selenium, tellurium, and polonium. Oxygen,
W
sulfur, and selenium are non-metals, while tellurium and polonium are
metalloids. The common feature is that their valence shell is ns2np4. They form
s
several covalent molecules with non-metals. As neutral elements, they are
oxidizing agents, because they gain two electrons to become a -2 anion with a
,{
filled octet. However, their reactivity decreases as you descend the column,
,0
because the first and second electron affinities are not as great. They are often
r@
insoluble, although it varies with their counterion (cation). Oxygen exists as a
rS
diatomic molecule (O), sulfur and selenium exist as octatomic molecules (sg and
dt
Se6), and tellurium and polonium exist in vast molecular matrices.
D
Halogens (Group VII) di
Halogens are non-metals from the seventh column of the periodic table. #
Included are fluorine, chlorine, bromine, iodine, and astatine. The common
feature is that their valence shell is ns2np5. They form covalent molecules with
non-metals and ionic compounds with metals. As neutral elements, they are
strong oxidizing agents, because they readily gain an electron to become a -1
anion with a filled octet. However, their reactivity decreases as you descend the
column, because the electron affinity is not as great. They are often soluble"
although it varies with their counterion (cation). They all exist as a diatomic
molecules (X2), although little is known of astatine due to its radioactivity.
Noble Gases (Group VIII)

Noble gases are non-metals from the eighth (and last) column of the periodic
table. Included are helium, neon, argon, krypton, xenon, and radon. The
common feature is that their valence shell is complete at ns2np6. For the mosl
part, they form no bonds and exist as monatomic atoms. Thanks to the work of
Neil Bartlett of U.C. Berkeley, xenon and krypton are known to form compoun&
with halogens. The compounds with fluorine show more electron densitn
around fluorine, implying that fluorine is more electronegative than either xenor"
or krypton.
Copyright @ by The Berkeley Review loa The Berkeley Reviw

General Chemistry Atomic Theory Light Absorption and Dmission
l..i$hfi ii1ffi il#ufi#ftndfi r.i'ffi diliibmission

Excitation and Relaxation
It requires energy to ionize an atom, because one of its electrons is removed from
a stable environment and placed into a less stable environment. However, when
a quantum of energy less than what is required to ionize the element is absorbed
bv the element, then an electron can be excited to a higher energy state (known as
an excited state). Different forms of energy may be absorbed to excite an electron
-rp to a higher energy level. For instance, heat energy can be absorbed to excite
:eleased as a photon. This is seen with fireworks. Some different forms of

.nergy include light energy, thermal energy (usually vibrational kinetic energy),
nechanical energy (usually translational kinetic energy), and electrical energy. It
-. important to consider different energy forms, because there are many things
:apable of absorbing one form of energy and emitting a different form.
:.!:sorption (Excitation): The gain of energy by an element or molecule, resulting

-:r the excitation of an electron from a lower energy state (often the ground state)
: r a higher energy state (an excited state). The form of energy absorbed can vary.
:.,tission (Relaxation): The loss of energy by

an element or molecule, resulting in
--:.erelaxation of an electron from a higher energy state (which must be an excited
':ate) to a lower energy state (which can be the ground state or another excited
':ate,
but of lower energy). The form of energy emitted can vary.
a3sorption of energy is defined as any process in which a photon is absorbed by

: compound to excite an electron in the compound to an elevated electronic
::.ergy level (excited state). This means that the electron goes to a higher energy
,:ite. The period of time that the electron remains in this elevated energy level is
:=ferred to as the lifetime of the excited state. A compound can store energy by
:-aintaining a high population of electrons in elevated energy states. When the
.-=ctron relaxes back down to the ground state, energy is emitted in the form of a
::.oton. Absorption and emission are therefore opposite processes. Figure 2-30
:ro\vs the absorption and emission processes for a theoretical pair of energy
.-,'els. Because the energy levels are equal, the energy of the photon absorbed for
- ,:itation is equal in energy to the photon released upon relaxation.
:rcited state Excited state
r,r'absorbed Electron excites Electron relaxes

hv emitted
up to a higher down to a lower
ANNA,> energy level energy level
..,AAAAA
I
I
,:ound state I
Ground state
{bsorption (Excitation) Emission (Relaxation)
Figure 2-30
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General Chemistry Atomic Theory Light Absorption and Dmission j
q qir generic example, the energy of the photon absorbed is equar to the energy d
of the photon emitted. In actuality, there is more than one singular energv level ffi
for the ground state and the excited state due to the coupling of electricafenergy s
levels and rotational energy levels associated with the atom. Transitions involve d
a change in electronic state as well as a change in the rotational energy of the
W
atom. hr molecules, there are vibrational energy levels to consider, in addition to ffi
the rotational and electronic energy levels. The result is that the ground state and iin
excited state exists as a band of energy levels, not a single level. This means that ffim
multiple possibilities exist for the energy of transition. Rather than a single line &
absorption or emission spectrum being formed, a range is formed. This is why
"hi
Figure 1-2is abroad peak and not a sharp line. Figure 2-31 shows different types ffim
of emission and absorption spectra where the color range is shown. Absorption tu
spectra show all light except what was absorbed, which appears as a black line, ffi
due to the absence of light. They are black lines in a rainbow. Emission spectra tu
show only the emitted light. They are colored lines against a dark background
(due to only selected frequencies being emitted). They are stripes of color.
Wavelength
Emission spectra
Wavelength
Figure 2-31
The lifetime of an excited state is often in the picosecond to nanosecond range, ss

the interval of combined excitation and relaxation is very fast. The conversicm
between energy forms is exploited in many devices. Incandescent bulbs
thermal energy resulting from the resistance associated with electrical flow and
emit light energy (although some energy is dissipated in the form of
through conduction and convection). The operation of tube lighting involves thi
conversion process. Plate charges build up at each end of the tube, creating
electric field. A cation in the gas tube is accelerated by the electric force. as
collides with other gas molecules, its kinetic energy is transferred to the
molecule, which absorbs the energy to excite an electron. Upon relaxing,
energy is released as light. In reality, the tubes must run on alternating
(AC), so that the cation never reaches a plate. This is why tube lights, such
fluorescent tubes, are actually high-frequency strobe lights.
Copyright @by The Berkeley Review llo The Berkeley

General Chemistry Atomic Theory Light Absorption and Emission
Atomic Spectrum of Hydrogen

Hydrogen is the most studied element in terms of its absorption of light.
separate samples of hydrogen gas exhibit exactly the same emission ind
absorption spectra. This repeatability of a spectrum is attributed to the
quantization of the energy levels. what is meant by "quantized energy levels" is
that the absorption and emission of light by hydrogen occurs in distinct
jncrements. Because hydrogen has distinct energy levels, it also has
distinct
lransitions between energy levels, so that photons of the same frequency are
absorbed by all hydrogen molecules. However, with the large numbei of energy
ievels, there are several transitions that are possible. For hydrog"n, gtonpr -of
lransitions are named for the energy level to which they relax. For instance, all
transitions down to the n = 1 level fall into the Llrman series and emit phoions in
-\e ultraviolet region of the EM spectrum. The energy levels and transition series
:or hydrogen are shown in Figure 2-32.
aE6-? =-he-
Le-z
AE". =b
hs-z
AE,^= hc
lt".+-z
n=2 68, " --he-

Lg-z
n=1
Figure 2-32
l--: series are named for electronic transitions within hydrogen alone. only the
::-rner series emits photons in the visible range. when a sample of hydrogen
i---",-S, it is because electrons are relaxing down to the n = 2level, which is stilian
',::ted state. Figure 2-33 shows the line spectrum associated with the Balmer
-J--.
'E- -t>.
Balmer series emission spectrum
lLl
l"s .z Lz-z Lo_z \s_z \+_z
Wavelength.----.>
Figure 2-33
lll Exclusive MCAT Preparation

The Balmer series emits photons in the visible range. In the Balmer series, 7q_2is
656 nm and 4.6-2is 410 nm, so they fall in the visible range of the spectrum. This
also means that x4-2 and 1,5-2 fall in the visible range. The Faschen series
involves photons in the infrared region of the EM spectrum. The Brackett series
involves photons in the low infrared and microwave regions.
Example 2.25
Given that 1"3-2 is 656 nm, which of the following is NOT true?
A. All Balmer series transitions are less than 800 nm.
B. All Lyman series transitions are less than 400 nm.
C. The lowest energy Paschen transition is greater than 800 nm.
D. The highest energy Brackett transition is less than 800 nm.
Solution
This requires looking closely at Figure 2-32. Transitions to the n=2 level fall into
the Balmer series. The lowest energy transition in the Balmer series is from n=3
to n=2 and is given as 656nm. All other transitions in the Balmer series are more
energetic, so these transitions emit photons with a wavelength less than 656nm.
Choice A is a valid statement. Transitions to the n=1 level fall into the Lyman
series. The lowest energy transition in the Lyman series is from n=2 to n=1, and
it is of significantly higher energy than the n=- to n=2 transition. This means
that all photons in the Lyman series are of higher energy and lower frequency
than the transitions in the Balmer series. According to Figure 2-33, the Balmer
series emits photons near 400nm, so transitions in the Lyman series emit photons &
with a wavelength less than 400nm. Choice B is a valid statement. Transitions to fr[m
the n=3 level fall into the Paschen series. The lowest energy transition in the @
Paschen series is from n=4 to n=3, and it is of significantly lower energ'y than the @
n=3 to n=2 transition. This means that the lowest energy photon in the paschen ffii
series is of lower energy and higher frequency than the transitions in the Balmer 0mk
series. The Balmer series emits a photon at 656nm, so the lowest energy he
transition in the Paschen series emits a photon with a wavelength greater than @mrfrc
656nm, and according to Figure 2-32, higher than 800nm. Choice C is a valid lflutilIli
statement. Transitions to the n=4 level fall into the Brackett series. The highest tu
energy transition in the Brackett series is from n=* to n=4, and it is of much -dtmme
lower energy than the n=3 to n=2 transition. This means that the highest energ'y ,iilMe I
photon in the Brackett series is of lower energy and higher frequency than the aflft a
transitions in the Balmer series. The Balmer series emits a photon at 656nm, so rrmq
the lowest energy transition in the Brackett series emits a photon with a
wavelength greater than 656nm, and according to Figure 2-32, higher than liH
800nm. Choice D is an invalid statement, and thus is the correct answer choice. -ire
ffiu'cq
'mf F,i
Electromagnetic Spectrum @-
Photons have associated with them a distinctive frequency, energy amount, and
wavelength. The relative energetics of various radiation must be known. If you
'rruiil
ever have difficulty recalling the electromagnetic radiation spectrum, think about
the fact that you wear sunglasses to protect your eyes from ultraviolet radiation,
not visible radiation. This means that ultraviolet radiation is of higher energy
than visible light. Also, lead shields are used to filter out x-rays, so they must be
:he
of even higher energy than ultraviolet photons. Conversely, we are fairly safe lnEle
from radio waves considering the fact that millions of radio waves pass through ;r:n
us every second. Common sense can be applied to recall the relative spectrum.
r0Et
Table Z.Alists the conunon EM ranges in terms of frequency and wavelength.
'lFr
Copyright O by The Berkeley Review tt2 The Berkeley Review \-o[T
General Chemistry Atomic Theory Light Absorption and Dmission
EM Radiation Wavelength (m) Frequency (Hz) Common Usage

Cheaper radio
AM to3 - to4 105 to 106
communication
Expensive radio
FVI t-702 107 to to8
communication
Satellite, cell phones,
\'{icrowave 10-4 - 1 168 1o 1612
radar, heating water
Line-of-sight com,
lnJrared 10'6 - 1o-3 1611 1o 1614
molecular ID, heat
Vision, fiber optic
|isible 4 xLo-7 -7 x1o-7 4.3 x 1.014 - 7.5 x1014
communication
Bond-breaking,
L-llraviolet rc-8 - rc-7 1615 1o 1616
exciting electrons
Nucleus detection,
\-ray 19-12 - 1g-8 1616 1o 1620
core e- ionization
giiTIITt? Nuclear excitation,

16-15 - 161-10 1918 1o 1923
world destruction
Table 2.4
- : lrmon practical uses of EM radiation are something that should be learned,

:':*ause of the tradition of test writers asking about such devices. It should be
::-l:r:Lon knowledge that radio waves and low-energy microwaves are used in
,:::.nunications. Microwave communications include satellite transmissions,
:::Le television, cellular phone networks, and airport landing systems.
l-::orvaves are also used for cooking and heating things that contain water,
:,::ause the frequency required to rotate a water molecule is found in the
:r::owave region. Remote control units (also known as line-of-sight
-::rnunicators) often use infrared signals to send information. The frequency of
:. E\{ radiation used in these common tools and appliances to which we are
:-:.ctly exposed cannot be near !700 cm-1,3000 cm-1, oi SSOO cm-1, because those
,:=
=e bond-stretching frequencies associated with molecular bonds common to
'.* :limal life. Ultraviolet light is used to break bonds, and x-rays are used for
-: : grng atomic structure (including bones and teeth).
,''oible Spectrum and Colors
-. ,= ','isible spectrum runs from red (around 700 nm), orange, yellow, green, blue,
:::':gh violet (around 400 nm). The relative wavelength, frequency, and energy
: ::.otons in the visible spectrum of light (by decreasing wavelength, increasing
::::-;ency, and increasing energy) is given in Figure 2-34.
Red
-.':.-627nm 627 lo594nm 594to561 nm 56L1o477nm 477to438nm 438to400nm
)
Figure 2-34 +?-
*-
= order of the colors of the visible spectrum is often recalled using the
r: r:ronic ROY G. BiV, an acronym for the spectrum of visible light in sequence
: :.:reasing energy. It is also important to know that the visible range of light is
::::. approximately 700 nm for red light to approximately 400 nm for violet light.
- -::,,-iolet spectroscopy ranges from 20 nm to 400 nm.
l16 Dxclusive MCAT Preparation

General Chemistry Atomic Theory Light Absorption and Emission I
T
Example 2.26 j
For some substance X, AE1 yields yellow light, while AE3 yields blue light. \Alhat
, ( .--, must be true of the photon associated with AE2? ":ii
' ;
Yl(
tr{\ '' 4' A. It is probably orange. -:I
B. It has a wavelength of 700 nm. r
C. It is probably green. j
D. It has a wavelength of 400 nm.
lii
Solution JL
AE2 falls between AE1 and AE3, so the photon emitted must be between yellow lfr!
and blue light in the visible spectrum. According to the spectrum mnemonic M
(ROYGBiV)/ green light falls between yellow light and blue light. This eliminates tu
choice A and makes choice C the best answer. A wavelength of 200 nm
corresponds to red light, and a wavelength of 400 nm corresponds to violet light,
eliminating both choice B and choice D.
Color is a phenomenon associated with vision. Light in the 400 nm to 200 nm

range can be detected by the eye and processed in the brain. Color is the result of
light within this range being absorbed by the cones of the eye. Rods also detect
light (in the green range), but this is for the purpose of intensity analysis of
details in the image. Consider the eye to function like a visible light
spectrophotometer, analyzing stimuli for intensity and wavelength. There are
three kinds of cones, each one responsible for detecting different frequencv
ranges of light. Color, in a photon sense, can result from one of two phenomena.
Color is perceived from either the emission of light at a specific frequency or the
reflection of light at a specific frequency. Hence, there are two types of color to
consider: emitted and reflected.
Emitted Color
Colors is emitted from a source that radiates visible photons. Atoms emit light
energy when an electron relaxes from an excited state to a lower level. Figure 2-
35 illustrates the concept of emitted color.
ssg
Figure 2-35
An electron relaxes from an excited state and releases a photon of some

wavelength. All of the photons in Figure 2-35 are of essentially the same
wavelength. The color that is observed is the color emitted. Simply put, witL
emitted color, "What you get is what you see." Emitted colors can be seen at
night, because their source is emitting light. A good test to determine whether a
color is an emitted color is to ask whether it can be seen in the dark. If the
answer is yes, then it is an emitted color. Examples of emitted light sources
include: neon light tubes, television screens, fireworks, and glow-in-the-dark ink.
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Reflected Color and the Color Wheel

Reflected colors are produced when incident light (we'll consider it to be white
1ight, for the sake of simplicity) strikes a surface, and the surface absorbs certain
trequencies, thus reflecting only a portion of the incident light to the eye. The
reflected radiation appears as a color that is a combination of the reflected
photons. The color we observe is the complementary color of the frequency that
had the highest intensity of absorption. This is where the color wheel can help.
Complementary colors are on opposite sides in the color wheel. Given that white
-ight is a combination of all colors, it is a combination of all complementary pairs.
This is a over-simplification, because the primary colors of light are different
nom the primary pigment colors, but we shall use the two interchangably to aid
n answering chemistry questions. Complementary pairs include red and green,
:lue and orange, and yellow and violet. A color wheel is shown in Figure 2-36.
The color wheel is used to determine complementary

colors. Red and green are opposing on the color wheel,
so they are complementary colors. Moving around the
wheel, violet is the complementary color of yellow
and blue is the complementary color of orange.
Figure 2-35
-hJorophyll appears green in the presence of white light. The conclusion is that
Sorophyll contains a pigment that has a maximum intensity absorbance of red
:Eht, the complementary color of green. One type of chlorophyll has an
rrsorbance maximum at740 nm, while another has an absorbance maximum at
:,50 nm. Both of these values correspond to red light. Figure 2-37 illustrates the
::ncept of emitted color as it relates to chlorophyll.
Incident Reflected color

white light (appears green)
red)
(absorbs red) I,out = 700tnm
Figwe2-37
Let'lected colors can be seen only in the presence of an extemal light source. If a
-:,lor cannot be seen in the dark, then it is a reflected color. Examples of reflected
-f,ht sources include paint pigments, pen inks, and fabric dyes.
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Example2.27
\A/hich of the following statements is NOT true?
A. A yellow paint pigment absorbs light with a Imax of 411 nm.
B. A green light bulb emits light with a l.-u* of 522nm.
C. A blue shirt has a dye that absorbs light with a fmax of 611 nm.
D. A television screen glowing violet emits light with & Imax of 573 nm.
Solution
This question entails comparing reflected and emitted colors. The first thing you
should ask yourself is whether the color can be seen at night. If the answer is yes, l
then it is an emitted color and what you see is the color involved in the electronic :
transition (emission). If the answer is no, then it is a reflected color and what you {
see is the complementary color of the light involved in the electronic transition
(absorption). Choice A is a paint pigment, which cannot be seen at night. The
yellow color is a reflected color, so according to the color wheel, violet light has i
been absorbed. Violet light has a wavelength near 400 nm, so choice A is valid. :
Choice B is a light bulb, which can be seen at night. The green color is an emitted T
color, so green light has been emitted. Green light has a wavelength between 561 L]il|
nm and 477 nm, so choice B is valid. Choice C is a fabric dye, which cannot be t
seen at night. The blue color is a reflected color, so according to the color wheel, {
orange light has been absorbed. Orange light has a wavelength between 627 nm e
and 594 nm, so choice C is valid. Choice D is a radiating screen, which can be
seen at night. The violet color is an emitted color, so violet light has been :xf1
emitted. Violet light has a wavelength near 400 nm, so choice D is invalid, anc T1
thus the best answer to this question.

h
The absorption of energy followed by the emission of a photon of light is a usef'ti

principle that can be applied to many forms of spectroscopy, including infrared
spectroscopy, in organic chemistry to identify bond types and functional groups.
It is also involved in UV-visible spectroscopy, where a compound is subjected tc
incident light at a specific frequency, and the relative intensity of transmitted T'
light is measured. Conclusions about the concentration and the kind o: c
compound itself can be inferred from the results. Classical experiments tha:
involve measuring quantities of components in a gaseous mixture often focus or. 8llrf,
analysis of the emission and absorbance spectra of the gases. This is at the hear: TU
of atomic absorption spectroscopy, used to analyze planetary gases. ilmlr
,ltoiill
The MCAT is not printed in color, so questions involving color will preser,l sg
numerical data for wavelengths or graphs of absorbance spectrum. Figure 2-35
shows an absorbance spectrum and its analysis. .,Jl|*i
dh
@tu
l,*u* is the wavelength at the greatest kqr

CJ
U Abs = absorbance. A Iô" at 520nm means that
yellow light is absorbed, so the compound
-o
L appears violet to the human eye.
o
th
-o
520 Wavelength (in nanometers)
Figure 2-38
Copyright O by The Berkeley Review l16 The Berkeley Relieu

Fluorescence .
Fiuorescence most simply understood is the conversion of ultraviolet light into
visible light. A material with a semi-stable excited state can absorb an ultraviolet
ohoton, relax a slight amount giving off infrared photons, and then relax
completely back to its original state. The visible photon emitted is of slightly less
energy than the ultraviolet photon absorbed, because of the loss of energy when
:he infrared photon was lost. The next energy range down from ultraviolet is
,.'iolet light in the visible range. This is why fluorescing materials appear purple.
The term "black light" refers to an ultraviolet light (it emits light outside of the
-.-isible range) that when shined upon fluorescing material appears purple. You
:ray have seen this in organic chemistry lab when you analyzed tlc plates. This
:oncept does not need to be interpreted at any higher level, so this rough
erplanation is adequate. Fluorescence will be addressed in a passage.
Photoelectric Effect
-he photoelectric effect is exactly what the name implies. An incident photon
:1uses the release of an electron. It is a fancy way of saying that a compound can
-: ionized with a photon, as long as the photon has energy greater than the
.:r:zation limit of the material. The energy holding the electron to the surface of
::te solid material is referred to as the binding energy. Excess energy (energy in
:,.cess of the binding energy) becomes kinetic energy for the electron that is
=::ritted. The photoelectric effect is really quite simple, but confusion sometimes
,:'qes from the different terminology used in chemistry and physics. Don't be
: - rled; just say no to physics (just kidding, but I'm a chemistry nerd and just had
:- say thet). Equation 2.9 is a physics equation for the photoelectric effect and
::uation 2.10 is a chemistry equation for the photoelectric effect. Both say the
: ii:'e thing, but use different symbols to do so.
hv =O + l*rr2 (2.e)
2
hv = B.E. + kinetic energy of emitted electron (2.10)
L-: photoelectric effect is the principle at work in solar panels. Photons of all
:-::erent wavelengths and energy are emitted by the Sun. This energy can be
. , -lected at the Earth's surface. Some solar photons are sufficiently energetic to
. ::i ar electron when they strike a metal surface. To do so, the photon must be
: rn energy high enough to remove the electron from the valence shell of the
:.:a1. The loss of an electron from the metal creates electrical flow (electricity),
:::h can be converted to either potential energy (stored in an electrochemical
: or mechanical energy (used to power a device).
-..-.:he energy of the incident photon increases, the kinetic energy of the
: r:rarged electron increases. Figure 2-39 shows an apparatus devised to
: : asure the photoelectric effect, while Figure 2-40 is a graph of the electron's
*-:ic energy as a function of the frequency of the incident photon.
- ::". right @by The Berkeley Review tt7 Exclusive MCAT Preparation
Incident beam of
Detector of KE
Battery Electric circuit
Figure 2-39
hv=hvo+KE"-
vo: threshold frequency
Frequency of incident photon (Hz)
Figure 2-40
The threshold frequency corresponds to the photon equal in energy to the
ionizing energy. Any photon with a frequency less than the threshold irequency
does not have enough energy to ionize the material, so no electron is ejected.
Example 2.28
which material probably has the LowEST threshold frequency for the
photoelectric effect?
A. Boron
B. Carbon
C. Sodium
D. Sulfur
Solution
The threshold frequency corresponds to the binding energy of the material (B.E
- hvo). Each atom holds onto its valence electrons with a different bind
energy, therefore each atom requires a different amount of energy to und
ionization. The lowest threshold frequency for the photoeiectric e
corresponds to the material that is easiest to ionize. This question is asking
the material with the lowest binding energy. of the choices, only one is a rrx
so only one has a low binding energy. The best answer is choice c, sodium.
answer corresponds with lowest ionization energy as well.
;rr-right Oby The Berkeley Review 1r8 The Berkeley

General Chemistry Atomic Theory Nuclear Chemistry
Nffin$ ::::ffieffi$ffi
Nuclear Particles
Simply put, nuclear chemistry is the chemistry that the nucleus of an atom can
r.rndergo. Instead of referring to it as reactiaity, it is referred to as instability of the
nucleus. The science community knows little of nuclear behavior at this point in
history, but there are theories. From our perspective, however, all we will
.oncern ourselves with is nuclear decay and nuclear capture. The process of
particle loss from the nucleus that results in a different nucleus is referred to as
nuclear decay. In physics, it may also be referred to as fission The process of
particle gain by the nucleus which results in a different nucleus is referred to as
ruclear capture. In physics, it may also be referred to as fusion. As a general
ru1e, particles with mass less than 55 amu undergo fusion, while particles with
mass greater than 56 amu undergo fission. Particles that we consider to be lost or
:ained are alpha particles (helium nucleus), beta particles (an electron), positrons
a positively charged particle with the mass of an electron), neutrons, and
:.eutrinos (an uncharged particle with the mass of an electron). The nucleus also
:.as ground states and excited states associated with it (just as the orbiting
:-ectrons have energy levels), so nuclei can also undergo photon absorption and
=:nission. The high-energy photon is a gamma ray. Table 2.5 lists some of the
:rlrunon nuclear processes. You should treat these reactions as exercises in
=-nple algebra. The total mass and number of protons should be equal on both
--les of the reaction. This is because mass and charge are conserved (along with
-romenfum) in each process.
Process Reaction Tracking Notes

The mass works: 720 = 4 + 176.
,:-Decay tSBx
-+ $u +r[fii The proton number works: 50 = 2 + 48.
The mass works: 120 = 0 + 120.
-Decay tBBx -+ le +rllz The proton number works: 50 = -1 + 51.
t38x -+ The mass works: 120 = 0 + 120.

. --Decay ?" * t?$q
The proton number works: 50 = 1 + 49.
* 138x" Mass and proton number do not change,

m1ss10n -+ hv + 1fr$x
The nucleus relaxes to emit a photon.
t!$x * $u -+1!$x The mass works: 120 + 4 = \24.

-r-Capture
The proton number works: 50 =2 + 48.
t38x *_roe The mass works: 720 + 0 = 120.

:-Capture +1lge The proton number works: 50 + -1 = 49.
t3$x The mass works: t20 + 0 = 120.

-Capture * le -+1!lz The proton number works: 50 + 1 = 51.
Mass and proton number do not change.
.-rbsorption t38x * rrv -+ 138X.
The nucleus absorbs a photon to excite.
Table 2.5
'* -iclear Decay and Capture

- :edvy element undergoes a decay process to increase its nuclear stability. A
,::.: element undergoes a capture process when struck by a high-energy particle
" stability. There are a few points you should note for these
':rcrease its nuclear
:: . :esses. With B-decay, the electron may or may not be added to the electrical
, "=,' of the atom. If it is, the atom remains neutral. If the electron escapes, the
- :'"'right @ by The Berkeley Review t19 Exclusive MCAT Preparation

compound becomes a cation. usually the particle escapes, and an ion is formed,
although we typically ignore this fact in nuclear chemistry. The representation of
the beta particle as having a -1 for its Z term is not accurate, but ii works for the
algebra of the equation. Beta capture and positron decay both result in the same
element being formed. Likewise, beta decay and positron capture both result in
the same element being formed. The positron behaves just as a beta particle
does, only it carries a positive charge and is an anti-electron. This makeJit anti-
matter, but for our purpose that doesn't matter.
The reactions in Table 2.5 are simplified. We have ignored conservation of

energy and conservation of momentum. To balance these more accurately, the
mass of the electron (beta particle) and positron (anti-electron) cannot be treated
as zero. A neutrino is required in some cases to balance the equation. Solving
decay and capture questions in the manner that these examples are presented
will work fine on test questions you may see. The questions you may see will
involve determining the particle that was lost in a process, or determining the
final elemental product after a nuclear reaction has taken place. It is sort of odd
that if you reverse the first two letters in nuclear chemistry the phrase becomes
unclear chemistry. Given the science community's level of understanding at the
present time, unclear is an accurate depiction of the subject.
Example 2.29
which of the following elements results from two consecutive alpha decays of
2I0 1.1z
4. 210p,
B. 2069i
C. 202y1
9. 202p;
Solution
Alpha particles are helium nuclei (alpha-helium sounds like alpha-helix, so
remember the phrase "alpha helium"). An alpha particle has a mass of 4 amu,
thus losing two alpha particles results in the loss of 8 amu. The element that
remains after two consecutive alpha decays has four fewer protons than the
original element (from 85 to 81) and has a mass eight less than the original
element (from 210 to 202 amu). At is element number 85, so the final element
must have atomic number 81. Consulting a periodic table shows that element 81
i" 11. 20211is the best answer, so pick C.
Example 2.30
Electron capture by a nucleus results in which of the following?
A. An increase in atomic number by one, and a mass increase of one amu.
B. An increase in atomic number by one, and no change in atomic mass.
C. A decrease in atomic number by one, and a mass decrease of one amu.
D. A decrease in atomic number by one, and no change in atomic mass.
Solution
Electron capture involves the gain of an electron by the nucleus. An electron
a -L charge and no mass. This means that the element should experience
decrease in its positive charge by one, and no change in its mass. This is
described in choice D.
Copyright O by The Berkeley Review 120 The Berkeley

Example 2.31
Which of the following processes would NOT result in the formation of tritium?
-{. Alpha decay of 7Li
B. Positron emission by 3He
C. Beta decay of 4He
D. Gamma emission from 3H
Solution
-\n alpha particle is a helium nucleus (4H"), so when 7Li loses a helium nucleus,
--he mass decreases by four to three and the number of protons decreases by two
to one. The final product is tritium 13H;. Choice A is valid. A positron is a mass-
iess positively charged particle that when lost, converts a proton into a neutron.
The mass remains the same, but the 3H" .onrr"rt into tritium (3H). Choice B is
valid. Beta decay involves the loss of an electron from the nucleus. This converts
a neutron into a proton. The mass does not change and thus remains at four.
The number of protons increases by one to three. The product is 4Li, which is
NOT tritium. The best answer is choice C. Gamma emission does not change the
particle, thus choice D is valid.
Example 2.32
L:i the conversion from 165go in157Gd,, at least two alpha particles were emitted.
What else was emitted?
A. A third alpha particle
B. One neutron
C. One beta particle
D. One positron
Solution
In converting from 1659e to 157Gd, the mass decreases by eight, which equates
to the mass of two alpha particles. This means that any other particles emitted
are massless. This eliminates choices A and B. The atomic number has decreased
bv three. Loss of two alpha particles decreases the atomic number by four, so the
other particle emitted must increase the atomic number by one. Loss of a
positron decreases the atomic number by one, so choice D is eliminated. A beta
particle must also have been emitted in addition to the two alpha particles.
Choice C is correct.
Copyright @by The Berkeley Review t2l Exclusive MCAT Preparation

Half-Life
The half-life of a sample of material is the period of time required for 50% of the l
concentration of material to decay to a different (possibly stabler) form. It is most l

corunon to see half-lives associated with first-order decay processes. The graphs I
shown in Figures 2-4'1, and 2-42 show the concentration of a component over time d
for first-order decay (exponential decay) and zero-order decay (linear decay). I
The graphs shown in Figures 2-43 and 2-44 ate the derivative graphs of Figures 'I
2-41 md2-42,whichrepresent the change in rate as a function of change in time. a
1U
txl x T
First-order decay Zero-order decay ft

(exponential decay) (linear decay) Ull
1
i
fl
Time+ Time+ G
Figure 2-4L Figure2-42 &
m
dlxl dtxl
First-order decay Zero-order decay
dt dt
(exponential decay) (linear decay)
l
I
I rate =
dtxl I
dt
- Time-+
Time+
Figure 2-43 Figwe2-44
In Figures 2-45 and.2-46, the graphs are marked al50% and 25'h of the initia1
concJnftation values. These are the various concentrations after consecutive haiJ-
lives. It takes one half-life to cut the concentration in half, and a second half-liJe
to cut that concentration in half again, which results in one-quarter of the originai
concentration. Figure 2-45 shows half-life as a function of time for a first-order
decay. Figure 2-46 shows half-life as a function of time for a zero-order decay.
txl txl
100o/o 100%
First-Order Decay Zero-Order Decar-

(exponential decay) (linear decay)
Half-life is constant Half-life decreases
50%
25%
t-L t-L tr tl
22 1)
Figure 2-45 Figure 2-46
Copyright @ by The Berkeley Review 122 The Berkeley Revieu

Figure 2-45 demonstrates that for a first-order process, the hatf-life is constant,
regardless of concentration. As the concentration decreases, the duration of the
halflife remains the same. Figure 2-46 demonstrates that for a zero-order
process/ the half-life is directly proportional to the concentration of the
compound. As the concentration decreases, so does the duration of the halflife.
The second half{ife is half as long as the first half-life, because the concentration
change is half as large. As a point of interest, for a second-order process, the half-
rije is indirectly proportional to the concentration of the compound. As the
concentration decreases, the length of the hatf-tife increases.
lihese graphs should look familiar from biology and physics. In biology,
bacterial growth is exponential, and enzyme kinetics can be either exponential or
linear. In physics, displacement, velocity and acceleration follow similar
:atterns. The point is that you must understand what these graphs tell you
about some values increasing or decreasing as a function of time. Half{ife
analysis is most commonly evaluated using the upper graphs.
ftr the MCAT, you can expect to have to solve some half-life questions. As far as
:lalf-life problems are concerned, there are two methods by which they are
=olved. One method is to use Equation 2.11, the first-order decay equation:
Ct = Co e-kt (2.LL)
is the concentration at a given time, Co is the initial concentration, k is

,---here C1
re rate constant for the decay process, and t is the elapsed time. This works but
:equires the use of natural logs, which can be time-consuming.
lhe second method involves the sequential summing of half-lives required to

:each a specific concentration. The test traditionally uses numbers that work
well
;-;ith this method. It is the most time-efficient method. When a problem asks
ion'much time passes until a certain percentage of the original quantity remains,
:: is easiest to figure how many half-lives are required to reach that percentage
nd then convert the quantity of half-lives to total time. When using this
:rethod, use reasonable approximations. For instance, if the halfJife is 1L0 years,
:en 335 years is three half-lives plus a little bit. There is 50% remaining after the
:rst half-life ,25"/o remaining after the second half-life, and 12.5"h remaining after
:re third half-life. Thus, there is just under 72.5oh rcmaining after 335 years.
Example 2.33
l-{orv many half-tves are required to decornpose93.75"h of some material?
A*2
ts.3
c-4
D.5
5olution
)ecomposing (decaying) 93.75% of the initial material results in 6.25%
:emaining. The quick and easy method is to cut the percentage in half
:;rntinually until 6.25 is reached.
100% -+ 50% -+ 25h -+ 12.5% -+ 6.25%
-: requires a total of four half-lives to reach a point where 6.25% remains, which
..:-. a decomposition of 93.75% of the material. The best answer is choice C.
---pyright @ by The Berkeley Review 123 Exclusive MCAT Preparation

Example 2.34
If the initial concentration of a toxic material is 1500 parts Per million and the
half-life is 4.5 days, how long witl it take for the level to reach a concentration of
100 ppm?
A. 13.6days \Set -' -l{o
B. 17.8 days
C. 1.8.2 days
D. 22.3 days
Solution
we must sequentially halve 1500 until a number close to L00 is reached.
1500ppm -+ 750Ppm -+ 375ppm -+ 187-5Ppm + 93.75ppm
After four half-lives, there is a little less than the target value of L00 ppm
remaining. This means that just under four half-lives are needed to reach 100
ppm. Four half-lives are eighteen days, so the best answer is slightly less than 18
days. The best answer is choice B'
Sequential halving of the concentration in first-order decay questions is far easier

than using Equation 2.1L or other rate equations. The test-writers may give you
the appropriite equations needed to solve the question in longhand, but this
methbd should be your method of choice. Just because the test writers provide
you with a piece of information, does not mean that you need to use it.
This technique can also be applied to exponential growth problems, as seen in

biology with population genetics that obey exponential growth behavior. With
gto*ih, yon iotttitnally double the concentration rather than cut it in half. For
instance, if a bacterial population doubles in L2 seconds, then in one minute it
increases 32 times (25).
X -+ 2X -+ 4X -+ 8X -+ 16X -+ 32X
Example 2.35
If the half-life of a particular atom is 20.4 minutes and the initial concentration b
L200 parts per million, what will the concentration be after exactly one hour?
\ !\ "
oo -! i oo _-' \r*n
,x1 sazppm \ zc o -)
('
'rB4-gstpp^ , 't- 3
1,,C./155ppm
2fr't+sppm
Solution
One hour is not exactly equal to three half-lives (three half-lives = t hour and
minutes). After three half-lives, we have the following:
1200ppm -+ 600Ppm -+ 300ppm + 150ppm
We haven't quite used a full three half-lives, so the concentration should
have decreased all the way down to L50 ppm. This means that the cor
answer should be just over 150 ppm (150+ ppm). The only ernswer choice that
slightly greater than 150 ppm is L55 ppm, choice C.
Copyright @ by The BerkeleY Review 124 The BerkeleY

I. Classical Experiments (l - 8)
II. Isotopic Abundance and Average Atomic Mass (e - 14)
III. Bohr Model of Hydrogen (15 - 2t\

ru. Paramagnetism and Liquid Crystal Displays (22 - 28)
V. Migration through a Membrane (2e - 55)
VI. Ionization Dnergy (36 - 42)

VII. Transition Metal Trends (43 - 4e)
VIII. Lasers (5O - 56)
IX. Paint Pigments (57 - 65)

X. Fluorescence and Phosphorescence (64 - 6e)
XI. Flame Test (7O - 76)
XII. Glyphosate (77 - Br)
XIII. Technetium Decay (82 - 88)
XIV. Cold Fusion (8e - e5)
Questions Not Based on a Descriptive Passage (e6 - lOO)
Atomic Structure Scoring Scale

Kaw Score MCAT Score
84 - 100 t5-15
66-85 lo-12
47 -65 7 -9
34-46 4-6
t-55 1-3
Passage I (Questions 1 - B)
Two of the more famous classical experiments in

of subatomic particles are the
:stablishing the properties
Thomson experiment and the Millikan oil drop experiment.
The Thomson experiment determined that the mass-to-charge Suspended
:atio for an electron is 5.686 x 10-12 kg/C. The Thomson charged oil drop
:rperiment involved the application of a perpendicular
:lectric field to a beam of electrons produced by a cathode ray
:ube. The Thomson apparatus is shown in Figure 1.
Upper cathode plate
Double filter Figure 2
The hole in the top plate allows for oil droplets to fall
into the chamber. The field between the two plates is
assumed to be uniform, so that the force on the oil droplet is
| .. Lower anode plate
I
w'
t' equal at any position between the two charged plates. The
Electron beam field is adjustable, so that droplets of variable mass can be
Figure L
suspended. Not all oil droplets are of equal mass, so an
average value is assumed.
The double filter ensures that the electron beam is in a
,.rsle direction. The electron beam, when exposed to the 1. An assumption of the Millikan oil drop experiment is
:.:ctric field generated by the two plates, is bent towards the
which of the following?
:': sitively charged plate. The curvature is constant as long as
:e field strength is constant. The bending of the electron A. Oil drops are naturally charged.
:t.im is attributed to both the attractive force of the
B. The pull of gravity is equal in all directions at the
.:positely charged plate and the repulsive force of the like microscopic level.
:. .rrged plate. A magnetic field may also be used to bend the C . The mass of electrons is negligible compared to the
: i.-tron beam. When using a magnetic field to deflect the mass of theoil drop.
: :--trons, the radius of the arc of the electron beam can be D . The magnitude of charge for an electron can vary.
:::ployed to determine the mass-to-charge ratio using
::.ration 1.
m=Br 2 . The electron beam bends downward as it passes between
qv the two charged plates in the Thomson experiment.
Equation 1 What can we expect for a beam of neutrons and
-,: Equation 1, the mass of the electron is m, the charge of protons?
r: electron is q, the strength of the magnetic field is B, the A. The proton beam would arc upwards as it travels,
*:,:rus of the arc of the electron pathway is r, and the velocity while the neutron beam would not arc at all.
l ne electron is v. B. The neutron beam would arc upwards as it travels
In the Millikan oil drop experiment, after ten years of while the proton beam would not arc at a1l.
r^::a collection, it was determined that the charge of an C. Both the neutron and the proton beams would arc
: ::Jtrorl is 1.6 x 10-19 C. The experiment involved charging upwards as they travel between the plates.
r -.il drop by bombarding it with an ionizing electron beam. D . Neither the neutron nor the proton beam would arc
as they travel between the plates.
i,:-.;121 oil drops passed through the ionizing beam, but only
, ':-* gained a charge. The oil drops then fell into an electric
i: j senerated by two charged plates in a glass cylinder. The
j
'i:. was aligned so that the lower plate repelled the oil drop
-:: ; ard, while the upper plate pulled the oil drop upward.
3. How could a value of 3.2 x 10-19 C in an oil drop in
the Millikan oil drop experiment be explained?
The force upward on the oil drop is thus qV, where q is
r: ;harge of the oil drop and V is the voltage of the field. A. The oil drop was doubly ionized.
-:: force pulling the oil drop downward is mg, where m is B. The oil drop gained an electron rather than lost an
electron.
r'r : :nass of the oil drop, and g is the gravitational force
i.stant. If the oi1 drop is suspended, then the two forces are
C. The oi1 drop lost a proton rather than lost an
electron.
::-a1. and it is possible to determine the charge of the oil
i:::. The charge of the oil drop must be a whole number D. The oil drop gained a proton rather than gained an
electron.
r -itiple of the charge of an electron. The apparatus used in
:,. \lillikan oil drop apparatus is shown in Figure 2.
- ::r'right O by The Berkeley Review@ t27 GO ON TO THE NEXT PAGE

.1. The Thomson experiment determined which of the Passage ll (Questions 9 - 14)
following?
To determine the relative abundance of the isotopes
A. The mass of an electron
an element, a mass spectrometer is employed. The ele
B. The mass of a proton
is first vaporized into its gaseous state, if it is not alreadl
C. The mass-to-charge ratio of an electron gas form. Because this is carried out in a vacuum, a
D. The mass-to-charge ratio of a proton temperature may not be required to vaporize the
The cationic compound is generated by high-energy
impact with the neutral atoms. A neutral atom loses
valence electron to ionization upon impact. The cati
species formed is then accelerated in an electric field unnl
5 . The Millikan oil drop experiment requires knowing all reaches a set velocity (v). The particle beam produce'J
of the following EXCEPT: projected through a double filter to ensure that no de
A . the mass of the oil droPlet. particles pass through to the detector.
B . the voltage of the electric field. Once particles are passed through the double filter.
C. the gravitational force constant. are subjected to a magnetic field perpendicular to the ori
D . the temperature of the chamber. electric field. This curves the pathway of the particles.
force on charged particles moving through a magnetic fieldri
found using Equation 1.
p=qvB
6 . In a neutral atom, what can be said about the number of Equation 1
electrons relative to the number of protons and where q is the charge of the particle (assumed to be +1) and
neutrons? is the magnetic field strength. According to Newton's
A . The number of electrons must equal both the law, the force on the particle is F = ma, where m is mass
number of protons and the number of neutrons. a is acceleration. The particle is moving along a curved
B. The number of electrons must equal the number of so it has angular acceleration, which is found using Equari
protons only, and the number of neutrons is 2.
irrelevant.
C . The number of electrons must equal the number of u=&
neutrons only, and the number of protons is R
irrelevant. Equation 2
D . The number of electrons must equal the sum of the where R is the radius of the arc. Substituting ma for F
protons and neutrons combined. Equation 1 and manipulating the variables yields Equation
qB=mv
R
Equation 3
7 . The STRONGEST attractive force is felt between: The equations support the intuitive perception of
A. aproton and a neutron. the path is affected by mass, charge, velocity, and ex
B. a neutron and an electron. field strength. Figure I shows a basic schematic of a
spectrometer.
C. an electron and an electron.
D . an electron and a Proton. Detector
8. If the oil drop were slowly descending once it was in

the electric field between the two charged plates, which
of the following corrections would NOT stop it from
continuing to fall?
A. Increase the number ofelectrons on the drop. Figure 1
B. Increase the mass of the oil droplet. Different isotopes have different atomic masses, so
C. Increase the voltage difference between the two isotope has a unique radius (R). The detector determines
plates.
relative quantities of each isotope. This information is
D . Decrease the gravitational pull.
used to determine the average atomic mass' a value that
into account all ofthe isotopes for a particular element.
Copyright @ by The Berkeley Review@ t2a GO ON TO THE NEXT P

fable 1 lists the isotopic abundance for the common isotopes 12. When a mass spectrum is to be obtained for a solid
:,f boron, magnesium, and silver. compound, the first step in the process is which of the
following?
Element Atomic Mass Percentage
A. Vaporization
Boron-10 10.013 amu 19.187o
B. Condensation
Boron-1 1 I 1.009 amu 8O.22Vo
C. Ionization
Masnesium-24 23.985 amu 78.7j%o D. Sublimation
Magnesium-25 24.986 amu lO.137o
Masnesium-26 25.983 amu ll.ITVo
S ver-107 106.91 amu 5l.80Vo
S ver-109 108.90 amu 48.20Vo
Table L
13. Identify the TRUE statement(s) from the following:
+. Why is carbon added to a sample before it is vaporized I. The average atomic mass of an element is always
in a mass spectrometer? greater than the mass of the heaviest isotope for
that element.
A. Carbon-12 is used as a standard for mass reference.
B. Carbon-13 is used as a standard for mass reference.
II. The average atomic mass of an element is always
greater than the mass of the lightest isotope for
C. Carbon helps to lubricate the atoms at an atomic that element.
level.
D. Carbon absorbs heat from the atoms and prevents
m. When there are two isotopes for an element, the
average atomic mass is closer to the more abundant
the sample from overheating.
isotope than the less abundant isotope.
A. I only
B. II only
C. I and III only
Which of the following plots represents the output D . II and III only
from the mass spectrometer for magnesium?
A. B.
C) 14. The difference between the two isotopes of boron is:

A. the isotope of boron with mass 11.009 amu has
Mass--> MASS+ one proton less than the isotope of boron with
mass 10.013 amu.
B. the isotope of boron with mass 11.009 amu has
one proton more than the isotope of boron with
mass 10.013 amu.
q C. the isotope of boron with mass 11.009 amu has
C) one neutron less than the isotope of boron with
mass 10.013 amu.
Mass# Mass+ D. the isotope of boron with mass 11.009 amu has
one neutron more than the isotope of boron with
mass 10.013 amu.
Which of the following calculations accurately

determines the average atomic mass for silver?
{.. 0.787 (23.985) +0.1013 (24.986) +0.1117 (25.983)
B. 0.11I1 (23.985) + 0.1013 (24.986) +0.787 (25.983)
C. 0.482 (106.91) + 0.518 (108.90)
D. 0.518 (106.91) +0.482 (108.90)
129 GO ON TO THE NEXT PAGE

Passage lll (Questions 15 - 20) 17. Which of the following transitions relates
GREATEST energy of absorption?
The Bohr model for hydrogen proposes that there are A. From the n = 2level to the n = 4 level
quantized energy levels in which an orbiting electron may be
B. From the n = Zlevel to the n = 1 level
found. The theory is derived from the observation that exact
frequencies of light are absorbed by hydrogen gas, no matter
C. From the n = I level to the n = 2level
what the concentration of the sample or intensity of the
D. From the n = 2 level to the n = 5 level
incident light source. Given that light frequency directly
relates to light energy, the idea is that quantized amounts of
energy are absorbed and emitted as an electron moves between
energy levels. Figure 1 shows the Bohr representation of
1 8. Which statements are valid regarding the energy
hydrogen.
of hydrogen?
n=4 I. As the value of n increases, proximity
n=3 nucleus decreases, therefore the electron is
in a higher energy state.
n=2
[I. As the value of n increases, the difference
adjacent energy levels (with n values di
one), gets smaller.
m. A larger nuclear charge has no effect on
energies, although it lower all of the energy
A. I only
B. II only
C. I andll only
Orbital levels D . tr and III only
Figure 1
Due to Coulombic attraction, the most stable energy

levels for the electron correspond to the closest proximity to
the nucleus. This means that the energetics of the orbiting
electron depend on the charge nucleus and the distance from 19. For some compound X, which emits orange light
the nucleus (or quantum level). The energy level for the transition from the n = 4 level to the n = 3 level,
electron ofhydrogen is found using Equation 1. must be TRUE?
A. A transition from the n =5level tothen=4
E=-2.t78* ro-rs14l emits green light.
\n2 /
B. A transition from the n =4leveltothen=2
Equation 1 emits red light.
C. A transition from the n =6leveltothen=4
15. What is the ionization energy for hydrogen? emits violet light.
A. 1.634 x 10-18 J D. A transition from the n =5leveltothen=3
B. 2.178 x 10-18 J emits yellow light.
C. 4.356 x 10-18 J
D. 8.712 x 10-18 J
2 0. Which of the following observation leads to

1 6. The deBroglie equation relates the energy of a photon to conclusion that energy levels are quantized?
its equivalent mass according to E =mc2. How can the
deBroglie wavelength of an electron be found?
A. A sample always absorbs the same amouil
light.
A. ,r- h B. A sample always absorbs the same color of
mc
C. A sample always emits different
B. 1_mc different temperatures.
h
t-2h D. A sample always emits different frequencier
C. different concentrations.
mc-)
)
D. 1_mc-
2h

:assage lV (Questions 21 - 27) 21. Which of the following can be used in an LCD?
A. CdCl2
Liquid crystal displays (LCDs) utilize the properties of
:.:amagnetic species. When plane-polarized light passes
B. Fz
: rugh a solution containing a paramagnetic species, it C. CoClz.6 HzO
-
..-"rles the plane-polarized light. If the paramagnetic species D. Hz
a magnetic field, then the particles align in the
, .:bjected to
' -'.i. and the plane-polarized light is not rotated. The display
..:rmonly seen in calculators and digital watches uses this
:::;iple to filter or pass light through templates.
The basic design of the display board involves passing 22, What are the quantum numbers associated with the
;rt through a polarizing plate into a cell containing the LAST electron in the nitrogen atom?
:.:a-rragnetic species and then having the light pass through
" i;cond polarizing plate that is rotated 90' relative to the A. n=2 1=1 ml=+1 ms _,1
2
' :;r plate. If the field is off, the light will rotate and thus be
B. n=2 l=1 ml =+1 __ I
: -sed through the second polarizer. This results in a bright rns
2
:':: on the display board. If the field is on, the light will
' .: rotate and thus will not pass through the second C. n=2 l=1 ml=-1 IIIg =+l2
- ."rizer. This results in a dark spot on the display board.
D. n=2 l=1 ml=-l __1
'' :rre 1 shows a simple display circuit. ms
2
Circuit on (Solution is aligned)
Vertical polarizer Horizontal polarizer

:ly vertical waves pass) (only horizo4fal waves pass)
2 3. What is the shape of Fe(CN)63-?

A. Octahedral
B. Squareplanar
C. Tetrahedral
D. Trigonal bipyramidal
light passes
. 'gned paramagnetic solution does NOT rotate light plane
Circuit off (Solution is random) 2 4. Which of the following compounds is polar?
Vertical polarizer Horizontal polarizer

A. r'ecl63-
::ly vertical waves pass) (only horizonJal waves B. Ni(CN)s3-
C. cis-Pt(NH)2C12
D. trans-Pt(NH3)2C12
25. Which ion has the MOST unpaired electrons?

Unaligned paramagnetic solution rotates light plane A. cr3+
Figure 1 B. Mn2+
C. Cu+
-\ paramagnetic species is defined as a compound that D. Ni2+
'.".' unpaired electrons. Many common examples involve
:.-:sition metals with a d-shell count of d1 to d9. Organic
. ::.pounds that are paramagnetic are referred to as radicals.
' r.:.
sen gas has two unpaired electrons; thus, when exposed
. magnetic field, oxygen molecules will with the field.
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2 6. Which of the following statements is NOT true? Passage V (Questions 28 - 34)
A. Cr has a higher formal charge in Cr(CN)6 than
In vivo, semi-permeable membranes are used by
Cr(NH3)63+.
body to control diffusion and osmosis (entropically fi
B. Cu(H2O)O+ has ten d-electrons. occurrences). In the kidney, Bowman's capsule functions
C. Fe(NHr)63* has the same shape as FeCl63-. such a manner. Semipermeable membranes
D. Scandium is more likely to have +4 formal charge microscopic pores that allow the passage of some
than titanium. or, in certain cases such as the sodium-potassium
ions. They function by allowing only selected ions to
from the solution on one side of the membrane to
solution on the other side of the membrane.
membranes can distinguish by size, charge, or both.
Semipermeable membranes can be applied to bench
2 7. Which of the following pairs of molecules does NOT
chemistry Qn vitro) as well. This application can i
have the central atom (transition metal) with the same
reaction's selectivity. Semipermeable membranes used
number of d-electrons in both compounds?
vitro,that separate by size, are often referred to as
A. Fe(NH3)63+ and FeCl63- 4nd atomic sieves. While some molecular sieves di
B. Co(H2O)63+ and MnCl64- by atomic radius, others differentiate by charge. To study
effectiveness of a semipermeable membrane, two
C. Cr(NH3)63+ and MoC63-
different solute concentrations are separated by the
D. Os(NH3)42+ and RhCl:(PRs)t Figure I shows a U-tube with a semipermeable
separating the two solutions.
Side I starts with solute that

cannot cross the membrane.
Side 2 starts with solute that

can cross the membrane.
le membrane
Side 2
After the solute migrates across

membrane, there is a conce
difference. Flow stops when
pressure equals hydrostatic
Figure 1
Table I
the rates of effusion from Solution I
synthetic membrane into Solution II for a generic study-
Cation Rate (M/s)

Li+ 4.7 x l0-2
Na+ 1.1 x 10-2
Ms2+ 2.9 x lO-2
K+ 3.5 x 10-3
ca2+ 8.3 x 10-3
Table I
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Note: The synthetic membrane used in the experiment 3 2. What is the charge on the MOST stable ion of
::rresented in Table 1 is believed to be aprotic and magnesium?
:iscriminates by atomic size. It is modeled after a protein A. +2
::at is found in the lipid bilayer. B. +1
It. Based on the data in Table 1, which of the following
c. -l
conclusions is valid?
D. -2
A. As cationic size increases, the rate of migration

across the membrane decreases.
B. As cationic size increases, the rate of migration
across the membrane increases.
C. The cationic size has no direct effect on the rate of 3 3. Which of the following atoms is LARGEST?
migration across the membrane. A. F
D. Because cations are larger than neutral atoms, the B. CI
effect of cationic size on the rate of migration
cannot be determined.
C. Br
D. I
The BEST explanation for why potassium (K) has a

lower ionization potential than sodium (Na) is that: 3 4. If the pore of the membrane used in the experiment
associated with Table I were to distinguish by both size
A. potassium is more metallic than sodium.
and charge, the SLOWEST rate would occur with which
B. potassium has a larger enthalpy of reaction with cation?
water than does sodium.
C. the 4s-orbital is larger than the 3s-orbital.
A. Li+
D. potassium has a larger electron affinity than does B. K+
sodium. C. Mg2+
D. ca2+
The BEST explanation for why fluorine is smaller than

carbon is which of the following?
.{. Fluorine's electrons are at a lower quantum level
than those of carbon.
B. Filled p-orbitals contract more than half-filled p-
orbitals.
C. Fluorine has a larger effective nuclear charge than
carbon.
D . Fluorine is heavier than carbon.
\Vhich of the following is the SMALLEST?

.\. F-
B. Ne
C. Na+
D. CI-
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Passage Vl (Questions 35 - 42)
o
o
E
-tz
ct)
1
1
I
F
q) 1
c
tIJ 1
/
c 1 o cl
o
(5 1
,N
c 11
o 1
Si
89101112
Atomic Number
Figure I
Figure 1 shows the first ionization energy for the first 35. Which of the following BEST explains the h:d
twenty elements in the periodic table. The first ionization ionization energy of helium?
energy is defined as the energy required to remove the first A. Helium has no valance electrons to remove. .5,9". 'l
electron from the valence shell of an element to form a B. Helium has an effective nuclear charge greater s
monocation. The general reaction, where E symbolizes any two.
element from the periodic table, is shown in Reaction 1. C. The electron must be removed from the
E(g) E+1g; + e- quantum level, which experiences the g
-> nuclear charge. t
Reaction 1
D. Helium requires a great amount of energy to (
To negate solvent effects, ionization reactions are done converted first into the gas phase.
in the gas phase. The first ionization energy is proportional
to the square of the effective nuclear charge of the element.
The effective nuclear charge is the charge exerted upon the T
valence electrons by all other charged species in the atom.
The effective nuclear charge takes into account the number of 3 6. What can be expected for the second
protons in the nucleus and the number of core electrons of lithium, sodium, and potassium?
(electrons in principal quantum shells lower than the valance A. The second ionization energies are only s1i
electrons). Ionization energy depends on the valence shell larger than the first ionization energies, becau:e
principal quantum number. Ionization energy decreases as Z6yhas not changed drastically.
you descend a family in the periodic table. A larger principle B. The second ionization energies are only sli '\fr
quantum number corresponds to a lower ionization energy. larger than the first ionization energies, becau-'e h
Figure I
shows deviations from the behavior predicted valance shell has changed.
A
from effective nuclear charge data. Deviations are seen with C. The second ionization energies are substan
B
elements having valance electronic configurations of ns2np1 larger than the first ionization energies, becau:e
2"6 has not changed drastically. C
and ns2np4, which is attributed to the filled s-level and the
D. The second ionization energies are substan D
half-filled p-level associated with the cations that are formed.
There is additional stability when the p-orbitals have equal larger than the first ionization energies, becau**
valance shell has changed.
occupancy of electrons. The symmetry associated with the
half-filled state results in cation stability.

3 7. How can the lower ionization energy for oxygen than 41. What can be expected for the first ionization energies of
nihogen BEST be explained? bromine, krypton, and selenium?
A. Nitrogen is more electronegative than oxygen, so it A. LE.g1 > I.E.K. > I.E.S"
does not share electrons as readily. B. I.E.p > I.E.Br > I.E.Se
B. Nitrogen has more protons than oxygen, so it C. I.E.5s > I.E.B. > I.E.Kt
carries a greater effective nuclear charge.
C. Nitrogen is larger than oxygen, so it is harder to
D. I.E.5s > I.E.Kr > I.E.B.
remove a valance electron.
D. Nitrogen has a half-filled p-level, so it does not
lose an electron as readily. Oxygen, when it loses
one electron, attains half-filled p-level stability.
42. The first ionization energy for sodium is 495 kJ/mole

and the second ionization energy is 4558 kJ/mole. The
first ionization energy of magnesium is 732 kJ/mole,
How can the trend in first ionization energy between and the second ionization energy is 1451 kJ/mole.
aluminum, silicon, and phosphorus BEST be How can the change in second ionization energy be
explained?
explained?
A. The effective nuclear charge increases as you move
A . The first and second ionizations of sodium are from
from Al to P in the periodic table. different quantum levels, while the first and second
B. The effective nuclear charge decreases as you move
ionizations of magnesium are from the same
quantum level.
from Al to P in the periodic table.
C. The number of core electrons increases as you
B. Sodium is less electronegative than magnesium,
which implies that the second ionization energy
move from Al to P in the periodic table. must be greater.
D. The number of core electrons decreases as you C. Once one electron has been lost from magnesium,
move from Al to P in the periodic table.
the second electron is repelled by the positive
charge of the magnesium cation.
D. Sodium metal gains half-filled stability by losing
one electron, while magnesium requires losing two
electrons to attain half-filled stability
\Vhy is the first ionization energy of fluorine greater

rhan the first ionization energy of chlorine?
A. Fluorine is less electronegative than chlorine, so it
shares electrons more readily than chlorine.
B. Chlorine has more protons than fluorine, so it
carries a greater effective nuclear charge.
C. Chlorine is losing an electron from a shell that is
farther from the nucleus than fluorine, so chlorine
can lose an electron more easily.
D . Chlorine has no electrons in the p-level, so it does
not lose an electron. Fluorine, when it loses one
electron, completes its valance shell.
rir it . 1yh'"n of the following elements can be oxidized

\IOST easily?
-{. Sulfur
B. Magnesium
C. Boron
D. Argon
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Passage Vll (Questions 43 - 49) Trends are predictable when based on the effective nucler
charge and the outermost electron shell (valence shelll
Transition metals do not follow the same periodic trends However, the effective nuclear charge and valence cloud of tb
associated with the main-group elements. The reasoning different transition metals do not follow the same pattern er
behind their separate trend is rooted in their valence electrons. main block elements. Similar reasons can be employed
The d-electrons of transition metals are not the outermost explain deviations in trends. Half-filled d-shell stability
electrons, despite the fact that the d-level is being filled as associated with chromium, and filled d-shell stability i
you move left to right through any row of the transition associated with copper, which accounts for deviations in
metals. When we look at first-row transition metals, we see electronic configurations from what is expected according
electrons fill the levels according to the Aufbau principle, so the Aufbau principle.
they fill the 4s-level prior to the 3dlevel. However, when
electrons are lost (when the element undergoes ionization), 4 3. What is the density of manganese at 1000"C?
the electrons are lost from the 4s-level before the 3d-level.
Table 1 shows the ionization energy data associated with the
A. Between 1.00 and 2.00 g per cm3.
first row of transition metals. The first three ionization B . Between 2.00 and 7.43 g per cm3.
energy values are listed for each of the transition metals. C . Between 7.43 and9.00 g per cm3.
D. Between 9.00 and 12.00 gper cm3.
M |./r2+ M3+ lst IE 2ndIF, 3rd IE
Sc 4s23d| tArl 63t 1235 2389

Ti 4s23d2 3d2 3d1 658 1309 2650
V 4s23d3 3d3 3d2 650 t4t3 2828 44 . What is true of the relative second
values of Mo, Tc, Pd, and Ag?
Cr 4s13d5 3d4 3d3 652 1591 2986
Mn +s23d5
A. Mo>Tc>Pd>Ag
3d5 3& 711 1509 3250
B. Ag>Pd>Tc>Mo
Fe 4s23d6 3d6 3ds 759 1561 2956 C. Ag>Tc>Mo>Pd
Co 4s23d7 3d7 3d6 160 1645 323r D. Ag>Pd>Mo>Tc
Ni 4s23dB 3d8 3d'7
'736 t75l 3393
Cu 4113610 3d9 3d8 745 1958 35',78
Zn 4123610 3d10 922 1172 4 5. How can the lower melting point and boiling
Table 1
zinc compared to other transition metals be exp
Periodic trends also include atomic radius, ionic radius,

A. Increased interatomic forces with the filled
and atomic density at 25"C. Transition metals also show a B. Reduced interatomic forces with the fil1ed
deviation from main group elements in terms of trends in C. Increased interatomic forces with the half-
atomic size. Table 2 lists radius data for selected metals. shell.
D. Reduced interatomic forces with the half-
Radius Physical Properties shell.
M }./r2+ M3+ M.P. B.P. Density
K 227 63.7 160 0.86
Ca 197 99 838 I44t t.54
2738 3.0
4 6. What can be concluded about the ease of removing
Sc 162 81 1539 electron compared to a 4s-electron?
Ti 147 90 11 1668 3259 4.51 A. The 4s is more easily removed because it is
V t34 88 14 1903 3447 6.1 to the nucleus.
Cr 130 85 64 1874 2667 '7.19 B. The 4s is less easily removed because it is
the nucleus.
Mn 135 80 66 t241 2t52 1.43 C . The 4s is more easily removed because it is
Fe 126 77 60 1536 3001 7.86 from the nucleus.
Co t25 75 64 1495 2908 8.9 D. The 4s is less easily removed because it is
from the nucleus.
Ni r24 69 1453 2'731 8.92
Cu t28 72 1083 2591 8.96
Zrr 138 74 4r9.5 906 '7.14
Table 2
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.17. What is TRUE about changes in density and atomic Passage Vlll (Questions 50 - 56)
radius as one scans across the 3d row of the periodic
The basic principle behind the operation of a laser is the
table?
excitation of electrons from the ground state of a compound
A. As atomic radius increases, density increases. to some meta-stable excited state. The term meta-stable
B. As atomic radius increases, density decreases. refers to an excited state where an electron can exist for a
C. As atomic radius increases, density increases' sustained period of time before it falls back to its ground
except for elements with filled d-shell stability. state. By constantly supplying energy to the compound, the
D. As atomic radius increases, the density does not electrons can be "held" in the excited state. This preference
vary in a predictable fashion. for a higher energy level is in accordance with Boltzmann's
distribution law of energy for any chemical or physical
system. Boltzmann's distribution law predicts that the energy
of a system will be distributed throughout the different levels
according to a standard probability function that follows a
I 8. How can the reduced radii of transition metal cations be bell curve. At higher total energy for the system, more
electrons are present in an excited state than at lower total
explained?
energy for the system. Figure 1 shows a molecular system
A. Transition metals lose their outermost electrons before and after energy has been added. The excited and
from the 4s-orbital, when becoming a cation.
ground states are represented as levels capable of holding
B. Transition metals lose their outermost electrons multiple electrons.
from the 3d-orbital, when becoming a cation.
C . Transition metals lose their highest-energy Before energy is added After energy is added
electrons from the 4s-orbital, when becoming a
cation.
D. Transition metals lose their highest-energy
11111111111111
electrons from the 3d-orbital, when becoming a M"""rubl""^"ir"dGil
cation.
hv in
M
+ 9. If the reduction potential of Mn2+ is -1.18 V and Co2+
11 1111 1111 11
Ground state energy level
1 1
is -0.28 V, what can be concluded about the reduction Figure I

potential of Fe2+? Energy is most easily introduced into the system by
A. E'reduction of Fe2+ is less than - 1. 18 V. incident light (photons). A system analogous to the laser is
the electrical capacitor, which can be filled with electrical
B. E'reduction of Fe2+ is between -1.18 and -0.73 V.
energy and then instantly drained, releasing a pulse ofenergy.
C. E'reduction of Fe2+ is between -0.73 and -0.28 V. Lasers can also store energy (light energy) and then release a
D. E'reduction of Fe2+ is greater than -0.28 V' pulse of photons. A laser emits light energy corresponding
to the transition-level changes. Once the crystal or gas in the
laser releases photons, the light is collected and reflected
between mirrors, before it is released through an aperture
emitting the laser beam. Light emitted from a laser is close
to being monochromatic (that is, light of one wavelength),
but not precisely monochromatic. To date, absolutely
monochromatic light has yet to be observed. This is
attributed to the fact that the ground state and excited states
are not single energy levels, but are in fact a band of
quantized levels with identical electronic energy' but varying
vibrational and rotational energies.
5 0. Which of the following electronic configurations is the

ground state electronic configuration for aluminum?
A. k22s22pqp3
B. rs22s22p63s3
C. 1s22s22p63r2301
D. ts22s21p63r13p2
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51. Monochromatic light is NOT observed for which of the 55. According to Figure 1, the photons emitted compare ir h
following reasons? what way to the photons absorbed by the transition
A. Lasers are not precise in their emissions. between energy levels in the laser system? I
B. Crystals always have some imperfections. A . The light emitted is of higher wavelength. mdim
C. The laser re-absorbs some of the energy emitted. B . The light emitted is of equal wavelengrh.
imhilnt
D. Each electronic energy level has many rotational C . The light emitted is of lesser wavelength. mry
rmrlrl
sub-levels. D. The light emitted is incomparable. rrwFm
tu
rm
mdilL
5 2. What is the energy in joules associated with a photon 56. For a laser to emit visible light, the material used m
of light with a wavelength of 330 nanometers? have an emission in what energy range, knowing
the visible range is approximately 400 nm to 750 nml
@= F,where h = 6.6 x lO-34,)"= wavelength in nm)
lL
(E- 1.24 - eV
- -' x 10-6 -',wherel,ismeasuredinmeters)
A. 6.0 x 10-28 J L
B. 6.0 x 10-19 J
A, 6.25 eV to 9.90 eV
C. 6.0 x 10-17 J
B. 3.10 eV to 6.25 eV
D. 6.0 x l0l5 J
C. 1.65 eV to 3.10 eV
D. 1.24 eV to 1.65 eV
5 3. Which of the following sets of quantum numbers are

associated with the last electron in neutral vanadium
(element # 23)?
A. n=3; l=2; m1 =0; ms=+l

2
B. n=3; l=2; ml=o; ms=J
2
C. n=4; l=0; m1 =0; ms={
2
D. n=4; l=0; ml = +1; m5=J
2
5 4. Which of the following elements would have an

electronic configuration of nsl1n-1;d due to half-filled
stability?
A. Copper
B. Silicon
C. Manganese
D. Molybdenum
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Passage lX (Questions 57 - 63)
Long before the advent of modern technology, colored

:aints existed. The pigments for these paints were extracted
-om natural sources, such as plants and mineral deposits. In
:urope and the Middle East, the majority of the pigments
-sed for painting were metal oxides. In the Orient, more
- sanic pigments were used. By tracing the origins of
::{ments, art historians have been able to determine the

,,urce not only of paintings, but of stylistic influences as Figure 2
' :11. Listed in Table I are some of the more common
-':rces of colors used in the early centuries A.D. White light is a combination of all colors, so when one
color is absorbed from white light by a pigment, the other
P igment Chemical Formula Color colors reflect. All the colors are no longer present, so at
i-izarin 1,2-dihydroxyanthraquinone Yellow least one of the colors has no complementary color present.
-,zurite 2CuCOq.Cu(OH)z Blue The result is that the reflected light takes on a hue of the
- -nnabar HgS Red color that has no complementary color to cancel it. When
l' f .i:sicot Pbo Yellow white light reflects off of a pigment, the reflected light can be
l'lrnium PbrO+ Scarlet analyzed for intensity versus wavelength after a prism splits
niment Yellow the light via refraction. The output is an absorption

As253
spectrum, which appears as a rainbow band with vertical
: :algar As2S2 Orange red
black lines, due to the absence of the light absorbed.
Fe2O3.nH2O Brick red Absorption spectra are the opposite of emission spectra,
:amarine blue SiS2/Al253 Blue although both require a prism to refract (grate) the light.
::digris Cu(CzHtO)2.Cu(OH)2 Greenblue
; rte lead 2PbCO:.Pb(oH)z White 5 7. Which of the following pigments absorbs light of the
SHORTEST wavelength?
Table 1 A. Alizarin
-\s a rule, inorganic paint pigments last for a far longer B. Azurite
:- :J of time than the organic paint pigments. For this C. Cinnabar
' *, :r. inorganic pigments are a more reliable source used to D. Verdigris
:-.-ir, the time and region from which many paintings
: rated. The colors in inorganic paint pigments are caused
.:e absorption of light in the visible range of the light
" : -,rurrr. The absorption is due to transitions between the
: : ,:a1s, which because of the asymmetry of the ligands are 5 8. When a sample is heated by flame, and the emitted light
,:senerate. The splitting of the d-orbitals results in is put through a prism, what result is produced?
:::nt energy levels within the d-level. Figure 1 shows the A. An emission spectrum of dark background with
' :'::iic splitting of the d-orbitals in an octahedral complex. some colored bands.
B. An absorption spectrum of dark background with
d*z - d", some colored bands.
rz
c. An emission spectrum of colored background with
some black bands.
D. An absorption spectrum of colored background
with some black bands.
dxy d*, dr"
Figure 1
l-e color we see is the reflected color, the 5 9. In the absorption spectrum of realgar, what color band
- : :nentary color of the color that is absorbed. If a paint
would contain black lines?
i;,- :.--. blue, it is because of a paint pigment is present in it
,. ; ,bsorbing orange light (the complementary color of A. Orangeandred
., Figure 2 shows an artist's color wheel, which can be B. Orange and green
: . determine complementary colors. Complementary C. Blue andred
-: -ppose one another on the color wheel. Blue opposes D. Blue and green
i.-:;. so they are complementary colors of one another'
L :.-- j Ereen are also a complementary pair.
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60. Given that the wavelength of visible light has a range Passage X (Questions 64 - 69)
from about 740 nm to 390 nm, what is the
approximate wavelength of light absorbed by the copper Fluorescence occurs with the absorption of a photon
dication in Cu(C2H3O )2.Cu(OH)2? a molecule, exciting one of its electrons to a higher
A.450nm state. Because the material is molecular and not
B.550nm there are also vibrational and rotational energy
associated with it. The molecule can change its vi
C.650nm
energy level (by changing its bond-stretching frequency)
D. 750 nm
give off energy in the form of IR photons or heat. Heat
released during collisions with less energetic
When the electron falls back to the ground state, a photon
less energy than was initially absorbed is given off.
fluorescing compound can thus absorb high-energy li
(such as ultraviolet) and give offlesser-energy light (such
61. White lead absorbs which colors?
visible light).
A. All colors
Phosphorescence also begins with the absorption
B. Green, blue, and violet
photon by a molecule, exciting one of its electrons Er
C. Red, orange, and yellow higher energy state. The electron can flip its spin in
D. No colors in the visible range excited state, dissipating some of the extra energy. When
electron relaxes, because it shares the same spin as
ground state electron, it cannot fall back to its ground
It must relax to an intermediate state, so a lower-
photon is emitted than was initially absorbed. Fi
62. All of the following exhibit reflected color EXCEPT: represents what goes on during both fluorescence
phosphorescence. The Xo potential well represents
A. Candle wax ground electronic state, and X1 represents the excited
B. Fabricdyes The lines within the well represent the different
C. Pen ink modes (vibrational energy levels) of the molecule.
D. Gas-filled light tubes
63 . Which of the following pigments will decompose first?

A. Alizarin
B. Azurite
C. Rust
D. Verdigris
Bond radius (A)

Figure I
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The wiggly urrrows in Figure 1 represent energy that is 6 7. According to the graph, how do the photons emitted
dissipated as an excited electron drops in vibrational energy,, from fluorescence and phosphorescence compare?
rvhich is released in the form of an IR photon. The A. The photons emitted from fluorescence have a
',ibrational energy thereby released can be measured as heat longer wavelength than the photons emitted from
siven off from the system. The amount of heat emitted phosphorescence.
r aries with different molecules, because the electronic energy
B. The photons emitted from fluorescence have a
levels are not singular levels (they have both vibrational and
shorter wavelength than the photons emitted from
:otational energy levels associated with them). The phosphorescence.
:ansition energy is thus the result of a random combination
rfenergy levels. Because the electronic energy levels are not
C. The photons emitted from fluorescence have the
same wavelength as the photons emitted from
singular levels and because the transition is random, it is
phosphorescence.
-mpossible for a molecule to absorb or emit light in such a
:nanner that all of the photons simultaneously have the same D. The photons emitted from phosphorescence are of
(or wavelength). For this reason, monochromatic higher energy than the photons emitted from
=equency fluorescence.
-rght is not physically possible.
6.1. A spin flip in the excited state is associated with which

of the following processes?
A. Fluorescence only
6 8. Which of the following transitions emits the
B. Phosphorescenceonly SHORTEST wavelength of light?
C. Both fluorescence and phosphorescence
A. Xt V = I toXg V = 0, whereV is the vibrational
D. Neither fluorescence and phosphorescence
energy level.
B. Xt V =0toX6 V = 0, where V is the vibrational
energy level.
6 5. What can be said about the photon absorbed relative to
the photon emitted by a fluorescing diatomic molecule? C. XoV = 1 toXl V =0, whereV is the vibrational
energy level.
A. The energy of the photon absorbed is greater than
D. XOV = 0 toXl V = 0, where V is the vibrational
the energy of the photon emitted, while the
energy level.
wavelength of the photon absorbed is less than the
wavelength of the photon emitted.
B. The energy of the photon absorbed is less than the
energy of the photon emitted, while the wavelength
of the photon absorbed is greater than the 69 . Which of the following statements about fluorescence
wavelength of the photon emitted. is FALSE?
C . Both the energy and wavelength of the photon
A. Fluorescence is possible with molecules.
absorbed are greater than the energy and wavelength
of the photon emitted. B. Fluorescence converts visible light into ultraviolet
light.
D. Both the energy and wavelength of the photon
absorbed are less than the energy and wavelength of
C. Fluorescence can dissipate energy in the form of
heat.
the photon emitted.
D. There are some atoms for which fluorescence is not
possible.
6 6. What is TRUE about monochromatic light?
A. Monochromatic light is not possible, because light
is not quantized.
B. Monochromatic light is possible, because light is
quantized.
C . Monochromatic light is not possible, because there
are vibrational energy levels of lower energy
difference than the electronic energy levels with
which they are associated.
D. Monochromatic light is possible, because there are
vibrational energy levels of greater energy
difference than the electronic energy levels with
which they are associated.
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Passage Xl (Questions 70 - 76) 72. Which of the following transition metals has rir:
GREATEST d-d transition energy, given that the coli':
A
student conducts an experiment where a series of observed in the flame test is due to a d-d electron-:
aqueous solutions of group I cations (alkali metals) or group transition? llr
II cations (alkaline earth metals) are each heated by a flame.
The heat of the flame, if hot enough, can stimulate electrons
A. Ni2+ lhtfl
iil'i
in the cations to leave their ground state. When they relax to B. cr3+ 'llua
the ground state, light is emitted. Because the light is a c. Co2+ linr i
narrow band of photons with predominantly one wavelength, D. V2+ ;iii
it appears colored. The color is used to identify the cation in t,l f,
solution. Table 1 shows the student's result. iir-

Barium Lime-green ring around flame
7 3. Identify the TRUE statement(s) from the following.
Lithium Brilliant crimson flame I. As ionic size increases; the energy of the transitj:
increases.
Potassium Light pumle ring around flame
Sodium Orange-yellow flame
II. The transition energy of K+ is greater than ::r
transition energy of Cr3+.
Strontium Red flame
Table 1
m. Cu+ and Ni2+ have the same electrol-;
configuration.
The student then conducts the same experiment using
transition metals rather than main-group metals. The trend
A. I only
in color is predictable with main-group cations of the same B. II only
lmm:
column (family) in the periodic table. The color of the C. I and II only iuull
transition metal cations depends more on the ligands attached D. tr and III only ru:
to the metal cation. Table 2 also shows the colors obtained. rh{}
,i,r!flr
Vanadium (tr) Violet flame 7 4. What are the quantum numbers associated of the .:-"
Copper (I)
llll]llilfim:
Orange flame electron of nickel dication? illtrrrtl!
Nickel (tr) Red flame
Chromium (tID Red flame
A. n=3 l=2 ml=-1 frr=-l tNl\ rl
2 l"@
Cobalt (D Green flame B. n=3 l=2 ml=0 Ift*=-1 umr.llt
Table 2 2
With transition metals, the color emitted by the flame is C. n=3 l=2 ml=+1 -r=-j ,iiiillfi.Ilu
often the color of the light absorbed when the cation in x1l'::1r
solution is exposed to white light. The color of the aqueous D. n=3 l=2 ml=+1 *r=*f thin
solution that is detected by the eye is the complementary

iil[E,u
color of the color absorbed. The color that is associated with
l'I!&
transition metals is due to an electronic transition within the
75. Given that lithium cation emits a red flame, sod:-m ,mfr0ri
d-orbitals (between the d-levels, which split due to the
cation emits an orange-yellow flame, and potass.:m ilhc
presence ofligands). These electronic transitions are referred
cation emits a violet flame, what color flame wili ru
to as d-d transitions, and they occur only with transition
emitted by rubidium cation?
metals that are not d0 or d10 in their electronic configuration.
A. Yellow
7 0. Which cation is paramagnetic? B. Green
A. Na+ C. Blue
B. Sr2+ D. Colorless (and thus the normal orange)
C. Cu+
D. cr3+
7 6. An emission spectrum of lithium would appear in ',i:ruult
manner?
A. It would be a rainbow with a black line in the :C
7 1" What is the electronic configuration of chromium? region of the spectrum.
n. 1ar1+s2:a4
B. It would be a rainbow with a black line in ;:mc'
green region of the spectrum.

B. [Ar]4s13ds
c. itul3d6
C. It would have a black background with a red lin:
D. It would have a black background with a green -Tnc,
D. tArl3d3
Copyright @ by The Berkeley Review@ t42 GO ON TO THE NEXT P.{.

Passage Xll (Questions 77 - 81) 7 9. The half-life of 32P is approximately 14 days. If the
concentration of a32P radiolabeled Glyphosate sample
l, is a synthetic compound
Glyphosate, shown in Figure (C3H8NO6P) is found to be 188 parts per million
.-r:tis currently the world's largest selling commercial initially, how long will it take until the concentration
:,::bicide. Glyphosate kills vegetation by binding metals is 25 ppm?
,:thin a plant, thus starving the organism of essential A. 27 days
.:ta1lic nutrients needed for the transport of other nutrients
..J waste, such as carbon dioxide and oxygen. When B. 33 days
;1,,phosate leeches metals from the plant, its respiration is
C. 41 days
::.lt down. Glyphosate is shown in Figure 1 in its salt D. 43 days
-:rn. as extracted from pH = 7 aqueous solution.
xu* -oy
n-
o
il Tfrt-
*\
Ho r- c// o- **u 8 0. Which of the following molecules have ionic bonding?
I. NHr
-i\
HHHH
-i\
II. COz
Figure 1 m. Na2POaH
After the plant has died, Glyphosate decomposes in the A. I only
:-:sence of moisture into phosphate, carbon dioxide, and B. II only
-,:-nonia. The decomposition products are environmentally C. III only
-::. and some are useful nutrients for the soil. In a study of D. I andll only
-: decomposition of Glyphosate in vivo, isotopically
-::led Glyphosate was applied to vegetation, and the
rpic abundance was monitored at regular intervals over a
:
.nn'-day period. Based on kinetic data associated with

" :iolysis and decomposition, the conclusion was reached
.-.: ihe decay time of Glyphosate to its inorganic products is 81. As 32P decays, it changes into a product that is still
.:::oximately fourteen days. The compound was radio- phosphorus. This is necessary in a marker so that the
-:,:ied in three separate experiments, using a different radio- chemical behavior of the labeled species does not
-::. in each experiment. The first experiment employed change. What is the MOST likely particle given off in
-: ':rr 13H), the second
experiment employed 14C, and the the decay of phosphorus-32?
- :: experiment employed 32P to monitor the half-life and A. A neutron
";:rv rates. Carbon-l4 was used as a marker, but not for B. An alpha particle
::iic purposes. The half-life of carbon-I4 is far greater
":= the lifetime of a typical lab experiment. The isotopic C. Abetaparticle
* ::i3r helps to study the migration of Glyphosate through D. A positron
'- :rYironment.
'-. Which of the following is an isotope of 32P?

.t . 32s
g. 32p-
c. 31p
o. 31si
The molecular geometry about a nitrogen in glyphosate

ls BEST described as which of the following?
-{. Trigonal planar

B. Trigonal pyramidal
C . Square planar
D. Bent
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Passage Xlll (Questions 82 - 88) 8 5. Electron capture by carbon produces the same elemeil
as which of the following processes?
In order to image vital organs by photon emission,
technetium-99 is ingested into the body so that its low-level
A. Positron capture by boron
gamma radiation (140-keV) may be detected. For brain B. Positron decay of carbon
imaging, 99Tc is introduced via the bloodstream, and it C. Beta capture by nitrogen
subsequently diffuses throughout the body, including to the D. Alphadecayofoxygen
brain. Technetium-99 has a half-life of approximately six
hours, so scanning and analysis must closely follow
ingestion. For 99Tc to migrate to all of the target organs in
a concentration high enough to be detectable requires roughly
two hours. After two hours, the concentration of active
technetium-99 is approximately eighty percent (807o) of its
8 6. Gamma radiation is considered to:
original value. Technetium-99 decays through gamma A . weigh 4 amu and have a nuclear charge of +2.
emission, meaning that its nucleons simply drop in one step B . be massless with a nuclear charge of -1.
from an excited nuclear state to a ground nuclear state when C. weigh 4 amu and have no nuclear charge.
they emit photons. The nucleus of technetium does not D. be massless and have no nuclear charge.
change upon the emission of the gamma photon.
For brain imaging, the skull is encompassed by a
detection device that collects and records the gamma radiation
at arbitrary sites. Radiation escapes more readily from the
areas of the brain that have a lower tissue density and fluid
87. The electronic configuration for 99Tc is which of
than those that have a greater density, but a complication in
following?
the analysis of brain images is that the radiation dissipates in
liquid. This means that slight variations in the texture and A. tArl 5s2 3d5
composition of brain matter can produce different imaging B. tKrl 5s2 4d5
patterns. The display pattern collected can be converted into C. tKrl 5sl 4d6
a contour map of the brain. This technique work well with D. tKrl 5s2 4d'l
organs that have a relatively low water content.
8 2. Beta decay of 210Po results in which of the following?

4. 21041
g. 2109i
g. 206p5 8 8. When 99Tc undergoes gamma decay, the final
is which of the following?
p. 20941
A. 99Tc
B. 99Ru
c. 95Nu
D. 99Mo
83. Alpha decay is observed in all of the following
fr ansformations EXCEPT:
4. 2549, 1o 2509p
g. 2389 6234.1y,
g.223pr62219i
g,247gn 6243pu
84. Ifthe initial dosage of99Tc gave a reading of 120 pCi,

what will the reading be after 12 hours?
A. 60 pCi
B. 40 pCi
C. 30 pCi
D. 20 pCi
Copyright O by The Berkeley Review@ 144 GO ON TO THE NEXT

Passage XIV (Questions Bg - 95) 91. Cold fusion is BEST described as:
A. an endothermic nuclear reaction capable ofrapidly
As of March 1989 physicists and chemists had yet to
cooling the environment.
Jarry out a nuclear fusion reaction that did not require more
B. an exothermic nuclear reaction capable of rapidly
3nergy input than output. Fusion reactions require high
cooling the environment.
:imperature and strong magnetic fields to be carried out.
C. an endothermic nuclear reaction capable of being
This is the reason that nuclear power generators are fission
carried out at room temperature.
:eactors. Reaction 1 is an example of a fusion reaction, D. an exothermic nuclear reaction capable of being
:i hile Reaction 2 is an example of a fission reaction.
carried out at room temperature.
!r-i * lu --> zlne

Reaction 1
2frlnn * 2. Nuclear power plants employ what reaction to generate
'3]u * fn -+ 3fn" *
9
fn power?
Reaction 2
Then in March of 1989, B. Stanley Pons and Martin
A. Fission, because fusion requires such a great energy
input that it is inefficient, and the net energy
Ieischmann announced that they has achieved a nuclear
change is unfavorable.
,lsion reaction in a test tube at room temperature. Pons and
:leischmann set up a simple electrochemical cell with a
B. Fusion, because fusion requires such a great energy
:alladium cathode in 0.1 M LiOD(DzO) and a platinum

input that it is inefficient, and the net energy
change is unfavorable.
-rode. The design of the cell was to form D2 gas by passing C. Fission, because fission requires such a great
.n electron flow from the platinum anode to the palladium
energy input that it is inefficient, and the net
::thode. The cell generated more heat than expected, so it
energy change is unfavorable.
;i as proposed that a nuclear reaction must have transpired.
D . Fusion, because fission requires such a great energy
The researchers believed that the deuterium migrated into input that it is inefficient, and the net energy
.:re palladium metal of the cathode and gathered in the change is unfavorable.
:,rckets of the lattice, so they hypothesized that the
:euterium fused together in the palladium electrode by either
R.eaction 3 or Reaction 4.
9 3. Which of the following is a fusion reaction?
lu*ln+ln+lH 2lfrn *
^. 'W [n
Reaction 3
+ -r lu"
ln *la - fn * ln" n. 23faP"
- 23nlu * lu"
Reaction 4 c. "nlru
* lln -2$lcr
Pons and Fleischmann in their original paper stated that n. ferr"- -+ ]errc + rr1
:.rth tritium and neutrons were observed in the cathode of
:eir electrochemical cell, but the concentrations were too
-,rrv to account for the extra heat generated. Since that time,
::e hypothesis of a "cold fusion" nuclear reaction taking 94. What is formed *1t"n 238g emits an alpha particle and
:race under these experimental conditions has been dismissed a deuterium nucleus?
.: improbable by most scientists in the field.
;. 2346"
g. 2326"
19. What is NOT a product when two deuterium atoms g.2369
undergo a fusion reaction? p. 232pu
A. Tritium
B. Helium-4
C. Helium-3
D. Hydrogen 9 5. Capture of which of the following particles would NOT
result in a change in the atomic number?
9 0. What evidence did Pons and Fleischmann point to that A. Alpha
would indicate that a nuclear reaction had transpired in B. Beta
the electrochemical cell? C. Neutron
A . Less heat was released than expected. D. Tritium nucleus
B. More heat was released than expected.
C . That electrons were emitted by the cell.
D. That electrons were absorbed by the cell.
Copyright @ by The Berkeley Review@ t45 GO ON TO THE NEXT PAGE
100. What is the MOST common shape for a
Questions 96 - 100 are NOT based metal with five ligands attached?
9 6.
on a descriptive passage.
Which of the following supports the conclusion that

A.
B.
C.
Squareplanar
Trigonal bipyramidal
Pentagonal planar
I
L
electrons have quantized energy levels?
D. Hexahedral
A. The existence ofa nucleus

B. Scattering of X-rays by a thin sheet of a material
C. The bending of nuclear radiation particles by a
magnetic field
D. Distinct lines in an electromagnetic radiation
specffa
97. The LONGEST wavelength of light would be

associated with:
A. X-rays.
B. violet light.
C. green light.
D. infrared light.
98. The ionization energy of H(g) is 1312 kJ . A good

mole
approximation for the second ionization potential of
helium (g) is:
A. 5248 kJ
mole
B. 2624 kJ
mole
c. 656 kJ 1,C 2.A 3.A 4.C 5.D
mole 6. B 7, D 8.B 9.A 10.B
D. 328 kJ 11. D 12. D 13. D 14. D 15. B
mole 16. A 11. C 18. C i9. D 20. B
2t. c 22. A 23. A 24. C 25. B
26. D 21. B 28. A 29. C 30. C
31. C 32. A 33. D 34. D 35. C
36. D 31. D 38. A 39. C 40. B
41. B 42. A 43. B 44. D 45. B
46. C 41. B 48. A 49. C 50. C
9 9. Which of the following is the electronic configuration 51. D 52. B 53. A 54. D 55. B
for an excited state of Na+? 56. C 51. A 58. A 59. D 60. C
A. k21s22p53s2 61. D 62. D 63. A 64. B 65. A
B. ls22s21p63rt 66. C 61. B 68. A 69. B 70. D
C. k22s21p6 71. B 72. D 13. C 74. B 15. D
D, ls22s22p53s1 16. C 17. C 78. B '.79. C 80. C
81. A 82. A 83. C 84. C 85. B
86. D 87. B 88. A 89. B 90. B
91. D 92. A 93. C 94. B 95. C
96. D 91. D 98. A 99. D 100. B
Copyright O by The Berkeley Review@ STOP, YOU'VE HAD ENOI

Atomic Theory Passage Answers
Choice C is correct. If oil drops were naturally charged, then the experiment could not work, because the total
charge on the droplet would not be generated by the electron beam alone. The charge determined from the
expeiiment would not necessarily reflect the charge of an electron. This eliminates choice A, because it is
asiumed in the experiment that the oit droplet is initially uncharged before exposure to the electron beam.
Because the gravititional pull on the oil droplet is calculated as opposing the electric field, it must be assumed
to be in one direction (downward). If the gravitational pull were in all directions, the experiment would not be
possible. This eliminates choice B. The mass used in the calculation is the average mass of an oil droplet, so
ih" *u5 of the electrons is in fact ignored. This can be assumed knowing that protons and neutrons are far more
massive than electrons. The changi in mass by gaining or losing electrons is negligible compared to the rest of
the atomic mass. This makes choiie C the best answeri an answer to be chosen by many, like you. The charge of
an electron is assumed to be constant, if you are solving for an exact value. The experiment could be solved for an
average value, but there is no reasoning behind one electron being of a different charge than another electron.
This is to say that charge is quantized (has an exact value).
Choice A is correct. In the tube in Figure 1, the electron beam is negatively charged, so it bends downwards due
to its attraction to the positively charged plate below and its repulsion from the negatively charged plate
above. This may seem odd that the cathode plate (plate above) is negatively charged and the anode plate
(plate below) is positively charged, but the plates form a capacitor, not a battery. For a discharging battery
and charging capacitor, the plate charges are opposite. Because a proton has the charge opposite from an
electron lptotonJ
^bend
carry a positi.re charge), protons exhibit behavior opposite from an electron. Proton beams
therefore upwaids. A neutron is neutral, so its pathway would not arc at all between the two charged
plates. The neutron does not arc, because it is unaffected by the charged plates. The correct answer is choice A.
Choice The value of the charge is twice as large as expected. This can be explained in terms of
A is correct.
magnitude of charge rather than sign of charge. A value that is twice as large as expected is attributed to a
aouUty charged oil droplet. Choice A, doubly ionized, would explain this. Choices B, C, and D all address sign
of charge and thus are eliminated.
Choice C is correct. The Thomson experiment, as stated in the passage, determined the mass-to-charge ratio of
the electron. It can be used to determine the mass-to-charge ratio for any charged particle, but in this
particular experiment, the particle was an electron. The best answer is choice C. A mass spectrometer is a
mechanical variation of the Thomson experiment.
Choice D is correct. The charge of an electron is determined by equating the mass of the droplet and the
gravitational force constant (mg) with the voltage of the electric field and charge of the oil droplet (qV). To
Jolve for q, the other three variables must be known. This means that choices A, B, and C are all values that
must be known. There is no temperature factor in the equation (mass, charge, gravity, and voltage do not vary
with temperature), so choice D represents the factor that is least important in the calculations.
Choice B is correct. An atom is neutral when it carries no net charge. Electrons caffy a negative charge, while
protons caffy apositive charge. Neutrons are uncharged. In order for an atom to be neutral, the number of
electrons must be equal to the"number of protons. The best answer is choice B. Choice A is not false per se, but
because there exist isotopes whose number of electrons does not equal the number of neutrons, no conclusion can be
drawn about the number of electrons and neutrons within a neutral atom.
Choice D is correct. The strongest attractive force is felt between particles of opposite charge. This is known as
Coulomb's law. An electron aid proton carry opposite charges, so the best answer is choice D. A proton and
neutron exhibit no Coulombic attriction, but because they are held tightly in the core of the nucleus, there must
be some attractive force between them. Taken literally, this question could not have a proton and a proton
Iisted as an answer choice because of the strong force associated with the nucleus that holds protons together.
This is a more advanced topic that you may see in courses in nuclear chemistry (atomic physics) but as it is
presented" in the MCAT, the ambiguity preiented by nuclear attractions (the uncertainty of the course of the
strong force) is not a probable topic for questions based on their past questions'
147 Section II Detailed ExPlanations

8. Choice B is correct' If an electron is descending, a net upward force must be applied
to accelerate the particle in
the opposite direction. To increase the net upward force, the force upward Lust
be increased or the force
downward reduced- This would slow the parti"le and eventually stop it from dropping.
This means that
either the mass must be decreased, the gravity must be decreased, Ur" charge must be increased,
or the voltage
of the field must be increased. The elsiesf thing to do is increase the iroltage of the field. In
the actual
experiment, this is what is done. Increasing the number of electrons in the drJf increases
the charge, which
should stop (or at least slow) the descent or change the direction of its path io an ascent.
Decreasing the
gravitational pull, which requires ptacing the apparatus in an anti-gravity environment,
would also alleviate
the descending difficulty. The only chbice that would definitely-not stop the descent, but
would in fact
increase the descent, is to increase the mass of the oil droplet. The best ur,rr"", is
choice B.
9. Choice A is correct. All atomic masses in the periodic table are referenced against carbon-12.
Carbon-12 is tlue
standard traditionally used. The carbon-l2 isotope is defined as having u *ui, of exactly 12.0000 amu.
Carbon
is-added to a sample to standardize the mass of the peaks given in thJ spectrum. Not all elements
have exact
whole number masses, so a reference is necessary. you ut" *ir" to pick A.
1"0. Choice B is correct. According to Table L, magnesium has three major isotopes. The isotope
with the lowest
atomic mass is the most abundant (78.70%). This means that the lowest p"ut Uy mass (the
iirst peak from left
to right) ismust be the largest peak. This is true only in the spectrum of choice B.
11. Choice D is correct. The average atomic mass for any element is the weighted average of all
of the isotopes of
the given element. Choices A and B are eliminated, tecause Table 1 lists"only two isotopes
for silver, and the
calculation shows three values being summed. Choice A is the calculation of average atomic mass
magnesium. The correct answer is choice D, because that has the correct percentages muttlpUea by the
cor
isotopic masses. You would be a very wisdom-laden soul, if you were to select D as
liour answer.
72. Choice D is correct. In order to send the isotopes of the element through the mass spectrometer,
the elen
must-be in the gas phase. This means that anlsample not in the gu" piur" initially must be
converted to
gas.phase to be analyzed u-sing mass spectroscopy. The process of lonverting a solid into
a gas is referred to
sublimation, thus making choice D correct.
13. Choice D is correct. Because- the.average atomic mass is an average of the masses of all of the isotopes,
average atomic mass must fall within the range of the isotopic musser, meaning that the average
atomic n
is greater than the lightest isotope but less thah the most mlssive isotope. Whin there are
twJ isotopes c
then the average atomic mass is the weighted average of the two. In i titty-titty mixture of two isotopes,
average atomic mass lies perfectly between the two masses of the isotopei. If the mixture favors
one of
isotopes, then the average atomic mass would be closer to the more abundant isotope than the
less abunc
isotope. The true statements are II and III, making the best answer choice D.
14. Choice D is correct. The difference between isotopes of the same element is found in the number of neutrons,
two atoms have a different number of protons, then they are not the same element. Choices A and B
eliminated, because they allude to a different number of piotons. The greater mass associated with the bo
11 isotope is attributed to an extra neutron being presenf in the Boron-I1 isotope as compared to the bo
isotope. The best answer is choice D.
15. Choice B is correct. The ionization of hydrogen involves an electronic transition from the n 1 energy lel
=
the n = - ener8Y level' Using Equation 1 to determine the transition energy yields the following:
2'778x's'B Q\(1-- 1 \r
\ni' "eJ'
where Z = I,^nt = 1, and nf = x. Having - in the denominator makes the number zero, which results in a vt
2.178 x rc-t9 Gzil. With a value of 2 = 1, tle ionization energy is 2.12t;-10-is-f.' rrr" ionization
ene
hydrogen from its valence level is 2.178 x 10-18 ], which makes tie best answer choice B.
Copyright @ by The Berkeley Review@ t4a Section II Detailed

16. Choice A is correct. This solution requires relating the formula for the energy of a photon to the energy
equation given in the question. The relationship is as follows:
h.
= *. =A =+ l, = -h-
E = mC and E = hc ... mC =
l. l,rlrr
which is choice A.
:[7. Choice C is correct. ChoiceB iseliminated,because fromthen=2energyleveltothen = l energYlevel,there

is a drop in energy, which corresponds to emission of light, not absorption. The best answer is choice C, because
the eneigy levelJ get closer together as the n value incteases, so the transition from the n = 1 energy level to the
n = 2 energy level is always of greater energy than any transition starting at an energy state where n > 1.
However, to be certain, the following mathematical relationship can be derived:
Given that the energy level of an electron is E = -2.178 * tO-t8(*^\1,"

\''t2 /
the transition energy is AE = -2.178x 10-18 ,t\(h -r), = 2.178xr0-18 tz1({ #) ,

The relative energies are therefore comparable by the value of
"" (# #)*trn
$ i).(i i),$ f)=(i'f'(l #'(l #)

,(E--4lt(g-r\
/r -r) > 27 >3, therefore choice C is the best answer.
\ +l \too 100/ \to 76t-34 100 1.6
li. Choice C is correct. Statement I is valid, because as an electron's principle quantum number (n) increases, the
electron is in an energy level (orbit) that is farther from the nucleus. Statement II can be viewed from the
pictorial representation of the energy levels in Figure 1. As the value of n is increasing, the energy levels
beco-e cloier to one another. This makes statement II a valid statement. According to the answer choices, this
makes choice C the best answer. A larger nuclear charge (Z) affects the energy at each level, and thus affects
the transition energies as well. This makes statement III incorrect, and confirms that choice C is the best
answer. Choose C and feel a little giddy.
:q. Choice D is correct. The electronictransitionfromthen = 5 energy level to then = 4 energylevelis of lower
energy than the electronic transition from the n = 4 energy level to the n = 3 energy level. Therefgle, fhe photon
emitied is of lower energy than a photon corresponding to orange light. Because green light is of higher energy
than orange light, choice A is eliminated. The electronic transition from the n = 4 energy level to the n = 2
energy level is of higher energy than the electronic transition from the n = 4 energy level to the n, = 3 energy
level. Therefore, thJphoton emitted is of higher energy than a photon corresponding to orange light. Because
red light is of lower than orange light, choice B is eliminated. The electronic transition from the n = 6
"t ".gy
level to the n = + eiiergy level is of lower energy than the electronic transition from the n = 4 energy level
"."tg!
to the n = 3 energy level. Tirerefore, the photon emitted is of lower energy than a photon corresponding to
orange light. Becilse violet light is of higher energy than orange light, choice C is eliminated. The electronic
transltion from the n = 5 energi level to the n = 3 energy level is of higher energy than the electronic transition
from the n = 4 energy level to itre n = 3 energy level. Therefore, the photon emitted is of higher energy than a
photon correSpondiirg to orange light. Because yellow light is of higher energy than orange light, choice D is
tl're best answer.
ll. Choice B is correct. Choice A is an invalid statement, because according to Beer's law, the absorbance of light
is proportional to sample concentration. Because samples can have varying concentrations, they can in fact
abiorb different utnontrtr of light. The color of light (or frequency) corresponds to transition energy. Because
the sample, independent of concentration, absorbs the same frequency of light each time, the transition energy
must be a fixed value. This leads to the conclusion that energy levels are fixed, and thus quantized. Choice B
is the best answer. The sample emits light of the same frequency, regardless of solution's temperature and
concentration. Temperature can affect the intensity of the light that is emitted, but not the frequency. The
frequency of the light remains constant. This eliminates choice C (temperature effects) and choice D
(concentration effects). Choice B is your answer choice'
-:pvright @ by The Berkeley Review@ 149 Section II Detailed ExPlanations

21. Choice C is correct. A liquid crystal display uses a paramagnetic compound in its polarizing cells to rotate (ol
not rotate) light. A paramagnetic species has at least one unpaired electron. Because chlorides are -1 each
cadmium in CdCl2 carries a +2 charge. This is the result of losing two 5s electrons from elemental cadmiur.
which results in an electronic configuration of 1s22s22p69"29q64t294104064410 for Cd2+. Each level is full, sc
there are no unpaired electrons. Choice A is eliminated. In elemental fluorine, the two fluorine atoms sha-re
their unpaired electrons in the form of a bond. This means that the fluorine molecule has no unpaired electron-i
Choice B is eliminated. Because chlorides are -1 each, cobalt in CoCl2.6 H2O carries a +2 charge. This is the
resultôf l-osi1g two 4s-electrons from elemental cobalt, which results in an electronic configuration for Co2+ cq
b22s22p6g"2gO6g6z. There is anodd number of electrons, so the species mustbe paramJgnetic. The correc:
choice is answer C. Just as was the case with F2, molecular hydrogen (H2) has no unpaired electrons.
i, Choice A is correct. Atomic nitrogen (N) has the electronic configuration 1.s22s22p3. Thu last electron is ttu
third electron to enter the 2p orbital. The principle quantum number is given as 2, and because it is a p-orbita*
the angular momentum quantum number (l) is equal to 1. All of the answer choices contain these two values, ;:
nothing is eliminated. To obtain the m7 and m, values, the electrons must be filled into their respective r-
orbitals. This is drawn below:
'1"
1" 1"
ml= -L ml= 0 ml=+7
Last electron is in the third p-orbital, so 14= +1'
Last electron is spin up, so *, = *
|
The correct answer is therefore choice A.
23. Choice A is correct. Having six ligands attached results in an octahedral shape. The correct answer is choire
A. Drawn below are generic structures for the other answer choices.
N3- L L
C
I I
L
I ....,.*CN
L=7w-r """tot
I I ...*'
ffi;=T L/\,'
T-'
C L
N L
Octahedral Generic square planar Generictetrahedral Generictrigonalbipyramidal
24. Choice C is correct. Polarity results from the asymmetric distribution of electron density. Cis compounds
always polar. The correct answer is choice C. The structures for the four choices are drawn below.
.1- .1-
CI CN
I I
':,/ l"- ''

..'nrCI
NC-i"s:il .|r=r"'d\Jh
CI
I
CN
"ll-z'"s1?
cis-Pt(NHr)2C12 trans-Pt(NH3)2C1"
FeC13- Fe(CN) 53-
Copyright @ by The Berkeley Review@ 15() Section II Detailed Explana

25. Choice B is correct. To determine the number of unpaired electrons (as well as which one has the most), the d-
electron count for each transition metal cation first must be worked out. To determine the d-electron count for
the^ four cations, you must consider the electronic configuration. Neutral chromium is [Ar]4s13d5, so when it is
Cr3+, it has lost the_4s-electron and two 3d-electrons, leaving iJ with an electronic configuration of [Ar]3d3. We
refer to Cr3+ as a d3-cation. Neutral manganese is [Ar]4s23-d5, so when it is Mn2+, it has lost both 4s-electron,
leaving it_with an electronic configuration of [Ar]3d5. We refer to Mn2+ as a ds-cation. Neutral copper is
[Ar]+st3dru, so when it is Cu+, it has lost its 4s-electron, leaving it with an electronic configuration of [Ar]3dro.
We refer to Cu+ as a d10-cation. Finally, neutral nickel is [Ar]4s23d8, so when it is Ni2{, it has lost both 4s-
electron, leaving it with an electronic configuration of [Ar]3d8. We refer to Ni2+ as a d8-cation. From here, it
is a matter of placing the d electrons into their respective orbitals. The electron filling is as follows:
cr3*: I
\=2.
I
r\=-1 n\=0 n\=+1 11q=+2
*., 11, 1L l_L l_L l_L
mr=-2 r\=-1 n!=0 rr\=+1 n!=+2
3 unpaired electrons 0 unpaired electrons
lrrfr2*:
l_ l_ l_ l_ l_
mr=2 n{=-1 ntr=0 r\=+1 rr\ = +2
*i., 1
n\=-2
I l_L i_L l_ l_
rr\=-1 n\=0 11\=+1 11\=+2
5 unpaired electrons 2 unpaired electrons
The most unpaired electrons is found with Mn2+, so choice B is the best answer.
Choice D is correct. The cyano ligand carries a -1 charge, so chromium must have a +6 charge in order for
CI(CN)6 to be neutral. The amino ligand is neutral, so chromium must have a +3 charge in order for CI(NH3)6
to have an overall positive three charge. The charge of chromium is in fact greater in Cr(CN)6 than
Cr(NH3)6, so choice A is valid. The water ligand is neutral, so copper must have a +1 charge in order for
Cu(H2O)6 to have an overall +1 charge. When copper is neutral its electronic configuration is [Ar]4r1r410, so
rvhen copper carries a +L charge, it has electronic configuration [Ar]3dru. This gives copper ten d-electrons
n'hich makes choice B valid. In both Fe(NH3)63+ and FeC163-, iron has six ligands attached, so the shape of
both molecules is the same. Choice C is valid. Scandium has the electronic configuration [Ar]4s23d1, so it can
lose only three electrons. It is not possible for scandium to have a +4 charge (at most it is +3). This means that
choice D is not true. Pick choice D, and feel a little peppier because of it.
Choice B is correct. To determine the number of electrons on the central metal, the formal charge of the metal
tirst must be determined. From the charge, the electronic configuration is found, so the d-electron count is found.
Fe carries a +3 charge in both Fe(NH3)63+ and FeCl53; so choice A is eliminated, because they both must have
the same d-count. Co carries a +3 charge in Co(H2O)63+, and Mn carries a +2 charge,in MnCl64-. Neutral Co is
[Ar]+s23d7, so Co3+ has a d-electron count of 6 (3d6). Neutral Mn is [Ar]4s23d5, so Mn2+ has a d-electron count of
5 (3d5). The d-electron counts are not equal, so cloice B must be the correct answer. Cr carries a +3 charge in
Cr1NH3;6a+, and. Mo carries a +3 charge in MoCfu3-. Neutral Cr is [Ar]4s13d5, so Cr3+ has a d-electron count of
: leae;. Neutral Mo is [Kr]5s14d5, so IiIo3* has a d-electron count of 3 (4d3). The d-electron counts are equal so
choice C is eliminated. Finally, Os carries a +2 charge in Os(NH3)42+ and Rh carries a +3 charge in
RhCl3(PR3)3. Neutral Os is [iie]6124114546, s,o Os2+-l'rut u d-electron count of 6 (5d6). Neutral Rh is
IKAS&4y7, so Rh3+ has a d-electron count of 6 (4d6). The d-electron counts are equal so choice D is eliminated'
:S Choice A is correct. The relative sizes of ions from smallest to largest radius is: Li+. Mg2* < Na+ < Ca2+ < K+'
The rate of effusion is: Li+ t Mg2* > Na+ > Ca2+ > K+. Li+ (the smallest) is the fastest while, K+ (the largest)
is the slowest. The best answer is A. Choice D is eliminated, because cations are smaller than neutral atoms.
:P Choice C is correct. Every trend in the periodic table comes back to the nuclear pull on the electrons. The
ionization potential is the energy required to remove an electron from the outermost shell, which in the case of
sodium and potassium is the 3s and the 4s, respectively. It requires less energy to remove an electron from the
larger 4s-orbital, because the electron is farther away from the nucleus than the 3s-orbital. This makes choice
C the best choice. Choice D is eliminated, because potassium has a lower electron affinity than sodium.
r5l Section II Detailed Explanations

30. Choice C is correct. The size of an ion or element is a result of the nuclear pull on the electrons orbiting the
nucleus. This is best explained by choice C. Because C (carbon) has six protons, F (fluorine) has nine protons,
and both have the same principle quantum number for their valence shell, the nuclear pull of fluorine is greater
than that of carbon. Because the electrons are pulled closer to the nucleus in fluorine, and because size of an
atom is determined by the electron cloud, fluorine is smaller than carbon.
c:'J,s2zs22p2 F: 1,s2zs2zp5
31. Choice C is correct. F-, Ne, and Na+ all have 10 electrons total, so Cl- (with 18 electrons) is eliminated. Of the
three choices left, the largest nuclear charge is found on Na+, making it the smallest (the one with the
electrons held most tightly). Choose C to choose correctness. The following chart of the protons and electrors
for the three choices shows that the greater the proton-to-electron ratio, the smaller the species, assuming
that the outermost electrons are in the same valance shell.
Element Protons Electrons Observation Radius
Na+ 11 10 protons exceed electrons, therefore it contracts 65pm
Ne 10 10 protons equal electrons 70pm
F- 9 10 electrons exceed protons, therefore it expands 136 pm
32. Choice A is correct. The electronic configuration for magnesium is 1s22s22p63s2. Magnesium must lose l
electrons (the two 3s electrons) to have a filled outer valance shell (the n = 2 shell). This would make
magnesium a +2 cation. Answer choice A is a fine selection if your goal is to be correct.
I
JJ. Choice D is correct. According to periodic trends, the size of an atom increases as you descend a column in tlre i{
periodic table. I (iodine) is the lowest in the periodic table of the halogen choices, so I is the largest of tlre 0
halogen choices. Trust periodic trends and choose D. u
34. Choice D is correct. If the pore were to distinguish by charge, then the greater the charge of the cation, (
slower the rate of migration for the cation. For example, if the pore were capable of forming attractiwe il
interactions with the cations such as polar attraction orhydrogen bonding, then the pore would distinguish hry fl
charge. The cations with the greatest charges are Mgzi gec"ause Ca2* is larger than Mgf*, Cai- fr
^nd"Cu2*.
wo.tid migrate more slowly than Mg2+ thiough a pore which distinguishes by both sile and chaige. Th
means that overall , CaZ+ would have the slowest migration rate. This makes choice D the best choice. (
d
T
fr
35. Choice C is correct. The electronic configuration for helium is 1s2. The two electrons of helium are both u
electrons, so choice A is eliminated. Helium cannot have an effective nuclear charge greater than2, because
contains only two protons. Choice B is thus eliminated. The ionization energy does not include Illti
vaporization energy. Helium is a gas at room temperature, so there is no need to add energy to vapon q,*
helium. This eliminates choice D. The electron must be removed from the first quantum level. The fi
quantum level experiences the greatest nuclear attraction, so the Ls-electrons are hardest to remove. It r-s ilh
your best interest to choose C.
36. Choice D is correct. The second ionization energy of the alkali metals (lithium, sodium, and potassium
substantially larger than the first ionization energy, because the second electron is being removed from a
octet. After the first electron has been lost and the alkali metals are cations, their electronic configuration
trr2^p6, and they each have a filled valence shell. To remove the second electron would be like removing G
electron from a noble gas, only harder, because the nuclear charge is greater for the alkali cation than tu
neutral noble gas. Given the answer selections, choice D is the best choice. ts
Copyright O by The Berkeley Review@ 152 Section Il Detailed Explana
Choice D is correct. As stated in the passage, there is half-filled stability for the p-level when each of the p-
orbitals contains one electron. Nitrogen as a neutral element has half-filled stability, so when it is ionized, it
loses its half-filled stability. Oxygen, on the other hand, has one electron beyond the half-filled state;
therefore, when oxygen is ionized, it attains half-filled stability. Losing half-filled stability raises the
ionization energy of nitrogen (ionization is less favorable), while gaining half-fitled stability lowers the
ionization energy of oxygen (ionization is more favorable). Nitrogen is less electronegative than oxygen, so
choice A is eliminated. Nitrogen has seven protons, while oxygen has eight, so choice B is eliminated.
Nitrogen is in fact larger than oxygen, but a larger radius implies that the electrons are farther from the
nucleus on average. Being farther from the nucleus, the electrons are not as tightly held, so the larger radius of
nitrogen would i*ply a lower ionization energy for nitrogen than oxygen. The best answer is choice D.
i]i. Choice A is correct. The ionization energies for aluminum, silicon, and phosphorus follow an increasing linear
trend. All three elements are in the same row (period) of the periodic table, so the number of core electrons for
all three is the same. This eliminates choices C and D. As you move from left to right across a period of the
periodic table, the atomic number increases, so the number of protons increases, and ultimately the effective
nuclear charge increases. The increasing nuclear charge best explains the trend in first ionization energy
between aluminum, silicon, and phosphorus. Be a hero or heroine by choosing A. Note that there is no half-
filled or unfilled p-orbital stability affecting the observed trend.
Choice C is correct. Fluorine and chlorine are in the same column (family) of the periodic table. Fluorine has
its valence electrons in the n = 2 quantum level, while chlorine has its valence electrons in the n = 3 quantum
level. The larger the quantum number, the easier it is to remove the electrons and thus the lower the ionization
energy. Fluorine is more electronegative than chlorine, so choice A is wrong and eliminated. The effective
nuclear charge is found from both the number of protons and the number of core electrons. It is true that chlorine
has a greater nuclear charge than fluorine, but chlorine has more core electrons than fluorine. This implies
that the effective nuclear charge is approximately equal for the two halogens, eliminating choice B. The
larger radius of chlorine implies that the valence electrons are farther from the nucleus on average than the
valence electrons of fluorine. This makes the ionization energy of fluorine greater than that of chlorine and
consequently makes choice C the best choice. Choice D is nonsensical, so ignore it.
Choice B is correct. The term "oxidation" refers to the loss of an electron. The lower the ionization energy, the
easier it is for an element to lose an electron. The chart lists the first ionization energies, therefore it can be
inferred that the element with the lowest first ionization energy is MOST easily oxidized. Of the choices,
magnesium has the lowest first ionization energy. Choice B is the choice of wirrners... be a winner.
Choice B is correct. The relative ionization energies of krypton, bromine, and selenium are predictable, because
they are in the same row (period) of the periodic table. By comparing the three to chlorine, argon, and sulfur,
a trend can be determined. The ionization energies of argon, chlorine, and sulfur follow: I.E.a, > I.E.C1 > I.E.S,
so the first ionization energies of bromine, krypton, and selenium should be LE.6, > I.E.B, > I.E.S", choice B.
Choice A is correct. \vVhen sodium loses its first electron, it gains a filled octet and thus stability in its valence
shell. If it were to lose the second electron, the octet would be lost and thus it would become an unstable cation.
This explains the drastic difference between the first and second ionization energies for sodium. For magnesium
to have a full octet, it must lose two electrons resulting in relatively low first and second ionization energies.
This answer is best explained in answer choice A. The following illustrates the point:
1st ionization: Na(g) -----> Na+(g) + e- Na: 1s22s22p63s1 and Na+: 1s22s22p5 Na+ has a filled octet.
2nd ionization: Na+(g) --> Nu2*(g) + e- Na+: 1s22s22p6 and Na2+: 322t22O5. Na2+ has lost filled octet.
Lst ionization: Mg(g) * Mg+1g) + e- Mg: Ls22s22p63s2 and Mg \s22s22p63r1. Mg+ has no filled octet,
2nd ionization: Mg*(g) ------> vtg2+1g; + e- Mg+:1.s22s22p63s1and Mg2+: :f.22s22p6. Mg2+ has a filled octet.
4i Choice B is correct. Table 1 lists room temperature density values of the transition metals. As a metal is
heated, it expands. The density of manganese decreases with increasing temperature, because volume increases
as mass remains constant. The density is slightly less than 7.43 grams per cmr, so the answer is choice B.
-:pvright @ by The Berkeley Review@ 155 Section II Detailed Explanations

44. Choice D is correct. The first, second, and third rows of the transition metals follow similar trends as you move
left to right across any particular row. The metals from the answer choices are all in the second-row of the
transitions metals. No information is given for the second-row transition metals, so their relationship must be
extrapolated from the information given for the first-row transition metals. The first-row transition metals
follow the trend Cu > Ni > Cr > Mn for the second ionization energy. According to periodic behavior trends, Mo
and Cr should exhibit similar properties, Tc and Mn should exhibit similar properties, Pd and Ni should
exhibit similar properties, and Cu and Ag should exhibit similar properties. This means that the correct
relationship between the 4d-transition metals is found by substituting the second-row transition metals inb
the relationship for the first-row transition metals. The relationship is Ag > Pd > Mo > Tc, making choice D
the best answer.
45. Choice B is correct. The boiling point and melting point of an element increase as the forces holding the at,
together increase. The greater the forces, the greater the energy required to break the forces. Because zinc
u i-o*", boiling and meiling point than other transition metals, it can be concluded that there are weaker fo
holding zinc itoms togethe? than the other first-row transition metals. Because zinc has a filled d-s
([Ar]+s23d10;, there sholld be no covalent interactions between the zinc atoms. This makes choice B the cor
choice.
46. Choice C is correct. All of the transition metals listed in Tabte 1 lose their 4s-electrons prior to losing their
electrons, implying that it is easier to lose the s-electrons. Because the 4s-level fills prior to the 3d-level
can also be concluded that 4s-electrons are at a lower energy level. hr theory, the 3d-electrons should requi
less energy to remove (since the 3d-level is of higher energy than the s-level). However, the 4s-electrons a
*ot" u*posed (further from the nucleus), so they are lost more easily than 3d-electrons. This makes choice
the best answer.
47. Choice B is correct. Within a row of the periodic table, atomic radius decreases as you move left to right
main-group elements. Table 2 shows that it is nearly true for the first row of transition metals, with zi
showing the only notable deviation. As you move left to right across a row of the periodic table, the mass
the elements increases. The density of an element is measured in terms of mass per volume. As the aton
radius increases, the volume increases, so moving left to right across a row in the periodic table results
greater mass and reduced volume. This means that the density of the element increases from left to right in
whele
ieriodic table. Data in Table 2 confirms this inverse relationship, except in the case of manganese,
iadius and density both increase. This eliminates choices A and C. Manganese is an exception, because it
Iarger radius due to half-fiiled stability, but it follows the same trend with density because its mass is g
thin chromium (the previous transition metal). Zinc follows the trend of greater radius associated with l
density, so it is not in exception to that rule. Choice D is eliminated, because a general trend is observ
despite the deviation due to manganese. Choice B is the best choice.
48. Choice A is correct. \zVhen a transition metal element becomes a cation, it loses electrons from the 4s-level
electrons are lost from the outer shell (valence shell), the radius must become smaller. As a note, the
nuclear charge is increasing, because the cation experiences less valence electron repulsion with the a
valence electrons. The best answer is choice A.
49. Choice C is correct. A negative reduction potential implies that it is less favorable to reduce the dication
it is to reduce hydrogen ioi (a proton). Th-e unfavorable nature of the reduction correlates to a low ioniz
energy. The easier it ir to ionize (lose two electrons to become the dication), the easier it is to oxirlize
element. The easier it is to oxidize the element, the harder it is to reduce the dication that forms. The sur
the first and second ionization energies of Mn is 2226 kl/mole, and the reduction potential is -1.L8 volts-
sum of the first and second ionization energies of Co is 2405kJ/mole, and the reduction potential is -0.28
The sum of the first and second ionization energies of Fe is 232Okl/mole, which is closer to the value of
(differs by 85 kjlmole) than the value of Mn (differs by 94ld/lnrtole). The reduction potential should be br
-1.18 voltl and -0.28 volts, but closer to -0.28 volts. The best answer is choice C. (The actual value for any
electromotive force trivia buffs is -0.44 volts.) The data are given below:
N&r -+ Mn2+ + 2 e- L lst and 2nd I.E. =2226 kj/mole E'oxidation = L.18 V .'. E"1s4r6tion = -1-
Fe --+ Fe2+ +2e ; 1st and 2nd I.E. =2320kjlmole E'oxidation = ??? Y i' E"reduction= ???
Co + C&+ +ze- L lst and 2nd I.E. =2405 kJlmole E'oxidation =0.28 V ;. E"1s6r6ti.. -
Copyright @ by The Berkeley Review@ t54 Section II Detailed
i0. Choice C is correct. It is grunt work when it comes to figuring out electronic configurations! You can save
yourself some time by eliminating choices with either too many or too few electrons. Aluminum has thirteen
electrons, as do all of the choices. This means that no choices are eliminated. Choice A is out, because an s-
orbital can hold no more than two electrons. Choices B and D are eliminated, because the s-orbital fills
completely before the p-orbital begins to fill. The correct answer is choice C. If it is needed, the Aufbau
principle can be applied to determine the filling order.
Choice D is correct. Monochromatic light is light that is composed of photons with exactly one wavelength (or
frequency). This would occur if every photon emitted came from exactly the same electronic transition between
energy levels. However, not all electrons are at exactly the same energy level, due to the close proximity of
rotational and vibrational levels. As a result, not every electron undergoes the exact same energy transition,
and thus not every photon that is emitted has the same energy (and thus neither the same frequency nor
wavelength). This is stated near the end of the passage. Choose D to be a stellar student.
Choice B is correct. This question requires determining the photon's energy from its wavelength
(6.6x1"0-3aJ.sec x 3.0 x 1084) x 10-26J.m
c-hc-
l.
_ 19.8
r E=+*r1o-1el
330 x 10-9m 3.3 x 10-7m J.J
The more important part of the answer is the power of ten. From that, you must select choice B.
Choice A is correct. The shorthand for the electronic configuration of vanadium is [Ar]4s23d3. For the quantum
numbers of vanadium, we are concerned only with the last electron in vanadium (V). We are therefore
concerned with the third 3d-electron. Drawn below is the 3d level:
3d
1o
l_
ffil=-z
1" 1'
ffil =-1 ml= o ml=+1 fll= +2
lr
r
n
4s Lml= 0
Last electron is in the third d orbital, so rn1 = 0; Last electron is spin up, so *r=+ j
lhe last electron is in the n = 3 level, because that is given by gd3. The electron is in the 1 = 2 level, because
that is given by d-orbital in 3d3. The m1 and ms values must be derived by filling electrons into their respective
-er-els. As listed in the box, rrll = 0, ms = +! / 2, which is choice A.
,rJr- Choice D is correct. Half-filled stability would come into play for atoms that can promote one electron from
::e lower energy s-orbital up to the higher energy d-orbital to yield a d5 species. The term "half-filled
s:ability" is derived from the half-filled d-level (the d-level has a maximum occupancy of ten electrons).
:{alf-filled stability is possible for only chromium (Cr), molybdenum (Mo), and tungsten (W), because they are
:-l in the column that should be s2d4. To be a quality chemistry student, pick choice D. Copper can excite one s-
.-ectron to fill the d-level completely (to make the species a d10 atom).
frffiiii ,Choice B is correct. Whatever goes in, must come out for normal behavior of light. There are situations where
: high-energy photon is absorbed that results in the excitation of an electron through multiple levels. From
:ere, the electron may relax (fall back to the ground state) by a variety of pathways (either gradually
::-isipating its energy or releasing the energy all at once). As a general rule, the energy that is absorbed is also
:ritted. Pick choice B. The exception to this rule is phosphorescence. With a phosphorescing species, light
:,:.ergy is absorbed, and the compound undergoes a change in its electronic structure. The excited state is
:.erefore a different complex than the ground state. \Atrhen the new complex gives off energy to fall to its
-ound state, the photon released is not of the same energy as the original photon absorbed. Phosphorescence
rd fluorescence were passage topics on a previous MCAT. Quantum numbers were also a passage topic.
,n- ::fht @ by The Berkeley Review@ 155 Section II Detailed Explanations
55. Choice C is correct. Visible light is found approximately in the range 390 x L0-9 m to 740 x 10-9 m. To be used
the formula provided, the wavelength must be in terms of 10-6 m. Visible light has a range from 0.39 x 1,0-6 m
0.74 x 10-6 m. The value for this range in terms of eV is 1"24 / 0.74 sy b 1,.24 f g.39 eV. This is a range from
number just over 1.5 to some number barely greater than 3.0, a range that fits choice C.
57. Choice A is correct. The reflected color of the four pigments are yellow for alizain, blue for azurite, red
cinnabar, and blue-green for verdigris. To determine the light absorbed, you must take the complementary
of the color observed. The absorbencies are thus violet for alizarin, orange fot azutite, green for cinnabar,
orange-red for verdigris. The shortest wavelength is associated with the highest-energy light. Violet
the highest energy in the visible spectrum, so it has the shortest wavelength. The correct answer is choice A
58. Choice A is correct. When a sample is heated, its electrons are thermally excited to a higher energy
When they relax back to their ground state, light is emitted at an exact wavelength. This results in light of
specific color, best described by choice A.
59. Choice D is correct. The absorption spectrum contains black lines where the complementary colors of or
(the colors reflected by realgar) should be. The complementary colors are blue-green, so the best ans
selection is choice D.
60. Choice C is correct. The reflected color of verdigris (Cu(C2H3Oz)z.Cu(OH)2) is green-blue, so the
color is red-orange. Red and orange lie at the low end of the visible spectrum as far as the energy is
so the wavelength lies at the high end of the visible spectrum. The spectrum goes red
blue-violet, so the wavelength of orange light falls below 700 nm, and the wavelength of red is around 700
This means that the wavelength is less than 700 nm by a small amount. The best answer is 650 nm,
makes the best answer choice C. The range of visible light in the EM spectrum is given on page 1L3.
61. Choice D is correct. Because white lead appears white in color, no light has been absorbed in the visible
When no light is absorbed, white light (the incident light) is reflected. The d-d transition associated
white lead must lie outside of the visible range. The best answer is thus choice D.
52. Choice D is correct. A reflected color can be seen only when white light is reflected off of it. This means
reflected colors cannot be seen in the dark (absence of white light). Candles cannot be seen in the dark, so
colored candle is made from a wax that contains a dye that exhibits reflected color. Clothes cannot be seen i
the dark, so a fabric dye exhibits reflected color. If you wish to argue that there are certain glow-in-
fabric dyes, you're absolutely right. Glow-in-the-dark dyes exhibit emitted color. You are wise in the wavs
trivia. Unfortunately, you get zero credit on this question, because it is not the best answer. Knowing a
special cases like that is a great way to impress your peers, but it hurts you on a standardized exam. Ink
pens cannot be seen in the dark, so ink exhibits reflected color. Gas-filled light tubes (i.e., neon lights) can
seen in the dark, so a glowing gas-filled light bulb exhibits emitted color. The best answer is choice D. I
I
53. Choice A is correct. The fastest decomposition is observed in the organic pigment. This is stated in t
passage. The inorganic pigments are already oxidized, so they should remain air-stable for some time. t
organic pigments can oxidize in air, so they do not last as long. The only organic compound among the choi
(and in Table 1) is 1,2-dihydroxyanthraquinone, which is the pigment of alizarin. This makes choice (
correct. Note that organic pigments contain conjugated n-networks and are found in oil-based paints. f

t
1
U. Choice B is correct. As stated in the passage, a spin flip is associated with the process of phosphorescence.
-F
the ground state, two electrons in the same orbital must be spin-paired (have opposite spins). Once an e e
has been excited to a higher electronic level where it occupies the orbital alone, it is free to flip its
Equally, the electron that remains in the ground state may also flip its spin. A spin flip changes the (
energy of the system. The excited electron may not be able to relax back to its original level, since it shares u
same spin as the lower level electron now. \A/hen the electron falls back to a lower level, it falls to a dif e
energy level, which emits a different frequency of light than it absorbed. Whether or not you know !'!
phosphorescence is, the answer is given in the passage. The best answer is choice B. B
Copvright @ by The Berkeley Review@ 156 Section II Detailed

55. Choice A is correct. A diatomic molecule can gain and lose energy in several ways, including changing
electronic levels, vibrating at different frequencies, and rotating at different frequencies. In a diatomic
molecule; when an electron is excited, the valence shell increases, which affects the bond length and bond
strength. The diatomic molecule is more susceptible to changing its vibrational frequency. This is the physical
cause of fluorescence. \Atrhen an electron in the diatomic molecule is excited, a photon is absorbed. Because
energy is dissipated from the excited state in the form of rotational and vibrational energy, the molecule is in a
lower energy state. When it finally relaxes back to its ground state, the energy of the photon emitted is less
than the energy of the photon absorbed. The energy of the photon absorbed is equal to the energy of the photon
emitted plus the dissipated energy (vibrational and rotational transitions). This eliminates choices B and D.
As the wavelength of a photon increases, it has less energy. This implies that the photon emitted @eing of
less energy) has a longer wavelength than the photon absorbed. This makes choice A correct.
l'ti. Choice C is correct. "Because the electronic energy levels are not singular levels and because the transition is
random, it is impossible for a molecule to absorb or emit light in such a manner that all of the photons
simultaneously have the same frequency (or wavelength). For this reason, monochromatic light is not
physically possible." These last two sentence from the passage state that monochromatic light (light of one
wavelength) is not possible, and give the reasoning for that. Because monochromatic light is not possible,
choices B and D are eliminated. The reasoning has to do with energy levels, not the quantization of light, so
choice C is the best answer. This question about a difficult concept is actually an easy question to answer, if you
don't get intimidated. Leaming to manage the intimidation factor associated with seeing new information is a
part of your MCAT preparation.
For the sake of learning the concept, we shall look at what choice C is stating. The diagram below shows two
scenarios, one where electronic transitions are not coupled with vibrational transitions (on the left) and the
other one where electronic transitions are coupled with vibrational transitions (on the right).
Electronic Transition (no vibrational transitions) Electronic Transition (with vibrational transitions
EExcitedV2
EExcited EExcitedVt
EExcitedVo
EGrou,.dV2
EGroutrd EGrorrr,dVl
EG.orr.rdVo
Electronic transitions occur without vibrational Electronic transitions occur withvibrational
transitions, so a single energy transition is possible. transitions, so a multiple energy transitions
Only one photon is emitted, which would result in are possible. Multiple photons are emitted, so
monochromatic light. the emission is polychromatic light.
From the diagram, it can be seen that when vibrational energy levels are closer together than electronic energy
levels, the transitions can couple. Single transitions between electronic levels are not possible, although single
transitions between vibrational levels appear to be possible. However, vibrational transitions couple with
rotational levels, so inJrared emissions are not of single wavelength. The best answer is choice C.
r.f Choice B is correct. The arrow in Figure 1 that represents emission due to fluorescence is longer than the arrow
that represents emission due to phosphorescence, so the energy associated with fluorescence is greater than the
energy associated with phosphorescence. This means that the light from fluorescence is of shorter wavelength
than the light from phosphorescence. Choice B is the best answer. Choices A and D are the same answer
worded differently (if fluorescence emission is of longer wavelength than phosphorescence, then
phosphorescence must have emission of higher energy than fluorescence), so both choices should have been
eliminated (assuming as we do that there is only one best answer per question).
rlrrlt' Choice A is correct. The shortest wavelength of light belongs to light of the greatest energy. This occurs with
the transition from the highest excited state relaxing to the lowest ground state. Choices C and D are
eliminated immediately, because the transitions they represent are increases in energy, which absorb light,
not emit light. The best answer is choice A, because the excited state is the highest of the choices left (A and
B), and both of the choices left drop energy to the same ground state.
157 Section II Detailed Explanations

59- Choice B is correct. Fluorescence is possible with molecules, because molecules can exhibit vibrational energl
transitions. This allows for the dissipation of energy via of heat. Choices A and C true, so they are
eliminated. Because atoms do not have vibrational energy transitions (they have no bonds, so they have nc
bending and stretching modes of their bonds), atoms may not necessarily exhibit fluorescence. It is possible tc
convert ultraviolet light to the lesser-energy visible light by fluorescence, but it is not possible to conver
visible light to the higher-energy ultraviolet light by fluorescence. This makes choice B the false statement.
f
'F.il-
70. Choice D is correct. The definition of paramagnetic is having at least one unpaired electron. The electron:r
configuration for Na+ is 7s22s22p6. All electrons_ are, pqire{, b-ecause the octet is complete, eliminating choi:e
A. The electronic configurationior Sr2+ is7s22s22p6it29064t236704r6. Ail electrons are paired, because tlu
octet is complete, elimiiating choice B. The electronic configuration for Cu+ is 1,s22s22p6is23063410 (copF*s
has filled d-shell stability, and it loses its 4s-electron before its 3d-electrons). All electrons are^pairea
because each level is filed, ehminating choice C. The electronic configuration for Cr3+ is k22s22p6gs2gp6aO3
(first-row transition metals lose their s-electrons before losing their 3d-electrons). Not all electrons can re
paired, because there is an odd number of electrons. Because Cr3+ is paramagnetic, choice D is the best answer.
71. Choice B is correct. Chromium has half-filled d-shell stability, giving it an electronic configuration cn
7s22s22p69t291647965. The correct choice is answer choice B. Without the half-filled stability, the ansrrm
would have been choice A. Molybdenum (Mo) and tungsten (W) also exhibit half-filled stability.
72. Choice D is correct. The largest transition is associated with the greatest energy. Vanadium dication (\-:-r
produces violet light, therefore the highest energy is associated with vanadium dication. Pick choice D.
/5. Choice C is correct. It can be observed from the data in Table 1 that as the first or second columns in rP
periodic table are descended, the light emitted frorn the transition is of progressively higher energy. Ti,:m
makes statement I a true statement. Because statement I is not included in choices B and D, choices B and D ae
eliminated. It can be deduced from the answer choices that rernain that statement III must be false. To verly'
this, copper has the electronic configuration[Ar14s13d10, so Cu+ has the electronic configuration [Ar]3d:r'
Nickel his the electronic configuratioir [Ar]4s23d8, so-Ni2+ has the electronic configuration [Ar]3d8. Statene
III is in fact a false statement, because Cu+ and Ni2+ do not have the same electronic configuration. I
transition for potassium cation (K+) emits purple light, while the transition for chromium trication (Cr-
yields red ligtrt. The transition for K+ is of high"t than the transition for Cr3+, making statemen:
true and choice C correct. "r"rgy
74. Choice B is correct. Nickel dication (Niz*, has the electronic configuration"J,s22s22p63s23p636s. *"
electron is the eighth electron in the 3d-orbital. The principle quantum number is given as 3 and being in a
orbital makes I equal to 2. From the answer choices, this is already known. To obtain the m1 and mr values,
electrons must be filled into their respective d-orbitals. This is drawn below:
N,2*, 'lf
t\=A'
"1r
n\=-1
'lf rr\=0
'l_
n\=+1
"1
n!=+2
Last electron is in the third d orbital, so n! - 0; Last electron is spin down, so ms = I
2
The correct answer is therefore choice B.
75. Choice D is correct. Because violet light is higher in energy than orange-yellow light, which is in tum
energy than red light, the electronic transitions for the group I cations increase as the column is descended.
transition for rubidium should therefore be of greater energy than violet light, which makes the tran-':
emit ultraviolet light. Ultraviolet light is not detected by the human eye, so the flame from heating I
should appear coloriess. The best answer is choice D. j
J
il
'n
Copyright @ by The Berkeley Review@ l5a Section II Detailed Ex

76, Choice C is correct. An emission spectrum shows just the color emitted by the compound after it has been
excited. The color observed in the flame test is an emitted color, so it is present in the emission spectrum.
Crimson was emitted by lithium cation, so the emission spectrum is simply a bright red line. The best answer is
choice C. Other minor emissions may be seen, but they won't be as intense as the red emission.
Choice C is correct. Two isotopes (of neutral elements) have the same number of protons and electrons, but a
different number of neutrons. Choice A has one more proton than phosphorus-32, choice B has one more electron
than phosphorus-32, and choice D has one electron less than phosphorus-32. This eliminates choices A, B, and
D. Choice C has a mass that is one less with the same number of protons as phosphorus-3Z, so it must have one
neutron less. This makes choice C the correct answer.
:3. Choice B is correct. Nitrogen in neutral molecules makes three bonds total (in this case, the three bonds are all
sigma bonds), and has one lone pair of electrons. The lone pair of electrons repels the electrons in the three
sigma bonds to form a trigonal pyramrj{al orientation about the nitrogen. This can be confirmed when looking
at the hybridization of nitrogen (sp3). The best choice is therefore answer B. Drawn below is a threel
dimensional picture of Glyphosate with the nitrogen isolated:
H/dXt*Co'-Na+
-crqoeorFf Nu*
ru. Choice C is correct. The concentration of 32P label at consecutive half-life points along the first-order decay is:
188 -+ 94 -+ 4 -+ 23.5. Each arrow represents one half-life, so after three half-lives the concentration is less
than 25 ppm (it has decayed to 23.5 ppm). To reach a concentration of 25 pprn, it takes a little less than three
half{ives. The best answer is a little less than 42 (3 x 14) minutes. Choice C, 41 minutes, is the best answer.
tr{il. Choice C is correct. An ionic compound is made up of ions. The quickestway, without just knowing the answer,
is to look for metals such as sodium. Ammonia is held together by three covalent bonds (sigma bonds). Carbon
dioxide is held together by two covalent bonds (two doubles bonds made up of one sigma bond and one n-bond
each). It is only in compound III, Na2PO3H, that we find ionic bonds. Choice C, III only, is the best answer.
Choice A is correct. Because 32P remains chemically equivalent after nuclear d.ecay, it is phosphorus. This
means that a proton was neither gained nor lost in the process. \Atrhen a neutron is lost, a phosphorus-32 isotope
becomes a phosphorus-31 isotope. This makes choice A the best choice listed. An alpha particle contains two
protons and two neutrons, so the loss of an alpha particle would form aluminum, eliminating choice B. The loss
of a beta particle converts a neutron into a protory which would form sulfur, eliminating choice C. The loss of a
positron converts a proton into a neutron which would form silicon, eliminating choice D. The answer choices
did not list a gamma ray. A gamma ray is a high-energy photon that, when given off, does not change the
chemical behavior, either. This was not listed as a choice, but it is food for thought.
m- Choice A is correct. Beta decay is the loss of an electron from the nucleus. No mass is lost, therefore the mass
should not change. Choices C and D are eliminated. Charge must be conserved, so losing a negative charge
should increase the atomic number by 1. This makes choice A the best answer. The reaction is shown below:
2$!ro+-!e+2$$et
ffi, Choice C is correct. An alpha particle is a helium nucleus (mass = 4 amu and z = 2), so the loss of an alpha
particle decreases the mass by 4 and the atomic number by Z. 250Sp is 4 mass units less than 254Es, so choice A
is eliminate4. 23a11t is 4 mass units less than 238U, so choice B is elimina L4. 22rgi is only 2 mass units less
ttran 223Fr, so choice C is the best answer . 243pu is 4 mass units less 11'rvyr247grr, so choice D is eliminated.
What else but berkeliuru could be right?
:qi.nght @ by The Berkeley Review@ 159 Section II Detailed Dxplanations

84. Choice C is correct. From the passage, the half-life is given as six hours. The twelve-hour duration is
therefore a total of two half-lives. The initial concentration should therefore be cut in half two successive
times to determine the final concentration. The math is as follows: 120 pCi 60 pci 30 pCi. The final
reading is 30 pCi, so the correct choice is choice C.
-> ->
85. Choice B is correct. Electron capture by a nucleus decreases the positive charge (converting a proton into a
neutron), which reduces zby 1,. This converts element # 6 (carbon) into element # 5 (boron).
tF * -or" -+ 1s2B
The question is asking for a nuclear process that forms boron. Positron capture increases the nuclear charge br
one, so positron capture by boron cannot yield boron. It yields carbon, one atomic number higher, which
eliminates choice A. Positron decay decreases the nuclear charge by one, so positron decay by carbon yield.
boron, one atomic number lower. This makes choice B the best answer. Beta capture decreases the nuclee
charge by one, so beta capture by nitrogen yields carbon, one atomic number lower. This eliminates choice C
Alpha decay decreases the nuclear charge by two, so alpha decay by oxygen yields carbon, two atomic numbers
lower. This eliminates choice D. The best answer is choice B, the only choice that didn't form carbon. The
processes in choices A,B, C, and D are shown below.
ChoiceA:1!B+!s+1[C;ChoiceB,lp.-+13B+t8;Choicec:1fN+-fe+1fC;Choiceo:1$o+1frC+3n
86. Choice D is correct. A gamma ray is high-energy electromagnetic radiation, not a particle. The energl
associated with a gamma ray is greater than the energy associated with an x-ray. Because it is a photc:,
(energy) and not a particle, a gamma ray is massless and without charge. \A/hen the nucleus of what emit-' a
gamma ray, it drops from a nuclear excited state to a lower (and possibly ground) state, as mentioned in tl,*
pu"rug". No -uri is lost by gamma emission. Choice D is the best answer. Choice A describes an alp:;
particie, and choice B sort of describes a beta particle (the charge is negative one, but it is not necessarily tF*
nuclear charge). Choice C is not a common nuclear particle and is probably a conglomeration of subatomr
particles.
87. Choice B is correct. The electronic configuration for 99Tc is no different than for any other isotope :r
technetium. Although isotopes have a different number of neutrons, they have an identical number of protc:,r
and an identical number of electrons in their neutral state. Technetium is element number 43, so it has 43 protcrs
and 43 electrons as a neutral element. The filling of electrons follows standard Aufbau principle rules, wh-:m,
makes answer B the right choice. It is sometimes a shortcut to look at the periodic table and see where the I'amtt
electron falls. In the case of technetium, it is directly below *ungunur", so its last electron should be a ;i*
electron (like manganese). The last electron is in a 4d-orbital, so choice B is best.
88. Choice A is correct. Gamma decay just involves the loss of nuclear energy, and not a particle. Technetium 5;
from an excited nuclear state to a iow"r nuclear state after it undergoes gamma decay. No nuclear particles ; {
lost or gained by technetium, so its mass and atomic number remain the same. This means that the nuc-; .
.o*poftion of iire element remains the same, so the element remains the same. The correct choice is thus A. .
"rl
89. Choice B is correct. Reaction 3 and Reaction 4 show fusion of two deuterium atoms. The fusion of two deuter: :
atoms can generate either a tritium (3H) and hydrogen 1tH) (as shown in Reaction 3), or one neutron and hel: ]
isotope 13tie; 1ut shown in Reaction 4). The only particle in the answer choices that is not shown as a proi :
l
is helium-4, so the correct answer is choice B.
90. Choice B is correct. We see in the passage, that the major piece of evidence for believing a nuclear reactiorr
transpired was the release of mole heat than can be explained by the electrochemical cell reaction.
expecied nuclear products were observed only in low concentrations however. The best answer is choice B'
abiorption or emission of an electron (beta particle) had no effect on the reaction.
91. Choice D is correct. As described in the passage, cold fusion is a nuclear fusion reaction that can be carrie;
at room temperature. The example in the passage takes place in an electrode within a test fube. Because i
energy is released than expected, it can be assumed that the fusion reaction is exothermic (because of the
heat tirat was released). The correct answer is choice D. Pick D, and you'll smile brightly.
Copyright @ by The Berkeley Review@ 16() Section II Detailed

92. Choice A is correct. In the passage, we read that nuclear power plants employ the fission reaction, because to
date, fusion reactions require both high temperature and strong magnetic fields. Fusion reactions require more
input energy than the fusion reaction releases, making them endothermic and unfavorable as a source of energy.
The best answer is choice A.
93. Choice C is correct. A fusion reaction results in the combination of the nuclei of the two particles undergoing
fusion. Answer choice C involves the combining of two particles to form one product (with an atomic number
greater than the two incident particles). This defines fusion. Choices A and B are both fission, and choice D
involves the emission of a gamma photon via the drop from a nuclear excited state to the nuclear ground state.
94. Choice B is correct. An alpha particle has a mass of four and two protons, and a deuterium nucleus has a mass of
two and one proton. After losing an alpha particle and deuterium nucleus, the mass of an element drops by six
and the number of protons drops by three. Choices A and C are not six mass units less, so they are eliminated.
Choice D is not three atomic numbers less, so it is eliminated. The process is shown below.
,t&u -+ 2T#"
la + lu*
Choice C is correct. A change in the atomic number results from a change in the number of protons in the nucleus.
The alpha particle has two protons, so the capture of an alpha particle increases the atomic number by two.
This eliminates choice A. The capture of a beta particle converts a proton into a neutron, so the atomic number
decreases by one. This eliminates choice B. The tritium nucleus carries one proton, so capture of a tritium
nucleus increases the atomic number by one. This eliminates choice D. A neutron capture increases the mass by
one, but does not affect the atomic number. Choice C is the best answer.
Choice D is correct. "Quantized energy levels" refer to states of finite energy where electrons may exist. For
this exam, you should know conceptually what behavior is expected. The existence of a neutron or proton at the
nucleus may exert Coulombic forces on an orbiting electron, but it does not have any bearing on the quantization
of energy levels. Choice A is therefore eliminated. The scattering of x-rays by thin sheets of material (metal
foil in the Rutherford experiment) shows that matter is mostly empty space, with dense uniformly spaced
nuclei. Choice B is eliminated. The bending of any particle when moving through a magnetic field simply
indicates that the particle in motion has a net charge of some kind, and that the direction of motion is not in
line with the field. Choice C is eliminated. Distinct lines (which can be reproduced in separate trials) show
that the same amount of energy is absorbed when an electron is excited. If the transition between levels is a
quantized value (an exact quantity), then it seems logical that the energy levels are also quantized. This
makes choice D the correct answer.
Choice D is correct. As the wavelength of a photon increases, the energy of the photon decreases. This question
is testing your recall of relative energetics of electromagnetic radiation. The lowest energy of the choices given
is associated with infrared light. This makes D the best choice.
Choice A is correct. The value oI Z"Sy for H is +1. The value of Zsff for He+, the starting point for the second
ionization of helium, is +2. Because the ionization energy is proportional to 22, the second ionization energy of
helium should be four times as great as the ionization energy of hydrogen. Both electrons in question are being
ionized from the 1s-orbital, so n = 1 for both ionization energies. You need consider only the effective nuclear
charge. To feel the sensation of correctness, pick choice A. Drawn below are the respective ionization
reactions:
\-
\"
-1
%
,A.n=1
/ra\
g/
@
H -----> tt* + 1e H"* --> + Le
""t*
ight @ by The Berkeley Review@ 161 Section II Detailed Explanations
99. Choice D is correct. Sodium cation has ten electrons, which eliminates choices A and B, both with eleven
electrons. Choice C is the ground state (all electrons fill sequentially) for sodium cation, given that it has ttre
ten electrons filled in order. In choice D, there are ten electrons and an electron has been excited from the 2p.
level to the 3s-level. This leaves choice D to be the best answer.
100. Choice B is correct. The most common shape for a transition metal with five ligands is trigonal bipyramideil
The best answer is choice B. Square planar has only four ligands attached, so choice A is eliminated-
Hexahedral does not exist; and if it did, hex is Greek for six, and only five ligands are attached. This wouM
also eliminate choice D. Drawn below is a chart for determining molecular shapes:
Coordination Number = 2 Coordination Number = 2 CoordinationNumber = 2

ao
.A.
/A:--
L-L ,/"\
LL
2
no lone pairs (sp hybr.) one lone pair (sp t-rybt.1 two lone pairs (sp3 hybr.)
Linear Bent Bent
Bond Angle - 180" Bond Angle <120' Bond Angle < 109.5'
Coordination Number = 3 Coordination Number = 3 CoordinationNumber=3

L L
I ro.7^\, lP';-' or
,-zA:-, L '-{,'
L
2
no lone pairs (sp hybt.l one lonepair (sp 3 hyur.; two lone pairs (dsp3 hybr.)
Trigonal Planar Trigonal Pyramidal Trigonal Planar or T-shaped
Bond Angles = 120" Bond Angles < 109.5' Bond Angles = 90', 120", 180'
Coordination Number = 4 Coordination Number = 5 Coordination Number = 6

L L L
I
I
|
'-ia' | L
-"'rrtl L
I
r,--rl-
'"'s u
,*/\,. ,/l
"l
L L
3
no lone pairs (sp t ytrr.; m lone pairs (dsp3 hybr.) m lone pairs (d2sp3 hybr.;
Tetrahedral Trigonal Bipyramidal Octahedral
Bond Angles = 109.5" Bond Angles = 90'& 120" Bond Angles = 90'
Copyright @ by The Berkeley Review@ t62 Section II Detailed Expl

Fundamentals of Dguilibrium
a) Definitions and Terminology
b) Dquilibrium Constant (Keq)
Section Itr c) Keaction Quotient (Qrx)
d) Case Specific K-Values
e) Keq Calculations
f) Using Keq to Calculate Shifts
Equilibrium g)
h)
Complex trquilibrium
Experimental Determination of K
by Todd tsennett
Le Chdtelier's Principle
A(S) + 6191 C(S) + D(g) a) Effect of Stress
==- b) Perturbations and Shifts
r{ products (Pc)(Po)
' 'e9
neactants (Pn)(Pn)
i. Direction of Shift
Uncatalyzed
Solubility
Catalyzed
a) Definitions
b) Solubility Rules
l-
c) Ionic Structures
L
(h
a
i. Nomenclature of Salts
a li
ii.Polyatomic lons
Rate reverse d) Solubility Product and lvlolar Solubility
e) Relative Solubility
Time f) Solubility trxperiments
s) Common lon Effect
h) Separation by Precipitation
i) Ion Exchange Columns
L) R.E.v.r.E.w*
Speci aLtztng in MCAT Preparation
Equilibrium Section Goals
ov Know how to determine an equilibrium constant from exDerimental data.
There are experiments that are designed to determine a change jn total pressure over time for a gas
equilibrium system. The change in pressure (from the time the reactants are mixed until the reactiorr
reaches a steady equilibrium pressure) can be used to calculate an equilibrium constant. The difference
in pressure is the shift requiied to reach equilibrium
Understand Le Chdtelier's principle and its effects on eguilibrium svstems.

@3 Le ChAtelier's principle predicts certain behavior in an equilibrium system once a stress is applied
to the system. Because changing one variable can affect another variable (for instance, changihg the ;
p_ressure may also change the volume), you must evaluate how the chemical reaction will a-djuit to
alleviate the applied stress in order to reestablish equilibrium. r
l
:llr
Understand the mathematical arrangement of the equilibrium expression. u
The equilibrium expression, simply put, is the ratio of products over reactants. The mathematical rtrrl
rules require that you do not put pure liquids (solvents) or solids into the expression. If more than "llrf1
one mole of product or reactant are involved in the reaction, then the stoich:iometric coefficient in
the balanced equation becomes an exponent in the equilibrium expression. The value of the
equilibrium constant changes only with temperature. ltit
J]ll
Know the effects of the system variables P, V, n, and T on reaction equilibrium.

@v It is not possible to change just one variable in an equality. Changing the conditions of the system filrntc
shifts an equilibrium, but it does not necessarily change the equilibrium constant. The nurnerical Lffi
t*
value of the equilibrium constant changes only with temperature. trh!
ilm
Know the relationship between molar solubility and solubility product. lmil
"V The molar solubility of a salt is the concentration of the salt (as measured in molarity) needed to
solvate an aqueous solution completely. The solubility product is an equilibrium consiant for the
dissociation reaction. What makes solubility products unique is that the reactant is alwaya a solid,
,$ilu
i$nu
tih
so the equilibrium expression has no denominator. Molaf solubilitv is a more useful quantity to trur{,
know thin solubility product, because it measures the amount of sali in solution. fihtrx
pllLu
Understand separation by precipitation and the chelation effect. Sils'
'w Chelating is the formation of a Lewis acid-base bond between a lone pair-donor (ligand) and a lone-
pair acceptor (central atom). Chelation changes the solubility of a salf by changing the concentration
of free ions in solution. When a ligand binds a central metal, there is a foimation constant that
dhra
iffilc
ifu.
measures the strength of the chelation. This allows for specific ions to be removed from solution mffi
by binding them to form a more soluble complex ion. Ions also can be removed from solution bv
m[g:ti
adding counter-ions that form an insoluble salt.
tdtos
mm&L
ov Understand the common ion effect.

The common ion effect is a twist on Le ChAtelier's principle as it applies to solubility. The addition
m0fi[rr
ffirrtl,
of products to an equilibrium mixture shifts the reaction in the reverse direction, which in the case
of solubility results in precipitation. This means that addition of an ion to solution or the presence l0llhuu
of an ion iri solution rehucei the solubilitv of a salt.
rmm[ril
{mmmllltu
dhflr,
,6mwJ[ilt
mfum,,llil
ffihmr
General Chemistry Equilibrium Introduction
Equilibrium, as you have leamed it, involves the balancing of a chemical reaction
between reactants and products. Equilibrium is a state that is achieved when the
reactants go on to form products at the same rate that the products go back to
form reactants. Equilibrium reactions take place in both the gas phase and
solution state, where reactant and product molecules are free to migrate and
collide. The kinetic theory model states that molecules must collide to react.
Equilibrium occurs only in a closed system, although steps in a pathway (an
open system) may be an equilibrium reaction.
Equilibrium is an odd yet obvious thing. It is the essence of nature and the foe of
permanence. We can't beat it... EVER! The concept of equilibrium pervades not
only chemistry, but politics, economics, sociology, health..-even our
relationships. A bank represents a good illustration of this concept. There are
deposits and withdrawals continually going on, but on the whole, the amount of
money in the bank remains essentially constant (except following a bank
robbery, after which a new equilibrium will be established). Everything lies in a
balance, and all one has to do is read the scale. Fortunately, in chemistry it is easy
to read the scale. To understand equilibrium better, consider the following saga:
In a certain house with a large backyard lived an elderly man with a plum tree.
Next-door to him lived a young boy who also had a plum tree. Given that
neither of these two were farmers by any means, the fruit generally fell to the
ground and rotted. One day, while out in his back yard cleaning up the plums,
Ere elderly man was struck by a flash of insight; instead of using all his energy to
;onsolidate the plums in a trash container, he would instead simply fling them
over the fence. The boy next-door saw this and decided that two could play at
this game. The next time he was out in the back yard, he flung a few plums over
the fence. This soon evolved into a daily contest with the advantage going to the
-lttle boy, for he was younger and quicker and could move around the yard
:aster. He was therefore able to fling the unlikely projectiles over the fence at
-Jrree times the rate of the old man. At first, there were roughly equal amounts of
:lums in each yard, but due to ihe boy's greater flinging Prowess, the old man's
.;ard gradually accumulated more. Finally, when the point was reached where
:he old man's yard had three times as much as the boy's, the overall amount in
each yard became stable and didn't change. Because the boy had so few plums in
ris yard, he spent the majority of his time running around collecting them. The
nan, however, could simply stand in one place, scooping and flinging. From the
reighbors' perspective, for every one that would sail through the air to the left,
jreie was one that would sail through the air to the right. The plum-flinging had
:eached its equilibrium. The ratio of the plums in each yard was equal to the
:atio of the rates at which the two could fling plums (known as the "plum-
:Jnging rate"). This in essence is as deep as equilibrium gets.
This example may not be the most eloquent, but it serves the purpose of
:enerating a memorable analogy to chemical reactions. It is the external
:onditions that affect the equilibrium between products and reactants, and a
:killed chemist knows how to manipulate this relationship. We will address how
.quilibrium plays out in a solvent environment and in the gas phase' We shall
,'iew the effect of factors governing the system, such as volume, pressure,
and concentration. We will finish by looking at the equilibrium of a
=mperature,
aqueous solution, and the factors that are involved.
'alt dissociating intodiscussion, Le Chatelier's principle will play a ro11.
lhroughout all of the
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General Chemistry Equilibrium Fundamentals of Equilibrium g
uriufi|ffiffiffi*ibfium Equ
The
Definitions and Terminology r a.
Equilibrium occurs in a closed system when the rate of the forward reaction is i Ol'1,
equal to the rate of the reverse reaction (rate forward = rate reverse). The result teaa
is that from a macroscopic perspective, the system appears not to change.
However, a net change of zero does not automatically mean the system is rn
equilibrium. Reactions may stop when there is no reactant present, which is a
case of no reaction, not equilibrium. As an introduction to equilibrium, consider
D., -
Reaction 3.1, where R = reactant, P = product, kf - forward rate constant, and k1
1..,
=
= reverse rate constant.
$
kt
r\ kr
r
E-xar
Reaction 3.1 Fo:
- COI-:<
The forward rate for this reaction is based on the amount of reactants and the :Cfr"-
forward rate constant (rate forward = kf[Reactants]). The reverse rate for thrs -{. I
reaction is based on the amount of products and the reverse rate constant (rate B.!
reverse = kr[Products]). Equilibrium is achieved when: c.i
D.!
k1[Reactants] = krlProducts] (3.11
Example 3.L
Which of the following graphs represents what is observed over time for a
reaction starting with all reactants?
A. B.
Reverse rate
CJ CJ
p / T-L].
Time+ Time+ -j,mcl

^/
Time-> Time--+
Solution
Choices A and B are eliminated, because the rates must be equal at equilibriurr,
and neither graph reflects this. Choice D is eliminated, because straight lines arr 1\hen
not very common for graphs in chemistry. A straight line would imply that tLo is usu,
reaction abruptly stopped, once equilibrium was reached. The reality is that tLr liquid
reaction gradually slows until it reaches equilibrium. The best answer is choic" are i*
C, which shows equal rates after time and constantly changing rates unti- are fre
equilibrium is reached. equilil
enerS-'
energl
Copyright O by The Berkeley Review 166 The Berkeley Revier Copr,-:'

General Chemistry Equilibrium Fundamentals of Equilibrium
Equilibrium Constant (Kgq)

The equilibrium constant is a mathematical quantity that is calculated for a
reaction at equilibrium. By definition, the equilibrium constant is the
concentration of products at equilibrium divided by the concentration of
reactants at equilibrium. Equation 3.2 shows this relationship.
K"n = [Prodr.tt] /[Ruu.tur,tr] (3.2)
By applying Equation 3.2 to Reaction 3.1, we find that the equilibrium constant is
equal to the forward rate constant divided by the reverse rate constant.
Example 3.2
For Reaction 3.1, if the forward rate constant is four times the reverse rate
constant, what is Ksq after a catalyst has been added that doubles the rate of the
forward reaction?
A. Ksq=2
B. 3*q=4
C. B*q=B
D, Xbq = 16
Solution
-ddding a catalyst lowers the activation energy, so the reaction speeds up. In this
.rample, the forward rate is doubled, because the forward rate constant is
ioubled. However, the activation energy is lowered for the reverse reaction as
i.;ell. The reverse reaction rate is also doubled. The ratio of the forward rate to
le reverse rate remains the same. This means that equilibrium is the same, so
-:.e equilibrium constant (K"q) is the same. Equilibrium is achieved sooner, but
same equilibrium conditions are reached. The forward rate is four times the
=.e
:er,-erse rate, so the equilibrium constant is equal to 4, choice B.
l:ble 3.1 lists some rules about the equilibrium constant you must know.
--:rong them is the rule that the numerical value of K"O changes only with
::-=Lperature. Knowing this rule would have made Example 3.2 easier to solve.
Stoichiometric values from the balanced equation become exponents

in the Kgq expression.
Do not include solids or pure liquids in the Ksq expression, only
solutes (for K6) and gases (for Kp).
The numerical value of Ksq varies only with changing temperature,
not with catalysts, pressure, volume, or moles.
Table 3.1
'"hen multiple reactants or multiple products are present in the reaction, which
. usually the case, rule # 1 applies. Because the concentration of a solid or pure
-:-urd (solvent) does not change, their values are constant' For this reason, they
::e ignored in the K"n determination. As a rule of thumb, only molecules that
::e free to move and aie rarely in contact with other reacting molecules affect the
:,;uilibrium expression. Lastly, because the equilibrium constant is a measure of
::,ergy distribution, only a change in temperature (a measure of the system's
=:,ergy) changes the value of K"q.
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General Chemistry Equilibrium Fundamentals of Equitibrium
j
Consider Reaction 3.2, (
k. -.!
2 A(s)
Kr
B(g) + C(s) .i
== 1i
Reaction 3.2
Applying the three rules to Reaction 3.2 generates the correct expression for Kgq.
We start by plugging in products over reactants: K"o = Pllgl

tAl
Invalid, because stoichiometric coefficients must be exponents tB]t^q]
'-
.'. K"o
IAIZ
Invalid, because Kgq does not include solids or liquids.'.
. _.1=l9l-
K"q
[A]2
Pu
K"o can be written as either K.- = JEI tr4-i orKo = atm.-l
tAl2 ' (po)t=
LE
Reaction Quotient (Qrx) ym
\.Alhen a reaction is not at equilibrium, the expression of products over reactants @T
is said to be the reaction quotient (Q.*). The relationship between K"O and Q.* mil
dictates the direction in which a reaction proceeds to reach equilibrium. \Atrhen K ryr
> Q, the denominator of Q (reactants) is too large and the numerator of Q
(products) is too small. To establish equilibrium, the reaction must shift to the
right. The reaction shifts to the right to increase the products (numerator) and
&
[i{s
decrease the reactants (denominator). When K < Q, the denominator of Q
(reactants) is too small and the numerator of Q (products) is too large. To W
establish equilibrium, the reaction must shift to the left. The reaction shifts to ttae
left to decrease the products (numerator) and increase the reactants
(denominator). A shortcut to determine the direction the reaction proceeds b -[b
reach equilibrium involves drawing the relationship of K and Q alphabeticall'r-.
and then converting the < or > sign into an arrow. For example: K > Q becomes
'&i
flfil
K so the reaction moves right to reach equilibrium, because the arrorr ls
-> Q, to the
pointing right.
Example 3.3
When the reaction quotient is greater than the equilibrium constant, which of the
following is NOT true?
A. The system has too many products and too few reactants.
B. The reaction is displaced from equilibrium.
C. The reaction must shift in the forward direction to reach equilibrium.
D. The reverse reaction rate is greater than the forward reaction rate.
Solution
When the reaction quotient is greater than the equilibrium constant, the sys
has an excess of products and shortage of reactants, relative to equilibri
Choice A is a valid statement. The system is not at equilibrium, so choice B is
valid statement. To reach equilibrium, the reaction must have a net shift in
reverse direction to reduce the amount of products and increase the amount
reactants. This means that the reverse reaction rate is greater than the fonr
reaction rate, making choice D valid. The system cannot have a net shift in
forward direction, so choice C is an invalid statement.
Copyright @ by The Berkeley Review r6a The Berkeley

Case Specific K-values

All equilibrium constants obey the same rules, but depending on the reaction,
there may be special features that recur. Different reactions have special K-
values. Table 3.2 lists the six types of K"O values we shall address'
K type Type of reaction to which the K applies

Kp K"o for the reaction of gases. Values are in pressure units.
K" Kgq for the reaction of solutes. Values are in concentration units.
Ksp K"o for salts dissociating into ions. Measures the solubility.
Ka Kuo for acids dissociating in water. Measures the acidity.
K6 K"o for bases hydrolyzngin water. Measures the basicity.
Kw Ksq for autoionization of water into hydronium and hydroxide.
Table 3.2
Understanding that the rules are the same for all types of K-values will enhance
-,-our journey through the wonderful world of equilibrium. Knowing that the
:ommon ion effect is nothing more than Le ChAtelier's principle applied to
of how the rules apply to all equilibrium
'olubility systems is a perfect example
sr-stems. There are just different names to describe the reaction conditions.
K"O Calculations
\ow comes the math part, which we will handle through practice! Getting
:eacquainted with equilibrium math is a matter of repetition and practice. Once
-,'ou feel sufficiently familiarized, then move on to the next topic.
Lxample 3.4
it 650K, the partial pressures of the component gases were determined for the
::liowing reaction: -1*
't
''
, ':., \
Hz(g) + Iz(g) + 2HI(g) (rrlt ,'.'i,
Ve' 6"'t
PHz 0.20 atm., PIz = 1.50 atm., and PHI = 3'00 atm' i-,:.'(t.,
1..._-r -i
j --
d)
?-,
',hat is the KO for this reaction? /-
rr.D
t 10.0 atm. o-"k'A I
ts. 15.0 atm.

: 30.0 atm.
l. 45.0 atm.
S,olution
::'ssible errors with this problem stem from forgetting to square the numerator
:r :gnoring 12, because you have seen it as a solid before (note that this reaction is
l: r50K). In this case, forgetting to square the numerator would yield an answer
::at is too small by a factor of 3. As long as you don't forget these things, the
:::,' lem merely involves doing your math quickly. The math setup is as follows:
r^= (Pur)2 _ (3)2 -9 _D=30

" (PHzXPrz) (0.2X1.5) 0.3 3
l-,rice C is the correct answer. To make this a more conceptual type of question,
may give the answer choices as ranges rather than exact numbers.
,J'"''
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Example 3.5 l
At 323'C, thereare 0.10 moles HZG),0.20 moles HCIOa(g), 0.10 moles HZO(g),
and 0.36 moles HCI(g) at equilibrium in a 400-mL flask. what is Kuo for this I
equilibrium mixture?
r HCIOa(s) + 4H2@)
A. 0.0362 t *rr )' - ti;; I
B. 0.0724
c. 1.8000 ' iti('" ="'T?;i";?!:\'
. L'-.!i tTl " ;
(
D. 44.100 I
Solution s
In this problem, the system is already at equilibrium, so no determination ot T
changes (x-values) is required. This problem is of the plug-'n'-chug (simpie h,r
substitution) type. Moles can be used directly in the equilibrium expression. ,m
because although it is technically correct to use concentrations, in this case
ilIfi
volume cancels out of both the denominator and the numerator, leaving just the
@
moles. This is true any time that the number of reactants is equal to the number
of products in either the gas phase or as solutes. The question is really just a W
math problem, solved in the following way: ffi
@
(PHcrXPH"o)a (0.36X0.10) 4 m
--.u-T
' -0.36-0.18-ro
(PHcroq)(PHz)o (0.20x0.10) 4 0.20 0.10 ffi
This makes choice C the correct answer. &
h
Example 3.6 ffi
At srP, the partial pressure of No is 152 torr and the partial pressure of 02 is 3-$
torr. If the mixture is at equilibrium, what is the K"o at STP for the follora'ing
reaction?
No(g)+Oz(g) + NO3(s)
A. 8.333 atm.-1
B. 4.167 atm.-I
C. 1.000 atm.-1
D. 0.240atm.-1
Solution
The key piece of information in this question is STP (standard temperature
pressure). This implies that the total pressure of the systems is 760 torr. The
of the partial pressures is the total pressure, so 760 = PNOg + PruO + PO2.
substitution , 760 = PNOg + \52 + 228, so PI.JO, = 380 torr. Because the ansrre
listed in atmospheres, the values in torr must be converted to atmospheres bet
they are useful. The conversion is 760 torr per atmosphere. The equation d
calculating K"O is:
K-^= PNo: =
3Solzeo tl,
=
(pNoXpor) (rurlruo\rrtlruo) (%X%o)=tl,-So.'e
3lso 6
Of the answer thoices given, only choice A is greater than 8. If you pick A
will definitely be a star!

General Chemistry Equilibrium Fundamentals of F,quilibrium
Example 3.7
For the following reaction, 0.20 moles Bi2S3(s) are mixed with 0.50 moles Hz(g).
Once equilibrium is established,0.225 moles of H2(g) remain. What is the value _ 1,
of K"O for this reaction? 2.
o i c. " )
1Bi2S3(s) + 3H2(g) ==:==- 2Bi(s) + 3H2S(g) 1r-+.-)

A. 0.57
B. 0.82
c. 7.22
D. 1.81
Solution
This question is best solved by determining the equilibrium concentrations for
both of the gases. Solids do not affect the equilibrium, so be sure not to include
any solids in the equilibrium expression. The equilibrium expression involves
partial pressures, but the answer is the same whether you use the partial
pressures of the gases or the concentrations of the gases. This is because there is
the same number of gas molecules on each side of the reaction. The solids are
ignored altogether as long as they are not the limiting reagent. Because you need
three times as much H2(g) as Bi2S3(s) and you have only 2.5 times as much,
hydrogen is the limiting reagent in this reaction, if it were to go to completion.
This means that to determine the value of Kgq, you must determine the ratio of
the two gases. The values are found in the following way:
Reaction: Bi2S3(s) 3 Hz(g) :t' 2Bi(s) 3 H2O(g)
lrLitially: 0.2 0.5 00

Shift: -X -3x ---+ +2x + 3x
Equilibrium: 0.2-x 0.5 - 3x 2x 3x
-n this case, we can solve for the value of 3x from the information given. At
equilibrium, there arc 0.225 moles of hydrogen gas remaining, so 0.5 - 3x = 0'225.
This means that 3x = 0.275. There is no need to solve for x, because 3x is present
n the gas terms, and solids are not going to be considered. Plugging1.271 tnfor
-r'r nto the equilibrium line of the reaction chart yields:
Reaction: Bi2S3(s) 3 Hz(g) -$ 2 Bi(s) 3 H2O(g)

:quilibrium: don't care 0.225 don't care 0.275
These numbers work nicely in determining the equilibrium constant. The math
*. shownbelow:
v
,-'ru*F= $nqt=\o.nsl g |
-(molessrs)3 -(0.2713 =p.zzs\3 -\
-(Puzs)3 =
"'"q=F;f -'-- =7.22+
=lU'1, =7.223
Jrr1y choice D is a value that is greater than L.22, so that is the best answer. If
-"-ou forget to cube the value, it is easy to choose answer choice C by mistake.
lhoices A and B are eliminated, because there are more products than reactants,
;r the value of K"n must be greater than 1,0. Be sure to use common sense to
=jminate incorrect answer choices. Developing intuition and learning to trust
'.-our common sense is more important in MCAT preparation than honing your
Jgebra and multiplication skills.
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General Chemistry Equilibrium Fundamentals of Equilibriun
Using K"O to Calculate Shifts

The equilibrium constant is used to calculate the quantity of the products and the
reactants present at equilibrium. This is achieved by following the moles of each
species from initial conditions to equilibrium conditions, specificalty by setting
up a table to keep track of the components systematically over the course of tln
reaction. There are three stages to consider: the initial stage, the shift, and
equilibrium. Consider Reaction 3.3:
Co(g) + HzO(g) COz(g) + Hz(g)
Reaction 3.3
At375'c, the equilibrium constant for Reaction 3.3 is 2.51 x 101. The equilibriuur
constant is unitless when the number of products equals the number of reactants
Consider the reaction to start with 1.0 atm of Co and 1.0 atm. of H2o. Figure 91
shows the setup for determining the shift and final pressures in Reaction 3.3.
Reaction: Co(g) Hzo(s) Coz(g) HzG)

initially: 1.00 1.00 0 0
shift: -X -X --+ +X +X
Equilibrium: 1.00-x 1.00-x XX
i
Figure 3-1
As mentioned, there are three considerations in the setup. The first line is what is
initially given. The second line shows the direction of the shift and the ri
stoichiometric consequences. You must be able to determine the direction of the
shift by comparing the initial concentrations to the equilibrium distribution. In
I
this case it was easy, because there are no products, so the reaction must shift in 4'
the forward direction. The third line accounts for what is present once
equilibrium is established. Values from line 3 are plugged into the equilibriur::r
i
expression, to solve for x, the shift in the reaction. The solution is as follows:
r"n =.(P.orXp"r) - (x)(x) = 2s.r = xz

' (PcoIPHzo) (1 - x)(1 - x) = 2s.L
(1 _ *)2
25.7= x2 - =95= x +5-5x=x.+5=6x...x=5=0.83
(1-*)2 1-x 6
The math was simpler that it first appeared in this case. The MCAT does not
seek to test your algebra skills, as much as it tests your reasoning ability. Being
able to estimate the magnitude of the x (the shift) relative to the initial values is
? 40' important.
Example 3.8
At 773K, the KO for the following reaction is 3.0 x 10-5. If the partial pressure of
'' Dilt f N2(g) is initially 3.75 atm., and the partial pressure of H2(g) is initially 2.0 atm,;
7 n -.>-(
-- ---'
'
''=
-. ? what is the partial pressure of NH3(g) once equilibrium is established, assuming
La,+s ) ' there is no ammonia in the system initially?
, /\ .'1 Nz(g) + 3Hz(g) T+ 2NHg(g)

t
1,,o_e |fitu\
l1-r'' -
A.
B.
0.0900
0.0300
atm.
a!m. I
': {/ ? C. 0.0100 atm. t
Iv,t '' ' D. 0.0010 atm.
,..ti
Copyright @ by The Berkeley Review t72 The Berkeley Keview (

Solution
This is a straightforward example. Because the reaction starts with all reactants,
it shifts forward to reach equilibrium. The reaction has a very small KuO and
starts with all reactants, so the shift is small. The x-term can be ignored when it
rs subtractedfrom or added to numerical values. The setup is as follows:
Reaction: NZ(g) 3 HZ(g) NHs(e)
Initially: 3.75 2.00 0
Shift: -x -3x - +2x
Equilibrium: 3.75 - x 2.00-3x 2x
->
Ignoring the x and 3x portions of the reactant quantities yields the following:
(PNSJ2
a-^ - - Q*)2 = 3x 10-5 = 3x \0-s = --4*- =4x2
8
(prurXpnr)3 (s.7s) e)3 3.75 x 30
x2 =30 x3x 10-5 =22.5x10-5+ x2=2.25x10-4...x =r[LzS x1,0-2=1.5x 10-2

4
The concentration of NH3 at equilibrium is 2x, which is 3.0 x 10-2 M. The best
answer is choice B. This is considerably more math than the MCAT requires you
to use, so think of this example as merely a step towards getting re-acquainted.
-\ concern you may recall from your general chemistry class involves whether it
is safe to ignore x when it is either added to or subtracted from a numerical term.
The x-value is ignored when the initial conditions are like the equilibrium
conditions, because the shift is minimal and the value of x is trivial. In Example
3.8, Keq is less than 1.0, so there are fewer products than reactants at equilibrium.
This m-eans that hardly anything shifts over to the product side, so x can be
ignored. Table 3.3 shows cases when x can and cannot be ignored.
Initial Equilibrium shift x-term?

Conditions Constant
All Q and K are SIMILAR .'. SMALL x Ignore
Keq < 1o-3
Reactants SMALL shift in the forward direction
All Q and K are DIFFERENT .'. LARGE x Consider
Keq < 1o-3
Products LARGE shift in the reverse direction
All Q and K are DIFFERENT .'. LARGE x Consider
Keq > 103
Reactants LARGE shift in the forward direction
All Q and K are SIMILAR SMALL x Ignore
Keq > 103 ".
Products SMALL shift in the reverse direction
Reactants & Q and K are SIMILAR .'. SMALL x Ignore
Products
K"q=1 SMALL shift in either direction
Reactants & Q and K are DIFFERENT .'. LARGE x Consider
Products
Keq )) or << L
LARGE shift in either direction
Table 3.3
Understanding the math associated with equilibrium is important. KeQ can be

used to find concentration values at equilibrium, and equilibrium concentration
r.alues can be used to find KuO. This fits nicely into an MCAT experiment,
because equilibrium constants r6sult from experiments conducted to determine
equilibrium concentrations, in several trials with different starting conditions.
Copyright O by The Berkeley Review t73 Exclusive MCAT PreParation

Example 3.9
At92.2'C, the KO for the following reaction is 0.2000 atm.-1. If you were to place
exactly 0.200 atm. of N2Oa(g) into a 1.00 liter vessel, what would the partial
pressure of NO2(g) be once equilibrium was established?
2 NO2(s)
A. 0.025 atm. NO2(g)

B. 0.200 atm. NOz(g) T
C. 0.350 atm. NOz(g) :
D. 0.400 atm. NO2(g)
]I
e
Solution
To solve this precisely, it is necessary to use the quadratic equation. on the fl
MCAT, it is unlikely that you will ever use the quadratic equation. Th_.
fl
question emphasizes the technique of eliminating answer choices throug:r
approximation. First, you must use the equilibrium expression to estimate tl:e
magnitude of x. In this case, Ksq is less than 1.0, and the reaction starts with a-
products. The value of x is goingto be significant (more than half shifts over). L
half of the 0.200 atm. of Nzo+ shifts over, then the partial pressure of nitroge:
dioxide is 0.200 atm. Considering that more than half of the N2o4(g) is going ic $
shift, the value of NOZ(S) is greater than 0.200 atm. However, not all of the s
NZO+(g) can shift over (which would result in 0.400 atm. of NO2), so the ans\\-e1 r
must be less than 0.400 atm. Only choice C falls within the range of 0.200 tc I
0.400. In a multiple-choice format, this question is rather easy to answer.
m
In the interest of developing an alternative method to answer the question
substitute one of the four answer choices (the one closest to the x you
approximate) into the equilibrium expression and then compare the answer you u
get to the given value ofK"n. Your answer either will equal X.eq or it won't equai
Keq. If it equals Keq, you picked well (go to Vegas with those'skills). If it does
not equal K, the error can be used to zero in on the correct answer/ depending on
whether your value is too high or too low. For this reason, always start br-
substituting a middle value.
Reaction: 2No2(g) : Nzo+(g)
Initially: 0 0.200
Shift: +2x *+ -X :-
Equilibrium: 2x 0.20 - x
u,
These numbers should be plugged into the equilibrium expression.
C,
vt - PNzo+ D
-0.2-x -o.z-x
(p*or)' (2*)2 4x2
Be sure not to substitute the answer choice values directly for x, because the
values in the answer choices are for Ppg, which is 2x. Choices B and C fall in the
middle of the range, so choose either one to plug in. For numerical ease, let's use
choice B. If PNg, is 0.200 atm., then x is 0.100.
v - 0.1 --o-04
^P --0.2-x -0.2-
(2# (orf
0.10 - 10 -
-4 '''r
o
This number (2.5) is too large (greater than 0.2000), which means that the x u'e
chose was too small, so we need to choose a larger value for x. Choice C is best.
Copyright @ by The Berkeley Review 174 The Berkeley Revieu'

General Chemistry F.quilibrium Fundamentals of Equilibrium
Cornplex Equilibrium
A complex equilibrium is a balance between two separate reactions that share a
common reagent. In essence, it is two reactions whose equilibrium states depend
on one another. In a complex equilibrium, a product in one reaction is a reactant
in the other reaction. As a result, if one reaction is displaced from equilibrium,
then the other reaction is also affected. When adding the component reactions,
the common reagent is absent in the overall reaction and is considered to be an
intermediate. The equilibrium constant for the overall reaction is found by
multiplying the individual equilibrium constants of the component reactions.
This is because the reagent that disappears when you add the reactions is in the
numerator of one reaction and in the denominator of the other reaction. To
eliminate it, K"Os are multiplied. Figure 3-2is a sample of complex equilibrium:
Reaction I: 2 So3(g)
Reaction iI: CaO(s) + SOZ(g) + CaSO3(s) KeqZ
Overall: 2CaO(s) + 2SO3(g): 2CaSO3(s) + Oz(g) Keqlx(K*qD2
Figure 3-2
Reaction II is multiplied by 2 to balance SO2 when you add the reactions.

Because Reaction II is multiplied by 2, its KuO value is squared. The addition of
calcium oxide to an equilibrium mixture of C,2, SO2, and SO3 reduces the partial
pressure of SO3. This occurs despite the fact that sulfur trioxide and calcium
oxide do not react directly. Complex equilibrium questions are essentially just
manipulations of the overall equilibrium and of Le Chdtelier's principle.
Example 3.10
Consider the following complex equilibrium:
2NO(g) + 1Oz(g) :1- 2 NO2(g) K"q1
2 NO2(g) l NzO+(g) Keq2
2 NO(g) + 1 Oz(S) ,- 1 N2O4(g) Keql x B.eq2
i\hen NzO+ gas is removed, how are the partial pressures of NO gas and NO2
:as affected?
-{. PXO and Pyg, both decrease.
B. Pyg and P111g, both increase.
C. Ppg decreases, while P11g, remains the same.
D. PruO increases, while P116, remains the same.
Solution
lhe second reaction shifts to the right to compensate for the loss of N2O4, so the
:artial pressure of NO2 decreases. A decrease in NO2 causes the first reaction to
.hiJt to the right as well, resulting in a decrease in the partial pressure of NO gas
:nd an increase in the partial pressure of NO2. However, the increase in NO2
:om the forward shift of the first reaction is less significant than the decrease in
\Q caused by the forward shift of the second reaction. This is because the shift
n the first reaction cannot completely replenish the lost NO2 without losing so
:'Luch NO that the reaction is beyond equilibrium. A shift never regenerates as
:uch as was lost. Both NO and NO2 decrease, making choice A the best answer.
-opyright @by The Berkeley Review 175 Dxclusive MCAT Preparation

General Chemistry Dquilibrium Fundamentals of Equilibrium
Experimental Determination of K
In this experiment, a 500-mL closed glass flask is employed, so the system is
isochoric (has V"6rrr1211). The pressure of the system is monitored continually
over the course of the experiment. The researcher tests Reaction 3.4by observing
the total pressure of the system during a fixed interval.
H2(g) + I2(s) + 2Hi(g)
Reaction 3.4
The researcher mixes together 1.00 atm. of hydrogen gas (H2) with excess iodine
solid (I2). The total pressure of the system is monitored by a small detector in the
wall of the flask throughout the reaction, which is said to be in equilibrium once
the total pressure of the system stabilizes. Ample time is given to allow the
system to reach equilibrium. The setup for the reaction is shown in Figure 3-3.
Reaction: Hz(g) Iz(s) 2 HI(g)

h"ritially: 1.00 excess 0
shift: _x _x ------.> +2x
Equilibrium: 1.00 - x who cares? 2x
Figure 3-3
The reaction proceeds forward to reach equilibrium. It is unknown how mudr

the reaction proceeds, so the shift value is assigned the term x. Hydrogen gas
decreases by x, while hydroiodic acid gas increases by 2x, because of the
stoichiometry. Because the number of gas molecules increases, so does the total
pressure of the system. Figure 3-4 shows the total pressure of the system as e
function of time. The pressures for H2 and HI are inferred from the total
pressure graph.
Pto,ul
increases from 1.00 to 1.00 + x
Psr
increases from 0 to 2x
P",
decreases from 1.00 to 1.00 - x
Figure 3-4
K"O is calculated from P1o1u1, because the shift in the reaction (x) is equal to
For instance, if P16131 is 1.60 atm. and Pir,itiul is 1.00 atm., then AP is 0.60 atrn-
AP is 0.60 atm., then at equilibrium PHt is 1.20 atm. and Pg, is 0.40 atm.
equilibrium expression for the reaction does not include iodine, because it is
solid. Plugging into the equilibrium expression yields a numerical value for

Determination of K
( PHr)2 (2*)2 (r.z)2 - t.2 6.2) = (3)(1.2) =
- -
-x 0.4 -o.2)(r.2)
Ko.
-r= 3.6
PH, 1.0 0.4 0.4
This experiment determines the value of Kgq under the ambient reaction
conditions. Changes to the system are made to study equilibrium further.
Effect of the Addition of Reactant
Once the pressure stabilizes at 1.60 atm., the researcher alters the system by
adding 0.10 atm. of isotopically rich hydrogen gas (predominantly molecular
deuterium, 2H-2H). The total pressure of the system increases as hydrogen gas
is added to the system. After the addition is complete, the total pressure
continues to increase, gradually slowing until it reaches a stable value of 1-.76
atm. P1s1n1 for the system increases by 0.16 atm., more than the 0.10 atm. added.
Analysis using infrared spectroscopy confirms that both 2H-I and 2H-H are
formed. From these observations, it is concluded that addition of a reactant gas
shifted the reaction in the forward direction to a new distribution of compounds.
Substituting the values for Pg, and Pg1 in the equilibrium expression reveals
that K"o remains the same, although the partial pressure of each gas has
changed. This means that addition of the reactant gas displaces the reaction from
equilibrium, following which the reaction shifts in such a way as to reestablish
equilibrium. In addition, the equilibrium is dynamic, given that the mixed
hydrogen eH-H) forms by the reverse reaction.
Following the addition of the labeled hydrogen, the researcher makes a second
addition to the system, after the pressure stabilizes at 1.76 atm., by adding 10.0 g
of isotopically rich iodine (predominantly 1271-tzzt;. the system is continually
monitored, but no change in pressure is detected. Again, the gases in the system
are analyzed by infrared spectroscopy The labels appear to be completely
scrambled, with H-1271,29-7271,H-[ and 2H-I all being observed. From
this, it is concluded that the addition of a solid reactant does not shift the reaction
rn either direction. It reconfirms that the equilibrium is dynamic, given that the
mixture of isotopically labeled compounds.
-\ major point of this experiment is to support the concept of dynamic equilibrium,

a state where the system is continually reacting in both the forward and reverse
directions. On the macroscopic level, there is no net change. This implies that
the forward and reverse reaction rates are equal and that the concentration of the
leactants and products remains constant. The scrambling of the isotopic labels
supports this idea. If this were a case of static equilibrium, tlne isotope would not
be incorporated into the product or back-react to form the mixed isotope
reactant. Any set of questions on the MCAT that accompanies the description of
an experiment like this, would include a question on dynamic equilibrium.
Such an experiment is typical for an MCAT physical sciences passage. It is to

.,-our advantage to ponder what types of questions might be asked. Questions
:ould involve total pressure and its relationship to equilibrium through partial
3ressure. The shift can be rationalized using Le Chdtelier's principle, so
questions on Le ChAtelier's principle are probable. To round out the questions,
*rere is the possibility of pH questions, solubility questions, and the relationship
':etween
the reaction quotient (Q) and the equilibrium constant (K). It is more
han worth your time to make up some multiple-choice questions to accompany
--his passage. If you know how to write a multiple-choice test, you will
'-nderstand better how to take one.
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General Chemistry Equilibrium Le Chdtelier's Principle
ffi1G :$liffiH6i l
t
Le Chatelier's principle is justified both mathematically and theoretically. The
basic rule is that whatever change you make to a system that is in equilibrium,
the reaction mixture will react in a way to undo the change and ieestablish
equilibrium. The formal definition of the principle is as followi: t
If an external stress is applied to a system at equilibrium, the system wiII shift itself in j
such a way that the stress is partially relieaed and equilibrium is reestabtished. l
:
Effects of Stress
An external stress on the system includes changing moles (concentration of a
component), pressure, volume, and temperature. In all cases, except changing
temperature, the numerical value of K remains constant, and the system will
continue to react until the K value is obtained once again. When a reaction
system is not in a state of equilibrium, the same calculation for the equilibrium
expression (K) is used, but it is referred to as the reaction quotient (e). If K is not
equal to Q, then the system is not in equilibrium. It is important to note that
changing an equilibrium system by adding a pure solid or u p,rr" tiquid does not
disrupt the equilibrium nor change the equilibrium constant.
This is why in the sample experiment on the preceding page, when iodine
crystals were added (a solid), the system was not moved from equilibrium.
However, when molecular hydrogen was added (a gas), the system was moved
from equilibrium, and it shifted accordingly, to reestablish equilibrium. It is
important that this conceptual view of equilibrium makes sense to you, because
the MCAT is a conceptual exam that evaluates your understanding at this level
We shall look at Le ehatelier's principle in terms of mathematics and intuitive
problem-solving. We shall address the mathematical relationships only to the :
extent necessary to support our observations. In generic Reaction 3.5, the
mathematical aspects of Le ChAtelier's Principle are considered.
ft
W
A(g) + B(g) C(s) @
-- 3.5
Reaction
Let's assume that K"o for the reaction is 1.00 and that initially, the partial
pressure of all three components is 1.00 atm. BY substitution into the equilibrium
expression, we see that the value is 1.0, meaning that the system is in
equilibrium. upon doubling the external pressure (i.e., by applying a stress tcr
the equilibrium), the system is displaced from equilibrium. According to le
Chatelier's principle, it will shift to reduce the pressure of the system, which rr e
predict will be in the forward direction. By shifting in the forward direction, the
reaction goes from the side with two molecules to the side with one molecule.
thereby reducing the number of molecules and thus reducing the pressure. Tfu
math to support this prediction is as follows:
Reaction: A(g) + B(g) + c(g) t / a.u State

Initially: 1.0 1.0 1.0 1.00 equilibrium
After Stress 2.0 2.0 2.0 0.5 not equilibri''rrn
Shift: -x _x __+ +x reacting
Final: 2-x 2-x 2+x 1.00 new equilibrium
The external pressure increased, causing internal pressures to increase. Thit
generated a system where K > Q, so to reestablish equilibrium, the reaction shi-fis
forward until once again Q = 11.
Copyright @ by The Berkeley Review t7B The Berkeley

General Chemistry Equilibrium Le Chitelier's Principle
The numerical value of K does not change with the change in pressure, although
*re equilibrium distribution does change.
K^^= PC - 2+x - x+2 =L=x2-4x+4=x+2)*2-5x+2=0

(pnXps) e-*)2 x2-4x+4
L-sing the quadratic equation yields a value of roughly 0.44, which means that
'J1e new partial pressules are P4 = 7.56 atm., Pg = 1.56 atm., and PC = 2'44 atm.
Table 3.4 shows different equilibrium distributions for Reaction 3.5. You should
rotice that the ratio of the compounds varies, but the value of K"O is constant.
P4 Pg Pq Pc/pn Pc/ra.r,g
0.80 0.80 0.64 0.80 1.000
0.90 0.90 0.81 0.90 1.000
1.00 1.00 1.00 1.00 1.000

1.10 1.10 1..21, 110 1.000
1..25 7.25 1.56 1.25 1.000
1.50 1.50 2.25 1.50 1,000
1.56 l.5h 2.44 1..56 1.003
0.80 7.25 1.00 t.25 1.000
t.20 1.50 1.80 1.50 1.000
1.33 0.50 0.67 0.50 1.000
Table 3.4
Example 3.11
\\4rat is the observed result of increasing the total pressure under isothermal
conditions in the following system?
nCl3(s) + C12(g) -- nC15(s)
A. No change in the Pp61, to Ppg1, ratio

B. An increase in the Pg1, to Ppglu ratio
C. A decrease in the ratio of Ppg1, to (Ppg1r) x (PCI2)
D. An increase in the Ppg1, to Ppq1, ratio
Solution
lncreasing the external pressure shifts the reaction to the right, so it can reduce
the pressure to counteract the stress associated with increasing the pressure of
the system. An alternative way to look at this is to say that when the total
pressure increases, the number of collisions between molecules increases, forcing
the reaction to proceed in the forward direction (only the forward reaction
depends on collisions). If the system shifts to the right, the partial pressure of
PC13 decreases, the partial pressure of Cl2 decreases, and the partial pressure of
PCl5 increases. This eliminates choice A, because choice A could be true only if
the reaction did not shift. Choice B is eliminated, because an increase in the C12-
to-PCl5 ratio results from a reaction shifting in the reverse direction. Choice C is
eliminated, because the equilibrium constant does not change unless the
temperature changes. The change is said to be isothermal, so temperature did
not change during the shift. Choice D results from the reaction shifting in the
forward direction, so it is the best answer.
Copyright @ by The Berkeley Review r79 Exclusive MCAT PreParation

General Chemistry Dquilibrium Le Chdtelier's Principle
Example 3.12
Which of the following reactions at equilibrium would NOT shift as the result oi
an increase in pressure?
A. CaO(s) + CO2(g) CaCO3(s)
B. PC13(g) + Cl2(s) +-L PCl5(g)
C. Nz(g)+3Hz(g) 2NH3(g)
D.Hz(g) +Iz(g):2HI(g)
-
Solution
The equilibrium reaction does not shift after an increase in pressure when there L.
an equal number of gas molecules on each side of the reaction. This is observed
in choice D. As a point of interest, CaCo3 cannot be stored in an open space for
this reason, because it will fully dissociate into Cao and Co2 over time, if the
carbon dioxide partial pressure is not high enough. Also take note that 12 is a ga-"
in choice D, which means that the reaction must be at a temperature abor-e
ambient conditions.
Perturbations and Shifts

Before conducting an experiment, it is important to consider the properties of the I
I
container in which a reaction transpires. Two common containers are the closeci
flask and the closed piston. Flasks are made of a rigid material, so their volume n
is fixed (Vconstant). The pressure varies when using a flask (Pvariable). Piston-o {
are flexible (a wall of the piston is free to move), so the volume can varr- u
(Vvariable). In piston reactions, the initial pressure equals the final p."rr.riu
if the volume of the piston exhibits no instantaneous change.
(Pmitlut = Pfinal), $
This is to say that for a piston that starts with a stationary lid, once the lid is ffi
stationary again, the internal pressure equals the external pressure. As a resu,lt rO
reactions are susceptible to environmental changes (perturbations) depending or: u
the container. Temperature may change in each container, but its effect on n
pressure and volume depend on the container itself. Le ChAtelier's principle
should be applied taking into account the features of the reaction container. ffi
ffi
with changes to a system that starts in equilibriunr-.

Le ChAtelier's principle deals io
When you have a system in balance, a change in environment results in the
disturbance of equilibrium. To compensate, the system will shift either left o:
right (increasing and decreasing concentrations in doing so) to reestablish"
equilibrium. The general rule is that the system will do whatever it takes to undc
or compensate for what you have done to disturb it. Table 3.5 lists the genenc
shifts a reaction undergoes to alleviate an applied stress.
Applied Stress System's Adjustment Direction of Shift

Add reactant Remove reactant To the Right
Add product Remove product To the Left
Decrease volume Decrease gas volume To the side with fewer molecules
Increase volume Increase gas volume To the side with more molecules
Decrease temperature React to generate heat ln the exothermic direction
Increase temperature React to absorb heat In the endothermic direction
Table 3.5
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General Chemistry Equilibrium Le Chitetier's Principle
Direction of Shift
To observe how these shifts work, each is applied to Reaction 3.6.
N2Oa(s) L}{= +146 k]/mol

Reaction 3.6
Situation #1 Add NzO+(g): This perturbation results in a system with too many
reactants. The value of K is greater than Q. To reestablish equilibrium, the
system reacts in the forward direction to absorb some of the excess reactants and
form more products. The system shifts to the right. The same result would have
occurred had NO2(g) been removed.
Situation #2 Add NOZ(g): This perturbation results in a system with too many
products. The value of K is less than Q. To reestablish equilibrium, the system
reacts in the reverse direction to form more reactants and absorb some of the
excess products. The system shifts to the left. The same result would have
occurred had N2Oa(g) been removed.
Situation #3 Increase the external pressure: This perturbation results in a system

rvhere the partial pressures are too high. This means that the space in which the
gases coexist has been reduced, so their molecules are more crowded and collide
more often. To reduce this crowding, the system goes from products (two
molecules) to reactants (one molecule) and reduce the total moles of gas in the
container. Also, if they collide more often, this forces the NO2 molecules to form
bonds and thus dimerize to N2O4. The system shifts to the left.
Situation #4 Increase the volume: This perturbation results in a system where

the concentrations are too low. This means that the space in which the gases
coexist has increased, so they are less crowded and collide less often. Using the
inverse of the reasoning from situation #3, the system reacts to make two
molecules of NO2(g) from N2O4(g). The system shifts to the right.
Situation #5 Heat the system: This perturbation results in a system where there
is too much free energy. By heating the system, we have added energy to the
reaction. To consume most of this additional energy, the system reacts in the
endothermic direction, which for Reaction 3.6 is the forward direction. The
system shifts to the right.
Situation #6 Cool the system: This perturbation results in a system where there
is too little free energy. By cooling the system we have taken energy away from
the reaction. To regenerate energy to balance this loss of energy to some degree,
the reaction moves in the exothermic direction, which for Reaction 3.6 is the
reverse direction. The system shifts to the left.
These scenarios all address a gas-phase equilibrium. The shifts are similar for a
solution-phase equilibrium, except that concentrations are considered, rather
than volume changes of the container. Changes in the concentration can result
from changes in the volume (quantity) of solvent. The only effect is that
situations #3 and #4 arc now dilution and evaporation of solvent. The system
still reacts by asserting the inverse of the stress done upon it. When diluted, it
reacts to increase its concentration. When solvent is removed, increasing the
concentration, it reacts to reduce the concentration. The rules of Le ChAtelier's
principle work very well, if you apply them correctly.
Copyright @ by The Berkeley Review lal Dxclusive MCAT Preparation

General Chemistry Equilibrium Le Chitelier's Principle
Example 3.13
\zVhich of the following is the result of cooling an endothermic reaction that starts
at equilibrium?
A. The amount of products decreases.
B. The amount of reactants decreases.
C. The equilibrium constant increases.
D. A11 partial pressures increase. i
(
Solution T
Cooling the system causes it to move in the direction that generates heat. Heat is
released when a reaction that is endothermic as written goes from products to 5
reactants. Endothermic reactions are viewed as follows: i_
I
Reactants + heat --:: Products :

Heat can be treated as a reactant. As the reaction shifts to the left, the amount of :
products decrease, the amount of reactants increase, and the equilibrium -;
constant decreases. This eliminates choices B and C, and makes choice A the ;
correct answer. Cooling a system decreases the pressure, so in all likelihood, al1
partial pressures would decrease, not increase. Even if the reaction shifts enough
to offset the pressure decrease due to reduced temperature, that is true only for E.
reactants. Partial pressure of products must decrease. This eliminates choice D.
You should recall that AH is positive for an endothermic reaction.
i't
Example 3.14
If the following reaction represents a system at equilibrium, indicate which _&"
statement is NOT true. m.
lC13(s)+CI2(g): PCl5(s) c.
]D,
A. Increasing the pressure would cause a decrease in pCl3.
B. Adding PCl5 would cause an increase in PCl3. 5@'
C. Increasing the volume would cause an increase in pCl3. j*e.
D. Removing Cl2 would cause a decrease in PCl3.
\'
Solution i':;
The term "Nor true" means false. Do not forget halfway through the problem. --_t:
that you're looking for the false answer choice. A common mistake on "NoI
=_]a
problems is to forget that the correct answer is a false statement. To avoid thr-. -:_
*k
write either "T" or "F" next to each answer choice as you run through them. Ther
choose the answer choice with the unique letter.
:
E'r,a
To compensate for increasing external pressure, the reaction shifts to the right, su.
,t*1
it can reduce the pressure to counteract the increase in pressure felt from th.
change to the system. If the system shifts to the right, PCl3 decreases, so choice -i
is true. Adding a product to an equilibrium mixture shifts the reaction to th;
reactant side in order to counteract the increase in PC15 (the product). If thr
A
ts.
system shifts to the left, PCl3 increases, so choice B is true. Increasing the volurnt
C',
decreases the crowding in of the system. To compensate for increasing volumE
D"
the reaction shifts to the left, so it fills in the empty space created by the volume
increase. If the system shifts to the left, PC13 increases, so choice C is true 5oilra
Removing a reactant shifts the reaction to the reactant side in order to make u: .*:
for the lost reactant (Clz). If the system shifts to the left, PCl3 increases, so choi;:
D is a false statement, and is thus our answer choice. l:e:
]4{ -
Copyright @ by The Berkeley Review t82 The Berkeley Revier

General Chemistry Equilibrium le Chdtelier's Principle
Example 3.15
For the following equilibrium reaction, what is the effect of increasing the
external pressure?
ZSO2(g) + rO2(s) 4 ZSO3(g)
A. A decrease in the moles of sulfur dioxide
B. An increase in the moles of oxygen
C. A decrease in the moles of sulfur trioxide
D. An increase the equilibrium constant
Solution
Increasing the pressure crowds the molecules in a reaction and forces the reaction
to shift to the side of the equilibrium with fewer gas molecules (in this case, the
product side). This means that the moles of products (sulfur trioxide) increase
and the moles of reactants (sulfur dioxide and oxygen) decrease. This eliminates
choices B and C, and makes choice A the best answer. The equilibrium constant
does not change with pressure changes, so choice D is eliminated.
Example 3.16
NO2 is a brown gas, while NZO+ (the product of dimerization) is a clear gas. The
two are in equilibrium in a 1.00 liter flask. Upon heating, the contents of the flask
became darker brown. \rVhat can be said about the following reaction as written?
2 No2(e) NzOa(g)
A. The reaction is endothermic as written,

-
B. The reaction is exothermic as written.
C. The reaction is isothermal as written.
D. The reaction is adiabatic as written.
Solution
Because the reaction produced a darker mixture with the addition of heat, the
reaction must have shifted to the left, since it formed more of the brown gas
f'lo21g1;. This means that heat is acting as a product in this reaction. If heat is a
product, then the reaction is exothermic as written. This makes choice B correct.
The term isothermql means that there was no change in temperature during the
reaction, and the term adiabatlc means that there was no change in heat during
:he reaction. Both of these statements (choices C and D) are incorrect.
Example 3.17
i\hat is the effect of adding CaO(s) to the following equilibrium mixture?
CaCO3(s) + COz(g) + CaO(s)
A. The products will decrease.
B. The reactants will increase.
C. The equilibrium constant wiII increase.
D. There is no change in the equilibrium.
Solution
{dding a solid to a reaction mixture that is already at equilibrium has no effect
rn the equilibrium. This means that the correct answer is choice D. A solid
:tfects a reaction mixture only if the reaction is not yet at equilibrium. This is to
'av that the solid is involved only when it is the limiting reagent for the reaction.
Copyright O by The Berkeley Review ra5 Exclusive MCAT Preparation

General Chemistry Buffers and fitration Indicators
Solubility
Solubility is a popular topic on the MCAT. However, for many people, it was a
topic covered only briefly during their general chemistry course. For this reason,
we shall look thoroughly at solubility. Conceptually, solubiiity is the breaking
apart of a lattice to allow particles to move freely in solvent. In this section, we
focus on the dissociation of a salt into water. When a salt dissociates into water,
the ionic forces holding the charged species together break, and interactions with
the dipoles of the water form. The fundamental rationale behind solubility
involves lattice energy (the interionic forces in the crystal form), the solvation
energy (the strength of the attraction between solvent and dissociated ions), and
entropy (the solute form is more disordered than the crystalline form). Whether
a salt remains in its crystalline form or dissociates into solution depends
completely on the relative energetics of the three key features. Figure 3-5 shows
the process of dissociation into solvent (water) for sodium chloride.
Figure 3-5
The base of the container holds ihe undissociated salt, while above the salt are
ions in solution. Salts dissociate from the surface, where they have the least ionic
interactions with neighboring ions in the lattice, and thus are held least tighth'.
Surface ions have the greatest contact with solvent, so they are more susceptible
to solvation. Corners dissolve away fastest, followed by edges and then faces.
Definitions
For every solute, there is a maximum amount that dissolves into a given volume
of solvent at a set temperature. The solubility of most salts has been measured at
25"C and are compiled in iables (like Table 3.8). You should know how to extract
information from a table. Information listed in solubility tables measures the
degree to which a salt dissociates into water. As a rule, some salts have a verv
lor.i solubility, leading to a low numerical value for the equilibrium constan: .l
associated with dissociation (KrO). The equilibrium constant associated with.
il
dissociation is knor,r,'n as the solubility product. However, the relative KrO values
for a group of salts is not always a good indicator of their relative solubility. This
is because the units of solubility product (KrO) vary with the number of ions. LT
ij
nii
Copyright @ by The Berkeley Review ta4 The Berkeley Revie*

General Chemistry Equilibrium Solubility
The subject of solubility requires being familiar with several terms. Defined
below are eleven that are regularly encountered in this subject.
Dissoloing: The breakdown of intermolecular forces between molecules as a solid
becomes a solute within a solvent. The molecule remains intact when dissolving
into solution. An example is the dissolving of sucrose into water, where atoms in
the sucrose molecule remain covalently bonded, but the forces between sucrose
molecules are eliminated.
Dissociqtion: The breakdown of ionic bonds between atoms within a lattice
strucfure as a salt turns into a solute within the solvent. The crystal lattice of the
salt breaks apart when it dissociates into solution. An example is sodium
chloride dissociating into water. The ionic bonds between sodium cations and
chloride anions break, and the ions are stabilized by the partial charges of water.
Soluent: The species in greatest concentration into which the solute dissolves, or
salt dissociates. A solvent must be a fluid (have the ability to flow).
Solute: The species not in highest concentration that dissolves into the solvent, or
in the case of a salt, dissociates.
Solubility: A measurement of the degree of dissolving that a solute undergoes
rvithin a particular solvent. The driving force for solubility is a preference for
solvation of molecules (or ions) over the lattice strength of the solid. In addition,
entropy favors the dissolving process. As the solubility of a compound increases,
it is deduced that either the lattice energy of the solid is decreasing, the solvation
energy of the solute form is increasing, or both effects are taking place.
Saturated: Describes the state of a solution at the point where no more solid
i,solute) can dissolve into solution. When an aqueous salt solution is saturated,
the rate of dissociation of the salt equals the rate of precipitation.
Supersaturated: Describes the state of a solution where the amount of solid
isolute) that is dissolved into solution is beyond the maximum amount at a given
temperafure. The solution is actually a suspension that when disturbed can form
a precipitate rapidly. This state can be achieved by first heating a solvent, then
adding solute to the solution until the solution is saturated at that temperature.
Slowly cooling this solution causes the amount of solute in it to exceed what
should dissolve at the reduced temperature.
Solubility product (Ks/: The equilibrium constant for a dissociation reaction,
Cetermined from the molar solubility according to standard rules for calculating
:quilibrium constan ts.
ilolar solubility: The quantitative measurement of the maximum number of
moles of solid (solute) that can dissolve into enough solvent to make one liter of
solution under standard conditions. For all practical purposes, the solvent is
ahvays water in inorganic chemistry and thus the calculations are similar in
rearly every example. Molar solubility can be thought of as the x-value in the
:alculation of the solubility product (Krp).
3ram solubility: The quantitative measurement of the maximum number of
irams of solid (solute) that can dissolve into enough solvent to make one
htindred milliliters of solution under standard conditions.
Jommon ion effect: This results in a reduction in the amount of solid (solute) that
;an dissolve into solution due to the presence in the solution of an ion that is also
uesent in the solid. This concept is similar to Le ChAtelier's principle, except that
Le ChAtelier's principle, the addition of one of the products (ions) causes
"-,-ith
:recipitation (reduced solubility). With the common ion effect, the ion causing
Ie reduced solubility is present in solution at the beginning of the reaction,
iather than being added once the solution has reached a solubility equilibrium.
Copyright @ by The Berkeley Review ra5 Exclusive MCAT Preparation

General Chemistry Bquilibrium Solubility
Solubility Rules
You may recall from general chemistry a list of general rules for predicting
solubility. We will emphasize using data from tables to determine solubility, but
here is a paraphrased version of the solubility rules. The rules as they are
typically written in general chemistry textbooks are listed on page 26 of this
book. These rules may be used to give a good estimate of solubility and should
be used when no solubility data are available.
1. Most salts composed of a +1 cation (excluding transition metals)
and -1 anion are soluble in water at room temperature.
2. Nitrate (NO:-) is a large anion that forms weak lattice
interactions and forms strong hydrogen bonds with water, so
most nitrate salts are water-soluble.
3. Most salts containing sulfate anions (SOnz-; with +1 cations
(excluding transition metals) are water-soluble.
4. Most salts with -2 or -3 anions are insoluble in water, excluding
the sulfate salts.
5. Most oxide 1O2-; and hydroxide anion (OH-) salts are only
slightty water-soluble. KOH and NaOH are notable exceptions
that are substantially soluble.
{
Ionic Structures r
Composed of ions (charged species) held together by ionic bonds (electrostatic n
forces). In ionic structures, electrons are not shared; they are transferred between I
atoms, so that atoms with a deficiency of electrons (cation) and atoms with an fl
excess of electrons (anions) are formed. A typical example of an ionic compound il

d
is sodium chloride (NaCl).
fi
Cation: An atom in which the number of protons exceeds the number of
electrons, thereby resulting in an excess of positive charge. A cation is a
positively charged atom. Potassium cation (K+) carries a +1 charge, implying
that there is one more proton than the number of electrons in the atom"
Potassium has nineteen protons, so potassium cation has eighteen electrons'
Anion: An atom in which the number of electrons exceeds the number ot
protons, thereby resulting in an excess of negative charge. An anion is a
negatively charged atom. Fluoride anion (F-) carries a -1 charge, implying that
there is one more electron than the number of protons in the atom. Fluorine has
nine protons, so fluoride anion has ten electrons. Note that the name changes
from "fluorine" (used when the atom is neutral) to "fluoride" (used when the
atom carries a negative charge). Negatively charged species are given the "-ide'
suffix.
Nomenclature of Salts
Scientific convention says that when you name a salt, the name of the cation
precedes the name of the anion. That is why we refer to NaCl as sodiuqt
chloride, rather than chloride sodium. The rules for naming a simple binary salt
are as follows:
O Name the cation before the anion in the salt.
@ The cation name is derived from the element forming the cation (oftm
ending in "-ium")
O The anion name is derived from the element forming the anion with an'-
ide" suffix added.
Copyright O by The Berkeley Review la6 The Berkeley Revier

General Qhemistry Equilibrium Solubitity
Example 3.18
\Alhat is the proper chemical name for the salt BaF2?
A. Barium difluorine
B. Barium fluoride
C. Difluorobarane
D. Fluorinium baride
Solution
The cation of this salt is derived from barium, and the anion is derived from
fluorine. Thus, the name begins with barium and ends with the "-ide" form of
tluorine (fluoride): barium fluoride, which makes choice B the correct answer.
The subscript two in the formula (showing that there are two fluoride anions)
need not be named, given that fluoride can be only -1 and barium is +2. The ratio
is implied. It was fun to write wrong answers for this question. Granted, I am a
chemistry-loving geek, so my credibility when it comes to determining what is
;ool and what isn't is dubious, but nevertheless, choice C is a cool wrong answer.
Polyatomic Ions
or,'er the course of your academic science career/ you may have seen the same
:ons recurring in a variety of contexts in different subjects. In biology, the
nteractions of bicarbonate with carbonate and dihydrogen phosphate with
ivdrogen phosphate are essential in blood buffering and in the action of the
<idney. Kidney stones result from the precipitation of calcium with various
:olyatomic ions. Because of the frequency with which molecular ions appear as
: factor in many problems, the MCAT test writers expect you to be familiar with
some common ones. Table 3.6 lists a few that you should know.
-1 Anions -2 Anions
Acetate C2H1O2- Carbonate Co32-
Bicarbonate HC03- Chromate CrOn2-
Bisulfite (hydrogen sulfite) HS03- Dichromate Cr2072'
Bisulfate (hydrogen sulfate) HSOa- Hydrogen phosphate HPc)42-
Dihydrogen phosphate H2POa Oxalate C2O42-
Hypochlorite CIO- Oxide 92-
Chlorite ClO2- Peroxide oz2'
Chlorate ClO3- Sulfite Sos2
Perchlorate ClOa- Sulfate Sonz-
Cyanide CN.
Hydroxide oH- -3 Anions
Superoxide O2- Phosphate PO43-
Nitrite Noz-
Nitrate Nos- +L Cations
Permanganate MnO4- Ammonium NH+*
Table 3.6
r -.; should know these twenty-six ions by charge, structure, and nomenclature.
t,:.oving a little about their common applications may help, too.
187 Exclusive MCAT Preparation

Solubility Product and Molar Solubility (Mathematical Applications)

With solubility, calculations typically involve converting between molar
solubility and solubility product (KrO). Molar solubility and solubility product
show up together in calculations, bul they are very different terms. If one salt
has a lower KrO value than another salt, it does not mean that it is less soluble
(has a lower molar solubility). Solubility is determined by the molar solubility of
a salt, not the solubility product. KrO values are calculated as products over
reactants, but because solids are ign6red, there is no denominator. Table 3.7
shows different ion combinations for salts, where x represents molar solubility.
Solubility Reaction Kro Expression Kro Calculation
MXls; --: M"(uq) + X-(aq) Ksp = M*llxl KsO =(x[x) = x2
MX2(s) M2*(uq) + 2X-(aq) Ksp = M2*l[xl2 Kro =(x{2xY =q*3
MX3(s) - M3*(uq) + 3X-(aq) Ksp = M3*l[r]3 Kro =(x{3x)3 =27*a
M2X(s) -
.* 2M+(aq) + X2-1aq) t<ro =1tvl+121x2-1 Ksp =(2xf(x) =4x3
M1X(s) + 3M+(aq) + X3-1aq1 rro =1M+131x3-1 rcro =(ex)31x)=27x4

Table 3.7
Example 3.19
What is the molar solubility for the hypothetical compound MX, if it is known to
have KrO = 4.0 x 16-10 142 in water?
A. 1.0 x 10-5 M
B. 2.0 x 10-5 M
C. 4.0 x 10-5 M
D. 2.0 x 10-10 M
Solution
For an MX salt, K5p = [M+][X1 = x2, where x is the molar solubility. This means
that the molar solubility is the square root of the KrO value.
Krp =*2 .'.*=y'Krp ={cotlo:ro =,{4n */torTO* =2.0x 10-5
This makes choice B the best answer.
Example 3.20
\zVhat is the molar solubility for the hypothetical compound MX2, if it is knor'r'n No
have Ksp = 1.08 10-7 Nts in water? ,,

" ?^
A. 1.65 x 10-4 M
''
t, 1 -
'\
\C6z: "
B. 2.10 x 10-3 M - ''-"

C. 3.00 x 10-3 M Y-' "''-1
D. 4.80 x 10-3 M ta: ' t r)
."\
t' '.'
Solution
For an MXI salt, Kso = [M2+][X]2 = 4x3, where x is the molar solubility'
means that the molai solubility is the cube root of one-fourth of the KrO value
.t- a-
4
=ntl
'/ro8;lnq
n
=4127 ,"^'{rc'e = 3.0x 10-3
This makes choice C the best answer'
Copyright O by The Berkeley Review l8a The Berkeley

General Chemistry Equilibrium Sotubility
It is good to understand the hypothetical examples, because actual salts are done
the same way, except the numbers are not as clean. The key fact to recognize is
found in the units. If Kro is M2, then square root must be found. squaie roots
are easier to solve if the ljower of ten is divisible by two. if Ksp is M3, then cube
root is necessary. Cube roots are easier to solve if the power often is divisible by
three. From that point it requires approximating square roots and cube roots by
ranging the values based on squares and cubes you know.
Example 3.21
\zVhat is the molar solubility of lead(Il) iodide, PbI2, if it is known to have KrO =
7.42 x 70-8IrzF in water?
A. 1.19 x 10-4 M Ii.>"
.:
jii
B. 8.83 x 10-4 M ..,

C. 1.52 x 10-3 M ,.1 tLl I
D. 2.42x 10-3M
Solution
For PbI2, KrO = [Pb2+][I-]2 = 4x3, where x is the molar solubility. This means that
the molar solubility is the cube root of one-fourth of the KrO value.
5!P
"'t -
Krp =4"3
4
1-
=ilUZ
Vq
"-
*",llO-e =Vl.SS x 10-3 = 1.5 x 10-3+
rhe cube root of 3.55 is not a common piece of knowledge. Flowever, the cube
:oot of 1 is 1 and the cube root of 8 is 2. This means that the cube root of 3.55 falls
:etween 1 and 2. This makes the best answer choice C.
-:- the previous three questions, you were asked to derive the molar solubility
,':om the solubility product. An alternative way to pose this question is to ask
ru to derive the solubility product from the molar solubility. Before you attack
----ese problems, it is important that you make a conscious note of potential
.-,:stakes. Remember to multiply the ions by the coefficient from the balanced
equation! This is the most common error on these problems. The second trick is
:, remember cube roots by thinking of common numbers cubed, such as 23 = 8,
',1 = 27, and 43 = 64.
:rample 3.22
: at is the solubility product of an M2X salt with molar solubility = 5.0 x 10-2 M?
r". 1.25 x 10-4 M3
: 2.50x10-4M3 (l'- (i ''
-- 1.00 x 10-4 M3
- 1.25 x 10-3 M3
: - lution
: : ar1M2X salt, KrO = [M+]2[X2-] = 4f, where x is the molar solubility. This
-' :;r1s that the KrO value is four times the molar solubility cubed.
1 I rr?
Krp =4xj = +x(S.0 rt0-2)t = 4x725x 10-6 = 500x 10-6 = 5.0x 10-4
--,; makes choice C the best answer.
:-. right @ by The Berkeley Review la9 Dxclusive MCAT Preparation

Relative Solubility
It is difficult to prldict relative solubility. The only way to comPare is through
experiments or data analysis. We'll start by comparing the solubilities of calcium
carbonate (CaCO3) and calcium fluoride (CaF). When a question asks for the
highest solubility, it refers to the compound that produces the greatest amount of
dissociated salt, which refers to greatest molar solubility, not solubility product!
The solubility product of CaCO3 is 8.7 x 70-9 \,/P, and the solubility product for
CaFr is 4.0 ri0-11M3. whlch of the two salts is more soluble?
Witli questions like these, keep in mind that you never compare numbers with
unlike units. Solubility products are used to determine the molar solubility'
CaCo3 is an MX salt, sJ iro = while CaF2 is an MX2 salt' so KsP = 4x3' The
"t,
determinations of molar solibility for both calcium salts is shown below.
CaCo3: * = lR* =t[ei;i'ug ={87 xfio-1o = 9'? x10-s M
af-
- =:V4
CaFr: x E9Y =Vro "{tr'FT =2.?x1o-4M
The molar solubility for CaCO3 is 9.3 x 10-5 M_ and for CaF2 it is 2.2 x 10-4, but l
exact values are not necessary, b".urrr" 9.? x 10-5 M is less than2.? x 10-4 M. CaF:
is more soluble than CaCO3, even though it has a smaller solubility product'
Relative solubility questions are asked in many ways such as: "\Alhich salt
exhibits greater solvation?" and "Which salt precipitates first?-'' Use molar
solubilitylo answer questions that address relative solubility' Solubility product x
is employed only for calculation-based questions' (
I
Example 3.23
Vr4rich of the following salts yields the LEAST amount of silver ion in water?
A. AeBr(s) K". = 7.9 * 1g-13142
B. a[cri'i r,i = i.o * 1s-10 142
C. a[zcto+t'i Krp = 9.0 * 19-12 tr43
o. a!3ro41r1 frf'= 1.6 * 19-18144
Solution
You must recognize that the choices ale not all the same type of salt. Choices A
and B are MX ialts, so their solubility products may be compared^ AgBr has
a
lower solubility product than AgCl, soAgBr also has a lowerrnolar solubiLit''-
This eliminates choice B. Choice C is an M2X salt, and choice D is an M3X sai:
To solve the question, you need molar solubility values- The calculation of
th'e
molar solubiliiy for the three remaining salts is shown below'
Choice A: *=y'K; ='[zs *taB ='[7g x^tlT{ = 8'9x 10'7M
Choice C: x=
Rr" ffi" 1g-TT
I z
=1'lri , t0-12 = 1.3 x 10-4 M
V4 V 4
4
R; ' o,fs t lcrlF (,.7 x M
D: x = 4l =\ 10-20 = 1..6 x10-5
Choice
Yzz Y =4t1'=-
zz )
AgBr, choice A, has the lowest molar solubility' However, the question asked fll tr
loivest [Ag*], not lowest molar solubility. For choice C, Ag2CrO+, there are tf
i: d
sltver cations, and choice D, Ag3PO4, has three silver cations, so the [Ag*] :-' s
actually double and triple their iespective molar solubilities, making them mu::
too high to be the actual answer. dll
rf,
Copyright O by The BerkeleY Review 190 The BerkeleY Revier
General Chemistry Dquilibrium Solubility
Solubility Experiments
The molar solubility of a salt is an empirical value, determined from experiments
involving saturated solutions. While forming a saturated solution is easy to do,
determining the ion concentration is not necessarily an easy task. To form a
saturated solution, enough salt is added to water so that precipitate remains on
the bottom of the container. Determining the amount of dissolved salt may be
accomplished in many ways, of which we shall discuss three. The first method
involves spectroscop!, where the amount of absorbed light at a fixed wavelength
depends on the concentration of ions, according to Beer's law (Equation 1.3).
This method works only if one of the ions absorbs electromagnetic radiation. The
second method involves measuring the amount of salt added and then collecting,
drying, weighing, and then subtracting the mass of precipitate from this value.
This method works only if the salt is highly soluble. The third method involves
using an ion exchange column to exchange the cation in solution for hydronium.
The concentration of hydronium is determined via pH. This method works only
if the salt does not exhibit acid-base properties and has a cation concentration of
at least 10-5 M. You may encounter passages about all three methods.
Example 3.24
What is the molar solubility of calcium carbonate in water given that the addition
of 4.00 mg of CaCO3(s) to enough water to form exactly 500.0 mL of an aqueous
CaCO3 solution yields 0.55 mg of anhydrous precipitate?
A. 6.90 x 10-3 M CaCO3
B. 3.45 x 10-3 M CaCO3
C. 6.90 x 10-5 M CaCO3
D. 3,45 x 10-5 M CaCO3
Solution
You must keep in mind the units of the question and then solve for each unit. In
other words, the answer is in terms of moles/liter, which implies that you must
find both moles and iiters to solve the question. The liters of solution are simple,
in that 500.0 mL is equal to 0.500 liters. The amount of calcium carbonate that
Cissociates into solution is 3.45 mg. The amount of calcium carbonate in
milligrams is converted to grams by multiplying by 10-3, and then to moles by
Cividing by the molecular mass of calcium carbonate (100 grams per mole). The
mathematical set-up is shown below
3'45 x 10-3 gramsCacoa

Moles: = 3.45x 10-5 molesCaCo3
gramTmole
1oo
Volume: 500.0 mL . = 0.500L CaCo3(aq)

*#h
Concentratio',. 3.45
x L0-5 molesCaCO3
= 6.90x 1o-5 MCaCo3laqy
0.500 L solution
The correct answer is choice C.
>olubility looks daunting, but is actually quite simple conceptually. Don't be

-ntimidated by difficult-looking topics. They're usually pretty easy. Some
applications of solubility include ion exchange (ion exchange columns), selective
solubility (precipitation of a selected cation or anion), and the common ion effect.
iJf ion exchange, selective solubility, and the common ion effect, only common
-on effect involves heavv mathematics.
-opyright O by The Berkeley Review t9t Exclusive MCAT Preparation

Common Ion Effect

(salt) in
The common ion effect is the reduction in solubility of an ionic solid
solution, because one of the ions in the salt is already present in solution.
In a
way, the concept is similar to Le Chatelier's principle. According to Le
ChAieter's principle, when you add one of the ions to a saturated salt solution,
of a
the reaction shifti to the lefi (reactant side). This results in the formation
is less soluble. Addition of an ion to solution
frecipitate (more solid), so the salt
,"d.r""d the solubility. According to the common ion effect, if one of the ions is
already present in iolution, then less salt is capable of dissociating, so
the
The results are the same when an ion is added to solution;
sotufiiity is reduced.
the difference between Le Chdtelier's principle and the common
ion effect is the
timing of when they are added. Consider Reaction 3'7'
AgCl(s) + HrO(l) =- Ag*(^q) + Cf(aq)
Reaction 3.7
with the addition of either Ag+ or Cl- to solution in Reaction 3.7, there is a
in
reduction in the amount of Agcl that can dissociate into it, due to the presence
the solution of one of the ions-constituting the salt (Ag+ or Cl-).
This is similar to
Le Chatelier's principle, except that either Ag+ or Cl- is present in solution
in the
beginning rather than being added once the solution has reached a solubilitl
ion
uqii6U.i i*. euestions ot ih" MCAT may be asked from either a common
perspective or a Le ChAtelier's principle's perspective'
Le Chatulier's style question: which way will the reaction shift when
Ag+(aq) is
added to a saturated aqueous silver chloride solution? According to
Le
side' so
Chatelier's principle, adding a product shifts the reaction to the reactant
a
precipitate ?ortnt. This means that the salt becomes less soluble.
Common ion effect style question: Is silver chloride more soluble
in pure water or a
M Naciiaq) sbluiionl According to the common ion effect, because the
0.10
already
sodium chloride solution has chloride i-ons (also found in silver chloride)
present in solution, the solubility of the salt is reduced. we shall
look at this
'question from a mathematical perspective, later in the discussion of this topic'
The common ion effect, simply put, says that the presence of a mutual ion
sharing that
already dissolved into solution tldn."t the solubility of a second salt
stannous fluoride is less soluble in a solution of sodium
mutual ion. For instance,
fluoride than distilled water because of the presence of the fluoride anion'
concentration.
Common ion effect questions can incorporate pH and hydroxide
Example 3.25
rurufirir- hydroxide is MoST soluble in which of the following solutions?
A. Vinegar (PH = 2.5)
B. Citric acid (PH = 4.5)
C. Los Angeles taP water (PH = 5'5)
D. Distilled water (PH = 7.0)
Solution
question involves the common ion effect, where the common ion
is
ihis with the
hydroxide anion. Magnesium hydroxide is most soluble in the solution
corresponds to the most acidic solution. The most
least hydroxide anion)which
lowest pH, wirich makes choice A the best answer' This is
acidic solution has the
salts'
the reason that acid rain is tr.h u serious problem: it dissolves basic
192 The BerkeleY Review

Copyright @ by The BerkeleY Review
Example 3.26
At what pH is Ca(OH)2(s) most soluble in water?
A.3
8.5
c.9
D. 11
Solution
The pH at which Ca(OH)Z(s) is most soluble is the pH at which there is the least
common ion (OH-) present in solution. There is the least OH- present at lower
pH values, where the solution is acidic. The best answer is choice A. Note that
basic salts are most soluble in acidic solutions.
Example3.27
(NHa)3(CoCl6)(s) is MOST soluble at which pH?
A.3
8.5
c.9
D. 11
Solution
The pH at which (NHa)3(CoCl6)(s) is most soluble is the pH at which there is the
most OH- in solution. This is because of a complex equilibrium. The OH- in
solution can deprotonate the ammonium cation (NHa+) to form ammonia, which
reduces the amount of ammonium present in solution. As the amount of NH4+
in solution decreases, the (NHa)3(CoCl5)(s) equilibrium shifts to products to
generate more NH4+. The most OH- is present at higher pH values, where the
solution is basic. The best answer is choice D. Note here that acidic salts are
most soluble in basic solutions. The two equilibrium equations are as follows:
(NHa)3(CoCl5)(s) -_- 3 NH4+(at) + CoCl63-(at)
NH4+(aq) + OH-(aq) =- NH3(at) + H2O(aq)
-{s the second reaction shifts to the right, the first reaction is displaced from
equilibrium, so it too shifts to the right. This is a complex equilibrium. The two
:eactions are flependent on one another.
Be able to make qualitative predictions about solubility based on both the

;onunon ion effect and complex equilibrium. Example 3.25 and Example 3.26 are
:ramples of the common ion effect. Example 3.27 is an example of increased
'olubility due to the presence of a complexing ion in solution.
Both of these
:oncepts play a role in determining solubility. \Alhen doing calculations with the
:rmmon ion effect, be sure not to plug variables into the solubility product
::rmula blindly. In the case of an MX salt, for instance, KrO still is equal to
\l+l[X], but the values of [M+] and [X-] are not just x with the common ion
-ifect. The concentration of the ion that is already present in the solution is
:rund by summing the initial concentration and the additional ion formed from
-:.e dissociation of the salt (x). This is [X-]61g61 + x. In most cases, the x will be
:significant relative to the [X-]nitiul, so it can be ignored. Most common ion
:tect questions should be simple and fun after you have done enough of them.
*rpvright @ by The Berkeley Review 193 Exclusive MCAT Preparation

General Chemistry Equilibrium Solubitity
Example 3.28
What is the molar solubility of CaCl2(s) in 0.01 M NaCl(aq) solution?
CaCl2(s) 4 Ca2+1aq; + 2 Cl-(aq) Ksp = 2.5x 10-10 M3
A. 2.5 x 10-4 M
B. 2.5x10-6M . ." '' :'l t"i";
c. 2.5 x 10-8 M
D. 2.5 x 1o-10 M
Solution
This question is purely mathematical. The key fact is recognizing that there
0.01 M Cl- in solution initially. The setup and solution are as follows:
Reaction: CaCl2(s) : Ca2+1aq; + zCI-

Initially: excess 0 0.01
Shifl - x ---+ +x +2x
Equilibrium: whocares? x 0.01 + 2x
Kro = pa2+ltcrl2 ...Kro =1x{0.01. +zxf

If weignore2x: Ksp =2.5x1g-10 =1x{0.01f = 0.0001(x) .'.x = 2.5x 10-6M
The correct answer is choice B.
Example 3.29
\Alhat is the molar solubility of Ca(OH)2 in an aqueous solution at pH = 13, giveur
that the KrO for Ca(OH)2 is 6.5 x 10-o Mr?
A. 6.5 x 10-5M
B. 6.5 x 10-4M
C. 'J..2x10-2M
D. 6.5 x 1,020 M
Solution
This question is purely mathematical as well. You must recognize that there is
0.10 M OH- present in a pH = 1?_solution, because pH + pOH = 1.4 fot an
aqueous solution and [OH-] = 10-PoH. The equation, set-up, and solution are as
follows:
Reaction: Ca(OH)z(s) Ca2+1aq; + 2OH-
Initially: excess 0 0.10
Shift: -x -
--+ +x +2x
Equilibrium: whocares? x 0.10 + 2x
Kro = [Ca2+]toH-12 .'.Kro =(x{0.10 +zxf

Upon ignoring 2x: Kro = 6.5x 19-6 =1x{O.t0P - 0.0{x) .'.x = 6.5x 10-4 M
Calculation questions involving the common ion effect are actually rather simpL+
but in most cases the average student is not familiar with the process. Si-pS
plug in the value for the preexisting concentration, and solve for x from the K*
expression.
Copyright O by The Berkeley Review 194 The Berkeley Revicn

Separation by Precipitation
Removal of certain ions (cations or anions) from solution can be done in a
selective fashion, by precipitation of cations with various anions, according to
their relative solubility values. The least soluble salt precipitates from solution
first. Questions about selective precipitation involve comparing molar solubility
values. Be careful not to fall into the trap of thinking that the smallest KrO is the
least soluble. You must consider what type of ionic system it is. The compound
with the smallest value for x (molar solubility) precipitates from solution first.
Table 3.8 lists the solubility products for some common salts at standard
temperature. The values are listed without units, as is conventional in general
chemistry textbooks, but you should always consider the units when they are
provided.
Salt Ksp Salt Ksp Salt Ksp

BaF2 2.4x10-5 CaF2 4.0 x 10-11 MsFr 6.4 x 10-9
PbF2 4.1x 10-8 SrF2 7.9 x10-10 ZnF2 2.5 x 10-8
BaS04 1.5 x 10-9 CaSOa 6.1x 10-5 MgSOa 7.2x\0-5
PbSOa 4.1x 10-u SrS04 7.9 x10-10 ZnSO4 8.3 x 10-9
BaC03 L.6 x 10-9 CaCO3 6.1x t0-9 MgCOs 1.1 x L0-15
PbCO3 1.4 x 10-15 SrCO3 8.4 x 10-10 ZnCOs 2.2x 10-12

Ba(OH)2 5.3 x 10-3 Ca(oH)2 7.4x 10-6 Mg(oH)2 L.2 x L0-11
Pb(oH)2 1.3 x 10-15 Sr(OH)2 4.7 x 1,0-4 zn(oH)2 2.1 x 1O-16
Table 3.8
Figure 3-6 shows a precipitation flow chart from a qualitative analysis

experiment designed to identify cations in solution. The cations are selected
from Table 3.8. All of the cations are +2 cations, so they all form the same type of
salts. As such, solubility products can be directly compared. Each step shows
the salt that precipitates.
Ba2*,ca2*,Pbz*,srz*
Ba2*,ca2*,sr2r
SrSOa(s) Ba2*, ca2+

a small amount of BaSOa(s)
also forms a precipitate
CaF2(s) Ba''
Figure 3-6
Copyright @ by The Berkeley Review 195 Exclusive MCAT Preparation

Example 3.30
According to data in Table 3.8, to remove strontium by precipitation from a
solution with Ca2l Mg2*, and Sr2+, it is BEST to add:
A. F-
B. SO42-
c. Cotz'
D. OH-
Solution
The best anion to add to solution to remove a cation is the one that forms a sali
less soluble than the salts of the other cations in solution. Of the three cations
(Cu2*,}y'rg2*, and Sr2+), the least soluble fluoride salt is CaF2, eliminating choice
A. Of the three cations, the least soluble sulfate salt is SrSO4, so choice B is the
best answer. Of the three cations, the least soluble carbonate salt is MgCO3, and
the least soluble hydroxide salt is Mg(OH)2, eliminating choices C and D.
Example 3.31
Mercury II cations are MOST soluble in which of the following solutions?
A. 0.10 M NaCl
B. 0.10 M Na2S
C. 0.10 M NaI
D. 0.10 M NaNO3
Solution
This is a question of relative solubilities. This question is asking what the relative
solubilities of HgCl2, HgS, HgI2, and Hg(NO3)2 are. The key fact to keep in
mind is that nitrates are infinitely soluble in water (one of the solubility rulesi.
Of the anions, only nitrate can form hydrogen bonds with water, so it has the
greatest solvation energy of the four anions. It is also the largest of the anions, sc
it has the weakest electrostatic forces in its lattice structure. The conclusion is
that nitrate salts are the most soluble, so the best answer is choice D. This is
purely a qualitative argument for the solubility. There is mathematical evidence
to back this up as well, but the numbers were not given in the problem.
.1
| ..) -, ,
Example 3.32
t,)
1-J
Given a solution that combines Ag+(aq), Pb2+1aq;, Sr2+1aq;, and. Zn2+1aq), what i-.
,,, x the sequence of precipitation when NaCI(aq) is added to solution?

Ksp AgCl =2x70-10,Ksp PbClz =2x10-5,Ksp SrCl2 =9 x10-3,Ksp ZnCl2 = 1 x 104
tL ^l
- (D .K.. 1.st: AgCl, 2nd: SrCl2, 3rd: ZnCl2,4th: PbCl2
E. 1sl AgCl, 2nd:PbCl2,3rd: ZnCl2,4th: SrCl2
t^
r \ t.
,C. 1st: SrCl2, ?nd ZnCl2, 3rd: PbCl2, 4th: AgCl
1-st: PbCl2,2nd: ZnCI2,3rd: SrCl2, 4th: AgCl
"8.
Solution
The salt with the lowest molar solubility forms a precipitate first. AgCl has tle
lowest solubility product, and the molar solubility is the square root of KrO. Fcn
the other three salts, use the cube root of KrO to obtain molar solubility. Thls
makes AgCl the least soluble, and the first to-precipitate, eliminating choices C
and D. The remaining salts have +2 cations, so the order of precipitation is frcm
the lowest KrO value to the highest KrO value. This makes choice B correct.
Copyright @ by The Berkeley Review 196 The Berkeley Reviw

Ion Exchange Column

An ion exchange column exchanges one ion in solution for another (which is
initially bound to the column), by precipitating out the ion that forms the less
soluble salt and releasing a more soluble ion into solution to_replace it. A water
softener is an ion exchange column. Hard water (rich in Ca2+1aq;) travels down
the column where the anion in the ion exchange resin binds calcium cations to
form an insoluble salt while releasing sodium cations (Na+(aq)) into solution.
Aqueous sodium cation is referred to as soft water. As calcium precipitates
through the ion exchange column, it is filtered from the water, preventing it from
forming precipitates in the plumbing lines of appliances (such as a washer or
water heater). To evaluate the viability of an ion exchange column, the molar
solubility values are compared. Figure 3-7 shows an ion exchange column.
top of
Ca2*1aq; enters at the
the ion exchange column.
The column is filled with an ion

exchange resin. The cation to be
precipitated must have a lower
molar solubility with the anion of
the resin than the salt in the resin.
Na"(aq) exits from the base

I of the ion exchange column.
Figure 3-7
ln the water softening example, the removal of calcium ions from tap water is
accomplished by passing the water across rock salt (large chunks of NaCl) and
then filtering out the calcium chloride. Reaction 3.8 is the exchange reaction in a
ivater softener.
2 Na+(aq) + CaCl2(s)
=+ Ca2*1aq; + 2 NaCl(s)
Reaction 3.8
Rock salt is employed to minimize surface area, and to prevent sodium chloride
trom dissociating into solution too rapidly. Sodium chloride is used because its
ions are non-toxic, and it does not change the pH of the water.
Selectiae Precipitntion and lon Exchtange: The addition of an ion to solution with the
i:rtention of precipitating an existing ion out from the solution. This is achieved
ivhen the salt being precipitated is less soluble (has a lower molar solubility) than
any other salt combination in solution.
2AgCl(s) + Hg2*{ug) 2Ag+(aq; + HgCl2(s)
Reaction 3.9
-
Because mercury chloride is less soluble than silver chloride, the addition of
silver chloride to the mercury solution precipitates mercury out of water. This is
-he same principle applied in ion exchange columns and can also be applied in
qualitative analysis when we look for ions in solution.
Copyright Oby The Berkeley Review 197 Exclusive MCAT Preparation

Complex lon Formation: Complex equilibrium occurs when two reactions are
summed to form one overall reaction. This is possible when the product of one
reaction is a reactant in a second reaction. A great example involves the addition
of ammonium to salt buildup in sinks in order to remove the deposit. To check
this, take a small whiff of a bathroom cleaner, and you will detect ammonia.
CaCo3(s) + H2o(t) =:> Ca2*1aq; + Co.?2-(aq)
Reaction 3.10
Ca2*1aq; + 4NH3(aq) + Ca(NHr)n2+1aq;

Reaction 3.11
Because ammonia forms hydrogen bonds with water, the calcium-ammonia

complex is more soluble than the calcium cation. By the addition of ammonia to
solution, free calcium cation forms a complex ion (the result of Reaction 3.11
shifting in the forward direction), which reduces the amount of free calcium and
forces the Reaction 3.10 to proceed in the forward direction. As mentioned prior,
when reactions are added together, the equilibrium constant for the overall
reaction is the product of the equilibrium constants of the component reactions.
Complex lons (Coordination complexes): Complex ions form when a ligand (lone
pair donor or Lewis base) donates a pair of electrons to a central atom (Lewis
acid), which is typically a metal, to form a coordinate covalent bond. This
process is referred to as chelation, where the Lewis base is a chelating agent. A
prime example is hemoglobin whose porphyrin ring serves as a polydentate
ligand by chelating the central iron.
Example 3.33
Silver chloride is MOST soluble in which of the following solutions at 25"C?
A. 0.10 M HgNO3(aq)
B. Pure water
C. AgNO3(aq)
D. NaCl(aq)
Solution
Silver chloride (AgCl(s)) is most soluble in a solution where Hg+ is present.
is because of a complex equilibrium. The Hg* i.t solution can bind the ch
anion (Cl-) to form a precipitate. As the amount of Cl- in solution decreaserl
more AgCl dissolves into solution to replace it. The best answer is choice
Both choices C and D are eliminated, because of the common ion effect.
Copyright @ by The Berkeley Review r9a The Berkeley

I. Carbon Dioxide and Carbon Monoxide Equilibrium (r -7)
II. tlydrogen and Bromine Equilibrium (8 - 15)
III. Equilibrium Constant Magnitude (r7 - 22)

IV. Qas-Phase Equilibrium Constant Experiment (23 - 29)
V. Equilibrium Reactions (5O - 56)
VI. Le Chatelier's Principle (37 - 42)

VII. Solubility and Qualitative Analysis (45 - 4e)
VIII. Solubility Experiment (5O - 56)
IX. Qualitative Analysis Experiment (s7 - 62)

X. Solubility Chart (65 - 6e)
XI. Calcium Salts Solubility (7O - 75)
XII. Complex Equilibrium (76 - 82)

XIII. Hemoglobin and Acclimation (85 - Be)
XIV. Equilibrium Keaction of NO2 and NzOA (eo - e6)
Questions Not Based on a Descriptive Passage (e7 - 1OO)
Dquilibrium Scoring Scale

Kaw Score MCAT Score
84 - IOO 15-15
66 B5 10 l2
47 65 7 -9
34 46 4-6
l-33 t-3
Passage I (Questions 1 - 7) 3. According to Table 1, the reaction is which of the
following?
A researcher studies the equilibrium of carbon monoxide A. Exothermic as written
ith carbon dioxide in the presence of oxygen gas at various
,'.
B. Endothermic as written
::nperatures. The relationship is shown in Reaction 1. C . Adiabatic as carried out
2 CO(g) + Oz(g)=+ 2 COzG) D. fsothermal upon reaction
Reaction L
This is accomplished by monitoring the total pressure of

system as it depends on temperature. There are different
3
.-
:-'ichiometric amounts of gases on each side of Reaction 1'

4. The equilibrium constant (K) varies only with which of
the following?
: ':he reaction can shift with changes in pressure or volume.
. : quantify the contents in the flask at equilibrium, the A. A change in the pressure ofthe system
::3ssure for the system is analyzed. It is assumed that B. A change in the volume of the system
::3ssure changes are due to shifts in equilibrium and changes C. A change in the concentration ofthe system
- :he system that obey the ideal gas equation (PV = nRT). D . A change in the temperature of the system
- -:anges in the total pressure are evaluated for the system and
:: equilibrium constant is derived from the values for
::essure. The reaction is monitored for three trials at each
::rlperature over a wide range of temperatures. The results 5 . If a flask were filled with pure COZG) to a total pressure
.:: summarized in Table l. of 1.00 atm., then once equilibrium is reached' the total
Temperature (K) Ko (atm-r) pressure of the system is which of the following?
375 09.0 A. Less than 1.00 atm.

425 20.8 B. Exactly 1.00 atm.
500 32.2 C. Between 1.00 atm. and 1.50 atm.
600 60.5 D. Exactlv 1.50 atm.
Table 1
Data in Table I demonstrate that the value of the

:luilibrium increases with increasing temperature. Although 6. According to Reaction I, compressing the reaction
::e equilibrium system shifts upon changes in the moles of vessel leads to which of the following?
-3actant, moles of product, external pressure, and volume, the
:quilibrium constant remains constant.
A. An increase in the partial pressure of COZ(g)
B. An increase in the moles of OZ(g)
1. At 102'C, PCo = 2.0 atm. and Pg, = 1.0 atm. What is C. An increase in the mole fraction of CO(e)
the partial pressure of CO2 at this temperature?

D. An increase in the equilibrium constant
A. 2.2 atm.
B. 6.0 atm.
C. 9.0 atm.
D. 18.0 atm. 7 . Based on the following reaction, the addition of
Ca(OH)2(aq) to Reaction I at equilibrium results in
which of the following?
ca(oH)2(aq) + CO2(g):- caco:(s) + HzO(l)
A. No change in the moles of COZ(g).

Z . Addition of COz(g) to the equilibrium mixture results in B . A decrease in the concentration of O2@).
which of the following? C . An increase in partial pressure of CO(g).
A. A decrease in the moles of O2(g). D. An increase in the total pressure'
B. A decrease in the moles of CO(g).
C. An increase in the value of Ko.
D. No change in the value of Ko.
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Passage ll (Questions 8 - 15) I 1. Subsequent experiments show that as the temperature
increases, the mole percent of the hydrogen bromide ga.
Hydrogen bromide gas is one of the strongest acids increases. Which of the following is TRUE about the
available in gas form. In aqueous solution, HBr has a pKu
equilibrium reaction as written? $
value of approximately -12. A pKa value of -12 is indicative
of a very strong acid. By comparison, HCI has a pK6 of . lt is endothermic.
A fi
approximately -9. Hydrobromic acid (HBr) can be produced B. tt is exothermic.

by Reaction 1. C. It is isobaric. m
D. It is not an equilibrium mixture. tr

H2(g) + Br2(l) m
Reaction 1
I 2. How can it be explained that a reaction mixture of f .ir l{u
A student decides to study the equilibrium distribution atm. HBr(g) and 1.0 atm. H2(g) results in no change iu r!
for Reaction 1 Under ambient conditions, Reaction 1 hydrogen gas partial pressure? um
reaches equilibrium at some temperature T and pressure p.

A. The reaction is in equilibrium.
Once at equilibrium, measurements are taken for the partial
pressure of each gas and the mass of bromine liquid. The
B. The reaction cannot move in the forward direc
due to a limiting reagent in zero concentration.
values are listed in Table 1.
C . The reaction cannot move in the reverse di
B12(l) 10.0 grams due to a limiting reagent in zero concentration.
Hz(e) 1.36 atm. D . The reaction is moving forward and backward ar
same rate.
FlBr(e) 2.'72 atm.
Table 1
13. Mixing 3.0 atm. HBr(g) with 1.5 atm. H2(g) orw
The student takes notice that Reaction I shifts with Br2(l) shows which of the following in time?
changes in the conditions of the system, such as the addition
of bromine liquid, the removal of hydrobromic acid, and
A . A large increase in the partial pressure of HBr@:
increases in volume. The student irreversibly increases the
B . A small increase in the partial pressure of HBrtg
volume of the system by opening a valve on the reaction
C. A large increase in the partial pressure ofH2(gl
D . A small increase in the partial pressure of H2(g
flask that is connected to an evacuated column. Not all
changes shift the reaction. Changes in the equilibrium
concentrations are not accurately recorded. I4. A flask is inirially filled with pure HBr(g). Which
the following graphs represents the partial pressure
8 . What is the value of K at ambient temperature, T?
gLFb
H2(g) over time?
A. 0.20 atm. A. B.
B. 0.544 atm.
C. 2.00 atm.
D. 5.44 atm,
trme time
9. Addition of HBr(g) to an equilibrium mixrure of C. D.
nl-
Reaction 1 results in which of the fbllowing? el 9)
A. An increase in the partial pressure of [email protected]

()
B. A decrease in the partial pressure ofH2(g) !
A
C. An increase in the concentration of Br2o N
+r
D. A decrease in the concentration ofBr2(1)
time
15. Addition of which of the following to the equili

10. Which of the following starting conditions results in mixture will NOT affect the partial pressure of H2(gri
the GREATEST amounr of H2(g) at equilibrium?
A. NaOH(aq)
A. 0.80 atm. Hz(g) and2o g Br2(l) B. Br2(l)
B. 1.00 atm. H2(g) and 20 gBr2e) c. Hz(e)
C. 0.80 atm. H2(s) and 30 g Br2(l) D. HBr(g)
D. 1.00 atm. HBr(g) and 30 g Br2(l)
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Passage lll (Questions 16 - 22) 18. What is the equilibrium constant for the following
reaction?
Chlorine gas has a high reduction potential (large NOCI(g) 2 NO(e) + Cl2(g)
positive voltage for its reduction half-reaction). Chemically
2
=-
speaking, chlorine gas is very easily reduced. Chlorine gas is A,. 4.9 x 10-17 atm.
a strong oxidizing agent that can dissolve away most metals B. 4.9 x 10-5 atm.
in short periods of time. The dissolving is the result of an C. 1.4 x 102 atm.
oxidation-reduction reaction. The relative ease with which D . 2.1x 104 atm.
metals are oxidized accounts for this strong tendency to lose
electrons to chlorine. Chlorine gas is not as successful at
oxidizing non-metals as it is at oxidizing metals. This is
attributed to the decreased desire for non-metals to be oxidized
relative to metals. Non-metals have a higher ionization
19. If there is initially 1.00 atm. of NOCI in a flask, what
3nergy and electronegativity than metals. With non-metals,
is the partial of NO gas, once at equilibrium?
;hlorine may only partially oxidize the corresponding
reducing agent. Reactions 1 and 2 are prime examples of the A. 0.0230 atm.
rxidation capability of chlorine on non-metal compounds. B. 0.0460 atm.
Pcbtel + Cl2G)
C. 0.0025 atm.
=- PClste)
D. 0.0050 atm.
Reaction 1
2 NO(e) + Cl2(g) =+ 2 NOCI(g)

Reaction 2
The equilibrium constant for Reaction 1 is 1.95 atm.-1 20. The GREATEST concentration of CIZ(g) is in which of
rr 100"C, while the equilibrium constant for Reaction 2 is the following systems, once equilibrium is reached?
1.1 x 104 atm.-l at i00"C. Both reactions favor products as A. A system initially with 1.0 atm. PCl3
'.',ritten, but not to the same degree. B. A system initially with 1.0 atm. PCl5
In these examples, the non-metals (phosphorus in C. A system initially with 1.0 atm. NO
Reaction 1 and nitrogen in Reaction 2) are already in a D. A system initially with 1.0 atm. NOCI
:ositive oxidation state in the reactants. The greater the
. alue of the equilibrium constant, the more favorable the
.:action, and thus the more product that is formed.
1 6. According to the equilibrium constants associated with

21. Which of the following statements is true about the
Reaction 1 and Reaction 2, which compound is most
effect of adding chlorine gas to each equilibrium?
readily oxidized by chlorine?
A. PCI: A . It will cause the greatest change in Reaction l.
B. PCl5 B. It will cause the greatest change in Reaction 2.
C. NO C. It will cause equal changes in both reactions.
D . It will change the equilibrium constant.
D. NOCI
[ 7. If a flask were filled with PCl3 and C12 to a total 22. A flask at 100"C is charged with 0.40 atm. each of
PCl3, PCl5, and Cl2. In which direction will it react
pressure of 1.50 atm. such that the mole fraction of
to reach equilibrium, according to Reaction I ?
PCl3 is twice that of Cl2, then what is the total
pressure of the system once at equilibrium? A . It is already at equilibrium.
A. Less than 1.00 atm. B. To the left (reactant side)
B. Between 1.00 atm. and 1.25 atm. C. To the right (product side)
D . It varies with a catalyst.
C. Between 1.25 atm. and 1.50 atm.
D. Greater than 1.50 atm.
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1 CSz(g) + 4H2G) 1 CH+(e) + 2 HzS(er
Passage lV (Questions 23 - 29) =:
Reaction L
The equilibrium constant for a reaction involving gases The final internal pressure is the sum of the parrr:zu
can be determined by experimentation, using a glass column pressures. The total pressure can be found using Equation 1
as a closed system. The apparatus used in equilibrium

Ptotal = PCSz + Pg, + Pggo + PHzS
experiments, shown in Figure 1, is connected to a vacuum
pump at one end and is sealed at the other' On the column Equation 1
u." ih."" stopcocks with air tight fittings, to which flasks
containing gut"t -uy be attached. At the sealed end of the 2 3. Which of the following is the BEST explanation a-< u
is
tube is a pressure gauge. The volume of the glass column why the reaction temperature must be held at 25'C?
exactly 1.00 liters, when all stopcocks are closed' Each flask
A . A temperature change can cause the carbon disul6ja
and aitached stopcock contain volumes of exactly 250 mL' to decomPose to carbon dioxide'
This means that when all three stopcocks are open in a
B. The reaction will not proceed unless ma
manner where gas is free to flow between the glass column temperature is exactlY 25"C.
and any of the ;ttached flasks, the total volume for the closed C. The glass will begin to melt at temperatures ru
system is exactly 1.75 liters. Figure I shows the apparatus' excess of 25"C.
Connected D . The equilibrium constant can change rr----m
Pressure gauge to vacuum
temperature'
reaction vessel m'rs

24. The temperature of the closed
qlon:di
increased. This resulted in the pressuls ef ths
system decreasing, rather than increasing as expeci*ix
Which of the following explanations BEST expla:mn
this observation?
Flask 3 A. The pressure of a closed system decreases a-i fu

Flask I Flask 2
temperature increases according to Charles's laq
Figure 1 B. The reaction is endothermic as written'
During an experiment, the closed glass cylinder is filled C. The reaction is exothermic as written'
with 1.00"ut-. of hydrogen (H2) according to the gauge in D. Heavier molecules are being formed causing
the cylinder. Flask I is filled with 1.0 atm' carbon disulfide number of collisions to increase'
(CS;). The reaction starts when the stopcock is opened'
allowing the two gases to mix. The temperature of the glass
25. How can the partial pressures of CH4 and H'S
column is maintained at 25"C using an external heat sink'
The internal pressure is monitored until it stays constant' equilibrium be determined from the experiment?
Figure 2 shows the internal pressure over time, where t = 0 A. At equilibrium, the partial pressure of CH4
represents the time at which the two gasses were mixed' the value for the change in the pressure of
system (APtotut), while the partial pressure of X{
equals twice the value for the change tn
pressure of the system (2AP16161)'
B. At equilibrium, the partial pressure of H2S eq
the value for the change in the pressure ot
system (APtotut), while the partial pressure of
(
equals twice the value for the change tn

pressure of the system (2APtotal).
C. At equilibrium, the partial pressure of CH4 eq
the value for the change in the pressure ot
system (APtotuil, while the partial pressure oI
Time(minutes) equals half the value for the change in the pre:
Figure 2 of the system (lAPtotat).
The pressure of each gas in the reaction mixture can be D. At equilibrium, the partial pressure of H2S
calculated from the change in internal pressure' The initial the value for the change in the pressure o;
partial pressure of hydrogen gas is 0'8 atmospheres in the system (APtotat), while the partial pressure ot
{
l.ZS tit"t closed system. The decrease in partial pressure of equals half the value for the change in the pt
hydrogen gas is double the decrease in the internal pressure' of the system (lAPtotat).
based on the stoichiometry of the Reaction 1, which shows
the reactivity of the comPounds.
204 GO ON TO THE NEXT P.

Copyright @ by The Berkeley Review@
26. Which of the following relationships between partial Passage V (Questions 30 - 36)
pressure for the gases in the mixture at equilibrium will
ALWAYS be true for the reaction as it is set up? Chemical equilibrium obeys the rules of Le Chdtelier's
principle. Le Chatelier's principle states that when a system
4. PCSz > PCH+
at equilibrium is stressed, the reaction will shift in a manner
3. PCH+ > PgzS
to partially relieve the stress and reestablish equilibrium. In
C. PH2 > PCS2 a gas phase equilibrium, stresses that can be applied include
D. Pgr5 > Pg, changes in pressure, volume, temperature, and moles of
either reactant or product. It is not possible to change just
one of the variables, so a change in one variable will lead to
in a change in another variable. For instance, if the volume
is increased, the pressure must decrease. Written below are
27. Which of the following equations represents the three reactions and their respective equilibrium constants at
equilibrium expression for the reaction? 500'C:
(PcH/(PHrs)2 Reaction l:
A. Ko=
(P65r)GH2)a 2 SO2(g)+ I O2(g) -$ 2 SO:(e)
(Pcsr)(PHr)a- Kp = 5.82 x 102 atm.-l at 500"C
B. Kn-
v lP6goXPgr5 )' Reaction 2:
(Pcno)tPu's) 1 H2O(g) + I Cl2O(g) -$ 2 HOCI(g)
C. Kn' - Kp = 8'61 x 10-3 at 500'C
(P6grXPs2)
(Pcs,xPH,) Reaction
D.
' - (pggoXpn2s)
Kn 3:
1 HCI(g) + I CO(e) + I HCOCI(g)
Kp = 3.26 x 10-6 atm'-l at 500'C
The equilibrium constant is derived by dividing the

partial pressures of the product gases by the partial pressures
I8. The final total pressure of the system must be:
of the reactant gases. In Reaction I and Reaction 3, the
A. greater than 1.6 atmospheres. equilibrium constants were determined using a piston system
B. greater than 1.0, but less than 1.6 atmospheres. where the total pressure and volume were monitored, and any
C. greater than 0.6, but less than 1.0 atmospheres. change in pressure or volume can be attributed to a shift in
D. less than 0.6 atmospheres. the reaction equilibrium. Because the number of products
equals the number of reactants, the total pressure and volume
cannot change in reaction 2, so equilibrium concentrations
were determined using infrared spectroscopy.
I9. Which of the following stresses on the system will 30. Given the initial partial pressure for Pgrg is 0.5 atm
change the value of the equilibrium constant?
and for P61rg is 0.5 atm, which graph accurately shows
A . Opening the stopcock to Flask 2, which was filled the rate as a function of time for the reaction?
with hydrogen gas.
B. Turning on the vacuum pump to remove some of
A. B.
the gas in the column. .9 (.)
d
C . Opening the stopcock to Flask 3, which was filled ! !
with hydrogen sulfide (H2S) gas. o o

o o
D. Heating the gas in the glass column by heating the d
o o
glass with a hot air blower. &
Time Time
C. D.
C) 0)
2
H !
o
o o
o 6)
& &
Time Time
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31. Which reactions will shift when the pressure changes? 3 5. To convert a Kp_ value in terms of torr-l to a Kn valrc
A. Reaction 1 only in terms of atm-1, you should:
B. Reactions I and 2 only A. multiply the Kp value by 760.
C. Reactions 1 and 3 only B. divide the Kp value by 760.
D. Reactions 1, 2, and 3 C. multiply the Kn value by 0.76.
D. divide the Kp value by 0.76.
3 2. Upon increasing the volume at constant temperature of

a vessel holding Reaction 3, how are the partial
pressures affected? 3 6. Cooling an endothermic equilibrium reaction results
Pucoct Pgcoct which of the following?
4. increases; increases
.
PSCT.PCO PHC1 A The mole fraction of products will decrease.
g. PHcoct PHcoct B. The mole fraction of reactants will decrease.

decreases; decreases C. The mole fraction of products will increase.
PHcr'Pco PHcr
D. The ratio ofproducts to reactants will increase.
g. Pucoct remains constant;
PHcoct
increase
PUCT.PCO PHC1
p. Pgcoct remains constant;

Pgcoct
decreases
Pucr'Pco PHcr
33. Which graph depicts partial pressures as a function of

time after 0.75 atm SO2 is mixed with 0.50 atm 02?
SO2 ------ 02
A. - B. -So:
o
! I
a 6
q 0)
k
tJr Or
C. D.
() C)
k L
a a
0-) 6)
!
H o.
Time
3 4. Which IGq value does NOT match the reaction?

A. 2 HOCI(g) I HzO(e) + 1 ClzO(e)
=-
Kp = 8.61 x 10-3 at 500'C
n. Iszo(ey+|ct2o1g)
2
1HoCl(g)
--
Kp = 9'28 x l0-2 at 500'C
c.;Hcocl(e) * |Hcrlg;+f co1g;
Kp = 5.54 x 102 at 500"C
D. 2 HCI(g) +2CO(s) 2HCoCl(e)
Kp = 1.06 x 10-11 at 500'C
-
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Passage Vl (Questions 37 - 42) 3 9. As heat is added to Reaction l, what occurs?
A . Both the equilibrium constant (K"O) and the partial
Le ChAtelier's principle is invoked to explain reaction pressure of CO2 decrease.
rrifts following the disruption of equilibrium. A system in B. Both the equilibrium constant (K"O) and the partial
:r namic equilibrium is a closed system where the forward pressure of CO2 increase.
::action rate and reverse reaction rate are equal. Components C . The equilibrium constant (K"O) remains constant
,i the mixture maintain fixed concentration. Equilibrium is while the partial pressure of CO2 increases'
:ifferent from steady state. In steady state systems' an
D. The equilibrium constant (K"q) remains constant
:termediate has a static concentration, because the formation while the partial pressure of CO2 decreases.
::action and the consumption reaction have equal rates.
A system can be disturbed from equilibrium by applying
. stress, such as changing the temperature, volume, pressure, 4 0. What effect would an increase in pressure have on the
: moles of a reagent. According to Le Chdtelier's principle, equilibrium system of Reaction 1?
:re system reacts in a manner to partially alleviate the stress A. The reaction would shift to the right and the
.rd reestablish equilibrium. Reaction 1 starts with three equilibrium constant would increase.
::iferent starting concentrations on its way to equilibrium. B. The reaction would shift to the left and the
CO(e) + HzO(e) COz(e) + Hz(e) equilibrium constant would decrease.
I C. The reaction would shift to the right and the

-
Reaction equilibrium constant would remain constant.
Table 1 lists the starting and equilibrium concentrations D . The reaction would not shift in either direction and
ri each of the three trials. The reactions are observed at the equilibrium constant would remain constant'
-r00'C and the equilibrium constant is found to be 0'569'
Trial III 4 1. Which of the following graphs represents what would
\folarit Initial Initial be observed over time if equal parts of CO(g)' COZ(g)'
and H2(g) were mixed in a closed system?
A. R'-
() ,l3l
Table 1 o
k
nv'
Once at equilibrium, a separate stresses were applied to
,.;h system. To reaction System I, an additional 0.10 moles Time Time
': CO was added to the 1.00 liter vessel in which the reaction
,.:s housed. To reaction System II, all of the H2O was
':noved from the 1.00 liter vessel in which the reaction was 6)
!r
c-)
k
'rused. The 1.00 liter vessel containing reaction System III a
I 6)
:s cooled to 500'C. Once equilibrium was reestablished in q Ai
.e three reaction vessels, the partial pressure of CO2 had
-:reased in reactions systems I and Itr and decreased in II. Time Time
= Total Pressure
rI . All of the following affect the reactant/product ratios of
the equilibrium mixture EXCEPT: HzO Pressure
=
A . increasing the volume of the reaction vessel. -
= CO Pressure
B. heating the reaction vessel.
C. cooling the reaction vessel.
D . adding reactant to the reaction vessel'
42. For an exothermic reaction at 100'C, the equilibrium
concentration of the products equals the equilibrium
concentration of the reactants. What is true at 25"C?
I 8, If 1.00 moles of both CO2 and H2 were mixed in a A . Keq > l; fProducts] > [Reactants]
1.00 liter container at 1000'C, what will the B. Keq > l; lProducts] < [Reactants]
equilibrium concentrations be for both CO2 and H2? C. Keq < 1; lProducts] > [Reactants]
A. [COz] = 0.57 M; [Hz] = 0.57 M D. Keq < 1; lProducts] < [Reactants]
B. [COz] = 0.57 M; [Hz] = 0.43 M
C. [COz] = 0.43 M; [Hz] = 0.57 M
D. [COz] = 0.43 M; [Hz] = 0.43 M
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-opyright
Passage Vll (Questions 43 - 49) 44. The Kro value for which of the following salts is the
MOST accurate in terms of smallest percent error?
The solubility of a salt in water is measured by its molar
solubility. The molar solubility is defined as the moles of A. Ag2SOa
salt that dissociate into one liter of aqueous solution. The
B. Pb(oH)2 :!t!,
solubility product (KrO) is the equilibrium constant for the C. SrCO3 lm:.
dissociation reaction. Table 1 lists solubility data for various D. ZnS hrl
lml
salts of siiver, lead, strontium, and zinc.
fr$
Compound Krp Molar solubility 4 5. Which anion should be added to selectively remole uuilI
Zn2+ from an aqueous solution that contains Ag- W
AgCl 17*19-10y2 1.3 x 10-5 M Sr2+, and Zn2+? gmU,l
PbClr 1.6 x o-5 u3 1.2 x 10-2 M A. Cl- wllr

SrCl2 8.8 x o-3 u3 1.3 x 10-1 M B. COr2' j
ZnCl2 1.1 x o-4 lt3 3.1 x 10-2 M C. OH- T
Lg2CO3 8.1 x g-12 y3 1.2 x 10-4 M D. so42- m
PbCO3 8.3 x 0- l1vp 9.1 x 10-6 M ilh
SrC03 7.1 x 6-10 y2 2.6 x 10-5 M 46 , If a precipitate forms when NaCl is added to an aqueor$ @
hr
ZnCO3 2.0 x g-10 y2 1.4 x l0-5 M salt solution, what conclusion can be drawn?
$ii
AgOH 2.0 x o-8 M2 1.4 x 10-4 M A. There is no Zn2+1aq) present in solution. T1.
Pb(oH)z 1.2 * 19-15 143 6.5 x 10-6 M B. There is Ag+(aq) present in solution. W
Sr(OH)2 3.2 x lT-a M3 4.3 x 10-2 M
C. There is both Sr2+1aq; or Pb2+1aq; presenr r! ;ilo
solution.
Zn(OH)2 2.1 * 19-16 y3 3.8 x 10-6 M D. There is no Sr2+1aq) present in solution. ,{h
AgzS 1.6 * 19-49 143 3.4 x 1o-17 tvt m
PbS 2.6 * 19-27 YP 5.1 x 10-14 M flh
47. If an aqueous solution containing Ag+, Pb2+, Sr2*. i
&
SrS 4.0 x 10-6 M2 2.0 x l0-3 M Zn2+ is treated first with chloride anion, secondh'n
Wd
ZnS 2.5 * 1g-22 YP 1.6 x t0-1 I M sulfide dianion, and lastly with hydroxide anion.
what cation is most likely still present in solutionl
flp!
Ag2SOa 1.4 x 10-5 M3 1.3 x 10-2 M
'!
PbSOa 1.7 x 10-8 M2 1.3 x 10-4 M A. Ag*
SrS04 3.2 x l0-1 M2 5.6 x 10-4 M
B. Pb2+
ZnSO4
C. sr2+
7.6 x l0-8 M3 2.1 x I0-4 M
D. zn2+
Table 1
The relative molar solubility values can be used to 48. Adding acid to an aqueous solution containing a
determine which salts precipitate out from solution when salt has what effect?
various cations or anions are added. For instance, PbSOa
precipitates first when sodium sulfate is added to a solution
A. It will increase the solubility.
containing lead, strontium, and zinc cations, because lead
B. It will decrease the solubility.
C. It will have no effect on the solubility.
sulfate is the least soluble (has the lowest molar solubility)
D. It will lower the temperature of the solution.
of the sulfate salts.
4 3. Which of the following statements are valid? 49. Silver hydroxide is MOST water-soluble at $'ll
L Sulfates are more soluble than carbonates. the following pH values?
II. Insoluble cations can be dissolved into solution by A. 3
adding a complexing agent such as EDTA. B. 5
m. The solubility of chloride salts show pH c. 9
dependence, while the solubility of sulfide salts D. 11
show no pH dependence.
A. I and II only
B. I and III only
C. II and III only
D. I, II, and III
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Passage Vlll (Questions 50 - 56) 5 0. How do the solubility products for the three salts in the
passage compare to one another?
The solubility of salts is often measured in terms of A. KspMx > KspMy > KspMZ
moles solute per liter solution in a saturated solution. I t B. KspMy > KspMX > KspMZ
may also be measured in terms of grams solute per 100 mL C. KspMZ > KspMX > KspMy
solution. The term saturated refers to a solution in which the D. KspMZ > KspMy > KspMX
maximum amount of salt that can dissociated into solution is
dissociated. The more salt that dissociates into solution, the
more scluble the salt. Solubility measurements cannot be
used interchangeably when comparing the solubility of two
salts without first considering the molecular mass of each 51. Which of the following solutions has the GREATEST
salt. This can be observed in the following experiment. molarity?
Experiment I A. Saturated MX at 31.6 "C
Water at 25"C is added to a calibrated burette, to the 25- B. Saturated MX at 25.0'C
mL mark. A salt is added in 1.0 grams increments, until C. Saturated MY at 27.4 "C
the salt no longer dissociates into solution. At this D. Saturated MY at 25.0 "C
point, a precipitate should settle to the bottom of the
burette. The temperature of the solution in the burette is
slowly increased until the salt completely dissociates.
The solution is slowly cooled until the first signs of 5 2. Roughly how many grams of MX will dissociate into
precipitate are observed. At this point, the temperature 25 mL of water at25.0'C?
and volume of the solution are recorded.
A. Less than 4.0 grams.
Experiment 2 B. Greater than 4.0 grams, but less than 7.0 grams.
C. Greater than 7.0 grams, but less than 9.0 grams.
The solution continues cooling until it reaches 25"C. At
D. Greater than 9.0 grams.
this point, pure water at25"C is added quantitatively until
the last detectable sign of the precipitate dissociate into
solution. The volume of the solution is recorded as
precisely as the burette reads.
Table 1 lists data for this experiment using hypothetical 5 3. What is the molarity of a saturated solution of MY at
25"C?
.alts MX, MY, and MZ. Column 3 lists data from
Erperiment 1 and column 4 lists data from Experiment 2. 9 grams
A.
Salt Mass Volume when heated Volume w/ H2O added 12g Srams x 0.0261 liters
mole
\x 7.0 e 26.2mL (@ 31.6'C) 28.9 mL (@ 25.0'C)
U. 9 grams
\IY 9.0 e 25.3 mL (@ 27.4'C) 26.1mL (@ 25.0'C) grams
120 x 0.0253 liters
\12 4.0 c 25.7 mL (@ 30.3'C) 28.7 mL (@ 25.0'C) mole
9 srams x 0.026 I liters
Table 1
120
grams
The molecular mass for MX is 100 grams per mole, for mole
\[Y is 120 grams per mole, and forMZ is 150 grams per n 9 grams x 0.0253 liters
grams
:ole. The concentration of each solution is measurable in 120
mole
,:11' standard units, including molarity (moles solute per liter
r:lution), grams per mL, mass percent, and density.
* ucentration units can be inter-converted. For instance, the
:,3rcent solution by mass can be multiplied by the density to
::termine the mass solute per volume of solution, which can 5 4. As temperature increases, what happens to the various
:e converted to molarity using molecular mass. concentration measurements of a solution, assuming no
Adding solvent to a solution dilutes the solution and evaporation of solvent and no addition of solute?
::rs reduces the concentration of the solution. All of the A. The density and molarity both increase.
:.iasurements of concentration decrease upon the addition of B. The density increases, while the molarity decreases.
;,:1r.ent, with the exception of the density. The density C. The density decreases, while the molarity increases.
:.1f,nge depends on the relative density of the solvent and D. The density and molarity both decrease.
s, lution. In these experiments, water is the solvent for each
;.:lution, and the density of water at 25"C is found to be
, 9971 grams per mL.
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5 5. Which of the following relationships at 25"C accurately Passage lX (Questions 57 - 62)
shows the relative density values of saturated solutions
of MX(aq), MY(aq), andMZ(aq)? The qualitative analysis of an aqueous salt sol
A. 1.00 > MX(aq) > MY(aq) >MZ(aq) involves the systematic addition of reagents designed
identify certain component ions. For instance, mercury
B. 1.00 > MY(aq) > MX(aq) >MZ(aq)
be distinguished from alkaline earth metals by adding su
C. MX(aq) > MY(aq) >MZ(aq) > 1.00 (S2-) to solution by the formation of an insoluble precipi
D. MY(aq) > MX(aq) >MZ(aq) > 1.00
with mercury dication. Silver can be distinguished
alkali metals by the addition of either chloride, bromide,
iodide. The precipitate that forms between chloride and
can be re-dissolved by adding ammonia to solution.
Once a precipitate is formed, it can be removed

5 6. Which solution has the HIGHEST boiling point? solution by centrifuging the mixture and decanting away
A. 1.0 grams MX with 10 mL water at25"C supernatant or by filtering away the filtrate. The soluti
B. 1.0 grams MY with 10 mL warer at25"C can then be further analyzed for other ions. Table 1
C. 1.0 grams MX with l0 mL water at 50'C the results of a matrix involving the mixture of four cai
D. 1.0 grams MY with 10 mL water at 50'C nitrate solutions mixed with five potassium anion soluti
mixed one at a time. All solutions are 0.05 M, with
exception of KOH(aq), which has a concentration of 0.10
Any compound that forms a precipitate is assumed to
molar solubility less than 0.001.
Tahle 1
Table 2 shows the results of a similar experiment

anions were exposed to a sequence of multiple reactions-
anions selected for testing are chloride, iodide,
sulfate. The test solutions are silver nitrate, barium
ammonia, and nitric acid. The matrix of Table 2 lisrr
observations of sixteen different test tubes. Nitric acid
with carbonate anion to form carbon dioxide gas, which
bubbles out of solution.
Table )
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5 7. What anion should be added to a solution in order 62. The information from Table I was used to derive the
identify any barium cation present in the solution? following flow chart:
A. CrO42' Ba2*. sr2*, ca2*. Mg2*
B. so42-
C. C2Oa2'
lv
D. co32- 7Al 1L )L )L
BaV(s) Sr-'. Ca- , Mg-
8. What reaction took place when nitric acid was added to )+ )-+
5 SrW1s.1 Ca- , Mg'
the precipitate formed from mixing Ba2+ and COtz-,
A. Ba2CO3(s) + 2 HNO3(aq) -+ lxorY
2 BaNO3(aq) + CO2(g) + H2O(1) / \
B. BaCO3(s) + 2 HNO3(aq) -+ CaXG) Mg'*
Ba(NO3)2(aq) + COz(e) + H2O(1) of
C . Ba2CO3(s) + HNO3(aq) -+ CaY(s)
BaHCO3(aq) + BaNO3(aq) V
MgzzG)
D. BaCO3(s) + 2 HNO3(aq) -+
Ba(NO3)2(aq) + CO2(s) + Hz(e) + OzG) Which of the following choices represents an
INCORRECT anion-toletter correlation?
A. V = COtz'
B. W = SO42-
5 9. Why is it NOT possible to use hydrochloric acid instead
C. X = CzO+2-
of nitric acid in experiment II?
D. Z=OH-
A. Chloride anion will interfere with the reactions.
B. Nitrate anion will interfere with the reactions.
C. Hydrochloric acid is too weak to react.
D. Hydrochloric acid is too strong to use.
6 0. If an unknown mixture was treated with K2SO4 and a

precipitate formed, what can be concluded?
A. The unknown contained no calcium or magnesium
cations.
B. The unknown contained a barium cation.
C. The unknown contained a strontium cation.
D . The unknown contained either a strontium cation, a
barium cation. or both.
tfr 1. Which of the following anions does form a white

precipitate with silver cation but does NOT react with
nitric acid?
A. Sulfate
B. Carbonate
C. Chloride
D. Iodide
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Passage X (Questions 63 - 69) 64. It is best to_a visually distinguish a sample tube
containing Znz+ from a separate sample tube
Water can be analyzed for various inorganic components containing Ag* by the addition of:
using a series of qualitative tests for metals in their various
oxidation states. This process is referred to as qualitative
A. 0.10 M Na2S.
analysis. Many of the tests involve the formation of an
B. 0.10 M NaCl.
insoluble salt. The formation of a precipitate results from
C. 0.10 M NaNO3.
D. 0.10 M Na2CO3.
the addition of an anion to an aqueous cation solution. Some
anions may complex with more than one metal, so multiple
tests are necessary. Molar solubility is different for each salt,
so occasionally an anion may precipitate with one cation 65. In which solution is Ag2S MOST soluble?
over another and the second metal can be "masked". For this
reason a schematic of the series of tests is evaluated. A. 0.10 M Ag+(aq)
Insoluble to the eye is defined as less than one mg B. 0.01 M Ag+(aq)
dissociating into one mL of solution. By looking at the C. 0.10lr4 S2-(aq)
combination of precipitates formed, the cations can be D. 0.01 M S2-(aq)
narrowed down until one is chosen with reasonable accuracy.
A researcher analyzed an aqueous sample believed to
contain roughly equal concentrations of Ag+, gu2+,7n2+, 66. What is the molar solubility of ZICO3 in 0.010lf
and Na+. Table 1 lists solubility data useful in developing a ZnCl2?
schematic for the tests. An ideal schematic sequentially
identifies one cation at a time, leaving the remaining cations
A. 2.0 x 10-12 M
B. 2.0 x 10-10 M
in solution. C. 2.0 x 10-8 M
Compound Ksp Molar solubility D, 1.4 x 10-8 M
AgzS 1.6 y3 3.4 x 10-17 M

" 19-49
ZnS 2.5 * 19-22 YP 1.6 x 10-11 M
CaS 1.1 * 16-11 142 3.5 x 0-6 M
67. Which of the following salts is MOST soluble
water?
CaCO3 8.7 x l0-9 M2 9.3 x o-5 M
A. CaCO3
Ag2CO3 3.1 19-12 tr43 1.2 x o-41,t B.
" Ag2CO3
ZnCO3 2.6 ,. 16-10 142 1.4 x o-5 v C. ZICO3
AgCl 1.6 * 16-10 y2 1.2 x l0-5 M D. AgCl
ZnCl2 1.1 x 10-4 M3 3.1 x l0-2 M
Table 1
68. Which of the following values accurately depicts
The values listed in Table 1 are all determined in distilled solubility product of Car(PO+)2 if the molar
water at 25"C. h is occasionally necessary to conduct tests at of Ca3@Oa)2 is represented by x?
an elevated temperature, in order to carry out qualitative
analysis and the separation of cations. Sodium salts are not
A. 18 x3
listed in the table, because sodium salts are infinitely soluble
B. 27 x4
with nearly all anions, compared to the other metals listed in
C. 54 x5
the data. To identify sodium cation, a flame test is often
D. 108 x5
applied. By applying a flame to a small sample of the
solution, electrons in sodium are excited. When they relax
back to their ground state, photons are emitted. In the case 69. To remove a cation from solution, the solution
of sodium, the light emitted is orange in color. flowed through an ion exchange column where i
precipitate the cation while releasing a more
63. When 0.1 gram ZICO3 is added to 100 mL of water at
cation. Which of the following filters will NOT
25'C, which of the following statements is true?
A. It dissolves completely. A. Ag+(aq) through a column containing NaCI(sl
B. It dissolves almost completely, with only a small B. Zn2+laql through a column containing CaS(sl
portion not dissolving.
C. Ca2+(aq) through a column containing
C. It dissolves slightly, with most of the ZnCO3 D. Ca2+1aq1 through a column containing
remaining not dissolving.
D . None of the sample dissolves.
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Fassage Xt (euestions 70 - 75)
77. The maximum lcu2*l in apH
= 14 solution would be
which of the following values?
Calcium salts are generally insoluble in water at standard
::rperature. Biologically, this is beneficial in that the
Ca2+
A. 4.3 x 108 M Ca2+
"n_is soluble enough to be transported through aqueous B. 4.3 , 1g-2 y1 gu2+
,.edium, yet insoluble enough to be a major component C, 4.3 * 16-6 14 6u2+
of
:-:uctural features in the human body, such as bones.
Listed
D, 4.3 x 10-10 M Ca2+
- Table I are some Ksp values at2l.C for various
calcium
;..1t s :
72. Enough CaCl2 is added to water so that not all of it

Calcium Satt Ksp (@ 27'C) dissolves, and thus some CaCl2 remains as a solid
on
the bottom of the flask. The [Cl-] is then measured.
CaF2 4.9 * 16-11 y3
Addition of which of the following ro the solurion will
CaS04 6.t x 10-6 u2 increase the chloride ion concentration (iCl-l)?
CaC03 9.t x t0-9 M2 A. Water
Ca(OH)2 4.3 x 10-6 M3 B. Silver nitrate
Ca3(POfi2 1.3 * 19-32 y5 C. Calcium fluoride
D. Sodium phosphate
Table I
The solubility products of the given salts can be
: , npared only when the anions bonded to calcium 73. Which of the following graphs depicrs the log
carry the lCa2+1
ir-ne.negative charge. For instance, the solubility products versus the buffered pH of an aqueous buffer solution
as
: - CaF2 and Ca(OH)2 can be directly
compared to determine calcium hydroxide is dissolved into different solutions?
:"::ir relative solubilities. To enhance the solubility
of a
:r-cium salt, an anion that complexes calcium can be
added
: solution. The anion competes for calcium in a complex
:,qrilibrium. A complex equilibrium is defined as the
:--upling of at least two equilibrium reactions where the
::rduct of one reaction is the reactant in another equilibrium
::rction. Reaction 1 and Reaction 2 combine to form a
;,,nplex equilibrium involving calcium cation. BufTerpH
--+ BufferpH
--->
Ca(OH)Z(s) + HZO(I) E- Ca2+1aq1+ 2 OH-(aq)
Reaction 1
Ca2+1aq1+ Na2CO3(s) T.L CaCO3(s) + 2 Na+(aq)

Reaction 2
A change in calcium cation concentration affect both BufferpH _+

BufferpH
:rirtions. If the Reaction 2 shifts to the right, then Reaction ->
- rs forced to shift to the right in order to maintain its
s-.rilibrium.
7 4. If addition of salt to water makes the water warmer once
-{.1 . the salt has dissolved, which of the following are true
What is observed when sodium carbonate is added to a
saturated calcium hydroxide solution with undissolved
for solvation of that salt?
calcium hydroxide on the bottom ofthe flask? A. AH is positive, AS is negative.
A. The pH of the solution will increase more than ir
B. AH is negative, AS is positive.
would increase had it been added to an unsaturated
C. AH and AS are borh positive.
solution of calcium hydroxide.
D. AH and AS are both negative.
B. The pH of the solution will increase less than it
would increase had it been added to an unsaturated
75. Which of the following, when added to water at 300 K.
solution of calcium hydroxide.
will yield the highest
C . The pH of the solution will decrease more than it LCa2+l?
would decrease had it been added to an unsaturated A. CaF2

solution of calcium hydroxide. B. CaSO4
D. The pH of the solution will decrease less than it C. CaCO3
would decrease had it been added to an unsaturated D. Ca(oH)2
solution of calcium hvdroxide.
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Passage Xll (Questions 76 - 82) 7 6. Which of the reactions has a negative entropy change?
Smog is a collection of several gas pollutants. Most

A. Reaction 2
prevalent in the conglomeration of impurities are the sulfur B. Reaction 3
and nitrogen oxides. The brown color so familiar in smoggy

C. Reaction 5
skies is due to the presence of nitrogen dioxide (NO2). This, D. Reaction 6
along with nitric oxide (NO), make up the majority of the
airborne nitrogen oxides. The nitrogen oxides can be inter-
converted by a series ofequilibrium reactions.
2NO(e)+Oz(g)5*2NO2(g) 7 7. Which of the following will NOT increase the [N2Oa]?
Reaction 1 A. Decreasing the temperature.
2 NOz(e)
B. Increasing the pressure.
-q== NzO+(e)
C. Addition of water vapor to the air.
Reaction 2 D. Addition of NO2 to the air.
NOz(e) + Oz(e): NO(g) + O3(g)
Reaction 3
Reactions I and 2 are both exothermic while the

Reaction 3 is endothermic. Reaction 3 requires the addition 78. If the following reaction is carried out in a closed
of light to transpire. As the day progresses, sunlight carries reaction vessel, what will be observed for the
out Reaction 3, resulting in the highest ozone concentration of the system if the temperature is doubled?
in the early afternoon. Figure 1 depicts the concentration of A(e) + B(e) C(e) + D(g) + E(g)
pollutants during a hypothetical day: =-
AH = -1l2kJlmole
I I
A. The pressure will remain the same.
I
n.-i I B. The pressure will increase by less than lO}Vo.
I
C. The pressure will exactly double.
I D. The pressure will increase by more than l00%o.
o
o O
o c
o o o
o o o
6 ci z o 9
c! + I(o I@ 7 9. What can be concluded about the change in enthalpy
Time Reaction 2?
II
NO Noz o3
A. Because a bond is broken, the reactior
endothermic in the forward direction.
Figure 1 B. Because a bond is broken, the reaction
- exothermic in the forward direction.
The amount of the nitrogen oxides in the air can be
reduced by bubbling air through an aqueous transition metal C. Because a bond is formed, the reactim
halide solution such as MnCl2(aq). Nitrogen dioxide (NO2) endothermic in the forward direction.
reacts with the water to form nitric acid (HNO:) and nitrous D. Because a bond is formed, the
acid (HNO2), both of undergo deprotonation and bind the exothermic in the forward direction.
manganese, forming a complex ion. Reactions 4 and 5 make
up a complex equilibrium, as do Reactions 4 and 6.
2 NOzG) + HzO(t) : HNO2(aq) + HNO3(aq)

Reaction 4
80. If Reaction 1 is carried out in a closed piston
with an external pressure of 1 atm, what occurs
MnCl2 + 2 NO2-(aq) 0.1 atm of NO gas is added to the system?
Reaction 5
-Mn(NOz)z+2Cl'(aq) A. The volume decreases bv more than ten
MnCl2 + 2 NO3-(aq) + Mn(NOiz + 2 Cl- (aq) B. The volume decreases by less than ten perceril.
C. The volume increases by less than ten
Reaction 6
D. The volume increases by more than ten
When reactions are added to produce an overall reaction,
the equilibrium constants for the reactions are multiplied to
obtain the equilibrium constant for the overall reaction. This
is true for any type of equilibrium reaction.
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81. Which will shift reaction 4 to the left? Passage Xlll (Questions 83 - 89)
A. Addition of sodium hydroxide to the solution
B. Addition of manganese(Il) chloride to the solution Physiological response is correlated with climate. This
C. Removal of nitrate from the solution can be proven by observing the shortness of breath and/or
D. Removal of water from the solution headaches experienced by mountain climbers and skiers when
they rapidly change altitudes. These symptoms are associated
with a disorder referred to as hypoxia, a deficiency in the
amount of oxygen that reaches body tissue. Hypoxia is a
temporary disorder that in some cases can be fatal in the short
term. After time, the disorder will disappear because the
8 2. Which of the following graphs accurarely depicrs the body becomes acclimated to the new environment.
NO2 concentration in a flask containing reaction 2
The cause of hypoxia is a result of the decrease in
before and after it has been bubbled through MnCl2(aq)?
oxygen in the environment caused by the increase in altitude.
A. B. The partial pressure of oxygen gas at sea level in most parts
of the world is just over 0.20 atm. At an altitude of one
mile above sea level, the partial pressure of oxygen gas is
roughly 0. 16 atm. Over time, the body adjusts to the lower
oxygen content by increasing the production of hemoglobin
(Hb), the molecule that binds oxygen. Reaction 1 expresses
time time the binding of oxygen by hemoglobin.
Hb(aq) + 4O2@e + Hb(O2)a(aq)
Reaction 1
The equilibrium expression for Reaction I is:
1q = [Hb(ozl+l
tHbltozla
time Figure 1
Hemoglobin is composed of four separate polypeptide

strands, each capable of binding a ferrous (Fe2+) cation, held
together as one molecule. By producing more hemoglobin,
the body can shift the equilibrium to the right (forward
direction). This results in more oxygen diffusing across the
cell membrane. Once in the cell, myoglobin transports one
oxygen molecule from the interior of the cell membrane to
the mitochondria.
In acclimation, the amount of myoglobin does not

change. Acclimation takes a period of time that ranges fiom
a week or two to months. For the 1968 Mexico City
Olympics, several athletes trained in high altitude to
approximate the environment of Mexico City (elevation
7500 feet above sea level). For those athletes that trained
closer to sea level, many did not perform well in the
"thinner" air. Conversely, many current runners train in the
mountains for sea-level races so that their blood can provide
extra oxygen to starving muscle cells.
83 . Once hemoglobin transfers oxygen to the cell

it is absorbed, how many myoglobin
membrane where
molecules should be present per hemoglobin?
A. 1
B. 2
c. 4
D. 8
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84. Which of the following changes will NOT increase the 8 8. What activity will most likely result in hypoxia?
amount (in moles) of free oxygen in the body?
A. Repelling down a mountain
A. Increased ventilation, resulting in an increased B. SCUBA diving
amount of air transferred through the lungs. C. Water skiing on the ocean
B . An increase in the production of Hb D. Snow skiing
C . Increasing the partial pressure of CO consumed in a
normal breath.
D . Increasing the total amount of blood.
89 . Why should an athlete choose to train at high altitudes?

A. At higher altitudes, the partial pressure of oxygen
is greater, thus the athlete's body will increase its
8 5. What will be observed when a long-time mountain hemoglobin count.
resident travels back to sea level? B. At higher altitudes, the partial pressure of oxyger
is less, thus the athlete's body will increase irr
A. They will experience hypoxia due to the lower hemoglobin count.
partial pressure of oxygen at sea level. C. At higher altitudes, the partial pressure of oxyger
B. They will experience hypoxia due to the higher is greater, thus the athlete's body will decrease ib
partial pressure of oxygen at sea level. hemoglobin count.
C . They will experience an increase in vitality due to D. At higher altitudes, the partial pressure of oxyger
the lower partial pressure ofoxygen at sea level. is less, thus the athlete's body will decrease
D. They will experience an increase in vitality due to hemoglobin count.
the higher partial pressure of oxygen at sea level.
8 6. In the presence of carbon monoxide, hemoglobin

preferentially binds CO over 02 in a ratio close io 200
: 1. Over time, what occurs in the blood of someone
moving to a carbon monoxide rich environment?
A. The increased CO reduces rhe amount of Hb that
binds oxygen, so the Hb(Oz)+ decreases. To
compensate, the bgdy produces more Hb and
increases its rate ofrpspiration.
B. The increased CO reduces the amount of Hb that
binds oxygen. sor' the Hb(O)a increases. To
compensate, the i body produces more Hb and
increases its rate dfrespiration.
C. The increased CO reduces the amount of Hb that
binds oxygen, so the Hb(O)a decreases. To
compensate, the body produces less Hb and
decreases its rate ofrespiration.
D. The increased CO reduces the amount of Hb that
binds oxygen, so the Hb(OZ)+ increases. To
compensate, the body produces less Hb and
decreases its rate of respiration.
87 . How does hypoxia affect the amount of myoglobin?

A. Myoglobin increases initially and then decreases.
B. Myoglobin increases initially and then remain at
higher concentration.
C . Myoglobin decreases initially and then remain at
lower concentration.
D. Myoglobin remains constant.
Copyright @ by The Berkeley Review@ 216, GO ON TO THE NEXT

Passage XIV (Questions 90 - 96) 93. What is NOT true for a reaction with an equilibrium
constant of L0 x 105?
The equilibrium of a gas-phase reaction can vary with
fie dimensions of the container. This is observed when a A. There is mostly product present at equilibrium.
:eaction has a different number of gas molecules on the two
B. When starting with all reactants, the shift to reach
equilibrium is insi gnificant.
sides of the reacrion equilibrium. Although the equilibrium
;onstant remains constant when pressure, volume, and moles
C. The K"O for the reverse reaction is 1.0 x l0-5
.ire altered, the ratio of product to reactant can vary. The
D. The same reaction when carried out with a catalyst
will have the same equilibrium constant.
following reaction is a typical reaction which shows a
'jependence on the dimensions of the container:
NzO+(e) --! 2 NO2(g)
9 4. If the value of K"q at a certain temperature is greater
Reaction 1 than one, what will be observed after radiolabeled
15NzO+ is added
The reaction may be carried out in a glass flask, where to an equilibrium mixture of NO2 and
:ne volume of the container remains constant while the N2O4 in a rigid container?
.nternal pressure may vary. The reaction may also be carried A . The amount of radio-labeled NO2 increases, while
:irt in an enclosed piston, where the internal pressure remains the amount of radio-labeled N2O4 decreases.
:onstant while the volume of the container may vary. Le B . The amount of radio-labeled NO2 decreases, while
ChAtelier's principle predicts that when the internal pressure the amount of radio-labeled N2Oa increases.
rses, Reaction I will shift to the left to alleviate the increase C . The amount of radio-labeled NO2 increases, while
:m pressure. Le Chdtelier's principle also predicts the amount of radio-labeled N2O4
that when remains
:e volume of the container is increased, Reaction 1 will constant.
;hift to the right to fill the volume. The equilibrium D . The amount of radio-labeled NO2 decreases, while
:onstant for Reaction I at 25"C is 4.i2 x 10-3 atm. the amount of radio-labeled N2O4 remains
Independent of the starting conditions and presence or constant.
.rbsence of an inert gas, the ratio of the square of the partial
:ressure of nitrogen dioxide to the partial pressure of
:rritrogen tetraoxide is constant, given that the temperature 95. As the handle of a piston container filled with an
.tJes not change. The ratio of nitrogen dioxide to dinitrogen
equilibrium mixture of NO2 and N2O4 is lifted, what
-atraoxide increases
as the temperature is increased. occurs?
I tl . The reaction as written is: PNon
l. Ihe
A. endothermic with AS > 0. PNzoo
B. endothermic with AS < 0.
C. exothermic with AS > 0. II. The piston cools down.
D. exothermic with AS < 0. m. The mole percent of N2O4 increases.
A. I only
I 1. The reaction will shift ro the right with all of the
B. II only
following changes EXCEpT: C. I and II only
A . addition of N2Oa(g).
D. II and III only
B. an increase in volume at constant pressure.
C. a decrease in pressure at constant volume.
D. addition of He gas to the system at constant 9 6. The Ks, for the reaction as written is:
volume.
A. K-"Y= P*o,
PNroo
I L Which of the following accurately shows K"q in terms
of AG? (Pruo")2
B.
A. Keq=- AG
' =- PNzo+
Ao
ln RT PNzo+
AG c. K^^
r
\ =
B. Keq = PNO,
ln RT
PNzo+,
C. IQq = eo%r D. K* =
(pNoz).
D. K* = e-a%r
Cmyright @ by The Berkeley Review@ 2t7 GO ON TO THE NBXT PAGE

Questions 97 - 100 are NOT based
on a descriptive Passage.
97 . If the molar solubility of an MX type of salt is defined

as y, then the solubilitY Product is:
A. y
B. 2v
c. v2
D.4y2
98. MgF2(s) would be most soluble in which of the

following solutions?
A. 0.10 M CaF2(aq)
B. 0.10 M NaF(aq)
C. 0.10 M NaCl(aq)
D. 0.10 M MgCl2(aq)
9 9. If the forward rate constant for a one-step reaction is

four times the reverse rate constant, then which of the
following is true?
O. Keg = 0-0625
U. KeQ = 0.25
a. Kee = 4.00
O. KeQ=16.00
4.D 5. C
r.e 2.D 3.B
6.A 7.8 8.D 9.A l0.B
11. A 12. B 13. D 14. C 15. B
16. C 17. B 18. B 19. B 20. B
2t. B 22. B 23. D 24. B 25. D
26, C 27. A 28. C 29. D 30. A
31. C 32. D 33. C 34. A 35. A
100. The amount of a salt that dissociates into water is 39. A 40. D
36. A 37. A 38. D
ALWAYS increased by which of the following 44. A 45. C
41. B 42. A 43. A
changes?
46. B 41. C 48. A 49. A 50. B
A . Increasing the temPerature' 51. c 52. B 53. A 54. D 55. D
B. Decreasing the temperature' 56. C 5',7. A 58. B 59. A 60. D
C . Increasing the amount of water' 61. C 62. A 63. C 64. B 65. D
D . Decreasing the amount of water' 66. C 67. B 68. D 69. C 70. A
'71. C '72. D '73. C '14. B ',75. D
16. A '7',7. C 78. B 79. D 80. c
81. D 82. A 83. C 84. B 85. D
86. A 87. D 88. D 89. B 90. A
91. D 92. D 93. B 94. A, 95. C
96.B e7.c elJ 99. C 100. c
2ra THAT'S
Copyright O bY The Berkeley Review@
Equilibrium Passage Answers
Choice B is correct' This question involves first determining the value of

the equilibrium constant (K".) at
the partial
l':i"Td 90? at 70i"C. Converting rozlc ,',to Kelvin yields tf! il".
'!32:^?I!,lT:,::t""T.t#
According to Table 1., at37S 6,IGg = 9 atm-l. The solution is as follows:
K"q =9 - (pcg')2 =(Pc9{ = PcgrY =g'"\-'

... (pcozY = 36 ...pcoz = 6 atm.,choice B
(Pco)2(Poz) e)2G) 4
Choice D is correct. Adding Co2 (a product) to an equilibrium mixture forces the reaction
to the left. \A/hen the
reaction shifts to the left, reactants (oz(c) and Co(g)i increase. This eliminates
choices A and B. Because Ko.
changes only with temperature, and the temperaiure did not change in this case,
choice C is invahdl tyq
default, (the elimination of three wrong choicei), choice D is the correct answer.
Choice B is correct' Because the value of K"o increases as- the temperature increases,
products increase upon the
addition of heat to the reaction. This means that heat lies on the reactant side of the reaction
and thus the
reaction is endothermic as written. The AH is positive for an endothermic reaction. pick
B and feel warm.
Choice D is correct. The equilibrium constant is just that, a constant. It is specific
for a given temperature, so it
varies only with a change in, temperature. The equilibrium may shift with
changes in either the pressure,
volume or concentration, but the value of K remains constant. This makes
choice D the best answer.
Choice C is correct. The following chart summarizes the partial pressures during
the course of the reaction:
Reaction: 2Co(g) oz(g) 2Co2G)
Initially: 0 0 1.00
Shif t: +2x +X _t-
- _2x
Equilibrium: 2x x I -2x
The total pressure of the system is the sum of the partial pressures_of each component
at any given time during
the reaction' The question here asks for the total pressure at equilibrium, ,o tir"
equilibrium"partial pressures
must be added. To solve this question, use the
"qr'ruiio.,,
Ptotul = PCOZ + PCO + POz = (1 -2x) +2x+ x= l- + x.
The value of x can be no larger than 0.5 atm., because you can lose no more
CO2(g) than you start out with (1.00
atrn')' The value of x must be somewhere between 0 and 0.5, because some of the carbon dioxide
is lost, but not
al] of it' This makes the following relationship 1.5 > Ptotul > 1 true, which is choice
C, your best choice.
Choice A is correct. Compressing the reaction vessel results in reduced volume and increased
pressure. Upon
decreasing the container volume, prior to any shifting of the reaction, the partial pressure
and concentration of
each gas increases, but the mole ratio is the same until the reaction shilts. This is
why no answer choices
contained the term concentration. Compressing the container decreases the free area in
which the gases can
exist' The more crowded environment favors the formation of CO2, because carbon dioxide lies on the less
crowded side of the reaction. This means that moles of Co2 increase, moles of CO
decrease, and moles of g)2
decrease' This eliminates choice B. When moles of Co decrease, the mole fraction
of Co decreases, so choice C
is eliminated. The temperature did not change, so the equilibrium constant remains
the same, so choice D is
eliminated' The best answer is choice A. As i note of interest, all of the partial pressures increase,
but carbon
dioxide increases by the greatest amount. The shift to re-establish equiiibrirrrn never
completely offsets the
stress, so the result is that Co and 02 have slight increases in partiai pressure
overall, *i1it" co2 shows a
significant increase in partial pressure.
Choice B is correct. Addition of Ca(oH)2(aq) to an equilibrium mixture of Reaction

1 serves to remove Coz(g)
from the reaction mixture- To compensate ior lost io21g;, Reaction 1 proceeds in a way
so as to regenerate
CozG), but it is not completely regenerated. This eliminaies choice A. ro produce CozG),
the reactiin must
shift right, which consumes both o2(g) and Co(g). This results in a decrease of both 0219
answer is choice B. Total moles of gas decrease, so the total pressure of the system
ind Co(g). The best
decreases.
r-;right @ by The Berkeley Review@ 219 Section III Detaited Explanations
8. Choice D is correct. Kst for the reaction is determined by plugging the values from Table 2 into the equilibriur
expression. Upon doing so, the value is found tobe5.44 atm., makirg choice D the best answer.
(PHnr)2
e-72)2 e.7z)(2.22)
PH2- 7.36-
r.,,= = 2.72x2.72 = 2.22x2= s.44atm.
' 7.36 7.36
9. Choice A is correct. Addition of the gaseous HBr (a product in Reaction 1) to the equilibrium mixture pusLos
the reaction to the reactant side (right), and thus increnses both the partial pressure and mole percent of H1. -:
you are of sound mind and body, then you should pick choice A. As long as the temperature remains consta:,:
the concentration of Br2[) (or any other pure liquid) remains constant. The concentration of a liquid is measure;
as density, which changes with temperature. This eliminates choices C and D, so don't pick them.
10. Choice B is correct. The greatest amount of H2(g) forms from the reaction that generates the greatest baii
reaction or smallest forward reaction. Choices A and C are eliminated, because less H2(g) is present initral;
mnftil
than rn choice B, therefore less H2(g) exists at equilibrium. In addition, the difference between choices A and f,
is the amount of Br2(l), and liquids do not affect the equilibrium distribution, so both yield the same amount ::
HZ(g). There is only one correct answer per question, so identical answer choices should both be eliminated. -'
choice D went one hundred percent in the reverse direction, then 0.50 atm. of H2(g) would be generated. Thr
value is haif of the amount of H2(g) in choice B, so choice D is eliminated. To generate an equivalent amount :r
H2(g) at equilibrium as starthg with 1.00 atm. H2(g) and excess Br2(1), requires starting with 2.00 atm. HBr(g,.
17. Choice A is correct. An increase in temperature results in the addition of heat to the equilibrium mixtur;
Because the mole percent of product (HBrf increases, heat must be viewed as a reactant in the reaction.
J]IL {
Heat + H2(B) + Br2(l) + 2HB(g)

J
When heat is viewed as a reactant, the reaction is defined as being endothermic, so choice A is the corre:l
answer. An endothermic reaction has AH value that is a positiue number. Choice C is eliminated, because lh:
pressure changed with both the influx of heat and the shift of the reaction, so it cannot be an isobaric (consta:ii,
pressure) process. Choice D is eliminated, because the passage states that Reaction 1 is an equilibrium mixtw-
12. Choice B is correct. The definition of equilibrium is a state where the forward and back reactions have equ
rate. Choices A and D are equivalent, so they are both eliminated. The reaction lacks Br2(I), and desp:
liquids not affecting equilibrium, keep in mind that the system is not in equilibrium. Liquids can be a limitrr
reagent. Because there is no Br2(1) present, the reaction cannot move in the forward direction, even if it wantei ih*
to. This makes choice B the best answer. At this point, we are uncertain it is correct, but it is the best ansrr Im.
choice. To determine the direction in which a reaction proceeds, it is necessary to compare the value of L
reaction quotient (Qr*) to the equilibrium constant (K"q). The two possible scenarios are: Qr* ) K"q, in whii
case the numerator is too large in the equilibrium quotient (products are in excess of reactants), making L t*
reaction shift to the left (reactant side) to reach equilibrium. The second scenario is where Q.* < K"q, in wh; ft:
case the denominator is too large in the equilibrium quotient (reactants are in excess of products), making t
reaction shift to the right (product side) to reach equilibrium. We solve for Q as follows: f "15
lllu:r
(Pu.e'.)2
q,^ =
pH2 =:1
= t .,'r?r) ... e,* < K*q xqT,l
Ip:
Because Qt* < K"q, Reaction 1 should shift right (to the product side). The problem here is that there is no
present, so there can be no reaction. This confirms that Br2 is the limiting reagent. To quickly determine
direction of a reaction, put K"O and Qr.* alphabetically and turn the greater than or less than sign into an
(i.e., the K"q > Q.* becomes K"q Q11, meaning the reaction proceeds forward to reach equilibrium).
-t
13. Choice D is correct. All reagents are present, so a reaction is possible. To answer this question, solve for Qr* frrw:u
llT''ri'*ti
e,* =(PHfuf
PH2 1.5
=+rryI...
1.36
Keg < e* by a smal amount :r*siiu,ul;
irl.UtreI
jr'.{ATs
Because Keg < Qt*, the reaction proceeds to the left (reactant side). This decreases HBr(g) and increases H2
so choices A and B are eliminated. The shift is small, because Q and K are close, so choice D is the best anslr-
4[J
Copvright O by The Berkeley Review@ 22o Section III Detailed Expl

14. Choice C is correct. If the flask is initially charged with only HBr(g), then the graph of H2(g) over time starts
'"fhe
at 0, eliminating choice A. Choice D is a iitration curve, so if is an incorrect unswe, choice. graphs depict
the progression of a reaction. Reactions proceed with a gradual tapering off (choice C), not an iirstantaneous
shut-off (choice B). Pick C, because H2(g) increases most rapidly initially, then levels off until equilibrium.
15. Choice B is correct. "...NOT affect the partial pressure of H2(g)?" Addition of NaOH(aq) removes HBr and
indirectly shifts the Reaction 1 equilibrium to the right, through a complex equilibrium. Addition of H2(g) and
HBr(g) directly affect the equilibrium, shifting the equilibrium to the opposite side of the compound aaald. If
the reaction is already at equilibrium, then neither a solid nor a liquid (such as Br2(l) in thiJ case) affects the
equilibrium. For this reason, choice B is a particularly swell answer choice. A solid or liquid can only affect
the net results (equilibrium conditions) if the system is not at equilibrium and the compound. being added (the
solid or liquid) is the limiting reagent. When added in, the system can then achieve equilibrium. -
16. Choice C is correct. According to the two reactions, only PC13 and NO react with C12, so PCl5 and NOCI are not
oxidized by CI2. This eliminates answer choices B and D. By looking at the oxidation states of the reactants
and products, PCl3 (P = +3), PCl5 (P - +5), NO (N = +2), and NOCI (N = +3), it shows that the forward
direction in both Reaction 1 and Reaction 2 as drawn are oxidation half-reactions for the non-metal compounds.
The reactants get oxidi zed by chlorine in the forward reaction as written. Comparing the two values of Ksq
shows that reaction 2 lies further to the right (product side) than does Reaction 1. Thus, Reaction 2 favors the
formation of products more so than Reaction 1. This implies that NO reacts with Cl2 more readily than pCl3
reacts with Cl2. The greater the reaction with Cl2 means more oxidation by C12. Choose C to feel good.
Choice B is correct. Initially, there is twice as much PCl3 as Cl2, and their sum pressure is 1.50 atm. \A/hen the
reaction shifts in the forward direction, total pressure decreases, so choice D is eliminated. According to the
mole ratio, the initial partial pressure of phosphorus trichloride is 1.0 atm. and the initial partial pressure of
chlorine gas is 0.5 atm. The chart below summarizes the partial pressures during the course of the reiction.
Reaction: PCl3(g) ClzG) E4 PC15(g)
Initially: 1.0 0.5 0

Shift: -x -x --+ +x
Equilibrium: 1- x 0.5-x X
The total Pressure of the system is a sum of the partial pressures of each component at any given time during
the reaction The question here asks for the total pressure at equilibrium, so the equilibrium partial pressures
must be added. To solve this question, use the formula I Pl = Ptotul. In this case the following holds true:
Ptotul = PpCls +PClz + Ppcls = (1 - x) + (0.5 - x) * x= 1.5 - x.
If everything reacted to the limiting reagent capacity, then x is 0.5. But the reaction does not go to completion,
so the value of x falls between 0 and 0.5. This is because some, but not all, of the reactant is lost. Choice A is
eliminated, because 1.5 > P16121 > 1. To solve this question, you must estimate the magnitude of x. The value of
x is greater than 0.25, because over half shifts to products to reach an equilibrium constant of 1.95. This makes
choice B the best answer. To solve it more precisely, assume P1s1n1 at equilibrium is 1.25 (the borderline
between answer choices B and C). If P1614 at equilibrium is 1.25 atm., then x = 0.25 atm., and at equilibrium,
PPCIa = 0.75 atm', Pclz = 0.25 atm., and Ppglu = 0.25 atm. The following Q would result:
Ppcts 0.25 -- 1 -
-',. -- (r'pcl3;(pcl2) =
,-r-- - (o'zsxo ,5) u?s
1.33 ... Ko^ ) O.", so more must shift over.
This means that x is between 0.25 and 0.50 atm., and thus P1s1; at equilibrium is between 1.00 and 1.25.
Choice B is correct. The reaction listed in the question is the reverse reaction of Reaction 2. When a reaction is
reversed, the equilibrium expression is inverted, because reactants and products are inter-converted. The
resulting equilibrium constant is the inverse of the original value. The inverse of something times 104 is
something times 10-5, making choice B the best answer. Choice A is an incorrect answer that could have been
reached if you inadvertently decided the values must multiply to 1.0 x 10-14 (a common value in acid-base
chemistry). Choice C was the result of taking the square root, which is wrong in this case. Choice D is
eLiminated because the forward and back reactions are different.
iight @ by The Berkeley Review@ 22t Section III Detailed Explanations

T9, Choice B is correct. Welcome to the wonderful world of math. The following chart summarizes the changes Lr.
partial pressures as the system goes to equilibrium. You must solve for the x value. Keep in mind that the
answer you seek is actually 2x,but you must first solve for x before you solve for 2x.
Reaction: 2 NO(g) CIZ(g) : 2 NOCI(g)
Initially: 0 0 1.0 atm.

Shift: +2x +x --+ -2x
Equilibrium: 2x x 7 -2x
From here, it is a matter of plugging the equilibrium values into the equilibrium expression.
r_= (PNocrF -G.0-2x)2 72 - 1

=(2x)2(x) -2.7x704
(prvo)2(pcrr) 1z*;21*) 4*3
The easiest thing to do here is to take the reciprocal of each side and then solve for x, keeping in mind that i|,:
answer choices are 2x.
4x3 = 7 =4.9x10-5 = 49x10-6.'. x3= 12.25x10-6.'. ,=!tZmrtO-Z

2.1x 704
Thecuberootof 12.25 liesbetween2and3(because23=8and 33=27),solet's ca\lit2.? PNO= 2(2.?x1.0-2)=='
xL0-2, which is choice B. The math is not so bad, if you approximate.
20. Choice B is correct. Immediately, choices A and C are eliminated, because there is no reaction possible, rti.*r
the reaction has only one reactant (and lacks C12). From here, it comes down to interpreting the magnituce :r
K"O values. The reaction that forms the greatest amount of Cl2 is the reaction with the Kgq that most fa',-;rs
formation of reactants (because C12 is a reactant in Reaction 1 and Reaction 2). Reaction 1, with the srr,iz
K"O, most readily favors the formation of reactants out of the two reactions. Because of the squared trrn '"9
need to look more closely in most cases, but the K"nvalues are so drastically different for the two reach::s
that you are safe ignoring the squared terms in the Kgq of Reaction 2. The larger K"n is ursssislsd -,r',il
Reaction 2, so choice D is out and the best answer is choice B.
21. Choice B is correct. This is a rehash of an ongoing theme in this passage. Addition of Cl2 shifts both Rea:- rqr
1 and Reaction 2 in the forward direction. The question here entails the magnitude of the shift. Reachc: ;,
with a K"O value of approximately 1, shifts the equilibrium to the product side to use roughly half of th.e -r:
gas that was added. Adding Cl2 to reaction 2, with a KuO that is extremely large, will shift the equiiibriu: nn
the product side to use nearly all of the Cl2 gas that was ailded. Choice B is the best answer.
22. Choice B is correct. To determine the direction of a shift requires solving for the equilibrium quotient (Q).
l
Plctr o.4o -
- (PpcrrIPcrr) (0.40X0.40) i
Qrx =,_---]j|' 1
-2.5 ... K"q < Q.*, so the reaction shifts left.
0.40
When K > Q, the Q is too small, so the products must increase and the reactants must decrease (K Q. ,
forces the reaction to move to the left (reactant side). You really should pick choice C. Choice D is->elirnr:
because a catalyst affects only the kinetics (rate), and not the thermodynamics of a reaction. A ca::- c
simply lowers the activation energy, but has no effect on the heat of reaction (AH), the free energy - ::
(AG) for the reaction, or the equilibrium constant (K) for the reaction. 1t
fl,;
flT
This is an experiment that is used to determine the equilibrium constant for the gas phase reaction listed .:
passage. In interpreting the apparatus in Figure 1, you must note the two reactants are being reacted or-:'. c
valve is opened between the gas line and the flask. The reactants are mixed in a ratio of 4}l2 to 1CS- flto
they just-so-happen to react in a ratio of 4: 1". This means that the reactants always exist in a 4 :7 rat:-:
the products always exist in a 2 : I ratio. The reactants are never completely depleted, thus the total p:
(Pr,it - 2x) of the systern can never reach a value as low as 0.60 atm. Overall, the number of molecules of ln'
decreasing as the reaction proceeds, which accounts for the decrease in pressure experienced by the syste:
approaches equilibrium. The final total pressure is not given on the graph, but a AP is a negative valur
passages seems hard, but it is really testing your organization skills.
Copyright @ by The Berkeley Review@ 222 Section III Detailed

23. Choice D is correct' The purpose of the experiment is to determine the equilibrium
constant (K) for Reaction 1.
The value of the equilibrium constant varies with the temperature, so the
temperature must be held constant to
accurately evaluate the value of the equilibrium constint. This means that
the best answer is choice D.
Hopefully the other answer choices did not seem that tempting.
24. Choice B is correct. Ugon heating a closed, isochoric system, the internal pressure
increases according to the
ideal gas law (PV = nRT). This in essence is Charlei' law, eliminating choice A, which
has Charles' law
listed incorrectly' Because the pressure decreases rather than increases,*another variable
must be changing.
The system is in a flask, so the volume can't change. This means that moles must
be decreasing, causing the
pressure to decrease: T!" only way for moles to change in a closed system, is for a
- chemical reaction to take
place' Reaction 1 shifted from the reactant side (five gis molecules) to the product side (three gas molecules).
This means that the reaction proceeds in the forward direction to consume ihe heat added
to th"e system. This
means that the reaction as written must be endothermic, making choice B correct.
/.J. Choice D is correct. question requires setting up the equilibrium relationship that transpires during the
Tit
course of the reaction. The reaction goes as followsr
Reaction: CSz(g) 4HzG) CH+(g) 2H2S(g)

Initially: 0.20 0.80 00
Shift: -x -4x +x +2x
Equilibrium: 0.2-x 0.8-4x --.+ x2x
At any point, including equilibrium, the total pressure of the system is found according to Equation
1.
Ptotut = PCSz + Pg, + Pgpq + PUzS = (0.2 - x) + (0.8 - 4x) + x + 2x 7.0 _ 2x
=
The initial pressure of the system was 1.0 atmospheres when the valve was first opened
to start the reaction.
The pressure of the system at equilibrium is 1 - 2x atm., therefore the change in
inteinal pressure from the start
of the reaction until equilibrium is 2x. This means that the partial pr"rr.ri" at equilibrium
due to H2S (which
is also 2x) equals the change in internal pressure during th" ,"u.iiorr. The purtiut pressure
due to CH4 at
equilibrium is one-half of the change in internal pressure. -This makes choice p ihe best
answer.
Choice C is correct. This question requires that you deduce that the value of x can
never exceed 0.2. This upper
limit of 0'2 is due to the initial pt"tt,rt" of
CS2 being only 0.2 atm. You can lose no more CS2 than you hiv -
available as a reactant. Because of this, no matter what value for x is used (any
value between o and'0.2), 0.g -
4x will always be greater than 0.2 -x. This means that Pg, is always greater thin pgg,
because 4x must always
be less than 0'8. The best answer is choice C. If the reaction goes completely in
the forward direction, then
products will exceed reactants and Pgg, < PcH+, eliminating choice A. becar-,se there
is no CH4 or H2S in the
initial reaction mixture, the only CH4 or H2S present during the reaction or at equilibrium,
is the result of the
reaction proceeding in the forward direction. For every otr" CH4 that forms, two
molecules of H2S form, so pplrg
is always greater (not less) than Pggn, eliminating choice B. If the reaction barely proceeds
in the forward
direction, then the reactants will exceed the products and Pg, > Puzs. This eliminates
choice D.
Choice A is correct. The equilibrium constant is the pressure of the products divided by the
pressure of the
reactants. Answer choices B and D (which both have reactants aivided by products) are eliminated.
The
coefficients from the balanced equation must be included as exponents in the
expression, so choice A
is the correct choice. All of the reactants_and products are gur"r, thus they"qritlbri.r*
utl U"torlg in the K"n expression.
Keep in mind that solids and pure liquids are not includeJ in the equilibrium exprJssion.
tn-e'equihurium
constant for this reaction is referred to as Ko, because it is a gas system and the values
are partial pr"Jr.rr"r.
Choice C is correct. The total pressure of the system at equilibrium is a sum of the
partial pressure of each
component gas at equilibrium. The total pressure of the system is found as follows:
Ptoral = PCS2 + Pg, + Pggn + PHzS = (0.2- x)+ (0.8 - 4x) + x+2x=1..0 -2x
Choices A and D are eliminated, because the total pressure is less than 1.0 atm. The final pressure of the
;,vstem
at equilibrium is 7 - 2x. The value of x cannot be greater than 0.20 atm because the cS2 gas is the
limiting reagent and only 0.20 atm. of CS2 is initially pr"r".i. Because the value of 2x is subtracted,
the final
Dressure drops, but it cannot drop to a value less than 0.6 atmospheres. The
best answer is choice C.
:ight @ by The Berkeley Review@ 223 Section III Detailed Explanations

29. Choice D is correct. The equilibrium constant (a numerical value), changes with the temperature, but it dcrer
not change with volume, pressure, moles of reactants, or moles of products. Choice A involves adding hydroge
gas (a reactant). The reaction shifts to the right to reestablish equilibrium, but the equilibrium consta:r:
remains constant. This is to say that the equilibrium position may change, but the equilibrium constant doet
not. Choice B involves removing all four gases. To determine which escapes most readily involves molecu}:
mass and effusion rates, but that is irrelevant in this question. Losing both products and reactants causes the
reaction to shift to reestablish equilibrium, but the equilibrium constant remains constant. Choice B *
eliminated. Choice C involves adding hydrogen sulfide gas (a product). The reaction shifts to the letl ::
reestablish equilibrium, but the equilibrium constant will remain constant. Choice D involves increasing '-:u
temperature. The equilibrium position and the equilibrium constant both change with a change in temperatu:e
The value of the equilibrium constant can only be changed by temperature.
30. Choice A is correct. Given that the initial partial pressures of H2O and C12O are both 0.5 atmospheres, a:ufl,
both are reactants, it is possible initially for the reaction to proceed in the forward direction. As such. :e
initial forward rate cannot start at zero. This eliminates choices C and D. There is no HOCI present iruhr{,
therefore the reverse reaction rate must start at zero. This reaffirms that choices C and D are invalid. A. :me
reaction proceeds to equilibrium, the reactant pressures decrease, thus the forward reaction slows gradu:Jl,rm'
until equilibrium is reached. Equilibrium occurs when the rate forward is equal to the rate reverse. Beca-.
the forward rate diminishes with time, the best answer is choice A.
31. Choice C is correct. Reactions that can shift when the pressure of the system changes are reactions that I
an unequal number of gas molecules on the reactant and product sides of the reaction. In Reaction 1, there
three reactant gas molecules and two product gas molecules, so Reaction 1 shifts in the forward direction rr
total pressure increases on the equilibrium system. In Reaction 2, there are two reactant gas molecules and
product gas molecules, so Reaction 2 cannot shift in either the forward or reverse direction if the total pres
increases. In Reaction 3, there are two reactant gas molecules and one product gas molecule, so Reaction 3 si
in the forward direction if the total pressure increases on the equilibrium system. This means that i
Reaction 1 and Reaction 3 shift when the total pressure of the system changes. The best answer is choice C
32. Choice D is correct. The equilibrium constant of a reaction remains constant unless the temperature ct
system is changed. Changing the volume of the system does not change the equilibrium constant (althoue:
reaction may shift and the equilibrium ratios change). This eliminates choices A and B, which show th;
in its equation form. As the volume of the system increases, the reaction shifts to the side of the reactior
more molecules (in this case the reactant side), thus the ratio of HCOCI (a product) to HCI (a rea;
decreases as the reaction reestablishes equilibrium following a change in volume. The best answer is cholce
JJ. Choice C is correct. Sulfur dioxide and oxygen are both reactants, according to Reaction 1. When mixin=
atm. SO2 with 0.50 atrr.. 02, Reaction 1 proceeds in the forward direction to esiablish equilibrium. The r
of K"O for this reaction (582), as listed in the passage, is well above one. At equilibrium, there is signii;t
more SO3 than both SO2 and ()2. This eliminates choices B and D. The SO2 should start higher than Se
but it diminishes twice as fast as 02, thus the SO2 line should drop below the 02 line at equilibrium. U
completely depleted (alI 0.75 atm. are consumed), 0.375 atm. of 02 would be consumed, leaving 0.125 a[*
This is because SO2 is the limiting reagent, if the reaction goes to completion. This makes choice C '$rl
answer. {
:
34. Choice A is correct. The equilibrium constant for reaction 2 is 8.67 x 10-3 at 500'C. Choice A is the re t
reaction from Reaction 2, so the equilibrium constant is the reciprocal of 8.61 x 10-3 at 500"C. This leai {
value with 102, not 10-3 in it. This makes choice A the mismatch of K"O and reaction. Choice B is the : u
Reaction 2 except the values have been cut in half. The result is that the K"n as written should be the
root of 8.61 x fO-3. fhis leads to a value with 10-2 in it, therefore choice B sLems reasonable and thus (
The equilibrium constant for Reaction 3 is 3.26 x 10-6 at 500"C. Choice C is the reverse reaction from s
il:
where all the values have been cut in half. The equilibrium constant as written should be the square roilt e
reciprocal of 3.26 x 10-6 at 500'C. This leads to a value with 102 in it, so choice C seems reasonable a.r,j ffi
Choice D is Reaction 3, where all the values have been doubled. The equilibrium constant as written sl M
the square of 3.26 x 10-6 at 500'C. This leads to a value with 10-11 or 10-12 in it, so choice D seems re: A
and valid. The only mismatch is found with choice A ffi
Copyright @ by The Berkeley Review@ 224 Section III Detailed Ex

J5. Choice A is correct. The conversion from the pressure unit of torr to the pressure unit of atmospheres involves
dividing the value in torr by 760 (the conversion factor from torr to atm.). Because the Ko value is given in
terms of torr-1, the value must be multiplied by 760 in order to convert it into a value in terms'of atm-l. The best
answer is choice A.
36. Choice A is correct. An endothermic reaction is set up as follows:

heat + reactants q*products.
The cooling of the reaction can be treated as the removal of heat. When heat is removed from an endothermic
reaction, because the heat is acting like a reactant, the reaction shifts to the left (reactant side) to regenerate
the lost heat. This shift causes an increase in reactants and a decrease in products. The product to reactant
ratio therefore decreases. Choices B, C, and D all account for the same shift, so the three choices can be
eliminated. The best choice is thus choice A.
The interesting feature of this reaction is that the ratio of the reagents is 1 : 1 : 1 : 1, so the total pressure of the
system never changes. The reactants always decrease by the same amount, and the products always increase by
the same amount as the reaction proceeds from the initial conditions to the equilibrium conditions. The purpose
of this experiment is to prove that equilibrium is pathway independent, implying that whether the reaction
starts with all reactants or all products, it will reach the exactly the same equilibrium.
5/. Choice A is correct. Increasing the volume of the reaction vessel has no effect on the equilibrium, because there
are equal moles of gas molecules on both sides of the reaction. Adding moles of either reactant or product will
shift the equilibrium to the opposite side. Because the reaction is exothermic, it will shift forward with a
decrease in temperature and reverse with an increase in temperafure. Thus, the best answer is choice A.
38. Choice D is correct. The equilibrium constant is less than 1.00, so the reactants are more abundant than the
products. This means at equilibrium, both CO2 and H2 have concentrations less than half of their initial
concentration (1.00 M). The only answer that shows this is choice D. Note that the final concentrations are the
same as in trial I.
Regardless of the starting concentrations, the equilibrium concentrations will be the same if
the total pressure and the temperature are the same.
39. Choice A is correct. When reaction vessel III was cooled from 1000"C to 500'C, the partial pressure of carbon
dioxide gas (CO2) increased. This increase in partial pressure for carbon dioxide indicates that the reaction
shifted to the right (product side). The reaction must therefore be exothermic, because as heat is removed from
the system, the reaction shifts to the product side to produce heat. Any reaction that releases heat in the
forward direction is exothermic. This means that as heat is added to the reaction, the reaction shifts to the
left (to the reactant side). This results in a decrease in the partial pressure of CO2 and a decrease in the
equilibrium constant . The correct answer is choice A.
Choice D is correct. A change in pressure will never change the equilibrium constant. This eliminates choices A
and B. Because there is the same number of gas molecules on both sides of the equation, a change in pressure has
no effect on the equilibrium. This means that the equilibrium does not shift so the best choice is D.
Choice B is correct. Because there is an equal number of gas molecules on both sides of the reaction (two
molecules on each side), the total pressure of the system will not change with shifts in the reaction. This
eliminates choices A and C. Because there is no water present initially, the reaction must shift left to reach
equilibrium. This results in an increase in both water and carbon monoxide, therefore both slopes should
increase equally. This is shown only in choice B.
Choice A is correct. V\4ren the equilibrium constant (K"q) is greater than 1, the concentration of products is
greater than the concentration of reactants. As such, choices B and C are incorrect statements, and can be
eliminated. For an exothermic reaction, the equilibrium of the system shifts to the right (product side) as the
temperature of the system decreases. This means that the products increase and the reactants decrease as the
temperature of the system decreases. Both choices B and D are eliminated because of this, leaving only choice
A still standing. If the products out number the reactants, then the equilibrium constant is greater than 1.0, so
the best answer is choice A.
pyright @ by The Berkeley Review@ 225 Section III Detailed Explanations

43. Choice A is correct. The molar solubility values of the sulfate salts are greater than the molar solubilitl-
values of the carbonate salts, as shown by the values in Table 1. This makes statement I valid. The addition of
complexing agents helps to dissolve cations into aqueous solution by forming ligand bonds to the metal. The
most common example is hemoglobin, which serves to make iron dication and trication more water soluble.
This makes statement II valid. Given that both statements I and II are true, choices B and C are both
eliminated. Hydrochloric acid is a strong acid, therefore chloride anion is not affected by the presence of
hydronium ion. As a result, chloride salts show no pH dependence. Sulfide is a weak base, therefore sulfide
shows a pH dependence. This makes statement III invalid, so the best answer is choice A.
44. Choice A is correct. The most accurate value for KrO is found when the most accurate measurement of the molar
solubility is used in the calculation. The most accurate measurement of the molar solubility is found with ttle
salt having the greatest molar solubility. As a general rule, the larger the value, the less significant the errorr
in its measurement. The highest molar solubility is found with Ag2SO4, at 7.3 x 70-z M. The best answer fu
choice A. This question is just a different way of asking which compound has the greatest molar solubility.
45. Choice C is correct. The anion chosen to remove Zn2+ selectively is the anion that forms the least soluble sah
with zinc dication, rather than with silver cation or strontium dication. According to molar solubility values
the least soluble chloride salt is AgCl, so chloride anion is not a good choice. According to molar solubilitry
values, the least soluble carbonate salt is ZnCOg, so carbonate anion is a possible choice. According to molm
solubility values, the least soluble hydroxide salt is Zn(OH)2, by a substantial margin, thus hydroxide anicm
is the best choice so far. According to molar solubility values, the least soluble sulfate salt is ZnSO4 so su-l-fa@
anion is a possible choice. The greatest difference between zinc and the next most soluble cation comes n-idh
hydroxide anion. The best answer is thus choice C.
46. Choice B is correct. Silver chloride is the only chloride salt that is highly insoluble. A precipitate
when chloride is added to solution indicates that silver cation must be present. This makes choice B the
answer. Choices A and D cannot be concluded, because no precipitate is expected between chloride and
zinc or strontium. This means that zinc or strontium may or may not be present.
47. Choice C is correct. When the cation mixture is treated with chloride anion, the least soluble chloride sa,lt
silver chloride, therefore chloride will remove the Ag+ from solution. When the solution with the
remaining cations is treated with sulfide dianion, the least soluble sulfide salt is lead sulfide, ther
sulfide will remove the Pb2+ from solution. When the solution with the two remaining cations is treated
hydroxide anion, the least soluble hydroxide salt is zinc hydroxide, therefore hydroxide will remove the
from solution. The cation that will remain in solution is strontium (Srz+), thus the best answer is choice C.
48. Choice A is correct. An acid can protonate a basic salt in solution (which in some cases serves to form the
soluble ionic form of the product). The acid serves to reduce the hydroxide concentration which allows
the basic salt to dissociate. This is a complex equilibrium that develops as a result. A complex equilit'
usually enhances the solubility in aqueous solution. Pick A to feel perky.
49. Choice A is correct. Because the solution has OH- present already, the solubility of AgOH will be hindered
the common ion effect where hydroxide is the common ion. AgOH will be most soluble in the solution with
least hydroxide anion present. The least hydroxide is found in the solution with the most H+ presenl
solution consequently has the lowest pH. Pick A to feel spunky.
50. Choice B is correct. Because all three salts dissociate into one cation and one anion, the compound rt
greatest molar solubility also has the greatest value for its solubility product (Ksp). The MZ salt fo
heaviest and has the least mass dissociate into solution, so MZ has the lowest moles of salt in solution and
has the lowest solubility product. This eliminates choices C and D. Deciding between MX and MY
more work. More mass of MY dissociates that MX, but MX has a lower molecular mass. The moles of ND(
over 100 while the moles of MY equal 9 over 120. This means that there are 0.07 moles MX and 0.075
MY is present in a smaller volume of solution than MX, so MY has a greater molarity and solubili['
than MX at 25"C. The correct answer is choice B.
Copyright @ by The Berkeley Review@ 226, Section III Detailed

51. Choice C is correct. Because the solubility of a salt increases with temperature, answer choices B and D are
eliminated. It can also be read from the third column in Table 1 that more MX and MY dissociate into water at
a temperature greater than 25'C than what dissociates at 25.0". This also eliminates choices B and D. The
molarity of MX at 31.6'C and the molarity of MY at27.4"C are found as follows:
7g Qo
7M 7.5M
0.0262L 0.0262L=2.62 L = 2.53
Mrtxo31.6.c=100g'mole-1 =0.070mo1 Mrrrryozz.+.a-120g'mole-1 =0.075mo1
0.02s3 L 0.0253
There are more moles of MY than MX in a smaller volume of solution, therefore saturated MY at 27.4"C is more
concentrated than saturated MX at 31.6'C. The best answer is choice C.
-)2.
Choice B is correct. Exactly 7.0 grams of MX dissociates into 28.9 mL of water at 25.0'C according to Table 1.
The mass that will dissolve into 25.0 mL is proportionally less. The volume ratio is just under ninety percent, so
roughly ninety percent of 7.0 grams MX will dissociate. The best answer is choice B.
53. Choice A is correct. As with any question like this, first consider units. liters must be in the denominator, so
choices C and D are eliminated. At 25"C,9.0 grams of MY requires that enough water be added to reach 26.7 mL
of solution when fully dissociated. This makes choice A the best answer. To determine the molarity of the
solution, the 9.0 grams must first be converted into moles, by dividing 9.0 grams by the molecular mass of MY
(120 grams per mole). This value is divided by the volume of the solution as measured in liters (0.0261 L). The
value of 0.0253 preys upon the possibility you read the wrong column. The best answer is choice A.
5"r. Choice D is correct. As the temperature rises, the volume of the solution increases according to Table 1.
Liquids, as a general rule, expand with increasing temperature. As the volume increases, both the molarity
and the density of a solution decrease. The best answer is therefore choice D.
Choice D is correct. Density is defined as mass per volume. The densities of all of the solutions are greater
than pure water (1.00), so choices A and B are eliminated. It is easy to forget to consider the mass of the water
when determining the density. At 25'C there are 7 .0 grams of MX and 25.0 grams of H2O in 28.9 mL of solution,
9.0 grams of MY and 25.0 grams of H2O :rl26.1mi, of solution, and 4.0 grams of MZ and 25.0 grams of H2O n28.1.
mL of solution. The densest solution (greatest mass in the least volume) is found with the saturated MY
solution. This makes choice D the correct choice.
Choice C is correct. The solution with the highest boiling point is the solution with the highest molality of
impurities. Molality is defined as moles solute per kg solvent. MX has a lower molecular mass than MY, thus
1.0 grams of MX generates a greater moles of solute than 1.0 grams of MY. Because the density of water
decreases as the temperature of water increases, the mass of 10 mL water is greater at the lower temperature.
This means that the largest molality is found with 10 mL water at 50'C, because the mass solvent is least. The
best answer is therefore choice C.
Choice A is correct. An anion can be used to identify a cation when it reacts differently with that cation than
the other cations. Of the five anions used in table I, all five form a precipitate with barium cation. This
means that to identify barium (distinguish barium from the other cations) the anion chosen must precipitate
exclusively with barium. Only chromate CrO42- forms a precipitate with barium and no other cation. To
distinguish barium cation from the others, chromate should be added to solution. If a precipitate forms, then
barium was present in the solution. If no precipitate forms, then barium was not present in the solution. The
best answer is choice A.
Choice B is correct. Nitric acid protonated carbonate anion to form carbonic acid (H2CO3), which subsequently
decomposed to form water and carbon dioxide. Because the carbonate anion carries a -2 charge, two equivalents
of nitric acid are required. The two nitrate anions and barium cation are spectator ions. The best answer is
therefore choice B. This can also be inferred from the passage, where it is stated that nitric acid is added to
react with carbonate anion to form carbon dioxide gas. The barium cation carries a +2 charge and carbonate
anion carries a -2 charge, therefore the two must be in a one-to-one ratio in the salt. This eliminates choices A
and C.
r";right @ by The Berkeley Review@ 227 Section III Detailed Explanations

59. Choice A is correct. Hydrochloric acid is not used, because it would introduce the chloride anion, which
according to table II, forms a precipitate with silver cation. This means that chloride interferes, making
choice A the correct choice.
60. Choice D is correct. The salt K2SOa delivers the anion SO42- (sulfate) to solution. From table I, sulfate
precipitates with both barium and strontium cations. The conclusion reached upon observing the formation of a
precipitate should be that either strontium or barium is present in solution. It cannot be determined whether or
not calcium or magnesium cations are present because they do not form any detectable precipitate with sulfate.
The best answer is choice D.
61. Choice C is correct. Looking at the third reactivity column of table II shows that a white precipitate forms
upon the addition of silver cation with both carbonate and chloride anions. Addition of nitric acid dissolves
the carbonate away, but it does not react with the chloride. The best choice is the chloride anion, choice C.
62. Choice A is correct. The first anion added precipitates with only barium. This according to the chart is
chromate (CrOa2-\. Answer choice A shows this to be carbonate (CO32-), making choice A an incorrect choice
Just to be certain, anion W precipitates with strontium but not calcium and magnesium. According to the chart,
this is sulfate (SO4Z-; so choice B is valid. Anion X precipitates with calcium but not magnesium. According to
Table 1, it is either carbonate (COrz-, or oxalate (CzO+z-), so choice C (oxalate) is valid. Anion Z precipitates
with magnesium. According to the chart, this is hydroxide (OH-), so choice D (hydroxide) is valid.
The focus of this passage is on the solubility of different cations in the presence of anions. Solubility is one
the more favored topics on the MCAT so far, so be certain to make sense of this passage. The key fact
remember is that when comparing solubility, look at the molar solubility, not the Ksp value.
63. Choice C is correct. This question boils down to whether Qsp or KrO is larger. When Q > K there are too ma
products, in which case the salt cannot completely dissociate. \zVhen Q < K, there is room for more products'
which case the salt completely dissociates. When Q = K, it is exactly saturated. In this question, it is
easier to decide whether the molarity of ZnCOg in the event it fully dissociates exceeds the molar
conveniently listed in Table 1. The molarity if ZnCOg fully dissociates is calculated as follows:
0.1 grams 0.1 mole = 0.8 mole=0.0008mo1e+0.0008mole =0.008M
t25.4l#anf.sl/mole 125 1000 L 0.10
0.008 M > 0.000014 by a large amount. This means that very little of the ZnCO3 dissociates. On this q
you must go even further. It will barely dissociate according to the numbers which implies choice C. Do
is expected of you: be kind to strangers, brush after every meal, and pick choice C.
64. Choice B is correct. To distinguish one thing from another visually, you must be able to see a difference in
behaviors. The behavior here is the formatLn of a precipitate. Tb visually distinguish a tube wltt. Zn2+
a tube with Ag+, an anion that precipitates with only one of them must be used. The passage defines the
for seeing a precipitate as one mg per mL solution. Assuming the average salt to have a molecular mass
L00 grams pet *o1", means that the cut-off for visual delectability is roughly 0.010 M. You must locab
anion that shows a greater molar solubility than 0.01 M for one cation, but less for the other. Sulfides show
biggest ratio of numerical values, but in a practical sense, neither dissolves to a detectable extent to r-
distinguish. The numbers are different in a multiplicative manner, but they are close in an additive
Choice A is eliminated. With the chloride salts ([Ag+] = 1..2x 10-5, while lZnz+t = 3.1 x 10-2), there is a
where the silver chloride precipitates while the zinc chloride dissociates. The zinc concentrati
detectable to the eye. In other words, we can see the quantity of salt that dissociates. Choose B, and feel
65. Choice D is correct. This question addresses the common ion effect from a conceptual perspective. Silver s
is most soluble in a solution with the least amount of common ion. This eliminates choices A and C
question is whether or not silver cation or sulfur dianion more affects the calculation. In this case/ u
deciding which leads to a greater x value, Krp = ( 91]1(x) gt Krp = (2x)2(0.01). in a solution with 0-01 \[
the sohibility is 104 x Ksp. In a solution with'0.01 M S2-, the sdlubility is 5 x square root of KrO. Beca
KrO for Ag2S is so small, ihe sq.rare root of KrO is a larger number than KrO. The best answer is choice D.

66. Choice C is correct. This question is purely mathematical. The key fact is recognizing that there is 0.01 M Cf
present in solution initially. The set-up and solution are as follows:
Reaction: ZnCO3(s) + zn2+1aq) + co32-

Initially: excess 0.01 0
Shift: -x .#+x +X
Equilibrium: whocares? 0.01 + x X
Ksp=[zt+]tcoe2-l ...Kp =(o.ot + x)1*;
Uponignoringx: Kro =2.0x10-10=(O.Of +x)1x; = 0.01(x) .'. x=2.0xt0-8M

The correct answer is choice C.
n/. Choice B is correct. The most soluble salt is the salt with the highest molar solubility (not necessarily the
highest solubility product). This is a "read-the-chart" type of question. According to data in Table 1, the
largest molar solubility of the choices is found with Ag2CO g (1,.2 x 10-4 M). The trick here is picking the
correct column in the table to reference (molar solubility rather than KrO). To be more than you can be, pick B.
68. Choice D is correct. To calculate the solubility product for the calcium phosphate salt, the solubility reaction
is needed:
Ca3(POa)2 -q* 3Ca2+1aq; +ZPOa3-(aq)
Kro = [Ca2+]s1e9ne1z = 1ax)3(2x)2 = (27 xr1ro^ *2) = 108 x5
The best answer is choice D.
59. Choice C is correct. An ion exchange column involves competition by two cations for an anion bound to the
column. The cation of the less soluble salt will precipitate with the anion, which is bound to the column. The
two cations to consider are the one in solution and the one originally bound to the column. The columns works if
the cation in solution is less soluble with the anion in the column than the cation originally coupled with the
anion in the column. Silver chloride (AgCl) has a lower molar solubility than sodium chloride (NaCl),
therefore silver cation precipitates with chlorine anion preferentially over sodium cation. Choice A is a valid
statement. Zinc sulfide (ZnS) has a lower molar solubility than calcium sulfide (CaS), therefore zinc cation
precipitates with sulfide anion preferentially over calcium cation. Choice B is a valid statement. Calcium
carbonate (CaCO3) has a higher molar solubility than zinc carbonate (ZnCOg), therefore calcium cation does
not precipitate with carbonate anion preferentially over zinc cation. The column of choice C will not work,
thus choice C is the best answer. Calcium sulfide (CaS) has a lower molar solubility than sodium sulfide
(Na2S), therefore calcium cation precipitates with sulfide anion preferentially over sodium cation. Even
though the two salts have different stoichiometry, they can be compared directly through their molar
solubility values. Choice D is a valid statement.
pn. Choice A is correct. Because there is solid calcium hydroxide at the base of the flask, it can safely be assumed
that the solution is saturated. As sodium carbonate is added to the flask, calcium carbonate will begin to
precipitate. This reduces the calcium ion concentration, causing more of the calcium hydroxide solid can begin
to dissociate in order to regenerate calcium ion in solution. As calcium hydroxide dissociates into solution, the
hydroxide concentration increases. As the hydroxide ion increases, the solution's pH increases, eliminating
choices C and D. Had the solution not been saturated, there would not be any solid calcium hydroxide present
to dissociate into solution. This means that the pH increases more in the solution with solid calcium hydroxide
present than the solution with no calcium hydroxide present. The best choice is therefore answer A.
Choice C is correct. The maximum calcium ion concentration at pH = L4 can be determined using the solubility
product of calcium hydroxide (Krp = [Ca2+][OH-]2). Because the pH is 14, the pOH is 0, so the hydroxide anion
concentration is 1.00 M. This means that when plugging into the solubility product to determine the calcium ion
concentration, it can be determined that the calcium ion concentration equals the numerical value of the
solubility product (Krp = [Ca2+]). The solubility product is 4.3 x 10-6 M3. The best choice is C, 4.3 x 10-6 M.
:nvright @ by The Berkeley Review@ 229 Section III Detailed Dxplanations

na Choice D is correct. In order to increase the chloride concentration in solution, an anion must be added that
precipitates calcium cation out from solution. This allows the calcium chloride solid present on the bottom oi
the flask to dissociate into solution to regenerate the lost calcium cation. As the calcium chloride dissociates
I
the chloride anion concentration increases. Choice C should be eliminated immediately, because the solubilitr
of calcium chloride is reduced by the common ion effect. Choice B is eliminated, because the silver cation n'il-
precipitate chloride anion from solution. This is one of the solubility rules you may want to know. Silver
halides are insoluble in water. The answer is either choice A or D. The sodium phosphate adds phosphate
anion into solution, which then precipitates out of solution as calcium phosphate and thus decreases the
calcium cation concentration. The solid calcium chloride dissociates to counteract the decrease in calciur.
concentration and in doing so increases the chloride ion concentration. The best answer is choice D.
73. Choice C is correct. It is important to realize that the solution is buffered, so the calcium hydroxide tha:
dissociates does not drastically affect the pH. The buffer absorbs the hydroxide that is released as calcir.r:-
hydroxide dissociates. The amount of calcium hydroxide that dissociates is controlled by the pH of the
solution. At a high pH, there is a large amount of hydroxide present in solution, so only a small amount i
calcium hydroxide dissociates. As the pH decreases, the hydroxide anion concentration decreases, resulting =
an increasing calcium ion concentration. The overall effect is that as the pH of the buffer increases, calci r-r
hydroxide is less soluble due to the common ion effect. This results in an inverse relationship, so choices A ar,l
B are eliminated.
The question may also be addressed from a complex equilibrium perspective. As the buffer pH decreases, '.:uP
amount of hydronium in solution increases. Increasing the hydronium concentration forces the second reaction:m
the forward direction. This reduces the hydroxide concentration. To compensate, the first reaction shrnm
forward to regenerate hydroxide. In doing so, calcium cation is released into solution. This confirms that lw
calcium ion concentration increases as the pH decreases.
Ca(OH)2(s) + H2O(l) --- Ca2+1aq; + 2 OH-(aq)
H3O+(aq) + OH-(aq).$2HzO(I)
Ca(OH)2(s) + 2H3O+(aq): Ca2+1aq; + aH2O(l)
The net result is that as the [HSO*] increases, the [Ca2+] increases. As the calcium cation concentra
increases, the log of the calcium cation concentration increases, therefore the log of the calcium :
concentration increases as the pH decreases. Because both the x-axis and y-axis are based on a log scale
relationship is linear, but not necessarily with a slope of one. The slope is negative (due to the negative sigr
determining pH). The best answer is choice C.
74. Choice B is correct. If the dissociating of a salt into water increases the temperature of the water, *
dissociation (the solvation process) releases heat. The release of heat makes the solvation process e
which makes the enthalpy change (AH) a negative number. This eliminates choices A and C. The entr;
increases when a salt dissociates into solution, because the ions have more freedom to randomize within
solution than within the lattice. The change in entropy (AS) for dissociation is therefore positive. The cos
answer is choice B.
75. Choice D is correct. This question requires viewing Table 1. The solubility of calcium fluoride and ca,
hydroxide are directly comparable using the solubility product, because fluoride and hydroxide carry the
anionic charge. The solubility of calcium sulfate and calcium carbonate are directly comparable usin::
solubility product, because sulfate and carbonate carry the same anionic charge. Choices A and C
eliminated due to their lower solubility product values. Because calcium hydroxide forms thlgg isrLs ',cft
dissociating into solution, the solubitity product is 4x3, where x is the calcium ion concentration 1[CaZ-] . 1
value of i[Cu2*]) is some number times 10-2 for Ca(OH)2. For calcium sulfate, the solubility product :s
where x is" the calcium ion concentration ([Ca2+]). The value of x ([Ca2+]) is some value times 10-3 for cd
sulfate. The value is greater for calcium hydroxide, so the best answer is calcium hydroxide, choice D.
Copyright @ by The Berkeley Review@ 230 Section III Detailed Exp

This is a difficult passage because as one reaction shifts, it affects the other reactions. It is easiest to view the
reactions as independent, and observe how specific reagents are changing during each step. For instance, the
shift of reaction L will affect the partial pressure of NO2 which will in turn affect reactions 2,3, ar.d 4. The
result is a complex equilibrium.
Choice A is correct. A negative change in entropy results when the system becomes more ordered. The system
becomes more ordered when it decreases in volume or changes phase to a more ordered phase. Reaction 2 goes
from two gas molecules to one gas molecule, therefore in has lost in entropy. Reaction 3 goes from two gas
molecules to two gas molecules, therefore entropy has not changed. Reaction 5 goes from three ions in solution to
three ions in solution, therefore entropy has not changed. Reaction 6 also goes from three ions in solution to
three ions in solution, therefore entropy has not changed. The best answer is therefore choice A.
'7. Choice C is correct. Decreasing the temperature shifts reaction 2 in the forward direction, because it is
exothermic. This results in an increase in [N2O4]. Increasing the pressure shifts reaction 2 in the forward
direction. This results in an increase in [N2Oa]. Water vapor in the air reacts with the NO2 in the air
(according to reaction 4), and thus reduces the amount of NO2. Reaction 2 shifts in the reverse direction to re-
establish equilibrium. This decreases (NOT increases) the [N2Oa]. Choice C is the correct choice. Addition of
NO2 shifts reaction 2 in the forward direction which increases the [N2Oa].
-3. Choice B is correct. According to the ideal gas law, when the temperature of a gas system is doubled, the
pressure doubles, as long as the volume of the system and moles of gas remain the same. The reaction vessel is a
closed steel container, so the volume of the system cannot change. The problem here is that the moles of gas
change with the increase in temperature. Because the reaction is exothermic, an increase in temperature
pushes the reaction in the reverse direction. This increases the reactants and decreases the products. There are
more products than reactants in the balanced equation, so a shift in the reverse direction results in fewer moles
of gas in the system. The increase in pressure due to the ideal gas law is not be as great as expected, due to the
decrease due to the shift in equilibrium. The ideal gas law predicts that change in temperature doubles the
pressure, while the shift in reaction (reduction in moles of gas) predicts that the pressure decreases. The
change in moles is a smaller factor than the increase temperature, because at the least, the moles of gas would
be two-thirds of their original value. The moles cannot be cut in half according to the balanced equation.
Therefore, the overall change in pressure is a little less than double. This is best described as choice B.
-9. Choice D is correct. A bond must be formed in reaction 2, because the two NO2 molecules are combining to form
one N2O4 molecule. This eliminates choices A and B. Bond formation is an exothermic process, therefore
choice D is the correct answer.
ff,1. Choice C is correct. The total pressure of reaction 1 at equilibrium is 1.00 atmospheres, because the internal
pressure can equilibrate with the external pressure in a piston system. The pressures equilibrate by having the
piston plunger either rise up (increasing the volume) or drop down (decreasing the volume). The addition of
0.10 atmospheres of NO gas initially increases the total pressure of the system to 1.1,0 atmospheres, before the
system can equilibrate. The piston rises to accommodate the change in pressure (and equilibrate the internal
and external pressures), thus increasing the volume of the piston. The addition of NO gas displaces the
reaction from equilibrium. The reaction is no longer at equilibrium, so it reacts to re-establish equilibrium.
Excess reactant is present, so the reaction shifts in the forward direction (io use up the excess reactant). There
are three moles of reactants and only two moles of products, so the number of moles decreases, causing the
volume to decrease slightly. The overall result is a slight increase in volume, making choice C correct. If there
was no shift in the reaction, the volume would increase by exactly ten percent, therefore the increase in volume
must be less than ten percent.
tl,. Choice D is correct. Addition of sodium hydroxide to solution deprotonates HNO2 (HNO3 is a strong acid and
has already fully dissociated), and thus shifts reaction 4 to the product side to re-establish equilibrium.
Addition of manganese(Il) chloride (MnCl2) to solution removes both NO2- and NO3- from solution through
complexing of the ligands. To re-establish equilibrium in reaction 4, the reaction must shift right to make more
NO2- and NOg-. Removal of nitrate (NOS-) from solution results in a shift in the product direction to re-
establish equilibrium. Removal of water (a reactant) results in a shift in the reverse direction (left) to re-
establish equilibrium. Choice D is the best answer available to you.
-:p;zright @ by The Berkeley Review@ 231 Section III Detailed Explanations

82. Choice A is correct. At equilibrium, the NO2 concentration is constant. \A/hen bubbled through water, it rea;m
to form nitrous acid (HNO2) and nitric acid (HNO3), which can both deprotonate and form ligand bonds to tne
manganese cation. This means that the NOZ(g) is depleted when it is bubbled through an aqueous solutio:- t
I
rtuttgutr"r" chloride. Graphs C and D are eliminated, because they show that the concentration of \C!
increises with the addition of aqueous manganese chloride solution. The NO2(g) is gradually regeneratec bu
both the reverse reaction of reaction 2 and the forward reaction of reaction 1. This means NO2 is regeneraed
(and thus increases), but not to the level it was initially at. This is best shown in graph A.
83. Choice C is correct. The passage states that hemoglobin binds four oxygen molecules while myoglobrn brub
only one oxygen molecule. To transfer all of the oxygen, there must be four myoglobin molecules per hemoglo'hm
This should be co- on knowledge from biology. Pick choice C, and start the passage off on the right foot.
84. Choice B is correct. Increasing the rate of respiration increases the uptake of oxygen. This results in an incl"eam
in free oxygen, which lessens-slightly by the shift in equilibrium to the oxygenated hemoglobin. Overall" :iue
amount oi fiu" oxygen increases, so choice A is eliminated. An increase in the amount of hemoglobin results r rr
shift in the equilibrium in the forward direction. This reduces the amount of free oxygen. Choice B is thers;m
the best answer. An increase in CO consumed results in more bor.rnd sites on the iron of hemoglobin, so less or-r:
can bind. Less oxygen bound results in more free oxygen. Choice C is eliminated. More blood results in
moles of all components in the equilibrium including oxygen. Choice D is thus eliminated. Select choice B.
85. Choice D is correct. A long-time mountain resident has more hemoglobin in their blood than a long-time
level resident. When the long-time mountain resident descends to sea level where there is a higher abund
of oxygen, they experience increased vitality due to the increased partial pressure of oxygen gas. Pick D.
86. Choice A is correct. Because CO binds the iron of hemoglobin preferentially over 02, any CO present in ti'r,e
bind iron cation, and thus reduce the amount of 02 that can bind. To compensate, respiration increases, in
to increase the amount of air consumed. Over time, the body produces more Hb (this is a result of acclima
The best answer is choice A.
87. Choice D is correct. Because hypoxia does not directly affect the cellular uptake rate of oxygen/ onc
absorbed from the lungs, myoglobin (present in cells) is not affected directly by hypoxia. Without considi
any other factors, the myoglobin should remain constant. The best answer is choice D.
88. Choice D is correct. Hypoxia results from a drastic decrease in the amount of oxygen present in the air.
decrease is associated with an increase in elevation. Repelling down a mountain and scuba diving both inr
increases in the oxygen present. In scuba tanks, the gas may be mixed with helium (an inert gas) to comP
for the greater u*o.ttrt of air consumed per breath (due to the increased pressure under water). If the tanks
not paiiaily filled with helium, too mulh nitrogen and oxygen would enter the body. Of the last two ch;
only snow skiing involves a high elevation, so choice D is the best answer,
89. Choice B is correct. According to the passage, there is less oxygen present at higher elevations. By train::q
higher elevations, where the aii has less moles of oxygen, the body acclimates by producing more Hb One
atilete returns to a lower elevation, the increased amount of FIb remains for a short time, before the bod--
re-acclimate. For a short period of time, an athlete can increase their oxygen carrying capacity (ano
increase their cellular metabolism). The best answer is choice B.
Copyright @ by The Berkeley Review@ 232 Section III Detailed ExP

This passage mimics a passage that appeared on the MCAT years ago. The reaction is a typical example of gas
phase equilibrium, and is found in most every general chemistry text book. The reaction is often .tred to
demonstrate Le ChAtelier's principle. In this passage, the reaction is chosen because it has an unequal number
of reactant molecules as product molecules. This means that changes in the condition of the system (volume and
pressure) can shift the equilibrium reaction, but the equilibrium constant remains the same, as long as a
temperature change does not accompany the volume or pressure change. The passage also points out that an
inert gas does not disturb an equilibrium, as long as the container is rigid (which a glass container is assumed to
be). You may wish to note that if inert gas is added to an expandable container, it can disrupt the equilibrium,
because the partial pressures of the component gases are changed.
Choice A is correct. Because the reaction involves the breaking of a bond, it must be an endothermic reaction.
This is confirmed in the last sentence of the passage, which states that the ratio product to reactant increases
as the temperature increases. Because there are two molecules formed from just one, the AS for the reaction as
written is greater than zero (positive). The best answer is therefore choice A.
Choice D is correct. Addition of reactant (NZO+) shifts the reaction to the right (product side), thus choice A
isvalid. An increase in volume disrupts equilibrium, and results in the reaction shifting from the side with one
molecule to the side with two molecules. This results in a shift to the right, so choice B is valid. A decrease in
pressure disrupts equilibrium, and results in the reaction shifting from the side with fewer molecules (one) to
the side with more molecules (two). This results in a shift to the right, thus choice C is valid. Choices B and C
should both have been eliminated, because they are the same answer and cannot both be correct. When adding
helium gas (an inert gas) to the reaction at constant volume, the partial pressures of N2O4 and NO2 do not
change. Because the partial pressures do not change, the reaction is not displaced from equilibrium, thus it
does not shift in either direction. This makes choice D the correct answer.
Choice D is correct. The equation relating AG and K"n is AG = -RT * Keg. To isolate Ksq, both sides of the
equation are first divided by -RT. To eliminate the natural log function, the two sides of the equation must be
exponents of e. This makes choice D the correct answer. The derivation is shown below.
lnK-^ .'. Ir.K-^ = -

AG -Ac/
AG = -RT
RT
"&q=e /nr
Choice B is correct. When the equilibrium constant has 105 associated with it, it is said to be large. As such,
the reaction distribution at equilibrium is almost exclusively products, making choice A valid. If the reaction
starts as mostly reactants, it shifts nearly one hundred percent to form products, making the shift significant.
Choice B is NOT true. The equilibrium constant for the reverse reaction is the reciproial of the equitibrium
constant for the forward reaction. This makes choice C valid. A catalyst increases the reaction rate (in both
the forward and the reverse directions), but it does not affect the equilibrium constant. This makes choice D
valid. The best answer is choice B.
Choice A is correct. Because the equilibrium is dynamic, the forward and reverse reactions are continually
transpiring. When the equilibrium is disturbed by the addition of N2O4 [abeled or not), the equilibrium is
lost and the reaction must undergo a net shi.ft forward to compensate for the excess reactant. The reverse
reaction continues as well, but not to the degree of the forward reaction. The result is that the amount of N2O4
decreases and the amount of NO2 increases. The radiolabeled nitrogen will eventually be evenly distributed
between the products and reactants, once equilibrium has been re-established. This makes choice A the best
answer. This is referred to as scrambling of the label.
Choice C is correct. Because there are more molecules on the product side than the reactant side, the reaction
shifts to products as the volume of the piston increases. This makes statement I a valid statement. The
reaction is shifting in the forward direction, which is endothermic, therefore heat is absorbed by the reaction.
The result is that the temperature decreases. This makes statement II a valid statement. Do not mistakenly
think of PV = nRT, because the volume changes and the pressure changes, the temperafure was not changed to
cause the volume or pressure change. As the reaction shifts to the right, NZOa decreases and the amount of
NO2 increases, causing the mole fraction of N2O4 to decrease. This makes statement III an invalid statement.
The best answer is choice C, both statements I and II.
qiright @ by The Berkeley Review@ 233 Section III Detailed Explanations

96. Choice B is correct. In this case, the equilibrium constant is the product squared (because of the stoichi
coefficient) divided by the reactant. This makes choice B the best answer.
97. Choice C is correct. \Mhen an MX salt dissociates into water, it forms M+ cation and X- anion. The solu
product (KrO) is equal to tM*ltx-l = y2. You really have no altemative but to pick C.
98. Choice C is correct. This is a question involving the common ion effect. Because F- is present in solution
choices A and B, and Mgz+ is present in choice D, all of the choices except C are eliminated due to the comm
ion effect. It is only in choice C that the compound does not have a common ion (either Mg2+ or F-) present.
99. Choice C is correct. Equilibrium is the state in which the forward reaction rate equals the reverse reacti
rate. For a one-step reaction at equilibrium, k1[R] = kr[P]. K"O is defined as products over reactants, which
manipulated as follows:
Given kflRl = k,[Pland tqo =fil,x"q =*

Because the forward rate is four times the reverse rate,4k, can be substituted for kp and thus K"n is 4k,
by kr, which is 4. Choose with dignity; choose C.
100. Choice C is correct. Choice D is eliminated, because less solvent reduces the amount of a salt that
dissociate into solution. Because a solvation reaction can be either exothermic or endothermic, the effect on
system by a change in temperature varies, and is thus unpredictable. This eliminates choices A and B. In
cases/ an increase in temperature results in an increase in the amount of salt that dissociates into solutiorL
there are some exceptions. Only choice C, increasing the solvent, always increases the amount of a salt
dissociates into solution. As more solvent is added, more compound can dissociate. Be sure that you r
that this question is asking about the amount (in mass or moles) of salt dissociated, not the concentration (
solubility).

Terminology
a) Fundamental Definitions ,.
b) Water-based Acid.Base Chemistry:

i. Acid Dissociation
,$eCtion IV ii Base llydrolysis ' , ,l
c) Determination of Reagent StrenEtr
i. Strong Acids
ii. Weak Acids .
Acids and Bases iii. Very Weak AcidS I

iv. Strength and the pK Scale
l
by Todd tsennett v. StrongBses

vi. Weak Bases
vii Very Weak Bases
Strong Acid:
pH = -log [HXl Types of Acids and Baso ,
Strong Base: a) Haloacids

pOF{=-1ogIMOHI b) Oxyacids
Wbak Acid: , c) Metal Oiides and Metat fiydroxides
pH,=
|nr"- { r"g tHAl d) Organic Acids
WeakBase:
e) Polyprotic Acids
Calculating ptl
Buffer:
JS
a;t Determining pH ' '" :
' pH=pKa-ug
IHA I
b) LogiReview
or c)'pf1forStrongReagen[5''''.
rnoleq Coaiugate Basq
d) pH for Weak Reagents
' PH = PKa -log
moles Conjqqate Acid
Co4iugate faiis , ,
a) Typicat Conjugate Pairs

b) Relationship:of pKa and pKb
. c\ Ilenderson.flasselbalch,Hquation
'Ifu
trIEKrcLEY
l)6.E-y.1.fiv'
Speciahzing in MCATI Preparation
Acids & Bases Section Goals
av Know the definitions for an acid and some common examDles of acids.
An acid can be defined as either a proton donor, an electron-pair acceptor, or a com pound that yields
(H:CCOzg),1hydrochloric acid
Typlcal examples include acetic acid (F-I3CCO2H),
H3O+ when added to water. Typical
HgO+
(HCl), and sulfuric acid (H2SOa). You are expected to recognize the common acids.
av Know the definitions for a base and some common examDles of bases.
A base can be defined as either a proton acceptor, an electron-pair donor, or a compound that yields
OH- when added to water. Typical examples include sodium hydroxide (NaOH), ammonia (NHE),
and potassium tert-butoxide ((CHg)SCOK). You are expected to recognize the common bases.
av Be able to calculate the pIl of agueous solutions of base or acid.

The pH of a solution is defined as the negative log of the hydronium ion concentration in the solution.
You must be able to determine the pH of the solution, knowing the concentration and strength of
the.species. The pH of a weak acid is greater than the pH of a stiong acid when the two are inlqual
molar concentratrons.
Understand what is meant by the strength of a reagent.

The strength of a reagent is the measure of its degree of dissociation in water. A compound that fully
dissociates in water ls said to be strong, while only partially dissociates in water is
a reagent that
said to be weak. You should be able to determine the relative strengths of acid from chemical features
and its pH in the aqueous solution.
Know how conjugate pairs and buffers work.

"3 A buffer is formed when a weak acid and its conjugate base are combined in an aqueous solution.
An equilibrium exists between the two species, sb as long as both are present in solution, the
hydronjum ion concentration will remain fairly constant, and the pH will also remain constant. This
effect is known as "buffering." You must understand buffers and how pH is determined using the
Henderson-Hasselbalch equation.
Recognize and specific types of compounds.

'3 You should understand why metal oxides and metal hydroxides are basic. You should understand
why non-metal oxides axd non-metal hydroxides are aiidic. Be familiar with typical examples such
as jcid rain and soil pH. Recognize that the conversion from a non-metal oxide (Lewis aiid form)
to a non-metal hydroxide (Bronsted-Lowry form) involves hydration of the acid. The strength of
the reagent is not affected by this conversion.
o? Understand the terms associated with polvprotic acids.

Polyprotic acids have multiple pKa and pKb values. You must understand the conceptual and
mailiematical relationshlps <jt tn'e variable's to one another. You must be familiar with t6rms such
as "normaility" and "equivalents." Know the typical examples of polyprotic acids and their formulae.
General Chemistry Acids and Bases Introduction
Acid-and-base chemistry is a foundation for understanding organic chemistry,

biochemistry, and physiology. As such, we shall address it from several
perspectives, observing what effect the varying of a solvent has on the nature of a
reaction. Water and other protic solvents solvate charged species, so acid-and-
base chemistry can be monitored by the gain and loss of charge, associated
specifically with the gain and loss of an ionized hydrogen atom (H+). The terms
"protonated" and "deprotonated" are derived from the ionized hydrogen atom,
rvhich is just a proton. In a lipid environment, charges cannot be stabilized, so
acid-and-base chemistry is typically considered from an electron-transfer
perspective, where bonds are broken and formed. The different definitions of
acids and bases are the result of differences in solvent, not chemical reactivity.
Once the definitions are established, reactivity will be considered. There are two
common misconceptions to clear up, if we are to understand acid and base
chemistry better. The first common misconception is that the pH scale has fixed
limits. The second common misconception is that weak acids automatically have
strong conjugate bases. Let us address both of these before anything else.
Acidity is typically measured in terms of [H+] on the pH scale. The pH value of a
solution is determined by taking the negative log of the hydronium
concentration. Because neutral water has a hydronium concentration of 10-/ M,
due to autoionization of watet, neutral water has a pH = 7.0. Acidic solutions
have pH values less than 7.0, while basic solutions have pH values greater than
7.0. The only limits to the value of pH are associated with concentration and
solubility, so the pH scale is limitless in theory. In practice, there are limits.
The pH scale does not range from 0 to 1-4. The pH of a compound can be negatiae
for highly concentrated strong acids and greater than 14 for highly concentrated
strongbases (e.g.,10 M HCI has pH = -1, and L0 MNaOHhas pH = 15).
The relative strength of an acid can be determined from the relative strength of
its conjugate base. This relation is reversible: The relative strength of a base can
also be determined from the relative strength of its conjugate acid. Using the
relationship between pKu and pK6 for conjugate pairs in water at 25'C, either pK
l-alue can be determined from knowing the other. For instance, a weak acid with
a pKu of 7 has a conjugate base with a PKU of 7. Note that the conjugate base of
ihe weak acid is a weak base. This is not a typo! It is the relative reactivities that
are compared, not the absolute reactivities. If acid HA is stronger than acid HB,
then base A- is weaker than base B-. This can be demonstrated by comparing
Reaction 4.1 with Reaction 4.2:
HA(aq) + H2O(1)
=+ H3O+(aq) + A-(uq)
PKa=7 PKu=7
Reaction 4.L
HB(aq) + H2O(l) .- H3O+(aq) + B-(uq)

PKa=9 PKU=5
Reaction 4.2
The lower pK3 value indicates that HA is a stronger acid than HB while the
larger pK6 value indicates that A- is a weaker base than B-.
The stronger the acid, the weaker its conjugate base. lt is not necessarily the case
that weak acids haae strong conjugate bases. A prime example is a weak acid with
PKa = 7. The pK6 of the conjugate base is 7, which is not strong.

General Chemistry Acids and Bases Terminology
Terminology
Fundamental Definitions
A perfect place to start a discussion of acids and bases is with the definitions of
an acid, a base, and strength. There are three definitions proposed for both acids
and bases, although each considers an acid as the opposite of a base. The first
definition is the Arrhenius definition, which states that an acid yields Hgo*
when added to water, while a base yields oH- when added to water. An acidic
aqueous solution therefore has a higher hydronium concentration than
hydroxide. This definition is useful when doing calculations of pH and pKu. The
second definition is the Brsnsted-Lowry definition, which states that an acid is a
proton (H+) donor and that a base is a proton (H+) acceptor. This definition is
based on what occurs in a protic solvent, where reactions are viewed as proton-
transfer reactions. The third definition is the Lewis definition, which states that
an acid is an electron-pair acceptor while a base is an electron-pair donor. This
definition is based on what occurs in an aprotic solvent, and is typically used in
organic chemistry. For this section, o.rly thu Arrhenius aeiinition will be
emphasized. Table 4.1 lists the different definitions of acids and bases.
Term Definition Example

Arrhenius acid yields HgO* when added to H2O aq: [H3O+]> [OH-]
Arrhenius base yields OH- when added to H2O aq: [OH'] > [HeO*]
Bransted-Lowry acid Proton donor HX in protic solvent
Bronsted-Lowry base Proton acceptor KOH in protic solvent
Lewis acid Electron pair acceptor BF3 in aprotic solvent
Lewis base Electron pair donor NH3 in aprotic solvent
Table 4.1
Water-based Acid-Base Chemistry

For our purposes, acid and base chemistry is to be considered as reactions tha:
only occur in aqueous solution. Therefore, to understand water-based acidit'.'
and basicity, it is vital to understand the properties of water. water -,
amphoteric, meaning that it may act as either an acid or a base. Neutral wate:
naturally dissociates into hydronium and hydroxide, according to Reaction 4.3.
2H2O(t): H3O+(aq) + OH-(aq)

Reaction 4.3
Only a small fraction of water dissociates into solution. Water at 25"C, in r.:
absence of an acid or a base, dissociates enough to generate a solution with 1--
M H3O+(aq) and t0-7 M OFf(aq). This meanslhat neutral water has both a Lit-.
hydronium and a little hydroxide. A neutral aqueous solution is defined as c:ii
in which [HSO*] = [OH-], and therefore pH = pOH. If the solution is at 25"11
then the pH and poH are both equal to 7.0. For an acidic aqueous solutic:
[HsO+] > [OH-], pH < pOH, and the pH of the solution is less than 7.0. Equa-,
for a basic aqueous solution, [OH-] > [H:O*], pH > pOH, and the pH of r,:
solution is greater than 7.0. There are several perspectives according to whir,;
solution may be deemed acidic or basic, and regardless of the reasoning behr:,:
each one, you must know how all of these different perspectives relate to c:e
another. Any acidic solution has a pH of less than 7.0, hydronium in it be,:-s
more abundant than hydroxide, and it can turn blue litmus paper red. 4
Copyright @ by The Berkeley Review 23a The Berkeley Relienn i{r

Acid Dissociation
When an acid is mixed with water, it is said to dissociate. This is the reason we
use the term acid dissociation, expressed quantitatively with an acid dissociation
constant (K3). The acid dissociation constant is nothing more than the
equilibrium constant for the dissociation reaction of an acid in water. Each
molecule of an acid when added to water, dissociates to form hydronium ion
(HsO*) and its conjugate base (expressed generically as A-) upon reaction with
one water molecule. Reaction 4.1 is an acid dissociation reaction in water.
HA(aq) + H2O(l) : H3O+(aq) + A(aq)
Reaction 4.1
Equation 4.1 is the equilibrium expression (used to solve for the equilibrium
constant) for the acid dissociation reaction shown in Reaction 4.1.
K-" _[H3O+][A] (4.1)

[HA]
Equations 4.2 and 4.3 are the equations for converting between PKa and K".
(4.2)
PKa=-logK3
Ka = 10-PKu (4.3)
As the relative strength of an acid increases, its Ka increases and its pK3
decreases. This means that stronger acids have higher K6 values and lower pKn
values. The K3 and pK6 of an acid depend on the strength of the acid, but nof its
concentration.
Base Hydrolysis
When a base is mixed with water, it is said to undergo hydrolysis. This is the
reason we use the term base hydrolysls, expressed quantitatively with a base
hydrolysis constant (K6). The base hydrolysis constant is nothing more than the
equilibrium constant for the hydrolysis reaction of a base in water. Each
molecule of a base when added to water, hydrolyzes one water molecule to form
hydroxide ion (oH-) and its conjugate acid (expressed generically as HA).
Reaction 4.4 is a base hydrolysis reaction in water.
A-(aq) + H2O(l) -- HA(aq) + HA(aq)
Reaction 4.4
Equation 4.4 is the equilibrium expression (used to solve for the equilibrium
:onstant) for the base hydrolysis rpaction shown in Reaction 4.4'
r. _=[HA][OH-]
r'b @.4)
LA-l
Equations 4.5 and 4.6 arc the equations for converting between PKI and K5.
pKb=-1ogK6 (4.s)
K6 = 1g-PK6 @.6)
,\s the relative strength of a base increases, its K6 increases and its pK6 decreases.
-his means that stronger bases have higher K6 values and lower pK6 values. As
a base depend on the strength of the base,
=een with the acids, the K6 and pK6 of
':'tt
not its concentration.
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Tying everything together for a conjugate set, we observe that as the acid gets
stronger, its conjugate base gets weaker. The overall correlation is shown in
Figure 4-1.
Overall Relationship
As acid strength t, Ku 'l., pKa I, conjugate base strength J, K6 J, pKU T
Figure 4-1
Determination of Reagent Strength

The strength of a reagent is determined strictly from the Ku (or pKu) and the K6
(or pK6). Strength is a measure of the completeness of a reaction in water. Terms
that are sometimes used instead of "dissociation" are ionization and electrolytic
nsture. The stronger the acid, the more electrolytic it is, because it conducts
electricity better due to the greater number of ions in solution. For water to
conduct electricity, there must be ions in solution to transfer the electron charge.
Because the equilibrium expressions are comparable, the values can be correlated
for a conjugate pair. At 25'c, Equation 4.7 describes the relationship between
pKu and pK5.
pKa (HA) + pKU (A) = 14 (4.7)
The strength of a reagent is measured by its ability to carry out a reaction in

water. The stronger an acid, the more readily it dissociates into water. The
stronger the base, the more readily it undergoes hydrolysis when mixed with
water. Be careful not to confuse the concentration of a reactant with its strength.
A highly concentrated weak acid may have a lower pH than a strong acid in low
concentration.
Example 4.1
what can be said of the pK6 associated with the conjugate base of the more
electrolytic acid of a pair of acids?
A. The pK6 associated with the conjugate base of the more electrolytic acid is
greater than the pK5 associated with the conjugate base of the less
electrolytic acid.
B. The pK6 associated with the conjugate base of the more electrolytic acid is
smaller than the pK6 associated with the conjugate base of the less
electrolytic acid.
C. The pK6 associated with the conjugate base of the more electrolytic acid is
equal to the pK6 associated with the conjugate base of the less electrolytic
acid.
D. The pK6 values associated with the conjugate bases of two electrolytic acids
cannot be compared.
Solution
The acid that is more electrolytic is the acid that forms more ions, and thus is
better able to conduct electricity. The stronger acid dissociates more, and in
doing so, produces a greater ion concentration. The more electrolytic acid is the
stronger acid, and according to Figure 4-10, the stronger acid has a conjugate
base with a higher pK6 (associated with the weaker conjugate base.) This makes
choice A the best answer.
Copyright @ by The Berkeley Review 24o' The Berkeley Review

Strong Acids
Strong acid.s are acids that dissociate fully when mixed with water. That is to say
that irong acids ionize completely into hydronium and a conjugate base when
added to water. Reactants into products, so the Ku value of a
"o.rr"tf "ompletely
strong acid is very large. It is safe to assume that an acid that does not have a
measirable Ka (i.;., it has a Ku that is too large to measure, making it greater than
1.0) is a strong acid. Reaction 4.5 shows the dissociation of a strong acid, HX.
HX(aq) + HzO(l) H3O+(aq) + X(aq)
Reaction 4.5
-
The equilibrium constant for the acid dissociation reaction shown in Reaction 4.5
has a Lrge numerator and a minuscule denominator. As such, Ku is significantly
greater tian 1.0, and pKu is negative for HX. This is summarized in Figure 4-2.
r"- = [Hr-O*Ir] >> 1 ... PKa < o

tHX]
Figure 4-2
It happens that all of the strong acids can be classified as either haloacids or
o*yuiidr. Some typical strong acids are listed in Table 4'2'
Acid Name PKa
HCI Hydrochloric acid -7
HBr Hydrobromic acid -7
HI Hydroiodic acid -9
H2SOa Sulfuric acid -9 (PKar)

a
HN03 Nitric acid
HCIOa Perchloric acid -10
Table 4.2
Weak Acids
Weak acids are acids that only dissociate partially when dissolved into water'
They do not fully ionize into conjugate base and hydronium ion in water.
Reactants are converted partially into products, so dividing products by reactants
indicates a small value for Ku (a value that is less than 1.0). Any acid with Ku less
than 1".0 is a weak acid. Reaction 4.1 shows the dissociation of a weak acid'
HA(aq) + H2O(l) .- H3O+(aq) + A(aq)
Reaction 4.1
The equilibrium constant for the acid dissociation reaction shown in Reaction 4'1
is less than 1.0. However, because our definitions must apply to biochemistry as
well as general chemistry, weak acids are classified as weak or very weak. For
instance] aspartic acid is iaid to have an acidic side chain, while the side chain of
leucine is considered to be neutral. We will define any acid with a K2 less than
1g-1a (and thus a pKu greater than 14) as a very weak acid, meaning that the pKn
range for a weak icid is from 0 to 14. This is summarized in Figure 4-3.
K"" -[H3o+][A].where 1 > Ka > 10-14 ... 0 <pKu < 14

tHA]
Figure 4-3
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General Chemistry Acids and Bases Terminology I
Weak acids are members of a number of different classifications, including

oxyacids of low oxidation state, one haloacid, carboxylic acids, alky-l I
ammoniums, and phenols. Table 4.3 lists some typical weak acids and their t
corresponding pKu values.
t
Acid Name PKa
CI3CCO2H Trichloroacetic acid 0.64
Cl2HCCO2H Dichloroacetic acid 7.27 t
H2SQ3 Sulfurous acid 1.82 (pKu1)
HCIO2 Chlorous acid r.90
t-
CIH2CCO2H Chloroacetic acid 2.82
HF Hydrofluoric acid 3.15
HNO2 Nitrous acid 3.41 t_
HC02H Formic acid J./4

H3CC02H Acetic acid 4.74
2,4-(H1C)2C6H3NH3+ 2,4- dimethylanilinium 5.08
4-H2NC6HaNHg* 4-aminoanilinium 6.18
H2CO3 Carbonic acid 6.36 (pK61)
4-O2NC5HaOH 4-nitrophenol 7.75 ,rl
HCIO Hypochlorous acid 7.46 ;a
HBrO Hypobromous acid 8.72

NH,r+ Ammonium 9.26
HCN Hydrogen cyanide 9.32
HIO Hypoiodous acid 10.66
,JIL
Table 4.3 fi,
Very Weak Acids D"

Very weak acids dissociate less than water. The Ku value of a very weak acid b
less than 10-14, because products divided by reactants is less than 1.0 * 10-1i $rIr
(K*). Given that water is thought to be neutral, an acid with a Ku less than 10-1{ I
(and pKq greater than 14) is a very weak acid. This is summarized in Figure 4-4.
l
." ==rr9!I4; where Ka < 10-14 ... pKu > 14
Huc
Figure 4-4 il[Mi']r
,4"
Strength and the pK Scale
The same rules that apply to acids also apply to bases, except that hydrolysl.
t
c.
rather than dissociation, is considered, and K6 replaces Ku. As the pK value for ; nn
compound decreases, its strength increases (this is true for both acids and bases
As a rule, the stronger the acid, the weaker its conjugate base. strong acids har-" S@u
very weak conjugate bases, and strong bases have very weak conjugate acid-* fru
The odd sounding relationship is that weak acids have weak conjugate bases. It idtibm
may seem peculiar, but the conjugate base of a weak acid is most often a wea_li rl{nilui'
base. You have seen this relationship before with buffers, although it is unlike.-* Sumr
that it was emphasized in your general chemistry courses.
iltE

'mmm
Table 4.4 defines the strength of an acid and a base in relative terms.
Numerical Numerical
Compound Conjugate
Data Data
Strong acid Very weak base
Ku>>1 K6 < 19-14
(Fully dissociates in H2O) (Hydrolyzes less than H2O)
PKa<0 pK6 > 14
e.g., HCI (PKa = -7) e.g., Cl- (PKU = 21)
Weak acid Very weak base 10-14<Ku<1
10-14<Ku<1
(Partly dissociates in H2O) (Partly hydrolyzes in H2O)
0<pKu<14 0<pK6<14
e.g., RCO2H (PKa = 3-5) e.g., RCO2- (pKU = 9-11)
Very weak acid Strong base Kb>>1

Ku < 19-14
(Dissociates less than H2O) (Fully hydrolyzes in H2O)
pKz > 14
e.g., CH3- (PKa = -35) PKU<o
e.g., CH4 (PKa = 49)
Table 4.4
The strength of a reagent is measured by its ability to react in water. The more
readily an acid dissociates into water, the stronger it is. The more readily a base
undergoes hydrolysis, the stronger it is. Do not confuse the concentration of a
reactant with its strength. Both affect pH. Within conjugate pairs, to calculate
the strength of one reagent from the strength of its conjugate, use Equation 4.7'
On the exam, one of the required skitls will be determining what the question is
asking. In terms of acid and base chemistry, many of the questions will be more
complicated versions of the basic question of "which acid is stronger?"
Example 4.2
\Atrhich of the following acids would yield the highest pH in water?
-A; 0.10 M HCI

B. 0.i0 M HCloa
"e. o.1o M HBr
p. )o.ro M HCo2H
Solution
The highest pH in water results from the lowest hydronium concentration. This
is associated with the weakest acid, which in this case is carboxylic acid, choice
D. Choices A, B, and C are all strong acids that fully dissociate in water.
Example 4.3
Which of the following is the BEST choice to titrate 0.10 M H3CNH2(aq)?
A. O.5O M KOH
B. 0.05 M NH3
C. 0.10 M HBr
D. 0.10 M HCO2H
Solution
To ensure complete reaction, the titrant must always be a strong reagent. This
eliminates choice B (a weak base) and choice D (a weak acid). In this case, the
solution being titrated is a weak base solution (H3CNH2 is a weak base), so
strong acid is added. Choices A is a strong base and choice C is a strong acid.
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General Chemistry Acids and Bases Terminology G
Example 4.4 m!
tffi,e
\A/hich of the following acids dissociates to the GREATEST extent
when added to
water? W'
qfimr
A. HNO3 !ilm- :
B. HNO2 'Meuu
C. H3PO4 aml
D. H2CO3
#m'ffi
/,fl*
Solution Imffi
The most complete dissociation is associated with the strongest acid. The & ud/il
strongest acid in this case is nitric acid (HNo3), choice A. These questions show mrn
1.fu-.of the -Ty ways relative acidity can be compared. In addition to
dissociation, acidities can als.o-be computed by pKu values (lower is more
acidic),
Ku values (larger is more acidic), pH varues (to-"t is more acidic for
equal acij
concentrations), electrolytic strength (more electrolytic is more acidic), and
reactivity with bases (stronger acids react with weaker'bases).
lhe
IIffi
Strong Bases lesil
strong bases, like strong acids, react completely when they are added to water. Flg:
strong bases fully hydrolyze water, so they completely ionize when dissolved
into water. Reactants are completely conveited inio products; thus, the K6 value
of a strong base is much greater than 1.0, because products divided by re"actants
is very large. Any base that does not have a meazurable K6 (or has a 16 that
is
much greater than 1.0) is a strong base. Reaction 4.6 shows tne hyarotysls of the
strong base, KOH: -t.H
MOH(s) + H2O(l) xril
M+(aq) + OH-(aq)
-rffi
--
Reaction 4.6
--4
The equilibrium constant for the base hydrolysis reaction shown in Reaction
4.6
has a large numerator and a minuscuie denominator. Its value, therefore,
is
significantly greater than 1.0. This results in a negative pKu value for a strong
base. This is summarized in Figure 4-5.
=tYlrl?Tr >> 1 .'. pKu < o

"o tMoHl
Figure 4-5
It happens that all of the strong bases are either hydrides, hydroxides, alkoxides,
amides, or carbides. some typical strong bases are listed in Table 4.5. No pK6
values are listed, because all of these bases when added to water will form
hydroxide.
Base Name
KH Potassium Hydride
NaOH Sodium Hydroxide
KOCH3 Potassium Methoxide
NaNH2 Sodium Amide
Li(CH2)3CH3 Butyl Lithium
Table 4.5
Copyright @ by The Berkeley Review 244 The Berkeley Review CoF
Weak Bases
Weak bases, like weak acids, partialiy react when added to water. Weak bases
partially hydrolyze water, so they only partially ionize when dissolved into
water. Reactants are only partia\ converted into products, so dividing products
by reactants is placing a small number over a large number, leading to a small
value for K6 (ess than one). As with the weak acids, because water is considered
to be neutral, we will define any base with a K6 less than 10-14 (and thus pK6
greater than 14) to be a base that is too weak to consider. This means that the
pK6 range for a weak base is from 0 to 14. It should be safe to assume that any
base on the test for which you are given a K6 value (or pK6 value), is likely to be
a weak base. A base with less than 100% hydrolysis is a weak base. Reaction 4.7
shows the hydrolysis of a weak base, A-.
A-(aq) + H2O(l) : HA(aq) + OH-(aq)
Reaction 4.7
The equilibrium constant for the base hydrolysis reaction shown in Reaction 4.7
has a small numerator and a larger denominator, making it less than 1.0. This
results in a small positive pK6 value for a weak base. This is summarized in
Figure 4-6.
Kb = tH4l-tqH l' where 10-14 < Kr < 1 .'. 74 >pKu > o

tA-l
Figure 4-6
There are many different types of weak bases. some typical weak bases are the
conjugate bases of the acids listed in Table 4.3. In addition, other common weak
bases include the carboxylates (RCo2-), the alkyl amines (RNH2), bicarbonate
(HCO3-), carbonate (COe2-), phosphate (PO+3-), and phenoxides (C6H5O-).
VeryWeak Bases
very weak bases do not undergo any significant (or detectable) hydrolysis in
water. The K6 value for a very weak base is less than L0-14, because the products
divided by reactants is less than 1.0 x 10-14 (K-). Given that water is considered
to be neutral, a base with a K6 less than 10-14 (and pK6 greater than 14) is a very
weak base. This is summarized in Figure 4-7.
xo tH4ll9H-1. where K6 < 10-14 pK6 > L4

= ...
IA-I
Figure 4-7

Example 4.5
Which of the following compounds when added to water does NOT yield a
solution where hydroxide ion is in greater concentration than hydronium ion?
A. Na2CO3
B. HCO2Na
C. HNO3
D. C6H5ONa
Solution
A base is a compound that hydrolyzes water to generate hydroxide, and thu-"
form a solution where hydroxide is more concentrated than hydronium. This
question is in essence asking, "Which compound is NOT a base?" Choice C, nitric
acid, is NOT a base, making choice C the answer.
Example 4.6
lzVhich of thefollowing bases has the STRONGEST conjugate acid?
A. O.5O M KOH
B. 0.50 M LiN(CH3)2
C.0.50MNaH
D. 0.50 M NaHCO3
Solution
The concentration does not affect the strength. No matter what concentration :rs
added to solution, the value of K6 is constant. This means that this questior:
simply addresses the strength of the compound. The strongest conjugate acid is
associated with the weakest base. In this question, choice A is a metal hydroxrde
choice B is a metal amide, and choice C is a metal hydride. Choices A, B, and C
are strong bases. The only weak base is the bicarbonate base, choice D.
Example 4.7
\Alhich of the following is the BEST choice to titrate 25 rnL of 0.10 M HCO2H(ac ?
A. O.1O M KOH
B. 0.05 M H3CNH2
C. 0.10 M HBr
D. 0.05 M H3CCO2H
Solution
To ensure complete reaction, the titrant must be a strong reagent. This eliminaM
choice B (a weak base) and choice D (a weak acid). In this case, the soluhcm
being titrated is a weak acid solution (HCO2H is a weak acid), so strong
must be added. Choices C is a strong acid, so the only strong base is choice A,
KOH.

General Chemistry Acids and Bases Types ofAcids and Bases
iilffiriffiffi iiii iiiiffi#$es

Haloacids
The haloacids are the series of HX acids, whose X represents a halogen. The
acidity of haloacids is predictable based on the size of the halide ion. The larger
the halide, the more acidic the haloacid. This means that HI > HBr > HCI > HF.
This trend in acidity is attributed to the increased stability of the conjugate base
as it increases in size. The negative charge is more diffuse on the larger anion.
The more diffuse, the less basic the anion, and thus the more acidic its conjugate
acid. A second, and perhaps easier, way to view the acidity of haloacids involves
estimating their bond strengths. The longer the bond, the weaker the bond, as a
general rule in chemistry. As you descend the halogen column in the periodic
table, halogen size increases. As halogen size increases, the bond length of an H-
X bond must also increase. As the bond length increases, the bond strength
decreases, and the H+ can be removed more readily. This approach works even
though bond dissociation energies are determined from homolytic bond
breaking, as opposed to the heterolytic cleavage associated with acid-base
chemistry. Ions (H+ and A) are the result of heterolytic bond breaking, but the
correlation between bond strength and acidity still holds for haloacids. Figure 4-
8 summarizes the effect of halide size on acidity.
H_F Descending a column:

Halogen size increases
H- CI .'. Bond length increases
H- Br .'. Bond strength decresases
.'. Dissociation increases
.'. Acidity increases
Figure 4-8
Example 4.8
\ /hich of the following conclusions can be made concerning the relative acidities
of haloacids?
A. Acid strength increases with increasing electron affinity of the halide.
B. Acid strength increases with increasing electronegativity of the halide.
C. Acid strength increases with increasing ionic radius of the halide.
D. Acid strength increases with decreasing isotopic abundance of the halide.
Solution
As you descend a column in the periodic table (such as the halogen column),
acidity increases due to the increase in atomic size. The anion formed upon
deprotonation is more stable as it increases in size, so acidity increases as the
column is descended. Electron affinity and electronegativity decrease as the
column is descended, and they have no bearing on acidity. Isotopic abundance
and atomic mass do not affect acidity, either, so choice C is the best answer.
An important fact to recall about haloacids is that they are all strong acids, except
for hydrofluoric acid (HF). HF has a pKa of roughly 3.3, so it does not fully
dissociate when added to water. As we have observed in studying other topics
related to the properties of this chemical family, this weaker acidity is attributed
to the smaller atomic radius of fluorine relative to the other halogens.
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General Chemistry Acids and Bases Types of Acids and Bases
Example 4.9
Which of the following acids has the largest Ku value?
A. HF
B. HCl
C. HBr
D. H2S
Solution
The largest Ku value is associated with the strongest acid. Because Br is the
largest anion of the halogens listed, it dissociates from the proton most readilr..
This makes HBr the most acidic, so you should pick choice C. Choices D (H2Sf
can be eliminated, because S is of roughly comparable size with, but less
electronegative than, Cl. This means that HCI is a stronger acid than H2S.
Within a period (row) of the periodic table, it is electronegativity that dictates the
strength of an acid, not atomic radius. A prime example of this idea is the
relationship between ammonia (H-NH2), water (H-OH), and hydrofluoric
acid (H-F). The strongest acid of the three compounds is the hydrofluoric acid,
because fluorine is more electronegative than both nitrogen and oxygen. The
atomic size does not change that noticeably between N, O, and F, because they al1
have the same valence level (n = 2). The periodic trend that most changes is the
electronegativity.
Oxyacids (Non-metal Hydroxides and Non-metal Oxides)

Oxyacids are also an acid type to be familiar with. They differ from haloacids, r,
that the hydrogen dissociates from an oxygen rather than a halide. In an oxyacid
the acidic hydrogen is bonded to an oxygen, which in turn is bonded to a centra-
atom (which in some cases can be a halogen). The simplest rule is that the more
oxygen atoms there are bonded to the central atom, the more the oxygen atoms
withdraw electron density from the central atom, and thus the more acidic the
oxyacid. This can be summarized as the resonance effect (which is typicall',
classified as an organic chemistry concept). Unlike the haloacids, where size is
important, in oxyacids, the electronegativity of the central atom is mos:
important. As a general rule, for every additional oxygen on the central atom
the pKa of the acid will drop by approximately 5 pK3 units. Table 4.6lists son.e
typical oxyacids.
Oxyacid Name Oxyacid Name

HN02 Nitrous acid HNO3 Nitric acid
H2S03 Sulfurous acid H2SOa Sulfuric acid
H3PO3 Phosphorous acid H3POa Phosphoric acid
H2CO3 Carbonic acid HO2CCO2H Oxalic acid
HCIO Hypochlorous acid HCI02 Chlorous acid
HCIO3 Chloric acid HCIOa Perchloric acid
HBrO Hypobromous acid HBrO2 Bromous acid
HBrO3 Bromic acid HBrOa Perbromic acid
Hio Hypoiodous acid HiO2 Iodous acid
HIOg Iodic acid HIOa Periodic acid
Table 4.5
Copyright @ by The Berkeley Review 24A The Berkeley Reviev

\rvhen comparing the relative strength of oxyacids, the number

of excess oxygen
atoms and the electronegativity of the centrai atom must
both be considered. For
carbonic acid, there is an exce-ss oxygen count of one. What is
meant by excess
oxygen count is the number of oxygen atoms exceeding the number
or hyaroge.
atoms. The excess oxygen count often turns out to be the number
or o*y[u.,
atoms double-bonded to central atom. The more n-bonds to oxyge'
central atom, the more resonance withdrawal from the central
fror'in"
atom, and thus the
3o11aci!5 the compound. This explains why H2so4 is a stronger acid than
H2so3' when two compounds hav-e the same excess oxygen count, the next
factor to consider is the electronegativity of the centril"atom. The more
electronegative the central atom, the more it withdraws electron density
from the
acidic proton, increasing the acidity. This is in essence the inductive effect.
sulfur is more electronegative than carbon, so H2so3 is a stronger acid than
lzCOg' As you leamed in organic chemistry, the resonance effect ii greater than
the inductive effect.
Example 4.10
\Mhich of the following acids has the LARGEST pKu value?
A. HCIO2
B. HIO2
C. HC1O3
D. HIO3
Solution
The largest pKu value is associated with the weakest oxyacid, which
is associated
with the acid having the smallest number of excess oxygens and the least
electronegative central atom. Choices C and D are elimin-ated,
because tht
contain two excess oxygens each. Choice B is better than choice A,
because thei
both have one excess oxygen, but iodine is less electronegative than
chlorine.
This question could have easily asked for the strongest acfr.
It is important to
realize that most questions will be asking for eithJr the strongest
acid or the
weakest acid among the answer choices. "The wording may be
in reference to
conjugate bases, electrolytic nature, ionizability, Ku ialues, pKn
values, pH
values, or re-activity. The secret is to do enough pru"ti." questioni
so that ytu
encounter all the different possibilities at least ifew times before
your test.
As a point of interest, oxyacids result from the hydration of non-metal

oxides.
This is the cause of acid rain, where most often nitrogen oxides and
sulfur oxides
(Lewis acids) react with moisture in the air to forri Bronsted-Lowry
acids. A
lgweling it pH for rainfall may also be observed in environments rich
in carbon
dioxide (which hydrates to become carbonic acid). Reaction 4.g shows
the
hydration of carbon dioxide, while Reaction 4.9 shows the hydration
of sulfur
trioxide.
Coz(s) + H2o(t) H2CO3(aq)
non-metal oxide oxyacid
Reaction 4.8
SOz(g) + H2O(t) H2SO3(aq)

-+
non-metal oxide oxyacid
Reaction 4.9

General Chemistry Acids and Bases Types ofAcids and Bases
Non-metal oxides act as Lewis acids (electron-pair acceptors), while their

hydrated counterparts (non-metal hydroxides, commonly known as oxyacids) act
as Brsnsted-Lowry acids. Both SO3 and H2SOa react with hydroxide to form
HSO4-, so they are equivalent in terms of strength. The difference is that SO3 is
hydrated to become H2SOa. By a similar reaction, sulfur dioxide (SO2) forms
H2SO3 (sulfurous acid) and nitrogen dioxide (NOZ) forms both HNO2 (nitrous
acid) and HNO3 (nitric acid). These are major components of acid rain. Acid
rain is a combination of rain and air-bome pollutants, such as sulfur oxides and
nitrogen oxides. It is often treated with steam to convert from the Lewis acid
form (non-metal oxide) into the Bronsted-Lowry form (non-metal hydroxide) and
then neutralized with calcium oxide.
Metal Hydroxides and Metal Oxides

Just as non-metal oxides are Lewis acids and non-metal hydroxides are Bronsted-
Lowry acids, metal oxides are Lewis bases and metal hydroxides are Bronsted-
Lowry bases. You should be familiar with these general classifications. Metai
oxides are basic and will form metal hydroxides when treated with water. A
prime example is calcium oxide (CaO), which forms calcium hydroxide
(Ca(OH)f when hydrated. Reaction 4.10 shows the Lewis acid-base reaction of a
metal oxide and a non-metal oxide, while Reaction 4.11 shows the Brsnsted-
Lowry acid-base reaction of a metal hydroxide and a non-metal hydroxide. The
reactants in Reaction 4.11. are the hydrated form of the reactants in Reaction 4.10.
SOs(g) + CaO(s) CaSO+(s)
non-metal oxide metal oxide neutral salt
Lewis acid Lewis base
Reaction 4.L0
H2SOa(aq) + Ca(OH)2(aq) $ Ca2+1aq; +SOa2-(aq) + 2H2C"

non-metal hvdroxide metal hydroxide cation anion
Bran-Lowiv acid Bron-Lowrv base
I
Reaction 4.11 ti:
s;
Organic Acids :llni
Let us consider three types of organic acids: carboxylic acids, phenols, and alk' - vll
ammonium salts. It is important that you recognize these functional groups ai.:
r
know their pKa ranges. For carboxylic acids and alkyl ammoniums, you shou*: ;m]t
know their organic pKu range and their range in amino acids. In carboxylic ac- ff,og
and phenols, the proton comes off of an oxygen that is involved in resonance. I:
an alkyl ammonium cation, the proton comes off of a nitrogen. Figure 4-9 sho''r,:
a generic carboxylic acid and its pKu range, a generic phenol and its pKn rar.t=
and a generic alkyl ammonium cation and its pKx range. The AA in parenthes*.
refers to amino acid terminals, while the R designation refers to an alkyl grouF.
:o: HH
\,S
,.A,," :olr
-/,'\^tO
RH
Carboxylic acid Alkyl ammonium cado:
pKulp; = 3-5 Phenol pKa(R) =9-11
pKu144y = 2-3 PKa = 9.5-10.5 pKa(AA) = 9-70
Figure 4-9
Copyright O by The Berkeley Review 250 The Berkeley Keliam

Polyprotic Acids
Polyprotic acids are acids which yield multiple equivalents of hydronium
(Hgo+) when treated with a base. The three most common examples from
general chemistry are carbonic acid (H2Co3), sulfuric acid (H2so4), and
phosphoric acid (H3Po4). In addition to these three acids, there are also common
amino acids that qualify as either diprotic (no active proton on the side chain) or
triprotic (an active proton on the side chain). Concentrations of polyprotic acids
are often given in terms of normatity (N). Normality is defined- is moles of
equivalents per liter solution. This is to say that a 1.0 molar diprotic acid solution
would be listed as "2.0 normal," because there are two equivalents of acid.
Example 4.11
\Alhich of the following acid solutions is 3.0 N?
A. 1.00 M alanine
B. 1.50 M carbonic acid
C. 1.50 M phosphoric acid
D. 7.25 M sulfuric acid
Solution
Normality (N) is found by multiplying the morarity of an acid by the number of
protons per molecule. In choice A, alanine (H3NCH(CH3)Co2H) is diprotic, so
the normality is 1.00 x 2, which equals 2.0 N. Choice A is eliminated. ln choice B,
carbonic acid (H2Co3) is diprotic, so the normality is 1.50 x 2, which equals 3.0
N. Choice B is the correct answer. In choice C, phosphoric acid 6jro4) is
triprotic, so the normality is 1.50 x 3, which equals +.5 N. -cnoice C is eliminated.
ln choice D, sulfuric acid (H2so4) is diprotic, so the normality is 7.25 x 2, which
equals 2.5 N. Choice D is eliminated.
Polyprotic acids have multiple pKu values, one for each dissociable proton. By
definition, the first proton removed is more acidic than the second or," ,"*or"d,
rc pKal is always lower than pKu2. some difficulty may arise when you consider
the,pKu y3ll"_r of a polyprotic acid and its conjugate base. For a diprotic acid
such as H2Co3, the first proton removed correiponds to the ru.or,d proton
gained by the conjugate base. H2co3 and HCo3- are a conjugate pair wiih prul
and pK62 summing to 14. The futl dissociation of carbonii acid is shown in
Reaction 4.1.2 and Reaction 4.13.
H2CO3(aq) + H2O(1)
-PK"t - H3O+(aq) + HCO3-(aq)
PKuz
Reaction 4.12
pK-"
HCO3-(aq) + l__::.-
H2O(l) H3O+(aq) + CO32-(aq)
PKtr
Reaction 4.13
Determining the amount of base-needed to neutralize a polyprotic acid is a

typical question from general chemistry. while the MCAT doeJ not emphasize
solving mathematical problems, understanding the setup is still important,
because understanding equivalents can help to determine th" pH of mixtures.
Copyright O by The Berkeley Review 251 Exclusive MCAT Preparation

) a.
Example 4.L2
How many mL of 0.40 M NaOH are required to neutralize 100 mL 0.25 M
H2SOa? .i
,,., i.
A. 62.5mL ',,. I... | ... ''1 :: i l<lL::': ':' 1''

'
B. 80.0 mL
C. 100.0 mL i . --.9'
P,,) t25.0 mL
Solution
In order to neutralize an acid, an equal mole quantity of hydroxide must be
added to the hydronium source. The general relationship is shown in Equation
4.8.
moles oH- = moles H* .'. (MoH-)ffoH-) = (M11+)(Vg+) (4.8)
Substituting into Equation 4.8 yields the following results:

(MoH-)ffos-) = (Mg+)(VH*)
(o'ao $ffeH-) = 2 x (o'25 M)(1oo mL)
voH- = zx (0.2s iralx 100 mL =(o.so )x 100 mL = 125 mL
\0.+O Vt/ \0.+o /
Choice D is the best answer. Choice A would have been the result of your
calculation, if you had forgotten to multiply the molarity by the number oi
equivalents, a common mistake with these types of questions.
Example 4.13
How many milliliters of 0.60 M HCI are required to neutralize 3.0 grams CaCOrl
A. 50 mL
B. L00 mL
C. 200 mL
D. 300 mL
Solution
According to the balanced equation, two molecules of HCI are required for eve:r
one molecule of CaCO3. The balanced equation is shown below:
CaCO3(s) + 2HCt(aq) CaCl2(aq) + CO2(g) + H2O(l)

The mathematical setup is:
-
moles OH- = 2 x moles COg2- = (Mg+)(Vg+)
z* 3'08
g/_ot"
=(0.60M)(Vs+)
1oo
0.05 moles = (0.50 M)(Vg+) .'. Vg+ = 0.10 L = 100 mL
Choice B is the best answer. Choice A would have been the result of vc'=
calculation, if you had forgotten to multiply the molarity by the number :,r
equivalents, a common mistake with these types of questions.
Copyright @ by The Berkeley Review 252 The Berkeley Reliw

Example 4.14
citric acid (C6H6o7) has three dissociable protons with pKu varues of
3.r4, 4.79,
and 5.20. \Arhich of the following solutions would have the
lowest pH values?
-Y mL 0.10 M citric acid(aq) + 25 mL 0.20 M NaOH(aq)
50
B. 25 mL 0.10 M citric acid(aq) + 50 mL 0.10 M NaoHiaqj
g,<5 mL 0.20 M citric acidlaql + 75 mL0.20 M NaoHiaqi
_
D. 50 mL 0.20 M citric acid(aq) + 50 mL 0.10 M NaoHiaqj
Solution
For questions involving mixtr res, it is important to think of the
reagents in terms
of equivalents. The lowest pH belongs io the solution that is most
acidic. The
most acidic solution is the solutiott *heru the fewest equivalents
of base relative
to citric acid have been added. In choice A, the NaoH(aq) solution
is 1.5 times
the volume and twice the concentration of the citric acid'solution,
so there are
three equivalents of NaoH(aq). In choice B, the NaoH(aq)
solution is double the
volume of the citric acid solution and of equal concentration, so
there are two
equivalents of NaoH(aq). In choice C, the NaoH(aq) solutionis
three times the
volume of the citric acid solution and of eqral concentration,
so there are three
equivalents of NaoH(aq). In choice D, the NaoH(aq) solution is
of equar vorume
and half the concentration of the citric acid solution, so there
is only one-half of
an equivalent of NaoH(aq). The fewest equivalents are found
in choice D, so
choice D is the best answer.
Copyright O by The Berkeley Review 255 Exclusive MCAT preparation

General Chemistry Acids and Bases Calculating pfl
ffiruuxfitiffi iiiiHffi I
T
Determining pH n
A solution's acidity is measured in terms of hydronium concentration ([H3O+]) t
using the pH scale. The pH value of a solution is determined using Equation 4.9. L
pH = -1og [HeO+] (4.e)

t
I
By manipulating Equation 4.9 so as to isolate hydronium concentration, Equation

4.10 can be derived. I
lHsO+l = 10-PH
Because neutral water has an HgO* concentration of 1,0-7 M, due to the
(4.10)
autoionization of water, neutral water has a pH of 7.0. Acidic solutions have pH

il-
t-
values less than 7.0, while basic solutions have pH values greater than 7.0. There
are no limits to the pH scale other than those imposed by the strength anC F
concentration of the acid or base in solution. F
On the test, you can almost assume that they will have questions about both pH
and pOH for an aqueous solution. Just as Equation 4.9 defines pH, Equation 4.11
i-
-
defines pOH. F
L-
pOH = -log [OH-] (4.11r il
This means that in order to calculate pH or pOH, it is necessary to determine the F--
HgO* concentration or the OH- concentration. Once this is accomplished, it i: t--
simply log math (negative logs, actually). There are no calculators allowed o:
this test. The volume of a solution does not matter in determinhg pH; only t|.; I
concentration is important. Equation 4.72 may be used to interconvert betu,'eer'
pH and pOH in an aqueous solution at 25'C.
l.-
pH+pOH=14 (4.1:
Example 4.15
What is the pH of a solution where the hydroxide concentration is 106 tir:.,e=
greater than the hydronium concentration?
A.4
B.6
c. 10
D. 13
Solution
Because hydroxide is in greater concentration than hydronium, the solutior'. :-.
basic, so the pH must be greater than 7. This eliminates choices A and B. Ti*
trick here is to use the log scale correctly. Because the concentrations differ l-,' ;
factor of 106, the pH and pOU differ by log 706, which is 6. If the pH is 10, r.,ur
the pOH is 4, which are different by 6. It the pH is 13, then the pOH is 1, anC -e
difference is 12. This means that the best answer is choice C. This is a tnrlr
question where understanding the conversion between the log scale a: i
concentration scale is pertinent. Most students choose D, because they add : rr
the neutral pH of 7. It is important to recognize why choice D is a tr1::ru
mistake.
Copyright @ by The Berkeley Review 254 The Berkeley Rer'itm

General Chemistry Acids and Bases Calculating pH
Log Review
Because pH is based on logs,it is helpful to do a quick review of logs. When you
multiply numbers, you add their logs. when you divide numbers, you subtract
their logs. You can solve for any log given that log 2 = 0.3 and log 3 = 0.48.
Drawn in Table 4.7 arc examples of how to solve for a log value.
Number Mathematical Calculation Log Value

2 G ven value 0.301
J C ven value 0.477
4 Log 4 = Log (2x 2) = leg 2 + 1og2 = .301, + .301 = .602 0.602
5 Log 5 = Log (10 - 2) = log 10 - Iog 2 = 1..00 - .301. = .699 0.699
6 Log 6 = Log (3 x 2) = 1s*2 + 7og,2 = .307 + .307 = .602 0.778
LogT is approximated as being closer to log 8 than log 6 0.845 +.01
8 Log 8 = Log(2x2x2) = 3 (log 2) = 3(.301) =.903 0.903
9 Log9 = Log (3 x 3) = lsg 3 + log 3 = .477 + .477 = .954 0.954
0.33 Log0.33 = Log (1 *3) = log 1 - log 3 = 0 - .477 -0.477
0.50 Log 0.50 = Log (7 - 2) = log 1 -log2= 0 - .301 -0.301
7.20 Log 1,2 = Log (6 * 5) = log 6 - 1og, 5 =,778 - .699 = .079 0.079
1.25 Log7.25 = Log (5 * 4) = log 5 - log 4 = .699 - .602 = .097 0.097
1.33 Log 1.33 = Log (4 * 3) = log 4 -log3 = .602 - .477 = .725 0.125
t.40 Log 1.40 =Log,(7 *5) = log 7 -log5 =.845 -.699 =.746 0.746
1.50 Log 1.50 = Log (3 - 2) = log3 - log 2 = .477 - .301. = .176 0.176
1.60 Log 1.60 = Log (8-5) = 1og8 -1og5 =.903 - .699 = .204 0.204
1,.67 Lo91,.67 = Log (5 + 3) = log 5 - log 3 = ..699 - .477 = 222 0.222
1.75 Log7.75 =Log(7 -4) = leg 7 -Iog,4=.845 - .602= .243 0.243
1.80 Log 1.80 = Log (9 - 5) = log 9 - log 5 = .954 - .699 = .255 0.255
Table 4.7
Log calculations should be carried out only to the level of approximation. Do not
forget that log of 10x = x, so knowing the power of 10 that some quantity is can
be a useful hint when selecting the correct log value. Often, only one answer
choice relates to the correct power of 10, which saves a great deal of time spent in
calculating. AIl sorts of shortcuts and tricks will be presented during the
following sample problems. Before moving on in this section, however, make a
concerted effort to work through Table 4.7 and understand thoroughly how to
estimate log values.
Determining pH for Strong Reagents

Calculating the pH for strong acid and strong base solutions is based on the
concept of full dissociation. The calculation of the pH for a strong reagent
follows an easy pattern. For a strong acid, Equation 4.9 is employed, where the
concentration of the strong acid ([HX]) is substituted for the concentration of
hydronium ([HSO+]). For a strong base, Equation 4.11 is employed, where the
concentration of the strong base ([MOH]) is substituted for the concentration of
hydroxide (tOH-l). Calculating pH and pOH from concentrations is most easily
done when the concentration is written in scientific notation. This is because
taking the log of a number in scientific notation is more convenient in terms of
bookkeeping.
Copyright @ by The Berkeley Review 255. Exclusive MCAT Preparation

General Chemistry Acids and Bases Calculating pll
Example 4.16
\Atrhat is the pH of 0.0020 M HCl(aq)?
A. 2.00
B. 2.70
e. 3.00
D. 7.00
Solution
Determining an exact numerical value involves calculations. The pH for anr'
solution is defined as pH = - log [H3O+], so for a strong acid, the pH is - log [HX].
It is best to use scientific notation for the concentration.
pH=-log(2x10-3)
pH = - (log2 +log 10-3; - - log 2 - log 10-3
pH = - log2- C3) = 3 -log2
pH=3 -0.3=2.7
The correct answer is choice B. Choice D should have been eliminated, because
the solution is acidic, so pH is less than 7.00. Choices A and C could also har-e
I
been eliminated, if you noted that the log values ended in ".00". For a log to be a
whole number, the concentration must be a power of ten. The fact that the
concentration was .002 tells us that the log could not be a whole number. From
I
this example, you should derive a shortcut for use in the future. You might take
notice thai the- log of 2 x 10-3 is equal to 3 - log 2, so why not remember this ani
T
skip a few steps in the future. Use the relationship: - log (z x 10-Y) = y - log z.
This shortcut applies to all negative log calculations, including the conversicr.
from Ku to pKu. For instance, the pKs for a weak acid with K6 equal to 4.L x 1Cr-f
is 6 - log 4.1. This value can be estimated to be greater than 5.0 (which is equal. t.
6 - log 10), but less than 5.5 (which is equal to 6 - log 3). A range of 5.0 to : :
should be good enough to choose the correct answer from four choices. \A'ir
exact numerical questions on the MCAT, your goal should be to narrow th.e
answer choice range enough so that three wrong answers may be eliminated.
I
Xm,l
Example 4.17 'trtn{
\zVhat is the pH of 100 mL of 0.030 M HBr(aq)?

]HI]
A. 1.30
,l
;9.-':1.r, -:w
2
\j
c. 2.30 \ ..r
/-!
1t
D. 7.00 -7"
;fuf
tr
Solution q]l
The volume of the solution does not affect the pH, unless another solutior. s
added. Using the shortcut, the pH is found as follows:
pH = - 1og (3 x 70-2) = 2 - log3
pH=2-0.48=7.52
The correct answer is choice B. Choice D should have been eliminated, becau-'*
the solution is acidic, so pH is less than 7.00. Choices A and C could also ha-''*
been eliminated, if you noted that the log values ended in ".30". This n'o::-rl
come from logarithmic insights.
Copyright @ by The Berkeley Review 256 The Berkeley Rerim

General Chemistry Acids and Bases Calculating pH
Example 4.18
What is the pOH of 0.050 M KOH(aq)?
d..'.i.go
B. 7.70 t.
c. 72.30
D. 72.70
Solution
The pOH of a basic solution is found in a manner similar to getting the pH of an
acidic solution. Using the shortcut, the pOH is found as follows:
pOH = - log (5 t0-2) = 2 - log 5
"
pOH=2-0.7=1.30
The correct answer is choice A. Choices C and D should have been eliminated,
because the solution is basic, so pH is greater than 7.00, and therefore pOH is less
than 7.00. The pH of the solution can be found using pH = 14 - pOH.
Example 4.19
lVhat is the pH of 200 mL of 0.00391 M KOH(aq)?
A. 2.41.
B. 2.67
C. 77.39
D) 11.59
Solution
This question would seem to be quite difficult at first glance; but if you follow the
rules, it is easy. Because KOH is a strong base, it will fully dissociate when
added to water. Plugging values into our shortcut method yields the following:
pOH = - log (3.91 x 10-3) = 3 - log 3.91
3 - log 10 < 3- log3,91 < 3 - log 3 .'. 2 <pOH <2.5
If 2 < pOH < 2.5, then 12 > pH > 11.5
The correct answer is choice D. Choices A and B should have been eliminated,
because the solution is basic, so pH is greater than 7.00. Choice C is eliminated,
because it does not fit into the range for the correct number. Some of you may
have chosen to approximate 3.91 as 4, and solved accordingly. This method is
fine, too.
You should be able to determine pH or pOH for strong compounds in less than
fifteen seconds. While the MCAT does not offer up many calculation questions,
if you are fortunate enough to get a pH calculation question, you should finish it
quickly, and carry the time you save over to more difficult questions.
Copyright O by The Berkeley Review 257 Exclusive MCAT Preparation

General Chemistry Acids and Bases Conjugate Pairs
Determining pH for Weak Reagents

Because weak acids and weak bases do not fully dissociate, it is necessary to use
the Ku and K6 values to determine their H3O+(aq) and OH-(aq) concentrations.
K6 and K6 are equilibrium constants for the respective compounds in water.
Equation 4.7 shows the relationship between the pKu and pK6 for an acid and its
conjugate base. Equation 4.13 is based on the relationship of equilibrium
constants to K* (the dissociation constant for water).
K3xK6=19-14 (4.13)
According to Reaction 4.1, weak acids dissociate into hydronium and conjugate
base when added to water. Equal parts of conjugate base and hydronium ion
form. To determine the [H3O+], the dissociation reaction and the dissociation
constant (K6) must be employed. This too, like the strong acids, is a systematic
process to master, in the course of which we shall discover another shortcut. To
understand the process, consider some concentration of a weak acid (HA) with a
pKu between 2 and 12. The setup for the reaction is shown in Figure 4-10.
Reaction: HA(aq) HzO(l)

Initially: [HA]nit excess negligible 0 =
Shift: -x -x -------+ +X +X I
Equilibrium: [HA]ini1-x irrelevant XX i
!
Figure 4-10
I
Substituting values into the acid dissociation expression leads to Equation 4.14" {
which can be applied if the concentration is greater than the Ku, and if pKu falls l
between 2 and 72. Equation 4.14 does not generate precise answers, but it does
give a very close approximation. fi
u
[A-l[Hgo*] - lHgO+llHso+l -[Hgo*]2
Given: [A-] = fi3o+1, then 11u =. lL
tHA] IHA] IHA] uffi
t119ilt ...[Hso*]2 = Ka x tHAl ...IH:o*j {ru ^ [He]

l@
"""
= = W
tHA] 0.
Plugging this value into Equation 4.9 for IHSO+], yields Equation 4.14
ifle
{t(" .
I
pH = -log tF Al
Equation 4.74 can be further manipulated to generate Equation 4.15 (the s
equation), which will save you time, once it is understood and mastered.
pH = -log1/K" tF Af = - logy'Ka + (- log fiHati
"
pH = -log(Ku;1/z *(-tog IHAIl/r) = -ttorKu -Llog [HA]
pH = Ku - =lpK" - log [HA]

+log lr"rtHAl I
pH =lpK" -llog [HA]
To ensure that Equation 4.15 makes conceptual sense, let's consider the pH
weak acid solution. If you add more acid, the pH should decrease. Accordi
Equation 4.15, increasing [HA] lowers the pH. Stronger acids have :
dissociation, so they should form solutions of a lower pH. Equation 4.15 s

this by including the pKu term. Getting the pH of a weak acid should be eagi.-
Copyright O by The Berkeley Review The Berkeley

General Chemistry Acids and Bases Calculating pll
Example 4.20
ri\hat is the pH of 1.00 M HF with pKa 3.32?
=
A. 0.50
B. 1,.66
c. 2.00
D. 6.64
Solution
This question is made easy by applying Equation 4.15. Two requirements for
Equation 4.15 to work are that: L) the weak acid concentration must be greater
ihan the K6 and 2) the pK2 must lie between 2 and 72. Both of these criteria are
:ret, so Equation 4.15 may be applied.
pH =lpK" -Ilog[HA]=l1a.Sz;- 1log 1.0= 1.66-l(O)
-2--2"22"2 = f.Oe
The correct answer is choice B. Because [HA] is 1.0 M, the pH is half of the pKu.
U the acid concentration is 0.10 M, then the pH is half of the pKa + 0.5. This
rreans that the pH of a weak acid can be estimated quickly.
Example 4.21
i\hat is the pH of 0.Q7562 M HCO2H with a pKu of 3.642?
.\. 2.259
B. 2.383
c. 2.759
D. 2.883
-\."., i -;1
Solution
The pH can be estimated from one-half of the pKu. If the acid concentration were
1.00 M, then the pH would be 1.821 (half of the pK6). If the acid concentration
.,r-ere 0.10 M, then the pH would be 2.321. (half of the pKu + 0.5). If the acid
-oncentration were 0.010 M, then the pH would be 2.821. (half of the pKu + 1.0).
The concentration falls between 0.L0 M and 0.001 M, so the pH must fall between
1,321 and 2.821. This eliminates choices A and D. Because the concentration is
rust less than 0.10 M, the pH should be slightly higher than2.321-, making choice
B the best answer.
To date, the MCAT has not presented numbers this difficult, so given that these
rumbers now can be handled without difficulty, any weak acid pH calculation
:an be made easy. The answer to a question like this one in a multiple-choice
exam can be approximated quickly and simply using this technique. The answer
-hoices may be considered as other expressions of.
A. 1.827 +0.438
B. 2.327 + 0.062
C. 2.327 + 0.438
D. 2.827 + 0.062
Equation 4.76 is the equivalent equation for the pOH of a weak base solution. It
s derived in the same fashion as Equation 4.15, but K6 replaces Ku, [A-] replaces
[HA], and base hydrolysis is considered instead of acid dissociation.
pOH =l pKo - I log [A-] (4.'t6)

'2-2

General Chemistry Acids and Bases Calculating pfl
Example4.22
\A/hat is the pH of 0.20M sodium propionate, if it has Kb = 7.2x 10-10?
A. Less than 3
B. Between 3 andT
,e} Between 7 andL1
D. Greater than 11
Solution
The solution is basic, so the pH is greater than 7.0, eliminating choices A and B.
The weak base concentration is greater than K6, and pK6 falls between2 and 12,
so Equation 4.1.6 can be applied. The pK6 for the base is 10 - log 7.2, which is
slightly more than 9. A good estimate is 9.2.
The pOH can be estimated from one-half of the pKg. If the base concentration I
were 1.00 M, then the pOH would be 4.6 (half of the pK6). If the base {
concentration were 0.10 M, then the pOH would be 5.1 (half of the pK6 + 0.5). I
The concentration is 0.20 M, so the pOH lies between 4.6 and 5.1. This means
that pH lies between 8.9 and 9.4, making choice C the best answer.
't-. 1 .t .t
i c.'
lL\- .\
r'c,::'\
,'i,ir. \ i r.'t
I
{v. } i
iL
{.!
-- 1.: -:, t{ . ! rl
"- t lt -
u
illr
A
M
c
D
5,
:r
-l..
*li
i-::rL
-&
:_
frd
IT
Copyright @ by The Berkeley Review 26() The Berkeley Revia

General Chemistry Acids and Bases Coqiugate rairs
rc$ffi iii
A conjugate pair consists of an acid and a base that exchange one proton; one
gains a proton and the other member of the pair loses that proton. An acid when
deprotonated forms its conjugate base, and a base when protonated forms its
conjugate acid. Reaction 4.1 and Reaction 4.4 show that HA and A- are a generic
conjugate pair. The charge difference between the acid and the base in a
conjugate pair is +L.
Example 4.23
The conjugate base of HCO3- is which of the following?
A. CO32-
B. H2CO3
C. COz
D. HCO2-
Solution
A conjugate base is formed when an acid loses one proton. This eliminates
choice B, which happens to be the conjugate acid of HCO3-. The conjugate base
of HCO3- is CO32-, so choice A is the best answer. The dissociation reaction of
bicarbonate into hydronium and carbonate is shown below:
HCO3-(aq)+H2O(t):$H3O+(aq)+CO32-(aq)
acid conjugatebase
Example 4.24
lAtrhich of the following pairs of compounds is NOT a conjugate pair?
A. NH3/NHa+
B. HzCOa/HCOe-
C. HzSOg/HSOg-
D. Po43-/nzPo+-
Solution
In choice A, NH4+ is formed when a proton is added to NH3, so NH4+ and NH3
differ by one proton. This makes them a conjugate pair, and it eliminates choice
A. In choice B, H2CO3 is formed when a proton is added to HCO3-, so H2CO3
and HCO3- differ by one proton. This makes them a conjugate pair, and it
eliminates choice B. In choice C, H2SO3 is formed when a proton is added to
HSO3-, so H2SO3 and HSO3- differ by one proton. This makes them a conjûgate
pair, and it eliminates choice C. Choice D is the best answer because, PO4r- and
H2PO4- differ by two protons, so they do not constitute a coniugate pair.
Recognizing conjugate pairs should be effortless. Knowing how to apply the

concept of a conjugate pair to solving problems is the more useful ability.
Copyright @ by The Berkeley Review 26t Dxclusive MCAT Preparation

Typical Conjugate Pairs

Typical conjugate pairs either are observed in biological examples or are common
laboratory buffer systems. There are many weak acids and conjugate bases, so it
is a good idea for you to recall classes of compounds, rather than specific
compounds. common conjugate pairs where both components are weak include
the carboxylic acids/carboxylates (RCo2H/RCo2-), the alkyl ammoniums/alkr1
amines (RNH3+ /RNH2), and phenols /phenoxides (C6H5OH/COHSO-) Specific
pairs that are likely to appear on the MCAT with great frequency are carbonic
acid / bicarbonate (H2Co3 /HCo3-) and phosphoric acidldihydrogen phosphate
(H1POa/H2PO+-), due to their presence in physiological systems. It is a good
idea to know the acid-base properties of compounds that are common in
physiology.
The distribution within a conjugate pair is dictated by the pH of the solution,
The conjugate pair favors the conjugate acid form in the presence of hydroniurrn-
The conjugate pair favors the conjugate base form in the presence of hydroxide-
The exact distribution is determined by the relationship between pH of the
solution and the pKu of the conjugate acid. Figure 4-11 shows this relationship.
If pH > pKu, the solution is basic relative to the compound, so it is deprotonated..
If pH < pKu, the solution is acidic relative to the compound, so it is protonated"
Figure 4-11
The pH refers to the surrounding solution (environment) in which the

compounds exist. The pKa refers to the conjugate acid that exists in solution-
The compound responds to the pH of the solution. Because of the importance os
relating pH to pKu, common pKu ranges should be known. Some common pK*
ranges are shown in Figure 4-9. Carboxylic acids have pKu values of 2 to 5. In
amino acids, the carboxyl terminal has a pKu between 2 and 3. Because of tlw
low pKz value relative to physiological pH, the physiological form of carboxr-i-rc
acids is the deprotonated form. Ammonium and alkyl ammoniums have pxe
values of 9 to 11. In amino acids, the amino terminal has a pKu between 9 and 11"
Because of the high pKu value relative to physiological pH, the physiologica,il
form of amines is the protonated form. Figure 4-12 summarizes some corunon
physiological compounds and their natural states:
Acid Conjugate Base
RCO2H (PKa = 3-5) RCO2- (pKu = 9-11)
physiological form, becauseT.4 > 5
RNH3+ (PKa = 9-10) RNH2 (pKu = 4-5)

physiological form, because 7.4 < 9
H2POa- (PKaz=7.2) HPO42- (pKtz = 6.8)

physiological form, becauseT.4 > 7 -
H2CO3 (PKar = 6.4) HCO3- @Kt 2=7.6)

physiological form, because 7.4 > 6.1
Figure 4-12

General Chemistry Acids and Bases Conjugate Pafos
Relationship of pKu and pK6

Because the members of a coniugate pair exchange one proton, their respective
equilibrium constants are related. An acid when deprotonated forms its
conjugate base, and a base when protonated forms its conjugate acid. Equation
4.7 shows the relationship of the pKu for the acid and the pK6 for its conjugate
base. This relationship is useful for interconverting between pK values.
Howevet, when polyprolic acids are involved, it gets a little more complicated.
The relationship is emphasized in Reaction 4.12 and Reaction 4.13. Also keep in
mind that Equation 4.7 applies only at 25"C in water.
Example 4.25
- rq
Whatls the pKu for ammonia, given that the pK6 for ammonia is 4'7?
,Lt
A. 4.7 Pku' '"3*
B. 7.0 l'{,r -'
c. 9.3 ..'r,-.t
D. 33 Ir"
,{.i t ,.,
,t r?.
{, 1l jl
Solution
It is not 9.3! The compound with a pIG of.9.3 is ammonium (NH4+), the
conjugate acid of ammonia. Ammonia is a weaker acid than ammonium, so it
has a pKu greater than 9.3 The best answer is choice D,33, indicating that
u*moniu is such a weak acid that when added to water, there is no detectable
dissociation. The mistake of choosing 9.3 is easy to make, one that most students
make routinely. But the equation pKa (HA) + pKb (A) = 14 is for conjugate pairs,
not for the same compound.
The test-writers are more likely to apply this concept to carbonic acid (H2CO3),
which has two dissociable protons, and thus has both pKul and pKa2' The
correct relationships between pKu and pK6 for the two respective conjugate pairs
are pK61 + PKUZ = 1+ and PKa2 + PKbl = 14' Also note that pK21 is always less
than pKaZ, because the first proton is more acidic than the second one, by
definition.
Copyright Oby The BerkeleY Review 263 Exclusive MCAT PreParation

Henderson-Hasselbalch Equation
The pH of a solution comprise of both components in a weak conjugate pair can
be determined using the Henderson-Hasselbalch equation, which is shown
below as Equation 4.17. For the Henderson-Hasselbalch equation to hold true,
both the acid and its conjugate base must be present in appreciable concentration
in solution.
basel
oH
r = IpK"* *,on[Conjugate
"[Conjugateacid]
(4.17)
The equation shows that as the [conjugate base] increases, the pH of the buffer
increases. It also shows that as the [conjugate acid] incfeases, the pH of the
buffer decreases. Equation 4.77 is derived from the Ku equation.
*"=ffiF.rHeo*r =""(ffi)
taking -log of everything yields: -1og I H3o+] = -logKa - bg(tl1:f
"\ta-l )
I
-rog B{3o+l =-rosKa r"r(ffi)= pH =pKa -r"r(ffi) =pKu +t"*(#)

Equation 4.17 can be used with either concentration units or mole quantities for
HA and A-. This means that Equation 4.17 can be rewritten as Equation 4.18.
moles Conjugate Base
pH =pKu+1og (4.18)
moles Conjugate Acid
According to Equation 4.17, tlre addition of water to a conjugate pair mixture has
no effect on the pH of the solution. The compounds are diluted, and thus less
concentrated, but the pH remains the same.
Exarnple 4.26
\Atrhich of the following solutions has the GREATEST pH?
A. L0 mL 0.10 M NH3 with 15 mL 0.10 M NH+*
/B-75 mL 0.10 M NH3 with 10 mL 0.10 M NH4+
-C. 10 mL 0.10 M HCO2Na with 15 mL 0.10 M HCO2H
.'D. 15 mL 0.10 M HCOiNa with 10 mL 0.10 M HCO2H
Solution
The pH of a conjugate mixture can be determined using Equation 4.18. To make
the pH high, the pKu must be high, and the mixture must be rich in terms of
conjlgate base. The pKu of ammonium is greater than the pKu of a carboxylic
acid (in this case, formic acid), so choices C and D are eliminated. Choice A ha-'
more acid than conjugate base, so the pH is less than the pKu for the acid' Choice
B has more base than conjugate acid, so the pH is greater than the pKu for the
acid. This means that choice B has the greatest pH.
Copyright @ by The Berkeley Review 26,4 The Berkeley Reviel

#ffi rusiiffi ii'i#e$#1'$5#fi#iii,iffi #$H$eC
I. Acid and Base Definitions (r -7)

II. Dissociation and Colligative Properties (B - 15)
III. Oxyacids (r4 - 2r)

IV. Acidity of Thiols and Alcohols (22 - 28)
V. Organic Acids (2e - 54)
VI. Electron-Withdrawing Effect and Acidity (42 - 48)
VII. Weak Acid pH Equation (35 - 4r)
VIII. Aspirin and Antacids (4e - 55)
IX. Household Acids and Bases (56 - 62)
X. Stomach Acid and pH (63 - 70)
XI. Tooth Decay and pH (7r - 76)
XII. Acid Rain and Scrubbers (77 - 84)
XIII. Amino Acids pK2 Values (85 - el)
Questions Not Based on a Descriptive Passage (e2 - lOO)
Acids and Bases Scoring Scale

84 - loo l5-15
66-85 to-12
47 -65 7 -9
34-46 4-6
t-55 t-3
t*
Passage I (Questions 1 - 7) V Which ol the lollowing is an Arrhenius base?
A. HCIO t, t, 1.-;t'>, --
A base can be defined in three different ways, depending
t-'" B. HBrO2 -
on its solvent. The definitions are:
(C
'-n.
)ri2co3
\._iC r a) -, ii . r-)
1. The Arrhenius definition states that a base vields HNO2 tt ;'...
OH-(aq) when added to water. \.2

r
I r.:,i
2. The Br6nsted-Lowry definition states that a base is a
c'*'l
r i lr' i'
proton acceptor.
3. The Lewis definition states that a base is an electron
pair donor. 4. Which of the following would be the BEST choice to
neutralize 25 mL 0.10 M HCIO3?
The same base can fit the description of all three
definitions. The perfect example of a base that fits the three L. 25 mL 0.10 M NaOH(aq)
definitions is ammonia (NH:), which can donate its lone pair B. 250 mL 0.010 M NH:(aq)
of electrons to accept a proton from water, to yield an .9. 25 mL 0.10 M HCI(aqt
aqueous hydroxide anion (OH-(aq)). D. 250 mL 0.010 M HCO2Htaq)
!
Although a base may simultaneously fit the three ; /--r | {'i r'r r"
definitions, each definition has its own unique application. ' r;" t \ L ' ':' 6l' \'\
For the calculation of the pH of water-based solutions, the .-,.-L,)i.,'i)
Arrhenius definition is the most applicable. The Brgnsted-
Lowry definition is applicable in a more general sense,
because it accounts for acid-base chemistry that takes place in
,\' As the conjugate acid for a base gets stronger, the base:
a protic solvent other than water. The Lewis definition is /-. A. exhibits a decreasing pK6 value.
most commonly applied to organic chemistry where bases
V
B. can react with weaker acids.
donate their lone pairs to empty p-orbitals. A Lewis base can

C. acquires a higher pOH value in water.
react in any solvent, including aprotic ones.
D. requires more moles of acid to be neutralized.
t I .l t."
,f -, .J. *(-.,.rr( -n. ri , / t''F
A Lewis base also may be referred to as a nucleophile. r c-*)

The electrons of the nucleophile are donated to the partially l"o g' e-c* q ( r"Eb
positive site on an electrophile (which also may be a proton
'')
Let i* '1"tis I
in addition to a partially positive carbon). The partial or full

cationic charge is often the result of an excess of protons on 6 . Which of the following definitions does NOT describe
the electrophile. The term "nucleophile" is derived from the an acid?
strong affinity of the substances for positive charge (the --4. Aelectron-pair acceptor
charge of protons in an atomic nucleus). All three definitions B. A proton donor
can account for the nucleophilic nature of a base. compound that produces hydronium ion in water
,-e ._A
D.,.
rA nucleophilic molecule
1. If the [OH-] of a pH = 8.0 solution is tripled, the new
pH will be: ,.! - \'l-l
rt (j'
' {'
.*., \" i lcl -t.L
). r
i
}Y. ir--
.
<- \2.
t-.i tl
C. i<-
As the strength of an acid increases, which of the
^ I.+ * i-,
.-l *,f, following does NOT happen?
r :i */
t. - |-\- --k: The acid becomes more electrolytic.

I
^-t+ ' B. The acid dissociates more.
.a ') i; .C. The acid has a lower pKu.
2. Which of the following bases would have the D. 'The acid has a lower Ku.
LARGEST pK6 value?
A. A base that undergoe s 20Vo hydrolysis in waier
.'p. Abase that undergoes 15% hydrolysis in water

-- . A base that undergoes 107o hydrolysis in water
D. 'A base that undergoes 57o hydrolysis in water
Copyright @ by The Berkeley Review@ 267 GO ON TO THE NEXT PAGE

Passage ll (Questions 8 - 13) 9. How can it be explained that there is no difference
between the current readings in Trial 5 and Trial 6?
The strength of an acid in water is defined by its ability
to dissociate into hydronium and conjugate base. Strong A. Both KOH and KOAc are strong bases.
acids generate more ions in solution. As the number of ionic
B. Both KOH and KOAc are weak bases.
impurities in the water increases, so does the solution's C. Neither compound dissociates into ions in water.
electrical conductivity. Current does not readily pass through D. The number of ions in solution does not depend rrm
the base strength.

distilled water, so the degree of an acid's dissociation can be
estimated by a solution's ability to conduct electricity.
To determine the correlation between acid strength and
electrical conductivity, a researcher places the two ends of an
open circuit into a container of water so that the solution I 0 . In Trial 2, the water is acting as:
becomes part of a closed circuit. Two volumetric tubes are A. aBrgnsted-Lowry base.
poised above the solution, allowing for an exact quantity of B. an Arrhenius acid.
solution to be added to the circuit solution. Figure 1 shows C. a Lewis acid.
the apparatus used in the experiment. D. an amphoteric species.
Tube A Tube B
1 I . Which of the following is NOT true?

A. The solution in Trial I has a higher boiling p'nm
than the solution inTrial 2.
B. The solution in Trial I has a higher freezing p',rm
than the solution inTrial 2.
C . The solution in Trial I has a higher ostr"nrc
pressure than the solution in Trial 2.
D. The solution in Trial 1 is more electrolytic than
12V solution in Trial 2.
Figure I
In different trials, 25 mL aliquots of acid are added, and
the current is measured at different points in the wire. An
average current was recorded. Any deviation in current at 12. All of the following would show a current of rou_eirS
different sites can be attributed to errors in measurement, as amps when added to the solution EXCEPT:
o
the circuit is a single loop, so current should be uniform A. 0.10 M HNO3. il
throughout. Table I lists the average current in the wire and B. 0.10 M H2SOa. &
the contents ofeach tube in six separate trials.
C. 0.10 M NaOH.
Trial Tube A Tube B Current
D. 0.10 M NH3.
1 0.10 M HCI Nothins 5.94 amns
2 0.10 M HCIO Nothing 0.42 amps
-t 0.10 M HCI 0.10 M KOH 6.03 amps
13. What might be the reason for the similarities
4 0.10 M HCIO 0.10 M KOH 5.98 amps
the results in Trial 3 and Trial 4?
5 0.10 M KOH Nothing 5.89 amps
0.10 M KOAc
A. A complete reaction transpires only in Trial l.
6 Nothing 5.92 amps
B. A complete reaction transpires only in Trial 4
Table I C. After reaction, whether it is a strong acid w
strong base or a weak acid with a strong ba-ie-
The voltage of the battery is constant for the duration of same concentration of spectator ions remains.
the experiment. D. Only anions conduct electricity, and both
have the same amount of anions after reaction
8. What current would be expected, if 25.0 mL of 0.10 M
HF were added to the aqueous solution?
A. 0.02 amps
B. 0.48 amps
C. 5.42 amps
D. 6.17 amps

Passage lll (Questions 14 - 21) t 6-: If HCIO has a pKu =7.26, then the pH of a 0.10 M
HCIO solution is which of the following?
The term oxyacid is coined from the oxygen, the key A. 3.63
component of this type of acid. Oxyacids contain a non-
metal atom (highly electronegative) bonded to oxygens, and
;. 1.1
c. 7.26
the acidic hydrogen is bonded to an oxygen. A typical D. 8.26
example where nitrogen is the
is nitric acid (HNO3), t_::
electronegative atom that is bonded to the oxygens, one of

i :.'. \
which is also bonded to a hydrogen. Some oxyacids of
interest are those containing halides, sulfur, phosphorus, and 17 . If pKnl for a diprotic acid is 7.8, then the BEST choice
nitrogen. for pKu2 for its conjugate base, formed when the acid
The primary rule for predicting the strength of an oxyacid loses a proton, is which of the following?
is that the greater the number of oxygens attached to the A. 3.9
central atom, the more acidic the compound. For example, B. 6.2
HCIOa is more acidic than HCIO3. The secondary rule for c. 7.8
predicting the strength of oxyacids is that it increases as the D. 12.9
electronegativity of the central atom increases when the
number of oxygens is equal between two oxyacids. Table I
shows the trend for the halide acids:
18. If the dissociation of an acid is exothermic, then
Acid Formula K" value PKa (assuming that entropy is negligible):
Perchloric HCIOa 1.4 x 10e -8.8 A. Ku should increase as the temperature increases.
Perbromic HBrO4 2.6 x l}s -4.6 . '8-. Ka should remain constant as temperatirre increases.
C; Ka should decrease as the temperature increases.
Periodic HIOa x 102
I .-5 1.8
D. Ku never changes with varying temperature'
Chloric HClO3 8.9 x 10-1 0.1
Chlorous HCI02 1.3 x 0-t 1.9
HyDochlorous HOCI 5.4 x g-8 I --'\
2.3 x g-e 8.6

19. Which of the following values MOST accurately
Hypobromous HOBr
describes the pKu for HBrO2'based on Table 1?
Hvooiodous HOI 1.7 x 0-11 10.8
A. 0.63
t\;-t{"-' [li'
" .,,
I.
Table 1 B. 1.44
I
c. t.gz
t, tj
Table shows that the more dominant of the two causes i "
D - 2.85 i,
.
of strengthened acidity is the increase in oxygens attached to
the central atom of the acid. This exceeds the effect of
changing the halide central atom. A rough approximation is
that each additional oxygen will lower the pKu of the acid by 20. Which of the following acids would show the
approximately 5. Fluorine cannot expand its octet to GREATEST dissociation in water?
accommodate multiple oxygens, so it is not among the A. H3POa
elements that form halogen-based oxyacids. B. HNO2
C. HIO2
1 4. The acidity of halide-containing oxyacids increases D. HCIOa
directly with which of the following?
A. The increasing electronegativity of the halide
B. The increasing bond length of the H-O bond
C. The increasing size ofthe halide 21. What is the pH for a 125-mL sample of 0.10 M
D. The increasing bond angle of H-O-X HClOa, given that HCIOa is a strong acid?
A. -1 \' i
B.0.1
15. Which sequence accurately describes the relative strength
C- t
ll-'. I |-''
of oxyacids?
A. HIOa > HCIOa > HCIO3 > HBrO3
-B. HCIOa > HBrO3 > HIO4 > HIO3
C. HIOa > HCIO4 > HBrO3 > HC1O3
D. HCIOa > HCIO3 > HBrO3 > HIO2

Passage lV (Questions 22 - 28) 24. Which of the following halogen-containing acids is the Pi
STRONGEST acid?
The acidity of thiols (RSH) is observed to be greater than
the acidity of alcohols (ROH). This is determined by A. HF
comparing the relative pKu values for corresponding alkyl B. HCI Ct
(R
groups attached to thiols and alcohols. Table I lists pKu C. HBr
values for various alcohols and thiols with comparable alkyl D. HI 8ri
thr
substituents. From these values, it is possible to determine
the relative acidities of the two classes of compounds.
Alcohol Thiol 25. HCI is considerably more acidic than H2S, because tL.
PKa PKa
relative acidities of the compounds formed by:
H3COH t6.1 H3CSH 10.3
H3CCH2OH t6.3 H3CCH2SH
A . atoms in the same row of the periodic table deper:
10.6
on the electronegativity of the non-hydrogen arc:
(H3C)2CHOH tt.o (H3C)2CHSH I 1.0 in the compound.
(H:c):coH 17.8 (H3C)3CSH 11.4 B. atoms in the same column of the periodic tab,:
depend on the electronegativity of the non-hydror::
Table I atom in the compound.
The difference in acidity between alcohols and thiols is C . atoms in the same row of the periodic table deper,:
attributed to the polarizability of their respecrive conjugate on the size of the non-hydrogen atom in t::
bases. The larger the anion (more correctly, the atom compound.
carrying the negative charge in the conjugate base), the more D. atoms in the same column of the periodic ta: :
diffuse the electrons will be, and thus the more polarizable depend on the size of the non-hydrogen atom iri _:{,:
the electron cloud ofthe anion. The result is that the electron compound.
cloud is spread over more area, increasing the stability of the
anion (conjugate base).
As the stability of the conjugate base increases, the 2 6. How does ethanol compare with its correspondine e::,
basicity ofthe conjugate base decreases. The final correlation thiol?
is that as the basicity of the conjugate base decreases, the . Ethanol has a greater value of Ku.
A
acidity of the conjugate acid increases. This leads ultimately
to the conclusion that as the size of the atom to which the
B. Ethanol dissociates more completely in water.
acidic hydrogen is attached increases, the acidity of the
C. H3CCH2O- is a stronger base than H3CCH1S-
compound increases. This can also be correlated to the bond
D. Ethanol yields a greater [H:O+].
length of the bond between the acidic hydrogen and the atom.
The longer the bond, the weaker that bond will be.
22. Which of the following compounds would be MOST

2 7. When an atom in question is not directly attachec :: :thm,
acidic hydrogen, then the acidity of that com:,-,mdl
acidic?
correlates to the electronegativity of that atom. ::,: ms
A. H3CSCH3 size. This is known as the inductive effect. Ac: ..
B. H3COCH3 to the inductive effect, which of these acid: :
C. H3CNHCH3 STRONGEST?
D. H3CCH2CH3
A. H3CCH2CO2H
B. H3CCCI2CO2H
C. H3CCSCO2H
D. H3CCI2CO2H :
23. From the table of pKu values, what conclusion can be iilfuc ,U
drawn about the role of alkyl groups? nfu ru
A . Alkyl groups are electron-withdrawing and decrease 28 . Which sequence accurately describes the relatir; s
rrfidji rrrnr
acidity. of these acids?

B. Alkyl groups are electron-donating and decrease
A. H3CCH2SH > (H3C)3CSH > H3CCO1H
acidity.
C . Alkyl groups
B. (H3C)3CSH > H3CCH2SH > H3CCO1H
are electron-withdrawing and increase
acidity.
C. H3CCO2H > H3CCH2SH > (H3C)3CSH
D. Alkyl groups are electron-donating D. H3CCO2H > (H3C)3CSH > H3CCH2SH

and increase
acidity. I
*J
Copyright O by The Berkeley Review@ 27o. GO ON TO THE NE\T

Passage V (Questions 29 - 34) 30. What is the mass percent of carbon in pheno-.
' (CoHsOH)? -_i _s -,7 . _
Organic acids are weak acids with positive pKu values.
A. 66.7Vo 1 ':* v loo = .u
Common types of organic acids include carboxylic acids
(RCOzH) and phenols (C6H5OH). Electron-withdrawing
'i'ii'on i' r{':-ilL
c. 76.670
groups along the backbone of an acid increase its acidity, and
thus lower its pKu. Chloro, fluoro, and nitro groups are
D.B2.4vo 3:r**,':o-,.
among the common electron-withdrawing groups. Table 1 lou -i. . .*
lists some organic acids with their respective pKu values. F- --t"
I,.n ''i''
They are all monoprotic organic acids.
Structure Formula
31 . Which of the following acids would yield the lowest pH
PKa
value once completely neutralized by strong base?
o I' '
A. Acetic acid (H3CCO2H) r\1 '. '"
il Cl3CCO2H 0.64 ..'8.
--
Trichloroacetic acid (CI3CCO2H)
ctrcl \oH C. p-Nitro benzoic acid (O2NC6H+COzH)

D. Benzoic acid (C6H5CO2H)
o
o,*{Ho" p-O2NC6H4CO2H 3.40
3 2. When comparing equal molar aqueous solutions of acids

from Table l, what is TRUE?
O-{"" C6H5CO2H 4.21

A. 1.0 M acetic acid has a higher boiling point than
1.0 M p-nitro benzoic acid.
o ' B. 1.0 M tricloroacetic acid has a higher boilirlg point
than 1.0 M p-nitrophenol (p-OzNCOH+QH).
il H3CCO2H 4.14
.4'. 1.0 M tricloroacetic acid has a higher freezing point
HrC/t- O" than 1.0 M benzoic acid.
.D . 1.0 M acetic acid has a higher freezing point than
p-O2NC6HaOH 7.18
l.oMphenol.
ozN OH 1...tr
OH C6H5OH 10.01
3 3. Which of the following acids has the $TRONGEST
conjugate base?
Table 1 .--A-;lPhenol (COHSOH)

D. p-Nitrophenol (p-O2NC6HaOH)
When a weak acid dissolves into water, it partially C. Acetic acid (H3CCO2H)
dissociates according to its Ka. Equation l, can be applied to D. Trichloroacetic acid (ClrCCOzH)
calculate the pH of an aqueous solution of a weak acid.
PH=|Pr'-|log[HA]
Equation weak acid HA are
-lL'.
L
*n"n 0.10 moles of an unknown
Equation 1 is derived from the equilibrium expression for -; dissolved into 100 mL of H2O, the pH for the solution
the dissociation of a weak acid into water. It applies only if
\ -i, 3.7. What is the concentration of its conjugate base
the acid concentration exceeds K6 by 100 fold and if the pKu (A-)?
of the weak acid is between 2 and 12' A. tA-l >2x10-4
log 2 = 0.3 log 3 = 0.48 B. tA-l =2 x 10-4
C . tA-l <2 x 10-4
2 9 . What is the pH for an acid solution with a concentration 'D?The Ka of the weak acid must be known to
of 0.50MandaKa-8x 10-8? , l,.t: 1-
l- .-)
A':OcPH<3.0 -, 7
l,'ri:''
.'8. 3.0 < pH 3 3.5
c:-'3.5<pH<z.o
.D. pH>7.0
Copyright @ by The Berkeley Review@ 27t GO ON TO THE NEXT PAGE

Passage Vl (Questions 35 - 41) 36. A 100 mL 1.0 M phenol solution has a pH of:
The strength of an organic acid varies directly with the

A. 10.0.
strength of any electron-withdrawing groups attached to its
B. 7.0.
organic backbone. For instance, the acidity of acetic acid can
c. 5.0.
be increased by adding an electron-withdrawing group to the
D. 1.0.
methyl carbon. The acidity ofacetic acid can be decreased by
adding an electron donating group to the methyl carbon. The
effect on the strength of the acid varies with the location and
electronegativity of the electron-withdrawing group and is 3 7. According to the pKu data in Figure 1, which compoun:
most substantial when the functional group withdraws by is the STRONGEST electron-withdrawing group? s
* av of resonance. The following set of phenols demonstrates a

the effect ofthese substituents on acidity:
A. O2N- :
B. H3CO-
Organic Acid
C. H3C-
-p& D. H3CCO-
1.2 L
D
E"
3 8. The conjugate base of p-nitrophenol has a pK6 of:
8.4 A. 10.4.
B. 1.2.
c. 6.8.
D.3.6.
G*
fi.
pF
r 0.0
39 . How many grams of methoxy phenol must be adde; m,
100 mL of pure water to reach a pH of 6.1 ?

t0.4
A. 12.4 grams
B. 2.48 grams
C. 1.24 grams
D. 0.62 grams
11.2
Figure 1
Increased acidity can be attributed to the withdrawal of

40 . What is the Ku associated with p-methyl phenol?
electron density (through either the inductive effect or A. 4.0 * 10-10
resonance) from the O-H bond of phenol. The loss of B. 2.5 x 10-10 "FL4
electron density weakens the bond, causing it to break in a C. 4.0 x 10-11
heterolytic fashion more easily. This makes the compound D, 2.5 x 10-11 l1
more acidic. Resonance withdrawal is most pronounced when

the substituent is in the ortho or para position, so the
strongest acids are those with electron-withdrawing groups
attached to the phenyl ring at the ortho or para positions.
Resonance is substantially weaker from the meta position.
41. What is the pH of a solution made by mixing i
0.15 M phenol with 10 mL water?
The inductive effect is weaker than resonance from any
position. A. 10.0
B. 1.0
3 5. The LOWEST pH value would be associated with: c. 5.8 t3.
A. 0.10 M O2NC6HaOH (p-nitrophenol). D. 5.5
B. 0.50 M O2NC6HaOH (p-nitrophenol).
C. 0.10 M C6H5OH (phenol).
D. 0.50 M C6H5OH (phenol).
Copyright @ by The Berkeley Review@ 272 GO ON TO THE NEXT

--,r-'
_.^ -r
'-/x
t
Passage Vll (Questions 42 - 48) ,44. ll the pH ol a 0.10 M weak solution is 2.70, what is'
the concentration of the conjugate base?
A strong acid fully dissociates when dissolved in water,
e-. A. 0.r0 M -l
and the pH of the resulting solution can be found by taking ,\ -. - l a1J r{
B. 2.0 x 1o-2 tvt P,.
the negative log of the strong acid concentration:
(f) x ro-3 M
z.o t 11 :
rr i .-)
_. a.
pH = Jog [strong acid] D. 2.0 x 10-4 M -i

/ ',\ f ; S'-
*r.F c-"
A"
Equation 1 91- )' '.' 11 seda'r5
;.,;;'i''-raiIr
For a weak acid, the determination of the pH is not as
simple, because the acid does not dissociate completely when
added to water. To find the pH of a weak acid in water, the
45. Which of the following equations can be used to
determine the pOH of an aqueous weak base solution?
[HfO+] must first be determined from the weak acid
7<1pOu=loglOH-l -"t V '4'"-'\ '"ni14'
equilibrium:
HA(aq)- B. pOH =lpK6 - \og tA-l

H+(aq)+A-(aq) 22
rc-7 lpK6 - -Lloe tA-l
Initial: lHAlinitt"r 0 v22 pou=
1C?
Dissociation: - x +x +x
P. poH = t+ - (Jpru - rroe FrAl)
Equilibrium: [HA]in1si.1-x x+10-7 x
10-7 is assumed to be negligible compared to x, and

x is assumed to be negligible compared to [HA]616u1
The [H3O+],can be determined from the Ku value. The 46, If a weak acid is titrated with enough strong base so that
following is a derivation of Equation 2, used to determine the [A-] > [HA], then for the resulting compound:
pH for an aqueous solution of a weak acid.
A. [H3O+] < K2. t*ul
B. pH < pKa.
Ka = [H3o+][A-] - [H:o*]2 ... Ka x [HA] = [H:o*]2
-{ luzo+l > tA-].
tHAl FrAl
D. [HA] < [HrO+]. t.L--*'k
[H:O+]={Ku*[HA] lr
t{<
".r-,--
' pH = -log [H:O*] = -log {Ku * [tt,q] .],-' ..1
-log {ru * 1He1 = -loe{G - log{iffi r ,\tr
= - ltogKu - llog tHAl = -1pK2 - llog tHAl An-- Wttl"tr acid yields the GREATEST conjugate base
2222 & concentration when 0.010 moles HA are added to
enough water to make the final volume 100 mL?
... pH = lpKu - log IHAI
22 -,A. HF
Equation 2
B. HNO3
C. HCN
Equation 2 works only when the value of Ks is less than D;. tt3CCO2U
lHAl, and when pK6 is between 2 and 12.
42, For which of the following acid solutions does Equatiort

2 NOT work?
48. A series of0.10 M weak acid solutions, each containing
A. HCIO
a different acid are compared. What is true for the acid
B. HzCOr in the series that has the GREATEST Ku value?
@ HI
D. A. Its aqueous solution has the lowest conjugate base
H5C6CO2H
concentration.
E'-_Itr aqueous solution has the lowest pOH.
G. -Liluqueous solution has the highest [H:O+].
43. What assumption is inherent in the derivation of D . Its aqueous solution has the highest ratio of HA to
Equation 2? A-.
Ai,'[HA] < [H:O+]
,8. [H3O+] = [A-l
Y. tHal = te-l
D. [HA] < [A-]

Passage Vlll (Questions 49 - 55) 51. Which antacid gives the MOST neutralizing strength
per gram?
When the pH of the stomach drops to a value less than
2.0, the excess acidity may be reduced by consuming an A. Magnesium carbonate (84.3 grams per mole)
antacid. The role of the antacid is to neutralize the HCI in
B. Calcium carbonate (100 grams per mole)
fluid. Some common bases found in antacids are
the gastric
C. Magnesium hydroxide (58.3 grams per mole)
CaCO3, MgCO3, Mg(OH)2, and NaHCO3. Calcium D. Sodium bicarbonate (83.9 grams per mole)
carbonate, magnesium carbonate, and magnesium hydroxide
neutralize acid in a two-to-one ratio. Sodium bicarbonate
neutralizes only in a one-to-one ratio. 5 2. Which of the following compounds would cause the
The gas buildup experienced after consuming an antacid MOST damage to stomac h lining?
A.
4
is due to carbon dioxide gas, which forms in the stomach o B.O
when carbonic acid (formed upon the full protonation of
u--.
.A,Aocu.
carbonate) decomposes into water and carbon dioxide. The
principal antacid ingredients of some common, commercially @Hg
available products are listed in Table 1. @Hs
Alka-Seltzer Aspirin, NaHCO:, citric acid
Bufferin Aspirin, MgCO3, aluminum glycinate o
d
Milk of Magnesia Mg(OH)2
Rolaids Dihvdroxvaluminum sodium carbonate
C. O D. O
Tums Calcium carbonate
Table 1
Aspirin (acetylsalicylic acid) can irritate the stomach

lining. In an acidic environment, aspirin does not
deprotonate, so the molecule remains neutral and thus lipid
o+ o
soluble. As a result, aspirin is able to work its way into the
membrane of the stomach lining and then into hydrophilic
pores within the membrane. It deprotonates inside the
hydrophilic pore, causing ion levels to build up in the 53 . How many acidic protons can be neutralized pm
pocket, until osmotic prgssure forces water into the interior molecule of dihyroxyaluminum sodium carbonam
region of the membrarie, where parietal cells swell and (Al(oH)2NaCo3)?
rupture. The net effect is to eat away the stomach lining. A. I
Figure 1 shows the structure of aspirin and its ionization
8.2
equilibrium.
c. 3
Y ct13
Y cll3 D.4
o? o
o+ o
o-
+H+ 54. The K"O for the ionization
acid in water is:
A
B
.
.
much greater than 1.00.
barely greater than 1.00.
reaction of acetylsali
Figure I C. barely less than 1.00.

49. At what pH is aspirin MOST soluble in water? D. much less than 1.00.
A. 1.5
B. 3.4
c.1.4 5 5. Which of the following mixtures results in a
D. 9.2 solution?
A. 1 equiv. acetylsalicylic acid + I equiv. HCI
5 0. How many acidic sites are there in acetylsalicylic acid?
B. 2 equiv. acetylsalicylic acid + I equiv. HCI
C. 1 equiv. acetylsalicylate + 1 equiv. HCI
A. 1 D. 2 equiv. acetylsalicylate + i equiv. HCI
8.2
c. 3
D.4
-,[
Passage lX (Questions 56 - 62) 57. What is the hydronium ion concentration ([H3O+]) of
an aqueous solution with a pH value of 1.7?
Many common products used every day have acidic and
basic properties. An example is the antacid taken by many
.*. l.'7 M H3O+
r2.0 x 10-2 M H3O+
heartburn sufferers to neutralize excess stomach acid (HCl). {B:
g1 1.0 x t0-7 M H3O+
Antacids often contain hydroxide anion, carbonate anion, or
D'. 5.0 x 10-13 M H3O+
both in their salt forms. The contents of a normally
functioning stomach can reach a pH as low as 1.7 (highly
acidic) and in extreme cases can reach a pH as low as 1.0.
Because the pH scale is a log scale, a decrease of 0.7 pH units "*. tf l0 mL of an aqueous solution of a strong acid with
'r,
| '/
pH = 2.0 were mixed with 100 mL of pure water, then
represents a hydronium ion (H3O+) concentration that is the linal pH value would be: n {""*. to w L 1. | , 'rL
500Vo greater. Equation I is used to determine the pH of a
A. less than 2.0. s"l** * r"''{ v
solution.
;: ;'"L:il''10""'o r'Q' {'un"'t " *t'" ' 'i
pH = -log [H:O+] '. C. exactlY3.0. ;''' i''"i"" '"\ "
n
Equation 1 . D. greaterthan 3.0. t-1 1.. . t t:1{{ > ----
""i'-'1 :' r r J & ",..-J !
Table I lists some common household acids.
'r. ?.i '' +'- " ..-",'
Acids Formula Product

59 . How many grams of CaCO3 are needed to neutralize 50
mL of stomach acid at pH = 2.0 completely, if the
Acetic acid H3CCO2H Vinegar
following equation represents the neutralization
Ascorbic acid C6HgO6 Vitamin C
reaction?
Hypochlorous acid HC1O Bleach
CaCO3(aq) + 2 H+(aq) Caz+1aq7 + CO2(g) + H2O(1)
Acetyl salicylate H3C2OC6HaCO2H Aspirin ->
Sulfuric acid H2SOa Battery acid A. 25 mg
B. 50 mg
Table I C. 100 mg
Table2lists some common household bases. D. 1.0 grams
Bases Formula Product

Ammonia NH: Windex 6 0. Which of the following household products would NOT
Sodium Bicarbonate NaHCO3 Baking Soda undergo an acid-base reaction with Windex?
Sodium Hydroxide NaOH Drano . A. Vinegm
Sodium Lauryl sulfate HrC(CHr) Na ."B1 Aspirin
Table 2 { 9, -Dtuno
Bases when added to neutral water raise the pH
-D:'Bleach
of the
solution to a value greater than 7.0. Acids when added to
neutral water lower the pH of the solution to a value less 61. Which of the following when added to an aqueous
than 7.0. A pH of 7.0 is considered to be neutral, because solution at pH = 6.0 would NOT raise the pH of the
pure (distilled) water has an [H3O+] = 1.0 x 10-7. solution?
Acid in solution may be represented as either H3O+ or ,. '1{. Distilled water
H+, depending on the solvent. Both representations are . B. Shampoo
equivalent ways ofdescribing an acid. ...e1 xnacid
D. -Vitamin C
i,_,_--
t
5F. A hydroxide anion is formed when water loses a proton
(H+) to another water (known as autoionization). If the
t 62, How many milliliters of 0.20 M H3O+ are required to
concentration of dissociated hydroxide anion (OH-) in
distilled water is 1.0 x 10-6 M, the pH of the solution neutralize 1.68 grams of baking soda completely?
must be: i, NaHCOI(aq) + H+(aq) Na+(aq) + COz(g) + HzO(l)
->
A. 1.0, becadse [H:O*] = [OH-]. A. l0 mL
.8. 7.0, becalrse water always has a pH of 7.0. B. 25 mL
.-C._6.0, because lHfO*l = [OH-]. C. 50 mL
'D,. 8.0, becAuse the solution is rich in base (OH-). D. 100 mL
.t{.
Copyright @ by The Berkeley Review@ 27s GO ON TO THE NEXT PAGE
Passage X (Questions 63 - 70) 64. Which solution has the LOWEST pH?
The average human being produces between two and

A. Carbonated water
three liters of gastric fluid in the normal day. Gastric fluid is

B. Distilled water
C. Salt water
highly acidic (due to the presence of hydrochloric acid). It is
secreted by the mucous membrane of the stomach lining to
D. Lime water (CaO(aq))
aid in the digestion of food. The average pH of this fluid is
around 1.5. The acid concentration necessary for this pH is 65. Which of the following metals can be oxidized b,'"
0.030 M, if the acid is a strong acid. The acid in gastric fluid gastric fluid?
is strong enough and concentrated enough to dissolve
(oxidize) metals with a positive oxidation potential. A. Copper
B. Gold
The lining of the stomach includes parietal cells that are C. Silver
tightly fused to form junctions in the stomach wall. These D. Zinc
cells have a cell membrane that is permeable to neutral
molecules (such as water), but not to ions (such as Na+ and
Cl-). Hydronium ion, responsible for the acidity of the 66. Which of the following reactions is NOT catalyzed b-'
stomach, is a byproduct of metabolism. Carbon dioxide, a acid?
byproduct of metabolism, is a non-metal oxide that converts
to an oxyacid when combined with water. The hydration of
A. Hydrolysis of disaccharides
carbon dioxide (CO2) to carbonic acid (H2CO3) is shown in
B. Hydrolysis of polypeptides
C. Hydrolysis of esters
Reaction 1. Carbonic acid is a weak acid that partially
D. Hydrolysis of alkanes
dissociates into bicarbonate anion and a proton, as shown in
Reaction 2.
COz(g) + H2O(l) H2CO3(aq) 67. Which will NOT reduce the hydronium ion (H3O-
concentration in the stomach?
Reaction 1
.- A. The consumption of water

H2CO3(aq) H+(aq)+ HCO3-(aq) B. The consumption of baking soda (NaHCO3)
Reaction 2 C. The consumption of aluminum metal
D. The consumption of solid food
The proton, along with a chloride anion, is carried across
the membrane into the stomach via active transport.
Enzymes assist the migration of both the proton and chloride 6 8. What is the pH of 0.030 M HCI(aq) solution?
anion from the blood plasma into the interior of the stomach.
These ions remain in the stomach until removed, because of
A. 0.7
the impermeability of the cell membrane to ions.
B. 1.5
c. 3.0
Eating stimulates the production of the enzyme D. 7.0
responsible for active transport and thus the release of acid
into the stomach to hydrolyze food molecules. Some protons
are absorbed by the mucous lining of the stomach wall, 69 . Which of the following beverages when consumed c,:':*
resulting in small localized hemorrhages. About 30 million NOT promote the decay of the stomach lining?
cells are destroyed per hour in normal stomach activity. As a
A. Orange juice (citric acid)
result, the stomach's entire lining is regenerated roughly once
B. Lemonade (citric acid)
every 72 hours. Excess acid production increases this C. Milk (lactose)
hemorrhaging and, in the worst case scenario, an ulcer D. Coca-Cola (phosphoric acid)
T
develops.
{
6 3. What can be concluded about the following reaction? 7 0. Which of the following has the LOWEST pH?
HZCO:(aq) + NaCl(aq) a NaHCOg(aq) + HCl(aq)
A. 0.03 M HCI(aq)
A. AG > 0; requires active transport in vivo. B. 0.01 M HCI(aq)
B. AG < 0; requires active transport in vivo. C. 0.03 M H2CO3(aq)
C. AG > 0; does not require active transport in vivo. D. 0.01 M H2CO3(aq)
D. AG < 0; does not require active transport in vivo.
Copyright O by The Berkeley Review@ 276 GO ON TO THE NEXT PT

Passage Xl (Questions 71 - 76) 7 2. Calctum hydroxide is BEST described as which of the
following?
As a general rule, the solubility for basic salts (conjugate A. A strong acid
bases of weak acids) increases as the pH of the solution B. A strong base
decreases. This is to say that basic salts are more soluble in C. A weakacid
acidic solution than in neutral solution. The calcium salts D. Aweakbase
such as calcium hydroxide (found in cement), calcium
carbonate (marble), and hydroxyapatite (tooth enamel) are
perfect examples. Hydroxyapatite is Ca5@O+):OH but can 7 3, If the solubility of enamel in a 1.00 M solution of acid
also be written as 3Ca3(PO4)2' Ca(OH)2. Cavities result HA is greater than the solubility of enamel in a 1.00 M
when the hydroxyapatite dissolves away. When small solution of acid HB, which of the following
crevices are formed in teeth, acid-producing bacteria build up conclusions can be drawn concerning to the two acids?
and further dissolve away the worn region in the enamel. The A. HA when dissolved into 100 mL pure water has a
acid that dissolves the enamel is formed when aldoses higher pH than HB.
(aldehyde sugars, such as glucose) are oxidized to their B. The conjugate base of HA is a stronger base than
respective aldonic acid compounds. To reduce the dissolving the conjugate base of HB.
of the enamel, toothpaste and mouthwash containing fluoride C. HA has a higher Ka value than HB.
are recommended. The fluoride will substitute for hydroxide D. HA has a higher PKa value than HB.
in the salt to form the less soluble fluorapatite Ca5(POa)3F
(also known as 3Ca3(PO12' CaF). This lengthens the
lifetime of tooth enamel. 74. Which of the following changes will ALWAYS
increase the amount of hydroxyapatite that dissolves
The solubility product (Ksp) for calcium fluoride (CaF2) into solution?
is 3.4 x 10-11 M3, for pure calcium phosphate (Ca:(PO+)z)
is 1.4 x 16-26 tr4s, and for calcium hydroxide (Ca(OH)2) free A. Adding a strong acid to the solution
of calcium oxide is 2.3 x 10-8 M3. The lower solubility of

B. Adding a strong base to the solution
C. Increasing the pH of the solution
calcium fluoride compared to calcium hydroxide is mimicked
in the reduced solubility of fluorapatite compared to D. Lowering the amount of water in the solution by
evaporation
hydroxyapatite.
The following chart lists the molar solubility of calcium
hydroxide at varying pH along with the gram solubility per 75. An example of an aldonic acid is drawn below. With
100 mL solution at varying pH. The temperature was held which of the answer selections listed should the aldonic
constant at25'C for all values: acid share a similar pKa value?
pH Molar solubility Gram solubility

1 2.3 x 10I8 1.7 x 101e
2 2.3 x lO16 Ll x 1017 l

3 2.3 x l}ra 1.7 x 1015
1 2.3 X 106 1.1 x 107
il 2.3 x lO-2 1.7 x 10-l
t2 2.3 x l}-a 1.7 x 10-3
Table L
Table I shows that the effect of pH on the solubility of

basic salts is drastic. This is because pH is measured on a A. Acetic acid (H3CCO2H)
1og scale, while solubilities are measured on a linear scale' B. Hydrochloric acid (HCl)
C. Nitric acid (HNO3)
71. As sodium fluoride (NaF) is added to an aqueous D. Sodium carbonate (Na2CO3)
solution with undissolved hydroxyapatite in it, what
happens to the solution?
7 6. ln which of the following solutions does tooth enamel
A. The pH of the solution increases. dissolve the FASTEST?
B. The pH ofthe solution decreases. i
C. The pH of the solution remains constant at a value A. 100 mL 0.10 M HCl

greater than 7.0. B. 100 mL 0.0010 M HCI
D. The pH of the solution remains constant at a value
C. 100 mL 0.10 M HF (Ka = 6.8 x 10-a)
D' loo mL o'oolo M HF (Ka = 6'8 x 1o-a)
less than 7.0.

Passage Xll (Questions 77 - 84) 79. Which of the following compounds would creare :
solution with the LOWEST pH when added to warer?
Normal rainfall has a pH between 5.6 and 6.0, depending
on the amount of carbon dioxide in the air. Excessive A. SO2
amounts of atmospheric carbon dioxide lower the pH of rain.
B. CO2
However, even with high carbon dioxide concentration, the
C. N2O5
pH of rain does not drop much below 5.4. While rain rich in D. MgO
carbon dioxide is more acidic than normal rain. it is not
considered tobe acid rain.
80. What is the pH of 0.10 M HOCI(aq), which has a pK.
Acid rain is attributed to non-metal oxides present in the of 1.46?
air, like sulfur trioxide, and the nitrogen oxides. These non-
metal oxides combine with atmospheric moisture to form
A. 1.00
non-metal hydroxides, known as oryacids. Reaction 1 shows

B. 4.23
the hydration of sulfur trioxide, converting it from a non-

c. 6.46
metal oxide into a non-metal hydroxide.
D. 1.46
SO:(g) + H2O(g): H2SOa(g)

81. Which of the following could be a component of ac:r
Reaction 1
rain?
Sulfur oxides are common by-products produced during A. Na2O
the combustion of coal. A scrubber (a chamber at the base of B. Nz
an exhaust stack filled with high pressure steam and calcium C. NO2
oxide) can help neutralize the non-metal oxides in the D. Hz
industrial emissions of coal-burning factories. As the
exhaust passes through the chamber, steam hydrates the non-
metal oxide and converts it from an aqueous Br/nsted-Lowry 82. A11 of the following qualifications affect the acidity c,
acid into an airborne Lewis acid. Then as this non-metal an oxyacid EXCEPT:
hydroxide solution flows across the calcium oxide in the A. the oxidation state of the central atom.
scrubber, it is neutralized by being converted into calcium B. the electronegativity of the central atom.
sulfate and water. This is shown in Reaction 2. C. the size of the central atom.
+ CaO(s): D. the number of n-bonds to the central atom.
H2SO4(aq) CaSO4(s) + H2O(t)
Reaction 2
83. All of these statements about H2S04, H2S03, an:
If the large quantities of acidic industrial waste generated
their constituents are true EXCEPT:
by burning fbssil fuel are not treated in this manner, they can
produce rain with a pH as low as 4.0. Acid rain is known to A. SOr2- has a lower pK61 than SO42-.
damage bodies of water by changing the bacteria population. B. 1.0 M H2SO4(aq) has a lower pH than 1.0 \l
Acid rain damages plants by changing soil pH. Changes in H25O3(aq).
pH affect the structure ofplant enzymes needed for the uptake C. H2SOa has a higher Ku1 than H2SO3.
and transport of nutrients. The enzymes become ineffective D. H2SO3 is more electrolytic than H2SO,1.
at lower pH because of their altered structures.
7 7. What chemical reaction is indicated in Reaction 1?

84. Which sequence correctly lists the four acids shou:
beiow according to their INCREASING pK. value?
A. The neutralization of sulfur trioxide
B. The acidification of sulfur trioxide A. PKal H2SOa < PKa HNO3 < PKal HzSO: < PK'
C. The conversion of a Br@nsted-Lowry acid into a HN02
Lewis acid. B. PKaHNO3 < PKal H2SOa < PKaHNO2 < pK''
D. The conversion of a Lewis acid into a Br@nsted- H2SOj
Lowry acid. C. PKal H2SO3 < PKa HNO2 < PKal H2SOa < PK,
HNO:
D. PKa HNOz < PKal H2SO3 < PKa HNOj < PKa.
78 . A non-metal oxide can be characterized as;
H2SOa
A. amphoteric.
B. an Arrhenius base.
C. aBronsted-Lowry acid.
D. a Lewis acid.
Copyright O by The Berkeley Review@ 27a GO ON TO THE NEXT PAGE

Passage Xlll (Questions 85 - 91) 8 6. At physiological pH, which of the following amino
acids exists predominantly as a cation?
Amino acids can be classified as either diprotic or
triprotic acids, depending on their side chain. A generic
A. Arginine
amino acid is shown below in Figure 1:
B. Glutamic acid
C. Glycine
o D. Histidine
il
HrN+1
c'-zc\ o- 87. What explains the lower pKa for the side chain
12
HR
associated with cysteine
serine (R = -CHZOH)?
than the one associated with
Figure 1
A. Oxygen is less electronegative than sulfur.
B. Sulfur is less electronegative than oxygen.
The chemical structure in Figure I represents an amino C. Oxygen has a greater atomic radius than sulfur.
acid in a pH - 7 aqueous environment. At a pH less than the D. Sulfur has a greater atomic radius than oxygen.
pKu of the carboxyl terminal (pKat ), the carboxylate group is
protonated and exists in its neutral carboxylic acid form.
Similarly, at a pH greater than the pKu of the amino terminal 8 8. The carbon chain associated with aspartic acid is shorter
(pK62 or pKa3), the ammonium group is deprotonated and than the one associated with glutamic acid, which
exists in its neutral amine form. results in a:
If
the R group (side chain) of an amino acid exhibits A . stronger inductive effect, making aspartic acid's side
acid-base properties, then the amino acid is triprotic. The chain more acidic.
side chain may be deprotonated at pH = 7, depending on the B. weaker inductive effect, making aspartic acid's side
nature of the functional group. The carboxyl terminal pKu chain more acidic.
lies between 1.8 and 2.6, and the amino terminal pKu lies
C . stronger inductive effect, making aspartic acid's side
between 8.8 and 10.6 for all twenty common amino acids. chain less acidic.
The pKa for the protonated form and the pK5 for the
D. weaker inductive effect, making aspartic acid's side
deprotonated form add up to a value of 14 at25"C.
chain less acidic.
PKa @rotonated form) + PKb (deprotonated form) = 14
Equation 1
89 . At pH = 7, what are the applicable values for histidine?
The pK2 values for common side chains range from 3.9 A. PKat - 1.81; PKa2= 6.05;PK63 = 4.85
to 13.2. Table 1 lists the R group and pK2 values for seven B. PKa: = 9.15 pKb2 = 7.95; pK61 = 4.85
common triprotic amino acids. C. pKtZ = 7.95; PKa2 = 6.05; pK6 = 9.15
Amino acid Side chain group pKa D. PKa: = 9.15; pKb2 = 1.95; pKU: = 12.19
Aspartic acid -CH2CO2H 3.88
Glutamic acid -CH2CH2CO2H 4.32
Histidine -CH2C=CH-N+H=CH-NH- 6.05
90. What is the normality of 0.50 M glutamic acid in
water?
Cysteine -CH2SH 8.36
Tyrosine -CH2C6HaOH 10.07 A. 0.50 N H3N+CH(CH2CH2CO2H)CO2H(aq)
Lysine -CH2CH2CH2CH2NH3+ 10.80 B. 1.00 N H3N+CH(CH2CH2CO2H)CO2H(aq)
nine -(CHz)rNHC(NH2)=lrt[12+ 13.21 C. 1.50 N H3N+CH(CH2CH2CO2H)CO2H(aq)
D. 2.00 N H3N+CH(CH2CH2COZH)COZH(aq)
Table I
Physiological pH is considered to be 7.4, although
gastric fluids and the fluid contained in lysosomes have
91. All of the following amino acids have a neutral side
chain at pH = 7 EXCEPT:
considerably lower pH. At physiological pH, a diprotic
amino acid exists predominantly in its zwitterion form. A. cysteine.
B. histidine.
8 5. What is the relationship between the pKu and pK6 for C. lysine.
lysine? D. tyrosine.
A. PKat + pK61 = l{
B. PKat + pK62= lQ
C. PKaZ + PK62 = l{
D. pKaZ + pK63 = l{
97. A 0. 10 M solution of unknown material has a pH
Questions 92 - 100 are NOT based 4.62. It can BEST be described as a:
on a descriptive passage.
A. strong acid.
B. weak acid,
C. strong base.
D. weak base.
ot Which of the following solutions has the LOWEST
pH?
98. The HIGHEST pH is observed in which of the
A. 0.01 M HCIO (pKa = 7.5) following solutions?
B. 0.05 M HCO2H (pKa = 3.6) A. 0.10 M HNO2(aq)
C. 0.10 M HF (pKu = 3.1) B. 0.10 M HNO3(aq)
D. 1.00 M HCN (pKa = 9.1) C. 0.10 M NaNO2(aq)
D. 0.10 M NaNO3(aq)
93. Acid rain can possibly contain all of the following

compounds EXCEPT:
9 9. What is the pH of 0.050 M H3CCH2CO2H? (pKa fcr
A. oxidized non-metals. H3CCH2CO2H is 4.89)
B. hydrated non-metal oxides.
A . 1.30
C. electron pair acceptors.
D. metal hydroxides.
B. 3.10
c. 4.89
D. 9.78
9 4. Which of the following conjugate pair-mixtures has the

LOWEST pH?
100. Which pH is INCORRECT for the corresponding
A. l0 mL 0.10 M HF(aq) with 15 mL 0.10 M KF(aq) solution ?
B. l5 mL 0.10 M HF(aq) with 10 mL 0.10 M KF(aq)
C. 10 mL 0.10 M NH3(aq) with 15 mL 0.10 M A. 0.10 M HBr(aq) has pH = 1.00
NH++(aq)
B. 0.10 M HCO2H(aq) has pH = 2.32
D. 15 mL 0.10 M NH3(aq) with 10 mL 0.10 M
C. 0.10 M NaOAc(aq) has pH = 5.13
NH4+(aq)
D. 0.10 M KOH(aq) has pH = 13.00
95. Which of the following relationships applies to

phosphoric acid?
A. pKat + pK61 = l{ 1.C 2.D 3.C 4.A 5.C
B. PKaZ + pK62 = l{ 6.D 1.D 8.8 9.D 10.A
C. pKa: + pK63 = l{ 11. B 12. D 13. C 14. A 15. D
D. pKat + pKrj = l{ 16. B 17. D 18. C 19. D 20. D
21. C 22. C 23. B 24. D 25. A
26. C 21. B 28. C 29. C 30. C
34. B
96. What is the normality of a solution made by mixing
31. B
36. C
41. D
32. B
31. A
42. C
33. A
38.
43. B
C 39. C
44. C
35. B
40. C
45. C
E
50.00 mL of 1.5 M H3POa with 50.00 mL of pure $"
46. A 47. B 48. C 49. D 50. A
water?
51. C 52. C 53. D 54. D 55. D
A. 3.00 N H3POa 56. C 5',7. B 58. D 59. A 60. C
B. 2.25 N H3PO4 61. D 62. D 63. A 64. A 65. D
C. 1.50 N H3POa 66. D 61. D 68. B 69. C 70. A
D. 0.75 N H3PO4 7t. A 72. B 13. c 74. A 75. A
16. A 11. D 78. D 19. C 80. B
81. C 82. C 83. D 84. A 85. C
86. A 87. D 88. A 89. D 90. C
91. C 92. C 93. D 94. B 95. B
96. B 97. B 98. C 99. B 100. C
Copyright @ by The Berkeley Review@ THAT'S ENOUGH CHEM FOR

Acids and Bases Passage Answers
1. Choice C is correct. A quick look says that the pH should increase when the hydroxide ion concentration
increases, which eliminates choices A and B. The pH should not increase by a full 3 units. An increase by 3
units would mean 1000 times the base concentration. This implies choice C is the most intuitive choice. This
problem can be solved longhand as well. The question deals with [OH-] and pH, so some form of conversion must
occur. First, pH must be converted to pOH, using the relationship pOH = 14 - pH (14 - 8 = 6.0). Then, pOH must
be converted to [OH-], usi_ng the relationship [OH-] = tO-poH_1[OH-] = 10-6). Tripling the amount of OH- yields
a concentration of 3 x 10-6 M. The new pOH is - log (3 x 10-o;, which equals 6 - log 3, which is approximately
5.5. The new pH is equal to 74 - 5.5 = 8.5, so choice C is in fact correct.
2. Choice D is correct. The larger the value of pK6, the weaker the base. The weaker the base, the less it
undergoes hydrolysis to form hydroxide anion when added to water. This makes choice D the correct choice.
3. Choice C is correct. An Arrhenius base is defined as a base that yields OH-(aq) upon addition to water. Of the
answer selections, only choice C is basic. Choice C must be correct.
4. Choice A is correct. HCIO3 is a weak acid that can be neutralized using a base of some sort. This eliminates
both choice C and choice D. Choice B is a weak base, so it cannot fully react, eliminating choice B. Pick choice
A. For titration, 25 mL of strong base is ideal, because there are 25 mL of equimolar acid present. Although we
haven't reviewed it yet, titration is the quantitative addition of an equal mole quantity of a reactant.
5. Choice C is correct. As the conjugate acid gets stronger, the conjugate base gets weaker. The weaker the
conjugate base, the higher its pK6 value, so choice A is eliminated. The weaker the conjugate base, the stronger
the acid that is required to react with it, so choice B is eliminated. The weaker the conjugate base, the lower
the hydroxide anion concentration, so the higher the pOH and the lower the pH. This makes choice C correct.
The weaker base requires the same moles of acid as a stronger base to be neutralized, as long as they are in equal
concentration. The strength of the acid required for reaction is different for the two bases, but the moles of
hydroxide are the same from equimolar bases, regardless of their strengths.
6. Choice D is correct. The passage provided the three definitions for bases. The definitions for acids is the
opposite of that for bases. tnir rr,uuns that the Lewis definition of an acid is an electron-pair acceptor. Choice
A is thus valid. The Brsnsted-Lowry definition of an acid is a proton donor, making choice B valid. The
Arrhenius definition defines an acid as a compound that produces hydronium ion upon addition to water. This
makes choice C valid. Choice D must therefore be the best answer. A Lewis base, not a Lewis acid, is defined
as a nucleophilic molecule.
n Choice D is correct. By definition, as the strength of an acid increases, it dissociates to a greater extent when
mixed with water. This eliminates choice B. By dissociating more, the acid produces more ions, making the
solution more electrolytic. Choice A is eliminated. A stronger acid produces more hydronium ion, so Ku should
increase and pKu should decrease. This both eliminates choice C and makes choice D correct.
8. Choice B is correct. Hydrofluoric acid, HF, is a weak acid, so it partially dissociates in water. The current
would be minimal. HC1O is also a weak acid, so an HF solution has conductivity similar to an HC1O solution.
The best answer is choice B. Pick choice B, and be a happy camper.
9. Choice D is correct. Both KOH and KOAc are salts. As such, they will both completely dissociate into water,
so the ion concentration is the same in both solutions. This eliminates choice C. KOH is a strong base, while
KOAc is a weak base, so choices A and B are also eliminated. The best answer is choice D,
10. Choice A is correct. HCIO is a weak acid, so water must be acting as a base by removing a proton from
hypochlorous acid. This eliminates choices B and C. Water can be an amphoteric species, meaning it can act as
either an acid or a base, but in this reaction it acts only as a base. Choice D is eliminated. By gaining a proton
from HCIO, water is acting as a proton acceptor, making it a Brsnsted-Lowry base. Choice A is the best answer.
Copyright @ by The Berkeley Review@ 2At Section IV Detailed Explanations
11. Choice B is correct. The solution in Trial 1 shows a greater current than the solution in Trial 2, so the solution in
Trial 1 is more electrolytic than the solution in Trial 2. Electrolytic is defined as the ability of a solution to
conduct electricity. This eliminates choice D. HCI is a strong acid, while HCIO is a weak acid. As such, more
ions are present in solution during Trial 1 than during Tfial 2. This explains the greater conductivity in Trial 1
than Trial 2. Other colligative properties include boiling point elevation, freezing point depression, and
osmotic pressure. Because the solution in Trial t has more ionic impurities (and thus more total impurities), the
solution in Trial t has a higher boiling point, lower freezing point, and greater osmotic pressure. This makes
choice B the correct answer.
't2. Choice D is correct. As seen in the experiment, full dissociation leads to a current of approximately 6.0 amps.
Nitric acid is a strong acid, so choice A should generate a current of roughly 5.0 amps. Sulfuric acid has one
strong proton, so choice B should generate a current of roughly 6.0 amps. Sodium hydroxide is a highly soluble
salt, so choice C should generate a current of roughly 6.0 amps. Ammonia is a weak base with no charge, sc
addition of ammonia to water forms only a few ions. The current cannot reach 6.0 amps, so choice D is the bes:
answer.
L3. Choice C is correct. A strong base is mixed with a strong acid in Trial 3. A complete reaction occurs, leavirrs
behind potassium cation (K+) and chloride anion (Cl-). A strong base is mixed with a weak acid in Trial4. -1.
complete reaction occurs, leaving behind potassium cation (K+) and hypochlorite anion (ClO-). A complete
reaction occurs in both Trial 3 and Trial 4, because in each case a strong base has been added. This eliminates
choices A and B. Because equal amounts of strong base (KOH) are added to equal mole quantities of acid in bot}'
Trial 3 and Trial 4, both reactions go to completion, generating the same number of ions in solution. This favor,
choice C. Choice D is invalid, because cations are also in equal concentration, and cations conduct electrons.
I
14. Choice A is correct. From the relative acid strengths derived from the pK. values, HCIOa is more acidic thr
HBrO4, which in turn is more acidic than HIO4. This same trend is seen with HOCI, HOBr, and HOI. Becau-.e
Cl is more electronegative than Br which is more electronegative than I, the trend indicates that tl-..
electronegativity of the halide dictates the relative acidity of an oxyacid. This fact was also given in tL=
passage. Pick answer A, and feel what it is to be correct. Choice C applies to haloacids, not oxyacids.
15. Choice D is correct. To determine the relative strength of the oxyacids, both the number of oxygens and ti.;
electronegativity of the halide must be considered. HCIOa is a stronger acid than HIO4, because chlorine *.
more electronegative than iodine, so choices A and C are both eliminated. Choice B is eliminated, becaus:
HIOa is a stronger acid than HBrO3, due to the extra resonance structure associated with the additior.:-
oxygen. The best answer is choice D, since it follows both the decline in number of oxygens trend and r:,=
decreasing electronegativity trend.
15. Choice B is correct. For a weak acid solution with [HA]1r.,itial > Ka, use the shortcut equation to determine --
pH. The shortcut equation, pH = lrpKu - llog [HA], applies if the pK6 lies between 2 and, 1,2. The math is ::
follows:
pH = l-pKu - llog [HA] =7-g.ZAy- llog (0.10) = 3.ffi - l(-t) = 3.63+ 0.5 = 4.13
2' 2- 2 2- 2
17. Choice D is correct. The pKu2 value must be larger than the pKul value, because the first proton is more aci:u
than the second proton (by definition), and the stronger the acid, the lower its pKu value. Given that pKu- s
7.8, the value of pKu2 must be a number larger than 7.8. The only answer larger than 7.8 ts L2.9, so pick chc:,*
D, and feel satisfied that you did. The pK6 (not pKu) for the conjugate is 6.2, but the question asks for pKu2.
18. Choice C is correct. Since the dissociation reaction is exothermic, heat is given off when forming the produ;;.
Thus when heat is added to the system, it acts as an inhibitor of product formation according to Le ChAteLe: i
principle. This means that products decrease and reactants increase, as the system is heated. The r*,
(equilibrium constant) is a measure of the products over the reactants, so the value of Ku decreases with :-*
addition of heat to the system. The best answer is choice C. Choice D should be eliminated immediately.
Copyright @ by The Berkeley Review@ 242 Section IV Detailed Explanatiom

t9. Choice D is correct. We know HBrO2 is less acidic than HCIO2, since both acids have the same number of
oxygen atoms, and chlorine is more electronegative than bromine. Given that HBrO2 is the weaker acid, the
pKu for HBrO2 must be greater than 1.9 (the pKu of HCIO2), so the only answer possible is choice D.
20. Choice D is correct. Dissociation refers to the breaking of the bond between the acidic proton and the conjugate
base, so that the conjugate base and a hydronium ion are formed. The greatest dissociation is associated with
the strongest acid. This question is asking for the strongest acid. The strongest acid is the acid with the
greatest number of excess oxygens and the most electronegative central atom. This makes choice D the best
answer. This answer could also have been determined by recalling the six strong acids listed in the text. Only
choice D is one of these strong acids. A strong acid fully dissociates, while weak acids partially dissociate.
The amount of dissociation can be determined from the Ku and vice versa. For instance, a 1.0 M weak acid with
10% dissociation results in 0.90 M HA undissociated acid, and the formation of 0.10 M A- and 0.10 M H3O+. The
equilibrium constant for the dissociation reaction (Ka) is shown below:
(0.1)(0.1)
6"" = [HeO"][Al _ =0.01 =0.0111
tHAl 0.e 0.e
2-1. Choice C is correct. The volume of the solution does not affect the pH; only the concentration and strength
affect the pH. The first step is to identify the type of acid. Since HC1O4 is a strong acid, it fully dissociates,
so the major source of protons in the aqueous solution is from the dissociation of HClOa.
pH = - 1og [H3O+] - -log [HCIO+] = - log(0.10) = - (-1) = 1
This best answer is choice C.
22, Choice C is correct. The most acidic compound is the compound that most readily loses H+. In choices A, B and
D, the hydrogens are bonded to carbon. In choice C, there is a hydrogen that is bonded to nitrogen. The size
difference between atoms is significant only when the atoms are in different rows of the periodic table.
Nitrogen and carbon are in the same row of the periodic table, so they are comparable in size. When atoms are
in the same row of the periodic table, the most important factor to consider when looking at acidity is
electronegativity. Nitrogen is more electronegative than carbon, making a hydrogen on nitrogen more acidic
than a hydrogen on carbon, so choice C is the most acidic. It is a common mistake to not notice that the
hydrogens are all on carbons in choices A and B. Be careful not to make mistakes like this.
23. Choice B is correct. It can be observed from the data in Table 1 that as the number of methyl groups increases,
the pKu value increases. An increase in pKu is indicative of decreased acidity. Acids are defined as electron-
accepting, so electron-withdrawing groups increase acidity, while electron-donating groups decrease acidity.
This makes choice B correct.
l1' Choice D is correct. In haloacids (binary compounds), the acidic proton is directly bonded to a halogen, so
relative acidity can be discerned from the features of the halide. Halogens are in the same column of the
periodic table, so the important factor when considering bonding is the size of the halide. Because iodine is the
largest of the halogens, the HI bond is the weakest, so HI is the strongest haloacid. Pick choice D, and smile to
the world.
15' Choice A is correct. Sulfur and chlorine are adjacent to one another in the same row of the periodic table, so
choices B and D are eliminated. Because chlorine is smaller than sulfur, the increasing size does not correlate
with acidity. This eliminates choice C. Chlorine is more electronegative than S, so Cl draws electrons from H
more than S does. This makes HCI a stronger acid that H2S. The electronegativity predicts the acidity best
for atoms in the same row, so pick answer choice A to get this one correct.
16. Choice C is correct. Table 1 shows that thiols have lower pKu values than their corresponding alcohols, so
ethyl thiol is more acidic than ethanol. Because ethanol is a weaker acid (has a lower Ku value than ethyl
thiol), ethanol dissociates less than ethyl thiol when added to water, and ethanol yields a lower [H3O+] than
ethyl thiol. These three facts eliminate choices A, B, and D. Because ethanol is a weaker acid than ethyl
thiol, the conjugate base of ethanol (CH3CH2O-) is a stronger base than the conjugate base of ethyl thiol
(CH3CH2S-), making choice C the correct answer.
, -,pvright @ by The Berkeley Review@ 243 Section lV Detailed Explanations

27. Choice B is correct. The most electronegative atom that differs from choice to choice is chlorine. This high
degree of electron withdrawal due to chlorine results in an increase in acidity. This implies that because
chlorine is more electronegative than the other atoms, it withdraws electron density the most and thus
increases the acidity to the greatest extent. The answer of answer choices is choice B.
28. Choice C is correct. Of the answer choices, the carboxylic acid is the most acidic, because of the resonance
associated with the carbonyl bond. This eliminates choices A and B. From this point, data in Table 1 must be
analyzed. Table 1 shows that as the substitution of the thiol decreases, the acidity increases, so the priman-
thiol is more acidic than the tertiary thiol. This makes choice C the best answer.
29- Choice C is correct. The solution is acidic, so the pH is less than7.0, eliminating choice D. For a weak acic
with pKu between 2 and 72 in an aqueous solution with [HA]6itial ) Ka, use the shortcut equation to determine
the pH. If Ku is 8 x L0-8, then pKu is 8 - log 8 = 7 - 0.9 = 7.1.. The [HA] is 0.5 M, and log 0.5 = - log 2 = -0.30.
11-o.s)
RH=|RKu -llog[HA] =L1z.t!-l"S(0.50) =r.55 - =3.55 + 0.75=3.7
The value falls in the range of choice C, so the best answer is choice C.
30. Choice C is correct. Mass percent is defined as the mass of one component atom relative to the total mass of tLe
compound. In this case, we are interested in carbon within phenol. Units cancel, so we can use atomic masses,
72g,C
mass yo carbon - mass of carbon - x100% + 72%= 72 <ZZ<ZZ=g1"h
mass of molecule 94 g C6H5OH 100 94 90
The mass percent of carbon is between 72'h and 80%. Choices A and B are too small, while choice D is too largt
Only choice C,76.6"/o, falls into the range, so choice C is the best answer'
31. Choice B is correct. When an acid is titrated to its equivalence point, it has been completely converted into r:.
conjugate base. The lowest pH value after neutralization is found with the weakest conjugate base, assumi-l
that the concentrations are all equal. The weakest conjugate base corresponds with the strongest acid (that r,'
the acid with the lowest pKu). This is because the stronger the acid, the weaker its conjugate base. Using f =
data from Table 1, the acid with the lowest pKu value is choice B, trichloroacetic acid. Pick choice B please"
32. Choice B is correct. Increasing the number of impurities dissolved into an aqueous solution raises the boi-lr:
point and lowers the freezing point of a solution. The total impurity concentration depends on the solu:*
concentration, the number of particles it dissociates into, and the degree to which it dissociates. All of ---*
choices are monoprotic weak acids of equal concentration (1.0 M), so it depends only on the dissociation of ':*
acid (acid strength). Acetic acid is weaker than p-nitro benzoic acid, so choice A is eliminated. Tricloroace-r
acid is stronger than p-nitrophenol, so choice B is correct. Tricloroacetic acid is stronger than benzoic acid --:
choice C is eliminated. Acetic acid is stronger than phenol, so choice D is eliminated.
JJ. Choice A is correct. The acid with the strongest conjugate base is the weakest acid. The highest pK6 vak;
''+
associated with the weakest acid. Referring to the data in Table 1, the acid with the highest pKa is phe:.---
I
Choice A is the correct answer, since the highest pKu value indicates the weakest acid.
34. Choice B is correct. This question appears to be difficult at first glance. Flowever, if you realize that whe: m
acid dissociates, equal parts of hydronium and conjugate based are formed, then you know that [H3O+] = l-i-
All that is required is converting from pH to [H3O+], using [HaO*] = 10-PH. The pH of the solution is 3'7, sc :u
[HeO*] is 10-3'7= 190.3x 10-4. E".urrr"log 2=0.3,itistruethat100'3 =2. This*"uttthat100'3x 10-4 = 2x'-+
ffre HgO+l is2x10-4 M, and [HSO+] = [A-], so [A-] =2x10-4. The correct answer is choice B.
35. Choice B is correct. The lowest pH is found in the solution with the greatest amount of hydronium. lrte
hydronium concentration is affected by the strength and concentration of the acid. The most acidic solu:lm
results from the strongest acid in highest concentration. In this question, p-nitrophenol has a lower pKu :m
phenol, so choices C and D are eliminated. Choice B has the higher concentration of p-nitrophenol, so choi:: B
is the best answer. Pick choice B for best results and greatest test satisfaction.
Copyright @ by The Berkeley Review@ 2A4 Section IV Detailed rlf"rn
36. Choice C is correct. The solution is acidic, so the pH is less than 7.0, eliminating choices A and B. For a weak
acid with pKu between 2 and 12 in an aqueous solution with [HA]initial > Ka, use the shortcut equation to
determine the pH. The pKu of phenol is L0, and the [HA] is 1.0 M. The log of 1.0 is zero, so the pH is simply
half of the pKa. Half of ten is five, so the pH is 5.0. Choice C is the best answer.
37. Choice A is correct. A stronger electron-withdrawing group on the aromatic ring of the phenol makes the
phenol more acidic, thus decreasing its pK" value. As a result, a substituted phenol with an electron-
withdrawing $oup has a lower pKu than phenol. From the acids listed in Table 1, the acid with the lowest
pKu is p-nitrophenol. The electron-withdrawing group on p-nitrophenol is O2N-, so choice A is terrific.
38. Choice C is correct. For a monoprotic acid and its conjugate base, pKa + pKb = 14. From Table 1, the pKu value
for p-nitrophenol is 7.2. This means that pK6 for the conjugate base (p-nitrophenoxide) is 14 - 7.2 = 6.8. The
correct answer is choice C.
39. Choice C is correct. This problem is a twist on the normal approach (i.e., it's harder than typical problems).
This problem is most easily solved using the shortcut equation, pH = Ipfu - hog [HA], to solve for [HA].
2- 2-
pH= -qogtHAl ;.6.L= L3t.z1-|l"flHAl= 5.6-LrogtHAl .'.0.5=-hog[HA],solog[HA1=-1
fRKa
log [HA] = -1 .'. [HA] = 10-1 M = 0.10 M
The concentration of the acid is 0.10 M, so the next step of the solution is to determine the moles of weak acid
needed to make 100 mL of a 0.L0 M solution. To make 100 mL 0.1 M H3COC5H4OH, 0.01 moles of the acid must
be added to enough water to make 100 mL aqueous solution. The final step is to convert 0.010 moles into grams.
The molecular mass of H3COC5HaOH is 724 grams per mole, so 0.01 moles is 7.24 grams H3COC5HaOH. The
correct answer is choice C.
40. Choice C is correct. To convert from pKu to Ku, tlle relationship is.Ku = 10-PKa. The pKu of p-methylphenol is
10.4 (as given in Table 1). The K, is therefore 16-10'a = 160'6 *-10-11, when expanded into scientific hotation.
Given log2= 0.3 and log4 = lo,g2+log2= 0.3 + 0.3 = 0.6. Accordingto the anti logrelationship,100'6 = 4. This
makes the value of Ku - 4 x 10-1I. Pick choice C and be a success story in acids and bases.
4't. Choice D is correct. The addition of water dilutes the aqueous phenol solution, but it does not react with the
phenol. Using the relationship, M1V1 = M2Y2, the new molarity is found to be 0.10 M. As is becoming the
norm, this problem is most easily solved using the shortcut equation, pH = lrpKu - qog tHAl.
pH =lpXu - hog [HA] =l(rO.O) - ltog (0.10) = S.0 - l(-1) = 5.0 + 0.5 = 5.5
2' 2- 2 2- 2
The correct answer is choice D. Because the solution is acidic, choices A and B should have been immediately
ruled out.
Choice C is correct. The shortcut equation, as presented in the passage, works only for weak acids. It does NOT
work with a strong acid. The only strong acid in the choices is hydroiodic acid (HI), which you should know is
a strong acid, because HI is stronger than HCl, a common strong acid. Choice B (carbonic acid) and choice D (a
carboxylic acid) should immediately be recognized as weak acids. Pick choice C for the greatest success here.
{3. Choice B is correct. In the first step of the derivation, [H3O+] is substituted for [A-], as shown in the conversion
from [H3O+][A-] to [H3O+12. The basic assumption is that when the acid dissociates, equal amounts of H3O+
and A- are formed in solution, and the little (10-l M) H3O+ formed from water is insignificant. This makes
choice B the best answer.
{1. Choice C is correct. Regardless of the molarity of the weak acid, when the pH of the solution is 2.70, the
[HsO+] in solution is 1,0-2J M. This means that the [HaO+] is equal to something fO-s (where "something" is a
" be concluded that
value less than ten). Because [HaO*] = [A-] when a weak acid dissociates, it should [A-] =
something x 10-3, which makes choice C the best answer.
Jopyright @ by The Berkeley Review@ 245 Section IV Detailed Explanations

45. Choice C is correct. Starting from the K6 relationship for the hydrolysis of a weak base in water, the
equilibrium expression can be manipulated to yield the relationship pOH - -log {G tAl This relationship
"
can be manipulated in the same way that the pH relationship was manipulated in the passage to yield the
same type of equation as the shortcut equation, except that it's for a weak base. The logic is that the pOH
depends on the base, hence the formula contains K6 rather than Ku, and [A-] rather than [HA]. This makes
choice C the best answer. Choice A is applied in general to all basic solutions, but it is not the best answer.
Choice D may sound tempting, but that is how the pOH for a weak acid solution is found, not for a weak base
solution.
46. Choice A is correct. According to the Henderson-Hasselbalch equation, when [A-] > [HA], the pH is greater
than the pKu, because the log of the [A-] to [HA] ratio is a positive value. This eliminates choice B. If pH is
greater than the pKu, then by definition -log [HSO*] is greater than the -1og Ku, hence iog Ku is greater than
the log [HsO*] (when both sides of an inequality are multiplied by -1, the inequality sign must be reversed).
Because log Ku is greater than the log [H3O+], Ku is greater than the [H3O+], making choice A the best answer.
Choice C cannot be true, because as pH goes up, [A-] increases as [H3O+] decreases, making [A-] > [HaO+] at all
points of a reaction after the initial mixing of the weak acid into water. This eliminates choice C. Choice D
I
5,5
can be true only if [HA] = 0, which is physically impossible with the equilibrium constant favoring HA. It
should always be true that [HA] > [HaO*], which eliminates choice D. The best answer is choice A.
47. Choice B is correct. The greatest conjugate base concentration is found with acid that dissociates to the greatesi
extent. The acid that dissociates most completely is the strongest acid, which describes choice B (HNO3), the
only strong acid among the choices. This question is just another way of asking, "Which acid is stronger?"
48. Choice C is correct. As the value of Ku increases, the strength of the acid is increasing. As the acid gets
stronger, the degree of dissociation when added to water increases. This causes the conjugate base concentration
to increase, which eliminates choice A. The amount of H3O+ increases, which causes the pH to go down anc
thus the pOH to increase. This eliminates choice B and confirms that choice C is the best answer. Because tht
acid dissociates more, the amount of HA decreases and the amount of A- increases, causing the ratio of HA to A-
to decrease. This eliminates choice D.
49. Choice D is correct. Aspirin (acetylsalicylic acid) when added to water dissociates into the anionic conjuga;=
base and a proton, just like all other carboxylic acids. The dissociation obeys the laws of equilibrium, resultir.:
in an equilibrium constant known as Ka. Because it obeys the laws of equilibrium, the anion form (more wate:-
soluble form) is most abundant when the H+ (proton) is removed from solution. The lowest concentration ::
protons ([HSO*]) is found at high pH. The highest pH results in the greatest water solubility for the aspir--.
because it exists in its anionic form. This, in essence, is the common ion effect. The best answer is thus choice D
50. Choice A is correct. Acetylsalicylic acid has only one hydrogen on the carboxylic acid functional group tha: ,'
acidic. All of the other hydrogens are bonded to carbon, which does not make them acidic. The correct ans-,\:::
for the number of acidic protons is therefore only one. Choice A is the best answer.
51.. Choice C is correct. The first three choices can all neutralize two equivalents of acid, while choice D, sod:-:n
bicarbonate, can neutralize only one equivalent of acid. This means that the most neutralizing strength :e'
gram is found with the compound having the lightest molecular mass of the compounds capable of neutralu:5
two equivalents of acid. Magnesium hydroxide has the lowest molecular mass of the first three answer cho:r=*
The correct answer is therefore choice C.
52. Choice C is correct. The molecule that can cause damage to stomach lining is the acidic molecule that ior-:Et:
once within the membrane pocket of parietal cells. The only acidic compound of the choices is benzoic a:ri.
answer choice C. It is the most similar in structure to aspirin, so it is the best answer.
53. Choice D is correct. Dihydroxyaluminum sodium carbonate is composed of the dihydroxyaluminum .;:rlmr
(which loses two hydroxide substituents when hydrolyzed), sodium cation (with no basic properties il'urd,
carbonate dianion (which can neutralize two acidic protons). The net result is that the two hydroxides arr; TrnE'
carbonate can neutralize four equivalents of protons, making choice D correct. You might also consider r:
carries a +3 charge and Na carries a +1 charge, so the sum charge of the bases must be -4.
Copyright @ by The Berkeley Review@ 2a6. Section IV Detailed Explana

54. Choice D is correct. Acetylsalicylic acid is a carboxylic acid, and carboxylic acids are weak acids. Weak acids
have K" values that are less than one. The pKu for a carboxylic acid ranges from 2.0 (as seen with the carboxyl
terminal of amino acids) to 5.0 (as seen with regular alkyl chains). This results in a range for Ku of 1O-2 to 10j5,
which yields a Ku that is much less than 1.00. This vague question is best answered by choice D.
55. Choice D is correct. A buffer forms when the conjugate acid and base of a conjugate pair are present in roughly
equal molar ratio. Choices A and B should immediately be eliminated, because the mixtures are made up of
two acids, and not of an acid and base pair. Choices C and D involve a strong acid and weak base, so the correct
choice involves partial titration of the weak base. It is in choice D that an equal molar ratio of the weak base
and its conjugate acid are present. The one equivalent of HCI will convert one of the two equivalents of
acetylsalicylate into acetylsalicylic acid, while one equivalent remains as acetylsalicylate. The equal
quantity of the two components of the conjugate pair results in a buffer (with a pH equal to the pKu of the weak
acid). The best answer is choice D.
56. Choice C is correct. The first word in the question is "If", so keep that in mind. The mantra that you chant
about water having a pH of 7 does not apply in this speculative question. If the only hydroxide ion in solution
is formed when one molecule of water loses a proton to another molecule of water, then the hydroxide anion
concentration [OH-] must equal the hydronium cation concentration ([H3O+]). This is true within distilled
water. This means that if [OH-] = 1.0 x 10-6 M, then [HSO*] must also equal 1.0 x 10-6 M. The negative log of 1.0
x 10-6 is 6.0, so the pH of the water must be 6.0. The best answer is choiie C. For this hypothetiLl solutiin, pH
= 6 and pOH = 6, which means that pH + pOH = \2, not 14. This may bother your sense of what is right in ihe
world of acid and base chemistry, but keep in mind that pH + pOH = 14 applies only at 25'C. At higher
temperatures, there is more autoionization, so more hydronium and hydroxide are generated. At 37'C for
instance, pH of distilled water is 6.8, so pH + pOH = 73.6.
57. Choice B is correct. The hydronium ion concentration in solution can be.found from the pH of the solution.
Because the pH is defined as pH - -1og [$eO+J, the hydronium ion concentration can be found by manipulating
the relationship to yield [H3O+] = 10-P_H. The hydronium ion concentration in a pH = 7.7 solution is i0-1.7 M-,
which is therefore roughly equal to 10-2 M. The best answer selection is choice B.
58. Choice D is correct. The volume increases from 10 mL to 110 mL when 100 mL of distilled water is added to the
solution, so the concentration of the acid must decrease by a factor of 11. The log of 10 is equal to 1, so the log 11
is slightly greater than 1. This implies that the pH increases by just a little more than 1.0, because the [H3O+]
goes down by a factor of 11. This makes the final pH greater than 3.0. The best answer is greater than 3.0,
which is choice D. This is true only of a strong acid solution. If the solution were an aqueous weak acid, the pH
increase would not be as significant as with the strong acid.
59. Choice A is correct. The hydronium ion concentration in a pH = 2.0 solution is 1.0 x 10-2 M. There are 50 mL
present, so the moles of H+ are found by multiplying 0.010 M by 0.050 L = 5.0 x 10-4 moles H+. Only half the
moles of CaCO3 are necessary to neutralize the H+, because it is a 2 : 1 ratio of H+ to CaCO3 in the balanced
equation. This means that 2.5 x 10-4 moles CaCO3 are required to neutralize all of the hydronium ion (HSO*).
2.5 x 10-4 moles when multiplied by 100 grams p"r tt oi" yields 2.5 x 70 2 grams Ca-O3, which equals 25
milligrams. Choice A is the best possible answer you can choose in a situation like this.
50. Choice C is correct. Windex contains ammonia, which according to Table 2 is a base. An acid can react with a
base, while a base cannot react with another base. The question is thus asking: "Which of the following
compounds is not an acid?" Vinegar, aspirin, and bleach are all listed as acids in Table 1, so they all can react
with ammonia (Windex). The best answer is choice C, Drano, because Drano is a base and not an acid.
61. Choice D is correct. Raising the pH of a solution requires reducing (or diluting) the concentration of hydronium
ion (H3O+). Adding distilled water reduces the hydronium ion concentration by diluting the solution. This
makes choice A invalid. Shampoo and antacid are bases, which when added to solution, react with the H3O+
ion and thus reduce the hydronium ion concentration and raise the pH of the solution. Choices B and C are
therefore invalid. Adding an acid lowers -- not raises : the pH of the solution, so choice D (vitamin C), an
acid, is the only answer choice that will NOT increase the pH of the solution when added. Pick choice D with
a smile.
Copyright @ by The Berkeley Review@ 287 Section IV Detailed Explanations

62. Choice D is correct. 1.68 grams of baking soda is equal to 0.020 moles NaHCO3 as determined by dividing the
1.68 grams by 84 grams per mole. The equation for the reaction shows a 1:1 ratio between baking soda and the
hydronium ion for full neutralization, so 0.020 moles of H3O+ are required to reach full neutralization. The
molarity of the acid solution when multiplied by the volume of the acid solution must equal0.020 moles HgO*.
The molarity of the acid solution is given as 0.20 M, so the volume of the acid solution must be 0.10 liters, which
is 100 mL. Selecting answer choice D in a situation like this, is the best thing to do.
63. Choice A is correct. The formation of a strong acid from a weak acid and neutral salt is unfavorable.
Hydrochloric acid is stronger than carbonic acid, so the reaction as written has AG > 0. To carry this o:ut itt
aiuo, it must be coupled with some other favorable reaction. As stated in the passage, this process is active
transport. The correct answer is therefore choice A.
64. Choice A is correct. The lowest pH is associated with the most acidic solution. Both salt water and distilled
water are neutral (have a pH of 7.0), so choices B and C are eliminated. Carbon dioxide (a non-metal oxide)
when dissolved into water gets hydrated to form carbonic acid (H2CO3, a non-metal hydroxide). Calcium
oxide (a metal oxide) when dissolved into water gets hydrated to form calcium hydroxide (Ca(OH)2, a metai
hydroxide). Non-metal hydroxides are acidic and metal hydroxides are basic, so the best answer is choice A.
65. Choice D is correct. Acid is capable of oxidizing any metal with a low ionization energy. ln this question, onlr'
one answer is correct, so it is better to ask yourself which metal is most easily oxidized (or least stable't.
Relying on either trivial knowledge or experience, you know that copper, gold, and silver are relatively air-
stable, as evident by their commercial uses in wiring and currency. All three tarnish over enough time. Zinc
metal is most readily oxidized (more so than hydrogen gas even). The best answer is choice D. If you are
interested in smugglin g zinc coins across the border, it is recommended that you refrain from ingesting them to do
so. If you don't know about the relative reactivity of these metals, you just have to take a guess and move on.
66. Choice D is correct. This is really a misplaced organic chemistry question. But then agakt, the passage is on a
physiology topic, emphasizing that acidity and basicity are applicable to many areas of study. Alkanes
cannot be hydrolyzed whether an acid is present in solution or not. Disaccharides, polypeptides, and esters ar
all broken down in the stomach by acid-catalyzed hydrolysis. The best answer is choice D.
67. Choice D is correct. Consuming water dilutes all solutes (including HgO* in an acidic solution), thus tl'e
hydronium ion concentration is reduced by consuming water. Baking soda can consume some of the hydronium ic:r
by way of an acid-base reaction. Aluminum metal can be oxidized by hydronium ion, resulting in the formatia:
oi aluminum trication and hydrogen gas. Therefore, choices A, B, and C are all eliminated' Consumption c:
solid food induces the release of hydrochloric acid into the stomach. The correct answer is choice D.
I
68. Choice B is correct. This answer is taken straight from the first paragraph of the passage. 0.030 M hydronirr.
has a pH of 1.5. However, in the event you skipped reading the passage, you can solve for the pH b-;
determining the negative log of the hydronium concentration (pH = - log [H3O+]). The pH of a 0.030 M HC
solution is --log (3 ;1 1O-Z; = 2 -log3. The value is less than 2, but greater than 1. The correct answer is choice B.
69. Choice C is correct. Stomach lining is deteriorated by reacting with acid. All of the answer choices exce:(
milk contain acid, so they all promote the decay of the stomach lining. The best answer is choice C. Ti:s
question is asking for you to identify which compound is not an acid, so look for th choice that is differe:-:"
Lactose is a disaccharide composed of galactose and glucose.
70- Choice A is correct. The lowest pH results from the presence of the strongest acid in the highest mc:,r
concentration. Hydrochloric acid ii the strongest acid (stronger than carbonic acid), and 0'030 M is a hig!*
concentration than 0.010 M. The correct answer is therefore choice A.
7'1., Choice A is correct. The first question is whether the pH of the solution changes. Because fluorapatite is rm
soluble than hydroxyapatite, hydroxide anion is released as fluoride anion exchanges for the hydroxide i
hydroxyapatite. When hydroxide anion is released, the pH of the solution increases. Although the ph :r
greater thin 7.0, choice C is incorrect, because the pH does not remain constant. The best choice is A.
Copyright O by The Berkeley Review@ 2aa Section IV Detailed ExPlanatioa,

72. Choice B is correct. Calcium hydroxide when added to water yields hydroxide anion (OH-), making it basic.
This eliminates choices A and C. The question is whether it is a strong or weak base. These questiois on the
YCAT are tough, because who knows what the test-writer wants? Beiause calcium hydroxide does not fully
dissolve into water at high enough concentrations, it can be considered a weak base. However, because it reacts
with weak acids, and it does fully dissociate at low concentrations, it must be a strong base. The best answer
beyond any questioning and rational argument you can present is choice B (unless, of course, you wish to choose
D)' On some questions, like this one, there are two reasonable answers, but the writer of the question wants you
to pick just one best answer.
/3. Choice C is correct. Enamel is more soluble in the more acidic solution. Because enamel is more soluble in the
HA solution than the HB solution, the HA solution must be more acidic than the HB solution. Both the HA
and HB solutions are of equal concentration, so it must be that HA is a stronger acid than HB. This means that
if HA is dissolved into water, it has a lower pH than when HB is dissolved into water. The conjugate base of
HB is a stronger base than the conjugate base of HA. HA has a higher Ku and a lower pfu thai HB. This
eliminates choices A, B, and D. Choice C is the best choice.
74. Choice A is correct. The hydroxyapatite dissolves most readily in acidic medium, so the addition of acid
increases its solubility. Thus, the amount of hydroxyapatite that dissolves into solution increases as acid is
added to solution. Addition of base increases the pH of the solution, meaning that choices B and C are the same
answer. The MCAT presents questions like this on occasion. When they hive two identical answers worded
differently, eliminate them both. Decreasing the solvent reduces the amount of salt that has dissolved into
solution. The best answer is choice A.
75. Choice A is correct. Sodium carbonate (choice D)should be eliminated immediately, because it is a base. Of
the three remaining choices, both hydrochloric acid (choice B) and nitric acid (choice C) are strong acids. The
aldonic acid drawn is not a strong acid, so choices B and C are eliminated. The structural similarit"y because of
the CO2H grouP on both acetic acid and gluconic acid (the aldonic acid drawn) makes answer A the best choice.
/b. Choice A is correct. Tooth enamel is a basic substance, so it dissolves fastest in an acidic solution. Table 1 shows
that the solubility increases as pH decreases. This means that the most acidic solution (solution with the
lowest pH) dissolves tooth enamel the fastest. The lowest pH results from the strongest acid in the highest
concentration. The highest concentration is found in choices A and C, so choices B and D are eliminated. The
stronger of the two acids is HCl, leading us to conclude that the 0.10 M HCI solution dissolves the tooth enamel
the fastest. The best choice is answer A.
Choice D is correct. In Reaction 1, sulfur trioxide is hydrated. The addition of water (hydration) does not
change the acidic or basic nature of a compound. This eliminates choices A and B. As stated in the passage, the
hydration of a non-metal oxide (a Lewis acid) converts the compound into a non-metal hydroxide (a Broirsted-
Lowry acid). This tells us that choice C is wrong and makes choice D the best answer.
78. Choice D is correct. A non-metal oxide acts exclusively as an acidic (and not a base), so it is neither amphoteric
nor an Arrhenius base. This eliminates choices A and B. A non-metal oxide has no protons, so it cannot be a
Brsnsted-Lowry acid. This eliminates choice C. By having n-bonds, a non-metal oxide is a good electrophile,
which makes it a Lewis acid. The best answer is choice D.
79. Choice C is correct. The most acidic compound when combined with water creates the solution with the lowest
pH, although the compound's concentration has an effect on the pH of the solution as weII. Metal oxid.es are
basic, so choice D (MgO) should be eliminated. The three acids formed when choices A, B, and C are added to
water are H2SO3 (from SO2 and H2O), H2CO3 (from CO2 and H2O), and HNO3 (from N2O5 and H2O),
respectively. If you knew that nitric acid is stronger than either sulfurous acid or carbonic acid, then you could
have picked choice C. However, if you didn't know that tidbit of trivia, then you could have determ-ined their
relative strength from their oxidation states and from the electronegativities of their central atoms. Sulfur
has a +4 oxidation state in SO2 (and H2SO3), carbon has a +4 oxidation state in CO2 (and H2CO3), and
nitrogen has a +5 oxidation state in NzOS (and HNO3). Nitrogen is the most electronegative and has the
highest oxidation state. The nitrogen-based oxyacid has the greatest propensity to gain an electron pair,
making HNO3 the most acidic. Pick choice C.
Copyright O by The Berkeley Review@ 289 Section IV Detailed Explanations

80. Choice B is correct. The solution is acidic, so the pH is less than 7.0, eliminating choice D- For a rveak acid
with pKn between 2 and, 12 in an aqueous solution with [HA]6itia1 ) Ka, use the shortcut equation to determine
the pH. The pKu is7.46 and the [HA] is 0.10 M.
pH = l, pKu - ltog [HA] = L1z .+e7 - (0. 10) = 9.7 s - \-1) = 3.73 + 0.50 = 4.23
ZL l"r
The best answer is choice B. Choice A can be eliminated, acid. A 0.10 M strong acid
because HCIO is a weak
has a pH of 1.0. An equimolar weak acid, because it dissociates less than a strong acid, would have a pH
greatei than 1.0. Choice C can be eliminated, because the pH is less than the pKu.
Choice C is correct. This is a freebie question, if you read the passage carefully. Non-metal oxides are found
in
81.
acid rain, particularly the oxides of sutfur and nitrogen. Choice A is eliminated, because it is a metal oxide'
making it is basic, not acidic. Choice B should be eliminated, because nitrogen is present in the air all the time
and can be found in all rain, not just acid rain. Choice D is eliminated, because it is neither acidic nor
veff
abundant in our atmosphere. This means that the correct answer is choice C'
82. Choice C is correct. As the oxidation state of the central atom in an oxyacid increases, the compound becomes
This
more acidic. This is because the number of n-bonds between oxygen atoms and the central atom increases.
increase in n-bonds results in more electron withdrawal (by way of resonance) from the central atom, making il
the
electron-poor. The compound therefore becomes more acidic. This means that both the oxidation state and
number of n-bonds to the central atom affect the acidity of the oxyacid, so choices A and D are eliminated' As
the electronegativity of the central atom in an oxyacid increases, the compound becomes more acidic. This i5
because of the inductive effect. The increase in electron withdrawal from the central atom, due to the inductire
effect, makes the central atom electron-poor. This means that the electronegativity of the central atom affects
the acidity of the oxyacid, so choice B is eliminated. The size of the central atom has no bearing on the aciditr
of the oxyacid, because the acidic proton is not directly bonded to the central atom. This makes choice C *re
best answer.
83. Choice D is correct. Because H2SOa has more oxygen atoms than H2SO3, it is more acidic. The more acidir
lo$-er
compound has a lower pKu, afrigher Ku, a weakei ionjugate base (with a higher pK5), and generates a
pH i,1 water. This makes choices A, B, and C valid stitements. The fact that H2SOa is more acidic thmr
H2SO3 means that H2SOa dissociates more when added to water, resulting in a higher ion concentration,
and'
D fo
tf,us a'nigner cond,rc-tivity. H2SO4 is more electrolytic (has higher conductivity) than H2SO3, so choice
an invalid statement, which makes it the correct answer.
Choice A is correct. The stronger the acid, the lower its pK6 value, so the lowest pKu is found with
I
84.
strongest acid. Having more oxygen atoms on an oxyacid increases its acidity, so HNO2 and H2SO3 cannot
whi
the niost acidic compJunds. This eliminates choices C and D. Sulfuric acid is stronger than nitric- acid,
you can determine fiom their oxidation states (S is +6 is H2SO4, while N is +5 in HNO3). This makes choice
the best answer.
85. Choice C is correct. Lysine is a triprotic acid. The first proton released (from the carboxyl
pair p
corresponds to the third proton gained by the conjugate base. This means that from a conjugate
so we next consider
the pti"-to-pK6 relationship is: iKul + pkue = r+. itris is not one of the answer choices,
corresponds to the second prc
,""o.alrotonln lysine. ti'," ,".ond protorireleased (from the amino terminal) +
gained. This means that from a conjugate pair perspective, the pKu-to-pK6 relationship is: pKs2 9KVZ---
and pKb'
This makes choice C the correct answer] buito finish our discussion of the correlation between pKu
must consider the third proton. The third proton released (from the side chain) corresponds to the
first proto
gained. This means that from a conjugate pair perspective, the pKu-to-pK6 relationship is: pK63 + pK61 = ld"
terminal is deprotonated (pH > pK.u (carboxyllerrr

86. Choice A is correct. At physiological "At pH, the carboxyl
so it carries a negative physiological pH, the amino terminal is protonated (pH < PKa (
"nutg". the amino acid to be a cation, the side chain must carrl
terminal)), so it cairies a positi-ve charge.--In order for
positive charge. Arginine has a sid"e chain pKu of 13,'21'., so pH'PKq: Thilmel:s,1111,'n:j^t:::i.T
charge. choice-A is the best unr*"i.. Choice B is eliminatedll"-..11t",^t:.*
;;;;;;;rJ,lJit ."rti"r u fositivebecausJ
anion. Choice C is eliminated, the side chain cannot carry a charge. Choice D is eliminated, becan
histidine is d.eprotonated (pH > PKu (side chain)), so it carries no charge'
Copyright @ by The Berkeley Review@ 29o. Section IV Detailed Ex
87. Choice D is correct. The difference between the side chains of serine and cysteine is that serine has an alcohol
group (O-H), while cysteine has a thiol group (S-H). This means that the difference in acidity lies in the
difference between oxygen and sulfur. Choices A and C are eliminated immediately, because we know from
their relative positions in the periodic table that oxygen has a smaller atomic radius and is more
electronegative than sulfur. When comparing the acidity of protons bonded to different atoms that occupy the
same column of the periodic table, we find that the most significant factor influencing the acidity is atomic
radius. The best answer is choice D.
88. Choice A is correct. Based on the pKu values in Table 1, aspartic acid (with a side chain pKu of 3.88) is more
acidic than glutamic acid (with a side chain pKu of 4.32). This eliminates choice C and D. A shorter chain
results in the electron-withdrawing NHg* group's being closer to the side chain carboxylic acid group, which
increases the acidity of the carboxylic acid group. This makes choice A the best answer.
89. Choice D is correct. According to Table 1 in the passage, the pK" values for histidine are: pKul between 1.8 and
2.6, pKa2 = 6.05, and pKu3 between 8.8 and 10.6. At a pH of 7.0, the carboxyl terminal and the side chain are
deprotonated, while the amino terminal is protonated. This is because pKa3 > pH > pKaZ > pKa1. Since the
carboxyl terminal is deprotonated, we consider pK53 rather than pKu1. Since the side chain is deprotonated,
we consider pK62 rather than pKn2. And since the amino terminal is protonated, we consider pKu3 rather than
pK61. This means that the pK values of interest are pK"3, pK62, and pK63, making choice D the best answer.
90. Choice C is correct. Normality is defined as the moles of equivalents per liter. Because glutamic acid is
triprotic, it yields three acidic protons per molecule. For each mole of glutamic acid, three moles of acidic
protons can be generated. The normality in this case is the molarity multiplied by a factor of three (N = M x 3).
The molarity is 0.50, so the normality is 1.50. The best answer is choice C.
91. Choice C is correct. Cysteine is neutral when protonated. The side chain pKu for cysteine is 8.36, so at pH = 7.0,
pH < pKu. Under such conditions, the side chain of cysteine is protonated, and thus neutral. Choice A is
eliminated. Histidine is neutral when deprotonated. The side chain pKu for histidine is 6.05, so at pH = 7.0,
pH > pKu. Under such conditions, the side chain of histidine is deprotonated, and thus neutral. Choice B is
eliminated. Tyrosine is neutral when protonated. The side chain pKu for tyrosine is \0.07, so at pH = 7.0, pH <
pKu. Under such conditions, the side chain of tyrosine is protonated, and thus neutral. Choice D is eliminated.
Lysine is neutral when deprotonated (as is the case with the three basic amino acids). The side chain pKu for
lysine is 10.80, so at pH = 7 .0, pH < pKa. Under such conditions, the side chain of lysine is protonated, and thus
cationic. Choice C is the best answer, because the side chain is charged.
q) Choice C is correct. The lowest pH is associated with the solution with the greatest hydronium concentration.
The greatest hydronium concentration depends on the concentration and the strength of the acid. To lower pH,
the concentration of an acid may be increased, or a stronger acid, with a lower pKu value, may be employed.
This means that the correct answer is a combination of lowest pKu and greatest concentration. Choice A gets
eliminated for having the lowest concentration and a high pKu value. Choice B gets eliminated, because it has
a lower concentration and greater pKu than choice C. The pH in choice C is half of the pKu + 0.5, which is 1.65
+ 0.5 = 2.15. The pH in choice D is half of the pKu, which is 4.55. Choice C has the lowest pH.
93. Choice D is correct. Acid rain is contains airborne Lewis acids. Non-metal oxides such as sulfur oxides and
nitrogen oxides make up most of the acid rain we study. This means that choice A is an example of acid rain.
Once these non-metal oxides react with moisture in the air, they become hydrated, so acid rain does contain
hydrated non-metal oxides (also known as non-metal hydroxides). A Lewis acid is an electron-pair acceptor,
and non-metal oxides qualify in this category. Choice C is a valid description of an acid rain component. Metal
hydroxides are basic, so they are not found in acid rain. Choice D is the best answer.
94. Choice B is correct. The pH of a conjugate pair is found using the Henderson-Hasselbalch equation. The lowest
pH is attributed to the conjugate pair having the acid with the lowest pKu and the mixture that most favors
conjugate acid. The pKu of ammonium is 9.26 (although you really just need to know it's between 9 and 11),
while the pKu of hydrofluoric acid is 3.17. This eliminates choices C and D. Choice B has more acid than
base, while choice A has more base than acid. The best answer is choice B.
Copyright @ by The Berkeley Review@ 29t Section IV Detailed Explanations

95. Choice B is correct. For a conjugate pair at 25'C, the pKu of the acid when added to the pK6 of its conjugate
base is equal to 14. This question boils down to which of choices represents a conjugate apair. Choice D can be
eliminated immediately, because both values are pKu values, and if they happen to sum to 14, it's purelr-
coincidental. Phosphoric acid is triprotic, so there are three pKu values. The first proton oTf (pK21)
corresponds to the third proton back on (pKUe), so pK^1 + pKOg = 14. The second proton off (pKu2) corresponds to
the second proton back on (pKfd, so pKu2 + pKUz = 14, making choice B the correct answer. The third proton off
(pKas) corresponds to the first proton back on (pKUr), so pKu3 + pK61 = l{.
H3Poa(aq) + H2o(t) H3o+(aq) + HzPo+-(aq)

#
First proton offlThird proton on .'. pK61 + pK63 = l{
PKaz -
H2POa-(aq) + H2O(1) H3O+(aq) + IlrLJ4'
n3L/'(aq) HPOa2-(aq)
-pKb,
Second proton offl Second proton on .'. pKu2 +pI<b2=14
HPOa2-(aq) + H2O(l) H3o+(aq) + Po43-(aq)

#
Third proton offlFirst proton o4 ;. pKu3 + pKbl = 14
96. Choice B is correct. 1.5 M H3POa = 4.5 N H3PO4, because there are 3 equivalents of H+ per H3PO4. The
normality is found by multiplying the molarity by the number of equivalents. Doubling the volume by adding
pure water cuts the concentration (measured in either normality or molarity) in half. This makes normality one
half of 4.5 N, so choice 8,2.25 N, is the best answer.
97. Choice B is correct. Because the pH is less than seven, the solution must contain an acid rather than a base.
This eliminates choices C and D. If the acid were a,strong acid, it would fully dissociate in water. This would
lead to a hydronium concentration of 0.10 M, which would make the pH = 1. Given that the pH is greater thart
1.0, the acid does not fully dissociate, so it is a weak acid. This eliminates choice A and makes choice B the
best answer.
98. Choice C is correct. The highest pH is found in the solution with the highest concentration of hydroxide.
Hydroxide concentration depends on the compound and its concentration. Choice A is a weak acid, so the pH is
low. This eliminates choice A. Choice B is a strong acid, so pH is very low. This eliminates choice B. Choice
C is the conjugate base of a weak acid, so it is a weak base. Choice C could be the correct answer. Choice D is
the conjugate base of a strong acid, so it is a very weak base, meaning it has no significant impact on the pH ot
the aqueous solution. Because the pH of choice D is7.0, choice D is eliminated. The best answer is choice C.
99. Choice B is correct. The solution is acidic, so the pH is less than 7.0, eliminating choice D. The acid is weak, so
it partially dissociates in water. If the acid were strong, it would fully dissociate, leading to a hydroniurn
concentration of 0.050 M and thus a pH of 1.30. Carboxylic acids are weak acids, so the pH is higher than 1.3
This eliminates choice A. The pH is less than the pKu, so choice C is eliminated. The only choice remaining is
choice B. If you choose to do so, you can solve for the pH exactly. For a weak acid with pKu between 2 and 12 in
an aqueous solution with [HA]6itial > Ka, use the shortcut equation to determine the pH. The pKu is 4.89. The
[HA] is 0.05 M, and log0.05 = - log20 = - (log 10 + log3) = - (1 + 0.3) = -1.3.
pH = lpK, - llog [HA] = 1 - ltog (0.050) = 2.45 - lf-t.Sl = 2.45 + 0.65 = 3.10
'2'-222-2 1+.AO;
The value confirms that choice B is the best answer.
100. Choice C is correct. Hydrobromic acid (HBr) is a strong acid, so a 0.10 M solution has a pH of 1.00. Choice A 1s
valid and thus eliminated. Formic acid (HCO2H) is a weak acid, so it does not fully dissociate. It has a pH
greater than 1.0 but less than 7.0. Choice B could be valid, so it is unlikely. To eliminate it with certainty, rr-e
need to do a calculation. We shall hold off on calculating until we have evaluated the other answers. Sodiurn
acetate (NaOAc) is a weak base, so it does not fully hydrolyze. It has a pH greater than 7.0 but less than 13-f .
Choice C is invalid, so it is the best answer. Potassium hydroxide (KOH) is a strong base, so a 0.10 M solution
has a pH of 13.00. Choice D is valid and thus eliminated.
Copyright @ by The Berkeley Review@ 292 Section IV Detailed Explanations

Buffers
Section V a) Buffer Compositiotr . ,

b) pH Range for Buffers
c) Buffer Recipe
:
.
d) Physiological Buffers
Buffers and Titration Curves
.
Titration a) Quantitative Keactions,

b) Fundamental Curve Shapes
by Todd Bennett c) Plotting a Titration Curve
d) Concentration Dffects
e) Strength Effects
f) Polyprotic Acids
Indicators
a) Composition and Function
b) Detecting the Equivalence Point
c) f,stimating Solution pll
o-5
Equivalents O,lO M KOH added
Specializing in MCAT Preparation

uffers & Titration Section Goals
Know how to a te the of a solution usi a titration cury.
By knowing the relative mole quantities of what has been mixed in solution, a pH value can be
estimated from the position on d titration curve corresponding to the mjxture. Tlis requires being
able to identify the Shape of a titration curve based on ihe com'ponents in the mixture.
Understand how polyprotic acids affect the plt of a solution.

Polyprotic acids have multiple
subset of-polyprotic acids. 'Be able to determine the pH at middle
Know that amino acids aie a"q.tiuul"
equivalents points by applying the eqriatibh for pl (averaging the two respective'pKs values).
Know the all titration curves.

On titration curves associated with strong reagents, the pH at equivalence is always equal to 7.0.
On titration curves associated with a weal a-cid orweakbase, titiated by,g strong r'eage'nt, tne pH
at the half-titrated point is equal to the pK2 of the weak acid. fhe ig ul ;;;'b;
approximated by averaging the pKa of the weak acid and the pH of the titrant. "qiiuuftn.;
Know the role of an indicator in titration and solution

An indicator is used to make the endpoint of the titration visible. An indicator is a species thai has
a different color for the conjugate acid and conjugate base. l\4ost indicators ut" o.gurii. .ornpo.rtrai
with
wlrn a_great degree of
a grear oegree conlugatlon/ and the
or -conjugation, color ls caused
tne colbr"is caused by
bv a transition
t from th"e ru level tb the n*
level. Indicators can also be used to predict the pH of a soluiion.
Know how and buffers work.

A buffer is formed when a weak acid and its conjugate base are added to the aqueout roi"ti"tt
Because there exists an equilibrium between the
lwg Jpecies, as long as both are prdsent in solution,
the hydronium_ion
tne concentration will
nyclromum-lon concentratlon wrll remain
remarn tatrly
fairly'constant, pil will also remain
the"refore the pH
constant, therefore
constant. The effect is know-n as."buffering." You mu"st understand buffers andhow the pH is found
from the Henderson-Hasselbalch equatioh.
I
'v and be able to titration curves for titration.

You must be able to identify the titrant and the species being titrated when you look at the titration
curve. Features to note are the weak acid lip, the'strong acid-sigmoidal shap'e, the ascent (associated
with the titration of an acid by a base) or di:scent (asso"ciated #lth tne titraiion of a base bv an acid)
of the_ curve, and the numberbf inflection points (indicative of whether the compound is
or polybasic).
folyproti6
T
{ll'
:'m
J![
ur
mr
m
fil
General Chemistry Buffers and fitration Introduction
A buffer is a solution where pH remains relatively constant after the addition of

either strong acid or strong base. The pH may vary slightly, but for all intents
and purposes, it does not change significantly. Buffers play a major role in
physiology and biochemistry, so understanding how they work is critical. They
can be made in one of two ways. The first method involves combining a
conjugate pair in roughly equal mole portions. The second method involves
partially titrating a weak acid with roughly half of an equivalent of strong base,
or by partially titrating a weak conjugate base with roughly half of an equivalent
of strong acid. The pH of a buffered solution is determined using the
Henderson-Hasselbalch equation. The data associated with buffers are generally
easy to work with in a conceptual sense. Titration curves have buffering regions,
so understanding buffers can help you to understand titration better.
Neutralization is the mixing of equal mole portions of an acid with a base,

regardless of their concentrations and strengths. To neutralize an acid, an equal
mole quantity of base must be added to solution. To neutralize a base, an equal
mole quantity of acid must be added to solution. A neutralized solution has
moles HgO* equal to moles OH-. Addition of a base to an acid (or acid to a base)
yields water and a salt upon neutralization. This is shown in Reaction 5.1:
HX(aq) + MOH(I) ===- HzO(i) + MX(aq)
Reaction 5.1
Depending on the strength of the acid and base, the pH at the neutralization
point (also referred to as the endpoint and the equivalence point in titration)
varies. Neutralization does not mean to make the pH of the solution equal to
7. When the base is stronger than the acid, the neutralized solution is slightly
basic, so the pH is greater than 7.0. When the base is weaker than the acid, the
neutralized solution is slightly acidic, so the pH is lower than 7.0. When the base
and acid are equally strong, the neutralized solution is neutral, so the pH is equal
to7.0. The three possible combinations are summarized below.
HX(aq)+MOH(I)-H2O(l) +MX(aq)
Strong acid + Strongbase PHat equivalence = 7'0
Strong acid + Weak base PHat equiva]".,." < 7'0
Weak acid + Strong base pHat equival"r,." ) 7.0
The pH is not alzaays 7 at the equioalence point of a titration. For a weak acid
titrated by a strong bnse, the equiaalence point is the point at which it is completely
conaerted into its conjugate base. The conjugate base will yield a pH greater than 7
so the pH is greater thsn 7 at the equiaalence point.
The last section in this chapter involves detecting the equivalence point. Visual
indicators that change color upon changing pH are a typical component of any
general chemistry curriculum. They are often highly conjugate organic
molecules. The color associated with an indicator is a reflective color, resulting
from the absorbance of a photon accompanied by the excitation of an electron
from a n-bonding molecular orbital to a ru-antibonding molecular orbital. The
transition energy changes when the compound gets deprotonated, so the energy
of the photon absorbed, and ultimately the color of light reflected also changes.
Hence, any pH-sensitive chromophore is an indicator.

General Chemistry Buffers and Titration Buffers
Buffers '
Buffer Composition
Buffers are solutions that resist drastic changes in pH. Buffers are made of a
roughly equal mole mixture of a weak acid and its weak conjugate base in an
aqueous solution. Both the acid and the base of the conjugate pair must be weak
in order to form a buffer solution. This is so that the equilibrium between the
two species can be controlled by the environment. With approximately equal
molar quantities of conjugate acid and conjugate base in solution, the solution is
resistant to pH change caused by the addition of either strong acid or strong base
to solution. When both of the species in the conjugate pair are weak, the buffer
can equilibrate in both the forward and reverse directions of the reaction to
absorb any hydronium or hydroxide that may be added to solution. Addition of
a strong acid to solution converts the weak base into its conjugate acid. This has
little to no effect on the pH. Likewise, addition of a strong base to the solution
converts the weak acid into its conjugate base and has little to no effect on the
pH.
To emphasize the need for roughly equal portions, the following experiment may
be studied. In this study, three mixtures of acid and conjugate base are
generated. In the first system, weak acid is in extreme excess relative to its
conjugate base. In the second system, the two species are in roughly equal
concentrations. In the third system, weak base is in extreme excess relative to its
conjugate acid. The results are shown in Figure 5-1.
System I: Mix 999 pafts HA with l part A-. To this mixture, add 1 part OH-.
Initiallv: [A-] = t = after addition of 1 oart ott-' [A-] - z
' [HA] 999 ' [HA] 998
Because Ka = [H+]* ++, and K3 is a constant, when -[A J- aorUtes, [H+]
tHAl IHAI
must be cut in half, and the pH changes. System I is NOT a buffer.
System II: Mix 500 parts HA with 500 part A-. To this mixture, add 1 part OH-.
Initially:
'
[A-] l part ott-' [A-l -sor
=soo -+afteraddition of
tHAl s00 [HAl 4ee
Because K6 = [H+] g+, and K3- is a constant, when 1{ 6ur"1y changes,
" tHAl [HA]
[H+] is constant, and the pH doesn't change. System II is a buffer.
System III: Mix 2 parts HA with 998 part A-. To this mixture , add 7 part OH-.
tnitially: lA-l l part o"-' IA-] -ggg

' [HA]=sga 2 =afteradditionof ' IHAI 1
Because Ka = [H+]* el, and K3 is a constant, when i{l aorutes, [H+]

tHAl [HA]
must be cut in half, and the pH changes. System IIi is NOT a buffer.
Figure 5-1
The conclusion is that the pH remains constant only if the weak acid and its
conjugate base are in roughly equal concentration. The addition of strong base or
strong acid shifts the ratio of weak acid (HA) to its conjugate base (A-), but the
pH does not change, if the A- : HA ratio is close to 1.0.
Copyright Oby The Berkeley Review 296 The Berkeley Revier'r'

pH Range for Buffers

The experiment in Figure 1 explains why the weak acid and weak conjugate base
must be present in roughly equal parts. If they are not relatively close in mole
quantity, then the system does not act as a buffer. According to convention, the
ratio can not exceed 10 : 1. Substituting 10 : 1 and 1 : 10 into the Henderson-
Hasselbalch equation shows us that the range of a buffer is the pKa of the weak
acid + 1. The pH of a buffer solution obeys the Henderson-Hasselbalch equation,
which is shown in Figure 5-2.
pH = pKu + togJ4 I .'.pH

r = IpKa + ro* Yolslg*gqt"
uu:g
" [H,ql Moles conjugate acid
Lowest pH =pKa + logl- =pK3 - I Highest pH =pKa + Iog10 =pK6 + 1
.'. PH range = PKu + 1
Figure 5-2
The derivation of the Henderson-Hasselbalch equation from the Ka equation is

on page 264. The Henderson-Hasselbalch equation shows that as [conjugate
base] increases, buffer pH increases. The Henderson-Hasselbalch equation also
shows that as [conjugate acid] increases, buffer pH decreases. It also offers
quantifiable verification of the concept that when pH is greater than the pKu, the
solution is rich in conjugate base.
Example 5.1
If water is added to buffer solution with pH = 3.96, what happens to the pH?
a
A. The pH increases slightly.
B. The pH decreases slightly.
C. The pH remains the same.
D. If the pH is greater than 7, then it decreases. If the pH is less than7, then it
increases.
Solution
Addition of water to a buffer equally dilutes the concentration of the weak acid
and its weak conjugate base. This means that the mole ratio of the weak base to
the weak acid does not change upon the addition of water. According to the
Henderson-Hasselbalch equation, the pH of the solution does not change because
pK3 is constant and the fraction has not changed. The result is that the pH of a
buffer does not change when it is diluted. This is why the Henderson-
Hasselbalch equation can be written as moles A- over moles HA, as well as [A-]
over [HA].
Knowing the buffer range is important when making a buffer, which is

accomplished in two steps. First, an acid within the range must be chosen. The
pKn of the acid should be as close as possible to the desired pH. Second, a
mixture containing both weak acid (HA) and its weak conjugate base (A-) should
be formed so that the two species are in roughly equal concentration. Select an
acid for the buffer whose pKa value lies within the +1 range of the desired pH.
For buffering at pH values between 2 and 5, carboxylic acids are typical. For
buffering at pH values between 8 and 11, amines are typical.

Buffer Recipes
Buffers can be made either by mixing the conjugate pair together, or by partially
titrating either component in a conjugate pair of weak reagents. The partial
titration method can be either to half-titrate the weak acid with strong base, or to
half-titrate the weak conjugate base with strong acid. First, a weak acid must be
chosen with a pKz value close to the desired pH. Buffers can be mixed by any of
the methods shown in Figure 5-3.
1. Weak acid + the salt of the conjugate base in roughly equal mole
proportions (e.g., HCO2H with HCO2Na)
2. Weak base + the salt of the conjugate acid in roughly equal mole
proportions (e.g., NH3 with NHaCI)
J. Weak acid and roughly half of an equivalent of strong base (e.g.,
HOAc with half equivalent KOH)
4. Weak base and roughly half of an equivalent of strong acid (e.g.,
H3CNH2 with half equivalent HCI)
Figure 5-3
When using either of the last two methods, titration takes place until the desired
pH is achieved within the buffering region. The buffering region (where the pH
does not change appreciably) is found in the middle area of the titration curve,
between the starting point and the equivalence point. Buffering occurs only with
the titration of a weak reagent by a strong reagent. A strong acid combined with
its conjugate base or a strong base combined with its conjugate acid do not
produce a buffer, so strong acid and strong base titration curves have no
buffering region.
Example 5.2
Which of the following solutions results in a buffer with a pH of 5.0, given that
HA has apKu of 4.7?
' *-l'<;-"
A. HA with one-half equivalent of A- Fr-
B. A- with one equivalent of HA
C. HA with one-third equivalent of OH- ,\
D- :A- with one-third equivalent of H3O+
Solution
The pH is greater than the pKu, so the solution must be rich in the deprotonatec
species. In choice A, [HA] > [A-], so the pH is less than pKu (4.7), meaning tha:
choice A can be eliminated. In choice B, [HA] = [A-], so the pH equals pKu (4.7,
meaning that choice B can be eliminated. [n choice C, one-third of an equivaleni
of A- forms from the reaction, and two-thirds of an equivalent of HA is left over,
In choice C, [HA] > [A-], so the pH is less than pKu (4.7), meaning that choice C
can be eliminated. In choice D, one-third of an equivalent of HA forms from the
reaction, and two-thirds of an equivalent of A- is left over. In choice D, [HA] <
[A-], so the pH is greater than pKu (4.7). Choice D is the best option for those
who like to pick the correct answer. To solve for the exact numerical value, the
Henderson-Hasselbalch equation must be employed, The values differ by 0.3
and the antilog of 0.3 is 2, so the correct answer must form a 2 '. 7 ratio a-
conjugate base to acid.
Copyright @ by The Berkeley Review 294 The Berkeley Revienr"

Example 5.3
\Vhich of the following combinations, when mixed in the correct ratio, produce a
buffer?
xiNuou/Nuct :,., t!
B. NaNO3/HNO3
C Hct/xot-l ' \'
D.:NHg/HCl , ':'
Solution
Choice A is a strong base and a neutral salt, which does not make a buffer.
Choice B is a neutral salt and a strong acid, which does not make a buffer.
Choice C is a strong acid and a strong base, which also does not make a buffer.
By elimination, choice D is correct. To be a buffer, the weak base (NH3) must be
half-titrated by the stlong acid (HCl). Ammonia and hydrochloric acid make a
buffer when mixed in the correct ratio (2 : 1)'
Example 5.4
\\4rich of the following does NOT form a buffer when added to NaHCO3(s)?
A. NaOH(aq)
B. HCI(aq)
C. H2CO3(aq)
D. H2o(l)
Solution
Adding half of an equivalent of NaOH to a sodium bicarbonate solution converts
half oflhe HCO3- to its conjugate base CO32-. The mixture of the two forms a
buffer, so choice A is correct. Adding half of an equivalent of HCI to a sodium
bicarbonate solution converts half of the HCO3- to its conjugate acid H2CO3. The
mixture of the two forms a buffer, so choice B is correct. Adding an equivalent of
H2CO3 to a sodium bicarbonate solution results in equal portions of the HCO3-
and its conjugate acid H2CO3. The mixture of the two forms abuffer, so choice C
is correct. Adding water does not make a buffer, because water is amphoteric, so
it does not convert sodium bicarbonate to either its conjugate acid or conjugate
base. To be a buffer, there must be both a weak acid and its weak conjugate base
present in solution at the same time. This means that choice D is correct.
Example 5.5
If the iatio of base to acid in a conjugate pair is 3:1, and the weak acid has d Ka =
1.0 x 10-5, what can be said about the pH of the buffer solution?
A" pH<5
B. pH=S ( 1:" t';
iCt' 5<pH<7
's. PF{>7
Solution
If the ratio of base to acid were 1:1, the pH would equal the pKu. Becauss the
base is in excess, the pH is greater than the pKa. The pKu is -1og 1.0 x 10-5 = 5.
This eliminates choiies A and B. According to the Henderson-Hasselbalch
equation, the pH is log 3 greater than the pKu. Log 10 = 1, and log 10 is greater
than log 3, so pH (= pKu + log 3) < 6. The best choice is C'
Copyright @ by The Berkeley Review 299 Exclusive MCAT PreParation

u{-\.-'r. -
.l
,'{ d-- -.' ,-) Example 5.6

r'\
If of a weak acid in 1.0 liters of water are treated with 0.4 moles of
1.0 moles
r it"'e' what is the pH of the solution? (Ku for the weak acid is 2.0 x 10-4)
?'- 2lrengrbase,
(a, -pfi <e.z
B. pH=3.7 f'+-'
C. 3.7 <pH <7 -
't(l
D. pH>-7 ,:''i
Solution
If the ratio of base to acid,were 1:1, the pH would equal the pKu. The pKu is - log
2.0 x L0-4 = 4 - 1og2 = 4 - 0.2 = 3.7,as hinted at by ttre unr*", cfioices. To be half-
titrated, it would require 0.5 moles o{ strong base. At the half-titration point, the
tH = pKu. with only 0.4 moles of base, the halfway point is not yet reached and
there is excess weak acid relative to conjugate base (0.6 moles to 0.4 moles).
According to the Henderson-Hasselbalch equation, the pH is less than the pKu.
The best answer is choice A. The pH is less than pKu,
-hl.h is 3.7. Be aware that
this question could about the [H+] as well as the pH of the solution. If a solution
is half-titrated, then the K6 = [H+]. This can belricky, but the answer is found
from the Henderson-Hasselbalch equation. pH = pKu + log Q.4, so pH < pKa.
Example 5.7
A buffer made by mixing 100 mL of 0.5 M HoAc (Ka = 1.g * t0-5) with 25 mL of
1.0 M KoH has a pH approximately equal to which of the following values?
A. 0.2
&> +,2
c. 7.0
D. 9.3
.: i'-'-1 /-"'
Solution 7 v
There are 0.05 moles or.Hoa" present and 0.025 moles of KoH present. This
means that exactly half of an equivalent of strong base has bebn added to a weak
acid, converting half of the original weak acid to its conjugate base. Half of the
original weak acid remains unreacted. This means that pFl= pKu. The value for
pKu is solved for as follows:
pKa = -log (1.8 x t0-s) = -log
1.8 - log 10-s = -log 1.8 - (-5) = -log 1.8 + 5
Log 1.8 is less than 1, so the pH is greater than 4 and less than 5. Choice B is best,
Example 5.8
A buffered solution initially has a pH of 8.31. when five drops of 12 M HCI are
added to a 500-mL beaker fitled with this buffered solution, what would be
expected for the final,pH value?
A. 3.31 "
,, ;t.\
.. -61 e.zo , j, L .
"18. g.31 i:'

E. 8.36
Solution
Adding a little acid decreases the pH slightly. Choice A shows a lower pH value
but a drastically lower pH value. The change is small, so the answer is ihoice B.
Copyright @ by The Berkeley Review The Berkeley Relier

Physiological Buffers
Physiological pH is considered tobe7.4 (although venous and arterial pHvary,
and gastric fluids are highly acidic). The pKu value for physiological acids
should be considered relative to this value in order to determine the structure of t-{ = {'ts* n} o P*l---{--/
the compound in aiao. When the pH of the environment is greater than the pKu a
,-[ t ?E^ ""'J**'*'c4

of the species, it exists predominantly in its deprotonated state. Equally, when
the pH of the environment is less than the pKu of the species, it exists
predominantly in its protonated state.
A prime example of physiological buffering involves carbonic acid, which is used
to buffer the blood of biological systems. Arterial blood is oxygen rich (and thus
carbon dioxide-poor), so it has a slightly higher pH than venous blood which is
carbon dioxide-rich. Carbon dioxide when added to water undergoes the
complex equilibrium shown as Reaction 5.2.
COz(g) + H2O(l) + H2CO3(aq) : HCO3-(aq) + H+(aq)

Reaction 5.2
This equilibrium regulates blood pH, so any conditions (or disorders) that affect
carbon dioxide levels in physiological systems also affect the pH and buffering of
blood. For instance, emphysema hinders the uptake of oxygen from the lung and
the release of carbon dioxide into the lung. The blood can compensate for the
reduced uptake of oxygen by increasing heart rate and producing more red
blood cells. But the release of carbon dioxide is not as easily adjusted for. The
consequence is that carbon dioxide levels in the blood increase, causing the blood
to be more acidic than normal. This condition is known as respiratory acidosis.
This can inhibit the binding of oxygen, as is demonstrated by the Bohr effect.
Using the same logic, it can be concluded thal respiratory alkalosis results from the
excessive loss of carbon dioxide.
Gastric fluids are highly acidic (rich in HCI), so the loss of gastric fluids results in
the loss of acid from the body, producing a condition known as metabolic alknlosis.
Loss of HCI can accompany vomiting or the pumping of the stomach. When the
stomach is pumped, the acidic solution that is removed must be replenished to
reduce the risk of metabolic alkalosis. As a point of interest, food poisoning and
drug overdose patients are given a solution of charcoal and water to drink, which
absorbs the organic toxin. The porous carbon matrix binds organic molecules
better than the water, especially compounds with n-bonds.
Waste products exit the body in a chemically neutralized state (and believe me
that if they didn't, you'd notice), so the lower end of the GI track must be basic.
Losing lower intestinal fluids results in the loss of basic metabolites, in particular,
HCO3- (bicarbonate). Diarrhea (which can be caused by Olestra consumption)
results in the loss of basic metabolites, producing a condition known as metabolic
acidosis. The intertwining of acid-base chemistry and physiology is a perennial
favorite on the MCAT. Figure 5-4 summarizes the pH-related disorders of the
body.
Retention of CO2: Blood pH .L .'. Respiratory acidosis

Loss of CO2: Blood pH t .'. Respiratory alkalosis
Loss of HCO3-: Blood pH J .'. Metabolic acidosis
Loss of H3O+: Blood pH t .'. Metabolic alkalosis
Figure 5-4
Copyright @ by The Berkeley Review 30r Exclusive MCAT Preparation

General Chemistry Buffers and Titration Titration Curves
ffif#affi$fir,i$fiffip$
Quantitative Reactions (Titration Theory)
Acid-base titration is the quantitative addition of a titrant acid to a base in
solution, or of a titrant base to an acid in solution. What is meant by quantitative
addition is that the volumes of acid and base are measured precisely. The
titration is said to reach its equivalence point when the moles of acid are equal to
the moles of titrant base. The volumes must be known precisely in order to
determine the relative concentrations, using the relationship that moles are equal
to the product of volume and molarity. we shall consider two versions of
titration. The first case is the titration of a strong reagent by a strong reagent,
such as strong acid by strong base or strong base by strong acid. The second case
is the titration of a weak reagent by a strong reagent, such as weak acid by strong
base or weak base by strong acid. There is no titration of a weak reagent with a
weak reagent, because the two weak reagents do not react with one another.
We shall first consider what is in solution at different points during the titration.
The two species can be mixed in three different ways: excess of one, excess of the
other, or in equal portions. Let us address each of these scenarios, along with the
initial point of titration. When less than one equivalent of the titrant is added to
the original reagent, this mixture is found in a region on the curve before the
equivalence point. When exactly one equivalent of the titrant is added to the
original reagent, this is the equivalence point. When more than one equivalent of
the titrant is added to the original reagent, this mixture is found irr a region on
the curve beyond the equivalence point. Table 5.1 shows the different conditions
and pH calculations along a strong-by-strong titration curve.
Strong Acid titrated by a Strong Base

Point on Curve in Solution pH Range
Species pH Calculation
Initial Pure strong acid pH 7 pH=-log[HX]ir1i112i
Before equivalence Leftover HgO* pH <7 pH=-log[H3O+]u*""",
At equivalence H2O & neutral salt p}{=7 pH=Tatequivalence
Past equivalence Leftover OH- pH>7 pOH=-log[OH-]"*."r,
Table 5.1
When a weak reagent is titrated by a strong titrant, it's different than the strong-
by-strong titration. The difference when dealing with a weak reagent is that a
weak conjugate is formed as the product, so there is an equilibrium between
products and reactants. The pH calculations must consider all species in solutior'
that affect the pH. Table 5.2 shows the different conditions and pH calculation-.
along a weak-by-strong titration curve.
Weak Acid titrated by a Strong Base

Point on Curve Species in Solution pH Range pH Calculation
Initial Pure weak acid pH <7
)- -llog
-pH =1pKu ') - [H-r
Before equivalence HA and A- (Buffer) PKa+1 pH =pKa+togJal
At equivalence A- (diluted) pF{>7 pOH = f_ pfu - llog t-r I
Past equivalence Leftover OH- p}{>7 pOH=-1og[OH-]"r.g..

Table 5.2
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Fundamental Curve Shapes

The mixtures listed in Table 5.1 can be studied quantitatively with the help of
graphs. Strong acid and strong base titration curves have distinct features.
Figure 5-5 shows the titration of a strong acid by a strong base. We shall call this
Case 1a.
Equivalence point (pH = 7)

moles HXinit = moles OH addea
mL strong base added

Case 1a: Strong acid titrated by a strong base
Figure 5-5
Figure 5-6 shows the titration of a strong base by a strong acid. We shall call this
Case 1b.
j Note that strong curves share

an equivalence point atpH = 7.
Equivalence point (pH = 7)

moles OH- moles H\66"6
mL strong acid added

Case 1b: Strong base titrated by a strong acid
Figure 5-6
In Cases 1a and 1b, the equivalence point is at pH = 7.0, because the neutralized
product is a neutral salt formed from the reaction of a strong acid with a strong
base. The graph, although not extended far enough to tell, is symmetric about
the equivalence point. The shape of the curve is referred to as sigmoidal. The
reagent when initially added to water fully dissociates (or in the case 1b,
hydrolyzes with a base), giving the highest concentration at first. Over the
course of the titration, the concentration is reduced. This means that the pH
gradually increases during the entire titration, with rapid pH change near the
equivalence point. Because pH is measured on a log scale, the graph assumes the
characteristic sigmoidal shape. The reasoning behind this is that as you
approach pF{=7, each change of 1.0 in the pH requires ten times less titrant. For
instance, in going from pH = 1 to pH = 2, the hydronium concentration goes from
0.10 M to 0.01 M, a change of 0.09 M H3O+. In going from pH = 2 to pH = 3, the
hydronium concentration goes from 0.01 M to 0.001 M, a change of 0.009 M
HgO*. The change in hydronium concentration is ten times less when the pH is
one unit closer to 7.0.

The mixtures listed in Table 5.2 can be studied quantitatively with the help of
graphs. Weak acid and weak base titration curves have d.istinct features. Case
2a, shown in Figure 5-7, shows the titration of a weak acid by a strong base.
Equivalence point (pH > 7)

Because [HA]= [Al
PH = PKu
Lip-o-weakness

Case 2a: Weak acid titrated by a strong base
Figure 5-7
case 2b, shown in Figure 5-8, shows the titration of a weak base by a strong acid.
Lip-o-weakness
Because [A
PH = PKu
Equivalence point (pH < 7)
Note that strong curves share half-
equivaience point at pH = pKo.

Case 2b: Weak base titrated by a strong acid
Figure 5-8
Titration curves exhibit an initial cusp when the reagent being titrated is weak.
This is referred to as a lip-o-ueakness, and may be used to distinguish the nature
of the reagent from its titration curve. The lip-o-weakness is due to the fact that
the equilibrium between weak acid and conjugate base heavily favors one of the
two species, so the pH changes significantly. This can be seen the experiment in
Figure 5-1. The pH at half-equivalence point is always equal to the pKu, which
can be inferred from the Henderson-Hasselbalch equation.
In Case 2a, the equivalence pH is above 7.0, because the neutralized product is a
weak base (the conjugate base of the weak acid). The weaker the acid titrated.
the stronger the conjugate base formed at equivalence, and consequently the
higher the pH at the equivalence point. The pH of the conjugate base depends on
both the concentration and the K6 of the base at equivalence.
In Case 2b, the equivalence pH is below 7.0, because the neutralized product rs a
weak acid (the conjugate acid of the weak base). The weaker the base titrated.
the stronger the conjugate acid formed at equivalence, and consequently the
lower the pH at the equivalence point. The pH of the conjugate acid depends c::
both the concentration and the Ku of the acid at equivalence.
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Example 5.9
All of the following are feature of a titration curve in which both reactants are
strong EXCEPT:
A. an equivalence pH of 7.0.
B. a sigmoidal graph shape.
C. the most rapid pH change near pH = 7.
D. a large change in pH as the first few drops of titrant are added.
Solution
This question tests your knowledge about strong-by-strong titration curves.
When both reagents are strong, the neutralize each other and leave behind a pH
= 7 aqueous salt solution. This makes choice A valid. Because the reagent fully
dissociates (in the case of a strong acid) or hydrolyzes (in the case of a strong
base), the highest concentrations are initially observed. The result is a slow
change i. pH until just before equivalence. This causes the curve to be sigmoidal
and makes choice B valid. The pH change is always rapid near the equivalence
point, so for strong-by-strong curve, the pH change near pH = 7 is the most
drastic. Choice C is valid. The pH of the titration mixture is nearly constant at
the start of the titration. This is to say that a strong-by-strong curve is "lip-free"
in the beginning. Choice D is invalid, and is thus the best answer.
Example 5.10
All of the following are features of a titration curve in which one reactant is weak
and the titrant is strong EXCEPT:
A. a half-equivalence pH equal to pKu.
B. a sinusoidal graph shape.
C. a pH at equivalence that is not equal to 7.
D. a large change in pH as the first few drops of titrant are added.
Solution
This question tests your knowledge about weak-by-strong titration curves.
When a weak reagent is half-titrated by a strong titrant, half of the original
species in converted to its conjugate. This leaves half of the original reagent
unreacted in solution. Because the two components of the conjugate pair are in
equal concentration, the pH of the solution is equal to the pKu. This makes
choice A a valid statement and eliminates it. A sinusoidal graph implies a sine
wave, which is not observed with weak-by-strong titration curves. This makes
choice B invalid, and thus the correct choice. When a weak acid is fully
neutralized by a strong base, it forms its conjugate base. This results in a solution
with pH greater than 7. The equivalence pH is not equal to 7. When a weak base
is fully neutralized by a strong acid, it forms its conjugate acid. This results in a
solution with pH less than 7. The equivalence pH is not equal to 7. The pH at
equivalence for a weak-by-strong titration curve is not Z so choice C is valid and
thus eliminated. Early in a weak-by-strong titration curve, the equilibrium
between conjugates favors the one initially in solution. As a titrant is added, the
equilibrium shifts drastically, resulting in a big change in the hydronium
concentration. A big change in the hydronium concentration causes a significant
change in the pH of the solution. This makes choice D a valid statement and
eliminates it.
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General Qhemistry Buffers and Titration Titration Curves
To understand titration curves better, Table 5.3 shows how the pH is calculated
at different points along a titration. The equations used to calculate pH are all in
Table 5.2. The titration represents the titration of a hypothetical weak acid with a
pKu of 5.0 and an initial concentration of 0.10 M. The weak acid is titrated by
0.10 M KoH(aq). The pH represents the solution pH after the titrant base has
reacted with the weak acid in solution. The value points in Table 5.3 are plotted
in Figure 5-9, and by connecting the dots (yes, that's right, studying for the
MCAT involves a little connect-the-dots), a titration curve can be generated.
mL KOH pH calculation pH
0.00 On=of,^ -llog [HA] =7-+rog (0.10) =2.5 +0.5 = 3.0 3.00
1.00 pH =pKu- + log-rnL-QH- = 5.0 + togJ-L = 5.0 - log49

-50 - mLOH- "49 o 3.31
2.00 pH =pKu + log-rnl-Qtl-- = 5.0 + log2.0 = 5.0 - log24

-50 - mT.OH- "4R n 3.62
5.00 pH =pKu + log--ml-Q,H- = 5.0 + log*9 = 5.0 - log 9

-50 - ml.OH-"45 o 4.05
10.00 pH =pKu * tog#*fio- = 5.0 + tosfl* = 5.0 - los 4 4.40
12.50 pH =pKa + log--!0L-QH- = 5.0 + logg* = 5.0 - log 3

-50 - ml-OH-"i7 q 4.52
25.00 pH =pKa- + tog--![L-QH- = 5.0 + [og25 = 5.0 + Iog 1

"50 - mLOH- "ts 5.00
37.50 pH =pKu + log--InL,QH- = 5.0 + 1"g4+ = 5.0 + log 3 5.48

- 50 - mT.OH- "12 \
40.00 pH =pKa + log---mLQH-
"50 = 5.0 + log4!.0 = 5.0 + log 4
ml,oH-
- "1 o n 5.60
pH =pKu* + log-- nnL-QH- = 5.0 + 1og450 = 5.0 + log 9

45.00 "50-mLOH- "so 5.95
48.00 pH =pKu + log--rnlOH- = 5.0 + trST* = 5.0 + log24 6.38
pH =pKu- + log--mL-QH- = 5.0 + log49-} = 5.0 + 1og49

49.00 "50-mLoH- "to 6.69
+PHtitrant
50.00 o11= PKa =5.0 + 13 =18 8.85
')2)
51.00 pOH = -1og [OH-]"*"ur, = -log(0.10 x-L)- pH = 14 - pOH 11.00
55.00 pOH = -log [OH-]",,."r, = -1og(0.10 x-L)= pH = 14 - pOH 11.68
Table 5.3
Initially (at 0.00 mL added), the pH is found using the shortcut equation. Before
equivalence (from 1.00 mL added to 49.00 mL added), the pH is found using a
modified version of the Henderson-Hasselbalch equation, where the moles OH-
added are substituted for moles A- (given that the OH- converts to A-) and 50 -
mL OH- is substituted for moles HA, because that describes the leftover HA. -{:
equivalence (at 50.00 mL added), the pH is approximated by averaging pH of the
titrant base and the pKu of the acid. The approximation is off by 0.15, so the pli
column shows the actual pH at equivalence. After equivalence (beyond 50.00 n.L
added), the pOH is found by taking the negative log mL OH- - 50 (for what r.
reacted)over the total volume (50 + mL OH-).
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General Chemistry Buffers and Titration fitration Curves
Plotting a Titration Curve

The points from Table 5.3 are represented in Figure 5-9 as circles. The curves is
drawn to fit the circles. The shape of the curvJfor a weak acid is distinct. The
buffer region is not perfectly flat, showing that pH changes slightly in the buffer
region. The pH values at 1.00 mL and 2.00 mL are not eiuci, because the
Henderson-Hasselbalch equation does not hold as well outside the pKu + 1
range. Nevertheless, the values are close enough to generate a reisonable
titration curve.
pH
12
11.68
3.62
3.31
3.00
20 25 30
mL 0.10 M KOH added
Figure 5-9
The titration curve should become familiar with enough examples. What makes
curves useful is that they summafize a great deal of information. If you think of
titration curves in terms of equivalents and regions, you can extract a substantial
amount of information from them. For instance, when 2r.27 mL of 0.1 M KoH
has been_ added, the pH is roughly 4.7 to 4.8. That range is small enough that an
educated guess can be made on a multiple-choice q.testio.r. We shall elmphasize
using titration curves in lieu of calculating the pH, when it comes to buffers and
other mixtures.
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Example 5.11
What is the pH after 30 mL of 1.00 M NaOH has been added to 100 mL 0.50 M
HOAc? HOAc has a pKu = 4.74.
-"
p lld -t ' *:.
Klz.st rr
'f--=4'se ?'
- 1, )'a t-\ '" _.
a-A{-492
\
L
(-o
D. 5.97
Solution
Because the strong base is twice as concentrated as the weak acid, only half the
volume of strong base (relative to the weak acid) is required to reach the
equivalence point. This means that 50 mL of 1.00 M NaOH fully neutralizes the
100 mL of 0.50 M HOAc. The halfway point of the titration is reached when
exactly 25 mL of 1.00 M NaOH has been added. At the halfway point, the pH of
the solution equals the pKu of the weak acid. The additional strong base beyond
the 25 mL makes the pH of the solution slightly greater than the pKu of the acid,
4.74. The best choice is answer C. The titration curve below shows a summary of
the intuitive approach:
30 mL NaOH added
pKo-1<pH<pK pK"-<pH<pI{+1
25 50
mL0.10MNaOH(aq) added
When 30 mL has been added, the mixture is just beyond the half-titrated point on
the titration curve (as shown by the arrow). This makes the pH fall into the
range of pKu < pH < pKu + 1, according to the titration curve. According to the
Henderson-Hasselbalch equation, the pH equals the pK3 + log (conjugate base
over acid). Past the half-titrated point, the concentration of the conjugate base
exceeds the concentration of the acid, so the ratio of conjugate base to acid is
greater than one. The log of a number greater than 1.0 is a positive value. When
a positive value is added to the pKu, the final value is greater than the pKu"
confirming that pH > pKa. These questions should be answered quickly, using
either a titration curve or the Henderson-Hasselbalch equation in a purelv
conceptual manner.

General Chemistry Buffers and Tltration Titration Curves
Example 5.L2
What is the pH after 70 mL of 0.20 M HCI has been added to 50 mL 0.60 M
H3CNH2? H3CNH2 has a pK6 =3.42.
A. 9.44
B. 10.51
c. 10.65
D. 1.1..72
Solution
The strong acid is one-third as concentrated as the weak base, so three times the
volume of HCI (relative to the H3CNH2) is needed to reach the equivalence
point. This means that 150 mL of 0.20 M HCI fully neutralizes the 50 mL of 0.60
M H3CNH2. The halfway point of the titration is reached when 75 mL of 0.20 M
HCI is added. At the halfway point, the pH of the solution equals the pKu of the
weak acid. Less than the 75 mL has been added, so the pH of the solution is
slightly greater than the pKu of the conjugate acid, 10.58. The best choice is
answer C. The titration curve below shows how to estimate the value.
pK"-<pHcpI{+1 pKu-1<pH<pK
75
mL 0.20 M HCI(aq) added
Example 5.13
\Alhat is the pH of a solution made by mixing 10.0 mL 0.10 M HCO2H(aq) with 4.0
mL 0.10 M KOH(aq)? The pKu for HCO2H is 3.64.
A. L.34 +, -,.I
B. 3.46
c. 3.82
D. 9.36
Solution
The best way to solve this question is to think in terms of equivalents. The weak
acid and titrant strong base are of equal concentration, so 10 mL KOH is one
equivalent (the amount needed to reach the equivalence point.) If 5.0 mL are
added, then the acid is half-titrated, so pH = pKa. However, less than 5.0 mL has
been added, so pH is a little less than pKu. The pKu is 3.64, so the best answer is
choice B. Choice A is too much less than the pKu (more than 1,.0 is beyond the 10
: L ratio, which would be when less than 1.0 mL of KOH had been added.)
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General Chemistry Buffers and Titration Titration Curyes
Concentration Effect on Titration Curve Shape

The pH of a solution depends on the strength and concentration of the reagents,
so strength and concentration also affect titration curves. The concentration of
the reagents affects the dimensions of the titration curve, but not its basic shape.
A strong-by-strong curve maintains the same fundamental shape (sigmoidal),
but with varying concentrations, the curve may skew and elongate. The
equivalence point is always at pH = 7. A weak-by-strong curve also maintains
its same fundamental shape (i.e., has a lip-o-weakness), but with varying
concentrations, the curve also skews and elongates. The half-equivalence point is
always at pH = pKu.
For a strong acid titrated by a strong base, as the concentrations of both reagents
increase proportionally, the respective curves start lower and finish higher, but
they have the same distance in the x-direction (the mL axis). If the acid
concentration is increased but the base remains the same, then the curve starts
lower and stretches to a point farther from the origin along the x-axis for the
equivalence point. If the base concentration is increased but the acid remains the
same, then the curve finishes higher and contracts to a point closer to the origin
along the x-axis for the equivalence point. This is shown in Figure 5-10.
1.0 M KOH(aq)
0.1 M HCI(aq) + 0.1 M KOH(aq)
.01 M HCI(aq) + .01 M KOH(aq)
Note that strong curves share

an equivalence point at pH = 7.
mL titrant strong base added

Figure 5-10
In each titration, the concentration of the strong acid is equal to the concentration
of the strong base, so the volume of base required is the same in each case. This
is why the curves are similar in the x-direction. In the y-direction, the curve
depends on concentration. As the concentration lessens, the curve contracts with
respect to a line through pH = 7. Note that the initial pH is 0, 1., and 2
respectively for the three titration curves. The variation in the concentration of
base also causes the ends of the curves to vary (in the region of excess titrant).
But at equivalence, the pH is7,no matter what the concentrations are.
For a weak acid titrated by a strong base, as the concentrations of both reagents
increase proportionally, the curve starts lower and finishes higher but advances
the same distance in the x-direction (the mL axis) and has the same buffer region.
If the acid concentration is increased but the base remains the same, then the
curve starts lower and stretches to a point farther from the origin along the x-ais
for its equivalence point. If the base concentration is increased but the acid
remains the same, then the curve finishes higher and contracts to a point closer to
the origin along the x-axis for its equivalence point. This is shown in Figure 5-11.
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General Chemistry Buffers and Titration Tltration Curves
M HoAc(aq) + 1.0 M KOH(aq)

4--J.o
0.1 M HOAc(aq) + 0.1MKOH(aq)
.01 M HOAc(aq) + .01 M KOH(aq)
Curves are nearly identical

through the buffer regioq The equivalence points vary, because higher
initial HOAC concentration leads to a higher
On each curve, because
OAc- concentration at the equivalence point.
tAl = tHL pH = plf
The approximate pH at equivalence is an
average of the pI( and pH of the titrant base.
As acid concentration lessens, initial pH
increases, and the size of the lip lessens.
mL titrant strong base added
Figure 5-11
In each titration, the concentration of the weak acid is equal to the concentration
of the strong base, so the volume of base required is the same in each case. This
is why the curves are similar in the x-direction. In the y-direction, the curve
depends on concentration. As the concentration lessens, the curve contracts with
!
I pKu,l pKa + 0.5, and
respect to a line through pH = pKu. The initial pH is
PKa + L.0 respectively for the three curves. The variation in the concentration of
base also causes the ends of the curves to vary (in the region of excess titrant).
But at half-equivalence, the pH is pKn, no matter what the concentrations are.
Strength Effect on Titration Curve Shape
The examples in Figure 5-10 and Figure 5-11 show the effect of concentration on
titration curves. The shape of a titration curve is also a reflection of the strength
of the reagents. When the concentrations are uniform between titration curves,
then the shape of the curve and location of key points give clues as to the nature
of the acid being titrated. As the acid becomes weaker, there is a larger initial lip,
a greater midpoint (where pH = pKu), and a greater equivalence point. This is
shown in Figure 5-12. As acid strength increases, initial pH decreases, and the
size of the lip-o-weakness lessens.
0.1MHq
+ o.l MKoH(9
0.1MHOAc(aq)
0.1MHNOrt"o)
*-0'@
mL 0.10 M KOH(aq) added
Figure 5-12
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Polyprotic Acid Titration Curves

Polyprotic acids are acids which yield multiple equivalents of hydronium ion
(HSO*). Three common polyprotic acids with which every test-taker must be
familiar are carbonic acid (H2CO3), phosphoric acid (H3POa), and sulfuric acid
(H2SOa). Polyprotic titration curves have multiple equivalence points, one for
each dissociable proton. But the protons are removed one at a time, so the curves
for each proton are separate. Th"y should be treated as separate titration curves
that happen to overlap on the same graph. Figure 5-13 shows the titration curve
for a typical diprotic acid, where both protons are weak. Examples that share the
same basic curve shape include carbonic acid, glycine, or a mixture of two weak
monoprotic acids in the same solution. Figure 5-14 shows the titration curve for
a typical diprotic acid, where the first proton is strong and the second proton is
weak. An example that shares the same basic curve shape is sulfuric acid. Figure
5-15 shows the titration curve for a typical triprotic acid, where all three protons
are weak. Examples that share the same basic curve shape include phosphoric
acid, citric acid, and glutamic acid.
Second equivalence point
First equivalence point

Weak first PH = PKar
proton
Figure 5-13
First equivalence point
Figure 5-14
pH=pK
Third equivalence point
pH=pK
pH=pK First equivalence point
Figure 5-15
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General Chemistry Buffers and Titration Indicators
I ff. ruHffi
Indicator Composition and Function
An indicator is an organic compound with extended conjugation. Its weak acid
(protonated) form and conjugate weak base (deprotonated) form have two
distinct colors. The colors of both species are reflected colors. The energy state
transition that produces color involves the n-bonding and n-antibonding orbitals
and depends on the electron donating and withdrawing nature of substituents on
the n-system. The lone pair formed upon deprotonation affects this conjugation.
When the pH of the solution is less than the pKu of the indicator (pHsotrtton <
pKa (indicator;), the indicator exists predominantly in its protonated form (H-
Ind > Ind-). If this is true, the solution assumes the hue of the protonated form of
the indicator (H-Ind). when the pH of the solution exceeds the pKu of the
indicator (pHsolution > pKa (indicator)), the indicator exists predominintly in its
deprotonated form (Ind- > H-Ind). ir this is true, the solution assumes the hue
of the deprotonated form of the indicator (Ind-). When the pH of the solution is
equal to the pKu of the indicator (pHrolrrlion = pKu (indicator)) the indicator exists
equally in its protonated and deprotonated forms itFl-tncit = [Ind-]). If this is
true, the solution assumes a hue that is the result of a mixture of the protonated
and deprotonated forms of the indicator. When the pH of the solutionis near the
pKu of the indicator, the color varies with small changes i. pH. Reaction 5.3
represents the dissociation of an indicator in water.
r *'."
''"" i t
,," .' -y"uo*
H-Ind,..+ Ind- ar!'\:;i
H+ + ';l;" , "'-l'-'
Reaction 5.3
Table 5.4 shows the pH effects on the generic indicator in Reaction 5.3, along
with a ratio of protonated-to-deprotonated species, and the color of the indicator.
PHsolution Ratio of H-Ind to Ind- Mixture of colors to form solution color

pKu + 3.0 1 : 1000 1yellow : 1000 blue .'. blue
pK" + 2.0 1 :100 1yellow : 100 blue .'. blue
pKu + 1.0 1:10 1 yellow : 10 blue .'. greenish blue
pKu + 0.7 1:5 1 yellow : 5 blue .'. blue-green
pKu + 0.3 1:2 1 yellow : 2 blue .'. bluish green
PKa 1:1 1 yellow: l blue .'. green

pKu - 0.3 2:7 2 yellow : 1 blue .'. yellowish green
pK^ - 0.7 5:1 5 yellow : 1 blue .'. yellow-green
pKu - 1.0 10:1 10 yellow : 1 blue .'. greenish green
pKu - 2.0 100:1 100 yellow with l blue .'. yellow
pKu - 3.0 1000: 1 1000 yellow with l blue .'. yellow
Table 5.4
\Alhen the solution is bluish green, it can be concluded that the pH of the solution
is slightly (about 0.2 to 0.4 times) greater than the pKa of the indicator. This
means that the pH of the solution can be approximated from the color of the
solution. The color change range (and thus the useful range) of an indicator is
pKa (Indicator) t 1. An indicator is generally used for one of two purposes. The
first is to detect the endpoint of a titration, and the second is to approximate the
pH of a solution by observing the color of the indicator in the solution.
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General Chemistry Buffers and fitration Indicators
Detecting the Equivalence Point (Using Indicators)

Indicators make the equivalence point of a titration visible, either by converting
from an uncolored species to the colored conjugate or by converting from one
colored species to its conjugate, which has-a-differeni color. Ai indicator
changes color at a pH near the equivalence point of the titration. The change in
color can thus be used to determine the equivalence point. Indicators are added
in,small quantities, so they do not interfere with the titration. The pH of the
solution thus dictates the color of the indicator. As the titration approaches
equivalence, the pH changes rapidly, so the color changes rapidly. A color
change indicates that equivalence has been reached, if the correct indicator is
chosen.
The ideai scenario for an indicator is when the pH at equivalence equals the pKu
of the indicator. The range of a color change for an indicator is centered on its
pKa. For the titration of a weak acid with a strong base; the pH at the
equivalence point may not be known exactly, so a best approximation of the
equivalence pH must be made. When approximating the equivalence pH,
consider that the pH at equivalence is greater than the pKu of the weak icid
being titrated, but less than the pH of the strong base being added. The pH at
equivalence lies roughly half way between the pKu of the acid and the pH bf the
base being added. A good approximation of the pH at equivalence is an average
of the pKu of the weak acid and the pH of the titrant strong base. The pKu of tfie
indicator should be somewhere around (within + 1 unit) the average of the pKu
of the acid being titrated and the pH of the strong base. For the titration of a
weak base with a strong acid, the pH at the equivalence point is less than the pKu
of the conjugate acid of the weak base being titrated. The pKu of the indicator
should be somewhere around (within + 1 unit) of the average of the pKu of the
conjugate acid of the weak base being titrated and the pH of the strong acid. The
active range for an indicator is represented by the two titration curves in Figure
5-16 and Figure 5-17.
Equivalence
point
I mdi"u.o.
resion
J
pH at equivalence point > 7.0
PH = PKtu.ia)
Best scenario: PH"qr.ri'ulence = PKa(indicator) t 1
PKa(acid) + PH(titrant base)

Best approximation: = pKa(indicator) t 1
2
Choosing an indicator for the titration of a weak acid by a strong base
Figure 5-16
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PH = P41a"iay
Indicator
region
pH at equivalence point < 2.0

Best scenario: PHequivalence = pKalindicator) I 1
PKa(coniugate acid; + PHltitrant acid)

Best approximation: =P(a(indicator) tl
Choosing an indicator for the titration of a weak base by a strong
acid
Figure 5-17
You should make note of the fact that the pH
- at equivalence for the titration of a
weak acid by a strong base can be approximated quite .tor"iy uy
averaging the
pKu of the weak acid with the pH o? ?ne titrant stiong buse. 'This
value will be
within 0.5 of the actual value, meaning,that for the iitration of acetic acid
by
sodium hydroxide, the pKn of the iridicator should be greater
-the
than seven
(somewhere around nine.) As the titration is carried
out, pH of solution
increases; thus, the indicator starts out in its protonated form
irra
become deprotonated. For the sample indicator in Reaction 5.2, "rr"r,tuuiy
the solution
would go from yellow to green to blue.
For the titration of a weak base b-y a strong acid, the pH at equivalence
can be
approximated by averaging the pKu of the ionjugate acid of thl weak
base with
the pH of the titrant strong acid. This means that for the titration of
ammonia by
hydrochloric acid, the pKu of the indicator should be less than 2.0 (somewhere
around 5.0.) As the titration is carried out, the pH of solution decreases;
thus, the
indicator starts out in its deprotonated form and eventually becomes protonated.
For the sample indicator in Reaction 5.3, the solution #ould go frtm bl";-i;
green to yellow.
Copyright by The Berkeley Review

@
3t5 Exclusive MCAT preparation
Estimating Solution pH (using Indicators)

For a solution of unknown pH, if the pH is within one unit of the pKu of the
indicator, then the hue of the indicator can be used to estimate the pH of the
solution. Consider an indicator with a pKu of 6.83 that is used to test pool water.
It is yellow when protonated and red when deprotonated. Table 5.5 can be used
to estimate the pH of the pool water.
PHsolution Ratio of H-Ind to Ind- Solution Color

,i-,-Eo
-' i _
,1. pH > 7.83 1:10+ Red
' '-q-'
J'-,.tu
!
PF{=7.83 1:10 Oransish red
(_.- u-pL\ pF{=7.53 1:5 Red-orange
pH=7.73 1:2 Reddish oranse
' !:"; pH = 6.83 1:1 oranqe
,-t{'': ''' k--
\ pH = 6.53 2:1 Yellowish oranse
i r',"- "t'l'\
pH = 6.13 5:1 Yellow-orange
,t . ?V^ pH = 5.83 10:1 Oraneish vellow
G,f !
' ! ,,.. 1ci"l (- pH < 5.83 10+: 1 Yellow
tt"'
Table5-S
{.i*r':,*'i
If the results of the pool water test is red, the water is basic; and because red is
outside the color change range, the exact pH cannot be approximated. If the
results of the pool water test is yellow, then someone has left some acid in it.
Most people are aware that yellow pool water has some acid in it, and it should
not be swum in. The ideal color is orange with a slight hint of red. Indicators are
used in pH test kits for swimming pools and fish tanks. The kits usually contain
more than one indicator, increasing the accuracy of the approximation. All of the
indicators in such a test kit should have pKu values between 6.0 and 8.0, because
the pH of the water should be around 7.0. Indicators are also used in pH test
sticks, where a series of three or four indicators are on the stick. The pKu values
of the indicators differ by roughly two units. This allows for a wider range of pH
values from which one can correlate the color to the solution pH. For instance, a
pH stick with three indicators, with pKu values of 5.05, 6.98, and 9.11, has a range
of roughly 4.05 to L0.11. This is because each indicator has a two-pH-unit range.
Example 5.14
Given the following indicators on a pH stick, what is the pH of a solution that
yields X: red, Y: blue, andZ: red?
Indicator X: pK6 = 4'96; when deprotonated, it goes from yellow to red
Indicator Y: pKx = 7.01; when deprotonated, it goes from yellow to blue
Indicator Z: pKa = 8.98; when deprotonated, it goes from red to blue
A.5
8.6
c.7
D.8
Solution
Because Indicator Y is blue, the pH must be at least one unit greater than 7.01
(the pKz of Lrdicator Y). Because Indicator Z is rcd, the pH must be at least one
unit less than 8.98 (the pK3 of Indicator Z). The only value greater than 7.01 and
less than 8.98 is 8, choice D.

Buffers
and
Titration
Passages
15 Passages
lOO Questions
Suggested Buffers and Titration Passage Schedule:

I: After reading this section and attending lecture: Passages I, IV, VII, VIII & XI
Grade passages immediately after completion and log your mistakes.
II: Following Task I: Passages II, III, V, VI, IX, & XIV (41 questions in 55 minutes)
Time yourself accurately, grade your answers, and review mistakes.
III: Review: Passages X, XII, XIII, & XV
Focus on reviewing the concepts. Do not worry about timing
ffilll..,ffi 1,,. ;,...[...lirull ffi.*

Speciahztng in MCAT Preparation
I. Buffer pH and Weak Acids (r -7)
II. Buffer Composition (8 - 14)
III. Buffer Chart and pKz Chart Passage (15 - 21)
IV. Molecular Weight from Neutralization of an Organic Acid (22 - 29)

V. Conjugate Pair Titration Curve (5O - 56)
VI. Titration Curves and Concentration Effects (57 - 42)
VII. Titration Curves and Strength Effects (43 - 4e)
VIII. Normality and Neutralization (5O - 56)
IX. Titration Curve of a Polyprotic Acid (57 - 63)
X. Carbonate Titration Curve (64 - 70)
XI. Indicator Selection (7r - 76)

XII. Indicator Color and Solution pfl (77 - 85)
XIII. Indicator Table (84 - Be)
XIV. pH Sticks and Indicators (eo - e6)
XV. Acidity and Electronic Influences (97 - 100)
Buffers and Titration Scoring Scale

84 - IOO l5-15
66 a3 10-t2
47 65 7 -9
54-46 4-6
L-33 1-3
\
.{ .:,/
Passage I (Questions 1 - 7) 3. What should be mixed to make a pH = 4.2 buffer?
PKalbenzoic acid) = 4.2
An integral part of any biological study conducted in
vivo is the accurate simulation of body conditions with as __l . lO grams C6H5CO2Na + l0 grams C6H5CO2H
10 mL 0.10 M C6H5CO2H + 5 mL 0.10 M NaOH
much precision as possible. As important as any factor to ,,,Y.
biological systems is pH. To accommodate the need for a C. 10 mL 0.10 M C6H5CO2H + 10 mL 0.10 M
constant and accurate pH, organisms of all types use buffers NaOH
to maintain a relatively constant internal pH range. A buffer
exists when there is both a weak acid and its weak conjugate
' D. NaOH
10 mL 0.10 M C6H5CO2H + 15 mL 0.10 M
base present in solution in roughly equal molar i,'. ,-.L'^ { i'r.r'r' . /- ).
,''i'i ' t-''

concentrations. It is important that both the acid and the base
a
be water-soluble and exhibit no side reactions. Organic acids
!
l:l and their conjugate bases are best for this purpose.
The Henderson-Hasselbalch equation, Equation 1, is used

4. How many mL of 0.20 M NaOH must you add to 50
mL of 0.10 M HF to produce a solution with a pH of
to calculate the value of the pH for a buffer.
3.3? (pKa =3.3) .,
.
pH = PK6 + tog E3!91 A. 10.0 mL

lAcidl B. 12.5 mL .., : .,,,:, iir
Equation 1 C. 16.7 mL
D. 25.0 mL
In human blood, a buffer ofbicarbonate and carbonic acid ' \,
exists. Inorganic phosphates also play a role in buffering / irij Ji\.-
,I .
within the body. The buffer must have a pH that is relatively

close to 7.4, known as biological pI1. This can be simulated ')'' ''' I
in the lab by starting with a weak acid whose pKu is as close 5. What is the acetate anion concentration in a solution
to 7.4 as possible. After the acid has been added to water, the made by mixing 20 mL 0.30 M HOAc with l0 mL 0.30
solution is titrated with strong base until a pH of 7.4 is MNaOH?
obtained. This method ensures an accurate value. Buffers can A. 0.07 M H3CCO2-
also be made by mixing equal molar portions of the weak B. 0.10 M H3CCO2-
acid and its conjugate base (the conjugate base may come in
its salt form). The pH equals the pKu of the acid when a
C. 0.15 M H3CCO2-
buffer is made with equal molar portions of acid and

D. 0.20 M H3CCO2-
conjugate base.
l. What is the pH of a solution made by adding 0.839

grams NaHCO3(s) (MW = 83.9 grams/mole) to 100 mL
0.10 M H2CO3(aq)?
6 . Which of the following combinations produces a buffer?
.x(tomL0.25 M NH:(aq) +20mL0.25 M HCI(aq)

PKal = 6.4 PKa2 = 10.8
y. 20 mL 0.25 M NHaCI(aq) + l0 mL 0.25 M
A. 3.20 .'" HCI(aq)
B. 6.40
9; l0 mL 0.25 M NH3(aq) + 20 mL 0.25 M NaOH(aq)
c. 8.60
/6,,'20 mL 0.25 M NHaCI(aq) + 10 mL 0.25 M
D. 10.80 1*' NaOH(aq)
2. Which of the following pH values is the BEST choice 7 , What is the pH of 100 mL of 0.10 M propanoic acid,
for the pH of a buffer initially at pH = '7.21 after HCl PKa(propanoic acid; = 5'0?
has been added? A.2.5 .-\1-
, "I---ri-l'-'
. (_8.3.O \-
A
B.
1.14
',7.21 -c. 5.0 ,, r{ - ., .". ,i ''
c. 7.28 D. 6.0 \ .l
D . 8.31

Passage ll (Questions 8 - 14) 9 . What is the pH of a solution that contatns two parts
weak acid and one part conjugate base?
A buffer is composed of a weak acid and its conjugate A. pKa(weak acid) + 2
base. In order to maintain buffering, the ratio of the B. pKa(weak acid; + log 2
conjugate pair must be less than 10:1, in favor of either
C. pKa(weak aciq - 2
component. According to Equation l, when the two
components of the conjugate pair are roughly equal in D. pKa(weak acid; - log 2
concentration, the pH of the buffer solution is approximately
the pKa of the weak acid.
10. At what pH would it be MOST difficult to establish a
PH = PKa + log
E3!91 pH buffer?
A. 1.0
Equation 1
B. 3.0
A buffer is capable of consuming any acid or base that is c. 5.0
added to solution. The pH of an aqueous buffer solution D. 7.0
changes only slightly after an acid or base is added. This is
because there is an equilibrium between the conjugates.
Table lists a series ofweak acids and conjugate bases, along
1 I 1. What BEST describes an aqueous buffered solution?
with the pKa values for each acid. The pKu value of the A. An aqueous solution where the hydronium and
weak acid and the acid-base ratio can be used to determine the hydroxide concentrations are equal
pH of a buffer from Equation l. B. An aqueous solution where the hydronium-to-
hydroxide concentration ratio never exceeds 10:l or
Weak Acid Conjugate Base pKu value is less than 1:10
CIH2CCO2H CIH2CCO2K 2.82 C. An aqueous solution where the hydronium and
HF NaF 3.t9 hydroxide concentrations are relatively constant
HCO2H HCO2Na 3.64 D. An aqueous solution where the hydronium-to-

hydroxide concentration ratio is within one unit oi
H3CCOCO2H H3CCOCO2Na 3.86 the pKs value fbr the weak acid
C6H5CO2H C6H5CO2K 4.19
C6H5NH3Cl C6H5NH2 4.62
H3CCO2H H3CCO2Na 4.',l4 12. Addition of 1.00 mL of 0.10 M KOH(aq) to a solution
made by mixing 15.00 mL 0.10 M H3CCO2HIaq) with
C5H5NHCI C5H5N 5.16 10.00 mL 0.10 M H:CCOZNa(aq) results in:
4-NO2C6HaOH 4-NO2C6HaOK 1.15
A. a solution with a pH less than 3'14.
HCIO KCIO 1.49 B. a solution with a pH between 3.14 and 4.14.
FIBlo KB10 8.61 C. a solution with a pH between 4'74 and 5'14.
NHaCI NH: 9.26 D. a solution with a pH greater than 5.14.
C6HaOH C6HaOK 10.01
H3CNH3CI H3CNH2 10.56

13. In which solution is there the LARGEST ratio o'
(H3C)2NH2Cl (H3C)2NH 10.78 conjugate base to conjugate acid?
Table 1 A. A solution of HCO2H and HCO2- with pH = 4'00
To make a buffer, an acid must be chosen that has a pKu B. A solution of HC1O and ClO- with pH = 7'00
value within one unit of the target pH. The closer the pKu C . A solution of HBrO and BrO- with pH = 8.50
value is to the pH, the better the buffer. Buffers are made D . A solution of NH3 and NH4+ with pH = 9.50
either by mixing the weak acid with its conjugate base, or by
partially titrating either the weak acid with strong base, or the
weak conjugate base with strong acid. When the pH exceeds 14. What is observed after 5'00 mL HzO(l) has been adde:
the pKu, there is more conjugate base present in solution. to 50.00 mL of a buffered solution with pH initialll ':
5.0?
8 . Which mixture does NOT produce a buffer?
A. The pH drops slightlY.
A . H3CCO2H with 2 equivalents of H3CCO2K B. The pH remains constant.
B . NH3 with 2 equivalents of NH4CI C . The pH increases slightlY.
C . H2CO3 1.5 equivalents of KOH D . The pH increases drasticallY.
D . H3CNH2 with 1.5 equivalents of HCI
Copyright @ by The Berkeley Review@ 32o GO ON TO THE NEXT PACE

Passage lll (Questions 15 - 21) 15. Combining all of the following results in a buffer with
pH = 9.5 EXCEPT:
Buffers are aqueous solutions of weak acids and their
conjugate base. The pH of solution is dictated by the
A. 1.8 equivalents NH3 with 1.0 equivalents NH4+.
Henderson-Hasselbalch equation: pH = pKa + 1og base/acid.
B. 1.6 equivalents NaCN with 1.0 equivalents HCN.
This means that a buffer solution should be mixed in a
C. 0.7 equivalents HCI with 1.0 equivalents NH3.
D. 0.65 equivalents NaOH with 1.0 equivalents HCN.
manner where the pKn of the acid is close to the pH desired.
Table I lists the Ku and pKu values for some common
monoprotic weak acids:
Acid Ka value pKa value

16. To make a buffer at pH = 10.83, which of the following
H2NCONH3+ 6.6 x 10-l 0.18
should be mixed?
HF 6.8 x 10-a 3.11
A. One-half equivalent of NaOH with one equivalent
HCNO 3.5 x 10-4 3.49 of H2CO3
HCO2H 1.'7 x 1O-+ 3.18 B. One and one-half equivalents of NaOH with one
H3CCOCO2H 1.4 x l0-a 3.89 equivalent of H2CO3
C6H5CO2H 6.5 x 10-5 4.r9 C. One and one-half equivalents of NaOH with one
equivalent of H3PO4
C6H5NH3+ 2.3 x 10-) 4.64
H3CCO2H 1.8 x 10-l 4.14
D. Two and one-half equivalents of NaOH with one
equivalent of H3PO4
C5H5NH+ 7.1 x l0-o 5.16
HClO 3.5 x 10-6 1.49
B(OH): 5.9 x l0-10 9.22
NH4+ 5.6 x l0-10 9.26
17. Which of the following solutions forms a buffer with a
HCN 4.9 x 10-ru 9.32 pH greater than 7.0?
H3CNH3+ 2.2 x 10-11 r 0.66 A. One and one-half equivalents of KOH with one
(H3C)2NH2+ 1.9 x 10-r r0.11 equivalent of H2C2O4
Table 1
B . One-half equivalent of KOH with one equivalent of
H2CO3
Polyprotic acids can also be used in making buffers. A C . One-half equivalent of KOH with one equivalent of
HCIO
difficulty that arises with polyprotic acids involves the two or
more pKu values. For any given polyprotic acid, the D. One-half equivalent of HCI with one equivalent of
C5H5N
conjugate pair will buffer at the respective pKa for the acid of
the conjugate pair. For instance, carbonate/bicarbonate will
buffer at a pH around 10.8 because pK62 of carbonic acid is
10.81. Carbonic acid/bicarbonate will buffer at a pH around
6.4 because pKul of carbonic acid is 6.31 . Table 2 lists the
18. Which of the fbllowing mixtures would NOT result in a
Ka values for some common polyprotic acids: solution with pH = 4.00?
Acid Krl value K"2 value K^3 value A. Excess HCO2' mixed with HCO2H
H2C2Oa 5.6 x 10-2 5.1 x 10-5
B. Excess C6H5NH3+ mixed with C6H5NH2
H25O3 1.3 x l0-2 6.3 x 10-8
C. Excess C6H5CO2- mixed with C6H5CO2H
D. Excess H3CCOCO2- mixed with H3CCOCO2H
H3POa 6.9 x 10-3 6.2 x l0-8 4.8 x 10-13
H2CO3 4.3 x lO-1 1.5 x 10-11
HzS 8.9 x 10-8 3.8 x l0-i3
Table 2 19. Carbon dioxide when dissolved into the blood forms
carbonic acid. What is observed in CO2-enriched blood?
As a point of interest, carbonates and phosphates are
believed to be the major contributors to buffering in human
A. The pH is less than 1.4.
blood. For years it was believed that carbonate played the

B. The tPO+3-l increases.
C. The [HCO:-] decreases.
major role, but recent research indicates that phosphate may
play a more significant role than carbonate in the overall D. The [HgO*] decreases.
buffering. Within the kidneys, phosphates are known to play
a significant role.

20. In which of the following solutions is rhe conjugate Passage lV (Questions 22 - 29)
base in GREATER concentration than the acid?
The formula weight of an acid can be determined by
A. HF(aq) with F-(aq) at pH = 3.00
titration, using a strong base of known concentration. The
B. H2CO3(aq) with HCO3-(aq) at pH = 6.00 process involves the titration of an exact mass of some
C. HC2Oa-(aq) with C2O42-(aq) at pH = 4.00 unknown acid. Once enough base has been added to reach
D. H2POa-(aq) with HPO42-(aq) at pH = 8.00 equivalence, the moles of base added are used to determine the
moles of acid that were present in the solution initially. The
mass of the acid divided by the moles of the acid gives the
formula weight for the acid, not the molecular weight. Often
both weights are the same, but a difference arises if the
unknown is a polyprotic acid. Only when the acid is
21. Biological pH is approximately 7.4. Which of the monoprotic is the formula weight equal to the molecular
following is NOT true about the concentration of buffer weight. Table I shows some phenols with their respective
species at this pH? pKu values. Al1 of the phenols are solids at room
temperature and are monoprotic acids.
A. [HCO:-] > [H2CO3]
B. tHCO:-l > [CO:2-] Structure Formula PKa
C. tH2POa-] > FIPOoz-,
D. [HPoa2-J t POo:-, p-O2NC6HaOH 7.2
Hsc
p-H3CCOC6HaOH 8.4
C6H5OH r0.0
OH p-H3CC6rH4OH 10.1
OH p-HTCOCaHsOH I 1.:
Table 1
If the molecular mass of an acid is known, the pH o: i

solution can be calculated from its gram concentration .'i
solution. To do this requires converting from grams ir..
moles. Once the concentration is.known, the shoni*:
equation, Equation 1, may be used to quickly calculate the iI
ofthe aqueous solution ofthe acid:
PH = pr^ [HA]
| tlog
Equation I
22. 1.0 gram of which of the above acids requires e\e;,r',
30.0 mL of 0.20 M NaOH to reach equivalence?
A. Acetic acid (HjCCO2H) MW = 60
B . Trichloroacetic acid (CI3CCO2H) MW = 151.-<
C. p-nitro benzoic acid (O2NC6HaCO2H) MW =-i-
D. Benzoic acid (C6H5CO2H) MW = 122
Copyright O by The Berkeley Review@ 322 GO ON TO THE NEXT P{6M

23. lf 1.0 gram of an unknown acid requires exactly 40.00 27 . TteBEST choice for a pH = 8.5 buffer would be whichA
mL of 0.25 M NaOH to reach the equivalence point, of the following?
what is the formula weight for the unknown acid? O2NC6HaOH with less than one full equivalent of
.1
A. 50 grams per mole NaOH
8.. 80 grams per mole H}COC6HaOH with less than one full equivalent
Q., 1o0 grams per mole ,",8. of NaOH
D . 125 grams per mole fuCC6H4OH with less than one full equivalent of
U
-,./. - NaOH
D. H3CCOC6HaOH with less than one full equivalent
. .:i *.-ls .- <i.t r.., of NaOH
2 4. Consider this graph:
pH
2 8. What is the formula weight (equivalent weight) of

oxalic acid (HOzCCOzH)? rti
lL-l
i-
rLi
A. 45 grams per mole
,..
*CB:90 grams per mole 2
. 135 grams per mole ,l

fi. tSO grams per mole
mL of titrant
The graph represents the titration of:
H3CCO2H by NaOH.
29. 25.0 mL of an unknown acid when titrated by exactly
--"k
.3.-, - 30.0 mL of 0.100 M KOH(aq), requires seven drops of
HCI by NaoH.
0. 100 M HCI(aq) to return to equivalence. What is the
C AH, by H3CCo2H. concentration of the unknown acid?
, D.-NH3 by HCl.
(,-'' A. 0.1217 M acid(aq)
B. M acid(aq)
0.1 183
C.0.0849Macid(aq)
D. 0.0817 M acid(aq)
25. Which of the following indicators would be BEST for
the titration of p-nitrophenol(O2NC6HaOH) by NaOH?
A. Thymol blue (pH range of color change is 1.2 to

' 2.8)
B. Methyl red (pH range of color change is 4.6 to 5.8)
\'-"''..Bromthymol Blue (pH range of color change is 6.0
z-.e
to 7.6)
B( Phenolphthalein (pH range of color change is 8.0
to 9.6) .. /1
,
;
i:, \:'
':l11.!
-''i'
2 6. Which of the following mixtures results in a buffered
solution?
.x-to mL 0.25 M NaoH + 10 mL 0.25 M H3cco2H
prl20 mL 0.25 M NaOH + l0 mL 0.25 M H3CCO2H
! c. to mL 0.25 M NaoH + 2o mL0.25 M H3cco2H
I lO mL 0.25 M HCI + l0 mL 0.25 M H3CCO2H
t
;
.i
-,.V.
'I
I
i
{
Passage V (Questions 30 - 36)
Conjugate acid/base pairs are connected by a relationship

between pKu and pK6. Equation I shows the relationship
within a conjugate pair at 25"C in aqueous solution.
PKa (conjugate acid) + PKb (conjugate base) = 14
Equation 1
When titrating a weak acid or weak base, the portion of

the curve following the initial drops of titrant up until just
before the equivalence point is an equilibrium mixture of the
conjugate pair. As such, the titration curve of one
component in a conjugate pair have similarities to the
titration curve of the other component.
The titration curves for conjugate pairs are inverse graphs 12.5 25.0
that intersect at the half-titrated point. At this point, the pH mL titrant solution added #
of the solution equals the pKu of the conjugate acid. At this
same point, the pOH of the solution equals the pK5 of the 25 mL 0.10 M CF{3NH3CI
conjugate base. Figure 1 shows the titration of acetic acid titrated by 0.10 M NaOH
(H3CCO2H) with strong base (NaOH) overlaid onto the
titration of sodium acetate (H3CCO2Na) with strong acid 25 mL 0. l0 M CFhNH:
(HCl). In both titration curves, all species are in equal molar titrated by 0.10 M HCI
concentrations. The pKu for carboxylic acids is generally
between 3 and 5.
Figure 2
Both a weak acid and weak conjugate base titration curr:

of a conjugate pair show the same pH at the half-titratio:
point (indicated by the empty circle on both graphs .
regardless of the initial concentration of the conjugal;

species. The pH at the half-titration point in Figure 1 is les.
than the pH at the half-titration point in Figure 2. This r.
because the pKu value of acetic acid is less than the pK,
value of methyl ammonium cation. At this point, th:
conjugate base concentration equals the acid concentratior
therefore, according to the Henderson-Hasselbalch equatioi-.
pH = pKa.
30. By roughly how much do the two equivalents points :-

the first graph differ?
A. Fewer than 2.0 pH units

12.5 25.0
B. Fewer than 4.0 pH units, but more than 2.0 pH
mL titrant solution added ---* unlts
C. Fewer than 8.0 pH units, but more than 4.0 pl-i
25 mL 0.10 M ECCO2H units
titrated by 0.10 M NaOH
D. More than 8.0 pH units
25 mL 0.10 M tLCCOzNa
titrated by 0.10 M HCI
Figure I 31. The pH at equivalence is GREATEST for which ol ti..
following titrations?
Figure 2 shows the titration of methyl ammonium A. The titration of 0.10 M H3CCO2H by NaOH
chloride (CH3NH3CI) with strong base (NaOH) overlaid onto B. The titration of 0.10 M H3CCO2Na by HCl
the titration of methyl amine (CH3NH2) with strong acid C. The titration of 0.10 M CH3NH3CI by NaOH
(HCl). In both titrations, all species are in equal molar D. The titration of 0.10 M CHjNH2 by HCl
concentrations. The pKu for amines is generally between 9
and 11.
Copyright O by The Berkeley Review@ GO ON TO THE NEXT PAGE

32. What is true in the titration of ammonia by 36. If a similar experiment with identical concentrations and
hydrochloric acid, when the pH of the solution is greater volumes were conducted using hydrofluoric acid and
than the pKu for ammonium chloride? fluoride anion, what would be true, knowing that the
pKu of hydrofluoric acid is lower than the pKu of acetic
A. [NH++] > [NH:]; Ka(ammonium chloride) > [H*]
acid?
B. [NHa+] > [NH:]; Ka(ammonium chloride) < [H+]
C. [NHa+] < [NH:]; Ka(ammonium chloride) > [H+] A. The initial pH for the titration of HF would be
D. [NH++] < [NH:]; Ka(ammonium chloride) < [H*] greater than the equivalence point for the titration
of H3CCO2Na.
B. When both HF and H3CCO2H are one-third titrated
by equimolar NaOH, [F ] > [H:CCOZ-] and
Ka(acetic acid) < [H+1'
C . When both HF and H3CCO2H are one-third titrated
33. How does the pH at point a in Figure 1 compare to the by equimolar NaOH, [HF] > [H3CCO2H] and
pH at point d in Figure l? Ka(acetic acid) < [H+1'
A. The pH at point a is more than 1.0 pH unit greater D. When both HF and H3CCO2H are one-half titrated
than the pH at point d. by equimolar NaOH, Ka(acetic acid) < [H+] in the
B. The pH at point a is greater than the pH at point d, HF titration.
but the difference is less than one pH unit.
C. The pH at point a is less than the pH at point d,
but the difference is less than one pH unit.
D. The pH at point a is more than 1.0 pH unit lower
than the pH at point d.
34. Given that H3CCO2H has a lower pKu value than

CH3NH3CI, which of the following statements is true?
A. H3CCO2H buffers at a higher pH value than
CH3NH3+.
B. H3CCO2H has a conjugate base with a lower pK6
value than the conjugate base of CH3NH3+.
C. H3CCO2H dissociates less than CH3NH3+.
D. H3CCO2H is a better electron pair acceptor than
CHrNH:+.
35. Given that H3CCO2H is a stronger acid than

CH3NH3+, which of the following statements is NOT
true?
A. H3CCO2H yields a lower pH value than
CH3NH3+ of equimolar concentration.
B. H3CCO2H has a conjugate base with a higher pKb
value than the conjugate base of CH3NH3+.
C. H3CCO2H produces more conjugate base than
CH3NH3+ when added to water.
D. H3CCO2H is a worse proton donor than
CH3NH3+.
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Passage Vl (Questions 37 - 42) In the second experiment, the researcher titrates the same
weak acid, HOAc, at three different concentrations, keeping
Titration involves the quantitative addition of one reagent the acid and titrant base in the same concentration as each
to another, where the concentration is known for only one of other. Figure 2 shows the three titrations overlaid onto one
the species. Acids are often titrated by strong bases, so that graph. It is found that all three titrations generated the same
the concentration of the acid may be ascertained. Once the pH at their half-equivalence points.
equivalence point has been reached, the volume of titrant is
measured. Using Equation 1, it is possible to solve for the
Titrations
molarity of the acid, if the molarity of the titrant strong base
is known.
Mlacid)V(aci41 = M6ase;V6ase;
Equation 1
Besides the quantitative aspects, qualitative features of

the acid may also be determined. The shape of the titration
curve varies with the strength of the acid. For strong acids,
the shape is sigmoidal, with a nearly horizontal initial
region. For weak acids, the shape is not sigmoidal, with an
initial vertical ascent before leveling off into a horizontal
buffering region. As the degree ofthe initial ascent increases,
it can be observed that the acid being titrated is weaker. The 12.5 25.0
concentration of the acid also affects the titration curve. The mLNaOH solution added -----*
same fundamental shape is observed, but the pH values are
different.
' 25 mL 0.01 M HOAc titrated by 0.01 M NaOH
A researcher conducts two experiments studying the
effect of acid concentration. In the first experiment, she
25 mL 0.10 M HOAc titrated by 0.10 M NaOH
titrates the same strong acid, HCl, at three different
concentrations, keeping the acid and titrant base in the same
concentration as each other. Figure I shows the three 25 mL 1.00 M HOAc titrated by 1.00 M NaOH
titrations overlaid onto one graph. She finds that all three Figure 2
titrations generate the same pH at their equivalence point,
regardless of the initial concentration of strong acid.
-
Weak acid titration curves show the same equivalencr
point, regardless of the initial concentration of weak aciti
The pH at the half-equivalence point in all three titratio:
curves in Figure 2 is equal to the pKu for acetic acid. At th:
half-equivalence point, the concentration of the conjugai:
base equals the concentration ofthe acid; therefore, according
to the Henderson-Hasselbalch equation, pH = pK2.
3 7. The initial pH is GREATEST in which titration?

A. The titration of 0.01 M H3CCO2H by NaOH
B. The titration of 1.00 M H3CCO2H by NaOH
C. The titration of 0.01 M HCI by NaOH
D. The titration of 1.00 M HCI by NaOH
t2.5 25.0
mL NaOH solution added --+
3 8. What is true in the titration of acetic acid by sodiut:
'' 25 mL 0.01 M HCI titrated by 0.01 M NaOH hydroxide when the pH of the solution is greater tha:
the pKu for acetic acid?
25 mL 0.10 M HCl titrated by 0.10 M NaOH

A. [H3CCO2-] > [H3CCO2H]; Ka(acetic acidl > [H--
B. [H3CCO2-]> [H3CCOzH]lKa(acetic acid) < [H-
C. tH:CCO2-l < [H3CCO2H]iKa(acetic acid) > [H*-
25 mL 1.00 M HCI titrated by 1.00 M NaOH
D. tH3CCO2-l < [H3CCO2H]i Ka(acetic acid) < [H-'
Figure I
-
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39. The BEST explanationfor the greater pH at the 42. Which of the following ,eraphs represents the :esLrlts
with the higher initial that the experiment described rr

would be observed if
equivalence point observed
the passage were carried out with ammonia (NH: t and
concentration of weak acid can be attributed to:
hydrochloric acid (HCIX
A . the greater number of mL of base solution added to
A.
reach the equivalence Point.
B. the lower number of mL of base solution added to A
reach the equivalence Point'
C. the greater conjugate base concentration at the I
25 mL 0.01 M NH
equivalence Point. pH
with 0.01 M HCl
D. the lower coniugate base concentration at the
25 mL 0.10 M NH 1
equivalence Point. with 0. l0 M HCI
- 25 mL1.00MNH3
'rith 1.00 M HC1
--
12.5 25.Q
mL HCI solution added 4
4 0. How would the titration curves in Figure 1 be affected if
the base concentrations were all doubled, while the acid
concentrations remained the same?
A. Equivalence would be achieved with half the
volume of titrant base, and the shape of the
titration curves would change. 25 mL 0.01 M NH i
B. Equivalence would be achieved with twice the with 0.01 M HCI
volume of titrant base' and the shape of the 25 mL 0.10 M NH j
titration curves would change. with 0.10 M HCI
C. Equivalence would be achieved with half the - 25 mL 1.00 M NH 3
volume of titrant base, and the shape of the with 1.00 M HCl
titration curves would not change. 12.5 25.0
+
D. Equivalence would be achieved with twice the mL HCI solution added
volume of titrant base, and the shape of the
titration curves would not change.
25 mL 0.01 M NH
with 0.01 M HCI
41. . Even though the NaOH concentration in the third trial 25 mL 0.10 M NH 3
with 0.10 M HCl
is 100 times greater than the NaOH concentration in the
first trial, the two graphs follow a similar slope' This - 25mL1.00MNH3
rvith 1.00 M HCI
is BEST explained by which of the following --
statements? 12.5 25.0
mL HCI solution added 4
A. The solution is a buffered solution, so the pH
change is minimal. D.
B. The NaOH is a weak base and does not fully react
with the HCl. A
C. The pH is a log scale, so as the pH increases up to
7.0, the amount of base necessary to increase the t
pH
pH becomes less. 25 mL 0.01 M NH
D. The pH changes only at the equivalence point' with 0.01 M HCI
25 mL 0.10 M NH 3
with 0.10 M HCI
-
*ith 1.00 M HCI
- -25mL1.00MNH3
t2.5 25.0
mL HCl solution added =+
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Passage Vll (Questions 43 - 49) 44. If pKu of HOAc is 4.14, the pH at the equivalence in
the titration of HCN is 11.01, and the initial pH in the
The four titrations curves shown in Figure 1, represent titration of HCIO is 4.23. then what else must be true?
the titration of three weak acids (HCN, HCIO, and HOAc)
A. Initial pH in the titration of HCN is 3.86; the pH
and the titration of the strong acid HCl. The equivalence
at equivalence in the titration of HCIO is 9.61.
point is represented by the dot at the vertical inflection point
B. Initial pH in the titration of HCN is 5.16; the pH
of each curve. The respective conjugate base is shown next
to its equivalence point. At the start of each titration, 25 mL
C. Initial pH in the titration of HCN is 6.12; the pH
of 0.10 M acid are present. All of the acids are titrated by at equivalence in the titration of HCIO is 11 .42.
0.10 M KOH(aq).
D . Initial pH in the titration of HCN is 1.42; the pH
4 5. Which of the following statements are valid when

comparing the titration curve associated with a weak
acid by strong base titration to the titration curve
associated with a strong acid by strong base titration?
I. Strong acid titration curves have an initial drop in
pH due to the dissociation of the protons, while
weak acid titration curves start with a plateau.
II. Weak acid titration curves have a buffer region
while strong acid titration curves do not.
m. All points before the equivalence point are less than
12.5 25.0 7 for both the titration of and weak acid and the
mL 0.10 M KOHaq) solution added + titration of a strong acid.
Figure I A. I only
B. II only
The initial and equivalence pH values were collected and C. I and II only
recorded for some of the titrations. Table 1 shows data D. II and III only
collected during the experiment.
Titration Initial pH Equivalence pH

HCl bv KOH 1.00 7.00
46. Given that 0.10 M HIO has a pH greater than that o,
HOAc bv KOH 2.81 8.12 0.10 M HCN, we can conclude that:
HCIO bv KOH 4.23 A. the pKn of HIO is 8.61.
HCN bv KOH r 1.01 B. the pH at equivalence in the titration of HIO b',
KOH is 10.06.
Table 1
C . the pH of 0.10 M HIO(aq) is 1.21.
The pKu for each weak acid can be found by measuring D . the difference between the pKu of HIO and the pH
the pH of the aqueous solution at the half-equivalence point at the equivalence point in the titration of 0.10 l'l
in its respective titration. For instance, the pKu for HCN is HIO(aq) by 0.10 M KOH(aq) is less than 3 p!-'
9.32, which is the pH at the half-equivalence point of the units,
titration curve. The values are approximated, because the
points on the curve cannot be read that accurately. The pH
values are listed in Table I were recorded from a pH meter, so
they are considered to be reliable.
47. When 10 mL 0.10 M HCIO is mixed with 10 mL t-r -:
43. The greatest Ku value is found with which of the M KCIO, the pH is 7.64. What is the pH after 30 :---
following acids? of water is added to raise the volume to 50 mL?
A. HCN A. 7.51
B. HCIO B. "/.64
C. HOAc c . 1.11
D. HCI D. 8.26
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tft" -fK
48. Which of the following curves accurately represents 4 9. Which of these sequences relates the pK2 values of
the titrations of 0.10 M NaCN(aq) by 0.10 M HCI(aq) indicated acids in descending order?
and 0.10 M NaCIO(aq) by 0.10 M HCl(aq)? A. PKa(ucN; > PKa@Clo; > PKa(HoAc) > PKa(HCl)
A. B. PKa(uoac) > PKa(HClo) > PKa(HC$ > PKa(HCl)
CN. C. PKa(uctl >PKa@CN; > PKa@Clo) > pKa@oAc)
cl0 D. PKa(Hct; > PKa@oAc) > PKa(HClo) > PKa(HCN)
pH
mL 0.10 M HCI(aq) added 25.0
mL 0.10 M HCl(aq) added 25.0

c.
CN-
cl0
pH

D.
clo
CN-
pH
'7
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Passage Vlll (Questions 50 - 56) 5 4. How many mL of 0.40 M H2SO4(aq) would require the
same amount of base to reach full neutralization as
A polyprotic acid is an acid that contains more than one would 25 mL 0.60 M H3POa(aq)?
acidic proton. The second proton lost by the acid is never as
strongly acidic as the first proton lost by the acid. The
A. 25.00 mL 0.40 M H2SOa(aq)
second proton can be removed using strong base, once the
B. 37.50 mL 0.40 M H2SOa(aq)
first proton has been completely removed from the acid. C. 50.00 mL 0.40 M H2SO4(aq)
D. 56.25 mL 0.40 M H2SOa(aq)
Concentrations of polyprotic acids are measured in terms of
normality. Normality measures molar equivalence. The
normality of an acid equals the molarity of the equivalent
base required to neutralize all of the acidic protons.
5 5. Which titration curve represents the complete titration
ofphosphoric acid?
A researcher sets out to determine the effect of mixing A.
solutions together, by studying their pH before and after
mixing. Into a flask (Flask 1) he places exactly 25.0 mL of pH
0.20 N H2SOa to be titrated by a solurion of NaOH of
unknown concentration. Into a second flask (Flask 2) he
places exactly 40.0 mL of 0.30 N H3POa, also to be titrated
by the same solution of NaOH. Both solutions are titrated in
succession to a visual endpoint, determined by the color
change of an indicator. The quantity of base needed to mL strong base added
achieve this is recorded accurately to the second decimal place.
B.
50. If Flask I requires exactly 20.0 mL NaOH solution to pH
be neutralized, what must be the concentration of the
NaOH solution?
A. 0.125 M NaOH(aq)
B. 0.200 M NaOH(aq)
C. 0.250 M NaOH(aq)
D. 0.500 M NaOH(aq) mL strong base added
C.
51 . Which of the following statements is true? pH
A. pKat is always larger than pKu2.
B. pKaZ is always larger than pKu1.
C. There is no rule for pKu2 or pKu1.
D. pKaZ is greater than pKul only for the oxyacids.

52. A solution of 0.30 M H3POa(aq) has which of the D.
following values for normality'/
A. 0.10 N H3POa(aq) pH
B. 0.30 N H3PO4(aq)
C. 0.60 N H3PO4(aq)
D. 0.90 N H3POa(aq)
53. When 0.1 moles NaH2PO4 and 0.2 moles Na2HPO4 mL strong base added
are mixed in 100 mL, what is the pH of the solution?
A. pH . PKal + PKa2
2
5 6. What is the phosphate concentration in Flask 2 after 4i
mL of 0.30 N NaOH has been added?
B. pKaZ > pH > PKul + PKu2
2 A. 0.050 M PO+3-(aq)
g. pKa2 + pKa3
> pH > pKa2
B. 0.100MPO+3-(aq)
2 C. 0.450 M PO43-(aq)
D. pH t PKa2 + PKa3 D. 0.900 M PO+3-(aq)
2
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Passage lX (Questions 57 - 63) 6 0. Which change requires that the MOST titrant be added
to the solution?
Polyprotic acids are acids that contain more than one
acidic hydrogen. A typical example is sulfuric acid (H2SOa).
A. Going from a pH < pKat to a pH> pKa2
The first proton is easily removed, while the second proton is
B. Going from the first equivalence point to the
second equivalence point
harder to remove. Sulfuric acid is a strong acid with respect
to its first proton, but weak with respect to its second proton.
C. Going from a pH > pKat to a pH <pKa2
The titration curve for a polyprotic acid looks like two
D. Going from the initial point to the first equivalence
point
separate titration curves that have been connected. The
endpoint of the curve for the first proton is the starting point
of the curve for the second proton. A student titrates an
unknown diprotic acid with strong base. The titration curve
for the experiment is shown in Figure 1.
61 . Il after the addition of 5 mL of titrant, the pH of the
solution is less than the pKul of a diprotic acid, what
volume of titrant is required to reach the second
equivalence point from the fully protonated state?
A. Between 5 and 10 mL
B. Between 10 and 15 mL
C. Between 15 and 20 mL
D. More than 20 mL
mL Tinant added
Figure 1
6 2. What is true the predominant species and any other
species present between points d and e on the titration
The exact pH and exact volume of titrant used are not ctrrve?
known, but the graph is proportional throughout the duration A. A2- (the fully deprotonated form) is all that is
of the titration. The student repeats the experiment three present.
times, and the graph in Figure I represents the best results of B. A2- is present along with some HA- (the partially
the three trials. protonated form).
C. HA- (the partially protonated form) is all that is
5 7. The unknown acid can BEST be categorized as which of present.
the following? D. HA- is present along with some H2A (the fully
A. A strong monoprotic acid protonated form).
B. A diprotic acid with both protons strong
C. A diprotic acid with one strong proton and one
weak proton
D . A diprotic acid with both protons weak
6 3. Which of these points in Figure 1 is NOT described
correctly below?
5 8. Which of the following relationships is NOT true about
the unknown acid? A. Point b is where [H2A] = [HA-].
A. pKat <pKa2 B. Point c is the first equivalence point.
B. pH at first equivalence point > pKal C. Point d is where pH = pK62.
C. pH at second equivalence point > pKn2 D. Point f is where tHA-l = ;62-1.
D. pH at first equivalence point > pKu2
59. In Figure 1, the titrant can best be described as a:

A. strong acid.
B. strong base.
C. weak acid.
D. weak base.

Passage X (Questions 64 - 70) 6 6. How can the pH of solution be determined at point d?
Polyequivalent bases are bases that can neutralize more

A. pH = 7.0
than one acidic hydrogen per base molecule. A typical B. pH - PKul + PKu2
example of a diequivalent base is carbonate (CO32-;. the 2
first proton added corresponds to the second proton removed. c. pH = * (pKrf
Carbonate is a stronger base than its conjugate acid D. ^4pK.rP
pH =2(pKat-pKa2)
bicarbonate (HCO3-), although both are considered weak
bases, because the pK6 values are 3.61 and 7.63 respectively.
The titration curve in Figure I is obtained when calcium
carbonate (CaCO3) is titrated with a strong acid, such as 6 7. What is NOT true at point e on the titration curve?
hydrochloric acid. A. Fewer than 1.5 equivalents of HCI have been added.
B. The pH is less than 6.37.
C. The pH is greater than pKul .
D. The pH is less than pK22.
6 8. In what pH range is the concentration of bicarbonate the

GREATEST?
A. pH less than 3.67
B. pH between 3.61 and7.00
C. pH between pH 7.00 and 10.33
D. pH greater than 10.33
0.5 1.0 1.5 2.O
Equivalents strong acid added
Figure 1 69 . Between which two points does the pH of the solution
change by the GREATEST amount?
The exact pH and exact volume of titrant used in this
titration are not provided, but the graph is proportional A. Between point c and point d
throughout its duration. The nine points marked along the B. Between point d and point e
titration curve note some of the key transitional points. C. Between point e and point f
Despite the fact that the pH is recorded for the titration of the D. Between point f and point g
base (rather than the pOH), the titration curve is still
predictable.
Among the key points recorded are the two equivalence 7 0. Which of the following graphs shows changing pOH a.
points, and the two points at which the pH = pKu (both the a function of equivalents strong acid when calciui:.
first and second pKu points are marked). It is interesting to carbonate is titrated by hydrochloric acid?
note that when pH = pKat, pOH = pK62. The other points
of the curve are interesting in that they represent different
points at which the pH is predictable from the trend in the pH
and the amount of acid added.
64. At which point is the pH equal to the value of pK61?

A. Point c
B. Point d Equivalents strong acid Equivalents strong acii
C. Point f
D. Point h
6 5. Which of the following relationships is NOT true?

A. pKat + pK62 = l{
B. pKaZ + pK62 -- 14
C. pHinitiuly > pKa2 Equivalents strong acid Equivalents strong a.-
D . PHut 2nd equivalence < PKa l
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Passage Xl (Questions 71 - 76) The change in shading represents the increase in th9\-
intensity ofthe orange color ofthe solution. The equivalence
When titrating an acid with a strong base, an indicator is occurs in the middle of the color change band'
added to the solution to indicate when the equivalence point
has been reached. An indicator works by changing color at or 7 L. The BEST indicator to use for the titration of an acid
near the equivalence point ofthe titration. Because indicators with a pKu of 5.0 would be one having a pKa of:
can lose or gain a proton, they are susceptible to the effects A . 1.5.
ofvarying solution pH during titration. A conjugate acid and B. 5.0.
its conjugate base have different colors (although in some c. 8.5.
cases, oneof the two is colorless.) With most indicators, D. 11.5.
both the conjugate acid and conjugate base are colored
species. When both species are colored, it is often harder to
see the color change, unless there is a pronounced difference 72, An indicator in a concentration that is too high could
between the two colors. An example with the hypothetical have what effect on a solution?
indicator HQ, and its dissociation to conjugate base Q-, is A. It could interfere with the acid and/or base
shown in Reaction 1. Assume HQ is colorless and Q- is properties of the solution being titrated.
orange. B. It could change the viscosity of the solution being
HQ(aq) -.-5- H:O+(aq) + Q (aq) titrated, resulting in a non-homogeneous solution'
Clear Orange C. The color change could be too extreme to be useful'
Reaction 1 D. The color change could be too subtle to detect.
When the conjugate base (Q-) is the predominant species

in solution, it appears orange. When the conjugate acid (HQ) 7 3. What is the ratio of the conjugate base to conjugate acid
is the predominant species in solution, the solution appears at two pH units above the PKu?
clear. When the pH of the solution is equal to the pKs of the A. 100: 1
indicator, there are equal parts of HQ and Q- in solution, so B. 2:1
the solution has an orange hue' Indicator are used in low C. l:2
concentration, so they don't become visibly detectable until D. 1:100
at least one-tenth of the indicator is in its deprotonated
(orange conjugate base) form. This occurs when the solution
pH iJ approximately one pH unit below the pKa of the 7 4. Agood indicator has which of the following properties?
indicator. Equation lists the active range of an indicator.
1
A. It should be transparent throughout the titration'
PH(at equivalence) = PKa(indicator)
+ 1' B. It should be unreactive with respect to acid-base
Equation 1 reactions.
C . It should be a strong acid or a strong base.
Because it is desirable to have the color change near the D . It should be a weak acid or a weak base.
equivalence point of the species being titrated, Equation 1
helps when selecting an indicator. If the equivalence pH is
not known, then the pH at equivalence can be approximated 7 5. For which of these titrations is the pH at equivalence
as pKu1u.i6; + 3 (where the pKu is for the acid being titrated)' the same, regardless of concentration?
This means that often the pKu of the indicator is about three A. The titration of a weak acid by a strong base
pH units higher than the pKu of the acid being titrated. This
B. The titration of a strong acid by a weak base
holds true only if the pK' for the acid is between 4 and 10' It
C. The titration of the first proton of a weak diprotic
is not affected by concentration factors. Figure 1 shows a acid by a strong base
titration curve for the titration of a weak acid by strong base D. The titration of the second proton of a weak
and the active range of an indicator: diprotic acid bY a strong base
pH
c
:ao 7 6. Which BEST explains why the indicator pKu may be
rE * one unit off from the equivalence pH?
l8;
J.2 A. A difference of one pH unit has an insignificant
'd effect on color at the pH of the indicator's pKa'
Equiva t\ point
B. The pH changes rapidly at equivalence'
C. At the equivalence point for the acid, pH = PKa'
D. An indicator's color change occurs at only one very
mL titrant added specific PH value.
Figure 1

Passage Xll (Questions 77 - 83) 78. Which combination of colors is NOT possible for a
solution?
Indicators have two main purposes in chemistry. The
first use is as an aid in determining the equivalence point in a A. I: red II: yellow III: purple
titration experiment. If the pH at equivalence is known, then B. I: mango II: yellow III: violet
an indicator that changes color at or near that pH value can be C. I: red II: yellow IfI: fuchsia
used to detect the equivalence point. The ideal indicator has D. I: yellow II: aquamarine III: clear
its pKu value within + I of the pH at equivalence.
The second use of an indicator is to approximate the pH 79 . If the ratio of blue species to clear species within an
of an unknown aqueous solution by examining the color of indicator equilibrium is 1000:l at pH = 6, what is the
the indicator in a sample of the solution. The indicator pK2 of the indicator, given that the deprotonated form
changes color at a pH value approximately one unit from its absorbs visible lighr?
pKu value, so if the pH of solution is within one pH unit of
the indicator's pKs value, then the pH can be estimated.
A. 3
B. 4
Table 1 shows the relationship between pH and the color c. 9
associated with three indicators.
D. 10
pH Indicator I Indicator II Indicator III

I Red Yellow Purole 8 0. What is the pH of a solution that is clear when Indicator
2 Red Yellow Purple III is added, faint chartreuse
when Indicator II is added.
3 Red Yellow Violet and faint mango when Indicator I is added?
4 Yellow
Red Fuchsia A. 7.0
5 Red Yellow Clear B.'7.5
6
l
Red-oranse Yellow Clear c. 8.0
Orange Yellow Clear D. 8.5
8 Manso Yellow Clear
9 Yellow Chartreuse Clear
10 Yellow Green Clear
81 . Which of the following accurately describes the pK,
ll Yellow Aouamarine Clear values for the three indicators?
t2 Yellow Blue Clear A. I: 6.86 II: 9.87 III:4.22
13 Yellow Blue Clear B. I: 8.94 II:7.21 III: 5.98
C . I:1.21 II: 8.28 III:4.11
Table I
D. I: 8.34 II:9.66 III: 3.85
For the titration of a strong acid by strong base, the pH
at the equivalence point is 7.0, while for the titration of a
weak acid by a strong base, the pH at equivalence is greater 82. The active range for Indicator III is which of the
than 7.0. Because the pH at equivalence is different, a following?
different indicator is required for the two titrations, although A.pH2topH6
for a weak acid with a pKu of 3 or less, the indicator usedln B.pH3topH4
the titration of a strong acid may work. C.pH3topH5
The equilibrium distribution of the deprotonated and D.pH4topH6
protonated forms of an indicator obeys Equation 1, where Ind-
is the deprotonated form and H-Ind is the protonated form. 83. The best description of the absorbance of light
llL associated with Indicator III is:
PHsolution = PKa(indicalorl + log
H-tnd A. The protonated form absorbs light with a L6u* of
Equation 1 426 nm, while the deprotonated form absorbs light
with a )"*u,. of 339 nm.
7 7. Which indicator could be used to determine the B. The protonated form absorbs light with a l"pa* of
equivalence point in the titration of 1.0 M benzoic acid 339 nm, while the deprotonated form absorbs light
by 1.0 M KOH(aq)? with a 1,.6" of 426 nm.
The pKu of H5C6COOH is 4.21.
C. The protonated form absorbs light with a )"p.x of
598 nm, while the deprotonated form absorbs light
A. Indicator II only with a l,-a* of 339 nm.
B. Indicator III only D. The protonated form absorbs light with a L.11ax of
C. Both Indicatorl and Indicatorll 339 nm, while the deprotonated form absorbs light
D. Both Indicator II and Indicator trI with a l"*u" of 598 nm.

Passage Xlll (Questions 84 - 89) 85 . Which of the following indicators CANNOT be used for
the titration of ammonia by hydrochloric acid?
In titration, it is common to use indicators to signify a
certain pH for the solution. Indicators are made, most
A. Phenolphthalein
commonly, from organic dyes that gradually change color

B. Bromcresol green
within a given pH range. A color change is observed,

C. Methyl orange
D. Bromphenol blue
because the indicator in its protonated state is one color and
in its deprotonated state is a different color. Reaction 1
shows the equilibrium for a generic indicator.
Hlnd(aq) + H2O(l) s- H3O+(aq) + Ind-(aq) 86. If KCN has pKb = 4.68 and KF has PKu = 10.83,
which indicator is NOT the ideal choice for the
Reaction 1
following proposed titrations?
Table 1 below lists a series of indicators, the pKu of the A. 1.00 M KF(aq) titrated by 1.00 M HCl(aq) with an
indicator, the active range for visual detection, and the indicator of cresol red
respective colors of the protonated form (acid) and B. 0.01 M KF(aq) by 0.01 M HCI(aq) with an
deprotonated form (base). The Henderson-Hasselbalch indicator of methyl violet
equation describes the relationship between the members of a C. 1.00 M KCN(aq) by 1.00 M HCI(aq) with an
conjugate pair. When the concentrations of the acid and base indicator of bromcresol green
are equal, the pH equals the pKu. When this occurs, the color
D. 0.01 M KCN(aq) by 0.01 M HCI(aq) with an
of the solution is an average of the colors listed in Table l. indicator of chlorophenol blue
fndicator pKa pH range Acid Base
Alizarin Yellow 10.8 10.0 - 1r.6 Yellow Red
Phenolphthalein 8.8 8.0 - 9.6 Clear Pink 8 7. Which of the following indicator : color correlations is
Thymol Blue 8.4 7.6 - 9.2 Yellow Blue NOT correct for biological pH (pH =1.4)?
Cresol Red 8.0 1.2 - 8.8 Yellow Rd A. Methyl violet : Violet
Bromthvmol Blue 6.8 6.0 - 1.6 Yellow Blue B. Methyl orange : Yellow
Chlorophenol Blue 5.6 4.8 - 6.4 Yellow Red
C. Thymol blue : Blue
D. Bromcresol green : Blue
Bromcresol Green 4.4 3.1 - 5.1 Yellow Blue
Methvl Oranqe 3.9 3.2 - 4.6 Orange Yellow
Bromphenol Blue -1- I 3.0 - 4.4 Yellow Blue
Ervthrosin B 2.8 2.2 - 3.6 Orange Yellow 8 8. Which of the following titrations requires thymol blue
indicator?
Thymol Blue 2.0 t.2 - 2.8 Red Yellow
Cresol Red t.6 r.0 - 2.2 Red Yellow A. A low concentration of strong base titrated by a
strong acid
Methvl Violet 0.8 0.0 - 1.6 Yellow Violet
B. A low concentration of weak base titrated by a
Table 1 sfrong acid
C. A highly concentrated strong base titrated by a
Depending on the concentrations and species being strong acid
titrated, there is one ideal indicator. To detect the equivalence D. A highly concentrated weak base titrated by a
point for a titration, a small portion of indicator is added to strong acid
solution. Ideally, the equivalence point of the titration
should be equal to the pK6 of the indicator. At the very least,
the equivalence pH must fall within the indicator's active
range. When a strong acid or strong base is titrated with a 8 9. Which of the following indicators should be chosen to
strong titrant, the pH at the equivalence point is always equal identify the equivalence point of a strong acid titrated by
to 7.0. For a weak acid titration, the pH at equivalence can a strong base?
be estimated by taking an average of the pKa of the acid
being titrated and the pH of the titrant base.
A. Methyl violet
B. Methyl orange
84. Which of the following does NOT form a blue
C. Bromthymol blue
solution?
D. Alizarin yellow
A. Bromphenol blue in a pH = 7.0 buffer
B. Bromcresol green in an aqueous ammonia solution
C. Thymol blue in an acetic acid solution
D. Bromthymol blue in a hydroxide solution
Copyright @ by The Berkeley Review@ ttD GO ON TO THE NEXT PAGE

Passage XIV (Questions 90 - 96) 91 . It is NOT possible to estimate pH for:
A pH stick is a device that can approximate the pH of an A. Solution 1 only.
aqueous solution by reference to a color blend band. It is a B. Solution I and Solution 2 only.
plastic stick with indicators attached to specific segments of C. Solution 2 and Solution 3 only.
the stick. Each indicator has a range of color change that D. Solution 1 and Solution 4 only.
extends to either side of a central pKu value. When the pH of
the solution is less than the pKu of the indicator, the
indicator exists predominantly in its protonated state. When 92. An aqueous solution that has a hydroxide concentration
the pH of the solution is greater than the pK" of the of 1.0 x 10-6 M would show what colors?
indicator, the indicator exists predominantly in its A. Yellow with bromcresol green
deprotonated state. An indicator is ideal when both the B. Red with methyl red
protonated and deprotonated species are colored. When the
species are primary colors, the change is easier to observe.
C. Blue with bromthymol blue
D. Clear with phenolphthalein
Typical pH sticks come with three to four indicators,
such as those listed in Table 1. Each solution must be tested
with a separate pH stick. A pH stick cannot be used for more 93 . What is the approximate pH of Solution 5?
than one test, because the acidity of the first test solution A. 4
affects other solutions that are added to the pH stick.
B. 5
Indicator PKa
Protonated Deprotonated c. 6
Color Color D.1
Bromcresol Green 4.31 Yellow Blue
Methyl Red 5.21 Red Yellow
Bromthymol Blue Yellow
9 4. When HCI is added to Solution 2, the colors on the pH
6.18 Blue
stick do not change. How can this be explained?
Phenolphthalein 8.',79 Clear Magenta
A. The hydronium concentration is too high for the
Table I pH to be affected by the addition of HCl.
A student uses a pH stick with four indicator markers to B. The hydronium concentration is too low for the pH
approximate the pH of five separate solutions. Table 2 lists to be affected by the addition of HCl.
the results for the five separate solutions. Each sequence of C. The solution is a buffer made from a carboxylic
colors represents what is observed for the four indicators in acid and its carboxylate conjugate base.
order of increasing pKu. D . The solution is a buffer made from an amine and its
ammonium conjugate acid.
Bromcresol Methyl Bromthymol Phenol-
Solution
Green Red Blue phthalein
I Yellow Red Yellow Clear 9 5. Which indicator could be used in the titration of a weak
acid by a strong base?
2 BIue Orange Yellow Clear
A. Bromcresol green
Greenish-
3 Blue Yellow
blue
Clear B. Methyl red
4 Blue Yellow Blue Magenta
C. Bromthymol blue
D. Phenolphthalein
Greenish- Reddish-
5 Yellow Clear
blue orange
Table 2 9 6. Which of the following statements is INVALID?
An indicator is
used to detect the endpoint in a titration.
A. A solution that turns bromthymol blue to blue
An ideal indicator for a titration has its pKu equal to the would turn Phenolphthalein to magenta.
equivalence pH of the titration. This is the ideal condition, B. A solution cannot show two green marks on the
but in practice, the exact pH at equivalence often cannot be pH stick.
determined. The general rule for titration is that the pH at C. A solution that turns methyl red to yellow would
equivalence should be within one of the pKo of the indicator. turn bromcresol green to blue.
D. The pH stick can estimate pH best when that value
9 0. What is the pH range of the pH stick? falls between 4.21 and 5.31.
A. 3.4 ro 8.8
B. 3.4 to 9.8
C. 4.4 to 8.8
D. 4.4 ro 9.8
Copyright @ by The Berkeley 336 GO ON TO THE NEXT PAGE

Passage XV (Questions 97 - 100) 9 8. For the titration of p-nitrophenol, which of the
following reagents would be best?
A common class of acids in organic chemistry is the
A. KOH
carboxylic acids. Their acidity is attributable to the electron- B. Potassiump-nitrophenoxide
withdrawing nature of the carbonyl group through resonance' C. Phenol
Short-chain carboxylic acids are water-soluble. As the alkyl D. HCl
chain length increases, the hydrophilicity decreases, making
carboxylic acids of five carbons or more rather insoluble'
Long-chain fatty acids are often used as surfactants because of 99 . What is the pH of a solution made by mixing 20 mL
their insolubility. 0.10 M phenol with 10 mL 0.10 M KOH(aq)?
Phenols constitute another common classof acids in A. 10.0
organic chemistry. Their acidity is attributable to the B. 1.0
electron-withdrawing nature of the benzene ring through c. 5.8
resonance. Because aromatic rings are less electron- D. 5.5
withdrawing than carbonyl groups, phenols are weaker acids
than their carboxylic acid counterparts. Most phenols are
insoluble in water in their protonated state. Table 1 lists a 10 0. Which of the following graphs represents the titration
few examples of carboxylic acids and phenols, along with of 50 mL 0.1 M p-nitrophenol by 0.20 M KOH(aq)?
their pKu values.
Organic Acid
-Pe
o
0.64
.r..Aot
25 50
mL 0.20 M KOt{aq) mL 0.20 M KOF{aq)
3.40
4.21.
25 50
7.18 mL 0.2014 KOHaq)
mL 0.20 M KOHaq)
10.01 1.B 2.A 3.8 4.8 5. 8

6.D ',1.8 8.D 9.D 10.A
11. C 12. B 13. A 14. B 15. C
Table 1 16. B r1. C 18. C 19. A 20. D
21. C 22, C 23, C 24. D 25. D
26. C 27. D 28. A 29. B 30. c
Because of solubility constraints, carboxylic acids and
31. C 32. C 33. C 34. D 35. D
amines are more often involved in aqueous buffering than 39. C 40. c
36. D 31. A. 38. A
phenols. However, it is possible to titrate phenols, because 42. D 44. B
41. c 43. D 45. B
their conjugate base is water-soluble, allowing for the
46. D 4-1. B 48. A 49. A 50. c
reaction to be monitored. 5r. B 52. D 53. C 54. D 55. B
56. A 51. D 58. D 59. B 60. A
9 7. Which of these mixtures produces the MOST effective 61. D 62. B 63. D 64. C 65. B
buffer for pH 4.0? 66. B 61. B 68. C 69. A 70. A
A. H3CCO2H + H3CCO2Na 'n. c 12. A 73. A 14. D 75. C
76. B 77. A 78. B '79. A 80. D
B. CI3CCO2H + CI3CCO2Na 82. C 84. C
81. A 83. C 85. A
C. O2NC6HaCO2H + O2NC6H4CO2Na 86. B 87. C 88. D 89. C 90. B
D. C6H5CO2H + C6H5CO2Na 91. D 92. C 93. B 94. C 95. D
96. A 97. D 98. A 99. A 100. A
Copyright O by The Berkeley Review@ cct THAT'S ENOUGH CHEM FOR NOW.
Buffers and Titration Passage Answers
1- Choice B is correct. The mixture is composed of NaHCO3 and H2CO3. Without considering how much
of each
component is present in solution, recognize first that they are a conjugate pair, meaning tiat the
solution is a
buffer. This means that the pH is close to the pKu. Carbonic acid is dlp.-toti", so be sure you understand that the
first proton is involved in this conjugate paia and that the pH shouli be close to pKu1. This makes choice B
the best candidate. If you wish to solve for the exact value, the first step is to convert 0.839 grams
NaHCO3(s)
into moles: (0.839 grams)(-l rnale-) = 0.01 moles NaHCo3. The number of moles of H2Co3 (0.10 L)(0.10 M)
84 grams
= =
0.01 moles H2CO3. The pH can be found using the Henderson-Hasselbalch equation:
pH = pKu*logMol"tconjugate u91g!I{!5
M.t"r .-rj"g"t" *l.t I r --or*to*
pH=pKal '-o =6.4+logll
- .01 =6.4+logr=6.4
Moles H2CO3
Since the log of 1 is 0, the pH of the solution is equal to pKu1, 6.4. The best answer is choice B.
, Choice A is correct. Even though the solution is a buffer, the addition of HCI decreases the pH slightly. A
buffer resists extreme pH changes, but a small change is often observed. The addition of an acid to the buffered
solution lowers the pH. Since the pH is initially 7.27, the final pH value must be lower than 7.27. The only
answer choice less than 7.21 is choice A,7.1,4.
J. Choice B is correct. To make a buffer, a weak acid and its conjugate base must be mixed. Benzoic acid is a weak
acid, so it must be mixed with benzoate, its conjugate base. The desired pH is equal to the pKu of benzoic
acid,
so according to the Henderson-Hasselbalch equation, equal parts of benioate an-d benzoic acid must be mixed.
This can be accomplished either by adding one-half equivaient (in terms of moles) of strong base (NaOH) to
convert half of the benzoic acid into benzoate, or by adding an equivalent amount (in terms of motes) of benzoate
to the benzoic acid solution. Choice A has the conjugate pair uaaed together in an equal gram ratio, not equal
mole ratio. This does generate equal mole portions, so the pH is not eqrial to the pKu. This etiminates choice A.
The remaining three dhoices involve the mixture of benzoic acid with i strong base, so they must be mixed in a
manner that half-titrates the benzoic acid. The only answer with half as much strong base as weak acid
(benzoic acid) is choice B. This mixture yields equal molar portions of the two componentJof the
conjugate pair
(benzoic acid and benzoate), so the best answer is choice B.
4. Choice B is correct. The concentration of the titrant strong base (0.2 M NaOH) is twice that of the weak acid
HF (0.1 M), so to reach equivalence, only half the volume of strong base is required. There are initially 50 mL
of 0.1 M HF present, so only 25 mL of 0.2 M NaOH are required to reach the equivalence point. The target pH
for the solution is 3.3, which happens to be the pKu of uf. fnis means that the pH of ,ol.rtion is equal io pku
of HF, which is true when [HF] = [F ]. This occurs when the HF(aq) is half-titrat"i. rf 25 mL 0.2 M lriaOHlaqy is
required for full titration, then 12.5 mL is required for half titration. Choice B is the best answer.
5. Choice B is correct. This question takes more than the usual amount of effort to answer. There are two factors to
consider: dilution and reactivity. Addition of sodium hydroxide solution converts some of the acetic acid to
acetate, and it dilutes the solution. After the completion of the reaction, 3.0 mmole of H3CCO2- are present in
30 mL of aqueous solution. From here on, it's strictly a matter of calculation, beginning with 3 mmqle = 0.1 M
30mL
Choice B is the best answer. The reaction chart below shows how the moles were detir-mined.
HOAc + NaOH Hzo + H3CCO2-
6mmols 3mrnols XXX 0
-3 mmols -3 mmols XXX +3mmols
3mmols 0 XXX 3mmols
6. Choice D is correct. A buffer is prepared by mixing (in this case) a weak acid with a half-molar equivalent o{
strong base. This is also referred to as half-titrating a weak acid. Choice A is eliminated, because twice as
much acid as weak base has been added. Choice B is eliminated, because both species are acids. Choice C is
eliminated, because both species are bases. In choice D, half of an equivalent of ,iror-,g base is added to a weak
acid. This results in a buffer, so the best answer is therefore answer choice D.
Copyright @ by The Berkeley Review@ 334 Section V Detailed Explanations
7. Choice B is correct. The solution is acidic, so the pH is less than 7.0. A11 of the answer choices are less than7,
so nothing is eliminated. For a weak acid with pKu between 2 and 12 in an aqueous solution where [HA];,i11u1 is
greater than Ku, use the shortcut equation to determine the pH. The pKu is 5.0, and [HA] is 0.1 M.
pH =|nKa -llog tHAl =l1s.o; -t./."r(0.10) = 2.5 -L..r) =2.5 + 0.5 = 3.0
The pH is 3.0, so the best answer is choice B.
8. Choice D is correct. A buffer results when a solution contains roughly equal concentrations of weak acid and its
conjugate base. This can be achieved by mixing the components of the conjugate pair in a roughly one-to-one
ratio, as is observed in choices A and B. In choice C, the acid is diprotic, so the 1.5 equivalents of strong base
completely remove the first proton (to form HCO3-) and then pull off a second proton from half of the
bicarbonate ions. The result is a solution with equal parts HCO3- and COr2-. Because these are a conjugate
pair, the solution forms a buffer. This eliminates choice C. In choice D, methyl amine is capable of gaining
only one proton, so the 1.5 equivalents of HCI completely converts the weak base (H3CNH2) into its conjugate
acid (H3CNH3+), with a leftover of 0.5 equivalents of HCl. The solution is a mixture of weak acid and strong
acid, which does not result in a buffer. The best answer is thus choice D.
9. Choice D is correct. Because the solution contains more weak acid than conjugate base, the pH is less than the
pKu of the acid. This eliminates choices A and B. According to Equation 1, it is a log relationship, so the best
answer is choice D. Plugging into Equation 1 would yield pH = pKa + log 7 / 2 = pKu - log 2.
10. Choice A is correct. The pH can be regulated (maintained at a relatively constant value) by a buffer. A buffer
is composed of a weak acid and its conjugate base. Because the pH of the buffer must be close to (within one unit
of) the pKu of the acid, the pH becomes harder to regulate as the weak acid becomes stronger. To regulate the
pH at 1.0 requires an acid with a pKu no greater than 2.0. An acid with a pKu of 2.0 or less would be one of the
strongest weak acids. Increasing acid strength diminishes its ability to buffer. You should note that Table 1
does not contain any acids that could be used to buffer at 1.0. The best answer is thus choice A.
11. Choice C is correct. A buffer serves to maintain relatively constant pH. Choice A is eliminated, because an
aqueous solution where the hydronium and hydroxide concentrations are equal has a pH of T.0,notnecessarily a
constant pH. A buffer solution is one in which the ratio of the acid and base in the conjugate pair never exceeds
10 : 1, but that does not address the hydronium-to-hydroxide ratio. Consider a pH = 4.0buffer, for instance. At
pH = 4.0, the hydronium concentration is 10-4 M, and the hydroxide concentration is 10-10 M. This results in a
ratio of 1,000,000 : 1. This is far greater than 10:1, so choice B is eliminated. Choice C is the best, because a
relatively constant pH implies that the hydronium concentration is relatively constant. If hydronium
concentration is relatively constant, so is hydroxide concentration. This makes choice C the best answer.
Choice D is eliminated, because the pH should be within one unit of the pKu value for the weak acid, not the
hydronium-to-hydroxide ratio. The best answer is thus choice C.
t2- Choice B is correct. The solution before adding the hydroxide has a 15 : 10 mole ratio of weak acid to conjugate
base. Addition of 1.00 mL of KOH converts some of the weak acid into conjugate base so that the ratio of 15 : 10
becomes 14 ; 77, still in favor of the weak acid. Because the weak acid is slightly more concentrated than its
conjugate base, the pH of the solution is slightly lower than the pKu. The pKu is 4.74, so the best answer is
choice B.
13. Choice A is correct. The largest ratio of conjugate base to weak acid is found in the solution with a pH greater
than the pKu of the weak acid by the largest amount. Formic acid (HCO2H) has a pKa of 3.64. In choice A,
when the solution pH is 4.00, the pH is 0.36 greater than the pKu. Hypochlorous acid (HCIO) has a pKu of
7.49. In choice B, when the solution pH is 7.00, the pH is 0.49less than the pKu. There is more yeak acid than
conjugate base, which eliminates choice B. Hypobromous acid (HBrO) has a pKu of 8.67. In choice C, when the
solution pH is 8.50, the pH is 0.77 less than the pKu. There is more weak acid than conjugate base, which
eliminates choice C. Ammonium ion (NH+*) has a pKu o19.26. In choice D, when the solution pH is 9.50, the
pH is 0.24 greater than the pKu. 0.36 is greater than 0.24, so the best answer is choice A.

'1.4.
Choice B is correct. Addition of water to a buffer equally dilutes the weak acid and its conjugate
base. The
result is that the ratio of base to acid has not changed, so the buffer does not shift. The equilibrium
has not
been disturbed, so the reaction exhibits no net shift. The pH remains constant. The best answer
is choice B.
15. Choice C is correct. Ammonium (NHa+) has a pKu value of 9.26 as given in Table 1. This means that
when the
acid and conjugate b_u:"_ut9 present in equal molar concentration, the-pH of the solution is 9.26.
To make the pH
of solution equal 9.5, the conjugate base must be in excess to suci a degree that the log of the base-to-acid
the
ratio is 0.24. Choice A lists the conjugate base (ammonia) in excess, so choice A is vahdl Hydrocyanic acid
(HCN) has a pKu value of 9'32 as given in Table 1. This means that when the acid and co.,lugate base
are
present in equal molar concentration, the pH of the solution is 9.32. To make the pH of the solltion equal 9.5,
the conjugate base must be in excess to such a degree that the log of the base-to-acid ratio is 0.18. Choice
B lists
the conjugate base (sodium cyanide) in excess, so choice B is valid. From choice A, we know that an ammonium
and ammonia solution must have excess ammonia for the pH to equal 9.5. If one-half equivalent of the strong
acid HCI were added to one equivalent of ammonia, then the pH would equal the pru p.zoy. The excess HCI
u.dd"9- lowers the pH, so the value is less than 9.5. This makes choice C invatid and thus the
answer you
should choose. From choice D, we know that an hydrocyanic acid and cyanide solution must have excess
cyanide for the pH to equal 9.5. If one-half equivalent of the strong base NaOH were added to one equivalent
of hydrocyanic acid, then the pH would equal the pKu Q.32). Ti-," NaOH added raises the pH to a
value greater than 9.32 and approximately equal to 9.5, making choice D """us
valid. Choose answer C.
't_6.
Choice B is correct. One half-equivalent of base when added to one equivalent of carbonic acid removes the
first proton from half of the carbonic acid molecules present in soluti,on. This results in a solution of half
carbonic acid and half bicarbonate ([H2Cog] = tH-o3-l). When the concentration of acid equals the
concentration of conjugate base, pH equals pKul for carbonic acid, which is 6.37, as given in the passag".
Wt
one and one-half equivalents of base are added to one equivalent of carbonic acid, tie first proton is c[mpletely
"r,
removed from all of the carbonic acid molecules present in solution. The remaining half of an equivalent
continues to remove the second proton from half of the bicarbonate molecules present in iolution. This iesults in
a solution where [HCO3-] = [CO32-]. When the concentration of bicarbonate equals the concentration of
carbonate, pH equals pKu2 for carbonic acid, which is 10.83, as given in the purrig". This makes choice B
correct. When one and one-half equivalents of base are added to one equivalent of
lhosphoric acid, the first
proton is completely removed from all of the phosphoric acid molecules piesent in solution. The remaining half
of an equivalent continues to remove the second proton from half of the dihydrophosphate present in solution.
This results in a solution where [H2POa-] = [HPoa2-1. When this equality irotds tr,re, tn" pH equals pKu2 for
phosphoric acid. From Table 2, we know that Ku2 for phosphoric acid is e .Z x 10-8, which to a pKu2
"qrrit",
value of 8 - log 6.2, which is a little over 7. This does r-,ot *ute a pH of 10.83, so choice C is eliminated. \iVhen
two and one-half equivalents of base are added to one equivalent of phosphoric acid, the first an4 second
Ptglolt are completely removed from all of the phosphoric acid molecules piesent in solution. The remaining
half of an equivalent removes the third proton from half of the hydrophosphate in solution. This results in a
solution where [HfOnz-1 = [POa3-1. \Alhen this equality holds true, the pH equals pKu3 for phosphoric acid.
From Table 2, we know that Ku3 for phosphoric acid is 4.8 x 10-13, which equates to a pKu3 value of tg - log 4.g,
which is a little over 12. This does not make a solution with a pH of 10.83,1o choice D is eliminated.
\7. Choice C is correct. One and one-half equivalents of base when added to one equivalent of oxalic acid
completely removes the first proton from all of the oxalic acid molecules present in soluiion and continues on to
remove the second proton from half of the bioxalate present in solution. This results in a solution where
[HC2oa-] = [Czoq2-]. When this equali_ty holds true, ihe pH equals pKu2 for oxalic acid. From Table 2, we
know that Ku2 for oxalic acid is 5.1 x 10-5, which equates to a pKl2 ,rul,r"-of 5 - log 5.1, which is less than Z, so
choice A is eliminated- One-half equivalent of base when added to one equivalent bf carbonic acid removes the
first proton from half of the carbonic acid present in solution. This produces a solution where
[H2CO3] =
[HCo3-]. When this equality holds true, the pH equals pK21 for carbonic acid, which is 6.27, as given in the
passage. Choice B is eliminated. One-half equivalent of base when added to one equivalent of hipochlorous
acid removes the proton from half of the hypochlorous acid present in solution. This results in a solution
where
[HCIO] = [ClO-]' \A/hen the concentration oJ acid equals the concentration of conjugate base, the pH equals pKu
for HCIO, which is 7.49 as given in the table, Choiie C is therefore correct. Onl-taff equivaleni of acid when
added to one equivalent of pyridine adds a proton to half of the pyridine present in solution. This results in a
solution where [C5H5N] = [C5H5NH+]. \zVhen this is true, the pH pKu for C5H5N, which is 5.16, as
given in Table 1. Choice D is eliminated. "qnuir
18. Choice C is correct. The pKu value for formic acid (HCO2H) is 3.78. In order to have a pH = 4.00, the solution
must be mixed with excess conjugate base (HCO2-). This makes choice A valid. The pKu value for anilinium
cation (C6H5NH3+) is 4.64. Lr order to have a pH = 4.00, the solution must be mixed with excess conjugate acid
(C6H5NH3+). This makes choice B valid. The pK6 value for benzoic acid (C6H5CO2H) is 4.19. In order to
have a pH = 4.00, the solution must be mixed with excess conjugate acid (C6H5COZH). This makes choice C
invalid. If excess C6H5CO2- were mixed with C6H5CO2H, then the pH of the solution would be greater than
4.19, which is greater than 4.00. This makes choice C invalid. You should select choice C. The pKu value for
pyruvic acid (H3CCOCO2H) is 3.89. In order to have a pH = 4.00, the solution must be mixed with excess
conjugate base (H3CCOCO2-). This makes choice D valid.
19. Choice A is correct. Blood that is rich in carbon dioxide is also rich in H2CO3. Since carbonic acid is acidic, the
pH decreases as carbonic acid is added to solution. The final solution thus has a pH lower than7.4. This makes
choice A the correct choice. Because the amount of acid is increasing, the phosphate buffer system is affected.
The additional hydronium ion present is absorbed by the phosphate buffer, thus increasing the amount of
H2POa- present and decreasing the amount of HPO42- and PO43- present in solution. This eliminates choice B.
If llzCbi is added to solution, it equilibrates by making hydronium ion (H3O+) and bicarbonate anion (COrz-;.
This results in increases in the concentrations of both bicarbonate and hydronium ions. This eliminates choices
C and D.
20. Choice D is correct. The concentration of the conjugate base is greater than the concentration of the acid when
the pH is greater than the pKu. When the pH is greater than the pKu, the log of the ratio of base to acid is a
positive value, indicating that the ratio of conjugate base to acid is greater than 1.0. The pKu for HF is 3.17, so
at pH = 3.00, the pH is less than the pKu. This eliminates choice A. The value for pKul for H2CO3 is 6.37, so
at pH - 6.00, the pH is less than the pKu1. This eliminates choice B. The value for pKu2 for H2C2Oa is 5 - log
5.1 (which is roughly 4.3), so at pH = 4.00, the pH is less than the pKu2. This eliminates choice C. The value
for pKu2 for H3PO4 is 8 - log 6.2 (which is roughly 7.2), so at pH = 8.00, the pH is greater than the pKu2. This
results in the base being more concentrated than the acid, making choice D the correct choice.
21. Choice C is correct. The value of pKul is 6.37 and pKu2 is 10.33 for carbonic acid (H2CO3). The pH is greater
than pKu1, so the conjugate base (bicarbonate) is in greater concentration than the acid (carbonic acid). This
makes choice A valid. The pH is less than pKu2, so the conjugate acid (bicarbonate) is in greater concentration
than the base (carbonate). This makes choice B valid. The value for pKu2 is7.20 and pKu3 is 12.32 for
phosphoric acid. The pH is greater than pKu2, so the conjugate base (HfOnZ-; is in greater concentration than
the acid (H2POa-). This means that choice C is invalid, making it the correct choice for the question. The pH
is less than pKuj, so the conjugate acid (UPO42-) is in greater concentration than the base (POna-;. This makes
choice D valid.
22- Choice C is correct. To reach equivalence, it takes (0.03 L)(0.20 M) = 0.000 moles of NaOH. Formula weight is
grams per mole equivalent, so the unknown acid has a formula weight of 1.0 g/O.OO6 moles = 767 grams per mole.
From the choices given, the only acid that is close to 1.67 grams per mole is p-nitro benzoic acid
(O2NC6HaCOZH). To verify your answer, add up the atomic weights of the molecule, O = 12, N = 14, C = 1,2
and H = 1 (all in grams per mole). The sum is 46 (for NO2) + 76 (for CoH+) + 45 (for CO2H) = 167 grams Pet
mole, so the answer is definitely C.
25. Choice C is correct. The formula weight of a compound is measured in grams per mole. The moles are
determined from 0.040 liters x 0.25 M = 0.010 moles. The formula weight is 1'0 8/0.010 moles = 100 grams per
mole. Pick choice C for best results.
24. Choice D is correct. Since the graph begins at a high pH, the initial solution must be basic. This rules out
choices A and B. The equivalence point is at pH = 4.6, which is < 7. This indicates that the neutra.lized
product is a weak acid, so the titrant must be a strong acid. (Because the equivalence point is not 7.0, the
compound must be a weak base). The graph represents D, the titration of a weak base by strong acid.

25. Choice D is correct. To predict the pH near the equivalence point, which is what you're doing when you choose
an indicator, you should use the Henderson-Hasselbalch equation. At 2 pH units beyond the pKu of the acid,
the ratio of conjugate base to acid is 100:1, which means that the reaction is almost at equivalence. This is the
point at which the indicator should start to show some color change. In this question, the pKu for the weak
acid is 7.20. The best indicator is active around pH = 9.20. This is choice D, phenolphthalein, which is active
between 8.0 and 9.6. You may remember using phenolphthalein in titration labs from general chemistry.
26. Choice C is correct. A buffer is formed when a conjugate pair (acid and base) are present in solution in roughly
equal molar amounts. To achieve this, you can: (1) mix the conjugate acid and base evenly, (2) add the acid and
half-titrate it (add a half molar equivalent of strong base), or (3) add the base and titrate it halfway (add
half an equivalent of strong base). Choice A is a case of full titration, which leads to the complete conversion
of the weak acid to its conjugate base, so that is out. Choice B is a case of over-titrating by adding double the
amount of base needed. In choice C, the weak acid (H3CCO2H) is added to a half-equivalent of strong base,
which results in a buffered solution. Pick C. Choice D is an acid with an acid, which doesn't react.
27. Choice D is correct. The best choice for a buffer of pH = 8.5 is a weak acid with a pKa close to 8.5 mixed in
solution with its conjugate base. The acid 4-ethanoylphenol (H3CCOC6HaOH) has a pKu of 8.4, which is
closest to the 8.5 value, so choose D. To make the buffer equal to 8.5 (slightly to the basic side of 8.4), there
should be a slight excess of the conjugate base relative to 4-ethanoylphenol. The log of the ratio of conjugate
base to weak acid should be 0.1, a positive number, so the ratio of conjugate base to weak acid must be greater
than 1.
28. Choice A is correct. The formula weight, also known as the empirical weight, is derived from the mass of
compound per mole of equivalent. Adding up the molecular mass of the compound yields 90 grams,/mole.
Because there are two equivalents of protons per oxalic acid, the formula weight is 45 grams/mole. Pick A. Be
sure not to pick B by mistake.
29. Choice B is correct. If the titration required 30.0 mL of 0.10 M KOH(aq) to neutralize 25.0 mL of 0.10 M HA(aq),
then according the relationship MacidVacid = MbaseVbar", the molarity of the acid must be 0.12 M. However,
seven drops (although the exact number is irrelevant) of HCI must be added to back titrate to the equivalence
point. This means that the molarity of the unknown weak acid is actually a little less than 0.12 M, making
choice B the best answer.
30. Choice C is correct. As a general rule, the pH at the equivalence point is either three units above or below the
pKu for the acid depending on the type of titration. This would mean that the pH at the two equivalence
points differs by approximately 6 pH units. This makes choice C the best choice.
To calculate the pH exactly for the two titrations, one can plug into the shortcut equation for both the conjugate
base (formed at point b) and conjugate acid (formed at point d). At the equivalence point, the volume is double
its original value, so the concentration is half of its initial value. At point b, there is 0.05 M OAc-, and at point
d, there is 0.05 M HOAc. From Figure 1, the pKu for HOAc is roughly 5.0. This means that pK6 for OAc- is
roughly 9.0 The two calculations are shown below:
ForHOAcatpointd:pH=lpKu-ltoglHAl =1tS.Ol -1log(0.05) =2.5-1(-t.3)=2.5+0.65=3.15
2' 2- 2 2- 2
ForOAc-atpointb: pOH=lpKu-ltoglA-l
' =4.5-lf-r.:l =4.5+0.65 =5.15.'.pH=8.85
- =ftO.Ol-llog(0.05)
2' 2 - 2 2 2
The difference in pH is 5.7, so the best answer is choice C.
31. Choice C is correct. The pH of a solution depends on the concentration and strength of the reagents in solution.
The highest pH at equivalence results from the presence of the strongest conjugate base (since all of the
conjugate bases are in equal concentration). At equivalence, choices B and D are both acids, so they are both
eliminated (pH at equivalence is less than 7.0). Methyl ammonium is less acidic than acetic acid based on the
relative pKu general values given in the passage. The stronger base is the conjugate base of the weaker acid,
making methylamine the more basic compound between acetate and the amine. The greater hydroxide
concentration results from the titration of 0.10 M H3CNH3C1, so choice A is eliminated, and thus choice C is
the best answer.
Copyright @ by The Berkeley Review@ Section V Detailed Explanations

32. Choice C is correct. When the pH is greater than the pKu, then according to the Henderson-Hasselbalch
equation, the conjugate base is in greater concentration than the acid. This eliminates choices A and B.
Because the pH and pKu are negative log values, if pH > pKu, then [H*] < Ku. Choice C is correct.
33. Choice C is correct. Initially in the titration of H3CCO2H by NaOH (at point a), the concentration of
H3CCO2H is 0.10 M. At the equivalence point in the titration of H3CCO2Na by HCI (point d), the
concentration of H3CCO2H is 0.05 M, due to dilution that occurs when the aqueous base solution is added. Note
in the graph below that the final volume is 50 mL, not 25 mL. The concentrations of H3CCO2H between the two
points in question differ by a factor of 2. This means that the pH of the two solutions differs by -log{2. With
the H3CCO2H concentration being greater at the initial point of the titration of H3CCO2H by NaOH than the
equivalence point of the titration of H3CCO2Na by HCl, the pH is lower at point a (the initial point of the
titration of H3CCO2H by NaOH). The best answer is therefore choice C. The graph below shows the data:
pH
Start with 25 mL Finish with 50 mL

0.10 M II3CCO2- 0.05 M II3CCO2-
Start with 25 mL ii Start with 50 mL

0.10 M H3CCO2H 0.05 M H3cco2H
mL titrant solution added 25.0
34. Choice D is correct. By having a lower pKu value, H3CCO2H is more acidic than CH3NH3+. Because it is
more acidic, H3CCO2H buffers at a lower pH than CH3NH3+, so choice A is eliminated. Because it is more
acidic, H3CCO2H has a conjugate base that is weaker (and thus has a higher pKb value) than the conjugate
base of CH3NH3+. Choice B is thus eliminated. Because it is more acidic, H3CCO2H dissociates more than
CH3NH3+, so choice C is eliminated. Because it is more acidic, H3CCO2H is a better electron pair acceptor
than CH3NH3+ making choice D correct. The point of this question is to view the many different ways in
which relative acidity can be expressed.
35. Choice D is correct. Because it is more acidic, H3CCO2H yields a lower pH value than CH3NH3+ of equimolar
concentration, so choice A is valid and consequently eliminated. Because it is more acidic, H3CCO2H has a
conjugate base with a higher pK6 value than the conjugate base of CH3NH3+. Choice B is valid and thus
eliminated. Because it is more acidic, H3CCO2H produces more conjugate base than CH3NH3+ when added to
water, so choice C is valid and consequently eliminated. Because it is more acidic, H3CCO2H is a better proton
donor than CH3NH3+, so choice D is not true. The correct answer is choice D.
35. Choice D is correct. Given that the pKa value for HF is lower than that of H3CCO2H, HF is a stronger acid
than H3CCO2H. This means that equimolar HF and H3CCO2H solutions result in a lower pH for the HF
solution. This makes choice A invalid and thus eliminated. \Alhen equimolar HF and H3CCO2H are titrated
equally, they both have conr.erted into the same amount of conjugate base in the buffer region, meaning that [F-]
equals [HgCCOZ-]. This eiiminates choices B and C. When both HF and H3CCO2H are half-titrated, the pH
of solution is lower for the FIF solution, because the pH equals the pKu of the acid and the pKu value for HF is
lower than that of H3CCO2H. This meeins that pH(HF solution) < pKa(acetic acid) which means that [H+]1gp
solution) > Ka(acetic acid)- This makes choice D the best choice'
97. Choice A is correcl The initiai pH is greatest in the solution with the lowest concentration of the weakest
acid. H3CCO2H is the rt-eaker acid of the two choices, and 0.010 M is the lowest of the concentrations. This
means that choice A is correcl
Copyright @ by The Berkelev Rerierva 343 Section V Detailed Explanations

38. Choice A is correct. When the pH of the solution exceeds the pKu for the acid, then there must be an excess of
conjugate base relative- to the conjugate acid, according to the Henderson-Hasselbalch equation. This
eliminates choices C and D. The pH is the negative log of the [H3O+] and the pKu is the negaiive log of the
Ka. If PH > pKu, then the [HeO+] must be less than Ku. This makes choice A iorrect. To make this clearer,
when pH = PKa, then [H3O+] = Ka. As the pH increases, the [H3O+] decreases, while both pKu and Ku remain
constant. The [H3O+] is thus less than Ku. The derivation from the equation for Ku is shown below:
ro =]f Ku,
whenpH>pKu,#L, 1.0,so- x-a >- 1 and Ka > [H:o*l
" =[H]o.llai
rcu
tHAl [Hso'l tHA] tHAl 1Hrorl
39. Choice C is correct. In all three weak acid titrations, the volume of sodium hydroxide solution added to reach
the equivalence point was 25.0 milliliters, so choices A and B are eliminated. The higher the acid
concentration initially, the more conjugate base that forms at the equivalence point. The higher the
concentration of conjugate base, the higher pH for the solution at the equivalence point. Pick choice C.
40. Choice C is correct. If the base concentration is doubled while the acid concentration remains constant, then the
base is twice as concentrated as the acid. Half as much titrant (base) is required, so the equivalence point is
reached in half the base volume. This eliminates choices B and D. The acid is still HCI (i strong acid), and
the titrant base is still NaOH (a strong base), so the pH is still 7.0 at equivalence, and the .rrrr" iti1 has the
same shape (lip-free and sigmoidal). The best answer is choice C.
41.. Choice C is correct. Choice A is eliminated, because a strong acid and strong base do not make a buffer when
mixed together. Choice B is eliminated, because NaOH is not a weak base. Choice D is eliminated, because
,f" pH changes throughout the titration; but it is at the equivalence point that the pH changes drastically.
Choice C is the best answer, because the log scale means that as long as the concentrations are 100 times
different, then the linear difference is 2.0 on the log scale. This in turn *"a.r that the slopes are equal through
most of the titration, excePt near the equivalence point. Perhaps the answer would be betier if it m;ntioned the
different concentrations of the titrant bases in each trial. The best answer is not always perfect.
A.' Choice D is correct. Ammonia is a weak base, so choices A and C are eliminated, because the curves do not show
the initial dip in pH (lip-o-weakness). The greater the concentration of ammonia initially, the greater the
pH initially, so the 1.00 M NH3 has a higher starting pH than the 0.010 M NH3. The correct choice is D.
43. Choice D is correct. The greatest Ku value correlates with the strongest acid. Of the acids in the experiment,
only HCI shows a strong acid titration curve (lip-free) and an equivalence pH of 7, so choice D is the answer.
44. Choice B is correct. The initial pH in the titration of HCN is greater than the initial pH in the titration of
HCIO, according to the titration curve in the passage. This means that the initial pH in the titration of HCN
must be greater than 4.23, which eliminates choice A. Because HCN is acidic, the initial pH must be below 7.0,
which eliminates choice D. The pH at the equivalence point in the titration of HCIO ls less than the pH at
the equivalence point in the titration of HCN, according to the titration curve in the passage. This means that
the pH at the equivalence point in the titration of HCIO must be less than 11.01, which eliminates choice C.
The only choice that remains is choice B, so choice B is the best answer. The numbers are reasonable, because
5.16 is greater than 4.23 (and 4.74 if you look at the titration curve), and 10.08 fits between 8J2 and 11.01 in the
equivalence pH data.
45. Choice B is correct. Statement is invalid, as the curves in Figure 1 show. Strong acids fully dissociate upon
addition to water, so the pH is low in the beginning, It remains relatively constant, because pH is a log scale.
It is the strong acid curve that has a plateau in the beginning. A buffer is defined ur u ro,tghly equai molar
mixture of a weak acid and its conjugate base. Based on the definition, a strong acid when mixed wiih a strong
base does not form a buffer. Do not be fooled by the flat region of the strong acid titration curve, which is
attributed to mathematics, not buffering. Statement II is valid. Statement IiI holds true for strong acids, but
not for weak acids. For instance, a weak acid with a pKu greater than 7,has a pH greater than seven for mosi
of the buffer region, which is observed before the equivalence point. For a weak acid titration curve, the pH is
greater than 7 at equivalence, so there must be a point on the curve before the equivalence point that is greate:
than 7. Only statement II is valid, so choice B is correct.

Choice D is correct. Because 0.10 M HIO has a greater pH than 0.10 M HCN, HIO must be a weaker acid than
HCN, and the titration curve associated with HIO would have all of the points greater than the titration
curve of HCN. The pKu of HCN is greater than 8.72 (the half-equivalence pH is greater than the equivalence
pH in the HOAc titiation curve). fhus, the pKu of HIO mustbe greater thund.7z, which makes choice A
incorrect. The pH at equivalence in the titration of HCN is 11.01, so the pH at equivalence in the titration of
HIO must be greater than 11.01, and choice B is thus eliminated. The pH of 0.10 M HIO must have a pH less
than7.0, because although it is a weak acid, it is still acidic. The pH cannot be7.2!, so choice C is eliminated.
The pKu of HCN is 9.32, so the pK" of HIO must be greater than 9.32. The pH at equivalence must be at least a
pH unit less than 13 (the pH of 0.10 M KOH), so the difference between the pKu and the pH at equivalence is
less than three pH units. This makes choice D a true statement. The other way of confirming choice D is to look
at the trend whereby as the acid gets weaker, the difference between pK" and the pH at equivalence gets
smaller. The difference for HCN is 11.01 - 9.32 = 1.69. For HIO, the difference should be less than 1.69.
47. Choice B is correct. When 10 mL 0.10 M HCIO are mixed with 10 mL 0.15 M KCIO, a buffer is formed. \zVhen
water is added to a buffer, the acid and conjugate base are diluted equally, so the pH does not change. The pH
consequently remains at7.64. The best answer is choice B.
48. Choice A is correct. Because CN- is a stronger base than CIO- (HCN is a weaker acid than HCIO), the titration
curve for NaCN should have a higher initial pH, higher pH at the half-titrated point (because the pKu for
HCN is greater than the pKu for HCIO), and higher pH at the equivalence point. This can be seen only in the
titration curve in choice A. Choices C and D should have been eliminated immediately, because their
respective graphs show that the two acids have the same pKu, which according to Figure 1 in the passage,
they don't have.
49. Choice A is correct. The stronger the acid, the lower its pKu value. HCI is the strongest acid, so it has the
lowest (and only negative) pKu value. Choices C and D are eliminated. From the titration data, it can be seen
that the next strongest acid is HOAc, meaning that the pKu for HOAc should be just ahead of the pKa for HCI
in the sequence. This makes choice A the best answer.
50. C is correct. The moles of NaOH can be calculated from the moles of the acid (H+) that were neutralized, since
the amount of base added is to the point of neutralization, where the moles acid equals the moles base. Keep in
mind that sulfuric acid is diprotic and that the units given are units of normality. Normality already takes
into account the two equivalents of hydronium ion per sulfuric acid. Given in the passage, the number of moles
of acid (H+) is (.025 LX0.20 M) = 0.005 moles. To reach equivalence, this must be the moles of NaOH as well.
The question asks for concentration, so the moles NaOH must be divided by the volume of solution.
Molaritv = moles = mole = 0.25M

0.005
' liter L
0.02
Thus, the concentration of NaOH(aq) is 0.25 M. Answer C is the best answer for you to choose. Do what is best!
51. Choice B is correct. The first proton is always the easiest to remove (that is, pKal is smaller or more acidic
than pK62). Reversing this wording gives the correct answer B. The first proton must be easiest to remove,
because it comes off first. This also a rare case where the correct choice contains the word "always."
52. Choice D is correct. Normality is based on the molarity of equivalent base required to neutralize all of the
acidic protons. Since there are three (3) acidic protons on H3PO4, the normality is three times the molarity.
NormalitY = 3(0'3 M) = 0.90 N H3POa'
Pick choice D if you want to be a supemova of chemistry wisdom. Or pick it because it's the right answer.
53. Choice C is correct. The conversion from H3POa to H2PO4- inv_olves the loss of the first proton, so the acidity is
calculated using pKu1. The conversion from H2POa- to HPO42- involves the loss of tne second proton, so the
acidity is calculated using pKu2. Mixing NaH2POa and Na2HPO4 yields H2POa- and HPO42-, so the pH of
the solution is close to pKu2. Because there is more of HPOnz- in solution than H2PO4-, the pH is greater than
pKu2. This eliminates choices A and B. If the solution contained pure HPO42-, the pH would be an average of
pK62 and pKaa. The presence of H2PO4- lowers the pH, making the best answer choice C. Using the
Henderson-Hasselbalch equation would give a pH = pKa2 +log2 = pKu2 + 0.3.
Copyright O by The Berkeley Review@ 345 Section V Detailed Explanations

54. Choice D is correct. Sulfuric acid has only two (2) acidic protons, whereas phosphoric acid has three (3) acidic
protons to neutralize. Thus, phosphoric acid requires only two-thirds the amount of base that is required for
sulfuric acid. The number of moles of phosphoric acid is (25 mL)(0.6 M) = 15 mmoles H3POa. This means that
there are 45 mmoles of H+ to neutralize. The question asks how many mL of 0.40 M H2SOa(aq) contains this
amount of H+. 0.40 M H2SOa(aq) = 0.8 M H+. This means that the number of mL ir, 45^mr-n9le, which equals
0.8 M
56.25rnL 0.40 M H2SO4, given as answer choice D.
55. Choice B is correct. Phosphoric acid is a triprotic acid, so choices A and C can be eliminated. Because the first
proton of phosphoric acid is weak, the start of the curve should have a cusp (lip-o-weakness). It is only in
choice B that the cusp is present, so the best answer is choice B.
56. Choice A is correct. Flask 2 is initially filled with 40.0 mL of 0.30 N H3POa. The concentration is equivalent to
0.10 M H3POa. Adding 40 mL of 0.30 N NaOH completely neutralizes all three protons on phosphoric acid,
leaving only the conjugate base PO43-1aq) in solution. All of the moles of phosphoric acid(H3PO4) present
initially are converted into phosphate (POnr-;. The addition of 40 mL of NaOH solution also doubles the
volume of the solution, increasing it from 40 mL to 80 mL. This cuts the concentration in half. Had the volume
remained 40 mL, and if all of the H3POa were converted into PO43-, then the concentration of PO43-(aq) would
have been 0.10 M. Flowever, the final concentration after the extra 40 mL of solution is accounted for is 0.5 x 0.10
M POa3-(aq). That equals 0.050 M POa3-(aq), which is choice A.
57. Choice D is correct. Because there are two vertical inflection points on the titration curve, the acid has two
equivalence points and thus is diprotic. Because of the lip-o-weakness (initial cusp in the titration curve), the
first proton is associated with a weak acid. The second proton is always weaker than the first proton, so both
protons are weak. Choice D is the best answer
58. Choice D is correct. The first pKu is always lower than the second pKa by definition, meaning that choice A is
valid for all polyprotic acids. The first equivalence point (point c) is greater than the point where pH = pKat
(point b). This makes choice B a valid statement and thus eliminates it. The second equivalence point (point e)
is greater than the point where pH = pKu2 (point d). This makes choice C a valid statement and thus
eliminates it. The first equivalence point (point c) is less than the point where pH = pKaZ (point d). This
makes choice D an invalid statement and thus makes it the best-answer. To go from the first equivalence point
to the point at which the pH equals pKu2 (where [HA-] = [A2-]), base must be added to the solution. This
means that pKu2 is greater than the pH at the first equivalence point (addition of base increases the pH),
confirming choice D.
59. Choice B is correct. To carry out the titration, a strong base must be added to react with the unknown weak acid.
The pH increases as base is added, and according to the curve in Figure 1, the pH does increase when moving
left to right. The best answer is choice B. A weak base is not strong enough to carry out the titration.
60. Choice A is correct. To go from one equivalence point to another requires that one equivalent (whatever exact
quantity that may be) of base titrant be added. Choices B and D can both be eliminated, because they require
an equal amount of base. It takes one equivalent of titrant to go from pH = pKal to pH = pKa2, so in choice A,
more than one equivalent is required. In choice C, less than one equivalent is required. This makes the best
answer choice A. On the graph, to go from one labeled point to the next labeled point, requires one-half of an
equivalent. So starting to before point b and finishing after point d clearly is more than one equivalent.
61. Choice D is correct. When pH = pKal (true at point a), exactly one-half of an equivalent of titrant has been
added to solution. To reach the second equivalence point, two equivalents must be added. If 5 mL does not reach
the point at which pH equals pKu1, then one-half of an equivalent must be greater than 5 mL. This means that
one equivalent is greater than 10 mL and thus, two equivalents are greater than 20 mL. More than 20 mL is
required to reach the second equivalence point, so the best answer is choice D.
62. Choice B is correct. Point d is the point at which pH = p_Ka2 (where [HA-] = tA2-l). Point e is the second
equivalence point (at which all of the species present is A2-). Between the two points (d and e), it is safe to
assume that 42- is the predominant species with some HA- present. This is best described by choice B.

63. Choice D is correct. Point b is the point at which pH = pKa1, so [H2A] = [HA-]. This makes choice A valid.
Point c is the first vertical inflection point, so it is the first equivalence point. Choice B is valid. Point d is the
point at which pH = pKa2, because [HA-] = [A2-]. Choice C is valid. Point f represents a point where excess
base is being added and all of the species exists in the fully deprotonated form (A2-). Pick D to feel good.
The passage is easier when all of the points in Figure 1 are labeled.
a (All exists as COq2-)
g(pH = pKuz)
b (pH > pKu2)
d (First equivalence point, all exists as HCO3-)
(pH =pK.r)
B (PH < PKur)
h (Second equivalence point,

all exists as H2CO3)
i (excess acid added)
0.5 1.0 1.5 2.0 Equivalents strong acid added
64. Choice C is correct. The pH equals the pKu of the acid when the titration is half way to the equivalence point.
The two points marked by x represent the points at which pH = pKu. The value of pKul is lower than pKu2, so
the correct answer is point f, choice C. Point c is where the pH = pKa2, point d is the first equivalence point
(where the species exists as HCO3-), and point h is the second equivalence point (where the species exists as
H2CO3).
65. Choice B is correct. Conjugate pairs have pK values that sum to 14. In the case of a diprotic acid, the first
proton to be lost in an acid dissociation reaction corresponds to the second (last) proton to be gained in a base
hydrolysis reaction. This means that the following conjugate pair relationships hold true.
HrCO3(ar) S H*(uq) + HCO3-(ar) HCo3-(ae) =--EL H+(aq) + cor2-(at)

Pxlz PKilr
The conjugate pair relationship yields pKal + pKbZ = 14 and pKa2 + pKbl = 14. This makes choice A valid and
choice B invalid. The question asks you to seek a statement that is not true, so choice B is best. According to
Figure 1, the initial pH is the highest point, and it is greater than pK32, making choice C a valid statement.
According to Figure L, the second equivalence point is lower than all pKu values, including pK21. This makes
choice D a valid statement.
66. Choice B is correct. In a fashion similar to the way in which we determine the isoelectric point of an amino
acid, the middle equivalence point can be determined by knowing that it lies exactly in the middle of the two
pKu values. The pH of the first equivalence point is thus found by averaging pKal and pKu2. The pH cannot be
7.0 for this titration, and the Kn when dealing with the acidity of bicarbonate would involve pKu2 (because it
is the second proton to be lost). The best answer for this question is choice B.
67. Choice B is correct. At point e of the titration curve, the amount of HCI added is greater than one equivalent
but less than one and one-half equivalents. This makes choice A a valid statement. The pH should be lower
than the pH of point c (the point at which pH = pKaZ), so choice D is a valid statement. The value of pK31 is
6.37, so choices B and C are contradictory answers. The pH is greater than the pH at point f (the point at
which pH = pKut), which makes choice B invalid, and thus the best answer. It is critical in this passage that
you recognize where pKul and pK32 lie.

68. Choice C is correct. Bicarbonate is in its greatest concentration at the first equivalence point. This point lies
midway between pKul and pKa2. From the passage/ the values for pK61 and pK62 are 3.67 and 7.63
respectively. The values for pKnl and pKu2 are thereforc 6.37 and 10.33, respectively. The bicarbonate
concentration is greatest midway between 6.37 and 10.33. The best answer is choice C.
69. Choice A is correct. The pH change between points c and d corresponds to the change between pK22 and the first
equivalence point. This is greater than the incremental change from point d to e (first equivalence to a point
with pH greater than pKul), greater than the incremental change from point e to f (a point with pH barely
greater than pKul to a point where pH = pKat), and greater than the incremental change from point f to g (a
point with pH = pKal to a point where pH is just less than pKat). The best answer is choice A. It may be easier
to answer this question by observing the titration curve and noting the change in pH (y-axis) between the two
points in question.
70. Choice A is correct. Changing the labeling of the y-axis from pH to pOH does not change the shape of the
graph. The base is still weak, so choice B can be eliminated. The pOH starts lower than 7 (because pH starts
greater than 7), so choices C and D are eliminated. The best answer is choice A, because the graph flips
vertically about the pH or pOH = 7line when pH and pOH are interchanged.
71. Choice C is correct. Because the indicator has to be active at the equivalence point, the pKu of the indicator
has to be greater then the pKu of the acid being titrated. This is because the equivalence pH is higher than
the pKu for the acid being titrated. Because the acid being titrated is weak, the pH at equivalence is greater
than 7,0. It is stated in the passage that the pKu values should differ by about 3. This makes the best choice C
(which differs by 3.5 pH units) the best. Choice C is roughly three units above the pKu for the acid and is
greater than 7.0.
72. Choice A is correct. An indicator concentration that is too high results in a second competing acid that affects
the titration and a faint color in the solution that is permanent. If the indicator were in concentration equal to
the acid being titrated, then the curve would look like a diprotic acid. While the color is affected by the
excess indicator, the color change is certainly not going to be too minimal, so choice D gets eliminated. It is a
color change, which involves frequency of light. A higher indicator concentration affects the intensity of the
light, so the color change would just be more intense, but every bit as detectable. This eliminates choice C.
While the viscosity may change with the addition of the indicator, this should not affect the reaction
equilibrium, only the rate. The best answer is choice A, because the indicator can react with the titrant base.
You may recall from titration experiments in general chemistry lab that you add only a few drops of indicator
to the solution.
/J. Choice A is correct. When the pH is greater than the pKu, the solution has more conjugate base than acid, so
choices C and D are eliminated. The difference between the concentrations is 2 on the log scale, so on a linear
scale, it can't be 2 : 1, (it must be 100 : 1). This eliminates choice B and confirms that choice A is the correct
answer. Using the Henderson-Hasselbalch equation, the value can be determined.
pH=pKa+togJ4l=pKa +2* loqlA-l

" =z= [A-] =102=1oo
tHAl tHAl
74. Choice D is correct. A good indicator changes color (thus it cannot be transparent) and it must be present in lou-
concentration in solution. This eliminates choice A. If it is not affected by acid-base reactions, it can't react in a
way that indicates a pH change. Choice B is eliminated. Because the indicator must undergo some acid-base
chemical reaction, it is best when the indicator is a weak acid or weak base, so it does not affect the pH much.
If it were a strong acid or strong base would alter the pH and affect the titration. The best answer is choice D.
75. Choice C is correct. The question calls for a titration in which the pH at equivalence is the same, regardless oi
the concentration of reactants. Choices A and B can be eliminated, because the pH of weak acids and base'
varies with the concentration. The pH at equivalence when the first proton of a weak diprotic acid has beer.
removed is the average of pKul and pKu2. You most likely can recall this from determining the isoelectric pH
of an amino acid. It applies to any polyprotic acid, including the amino acids. Because the pKu values do nc":
change, the pH at equivalence does not change, so the same pH at equivalence is observed. The best answer i.
choice C. The second proton of a diprotic acid is affected by the concentration, so choice D is eliminated.
Copyright @ by The Berkeley Review@ 34A Section V Detailed Explanations

76. Choice B is correct. Choice C should be eliminated first, because the pH at equivalence is greater than the pKu
of the acid. Choice D should also be eliminated, because the color changes over a range, not at one exact value.
At the equivalence pH (when the indicator is changing color), a change of one pH unit is substantial. This
eliminates choice A. The best answer is choice B, because the pH changes so rapidly that one drop of titrant
can change the pH by more than one pH unit at the equivalence point. The indicator can determine this value
to the accuracy of the one drop.
Choice A is correct. The titration of 1.0 M benzoic acid by 1.0 M potassium hydroxide has an equivalence pH
value greater than 7.0, because the acid is weak and the base is strong, so the conjugate base that is formed at
equivalence makes the pH higher than7. The conjugate base, benzoate, has a pK6 value of 9.79. Tl,:tis confirms
that benzoate is a weak base. The best indicator must have a color change range greater than 7.0. Indicator I
goes from reddish orange to mango as pH increases from 6 to 8, so Indicator I has a range that is too low.
Indicator I is eliminated. Indicator I may seem close, but as the benzoic acid titration reaches equivalence, the
indicator would have already turned yellow, so no color change occurs at equivalence. Indicator II goes from
chartreuse to aquamarine as pH increases from 9 to 1.1., so Indicator II is a good choice. The pH at the
equivalence point falls between 9 and 11, in all likelihood. Indicator III goes from violet to clear as pH
increases from 3 to 5, so Indicator III is eliminated. Only hrdicator II will work, so the best answer is choice A.
If you wish to solve for the pH at equivalence, keep in mind that the conjugate base has formed and that the
solution's volume has increased, diluting all components. The pOH at the equivalence point is found using the
shortcut equation.
pOH=lpru-llogtA-l =Lp.zo1-ltog(0.5)=n.39-11-0.3)=4.89+0,15=5.04.'.pH=8.96
2 2- 2 2- 2
This means that the pH at equivalence is about 9.0. The 0.5 M conjugate base is determined, because when the
strong base was added to the benzoic acid, it not only converted the benzoic acid to conjugate base, it also
diluted the solution. With an equivalence pH of 9.0, only indicator II can work. A faster way to get the
approximate pH at equivalence is to average the pKa of the weak acid and the pH of the titrant. This yields
an approximate value. In this case, the average of 4.27 and 14 is 9.1. The approximate value is usually off by
about 0.15, which is close enough for our purposes.
78. Choice B is correct. The combination of colors that is nof possible for a solution is the one that does not have a
pH value at which the three colors may exist. In choice A, Indicator I is red at pH values of 5 or less, Indicator
II is yellow at pH values of 8 or less, and Indicator III is purple at pH values of 2 or less. At a pH value of 2 or
less, the color combination in choice A is possible. In choice B, Indicator I is mango at a pH value of 8, Indicator
II is yellow at pH values of 8 or less, and Indicator III is violet at a pH value of 3. The solution cannot
simultaneously be pH = 3 and pH = 8, so the color combination in choice B is not possible. In choice C, Indicator I
is red at pH values of 5 or less, Indicator II is yellow at pH values of 8 or less, and Indicator III is fuchsia at a
pH value of 4. At a pH value of 4, the color combination in choice C is possible. In choice D, Indicator I is
yellow at pH values of 9 or greater, Indicator II is aquamarine at a pH value of 11, and Indicator III is clear at
pH values of 5 or greater. At a pH value of 11, the color combination in choice D is possible. Choice B is the
best answer choice.
79. Choice A is correct. If the ratio of blue species to clear species within the indicator equilibrium is 1000 : 1 at pH
= 6, and the deprotonated form absorbs visible light (which makes the deprotonated form blue), then at a pH
of 6, the indicator is predominantly in the deprotonated form. This means that the pKu value is less than 6.0.
This eliminates choices C and D. Because the ratio is 1000:1, the log value is 3, making the pKu 3 units less
than the pH. The equation is as follows:
pH = pKa(indicator)*,.tTH## = pKa(indicator) + log 1000

6.0 = pK6l6dicator) + log 1000 = PKa(indicator) + 3
Thus, the PKa(indicator) = 3.0, so the best answer is choice A.
80. Choice D is correct. The key colors are faint mango with Indicator I (which implies that the pH is just greater
than 8) and faint chartreuse with Indicator II (which implies that the pH is just less than 9). The best option
for pH is thus choice D, 8.5, which falls between 8 and 9. Pick D to feel a rainbow of happy colors shine down.

81. Choice A is correct. The color change range for Indicator I is from 6 to 8, so the pKu value for Indicator I is
roughly 7. The color change range for hrdicator II is from 9 to 11, so the pKu value for Indicator II is roughly 10.
The color change range for Indicator III is from 3 to 5, so the pKu value for Indicator III is roughly 4. The pKu
value for Indicator I is incorrect in choices B and D, the pKu value for Indicator II is incorrect in choices B and C,
and the pKu value for Indicator III is incorrect in choice B. The best answer is thus choice A.
82. Choice C is correct. In Indicator III the color change of detectability is from violet (at pH of 3) to the first sign
of clear (at a pH near 5). The pH range is thus best described as from 3 to 5" which makes choice C the best
answer.
83. Choice C is correct. Indicator III is purple when protonated (at low pH) and clear when deprotonated (at high
pH). This means that the absorbance by the deprotonated form is beyond the visible range, which eliminates
choices B and D. The visible range is 400 nm to 700 nm, so only the 339 nm absorbance can apply to the
deprotonated species. Because the protonated form is purple, the highest absorbance (I-u*) must be in the
range of the complementary color of purple, which is yellow. Yellow light lies in the middle of the visible
spectrum/ so it must have a value somewhere in the middle between 400 and 700 nm. A value of.426 nm is low
enough to be associated with violet light, so the value of 598 nm must be the best choice for the absorbance of
the protonated species. The best answer is choice C. As a point of interest, there is no known indicator which
goes from colored to clear when deprotonated, because the negative charge usually lowers the transition energy
between the ground state and first excited state in a highly conjugated organic molecule. A highly conjugated
organic molecule is typical for an indicator.
84. Choice C is correct. Bromphenol blue at pH = 7.0 has a pH value greater than the pKu, so the species is present
in its anionic (conjugate base) form. The base form of bromphenol blue according to Table 1 is blue, so choice A is
eliminated. Bromcresol green in ammonia solution has a pH > 7.0, so the pH value is greater than the pK2.
This means that the species is present in its anionic (conjugate base) form. The base form of bromcresol green
according to Table 1 is blue, so choice B is eliminated. Thymol blue in acetic acid solution has a pH < 7.0, so the
pH value is less than the pKu, and the species is present in its cationic (conjugate acid) form. The acid form of
thymol blue according to Table 1 is also yellow, so choice C is correct. Bromthymol blue in hydroxide solution
has a pH > 7.0, so the pH value is greater than the pKu. This means that the species is present in its anionic
(conjugate base) form. The base form of bromthymol blue according to Table 1 is blue, so choice D is eliminated.
85. Choice A is correct. The titration of ammonia with hydrochloric acid forms an acid at the equivalence point.
This means that the pH at the equivalence point is less than 7.0. Of the choices, only phenolphthalein has a
pKu greater than 7.0, so phenolphthalein cannot be used as the indicator. The pH at the equivalence point
should equal the pKu of the indicator, so bromcresol green (pKa = 4.4), methyl orange (pKa = 4.0), and
bromphenol blue (pKa = 3.7) should all be close enough together that they can all work. The better of the
indicators depends on the initial concentration of ammonia. Choice A is correct.
86. Choice B is correct. The ideal indicator has a pKu close to the pH at equivalence. To solve this question, the
pH at equivalence must be determined for each answer choice. In choices A and B, HF is formed at equivalence.
The pK6 for HF is 3.17. In choice A, the pH of 1.00 M HCl is 0. The average of the pKu for HF and the titrant L
pH leads to a pH at equivalence of approximately 1.6. Cresol red has a pKa of 7.6, so choice A has a valid
indicator for the titration. In choice B, the pH of 0.01 M HCI is 2. The average of the pK" for HF and the
titrant pH leads to a pH at equivalence of approximately 2.6. Methyl violet has a pKu of 0.8, so choice B has
an invalid indicator for the titration. Choice B is the best answer.
If you are highly observant, you'll note that as the concentration of the species decreases, the equivalence pH
gets closer to 7. This means that choice B requires an indicator with a higher pKu than choice A. This is also
true when comparing choices C and D. Chlorophenol blue has a higher pKu than bromcresol green, so choices C
and D fit the desired trend. To verify this, let's consider the pH at equivalence for the remaining choices.
In choices C and D, HCN is formed at equivalence. The pKu for HCN is 9.32. In choice C, the pH of 1.00 M HCI
is 0. The average of the pKa for HCN and the titrant pH leads to a pH at equivalence of approximately 4.7.
Bromcresol green has a pKa of 4.4, so choice C has a valid indicator for the titration. In choice D, the pH of
0.01 M HCI is 2. The average of the pKu for HCN and the titrant pH leads to a pH at equivalence of
approximately 5.7. Chlorophenol blue has a pKu of 5.6, so choice D has a valid indicator for the titration.

87. Choice C is correct. When the pH is greater than the pKu of the indicator, the conjugate base is the
predominant species in solution, so the solution assumes the color of the conjugate base. \rVhen the pH is less
than the pKu of the indicator, the conjugate acid is the predominant species in solution, so the solution assumes
the color of the conjugate acid. The pKu values for the four choices are: methyl violet (pKa = 0.8), methyl
orange (pKa = 4.0), thymol blue (pKa = 8.4), and bromcresol green (pKu = 4.4). At a pH of.7.4, methyl violet
exists in its violet conjugate base form, so choice A is valid. At a pH of 7.4, methyl orange exists in its yellow
conjugate base form, so choice B is valid. At a pH of 7.4, thymol blue exists in its yellow conjugate acid form, so
choice C is invalid. At a pH of T.A,bromcresol green exists in its blue conjugate base form, so choice D is valid.
The only choice that does not correctly correlate the indicator with the solution color is C.
88. Choice D is correct. Thymol blue has a pKu value of 2.0, so it changes color in a highly acidic medium. \Alhen
titrating a strong base with a strong acid, the equivalence point is 7.0, so choices A and C are eliminated. The
titration of a weak base by a strong acid leads to an equivalence pH value less 7.0, so choice thymol blue is
appropriate for choices B and D. A pKu value of 2.0 is rather low, so the conjugate acid present at the
equivalence point must dissociate readily and be in high concentration. The higher the concentration of weak
base initially, the higher the concentration of weak acid at the equivalence point. To ensure that the
equivalence pH is as low as 2.0, the weak base and titrant strong acid should both be highly concentrated. The
base must be very weak with a pKU of 10.0 or greater to be a reasonable choice for this problem. Given the
limited information, the best answer is choice D.
89. Choice C is correct. A strong acid when titrated by a strong base shows an equivalence pH of 7.0. The indicator
chosen should have a pKu value near 7.0. It is okay if the pKu is as high as 8.0, but not any greater than that.
The pKu values for the four choices are: methyl violet (pKu = 0.8), methyl orange (pKa = 4.0), bromthymol blue
(PKa = 6.8), and alizarin yellow (pKa = 10.8). Only bromthymol blue has a pKa value close to7.0, so only
bromthymol blue changes color at the equivalence point. The best answer is choice C.
90. Choice B is correct. The pH range of the stick is found by considering the pH range of each indicator attached
to the pH stick. Indicators have a pH range (color change band) of approximately pKullr.,dicator) + 1, depending
on the colors and intensity of the indicator. The four indicators have respective ranges of 3.37 to 5.37,4.21 to
6.2I,5.78 to 7.78, and 7.79 to 9.79. This means that the overall range of the pH stick is 3.37 to 9.79, which
makes choice B, 3.4 to 9.8, the best answer.
9L. Choice D is correct. If bromcresol green appears yellow, the pH of the solution is less than 3.37 (4.37 -l). At
this pH, the other indicators would be protonated, so the pH could not be determined from any of the
indicators. Because Solution 1 appears yellow with bromcresol green, it is not possible to know the exact pH.
Solution 1 could have any pH value less than 3.37. If phenolphthalein appears magenta, the pH of the
solution is greater than9.79 (8.79 +1). At this pH, the other indicators would be deprotonated, so the pH could
not be determined from any of the indicators. Because Solution 4 appears magenta with phenolphthalein, it is
not possible to know the exact pH. Solution 4 could have any pH value greater than9.79. The pH of Solution 1
and Solution 4 cannot be approximated from the pH stick, so the best answer is choice D.
92. Choice C is correct. An aqueous solution with a hydroxide concentration of 1.0 x 10-6 M has a pOH of 6.0 and
therefore a pH of 8.0. The pH of the solution is more than one unit greater than 4.37 (the pKu of bromcresol
green), so the bromcresol green indicator will turn blue. Choice A can be eliminated. The pH of the solution is
more than one unit greater than 5.21 (the pKu of methyl red), so the methyl red indicator will turn yellow.
Choice B can be eliminated. The pH of the solution is more than one unit greater than 6.78 (the pKu of
bromthymol blue), so the bromthymol blue indicator will tum blue. Choice C is the best answer. The pH of the
solution is roughly one unit less than 8.79 (the pKu of phenolphthalein), so the phenolphthalein indicator
appears clear. Choice D can be eliminated.
93, Choice B is correct. Solution 5 is greenish-blue with bromcresol blue, so the pH of Solution 5 is greater than 4.37
and less than 5.37. Solution 5 is reddish-orange with methyl red, so the pH of Solution 5 is less than 5.21 but
greater than 4.21. The pH of Solution 5 falls between 4.37 and 5.2L, so choice B is the best answer. Only when
the color of the indicator is a composite of the protonated and deprotonated colors can the pH of the solution be
approximated. Bromthymol blue and phenolphthalein are purely the protonated color, so they were not useful
in approximating the pH of Solution 5.

94. Choice C is correct. When HCI is added to a solution, hydronium ions are released. If the colors of the
indicators do not change, that means that the pH does not change significantly, and thus the hydronium ion
concentration does t ot chut g" significantly. There are three explanations for the pH not changing
significantly. One reason pH does not change is that the hydronium concentration is so high that any change in
hydronium is negligible on the log scale. A second reason pH does not change is that the hydroxide
concentration is so nlgn tnat any change in hydroxide concentration is negligible on the log scale. The last
reason is that the solution is a buffer. Because Solution 2 appears orange with methyl red indicator, the
approximate pH is around 5.2. This does not describe a solution rich in hydronium or hydroxide' The best
explanation is tnat Solution 2 is a buffer with a pH around 5. The pKu for a carboxylic acid is around 5, so the
best answer is choice C.
95. Choice D is correct. Remember in choosing an indicator for titration that the pKu of the indicator must be
within +1 of the pH at equivalence. When titrating a weak acid with a strong base, the products the,weak
conjugate base an^d water. An aqueous weak base solution forms at equivalence, which has a pH greater than 7,
ro thu lndi.ator should have a pku value greater than7. The best answer is phenolphthalein, choice D.
96. Choice A is correct. A solution that turns blue with bromthymol blue has a pH greater than 7 '78 (pK" = 6.68, so
the pure blue color starts at 6.68 + 1). A pH greater than7.78 does not guarantee that the pH is greater than
8.7i, t:ne pKu for phenolphthalein. This means that the solution may or may not turn magenta with
phenolphtihatein. Ctroi." A ir invalid. If a solution tums green with bromcresol green, the pH is roughly 4.37'
if a solution turns bromthymol blue green, the pH is roughly 6.68. The pH cannot simultaneously be 4.37 and
6.68, so the stick cannot simultaneouily hurre two green marks. Choice B is a valid statement. A solution that
turns methyl red yellow has a pH greater than 6.21 (pKa = 5.21,so the pure yellow color starts at5.21' + 1). A
pH greater than 6.2t guarantees that the pH is greater than 4.31, the pKu for bromcresol green' This means
inat tne solution *.rri t.r* blue with bromcresol green. Choice C is a valid statement. When the pH of the
solution falls between4.27 and5.37, it falls into the color blend range of two separate indicators. As a result,
the pH can be approximated with twice the accuracy. Choice D is a valid statement.
97. Choice D is correct. The best choice for a buffer of pH = 4.0 is a weak acid with a pKu close to 4.0 mixed with its
conjugate base. Benzoic acid has a pKu of 4.27 and nitrobenzoic acid has a pKu of 3.40. Benzoic acid is closer, so
choose D. If the buffer is to Ue a.O (the acidic side of 4.21), there should be a slight excess of benzoic acid
relative to the conjugate base.
98. Choice A is correct. To titrate a weak acid (such as p-nitrophenol), you must add a strong base. The only strong
base listed among the choices is KOH. Choose A, and move on.
99. Choice A is correct. The addition of 10 mL 0.10 M KOH(aq) to 20 mL 0.10 M phenol results in the half-titration
of the phenol. At the halfway point, pH = pK2. The pKu for phenol is 10.0, so choice A is the best answer.
100. Choice A is correct. This titration is of a weak acid with a strong base that is twice as concentrated (0.20 M
base with 0.10 M weak acid), so one-half the volume of the strong base is used. One-half of 50 mL amounts
to
25 mL at equivalence. This eliminates choice B and D. Since the titrant is a strong base, the neutralized
product is aieak base, so the equivalence pH is greater than 7. Only the titration curve in choice A shows pH
it equivalence and pKu for the phenol as being greater than7.
Copyright O by The Berkeley Review@ 352 Section V Detailed DxPtanations

ERI{ELEY
R.tr.V.t.E.W'"
PERIODIC TABLD OF TTID ELEMENTS
2
He
4.0
3 4t '7
8 g 10
l"tun Re: N o FNe
i 9.0 14.0 16.0 i9.0 20.2
ll 12 l5 tt l8
Na Mg P CI Ar
23.0 z+.2 l 31 .0 35.5 3:s
-, x l % ,=i]l
]t
19
K
39. r
20
Ca
40.1 45.0
zl
Sc
22
Ti
47.9
^!.J
V
50.9
24
Cr ll
52.0 rl
*. ll r"i."l
549 ii 558 58.9"
28
Ni
58.7
29
Cu
63.5
33
As
74.9
35
Br
79.9
Kr
83.8
371:s 39 40 1l 42 47 f 48 49 50 51 54
Rb ii sr Y Zr Nb Mo Ag cd In Sn Sb Xe
85.5 87.6 88.9 91 .2 92.9 95.9 107.9 112.4 I14.8 I 18.7 121.8
II 1 131.3
)) -- ta-'tf) 5'7 11 73 74 79 80 81 82 85 86
Cs Ba LaT Hf Ta w Au Hg TI Pb At,Rn
fiz.e r:;: I 38.9 178.5 180.9 r83.9 t97.0 200.6 204.4 207.2 ) n\
(210)
1 /a11\
(222)
rsr i ss ]1
89 s 104
irrRa Ac- Rf
Q23t 226.0 221.0 (26t )
67 69 70 71
Ho Tm Yb Lu
t64.9 168.9 173.0 i75.0
90 100 101 102 103
srh Fm
(2s7)
Md No
(258) (2s9)
Lr
(260)
232.0
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Unit Conversion

SpeciaLiztng in MCAT Preparation

Understand the difference between empirical and molecular formulas.

Know the effect of standard conditions.

..*S Un<lerstand dilution and its effect on concentration of a solute.

standard reactions from chemis

o? Ilnderstand the stoichiometric ratios in combustion reactions.

Copyright Oby The Berkeley Review Exclusive MCAT Preparation

Conversion o1 1i*". 100 mx s - h "{r"

Overall:100m* 1km * lmile *3600s= 100x3600 miles c.

T"p= 9 T.c+32 .'. T"6=5 1t"r-sz;

T"p= 9 T"c + 32becomes: T=2T +32,soT= 1.8 T +32

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mL solution L 100 g solution 58.5 g NaCl 1

3 moles NaCl 3.15 x lOmoles NaCl

Q =1, so the value

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A. 18.00 grams ffimmn$

B. 24.00 grams - p,mmiii

5 *,olujl_ro_ tt qt31 x S6ffi

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Elemental analysis determines the atomic composition of an unknown molecule.

mass percent - mass atoms x 100"h (1.1)

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Quick Calculation Technique:

C:roice D is the best answer.

Masspercen,N =,, gNHaNO3

Quick Calculation Technique:

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Empirical Formula rumPul

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empirical formula: C#+# = CtHtTs = C1H2.5 = C2Hs

An empirical formula of C2H5 when multiplied by a whole number cannot yield

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Combustion Analysis (an Experimental Procedure)

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laese questions can be trickier if the units are milligrams, milliliters, or

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Mir,itiul'Vinitiil = Mfinal'Vfinut (1.2)

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Vfinal -Minitial'vinitial =5.00Mx8OmL = 5x g0mL = 400ml

A solution can be diluted by adding solvent or another solution to it. The

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grams reactant mole reactant ,{/rlry

. grams oroduct gfZrfitS product

eliminated. The only answer that remains is choice C,37.5 g. gpflmimHndlTW

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C*H, +,. * o2(g) -------> x Co2(g) *I-uzo(g)

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CH, +,. o2(g) -------> x Co2(g) *I-uzo(g)