Apchemnotes
Apchemnotes
Apchemnotes
Stephen Akiki
Colchester High School
Download at http://akiscode.com/apchem
Contents
1 FOREWORD/DISCLAIMER
2 Solubility Rules
2.1 Soluble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Insoluble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Naming Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
5
5
5
6
6
7
7
6 Atomic Theory
6.1 J.J. Thompson . .
6.2 Robert Millikan . .
6.3 Ernest Rutherford
6.4 Chadwick . . . . .
6.5 John Dalton . . . .
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7
7
7
7
7
7
7 Naming
7.1 Binary . . . . . . . . .
7.1.1 Greek Prefixes
7.2 Ionic . . . . . . . . . .
7.3 Acids . . . . . . . . .
7.3.1 Polyatomic . .
7.3.2 Binary . . . . .
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8
8
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8 Cations
9 Reaction Type
9.1 Combination (Synthesis) .
9.2 Decomposition . . . . . .
9.2.1 Special Binary Salt
9.3 Combustion . . . . . . . .
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Splits
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9
9
9
10
10
10 Blackbody Radiation
10
11 Bohr Model
11.1 Energy Level Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.1.1 Energy Change during Level Jumps . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
11
11
12 Wavelength
12.1 De Broglie Formulas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
11
13 Quantum Values
13.1 Quantum Value Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13.2 Special cases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
12
12
14 Periodicity
14.1 Electron Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14.2 Isoelectricity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
13
13
15 Nuclear Chemistry
15.1 Isotopes . . . . . . . . . .
15.2 Radiation . . . . . . . . .
15.2.1 Alpha Radiation .
15.2.2 Beta Radiation . .
15.2.3 Gamma Radiation
15.2.4 Positron Radiation
15.2.5 Electron Capture .
15.3 Nuclear Equations . . . .
15.3.1 Radiation Table .
15.4 Nuclear Stability . . . . .
15.4.1 Forces Invloved . .
15.4.2 Belt of Stability .
15.4.3 Magic Numbers . .
15.4.4 Half-Life . . . . . .
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13
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14
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16
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17
17
17 Reactions of Metals
17
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18 Chemical Bonds
18.1 Intramolecular . . . . . . . . . . . . . . .
18.1.1 Ionic Bonding . . . . . . . . . . . .
18.1.2 Covalent Bonding . . . . . . . . .
18.1.3 Metallic Bonding . . . . . . . . . .
18.2 Intermolecular . . . . . . . . . . . . . . .
18.2.1 Ion-Dipole . . . . . . . . . . . . . .
18.2.2 Dipole-Dipole . . . . . . . . . . . .
18.2.3 Hydrogen Bond . . . . . . . . . . .
18.2.4 London Dispersion/Van der Waals
18.2.5 Intermolecular Flowchart . . . . .
18.3 Rule of Octet . . . . . . . . . . . . . . . .
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17
17
18
18
18
18
18
18
18
18
19
19
19 Lewis Structures
19.1 Structures for Atoms . . . . . . . . . . . . . . . . . .
19.2 Structures for Ions . . . . . . . . . . . . . . . . . . .
19.3 Structure for Ions of Molecules . . . . . . . . . . . .
19.4 Lewis Structures for Molecular Structures (Covalent)
19.5 Resonance Structures . . . . . . . . . . . . . . . . . .
19.5.1 Formal Charge . . . . . . . . . . . . . . . . .
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19
19
19
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20
21
21
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21
22
22 Electronegativity
22.1 Dipole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
22.1.1 Dipole Moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
22
22
22
23 Bond Enthalpy
23
24 VSEPR
24.1 Bond Shape Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
23
25 Organic Chemistry
25.1 Polarity . . . . . . . . . . . . . . . . . .
25.2 Alkanes . . . . . . . . . . . . . . . . . .
25.3 Alkane Branch Structure Naming . . . .
25.3.1 Branch Structure Naming Table
25.4 Alkenes . . . . . . . . . . . . . . . . . .
25.4.1 Alkene Naming . . . . . . . . . .
25.5 Alkynes . . . . . . . . . . . . . . . . . .
25.5.1 Alkyne Naming . . . . . . . . . .
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23
23
24
24
25
26
26
26
27
26 Functional Groups
26.1 Alcohol . . . . .
26.2 Aldehyde . . . .
26.3 Carboxylic Acid .
26.4 Ester . . . . . . .
26.5 Ketone . . . . . .
26.6 Ether . . . . . .
26.7 Amine . . . . . .
26.8 Amide . . . . . .
26.9 Haloalkane . . .
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27
27
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29
29
29
27 Complex Ions
27.1 Cations . . . . . . . .
27.2 Anions . . . . . . . . .
27.3 Coordination Number
27.4 Naming . . . . . . . .
27.4.1 Cations . . . .
27.4.2 Anions . . . . .
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29
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31
29 Thermodynamics
29.1 Enthalpy . . . . . . . . . . . . . . . . . .
29.1.1 Stoichiometry Problems . . . . . .
29.1.2 Calorimetry . . . . . . . . . . . . .
29.1.3 Hess Law . . . . . . . . . . . . . .
29.1.4 Standard Heat of Formation . . . .
29.2 Entropy . . . . . . . . . . . . . . . . . . .
29.2.1 State of Matter . . . . . . . . . . .
29.2.2 Number of Moles of Gasses . . . .
29.2.3 Pressure of Gas . . . . . . . . . . .
29.3 Gibbs Law of Free Energy . . . . . . . . .
29.3.1 H, S, G, Relationship Table
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31
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34
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35
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31 Reaction Mechanisms
31.1 Elementary Steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
36
37
32 Equilibrium
32.1 Types of Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32.2 Equilibrium Constant Expressions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32.2.1 Converting Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
37
37
37
37
33 Gas
33.1
33.2
33.3
33.4
33.5
33.6
37
37
37
38
38
38
39
Laws
Gas Units and Conversions . . . . .
Ideal Gas Law . . . . . . . . . . . . .
Real Gas Law . . . . . . . . . . . . .
Combined Gas Law . . . . . . . . . .
Daltons Law of Partial Pressures . .
Gas Collection over a Water Solution
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38 Electro Chemistry
38.1 Identifying Oxidation Numbers . . . .
38.2 Galvanic/Voltaic Cells . . . . . . . . .
38.3 Calculating Cell Potential . . . . . . .
38.3.1 Nernst Equation to Find E cell
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FOREWORD/DISCLAIMER
First and formost, I am going to say what everone has on their minds. No you really should not just forget
about taking notes anymore in AP Chemistry class because of this packet. This packet is meant to be a
review and should be used as such. However that does not mean you can use this packet as your main
notes and write notes in the margins to supplement your learning. Please take into account that this entire
thing was written over the course of 4 days. As such it is inevitable that I made mistakes in spelling and/or
formulas.
If you have any questions/comments/fixes to the text you can email me at [email protected]
Good Luck
4
Solubility Rules
2.1
Soluble
2.2
Insoluble
Carbonates CO32 - all carbonates are insoluble except alkali metals and ammonium compounds
Chromates CrO42 - all chromates are insoluble except alkali metals, ammonium, Ca+ 2, and Sr+ 2
Hydroxides OH 1 - all hydroxides are insoluble except alkali metals, ammonium, Ba+2 , Sr+2 , and
Ca+2 although the last two (Sr+2 and Ca+2 ) are only slightly soluble so a precipitate can form.
Phosphates P O43 all are insoluble except alkali metals and ammonium
Sulfites SO32 all are insoluble except alkali metals and ammonium
Sulfides S 2 all are insoluble except Alkali metals, alkali earth metals and ammonium
2.3
Naming Rules
All strong acids and bases are soluble and should be written as the ions when completing net ionic
reactions
. Sulfuric acid (H2 SO4 ) should be written as H + + HSO41
The strong acids are: HCL, HBR, HI, HN O3 , HClO4 , and H2 SO4
Strong bases are any alkali metal hydroxides (LiOH, N aOH, etc) and Ca(OH)2 , Sr(OH)2 , Ba(OH)2
All acids and bases should be left in their molecular form:
. Acetic acid HC2 H3 O2
Ate
Ic
Most Common Ion
Ite
Ous
-1 Oxygen
5.1
Fundamental Constants
Avogadros Number (N )
. 6.02214199 1023 mol1
Plancks Constant (h)
. 6.62606876 1034 J s
Speed of Light (c)
. 2.99792458 108 m/s
Hypo Ite
Hypo Ous
-2 Oxygen
5.2
Charge
5.3
Radius
Atomic Theory
6.1
J.J. Thompson
Discovered e and
charge
mass
ratio
6.2
Robert Millikan
6.3
Ernest Rutherford
6.4
Chadwick
Discovers neutron by shooting radiation at light elements and it watching it kick out a neutral particle
6.5
John Dalton
Four Postulates
. Everything made of atoms
. Atoms of one element differ from those of a different element
. Atoms will combine in whole number ratios
. Atoms can not be created or destroyed
Law of Constant Composition
. In a compound, atom ratios are constant
Naming
7.1
Binary
Greek Prefixes
1-Mono
2-Di
3-Tri
4-Tetra
5-Penta
6-Hexa
7-Hepta
8-Octa
9-Nona
10-Deca
Example
Cl2 O
Dichlorine Monoxide
7.2
Ionic
Finding Charge:
N a?3 Cl2+1
N adc Clba
(ab)
c
7.3
7.3.1
=d
Acids
Polyatomic
-ate
ic acid
. H + N O3 HN O3 (Nitric Acid)
-ite
ous acid
. HN O2 nitrous acid
Hypo...ite hypo...ous acid
. HN O hyponitrous acid
7.3.2
Binary
Hydro + (stem)ic
. H + Br Hydrobromic acid
. H + N Hydronitric acid
. Hydrocarbonic acid HC
. Carbonic Acid HCO3
8
Cations
Which cation forms a white precipate with HCL?
. Ag + (reversed proves Cl ).
What color is a typical Manganese solution?
. Pink/light purple. The precipate is dark black.
How would you test for Al+ and what would it look like?
. Add Aluminom, it will make a precipate red and leave the solution clear.
Which cation forms a gel like precipate?
. Aluminum.
Which cation turns deep red with KSCN ?
. Iron.
How do you confirm the presence of zinc and what color is it?
. Add acid, then ammonia, which results in a white/bluish precipate.
What cation turns a deep blue with ammonia?
. Copper.
Reaction Type
9.1
Combination (Synthesis)
9.2
Decomposition
2Ag2 O 4Ag + O2
= Heat
. M g(OH)2 M gO + H2 O
. 2N aCl 2N a + Cl2
. F e(ClO3 )2 F eCl3 + O2
9.2.1
9.3
Combustion
Hydrocarbon + O2 CO2 + H2 O
........
Cx Hy double x (multiply by 2) then add 2
C1 : meth
C2 : eth
C3 : pro
C4 : bu
C5 : pent
C6 : hex
C7 : hept
C8 : oct
C9 : non
C10 : dec
10
Blackbody Radiation
10
11
Bohr Model
Neils Bohr:
1. Only orbits of certain radii, corresponding to certain definate energies are permitted for the electron in
a hydrogen atom.
2. An electron in a permitted orbit has a specific energy and is in an allowed energy state. An electron in
an allowed state will not radiate energy and therefore will not spiral into the nucleus.
3. Energy is emmitted or absorbed by the e only as the e changes from one allowed energy state to
another.
4. Flawed theory because it only works for hydrogen
11.1
E1 : 2.18 1018 J
E2 : 5.45 1019 J
E3 : 2.42 1019 J
E4 : 1.36 1019 J
E5 : 8.72 1020 J
E6 : 6.056 1020 J
E : 0
11.1.1
n = 3 2 | 3.03 1019 J
n = 4 2 | 4.09 1019 J
n = 5 2 | 4.578 1019 J
n = 6 2 | 4.844 1019 J
12
12.1
Wavelength
De Broglie Formulas
=
h
mv
or
=
h
p
= Wavelength
h = Plancks Constant (6.626 1034 J s)
m = Mass of particle in Kg
v = Velocity of particle ( meters
second )
p = Momentum
Example
m = 9.11 1028 g
v = 5.97 106 m/s
6.6261034 Js
= (9.111031 Kg)(5.97106 m/s) = 1.22 1010 m
11
13
Quantum Values
3d
3. Magnetic Quantum number (orbital) - (ml )
-l and l including zero
m0 = 0
m1 = 1, 0, 1
m2 = 2, 1, 0, 1, 2
4. Spin magnetic quantum number - (ms)
+ 12 or - 21
13.1
n
1
2
13.2
Subshell
1s
2s
2p
3s
3p
3d
4s
4p
4d
4f
ml values
0
0
-1,0,1
0
-1,0,1
-2,-1,0,1,2
0
-1,0,1
-2,-1,0,1,2
-3,-2,-1,0,1,2,3
# of orbitals in subshell
1
1
3
1
3
5
1
3
5
7
Special cases
12
e in shell
2
8
18
32
-
14
Periodicity
14.1
Electron Configuration
14.2
Isoelectricity
Two atoms are considered isoelectric when they gain or lose electrons to become ions and have the same
electron configuration as each other.
Example
N a+1 : 1S2 , 2S2 , 2P6
N e: 1S2 , 2S2 , 2P6
15
Nuclear Chemistry
15.1
Nuclear
Reactions involve decay of nucleus i.e. transforming one element into another
Affected by the type of decay and the halflife of what is decaying
Reactions deal with huge amounts of energy
Isotopes
Isotopes: Atoms of the same element that have a different number of neutrons
X A
A
ZX
A
X = Element Symbol
A = Atomic Mass
Z = Atomic Number
13
15.2
15.2.1
Radiation
Alpha Radiation
15.2.2
Beta Radiation
When a neutrally charged particle (equal amount of p+ s and e s) ejects its e s leaving only the p+ s.
15.2.3
Gamma Radiation
When a particle experiences some type of radiation (called * here) that causes the remaining nucleus to
collapse. This causes gamma () rays to be emitted. Gamma radiation is also caused when a positron and
an electron smash into each other.
14
15.2.4
Positron Radiation
15.2.5
Electron Capture
When an electron in orbit falls into the nucleus (positively charged) and makes it neutrally charged.
15.3
15.3.1
Nuclear Equations
Radiation Table
Neutron:
Proton:
Electron:
Positron:
Alpha Particle:
Beta Particle:
1
0n
1 +
1p
0
1 e
0
1e
4
2 He
0
1 e
or 42
or 10
Example
Alpha
238
234
4
U
92
90 T h +2 He
Beta
131
131
0
I
54 Xe+1 e
53
11 p+10 e
Positron
11
0
C
11
6
5 B+1 e
1
0n
10 n+01 e
Electron Capture
81
0
81
37 Rb+1 e 36 Kr
1
1p
1
0
1 p+1 e
10 n
Positron-Electron Collision (Gamma)
0
0
0
1 e+1 e 0
15
15.4
Nuclear Stability
Understanding why are some nuclides are radioactive while others are not.
15.4.1
Forces Invloved
Electrostatic
. Try to rip apart the nucleus because of like charges
Strong Nuclear
. Try to pull together the nucleus because subatomic particles naturally stick together
The Glue
. Neutrons act as the glue and more of it is required when the electrostatic force gets really strong
15.4.2
Belt of Stability
Area A
. More neutrons than protons - Beta decay creates protons
Area B
. Less neutrons than protons - Positron emission (Smaller B) or Electron Capture (Larger B)
Area C
. Every element above 83 p+ is radioactive and no glue can hold it together - Alpha decay
15.4.3
Magic Numbers
The Magic Numbers tend to be stable if you have either a proton or neutron in those numbers. If you have
both, they are very stable.
(p+ )
(n )
2
2
8
8
20
20
28
28
50
50
82
82
126
15.4.4
Half-Life
1
2
1
2
Example
5g of nuclide
life of 15 years
(15 years)
2.5
(30 years)
1.25
(45 years)
0.625g
16
16.1
The energy needed to remove an e (how easy it is to lose an e ). Needs energy (+).
16.2
Electron Afinity
How much a gaseous atom will be attracted to a free e (how easy it is to gain an e ). Releases energy (-).
17
Reactions of Metals
18
Chemical Bonds
18.1
Intramolecular
18.1.1
Ionic Bonding
Covalent Bonding
Metallic Bonding
. Metal atoms are floating in a sea of e s. No one e belongs to any particular atom.
Orbital Bonding Model
. The valence e s are overlapped and shared so much you have bonds of delocalized e s that are
free to move but are still holding the atoms together.
Properties that result from metallic bonding include:
Conductivity of electricity and heat
Malibility and ductility
Ability to form alloys
18.2
Intermolecular
Ion-Dipole
Ions bonding to molecules with a dipole (polver solvent). The strongest intermolecular force.
18.2.2
Dipole-Dipole
Polar near another polar. Weaker than Ion-Dipole but still strong, based on how strong the
polarity is.
18.2.3
Hydrogen Bond
Either (H N ), (H O), or (H F ). No shielding e s on Hydrogen so central atoms e pair gets full pull
of Hydrogen nucleus.
18.2.4
An induced dipole between 2 polar molecules. An increase in pressure or decrease in temperature will cause
one side to have a more positive force as the majority of e s move to other side.
1 Of
18
18.2.5
18.3
Intermolecular Flowchart
Rule of Octet
Atoms tend to bond in such a way as to gain, lose, or share e s in order to gain a complete valence (outer s
and p).
19
Lewis Structures
19.1
19.2
19.3
19
19.4
CH2 Cl2
HN O3
CO2
HCN
20
19.5
Resonance Structures
Benzene
19.5.1
Formal Charge
Valence e s of an atom - (total unbonded e s +
1
2
total bonded e s)
Molecular structures that tend to be the common one have a formal charge is closest to zero and any negative
charge is on the most electronegative element.
20
E=
KQ1 Q2
d
+2 1
N aCl vs M g Cl2
+2 1
+1 1
LiCl vs N aCl
+1
+1
+1
+1
+1 1
21
21
Single - Longest
Double - Medium
Triple - Shortest
Length
22
Single
CO44
1.42 A
Double
CO2
1.24 A
Triple
CO
1.13 A
Electronegativity
22.1
Dipole
H F
Arrow points towards more electronegative atom.
22.1.1
Dipole Moment
22
23
Bond Enthalpy
24
VSEPR
VSEPR stands for Valence Shell Electron Pair Repulsion. Make sure when counting bonds to treat double
and triple bonds like a single bond. Also keep in mind that bonded pairs and lone pairs repel.
24.1
Shape
Linear
Trigonal Planar
Bent
Tetrahedral
Trigonal Pyramidal
Bent
Trigonal Bipyramidal
See-Saw
T-Shape
Linear
Octahedral
Square Pyramidal
Square Planer
25
25.1
Example
BeH2
BCl3
N O21
CH4
N H3
H2 O
P Cl5
SF4
BrF3
ICl2
SF6
BrF5
ICl4
Total e
2
3
3
4
4
4
5
5
5
5
6
6
6
Bonded Pairs
2
3
2
4
3
2
5
4
3
2
6
5
4
Lone e Pairs
0
0
1
0
1
2
0
1
2
3
0
1
2
Hybrid Orbital
sp
sp2
sp2
sp3
sp3
sp3
sp3 d
sp3 d
sp3 d
sp3 d
sp3 d2
sp3 d2
sp3 d2
Organic Chemistry
Polarity
Polarity in regards to organic chemistry relies on an element disrupting the symmetry of a molecule. For
example the double bonded oxygen in Acetone allows it to be more polar than Propane.
Acetone
Propane
23
25.2
Alkanes
25.3
24
25.3.1
25
25.4
Alkenes
Alkene Naming
Naming Alkenes is similar to naming Alkanes save for the naming of the root chain. To name the root chain
you must give side where the double bond is the lowest number and name all branches after using this number
scheme. You should end up with something like 2 Pentene
2 Pentene
25.5
Alkynes
26
25.5.1
Alkyne Naming
Naming Alkynes is similar to naming Alkenes. Identify the root chain as you would using Alkenes except
now you identify the triple bond instead of the double bond.
2 Hexyne
26
Functional Groups
When discussing functional groups, the letter R is used to signify any hydrocarbon or hydrocarbon
chain.
26.1
Alcohol
26.2
Aldehyde
27
26.3
Carboxylic Acid
26.4
Ester
z
}|
{z
}|
{
CH3 CH2 CO OCH2 CH3
26.5
Ketone
26.6
Ether
z
}|
{ z }| {
CH3 CH2 CH2 O CH3
28
26.7
Amine
26.8
Amide
26.9
Haloalkane
27
Complex Ions
Complex Ions are usually metal ions with attached ligands (Lewis Bases).
27.1
Cations
[Cr(H2 O)6 ]+3
a The charge of a cation is the charge of the transition metal (Cr in this case).
29
27.2
Anions
[Al(OH)4 ]1
27.3
Coordination Number
Generally (especially with cations) the coordination number is twice the charge of the transition metal.
Example
[Cr(H2 O)6 ]+3
Cr+3 3 2 = 6
27.4
Naming
27.4.1
Cations
z}|{
Cr
Hexa
(H2 O)
| {z }
z}|{
6
]+3
Aqua
Anions
28
28.1
1
2
reaction with e s
1
2
30
28.2
Basic
1
2
reaction with e s
1
2
+7
+3 2 2
+1
C2 O4 M n
+4
M n O4 +
O22 + C O32
(4OH + C2 O4 2CO3 + 2e + 2H2 O) 3
(2H2 O + M nO4 + 3e M nO2 + 4OH) 2
12OH + 3C2 O4 6CO3 + 6e + 6H2 O
4H2 O + 2M nO4 + 6e 2M nO2 + 8OH
4OH + 3C2 O4 + 2M nO4 2M nO2 + 6CO32
29
Thermodynamics
29.1
Enthalpy
Stoichiometry Problems
Example
How much heat is released when 3.2 grams of Hydrogen is reacted with excess Oxygen?
2H2 + O2 2H2 O
H = 572 KJ
3.2 g H2
1 mole H2
KJ
2.02 g H2 2572
1
mole H2 = 453.069 KJ
Released
Ratio = Coef f icientEnergy
of Hydrogen in f ormula
31
29.1.2
Calorimetry
Hess Law
H = 911 MKJ
ole
H2 + 12 O2 H2 O H = 242 MKJ
ole
Find H for:
SiH4 + 2O2 SiO2 + 2H2 O
SiH4 Si+2H2 H = 34 MKJ
ole
Si+O2 SiO2
H = 911 MKJ
ole
Standard heat (enthalpy) of formation (Hf )2 is the energy involved in forming one mole of a chemical from
its elements under standard conditions.
a Elemental substances (O2 , H2 , etc.) always have a H of zero.
Example
Find the H for:
2H2 O2 2H2 O + O2
Hf H2 O2 = 187
Hf H2 O = 285
2(285)
2(187)
2H2 O2 2H2 O + O2
}
|
{z
}
| {z
374
570
X
X
H =
product
reactant
H = 570 (374) = 196 MKJ
ole
2 This
32
29.2
Entropy
State of Matter
If:
Solid Liquid
. S = +
Gas Solid
. S =
Solid
Lowest S
29.2.2
Liquid
Gas
Highest S
Pressure of Gas
29.3
J
K
to
KJ
K .
T = Temperature in Kelvin
. To convert C K add 273
33
If:
G<0
. Spontaneous
G>0
. Not spontaneous
29.3.1
H, S, G, Relationship Table
H = H = H = +
H = +
S = +
S = S = +
S = -
G = G = G = +
G = +
Always spontaneous
Spontaneous at low temperatures
Spontaneous at high temperatures
Never spontaneous
Example
P OCL3 2P Cl3 + O2
H = 542 KJ
J
S = 179 K
What temperature is it spontaneous at?
0 = 542 KJ (T 0.179 KJ
K )
542 = 0.179T
T = 3027.93 K
30
30.1
Physical State
Solid
. An increase in surface area means in an increase in the rate.
Gas - Gas
Liquid - Gas
Liquid - Liquid
30.2
3
Concentration
Molarity =
moles
liter
[HCL] = 3M
An increase in concentration is generally an increase in rate.
30.3
Temperature
30.4
Pressure of Gas
30.5
A catalyst lowers the activation energy while an inhibitor increases the activation energy.
3 Molarity
is signified by []s
34
30.6
Rate Laws
A+B C +D
rate = k[A]m [B]n
k = Constant
m = Order of A
n = Order of B
a Order of 0 No effect
a Order of 1 Linear - Double the concentration and you double the rate
a Order of 2 Squared - Double the concentration and you quadruple the rate
Trial
1
2
3
Example:
[A]
[B]
Rate
0.1 M 0.1 M 0.04 M/s
0.2 M 0.1 M 0.08 M/s
0.1 M 0.2 M 0.04 M/s
Solve for m:
trial 2
[]
rate
0.2 m
0.08
= ( )m =
=(
) =
trial 1
[]
rate
0.1
0.04
2m = 2
m=1
Solve for n:
(
0.2 n
0.04
) =
0.1
0.04
1n = 1
n=0
Order Table
Comments
Rate Law
Integrated Rate law
Graph
K = Slope
Half-Life (t 12 )
Zero Order
rate = k
[A] [A]0 = kt
[A] = kt + [A]0
[A] vs Time
Slope = k
0
t 12 = [A]
2k
First Order
rate = k[A]1
ln[A] ln[A]0 = kt
ln[A] = kt + ln[A]0
ln[A] vs time
Slope = k
t 12 = 0.693
k
35
Second Order
rate = k[A]2
1
1
[A] [A]0 = kt
1
1
[A] = kt + [A]0
1
[A] vs time
Slope = k
1
t 12 = k[A]
0
Example:
2N2 O5 4N O2 + O2
[N2 O5 ]
0.1
0.0707
0.05
0.025
0.0125
0.00625
Time (s)
0
50
100
200
300
400
6= straight
ln[A] = straight
Order of 1
2. What is the k constant value?
ln(0.0707)ln(0.1)
500
0.347
50
= 0.00693
k = 0.00693
3. What is the concentration of N2 O5 at t = 150?
ln[A] = (0.00693)(150) + ln(0.1)
ln[A] = 3.34
[A] = 0.0354 M
4. What is the rate at 150 seconds?
rate = k[A]
rate = 0.00693 [0.0354]
rate = 2.45 104 M/s
5. What is the half life?
t 12 = 0.693
k
0.693
t 21 = 0.00693
t 12 = 100 s
31
Reaction Mechanisms
Many/most reactions do not take place in one step. If a reaction were to react in one step, then you could
use the balanced reaction to determine the rate law. For example, assume the following occured in one step.
M gCl2 + 2Hbr 2HCl + M gBr2
rate = k[M gCl2 ]1 [HBr]2
In reality though, things are not always as easy.
Through experimentation we figure out that the rate law for:
N O2 + CO N O + CO2
is
rate = k[N O2 ]2
Because the rate law does not link up with the equation, it is not a single step reaction.
36
31.1
Elementary Steps
Unimolecular - 1 reactant
Bimolecular - 2 reactants
Terrmolecular - 3 reactants
32
Equilibrium
The state where the concentration or partial pressures (if it is a gas) of all the reactants and products remain
constant with time. For equilibrium to occur, the forward reaction rate must equal the reverse rate. In other
words, the amounts do not have to be equal, but the rates must be.
32.1
Types of Equilibrium
Static No movement
Dynamic Movement such as a sealed container of water
32.2
[C]c [D]d
[A]a [B]b
(P C c )(P Dd )
(P Aa )(P B b )
Kc = Concentration constant
Kp = Partial Pressure constant
32.2.1
Converting Constants
33
33.1
Gas Laws
Gas Units and Conversions
1 Atm = 760 Torr (mmHg) = 101.3 kPa = 14.7 PSI
33.2
P = Pressure (Atm)
v = Volume (L)
n = Number of moles
R = 0.0821 (constant)
T = Temperature (Kelvin)
Example
3 grams of HCl at 26 C in a 3 Liter container. What is the pressure?
P (3)
3
3 grams
( 36.5
)(0.081)(26+273)
g/mole
3
P = 0.0664 Atm
37
33.3
For use when the ideal gas law fails. The ideal gas law fails when these two postulates fail:
Molecules do have volume
Molecules are attracted
This law is also used when there are conditions with high pressure and low temperature.
P v = nRT
(P +
n a
) (v nb) = nRT
v2
33.4
33.5
For a mixture of gases in a container, the total pressure (Ptot ) is equal to the sum of the pressures each gas
exerts as if it were alone.
Ptot = P1 + P2 + P3 + + Pn
Example:
A mixture of 1g H and 1g He in a 1 L container is at 27 C. Calculate the mole fraction of each gas, partial
pressures of each and total pressure.
H2 1 g
1
= 0.5 moles
2
x=
(H mole)
0.5
=
= 0.667
(H + He moles)
0.75
He 1 g
1
= 0.25 moles
4
x=
0.25
= 0.333
0.75
H2
P v = nRT
P (1) = (0.5)(0.0821)(300)
P = 12.3 Atm
He
P v = nRT
P (1) = (0.25)(0.0821)(300)
P = 6.15 Atm
38
33.6
Example:
A 0.986 g sample has Zinc and some impurities. Excess HCl is added and reacts with thte Zinc but not the
impurities. Find the percent Zinc in the sample if 240 mL of H2 are collected over H2 O at 30 C and 1.032
Atm (HINT: This is the Ptot ).
Ptot = P1 + PH2 O
1.032 = P1 + 0.042
P1 = 0.99 Atm H2
P v = nRT
(0.99)(0.240) = n(0.0821)(303)
n = 0.0096 mole H2
= 0.628 g Zn
1
M ole
0.628 g Zn
100 = 63.7%Zn
0.986 g total
34
Given initial values for a system at equilibrium and one of the equilibrium values, you should find:
a - The other equilibrium values
b - The equilibrium constant
Example:
A closed system initially containing 1 103 M H2 and 2 103 M I2 at 448 C is allowed to reach
equilibrium. Analysis of the equilibrium mixture shows the [HI] = 1.7 103 M . Find the equilibrium
concentration for H2 and I2 as well as the Kc value.
H2 + I2 *
) 2HI
Initial
Change
Equilibrium
1 103 M
0.935 103
0.065 103
2 103 M
0.935 103
1.065 103
0M
1.87 103
1.87 103
[H2 ] = 0.065 M
[I2 ] = 1.065 103 M
Kc =
35
35.1
[1.87 103 ]2
[1.065 103 ][0.065 103 ]
1. Arrhenius
. An acid dissociates in water to form H + ions and a base dissociates to form OH ions.
2. Bronsted-Lowry
. Acids are proton donors (H + ) and a base is a proton acceptor.
. Conjugate acid base pair
Acid 1
Base 2
Acid 2
Base 1
HN O3 + H2 O H3 O+ + N O3
3. Lewis Acid
35.2
pH and pOH
pH and pOH are measures of the amount of ions in a solution that either cause the solution to be acidic or
basic.
pH Scale
Basic 0 14 Acidic
Important Formulas
pH = log[H + ]
pOH = log[OH ]
pH + pOH = 14
[H + ] = 1 10pH
[OH ] = 1 10pOH
Example
What is the concentration of HCl with a pH of 3?
[HCl] = 0.001 M
35.2.1
Changing Concentrations
M1 V 1 = M2 V 2
(0.25 M )(5 mL) = M2 (50 mL)
M2 = 0.025 M
35.3
Strong Acids
HCl
H2 SO4
HBr
HI
HN O3
HClO4
35.3.2
Strong Bases
Group 1 - Hydroxides
. N aOH
. KOH
Group 2 - Heavier Hydroxides
. Ca(OH)2
. Sr(OH)2
. Ra(OH)2
35.4
40
35.4.1
Ka Constant
HA *
) H + + A
HA + H2 O *
) H 3 O + + A
Ka =
[H + ][A ]
[HA]
Example
Benzoic acid dissociates as follows:
x
HC7 H5 O2 *
) H + + C7 H6 O2
|
{z
}
x2
[HC7 H5 O2 ] = 0.4 M
Ka = 6.3 105
What is the pH?
[H + ][C7 H5 O2 ]
[HC7 H5 O2 ]
x2
105 = 0.4
Ka =
6.3
35.4.2
Kb Constant
The Kb constant is used when bases are involved in a reaction (as opposed to Ka which is used in reactions
with acids). To convert between Kb and Ka use the following formula:
Ka Kb = Kw
Kw = 1 1014
Example
F + H2 O *
) HF + OH
Ka = 7.2 104
What is the Kb constant?
11014
11
Kb = 7.210
4 = 1.39 10
Find the pH and pOH.
[HF ][OH ]
[F ]
x2
11
10
= ( 0.002
20+13.3 )
7
Kb =
1.39
x = 9.13 10
pOH = 6.04
pH = 7.96
35.5
The effect of ionization of a weak electrolyte (acid/base) is decreased by adding a strong electrolyte that
has an ion in common with the weak electrolyte.
35.6
Buffer
Made of 2 components:
1. Weak acid
2. The salt of that acid
41
36
6.7105
1
100.1
1mole
1 mole
143.35 g
g
L
10
10
= 1.3 106 Lg
= 9.11 109 m
L
37
37.1
42
37.2
3RT
M
J
R = 8.314 KM
ole
37.3
37.3.1
When you pass a gas through a small opening into an evacuated chamber.
37.3.2
Diffusion
10
x
x=
28
2
10
2
=
28
2.67 ml/min
The rate for the gas is 24 mL/min, at the same temperature methane has a rate of 47.8 mL/min. What
is the molar mass of the unknown gas?
.
24
47.8
16
x
x = 63.7 g/mole
38
38.1
Electro Chemistry
Identifying Oxidation Numbers
H2 O
H +1
O -2
H2 SO4
H +1
S +6
O -2
Cl2
Cl 0
The chemical that has been oxidized is the reducing agent. The chemical that has been reduced is
the oxidizing agent.
38.2
Galvanic/Voltaic Cells
There are two beakers with salt and e s in each solution. A salt bridge between the two solutions allows
passage of ions. One side is identified as the cathode an the other the anode. The cations go to the cathode
and the anions go to the anode. The e s go to the cathode.
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38.3
38.3.1
0.0592
log(Q)
n
[P roduct]
[Reactant]
Example
+2
+2
Cu(s) + Cu
| {z } Cu
| {z } +Cu(s)
1 M
0.1 M
Q = 0.1
1 = 0.1
n = 2 (2 e being transfered)
E = 0(1M 1M = N ovoltage
E cell = 0 0.0592
2 log(0.1)
This Nernst equation is to be used when the temperature is not standard and the concentrations
are not equal.
RT
E cell = E
ln(Q)
nF
R = 9.31
volt coulomb
mole Kelvin
0.5 M
0.5
E cell = 1.1 0.0592
2 log( 2 )
E cell = 1.1178 volts
39
39.1
+3
39.2
Basic
CN + M nO4 CN O + M nO2
Half-Reactions
+
2OH + H2 O + CN CN O + 2e + 2H
2OH }
|
{z
H2 O
+
(2OH + H2 O + CN CN O + 2e + 2H
2OH }) 3
{z
|
H2 O
H2 O + 3CN
2M nO4
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