Sol

Solutions: Terms
Solute, solvent, dissolution, precipitation,
solubility, molarity, molality, mole fraction.
Solute: substance in smaller proportion.
Solvent: substance in greater proportion.
Dissolution: process of dissolving.
Precipitation: reverse of dissolution.
Solubility: amount solute to saturate solvent.

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 Solutions: Terms
Molarity: moles of solute per liter of solution.
Molality: moles of solute per kg of solvent.
Mole fraction: fraction of moles of given
substance relative to total moles in solution.
• Xa = na/Σn
What is an electrolyte?
Free ions in a solution Ö conducts electricity.
What is the van’t Hoff factor, i?
Number of ions existing after dissolution of
one unit of substance: NaCl, CaCl2
2
 Colligative Properties:
Important!
What does a colligative property depend
upon?
Number of solute particles in solution (not
identity of solute) – van’t Hoff factor comes
up big!
There are three for the MCAT – name ‘em:
• vapor-pressure depression.
• boiling-point elevation.
• freezing-point depression.
3
 Vapor Pressure
Definition?
Sometimes a tough concept – pressure
exerted by the gaseous phase of a liquid that
evaporated from exposed surface of liquid.
My definition: pressure exerted by
molecules leaving liquid phase on the
atmosphere – let’s draw what I mean!

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Vapor Pressure

5
 Vapor Pressure
Think about my definition…what property of
the liquid will determine vapor pressure?
Intermolecular forces!
High ones will hold liquid in liquid form and
decrease pressure exerted by molecules leaving
liquid.
Low ones will allow liquid to escape into
gaseous form and increase pressure exerted by
molecules as they change phase – volatile.
6
Vapor Pressure Depression
Now for VP depression…
Given a solution of two liquids, A and B:
• Total VP is equal to sum of partial pressures of
each liquid.
• Partial pressure of A is equal to proportion of A
in solution.
What is the law called that describes this
situation?
Raoult’s Law: Pa = XaPa*…where * is pure A.
7
 Vapor Pressure Depression
From Raoult’s Law, the presence of liquid B
will lower Pa by lowering Xa.
Vapor Pressure Depression: ∆Pa = –XbPa*
Some deviations from Raoult’s Law are
possible.
Conceptually, what is going on?
Generally, presence of liquid B will add
intermolecular forces to solution A and make
phase change to gas harder…interference!
8
 Boiling Point Elevation
What happens to a liquid when it boils?
Input of energy overcomes intermolecular
forces of liquid to cause phase change.
Relation to VP Ö boiling point is
temperature at which VP = Patmosphere
• equilibrium between liquid pushing on air and
vice versa…free movement of molecules
between phases.
What causes BP change (elevation)?
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 Boiling Point Elevation
Intermolecular forces!
Addition of solute introduces extra
intermolecular forces between solute and
liquid, making it harder for phase change.
Real life example – cooking pasta.
What equation quantifies the temp change?
∆Tb = Kbim…define the terms!
A constant, van’t Hoff factor, molality.
Why does van’t Hoff factor matter?
10
Freezing Point Depression
What happens to liquid when it freezes?
Molecules assemble into an orderly, tightly-
packed array.
What might the addition of a different
molecule have on this lattice formation?
Interference! More difficult to achieve solid
state Ö FP will go down (need to be colder
to achieve the solid state).

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Freezing Point Depression
What is the equation that quantifies this
concept?
∆Tf = –Kfim …define the terms!
A constant, van’t Hoff factor, molality.
What is the effect of van’t Hoff factor here?
Higher number of ion species will cause
more interference!

12
 Kinetics: Some Terms
Define kinetics (Don’t confuse with
thermodynamics!!!).
How fast a reaction occurs…this says
absolutely nothing about spontaneity!!
Mechanism, intermediates, rate-determining
step…
Mechanism is a sequence, intermediates are
not reactants or products, rate-determining step
puts limit on maximum speed.
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 Kinetics: Some Terms
Rate-determining step: the slowest step in a
process determines the overall reaction rate.
In a two step reaction, if step two is slow,
then the speed of step one is irrelevant:
• 2NO N2O2 (fast)
bimolecular
• N2O2 + O2 2NO2 (slow)
• overall reaction: 2NO + O2 2NO2
termolecular
unlikely!
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 Kinetics: Reaction Rate

What three factors determine reaction rate?

They are…
• frequency of collisions.
• orientation of colliding molecules.
• energy of molecules.
The concept of activation energy…what is
it and why does it matter?

15
 Activation Energy, Ea
Activation energy is the extra “kick” of
energy that a reaction needs to proceed.
MCAT loves Ea diagrams, but first, what
are exothermic and endothermic reactions?
Two diagrams, one for each above type:

Ea
Ea
R P
∆H _ P R ∆H +

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 Activation Energy, Ea
From the activation energy concept, three
statements can be made:
Ea1
• low Ea Ö fast reaction rate. Ea2
• more reactants Ö fast rate
(more collisions possible).
• higher temperature Ö fast
rate (more reactant molecules
have sufficient kinetic energy
to overcome Ea).

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 Catalysts
What is a catalyst?
Substance that makes reaction go faster by
speeding up rate-determining step or providing
an optimized route to products.
Reactant vs. catalyst –
catalyst unchanged at
Ea
end of reaction. Ea,cat
Catalysts change rate,
not thermodynamics
(∆G, ∆H, ∆S, etc.).
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 Rate Laws
What does a rate law tell us?
The rate at which a reactant disappears.
Consists of rate constant, and
concentrations of reactants in slow step
only!!
Rate laws determined experimentally.
aA + bB ˆ cC + dD…rate law?

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 Rate Laws
Rate = k[A]x[B]y
x Ö order of rxn with respect to A.
y Ö order of rxn with respect to B.
x+y Ö overall order of reaction.
k Ö rate constant.
Note: cannot get orders of reactants or rate
constant from balanced equation.
Need to look at experiment to get rate law.
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 Rate Laws
A+B+CˆD+E
Experiment [A] [B] [C] Initial Rate,
Ms–1
1 0.2 M 0.1 M 0.05 M 1 × 10–3

2 0.4 M 0.1 M 0.05 M 2 × 10–3

3 0.2 M 0.2 M 0.05 M 4 × 10–3

4 0.2 M 0.1 M 0.1 M 1 × 10–3

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 Rate Laws
Look at two experiments where only one
reactant concentration changes.
Determine the factor by which it changes,
and compare to factor by which rate
changes.
[A] doubles Ö rate doubles Ö order 1.
[B] doubles Ö rate quadruples Ö order 2.
[C] doubles Ö rate uneffected Ö order 0.
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 Rate Laws
When order is 0, rate does not depend on
concentration of reactant.
Rate law for this example: k[A][B]2
Determining k…anyone remember the
formula for finding k?
Solve the rate law…k = rate/[A][B]2
Substitute numbers from any experiment for
[A] and [B].
• k = 1 × 10–3 / 0.2 × (0.1)2 = 0.5 Ms–1

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 The Equilibrium Constant
First, what is the definition of an equilibrium?
The rate of the forward reaction equals reverse.
Given this generic reaction, what is the Keq?
• aA + bB ' cC + dD
Mass-action ratio Ö ratio of products to
reactants: [C]c[D]d
Keq =
[A]a[B]b
Gases and aqueous molecules only!!
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 The Equilibrium Constant
The value of Keq for a reaction is a constant at a
given temperature Ö temp change causes Keq
change.
Equilibrium constants, in general, may have
different subscripts (eq, sp, a, b, etc.) but they all
obey the same rules of calculation and temp
dependence.
The value of K Ö what values favor react. vs. prod.
• Keq < 1 favors reactants.
• Keq = 1 balances reactants and products.
• Keq > 1 favors products. 25
 The Reaction Quotient
What is the reaction quotient? Symbol?
Ratio of concentrations of products to reactants, Q,
but NOT at equilibrium Ö differs from K.
How do the values of K relate to values of Q?
When Q < K Ö proceeding in forward direction.
When Q = K Ö at equilibrium.
When Q > K Ö proceeding in reverse direction.

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 Le Châtelier’s Principle
What does Le Châtelier’s principle state?
A system at equilibrium will try to neutralize any
imposed change (stress) in order to reestablish
equilibrium.
The effects of different stresses:
• Addition of product or reactant.
• Removal of product or reactant.
• Changing volume and temperature.
• Adding inert gas and adding catalyst.
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 Le Châtelier’s Principle
N2 (g) + 3 H2 (g) ' 2 NH3 (g) + heat
Adding or removing N2
Adding or removing NH3
Reducing volume? Increasing volume?
• cut volume, raise pressure Ö favor fewer moles
• raise volume, decrease pressure Ö favor greater moles.
Changing temp? Adding or removing heat.
Inert gas and catalyst Ö no change (catalyst
changes rate of forward and reverse equally).
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 Solubility Product
How is the solubility product constant defined?
The extent to which a salt will dissolve in water.
Ksp is determined just like Keq.
Solubility product constant is also temperature
dependent.
MnXm(s) ' nMx+(aq) + mXy–(aq)
Ksp = [Mx+]n[Xy–]m

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 Solubility Product: Example
The value of the solubility product for copper (I)
chloride is Ksp = 1.2 × 10–6. Under normal
conditions, the maximum concentration of an
aqueous CuCl solution will be:
• less than 10–6 M
• greater than 10–6 M and less than 10–4 M
• greater than 10–4 M and less than 10–2 M
• greater than 10–2 M and less than 10–1 M
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Ion Product and Common Ion Effect
What is an ion product?
Actually just the reaction quotient (Q) for
solubility reactions.
Allows us to make predictions just as before…
When Qsp < Ksp Ö more salt can be dissolved.
When Qsp = Ksp Ö solution is saturated.
When Qsp > Ksp Ö excess salt will precipitate.
Think of Ksp as the “saturation ceiling”.
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Ion Product and Common Ion Effect
What is the common ion effect?
Disturbing of a solubility equilibrium by adding a
common ion, one that already exists in the
equilibrium.
Follows Le Châtelier’s principle, causing a
decrease in solubility (equilibrium favors the
solid and not the aqueous).
Mg(OH)2(s) ' Mg2+ (aq) + 2OH–(aq)…after
OH– added (e.g. soluble NaOH(aq)).
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 Acids and Bases: Definitions
Arrhenius acids/bases, Brønsted-Lowry
acids/bases, Lewis acids/bases…differentiate!
Arrhenius: acids ionize in water to produce H+
and bases ionize to produce OH–.
Brønsted-Lowry: acids are proton (H+) donors
and bases are proton (H+) acceptors.
Lewis: acids are electron pair acceptors and
bases are electron pair donors.
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 Conjugate Acids and Bases
What are conjugate acids and bases, or how
would you recognize them?
When Brønsted-Lowry acid donates an H+ the
remaining structure is conjugate base.
When Brønsted-Lowry base accepts an H+ the
new species is the conjugate acid.
Name the acid, base, and conjugates:
• NH3 + H2O ' NH4+ + OH–
base acid conj. acid conj. base
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 Strengths of Acids and Bases
Brønsted-Lowry acids/bases placed in two
broad catagories: strong and weak.
What is a strong acid?
Strong acids dissociate nearly completely. Their
Ka > 1, favoring products considerably.
Examples (memorize!) For the MCAT, all
others not listed here are considered weak:
• HI, HBr, HCl, HClO4, HClO3, H2SO4, HNO3

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 Strengths of Acids and Bases

What is a weak acid?

Beyond the opposite of a strong acid, a weak
acid has a Ka < 1 because reactants are favored.
Ranking acid strength: higher Ka means
stronger acid…same for base strength.
How does this all work for conjugates?

36
 Strengths of Conjugate Pairs
Given a strong acid, is conjugate base strong
or weak? More importantly, why?
It is weak, because complete forward reaction
means essentially no reverse (conjugate cannot
take up H+) and therefore is weak.
Same holds true for strong base.
For weak acid?
Conjugate is weak base, but the smaller the Ka,
the stronger the conjugate base will be, relative
to other weak bases.
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 Strengths of Conjugate Pairs:
Example
Of the following anions, which is the strongest
base?
• I–
• CN–
• NO3–
• Br–

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 Strengths of Conjugate Pairs:
Example
Of the following, which acid has the weakest
conjugate base?
• HClO4
• HCOOH
• H3PO4
• H2CO3

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 Amphoteric Substances
What is an amphoteric substance?
A substance that can act as either an acid or a
base.
Where does this happen? Polyprotics!
When a substance has more than one proton to
donate, the conjugate base can either donate
another or accept a free proton.
H3PO4 ' H2PO4– + H+ ' HPO42– + 2H+ '

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Ion-Product Constant of Water
Water is an amphoteric substance.
H2O + H2O ' H3O+ + OH–
• reacts with itself in Brønsted-Lowry reaction.
Anyone know the term for this equilibrium?
Autoionization of water Ö Kw = [H+][OH–]
Value of autoionization constant at 25 °C?
Kw = 1.0 × 10–14…as in pH + pOH = 14

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 pH Calculations: A Shortcut
Normal formula: pH = –log[H+]…also,
pOH = –log [OH–]
Great when [H+] = 1 × 10–2 Ö pH = 2
But how about when [H+] = 2.3 × 10–4 M?
Use this shortcut…
• if [H+] = y × 10–n M (where n is a whole number).
• then pH is between (n–1) and n.
For above example, pH is between 3 and 4!
42
 pH Calculations
Remember the shortcut for estimating pH
from [H+].
When looking at weak acid (base), given its
initial concentration, use the ICE method to
find [H+] and pH.
What is pH of 0.2 M solution of HCN?
• Ka = 4.9 × 10–10
The Ka < 10–4 rule…the usual on the MCAT.

43
 pKa and pKb
We know pH is –log [H+], so what do you
think pKa or pKb is?
Any “p” function represents the –log!
pKa = –log Ka & pKb = –log Kb
High Ka or Kb (closer to 1) means strength, so
how about for pKa or pKb?
Lower is stronger! Think of it like pH Ö
lower is more concentrated.
Don’t forget Ö pKa + pKb = 14
44
 Neutralization Reactions
What is a neutralization reaction?
When an acid and base react to form a salt
and water.
Like when you take antacid (Tums, etc.).
A handy formula for complete neutralization:
• a × [A] × Va = b × [B] × Vb
• a is # acidic H, b is # H’s base can accept.
• [X] is acid/base concen. and V is volume.
45
 Neutralization Reactions
How much 0.1 M NaOH solution needed to
neutralize 40 mL of 0.3 M HCl?
HCl(aq) + NaOH(aq) ˆ NaCl(aq) + H2O(l)
a × [A] × Va = b × [B] × Vb
1 × 0.3 × 40 = 1 × 0.1 × Vb
Solve for Vb to get 120 mL.
Remember the formula to get you out of
jams…works with neutralization reactions
only to save time over the ICE method.
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 Indicators
An indicator marks the endpoint of a titration,
but why does it change color?
Indicator is actually weak acid whose
protonated form is one color and deprotonated
is another.
How does this help us?
Don’t forget that the indicator is a weak acid!

47
 Indicators
HIn ' H+ + In–
Ka = [H+][In–]/[HIn]…now rearrange:
[H+]/Ka = [HIn]/[In–]…and look at ratios:
• If [H+] » Ka, [HIn] » [In–]…see color 1
• If [H+] = Ka, [HIn] = [In–]…mix of two colors
• If [H+] « Ka, [HIn] « [In–]…see color 2
So indicator turns colors over short pH range
near its pKa.
48
 Picking an Indicator
When picking an indicator, use one whose
pKa value lies within the pH range that you
want to detect.
For indicator, pKa +/– 1 represents effective
range for color change.
So don’t expect to detect a pH change from
3 to 4 if your indicator has a pKa of 8 or 9!

49
 Hydrolysis of Salts
The reaction of a substance (salt/ion) with
water is a hydrolysis reaction.
Question…will the hydrolysis result in a
neutral, acidic, or basic salt?
NaCl in water Ö neutral because neither Na+
nor Cl– will react with water:
• Cl– is conjugate base of a strong acid.
• Na+ is conjugate acid of a strong base.
NH4Cl in water…acidic because NH4+ will
react with water (it is a weak acid).
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 Hydrolysis of Salts
NH4CN in water…NH4+ is weak acid, but
CN– is good base, so which wins??
Need to know Ka/Kb values!
Ka for NH4+ = 6.3 × 10–10
Kb for CN– = 1.6 × 10–5
Solution will be basic because CN– is better
base than NH4+ is an acid.

51
 What is a buffer?
A solution that resists changing pH when a
small amount of acid or base is added.
The resistance comes from the presence of a
weak acid or base and its conjugate in
roughly equal concentrations.
An expression to remember:

+ [conj.base]
Ka = [H ]
[acid]
52
 Buffer Compensation

A biochemical example: the blood.

The main buffer: carbonic acid:
CO2 + H2O ' H2CO3 ' H+ + HCO3–

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 Buffer Compensation
Compensation critical to prevent medical
disorders like acidosis and alkylosis.
Essentially Le Châtelier’s principle at work.
Addition of small amount of acid like HCl
causes added H+ to react with present HCO3–
to form H2CO3.
Equilibrium has shifted to the left, but existing
H2CO3 prevents large change in pH
(compensation reverses effects).
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 Buffer Compensation
Provided that acid and its conjugate are in
similar concentration, the pH change is
minimal.
Addition of small amount of base like KOH
causes added OH– to react with present H2CO3
to form HCO3–.
Equilibrium has shifted to the right, but
existing HCO3– prevents large change in pH
(compensation reverses effects).

55
 Dealing with Buffers
Henderson-Hasselbalch Equation:
[A–] [HA]
pH = pKa + log pOH = pKb + log
[HA] [A–]
If [A–] = [HA], then pH = pKa
An ideal buffer works under these
conditions. Small changes to the ratio are
acceptable, but the ratio should stay near 1.

56
Dealing with Buffers – Example
Which of the following compounds could be
added to a solution of HCN to create a buffer?
• HNO3
• CaCl2
• NaCN
• KOH

57
Acid-Base Titrations – Terms
Titration Ö experimental technique to
determine concentration or identity of
unknown weak acid or base by determining
pKa or pKb.
Titrant Ö strong acid or base of known
concentration that is added to solution of the
unknown base or acid.
Titration curve Ö a plot of pH vs. volume of
titrant added.

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Acid-Base Titrations – Terms
Buffering domain Ö the section of the
titration curve where the pH changes
gradually before the equivalence point.
Equivalence point Ö the point during a
drastic pH change in which there is
complete neutralization of acid and base.
End point Ö one or two drops of titrant past
equivalence point!
• indicator color flip visually detectable:
HIn GF In–
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Titration Curves – The Basics
Equivalence point and pH: not necessarily
at pH of 7 Ö salt hydrolysis?
Looking at the pH of the equivalence point
allows you to determine if unknown is weak
or strong.
Some quick rules for determining the pH at
the equivalence point.

60
Titration Curves – The Basics
weak acid + strong base:
• pH > 7 because product contains basic salt.
• HF + NaOH p NaF + H2O
strong acid + weak base:
• pH < 7 because product contains acidic salt.
• NH3 + HCl p NH4Cl
strong acid + strong base:
• pH = 7 because product contains neutral salt.
• HCl + NaOH p NaCl + H2O

61
Titration Curves – The Basics
Half-equivalence?
The volume of titrant at half-equiv. is half
that at equivalence.
More importantly, the concentration of
unknown at half equiv is equal to the
concentration of the unknown’s conjugate at
half equivalence.
• NH3 + HCl p NH4Cl Buffer!

62
Titration Curves – The Basics
In that case, the following must be true:
• [HA]half equiv = [A–]half equiv = [HA]i
By H-H equation, the pH at half equiv. must
be equal to pKa Ö this allows identification of
unknown.
Types of Curves:
• Slope to upper right Ö SA+SB, WA+SB
• Slope to lower right Ö WB+SA
• Polyprotic acids have multiple equiv points (why?)
63
Titration Curves – SA + SB

64
Titration Curves – WA + SB

65
Titration Curves – WB + SA

66
Titration Curves – Examples
Methyl red is an indicator that changes from
red to yellow in pH range 4.4 – 6.2. For which
of the following titrations would methyl red be
useful for indicating the equivalence point?
• HCN with KOH
• NaOH with HI
• C6H5COOH with LiOH
• C6H5NH2 with HNO3

67
Titration Curves – Examples
Draw the following titration curves, paying
particular attention to shape while labeling
the relevant parts:
• CH3COOH titrated with KOH
• C6H5NH2 titrated with HNO3
• H3PO4 titrated with KOH

68
 System and Surroundings
The system is the thing we’re looking at, for
example a melting ice cube or a solid dissolving
into water.
Everything else is known collectively as the
surroundings, for example the table the ice cube
sits on and the surrounding air or the beaker that
the solution sits in.
System + surroundings = thermodynamic
universe.
69
System and Surroundings: Energy
Flow
Remember conservation of energy?
When energy flows into a system from the
surroundings (+), the energy of the system
increases and energy of surroundings decreases.
When energy flows out of a system into the
surroundings (–), the energy of the system
decreases and energy of surroundings increases.

70
 First Law of Thermodynamics
The First Law Ö anybody know it?
Total energy of the universe is constant, so
energy can be transferred but not created or
destroyed.
Transfer of energy can occur as heat or work:
∆E = q + w Ö w = P∆V
Energy input Ö positive q (heat absorbed) and w
(work done on system).
Energy out Ö negative q (heat released) and w
(work done by system). 71
 First Law of Thermodynamics
Energy transfer in car air conditioner.
Air taken in through hose and moves over fins of
evaporator.
This hot air evaporates refrigerant inside (heat
transfer) which travels to condenser and is
changed back into liquid (heat transfer).
Air which was cooled when heating the fins of
the evaporator flows into the car’s interior.
No net change in energy for system…refrigerant
heated but then cooled to its original state.
72
 First Law of Thermodynamics
Adiabatic and isothermic?
Isothermic: expansion or compression of gas at
constant temperature (heat input or output).
Adiabatic: expansion or compression of gas
without a heat exchange (temperature changes;
q = 0 Ö ∆E = w )
Adiabatically expanding gases cool while
adiabatically compressing gases warm.
Adiabatic principle at work: snow-making
machine.
73
 First Law of Thermodynamics
Snow-making machines contain mixture of
compressed air and water vapor (20 atm).
When sprayed into the air, the mixture
undergoes a huge pressure change and expands
so rapidly that essentially no heat is exchanged
between system and surroundings (adiabatic
expansion).
Adiabatic expanding gases cool, so the water
vapor changes almost instantaneously to snow.
74
 Second Law of
Thermodynamics

The Second Law Ö what does it state?

All processes tend to run in a direction that leads
to maximum disorder. If a process is
spontaneous in one direction, then the reverse
cannot be spontaneous Ö makes sense!
From here, we can discuss entropy, enthalpy,
and free energy.

75
Entropy: Disorder or Randomness
∆S = Sproducts – Sreactants
• Increasing randomness (decreasing order) results in a
positive ∆S.
• Decreasing randomness (increasing order) results in
negative ∆S.
What are some situations in which entropy is
predictable?
Liquids have more than solids, gases more than
liquids, particles in solution more than solids,
two moles more than one mole.
76
 Enthalpy: Heat Energy
Two important principles Ö bond formation
releases energy (not needed to ensure stability),
energy must be added to break a bond.
∆H = Hproducts – Hreactants
Exothermic: heat released because products of
reaction have stronger, more stable bonds than
reactants.
Endothermic: heat absorbed because products of
reaction have weaker bonds and energy needed
to transition to this more unstable state.
77
 Enthalpy and Heat of
Formation
Amount of energy required to make one mole of
a compound from pure elements in their natural
or standard state.
If –∆H, heat given off…if +∆H, heat required.
What is standard state?
T = 298 K, P = 1 atm, [X] = 1 M.
Designated by ° superscript, standard state is
condition for determining heat of formation,
enthalpies, constants, etc.
78
 More Enthalpy
Each reaction has own ∆H Ö doubling reactants
will double the heat required or released.
Hess’s Law of Heat Summation, Remember?
If a reaction occurs in several steps, the sum of
the energies absorbed or released in all steps will
be the same as the overall reaction.
If reaction is reversed, the sign of ∆H reverses
too.
If equation multiplied by constant, so too is ∆H.
79
 Hess’s Law Example
C(s) + 2H2(g)
Direct path ∆Hnet
Indirect path = ∆H1 + 2∆H2 + (–∆H3)

+ 2O2(g) CH4(g)
∆Hrx = ∆H1 + 2∆H2
– 2O2(g)
∆Hrx = –∆H3

CO2(g) + 2H2O(g)
80
 Gibbs Free Energy
The energy available to do useful work from a
chemical reaction.
Spontaneity determined by enthalpy and entropy,
so spontaneity can be accounted for by ∆G.
∆ G = ∆ H – T∆ S
When…
• ∆G < 0 Ö spontaneous
• ∆G = 0 Ö at equilibrium
• ∆G > 0 Ö non-spontaneous
81
 ∆G and Temperature
∆G = ∆H – T∆S
∆H ∆S ∆G Reaction is…

– + – Spontaneous

+ + – at high T Spontaneous
+ at low T Non-spontaneous

– – + at high T Non-spontaneous
– at low T Spontaneous

+ – + Non-spontaneous

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Reaction Energy Diagrams Revisited
Two different diagrams Ö endothermic and
exothermic.
∆G ≈ ∆H when T∆S is small.
Do not confuse ∆G, ∆H, or ∆S with rate or Ea!
• catalysts lower Ea, but don’t touch ∆G!
Reversibility: the reverse of any reaction has the
same magnitude for all thermodynamic values
(opposite signs) and the same reaction pathway:
• Coming from products side, Ea is now forward Ea
plus ∆G…look at the graph.
83
Thermodynamics and Equilibrium
The two concepts are related by this equation:
• ∆G° = –2.3RTlogKeq
Should you know this equation? Probably not,
but know this for sure…
• ∆G° < 0 Ö spontaneous Ö Keq > 1
• ∆G° = 0 Ö at equilibrium Ö Keq = 1
• ∆G° > 0 Ö non-spontaneous Ö Keq < 1
Quick summary: for a spontaneous reaction,
products are favored; for non-spontaneous
reaction, reactants are favored.
84
 Oxidation-Reduction Reactions
Oxidation number: how many electrons an atom
is donating or accepting in moleculaar bonding.
Oxidation-reduction (redox) reaction: reaction in
which oxidation numbers of reactants change.
LEO says GER, LEO the GERman, OIL RIG
• Oxidation is loss, Reduction is gain of electrons.
Reducing agent causes reduction and is oxidized.
Oxidizing agent causes oxidation and is reduced.
85
 Galvanic (Voltaic) Cells

Harnessing flow of electrons from redox reaction

to generate an electric current.
Red cat, an ox Ö Reduction @ cathode; oxidation
@ anode. 86
 Galvanic (Voltaic) Cells
Half-reactions and potentials Ö positive E is
spontaneous.
∆G = –nFE…where F is Faraday’s constant
(96500 Cmol–1), n is number of electrons
transferred, E is half-reaction potential.
Flipping half-reaction changes sign on E.
More negative reduction potential Ö product
strong reducing agent…more positive
reduction potential Ö reactant strong oxidizing
agent.
87
Redox Electrode Potentials

88
 Nernst Equation
2.303RT 0.0592 V
E = E° – logQ = E° – logQ
nF n

Electrode potentials for non-standard

conditions, but T still = 298 K.
Zn(s) + Cu2+(aq) Š Zn2+(aq) + Cu(s)

0.0592 V [Zn2+]
E = E° – log
2 [Cu2+]
89
 Electrolytic Cells
Unlike a galvanic cell, electrolytic cells use an
external voltage source like a battery to create an
electric current that forces a non-spontaneous
redox reaction to occur Ö electrolysis.
Electroplating: plating a thin layer of metal on top
of another material Ö application of electrolytic
cells, often done in coin mints or with jewelry.
Red cat, an ox still applies!

90
 Faraday’s Law of Electrolysis
Determine amounts of species produced at
electrolytic electrodes using this law.
The amount of chemical change is proportional to
the amount of electricity flowing through cell.
Three steps:
• Determine amount of electricity in coulombs from
Q = It
• Convert Q to moles of electrons with Faraday
constant using Q = nF.
• Use stoichiometry of reaction to finish the calculation.
91
 Faraday’s Law of Electrolysis
A piece of steel is the cathode in a hot solution
of chromic acid to electroplate it with
chromium metal. How much Cr deposited after
48250 C of electricity was forced through cell?
• 1/12 mol
• 1/6 mol
• 1 mol
• 3 mol

92
 Concentration Cells
A galvanic cell that has identical electrodes but
whose half-cells have different ion
concentrations.
Electric current from potential difference arising
from unequal concentrations.
Electrons will flow in direction of highest
concentration of positive ions.
When concentrations of solutions become equal,
the reaction will stop.
93
 Concentration Cells

0.0592 V [Ni2+]dilute
E = E° – log
2 [Ni2+]concentrated
94