Chemistry 2 Physical Chemistry Lecture Notes

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Chemistry 2 - Physical Chemistry Lecture Notes
Chemistry 2 (University of Technology Sydney)
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CHEMISTRY 2 - PHYSICAL
CHEMISTRY LECTURE NOTES
Week 1 - Acid-Base Chemistry/Solubility
Revision of Chemistry 1
Acid: is a proton (H+) donor (produces H+ in aqueous solutions).

Base: is a proton (H+) acceptor (produces OH- in aqueous solutions).
● pH = − log[H + ]
● pOH = − log[OH − ]
● K w = [H + ][OH − ] = 10 −14
● pH + pOH = 14
Strong acids dissociate 100% to give H+ and A-, e.g. HCl, HBr, HI, HNO3, H2SO4, HClO4.
Weak acids don’t fully dissociate in aqueous solutions: (equilibrium lies to the left)
+
H A (aq) ⇌ H (aq) + A − (aq)
Extent of dissociation (acid strength) is measured by equilibrium constant, Ka.

- The larger the Ka, the stronger the acid.
- pK a = − log[K a ]
- The smaller the pKa, the stronger the acid.
The pKa measures how tightly a proton is held by a Bronsted acid. The lower the pKa of a
Bronsted acid, the more easily it gives up its proton.
Strong bases dissociate 100% to give OH- and a cation (NaOH, LiOH, KOH, etc).
Weak bases don't fully dissociate in aqueous solutions.
Kb and pKb
Weak bases partly react with water to give a small concentration of OH-.
E.g. N H 3 + H 2 O ⇌ N H 4 + + OH −
(Equilibrium lies to the left)
The equilibrium constant for this reaction is called Kb and its size tells us about the strength
of the base
+ −
[N H 4 ][OH ]
Kb= [N H 3 ]
● pK b = − log[K b ]

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Conjugate Acid-Base Pairs

A conjugate acid-base pair is a pair of species that differ by one H+, e.g. NH4+ and NH3, HF
and F-, CH3COOH and CH3COO-.
- When an acid donates a proton, one of the products will be a base.
- When a base receives a proton, the product will be an acid.
- pKa(weak acid) + pKb(its conjugate base) = 14, e.g. pKa(NH4+) + pKb(NH3) = 14
acid + base ⇌ conjugate base + conjugate acid
● A strong acid will have a weaker conjugate base.

● A weak acid will have a stronger conjugate base.
Polyprotic Acids
● Diprotic
H 2 CO 3 ⇌ H + + H CO 3 − ∣ K a = 4.5 × 10 −7
H CO 3 − ⇌ H + + CO 2 2− ∣ K a = 4.7 × 10 −11
- Ka1 >> Ka2 (i.e. pKa1 << pKa2)

- It is much harder to remove the second proton from the negatively charged HCO3-.
(Smaller Ka, i.e. larger pKa)
● Triprotic
H 3 P O 4 ⇌ H + + H 2 P O 4 − ∣ pK a = 2.12
H 2 P O 4 − ⇌ H + + HP O 4 2− ∣ pK a = 7.21
H P O 4 2− ⇌ H + + P O 4 3− ∣ pK a = 12.38

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Example Question for the pH of a Weak Polyprotic Acid

Determine the pH of a 0.0020M solution of carbonic acid (pKa1 = 6.35, pKa2 = 10.33).
- First dissociation is weak, second is 10,000 times weaker, therefore, ignore pKa2.
- Ka1 = 10-6.35 = 4.5 x 10-7
H 2 CO 3 ⇌ H + + H CO 3 −
H2CO3 H+ HCO3-
I 0.0020 0 0
C -x x x
E 0.0020 - x x x
[H + ][HCO 3 − ] [x 2 ]
Ka= [H 2 CO 3 ] = [0.0020−x] = 4.5 × 10 −7 (neglect x)
[x 2 ] = 0.0020 × 4.5 × 10 −7
x = √0.0020 × 4.5 × 10 −7 = 3.0 × 10 −5 = [H + ]
pH = − log[3.0 × 10 −5 ] = 4.5
Hydrolysis of Cations
Most cations (except Group 1 and some Group 2 metal ions) are weak acids and undergo
acid hydrolysis. This is the reason that transition metal ion solutions are unstable and
precipitate unless they are acidified. Typically seen as a cloudiness that develops in metal
ion solutions - adding acid clears the solution.
- Group 1 metal ions (Na+, K+, Li+, etc) do not hydrolyse in water, so they have no
effect on pH (they are pH neutral ions).
Hydrolysis of Anions
The anion (A-) of a weak acid (HA) is a weak base because it will react with water
(hydrolyse) to produce a small amount of OH-.
A − + H 2 O ⇌ HA + OH −
E.g. a solution of sodium acetate (NaCH3COO) is basic:
C H 3 COO − + H 2 O ⇌ CH 3 COOH + OH −
Most anions (except OH-, HSO4-, Cl-, Br-, I-, NO3-, ClO4-) are weak bases (note that the last 6
of the exceptions correspond to the anions of strong acids). Most are also ‘neutral’ in water
(does not affect pH).

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pH of Salt Solutions
Given the formula of many salts, we are now able to decide if they will produce acidic (pH <
7), basic (pH > 7) or neutral (pH = 7) solutions in water (cations: weak acid, anion: weak
base).
● NaF
○ Na+ is neutral (Group 1 metal ion).
○ F- is the anion of a weak acid, therefore, basic.
○ Overall, the salt solution will be basic.
● KCN
○ K+ is neutral (Group 1 metal ion).
○ CN- is the anion of a weak acid, therefore, basic.
○ Overall, the salt solution will be basic.
● NH4Cl
○ NH4+ is an ammonium ion, therefore, acidic.
○ Cl- is the anion of a strong acid, therefore, neutral (exception).
○ Overall, the salt solution will be acidic.
● NaNO3
○ Na+ is neutral (Group 1 metal ion).
○ NO3- is neutral (exception).
○ Overall, the salt solution will be neutral.
What happens if the cation is acidic, and the anion is basic? Look at pKa for acidic ions and
pKb for basic ions. Smallest pK (biggest K) outweighs the other.
- E.g. pKa(NH4+) = 9.24, pKb(F-) = 10.83. Therefore, salt is slightly acidic in water.
Example Question
Calculate the pH of a 0.0100M solution of sodium acetate (NaCH3COO), given that the pKa
of acetic acid is 4.76 at 25oC.
- Na+ is neutral, pKb = 14 − 4.76 = 9.24
C H 3 COO − + H 2 O ⇌ CH 3 COOH + OH −
K b = 10 − 9.24 = 5.75 × 10 −10
[CH 3 COOH][OH − ] [x 2 ]
Kb= [CH 3 COO − ]
= 0.0100−x = 5.75 × 10 −10
x 2 = 0.0100 × 5.75 × 10 −10
x = √0.0100 × 5.75 × 10 −10 = 2.4 × 10 −6 = [OH − ]
pOH = − log[2.4 × 10 −6 ] = 5.62
pH = 14 − 5.62 = 8.38

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Buffer Solutions
A buffer is a solution that resists a change in pH when small amounts of acid or base are
added to it. It is a mixture of a weak acid (HA) and its conjugate weak base (A-) in similar
concentrations.
- E.g. blood plasma is held at a pH of 7.35-7.45 by a H2CO3/HCO3- buffer; other buffers
in biology include phosphate (H2PO4-/HPO42-) and ammonium (NH4+/NH3) buffers.
The conjugate base consumes added H+, the conjugate acid consumes added OH-.
Best buffering occurs at pH values near the pKa of the conjugate acid. Different
conjugate acid/base pairs give buffering at different pH values. This gives us the ability
to prepare buffers at virtually any pH we choose. This is important in many different
applications – intravenous medicines, protein chemistry, analytical chemistry, etc.
Buffer Example
For buffering near pH 4 or 5, we can choose an acetate buffer (CH3COOH/ CH3COO-), since
the pKa of CH3COOH is 4.76. The buffer reactions would be:
+
C H 3 COO − + H → C H 3 COOH (adding strong acid)
or
−
C H 3 COOH + OH → C H 3 COO − + H 2 O (adding strong base)
Henderson-Hasselbalch Equation
−
[A ]
pH = pK a + log [HA]
This allows us to determine the concentrations of the conjugate acid and base for a desired
buffering pH (or vice versa).
1. Calculate the pH of a buffer which is 0.05M in acetic acid and 0.07 M in sodium
acetate. (Use pKa(CH3COOH) = 4.76)
[CH 3 COO − ]
pH = pK a + log [CH
3 COOH]
= 4.76 + log [0.07]

[0.05] = 4.91
2. How much will the pH change if 10mL of 0.1M NaOH is added to 20mL of water?
Before dilution: pH = 7. After dilution:
[OH − ] = n
v = 0.01×0.1
0.03 = 0.03333...M
pOH = − log[0.03333...] = 1.477
pH = 14 − 1.477 = 12.52 (increase)

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3. How much will the pH change if 10 mL of 0.1M NaOH is added to a 20mL of a

solution containing 0.005mol of NaH2PO4 and 0.006mol of Na2HPO4? (pKa of H2PO4-
= 7.21).
Before dilution:
[HP O 4 2− ]
pH = pK a + log [H 2 P O 4 − ]
= 7.21 + log [0.006/0.02]

[0.005/0.02]
pH = 7.29
After dilution (base (NaOH) reacts with acid (NaH2PO4-) to form NaHPO42-):
H 2 P O 4 − + OH −
→ HP O 4 2−
Since 0.005mol of H2PO42- reacts with 0.001mol of OH-, n[H2PO42-] will decrease by
0.001(0.004) and n[HPO42-] will increase by 0.001 (0.007)
pH = 7.21 + log [0.007/0.03]

[0.004/0.03] = 7.45
Buffer Capacity
This is the amount of added acid or base a buffer can tolerate before its pH changes
significantly. It is determined by the actual concentrations of the conjugate acid and base
that make up the buffer, i.e, you can only add so much strong acid before the conjugate base
in the buffer will run out; you can only add so much strong base before the conjugate acid
will run out.
Acid-Base Titration Theory

Titration is the incremental addition of a reactant of known concentration to another of
unknown concentration, in order to determine the unknown concentration through a
monitored reaction.
● Strong Acid and Strong Base

20mL of 0.1M HCl titrated with 0.1M KOH.

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- There is a very steep rise in pH around the equivalence point (volume does not
change as pH rises 6-7 units).
- This can be used to detect the equivalence point in a titration.
- Since the equivalence point solution is water and ions that do not hydrolyse (K+ and
Cl-), it has a pH of 7 - this just applies to SASB titration.
● Weak Acid and Strong Base
● Strong Acid and Weak Base
Other Titrations
Very weak (or dilute) acids/bases will not show well-defined equivalence
points (rise/fall is not steep).
Diprotic acids/bases can show two

equivalence points if the two Ka
values are different enough in value.

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Indicators in Acid/Base Titrations

An indicator is usually a weak acid or base that undergoes a dramatic colour change over a
reasonably narrow pH range. The endpoint of a titration corresponds to the change in
indicator colour. The equivalence point is the point at which an equivalent number of
moles of one reactant has been added to the other.
Choosing an Indicator
Indicator endpoint should be as close as possible to the equivalence point. A good indicator
changes colour in the steepest part of the titration curve to minimise error. Since different
titrations have equivalence points with different pH, different indicators are needed. Select
your indicator by comparing the pH range for colour change with the estimated pH of the
equivalence point.
If you look up pKa(indicator),you can estimate it will change in the range:
pH = pK a (Ind) ± 1
So, choose an indicator with pKa(Ind) close to pH of the equivalence point.
“Insoluble Salts”
- All soluble to some degree.
- Equilibrium point is a saturated solution.
- Some undissolved solid must be present for equilibrium.
- (Saturated solution is when no more solute will dissolve at a given temperature, and
undissolved solid is in contact with solution).
Salts that are Sparingly Soluble in Water

- Phosphates (PO43-)
- Carbonates (CO32-)
- Sulfides (S2-)
- Hydroxides (OH-)
- Some halides (Cl-, Br-, I-)
- Sulfates (SO42-)
- Exceptions: Na+, K+, NH4+ salts
The Solubility of a Salt

The solubility of a salt (sometimes denoted ‘s’) is the amount dissolved in a saturated
solution per unit volume. It is measured in gL-1 or molL-1. It also varies with temperature.
When calcium hydroxide dissolves, it dissociates according to:
C a(OH) 2(s) ⇌ Ca 2+ (aq) + 2OH −

(aq)
Because of the 1:1 ratio in this reaction, [Ca2+] is the same as s, the molar solubility of
Ca(OH)2. E.g. if 0.012mol of Ca(OH)2 dissolves per litre of water, then s = 0.012M and [Ca2+]
= 0.012M, [OH-] = 0.024M.

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The Solubility Product (Ksp) (not to be confused with solubility (s))

The equilibrium constant for the dissolution of an ionic compound is called the solubility
product, (Ksp).
E.g. AgCl (s) ⇌ Ag + (aq) + Cl − (aq)
[Ag + ][Cl − ]
K sp = [AgCl (s) ] = [Ag + ][Cl − ]
1. If the solubility (at a given temperature) of Ca(OH)2 is 0.012M, what is the value of the
solubility product (Ksp) for Ca(OH)2 at that temperature?
C a(OH) 2(s) ⇌ Ca 2+ (aq) + 2OH −

(aq)
[Ca 2+ ] = s, [OH − ] = 2s
K sp = [Ca 2+ ][OH − ] 2 = [s][2s] 2 = 4s 2
4(0.012) 2 = 6.9 × 10 −6
2. The solubility product for calcium phosphate, Ca3(PO4)2 is 1.2 x 10-29 at 25 C. What
concentration of calcium ions will exist in a saturated solution of this salt at this
temperature? What is the molar solubility of this compound?
C a 3 (P O 4 ) 2(s) ⇌ 3Ca 2+ (aq) + 2P O 4 3− (aq)
[Ca 2+ ] = 3s, [P O 4 3− ] = 2s
K sp = [Ca 2+ ] 3 [P O 4 3− ] 2 = [3s] 3 [2s] 2 = 108s 5 = 1.2 × 10 −29
s= √
5
1.2×10 −29
108 = 6.44 × 10 −7
The Ionic Product

The reaction quotient (for ionic dissolution) is called the ionic product. Like any reaction
quotient, the ionic product is determined by the current (probably non-equilibrium)
concentrations.
● If Q < K, the system is undersaturated, i.e. more solid can be dissolved.

● If Q = K, the system is saturated, i.e. at equilibrium.
● If Q > K, the system is supersaturated and precipitation occurs.

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Common Ion Effect

E.g. Take a saturated solution of AgCl in pure water (v. low concentrations of Ag+ and Cl-),
Add AgNO3 solution (high conc. of Ag+). The added Ag+ drives the equilibrium to the
left, reducing the solubility of AgCl (Le Chatelier’s Principle):
AgCl (s) ⇌ Ag + (aq) + Cl − (aq)
Ag+ is called a common ion here because it enters solution from two different sources (AgCl
solid and AgNO3 solution). Common ions usually reduce the solubility of ionic solutes.
1. Determine the solubility of AgCl in pure water (Ksp = 1.9 x 10-10).
s = [Ag + ] = [Cl − ]
K sp = [Ag + ][Cl − ] = s 2 = 1.9 × 10 −10
s = 1.38 × 10 −5
2. Determine the solubility of AgCl in 0.1M NaCl (common ion is Cl-). Compare this
result with the answer to part 1.
Let solubility = [Ag+] = s:
At equilibrium: [Ag + ] = s, [Cl − ] = s + 0.1
K sp = [Ag + ][Cl − ] = s(s + 0.1) = 1.8 × 10 −10
Neglect s in brackets: so 0.1s = 1.8 × 10 −10
s = 1.8 × 10 −9
Dependence of Solubility on pH
Most metal hydroxides (Cu(OH)2, Cr(OH)3, Fe(OH)3, etc.) are “insoluble” (sparingly soluble).
The solubility of many metal ions will depend on pH, since this is related to [OH-], e.g. if
pH = 9, [H+] = 10-9M, [OH-] = 10-5M. These small concentrations of OH become significant for
metal ions with sparingly soluble hydroxides. Therefore, we can use Ksp to decide whether a
metal ion (cation) will be soluble at a given pH.
1. Calculate the maximum pH required to prevent Cu(OH)2 precipitation from a 0.1M

solution of Cu(NO3)2. (Ksp(Cu(OH)2) = 2.2 x 10-20)

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C u(OH) 2(s) ⇌ Cu 2+ + 2OH −
K sp = [Cu 2+ ][OH − ] 2 = 2.2 × 10 −20
√ √
K
For equilibrium, [OH − ] = sp
= 2.2×10 −20
0.1 = 4.69 × 10 −10 M
[Cu 2+ ]
pOH = 9.33, pH = 4.67: above this pH, [OH-] will be high enough for ppte.
Week 2 - Kinetics
Chemical Kinetics
Is the study of the rates of chemical reactions and the mechanisms (series of steps) by
which they occur.
Applications
● Industry
○ Temperature and time for yields.
○ Adhesives and polymers.
○ Explosives.
● Environment
○ Atmospheric reaction rates, e.g. destruction and replacement ozone.
● Biology and Medicine
○ Enzymes.
○ Drug metabolism (pharmaceuticals).
○ Half-lives of toxins and drugs.
Factors that Determine Reaction Rates

● Concentration (surface area)
● Temperature
● Physical state
● Molecular structure/size
● Catalysts
Definition of Reaction Rates

Rate is the change in concentration per unit time. It is usually expressed in molL-1s-1
(“moles per litre per second”) (other time units may be more appropriate).
Reaction Rate
● Positive when expressed in terms of products (concentrations are increasing with
time).
● Negative when expressed in terms of reactants (concentrations are decreasing with
time).

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Instantaneous Rate
Instantaneous rate = slope of tangent to curve at
d[P ]
time t = − d[R]
dt or dt .
Generally, instantaneous rate is more useful than

average rate. So, “rate of reaction” here will usually
mean instantaneous rate.
The rate of reaction is usually given as a positive

number.
Points b, c and e are average rates, therefore, are

useless.
Points a and d are tangents to the curve, therefore,

they are instantaneous and useful.
Reaction Rates and Stoichiometry

In general, for:
aA + bB → cC + dD ,
1 d[A] 1 d[B] 1 d[C] 1 d[D]

a dt = − b dt = c dt = d dt
E.g. for the reaction:
H 2(g) + I 2(g) → 2HI (g)
HI must appear at twice the rate (in moles per litre per second) that H2 (or I2) is
disappearing.
I.e.
d[HI] d[H 2 ]
dt = −2 dt
OR
1 d[HI] d[H 2 ]
2 dt = − dt
1. What are the relative rates of change in concentration of products and reactants in
the following decomposition reaction?
2N OCl (g) → 2N O (g) + Cl 2(g)

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d[N OCl] d[Cl ]

Answer: − 21 dt = 21 d[NdtO] = dt 2
● Negative because NOCl is a reactant, therefore, concentration will decrease.

1
● 2 because the rate of change is double (2 moles).
2. Consider the reaction:
N 2(g) + 3H 2(g) → 2N H 3(s)
If ammonia is formed at the rate of 0.30molL-1s-1, at what rates are the reactants being
consumed?
d[N ] d[H] d[N H]

Relative rates of change: − dt = − 31 dt = 21 dt
N H = 0.30molL −1 s −1
N 2 = 0.30 ÷ 2 = 0.15molL −1 s −1
H 2 = 0.15 × 3 = 0.45molL −1 s −1
Dependence of Rate on Reactant Concentration: Rate Laws

A rate law is a mathematical expression of the form:
−
d[R]
dt (or + d[P ]
dt ) = k [R 1 ] a [R 2 ] b ...etc
It shows how the reaction rate varies with reactant concentrations (while other variables
such as temperature are kept constant).
● k is the rate constant.

● R1, R2... are the reactants.
● a, b... are the orders of the reaction with respect to R1, R2, ...etc.
● a + b +... is the overall order of the reaction.
Note that a, b... are not necessarily the numbers of moles of the reactants R1, R2...etc. in the
balanced equation – they can only be determined by experiment.
E.g.

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● If a reaction is zero order with respect to a reactant, then

the concentration of that reactant does not affect the rate.
● If k is large, the reaction is fast (e.g. k > 10sec-1, virtually
instantaneous).
● If k is small, the reaction is slow ( eg k < 10-3sec-1, more
than 100 min to reach equilibrium).
Meaning of Reaction Orders

If the reaction order for a reactant is 1, the rate is directly
proportional to the concentration of that reactant.
E.g. for the reaction: A + B → products.
If the rate law is found to be: rate = k[A][B]2 - this means that
doubling the concentration of A will double the rate of the
reaction.
As seen in the image, the higher the concentration of a species, the

steeper the tangent. This tells us that the rate of the reaction is
faster for species with a higher concentration.
Vice versa, the lower the concentration of a species, the gentler the
tangent. This tells us that the rate of the reaction is slower for
species with a lower concentration.
The graphs above confirm that 2N2O5(g) → 4NO2(g) + O2(g) is a first order reaction (the rate
of reaction is directly proportional to the concentration of the reacting substance).
Meaning of Reaction Orders

If the reaction order for a reactant is 2, then the rate depends on the concentration of that
reactant squared (and so on). So if rate = k[A][B]2, doubling the concentration of B will
quadruple the rate of the reaction.

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If a, the order with respect to A, is found to be equal to:

● Zero, then [A] has no effect on the rate.
● One, then rate is proportional to [A]
● Two, the rate is proportional to [A]2
and so on…
Determining the Rate Laws from the Experiment

1. Initial Rate Method
● Here the reaction is repeated in a series of experiments.
● The initial concentration of one reactant at a time is altered between experiments.
● The initial rate of the reaction is determined in each case.
E.g. The following reaction:
2I −
+ S 2 O 8 2− → 2SO 4 2− + I 2
is assumed to have a rate law of the form:
d[I − ]
− dt
= k [I − ] a [ S 2 O 8 2− ] b
Determine the values of k, a and b using the data collected in the following three
experiments:
Arithmetic method:
1. Pick a pair of experiments.
2. Find the reactant whose concentration does change between these 2 experiments.
3. Determine the ratio of that reactant’s concentrations in the two experiments; call this
ratio n.
4. If the order with respect to this reactant is a, then the corresponding ratio of rates is
na.
5. Solve for a.
E.g.
1. Experiments 2 & 3.
2. [S2O82-] remains unchanged.
3. [I-] has gone up by a factor of three from experiment 3 to 2. Therefore n = 3.
4. (1.5 x 10-4)/(5.0 x 10-5) = 3. Therefore 3a = 3.
5. a=1

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1. Experiments 1 & 2.
2. [I-] remains unchanged.
3. [S2O82-] has gone up by a factor of four from experiment 2 to 1. Therefore n = 4.
4. (6.0 x 10-4)/(1.5 x 10-4) = 4. Therefore 4b = 4
5. b=1
● a = 1, b = 1
● To find k, rearrange the rate law so that:
Rate = k [I − ] a [S 2 O 8 2− ] b becomes:
rate
k= [I − ] a [S 2 O 8 2− ] b
● Substitute the values for rate, [I-] and [S2O82-] from any one experiment in the table.
So:
6.0×10 −4
k= [6.0×10 −2 ] 1 [8.0×10 −2 ] 1
= 0.125Lmol −1 s −1
Graphical Alternative for Initial Rates Method (phy 3 experiment)

Instead of working out a (the order w.r.t. I-) by the previous method, it could be determined
using a graph. Since TBC
2. Integrated Rate Law Method (following rate and concentration vs time)

● The aim is to find a way of producing a straight line plot of the data.
● The linear plot required depends on the order of the reaction.
● If the reaction A → B + C is first order in A, the rate law is:
d[A]
− dt = k[A]
Which can be rearranged to give:

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[A] t t
d[A]
∫ [A]
=− k ∫ dt
[A] o 0
● Integrating both sides (∫ 1 = log e x = lnx) gives:

x
ln[A] t − ln[A] 0 = − k t
Or
[A] t = [A] 0 e −kt
Thus, for a first order reaction:

● A plot of a reactant concentration vs time shows an exponential decrease.
● A plot of ln[A] vs time gives a straight line of slope -k.
For exp phy-3, use:
[A] t = [A] 0 e −kt
E.g. The reaction 2N2O5 → 4NO2 + O2 was used to generate the following data:
● The linearity of plot 2 demonstrates that the reaction is first order in [N2O5], i.e. that
rate k = [N2O5].
● From this graph, k = -(slope) = 3.48 x 10-3min-1.
Half-Life (t1/2) of First Order Reactions

● The half-life of a reaction is the time taken for the
concentration to decrease by half.
● For a first order reaction, the half life is a constant, and
can be measured from any point in the reaction.
● It can be shown using the integrated first order rate law:
ln[A] t − ln[A] 0 = − k t , that the half-life of a first order
reaction is given by:

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ln2
t 1/2 = k
● Note that this is independent of reaction concentration.

What does this relationship graphically look like?
● If k is small (slow reaction), half-life is long.
● If k is large (fast reaction), half-life is short.
For the decomposition of N2O5 (examined earlier), k was

3.48 x 10-3min-1, so the half-life is:
ln2
t 1/2 = 3.38×10 −3
= 199min
If we want to know t1/2, we know k and vice versa.
E.g. (radioactive decay - radioactive decay processes

follow first order kinetics)
The half-life of carbon-14 is 5730 yr. A cloth shroud from
around a mummy was found to have a carbon-14
radioactivity of 8.9 disintegrations per minute per gram of
carbon, compared to 15.2 disintegrations per minute per
gram for living plants. How old is the shroud?
Treat carbon-14 levels as concentrations; can use integrated first order rate law to solve for
t, which will give the age of the shroud:
Rearrange: ln[A] t − ln[A] 0 = − k t
ln[A] 0 − ln[A] t
To give: t = k
ln2
To find k, rearrange: t 1/2 = k
ln2
To give: k = t 1/2
ln2
5730 = 1.2097 × 10 −4 yr −1
ln[A] 0 − ln[A] t
Substitute k into t = k
ln[15.2] − ln[8.9]
t= 1.2097×10 −4
= 4425 years
Integrated Second Order Rate Law

If the reaction 2A → B + C is second order in A, the rate law is: − d[A]
dt = k [A] 2
This expression can be rearranged to give:

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[A] t t
d[A]
∫
[A] 2
= − k ∫ dt
[A] 0 0
● Integrating both sides (∫ 1 =− x1 ) gives:

x2
1 1
[A] t − [A] 0 = kt
So, for a second order reaction:

1
● Plot of [A] vs time is linear, with slope = +k.
Distinguishing First and Second Order Reactions
● ln[NOBr] is testing for first order.

● 1/[NOBr] is testing for second order.
● Green graph (ln[NOBr]) is not linear, therefore, it is not first order.
● Blue graph ([1/[NOBr]) is linear, therefore, it is second order.
a) Deduce the rate law for the reaction.
For NO:
rate 2 0.040
● rate 1 = 0.020 =2

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8.0×10 −4
● 2a = 2.0×10 −4
=4
● a=2
For O2:
rate 3 0.040
● rate 1 = 0.010 = 4
b 8.0×10 4
● 4 = 2.0×10 −4
=4
● b=1
Therefore, rate = − d[N O]

dt = k [N O] 2 [O 2 ] 1
b) Calculate the rate constant.
2.0×10 −4
k= rate
= 0.020 2 ×0.010
= 50L 2 mol −2 s −1
[N O] 2 [O 2 ]
● Third order units because 2 + 1 = 3 (a + b)
c) Calculate the rate of disappearance of O2(g) at the instant when [NO] = 0.030M, and
[O2] = 0.020M.
rate = k [N O] 2 [O 2 ] 1 = 50 × 0.03 2 × 0.02 × 1

2 = 4.5 × 10 4 molL −1 s −1
● k = 50 (from b)
● ½ because [NO]:[O2] = 2:1. Therefore, the rate of NO is twice the rate of O2. Since
the question asks for the rate of O2, we must half our result. If they were to ask for
the rate of NO, nothing would have to be added to the calculation.
[A] t = [A] 0 e −kt
−6
= 1.00 × 10 −2 × e −1.16×10 ×24×60×60
= 9.01 × 10 −3 M
● 24 x 60 x 60 added to the calculation because k was given in seconds, therefore 24

hours must be converted to seconds.

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Reaction Mechanisms
Rate laws can be used to propose mechanisms for chemical reactions.
● Mechanism: series of elementary steps that describes the actual molecular events
taking place in the reaction.
● The slowest step in a mechanism is called the rate-determining step (RDS).
○ Can be thought of as a bottleneck.
● Since the reaction cannot go any faster than its slowest step, the rate of the overall
reaction is the same as the rate of the RDS.
The overall reaction:
NO2 + CO → NO + CO2
Is found by experiment to have the following rate law:
rate = k[NO2]2
One proposed mechanism that is consistent with this rate law is:
1. NO2 + NO2 → NO3 + NO (slow, RDS)

2. NO3 + CO → NO2 + CO2 (fast)
NO3 is an intermediate: produced, then consumed.
The rate law for an elementary step (unlike that for an overall reaction) can be determined
from its stoichiometry. E.g. for the elementary step:
2A + B → C
rate = k[A]2[B]
This is because the rate law of an elementary step represents the actual probability of
collision between reactant molecules.
Looking back at the proposed mechanism (1 and 2), Rate law of the slowest step is
rate = k[NO2]2
● Same as that found experimentally.

● So the mechanism is consistent with experiment.
In an Elementary Step

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The number of reactant molecules is called the molecularity of that step reactions are
usually unimolecular or bimolecular (i.e. 1 or 2 reactant molecules in RDS). E.g. hydrolysis
of 2-chloro-2-methylpropane.
(CH3)3CCl + OH- → (CH3)3COH + Cl-

● Two different mechanisms have been proposed, one unimolecular, and one
bimolecular.
Proposed unimolecular mechanism:
(CH3)3CCl → (CH3)3C+ + CL- (slow, RDS)
(CH3)3C+ + OH- → (CH3)3COH (fast)
Since the first equation is the RDS, the rate law predicted is:
d[(CH 3 ) 3 CCl]
− dt = k [(CH 3 ) 3 CCl]
Proposed bimolecular mechanism:
(CH3)3CCl + OH- → [(CH3)3CCl]- (slow, RDS)
[(CH3)3CCl]- → (CH3)3COH + Cl- (fast)
Since the first equation is the RDS, the rate law predicted is:
d[(CH 3 ) 3 CCl]
− dt = k [(CH 3 ) 3 CCl][OH − ]
Which Mechanism is ‘Correct’?

When kinetics are performed, the rate law is found to be:
rate = k [(CH 3 ) 3 CCl]
I.e. the unimolecular mechanism is supported.
Dependence of Reaction Rates on Temperature

Reaction rates increase by ~2x with every 10 degree increase in temperature (T). This
means that rate (and hence, k) increases exponentially with T. E.g. rearrangement of
methyl isonitrile.

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Arrhenius Equation
Arrhenius sought to explain this behaviour, proposing that reactant molecules need a
minimum energy (activation energy) to react.
k = Ae −(E a /RT )
● A: the pre-exponential factor (orientation factor - same units as the rate constant, k)
● Ea: the activation energy (Jmol-1)
● T: the temperature (K)
● R: the ideal gas constant (8.3145JK-1mol-1)
The fraction (f) of collisions of reactant molecules with sufficient

energy (≥ Ea) to react is:
f = e −E a /RT
Looking at this equation, f can be increased by:

● Decreasing the activation energy.
● Increasing the temperature.
At higher temperatures, a larger fraction of molecules has kinetic

energy exceeding Ea.
Summarising Arrhenius Equation Concepts

● A collision between reactant molecules is necessary for a reaction to occur.
● Not all collisions lead to a reaction, only the fraction f with energy greater than Ea.
● A is the number of correctly-oriented collisions per second (molecules, especially
large ones, must make contact at the right points).
Using the Arrhenius Equation

The logarithmic form of the equation represents a straight line:
Ea 1
lnk = lnA − R
· T

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If the rate constant, k, is measured at different temperatures, we can determine Ea by

plotting lnk vs 1/T.
Ea 1 1
● lnk 2 = lnk 1 − (
R T2 − T1
)
● Ea = 182kJmol-1 = 182000Jmol-1
● lnk1 = 1.57x10-5
● R = 8.3145 (constant)
● K1 = 700oC + 273.15 = 973.15K
● a) K2 = 600oC + 273.15 = 873.15K
● b) K2 = 800oC + 273.15 = 1073.15K
a) lnk 600 = ln(1.57 × 10 −5 ) − ( 182000 1

8.3145 ( 873.15 −
1
973.15 ))
lnk 600 = − 13.6379729
k 600 = e −13.6379729
k 600 = 1.19 × 10 −6 mol −1 s −1
b) lnk 800 = ln(1.57 × 10 −5 ) − ( 182000 1

8.3145 ( 1073.15 −
1
973.15 ))
lnk 800 = − 8.965831722
k 800 = e −8.965831722
k 800 = 1.28 × 10 −3 mol −1 s −1
Reaction Profiles
A reaction profile is a plot of potential energy
vs the extent of the reaction. It shows the
activation energy (Ea) as a barrier that must be
overcome for a reaction to occur.
Catalysis
● Increases the rate of reaction without
being consumed.

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● Is both a reactant and a product in the reaction mechanism.

● Reduced Ea by changing the mechanism of the reaction.
A catalyst can be:
● Heterogenous (different phase to the reactants), e.g. Pt catalyst in
hydrogenation of ethene.
● Homogenous (same phase), e.g. I- in the decomposition of H2O2.
Enzymes
● Biological catalysts that perform chemical reactions on “substrate” molecules.
● Very specific; enable reactions that are normally impossible (too slow) at
biological temperatures.
● Enzymes are proteins.
Relationship Between Kinetics and Equilibrium

At equilibrium, the rates of the forward and reverse reactions are equal. Thus, for the
following reaction at equilibrium:
aA + bB ⇌ cC + dD
We can write:
forward rate = reverse rate
I.e.
a b c d
k f [A] [B] = k r [C] [D]
[C] c [D] d kf
Therefore, = kr
=kc
[A] a [B] b
I.e. the equilibrium constant is the ratio of the forward and reverse rate constants.

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Week 3 - Thermochemistry
Thermodynamics is the study of transformations of energy, e.g. heat into work.
Thermochemistry is a branch of thermodynamics that examines heat released (or
absorbed) by chemical reactions. These ideas can be applied to fuels, combustion, nutrition,
biological metabolism, etc.
Enthalpy of Reactions
Enthalpy (H) of a system is defined such that a change in enthalpy (𝜟H) is the heat
transferred to a system at constant pressure. In many cases, 𝜟H is a good approximation to
the total energy change of a system.
Enthalpy is a state function, which means that 𝜟H depends only on final and initial
enthalpies of the system, and not on any intermediate values.
An exothermic process (𝜟H < 0) is one in which heat is transferred from system to
surroundings.
E.g. H2O(g) → H2O(l) 𝜟H = -44.0kJ
A endothermic process (𝜟H > 0) is one in which heat is transferred from surrounds to
system
E.g. H2O(l) → H2O(g) 𝜟H = +44.0kJ
Note that if a processed in reversed, 𝜟H has the same magnitude but the opposite sign.
Enthalpy change (𝜟H) is directly proportional to the quantity of material undergoing change.
E.g. 2H2O(l) → 2H2O(g) 𝜟H = +88.0kJ
𝜟H for this process is +44kJmol-1 for H2O(l).
Balanced chemical equations that show the associated enthalpy change in this way are
called thermochemical equations.
E.g. Given the following thermochemical equation:
H2(g) + Cl2(g) → 2HCl(g) 𝜟H = -185kJ
Calculate 𝜟H when:
a) 1 mole of HCl is formed.
ΔH = −185kJ =− 92.5kJ
2

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b) 1.00g of Cl2 reacts.
m 1g
n= mw = 2(35.45)mol/g = 0.0141mol
ΔH = 0.0141 ×− 185kJmol −1 = − 2.61kJ
Standard Enthalpy of Reaction

In order to compare enthalpies of different reactions, we need to define a standard state at
which enthalpies are reported. Standard enthalpy of reaction (𝜟H0) is defined as the
enthalpy change when all reactants and products are in their standard states.
Standard states:
● Liquids and solids - pure form at 1atm.
● Solutes in solution - 1molL-1 concentration.
● Gases - partial pressure of 1atm.
Most tabulated enthalpy values are for a temperature of 25oC (298K)
E.g. if we write:
2H+(aq) + Zn(s) → H2(g) + Zn2+(aq) 𝜟H = -154kJ
...we are saying that if we start with 2 moles of H+(aq) in a 1M solution and 1 mole of solid zinc
and finish with one mole of H2(g) at 1atm pressure and one mole of Zn2+(aq) in a 1M solution,
then the enthalpy change will be -154kJ.
Calorimetry
𝜟H values are determined experimentally by measuring the heat flow accompanying a
reaction at constant pressure. When heat flows into or out of a substance, the temperature
of the substance changes. The heat flow associated with a chemical reaction can thus be
determined by measuring the temperature change it produces. The measurement of heat
flow is calorimetry. The apparatus needed to measure heat flow is a calorimeter.
Heat Capacity
The heat capacity of an object or substance is the amount of heat required to raise the
temperature of that object by 1oC (1K). Heat capacity (C) is measured in JK-1 or JoC-1.
Heat capacities of pure substances are usually tabulated on a per mole or per gram basis:
● Molar heat capacity (Cm) in JK-1mol-1 or JoC-1mol-1.
● Specific heat capacity (Cs) in JK-1g-1 or JoC-1g-1.
To work out how much heat (q in joules) has been transferred by a temperature change
(𝜟T), we use the following relationships:
● q = nC m ΔT for n moles of substance.
● q = mC s ΔT for m grams of substance.
● q = C ΔT for an object such as a calorimeter.

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E.g. A 466 g sample of water is heated from 8.50oC to 74.60oC. Calculate the amount of
heat absorbed by the water. The specific heat capacity of water is 4.184JoC-1g-1.
q = mC s ΔT = mC s (T − T initial ) f inal
= 466 × 4.184(74.60 − 8.50)
= 1.29 × 10 5 J
= 129kJ
Constant-Pressure Calorimetry
A simple apparatus is known as a ‘coffee cup’ calorimeter. Used to
measure the heat transferred for processes at laboratory
atmospheric pressure. It consists of a known mass of solution in an
insulated container equipped with a thermometer and stirrer.
Tinital of the solution is measured.
As the reaction takes place, it is stirred and Tfinal is measured.
E.g. When 50.0 ml of 0.100M AgNO3 and 50.0mL of 0.100M HCl are
mixed in a constant-pressure calorimeter, the temperature of the
mixture increases from 22.30°C to 23.11°C. The temperature increase is caused by the
following reaction:
AgNO3(aq) + HCl(aq) → AgCl(s) + HNO3(aq)
Calculate 𝜟H for this reaction expressed in kJmol-1 of HCl, assuming that the combined
solution has a mass of 100.0 g and a specific heat capacity of 4.18J°C-1g-1.
Heat transferred during the reaction:
q = mC s ΔT
−1
= 100g × 4.18J C o
g −1 (23.11 o C − 22.30 o C)
= 338J
Heat gained by the solution is equal to heat released in reaction: q = -338J
nHCl = 0.100M × 50.0 × 10 −3 L = 5.00 × 10 −3 mol
−q
ΔH = n
ΔH = −338J
5.00×10 −3 mol
= − 6.76 × 10 4 Jmol −1
= − 67.4kJmol −1

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Constant-Volume Calorimetry
A constant-volume calorimeter (or bomb calorimeter) is
used to measure the heat released in a combustion
reaction.
An electrically heated coil ignites a substance within a

steel bomb containing O2.
Heat released from the combustion reaction is transferred

to the rest of the calorimeter and the temperature is
measured.
E.g. A 0.5865g sample of lactic acid (C3H6O3) is burned in

a bomb calorimeter, the heat capacity of which is
4.812kJ°C-1. The temperature increases from 23.10°C to 24.95°C. Calculate the enthalpy of
combustion of lactic acid per gram and per mole.
Heat transferred during the reaction: q = C ΔT

−1
= 4.812kJ o C × (24.95 o C − 23.10 o C)
= 8.902kJ
Heat liberated during combustion: q = 8.902kJ

0.5865g
n= m
mw = 90.8gmol −1
= 6.511 × 10 −3 mol
q
ΔH = n
ΔH = −8.902kJ
6.511×10 −3 mol
= − 1.367 × 10 kJmol −1 3
Hess’s Law
Hess’s law says that the enthalpy change of
an overall process is the sum of enthalpy
changes of its individual steps.
ΔH overall = ΔH 1 + ΔH 2 + ΔH 3
Hess’s law enables calculations of enthalpies

of reactions that we cannot directly measure
using other known enthalpies.
This is illustrated by the following scheme, in

which any one of three enthalpy changes can be calculated if the other two are known:

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Method for calculating unknown 𝜟H:
1. Identify target reaction with unknown 𝜟H.
2. Rearrange equations of known 𝜟H so that target reactants and products are on

correct sides with correct number of moles.
● Change sign of 𝜟Hif equation is reversed.
● Adjust moles and 𝜟H by the same factor.
3. Add altered equations, cancelling substances not in target reaction (which should be
present on both sides of reaction).
E.g. Given the following combustion reactions:
1. C(s) + O2(g) → CO2(g) 𝜟H = -393.5kJ

2. CO(g) + ½O2(g) → CO2(g) 𝜟H = -283.0kJ
Determine the enthalpy of combustion of C to CO:
C(s) + ½O2(g) → CO(g)
● Reaction 1. has the correct number of moles and reactants and products.
● Reaction 2. needs to be reversed to have CO(g) as a product
1. C(s) + O2(g) → CO2(g) 𝜟H = -393.5kJ

2. CO2(g) → CO(g) + ½O2(g) 𝜟H = 283.0kJ
C(s) + O2(g) + CO2(g) → CO2(g) + CO(g) + ½O2(g)

C(s) + O2(g) + CO2(g) → CO2(g) + CO(g) + ½O2(g)
C(s) + O2(g) → CO(g) + ½O2(g) 𝜟H = -110.5kJ
E.g Calculate 𝜟H for the reaction:
2C(s) + H2(g) → C2H2(g) (acetylene)
Given the following thermochemical reactions:
1. C2H2(g) + 5/2O2(g) → 2CO2(g) + H2O(l) 𝜟H = -1299.6kJ

2. C(s) + O2(g) → CO2(g) 𝜟H = -393.5kJ
3. H2(g) + ¹⁄ O2(g) → H2O(l) 𝜟H = -285.8kJ
Answer:
● Reverse equation 1.
● Times equation 2. by 2.
● Keep equation 3. the same.

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1. 2CO2(g) + H2O(l) → C2H2(g) + 5/2O2(g) 𝜟H = 1299.6kJ

2. 2C(s) + 2O2(g) → 2CO2(g) 𝜟H = -787.0kJ
3. H2(g) + ¹⁄ O2(g) → H2O(l) 𝜟H = -285.8kJ
2CO2(g) + H2O(l) + 2C(s) + 2O2(g) + H2(g) + ¹⁄ O2(g) → C2H2(g) + 5/2O2(g) + 2CO2(g) + H2O(l)
2C(s) + H2(g) → C2H2(g) 𝜟H = 226.8kJ
Enthalpy of Formation
Standard enthalpy of formation of a compound (𝜟Hof) is defined as the standard enthalpy
change for reaction where one mole of that compound is formed from its elements in their
most stable forms, e.g. for glucose at 25oC:
6C(graphite) + 6H2(g) + 3O2(g) → C6H12O6(s)
𝜟Hof(glucose) = -1268kJmol-1
Graphite is the most stable form of carbon at 1 atm, while hydrogen and oxygen are gases.
Note: standard enthalpy of formation of an element in its most stable form is zero.
E.g. O2(g) 𝜟Hof = 0kJmol-1
Standard enthalpies of formation have been tabulated for many compounds at 25oC and can
be used to calculate the enthalpy change for any chemical reaction without that reaction
being performed:
o o o
ΔH = ΣnΔH f (products) − ΣmΔH f (reactants)
● n and m are coefficients in the chemical equation.
E.g. Calculate the standard enthalpy of reaction for the following process:
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(g)
Useful data (𝜟Hof/kJmol-1):

● C2H6(g) = -84.7
● O2(g) is in its stable form
● CO2(g) = -393.5
● H2O(g) = -241.8
Answer:
o o o
ΔH = ΣnΔH f (products)
− ΣmΔH f (reactants)
o
ΔH = [4(− 393.5) + 6(− 241.8)] − [2(− 84.7) + 7(0)]
ΔH o = − 2855.4

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Entropy
A process that occurs of its own accord without any ongoing outside intervention is a
spontaneous process (e.g. ice melts at room temperature).
To understand spontaneity, we need to examine entropy.
Entropy (S) is a thermodynamic function

associated with the number of different
energy states or spatial arrangements in
which a system may be found – associated
with randomness Absolute entropies are
referenced to zero entropy for perfectly
crystalline solids at 0K.
Entropy is a state function (like enthalpy).
The change in entropy (𝜟S) depends only on the initial and final states of the system:
𝜟S = Sfinal - Sinital
Qualitative Predictions About 𝜟S

Expect the entropy of the system to increase for processes in which:
1. Gases are formed from either solids or liquids.
2. Liquids or solutions are formed from solids.
3. The number of gas molecules increases during a chemical reaction.
E.g. Predict whether 𝜟S is positive or negative for the following process:
H2O(l) → H2O(g)
● Molecules are distributed throughout a larger volume in a gaseous state.

● Increase in freedom of motion.
● Therefore, 𝜟S is positive.
E.g. Predict whether 𝜟S is positive or negative for the following process:
C2H2(g) + 2H2(g) → C2H6(g)
● Number of molecules decreases during reaction.

● Less random.
● Therefore, 𝜟S is negative.
Entropy Changes in Chemical Reactions

S calculated by measuring the change in heat capacity with temperature.
Standard molar entropy (So): entropy values of a substance in its standard state.

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Observations about So values:

1. S° of elements at 298K are not zero (unlike 𝜟H°)
2. S° values of gases are greater than those of liquids and solids.
3. S° values increase with molar mass.
4. S° values increase with an increasing number of atoms in a substance.
The entropy change in a chemical reaction equals the sum of the entropies of the products
less the sum of the entropies of the reactants:
ΔS o = ΣnS o (products) − ΣmS o (reactants)
● n and m are the coefficients in the chemical equation.
E.g. Determine the standard entropy change ΔS° for the following reaction at 298K:
Al2O3(s) + 3H2(g) → 2Al(s) + 3H2O(g)
Useful data (So/JK-1mol-1):

● Al(s) = 28.32
● H2O(g) = 188.83
● Al2O3(s) = 51.00
● H2(g) = 130.58
Answer:

ΔS o = [2(28.32) + 3(188.83)] − [51.00 + 3(130.58)]
−1
ΔS o = 180.39JK
Gibbs Free Energy

Both enthalpy and entropy affect reaction spontaneity. Gibbs free energy (G) reflects
balance between these driving forces. For a process occurring at constant temperature the
change in free energy is:
ΔG = ΔH − T ΔS
● T is temperature in K.
It provides a single function whose sign determines whether a reaction is spontaneous.
1. If 𝜟G is negative (𝜟G < 0), the forward reaction is spontaneous.

2. If 𝜟G is positive (𝜟G > 0), the reverse reaction is spontaneous.
3. If 𝜟G is 0, the system is at equilibrium (no tendency for reaction to occur in either
direction).

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Standard Free Energy Changes

To calculate the standard free energy change for a reaction:
ΔG o = ΣnΔG f o (products) − ΣmΔG f o (reactants)
● 𝜟Gfo is the standard free energy of formation.

● n and m are the coefficients in the chemical equation.
● As for 𝜟Hfo, the 𝜟Gfo of an element in its most stable form, is zero.
E.g. Determine the standard free energy change 𝜟G for the reaction:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
What does the sign of your answer tell you about the reaction?
Useful data (𝜟Gfo/kJmol-1):

● CO2(g) = -394.4
● H2O(g) = -228.6
● CH4(g) = -50.8
ΔG o = ΣnΔG f o (products) − ΣmΔG f o (reactants)

ΔG o = [− 394.4 + 2(− 228.6)] − [− 50.8 + 2(0)]
ΔG o = − 800.8kJ
● 𝜟G is negative, therefore, the forward reaction is spontaneous under standard

conditions.
Free Energy and Temperature

To estimate 𝜟G° at temperatures other than 25°C, use the Gibbs-Helmholtz equation:
ΔG = ΔH − T ΔS
● Assume that 𝜟H° and 𝜟S° do not change with temperature.
E.g. Determine the standard free energy change for the following reaction at 100°C
(373.15K):
Ca(s) + Cl2(g) → CaCl2(s)
At 25°C, the standard enthalpy change is -795.8kJmol-1 and the standard entropy change is
-159.8JK-1 (-0.1598kJK-1)
ΔG = ΔH − T ΔS
ΔG = − 795.8kJ − (373.15K ×− 159.8 × 10 −3 kJK −1
)
ΔG = − 736.2kJ

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E.g. The production of ammonia via the Haber process involves the equilibrium:
N2(g) + 3H2(g) ⇌ 2NH3(g)
Assuming that 𝜟H° and 𝜟S° for this reaction do not change with temperature, determine the
standard free energy change at 500°C (773.15K). If 𝜟G° is -33.3kJ for the Haber process at
25°C, comment on the effect of temperature on the equilibrium.
Useful data (𝜟Hf°/kJmol-1):

● NH3(g) = -46.2
Useful data (𝜟Sf°/JKmol-1):

● N2(g) = 191.5
● H2(g) = 130.7
● NH3(g) = 192.5
Answer:
ΔH = ΣnΔH f (products) − ΣnΔH f (reactants)

ΔH = [2(− 46.2)] − [0 + 3(0)]
ΔH = − 92.4kJ

ΔS o = [2(192.5)] − [191.5 + 3(130.7)]
ΔS o = − 198.6JK −1
= − 198.6 × 10 −3 kJ −1
ΔG = ΔH − T ΔS
ΔG = − 92.4 − (773.15K ×− 198.6 × 10 −3 )
ΔG = 61.1kJ
● As the temperature increases from 25°C to 500°C the 𝜟G° changes from a negative
value (-33.3kJ) to a positive value (61.1kJ), the reverse reaction is spontaneous.
Free Energy and the Equilibrium Constant

Most chemical reactions occur under non-standard conditions. Free energy change for any
conditions:
ΔG = ΔG o + RT × lnQ
● R is the universal constant (8.314JK-1mol-1).

● T is temperature in Kelvin.
● Q is reaction quotient (from Equilibria topic)

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● ln is loge.
When a system is at equilibrium, Q = K (equilibrium constant) so: 0 = ΔG o + RT lnK
ΔG o = − RT lnK
● More negative 𝜟G° = larger K

● More positive 𝜟G° = smaller K
E.g. Calculate the equilibrium constant at 25°C for the Haber process:
N2(g) + 3H2(g) ⇌ 2NH3(g)
For this process 𝜟G° = -33.3 kJ mol-1
● Note that ‘per mole’ means ‘per mole of the reaction as written’: 𝜟G° = -33.3kJmol-1
implies per 1 mol N2 per 3 mol H2 and per 2 mol NH3.
Answer:
ΔG o = − RT lnK
− 33.3 = 8.314 × 298.15 × lnK
K = 6.9 × 10 5
● This is a large K which indicates that NH3 is greatly favoured in the equilibrium
mixture at 25°C.

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Week 4 - Electrochemistry
Electrochemistry is the study of chemical reactions involving the transfer of electrons (e-).
Some applications of redox reactions include: batteries, fuel cells, metal refining,
environmental testing, neuroscience and biosensors.
An electrochemical or redox reaction involves transfer of e- between:

● An e- donor (reductant or reducing agent)
● An e- acceptor (oxidant or oxidising agent)
Galvanic Cells
Galvanic cells (or voltaic cells) use a spontaneous reaction to generate electrical energy. In
cell reaction, difference in chemical potential energy between reactants and products
is converted into electrical energy.
● 2 half-reactions (‘half-cells’ or ‘couples’) are

separated so that e- can be diverted
through a wire.
● 2 electrodes, anode (negative) and cathode
(positive), conduct electricity.
● Active electrodes: made of metals that
are components of half reactions.
● Inactive electrodes (e.g. graphite,
platinum) are used when no reactants or
products are capable of serving as
electrodes - conduct electrons but cannot
take part in half reactions.
● Electrodes are inserted into an electrolyte:
ions in solution involved in reaction or that carry charge.
● Circuit is completed with a salt bridge (or ion bridge) containing a salt solution (e.g.
NaNO3, NaSO4) that does not interfere with redox reaction.
● Oxidation half-cell is usually shown on the left (anode) and reduction half-cell
(cathode) on the right.
Cell Notation
● Anode (oxidation half cell) is written first.
● Single vertical lines represent phase boundaries (e.g. between solid and solution).
● Comma separates components in the same phase
● Double vertical lines represent the salt bridge Write reactant then product on each
side If concentrations of 2 solutions in a zinc-copper cell are each 1 M, then cell is
represented as follows:
Zn | Zn2+ (1M) | | Cu2+ (1M) | Cu

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E.g. A voltaic cell is constructed with an Ag / Ag+ half-cell and a Pb / Pb2+ half-cell.
Measurement shows that the silver electrode is positive.
1. Write balanced half-reactions and the overall spontaneous reaction for the cell.
● We know silver electrode is positive, therefore, it is a cathode.

● Reduction occurs at the cathode, therefore, silver is an oxidising agent (e- acceptor).
● Since reduction is at silver, oxidation must be at lead.
Reduction: [ Ag+(aq) + e- → Ag(s) ] x 2

Oxidation: [ Pb(s) → Pb2+(aq) + 2e- ]
Overall: 2Ag+(aq) + Pb(s) → 2Ag(s) + Pb2+(aq)
2. Label the cell, showing electrodes with their

charges and showing the directions of
electron flow in the circuit and of cation and
anion flow in the salt bridge.
Standard Reduction Potentials

Reduction potential – measure of tendency of a chemical species to acquire electrons.
Standard cell potential (Eocell) is the potential difference between 2 metal electrodes
measured in volts (V) when all substances are present in standard states.
Standard states are 1 M for solutions and 1 atm for gases.
Potential difference is also called voltage or emf (electromotive force).
It is impossible to measure the potential of a half-cell single electrode - it must be measured

relative to something else.
Problem is solved by making the potential of one

half-cell equal to exactly zero and measuring all
others relative to this cell.
Reference half-cell chosen by convention is

standard hydrogen electrode (SHE):
H+ (1M) | H2 (1 atm) | Pt
Consists of hydrogen gas being bubbled over a Pt

electrode in a 1M acid solution.
Standard reduction potential (E°) of any other half-cell can be obtained by measuring cell
potential (Eocell) when the half-cell of interest (with standard amounts of reactants) is
combined with SHE.

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Tables of Standard Reduction Potentials

Standard reduction potentials have been tabulated along with relevant half-equations
(written as reductions).
Comparing Oxidant and Reductant Strengths

When table is listed in order of decreasing reduction potential (electrochemical order):
● Species on the left hand side of equations at the top of the table are the strongest
oxidants (reduced easiest).
● Species on the right hand side at the bottom of table are the strongest reductants
(oxidised easiest).
E.g. Arrange the following species in order of decreasing strength as oxidising agents:
Fe3+, Br2, Cu2+.
Answer:
Using standard reduction potentials from the table:
Br2(aq) + 2e- → 2Br-(aq) Eo = +1.09V

Fe3+(aq) + e- → Fe2+(aq) Eo = +0.77V
Cu2+(aq) + 2e- → Cu(s) Eo = +0.34V
Strongest oxidising agent is species on left side of equation that has highest potential:
Br2 > Fe3+ > Cu2+

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Predict Cathode and Anode in Galvanic Cells

When a cell is to be constructed from 2 known half-cells, the cathode will be the half-cell that
sits highest in the table of standard reduction potentials.
Cathode (reduction) half-reaction will occur in the direction appearing in the table, while
anode (oxidation) half-reaction must occur in the opposite direction to that in the table.
E.g.
Cu2+(aq) +2e- → Cu(s) Eo = +0.34V (cathode)

Zn2+(aq) + 2e- → Zn(s) Eo = -0.76V (anode)
Reaction at anode: Zn(s) → Zn2+(aq) + 2e-
Predict Cell Potential

Once reduction and oxidation processes have been identified, standard potential of galvanic
cell constructed from them is given by:
o o o
E cell =E oxidant − E reductant
or
o o o
E cell =E (reduction process) − E (oxidation process)
E.g.
o
E cell= E o copper − E o zinc
o
E cell = 0.34V − (− 0.76) = 1.10V
Note: electrical potential measures potential energy per electrical charge (V = JC-1)
If the amount of substance in a reaction increases, then both the energy and charges
involved increase – ratio remains constant.

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Predict the Spontaneity of a Redox Reaction

● Eocell > 0: spontaneous reaction.
● Eocell < 0: non-spontaneous reaction.
E.g. A galvanic cell consists of a magnesium electrode in a 1.0 M Mg(NO3)2 solution and a
silver electrode in a 1.0 M AgNO3 solution. Calculate the standard cell potential of this cell at
25oC. Is the reaction spontaneous?
Useful data:
● E°(Ag+/Ag) = 0.80V
● E°(Mg2+/Mg) = -2.37V
Answer:
From standard reduction potential table:
Ag+ + e- → Ag Eo = 0.80V
Mg2+ + 2e- → Mg Eo = -2.37V
● Standard reduction potential for silver (0.80V) is higher than magnesium (-2.37V),
therefore, Ag+ is the cathode and is undergoing reduction (oxidising agent).
● Therefore, Mg2+ must be the anode and is undergoing oxidation (reducing agent).
Cathode - reduction: 2Ag+ + 2e- → 2Ag

Anode - oxidation: Mg2+ + 2e- → Mg
Overall: 2Ag+ + Mg2+ → 2Ag + Mg
o o o
E cell =E − E (oxidation process)
(reduction process)
E o cell = 0.80V − (− 2.37V )
E o cell = 3.17V
Positive value of Eocell indicates reaction is spontaneous.
Free Energy of Redox Reactions

Relationship between cell potential and free energy change:
ΔG = − nF E
● n is number of electrons transferred in reaction

● F is Faraday constant – quantity of electrical charge on 1 mole of electrons
● F = 96485Cmol-1 (JV-1mol-1)
When reactants and products are all in standard states:
ΔG o = − nF E o
Positive value of E (and negative value of ΔG) both indicate that reaction is spontaneous.

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E.g. Use standard reduction potentials to determine ΔG° for the reaction:
4Ag(s) + O2(g) + 4H+(aq) → 4Ag+(aq) + 2H2O(l)
Is this reaction spontaneous?
Useful data:
● Eo (O2(g), H+(aq) / H2O(l)) = 1.23V
● Eo (Ag+(aq) / Ag(s)) = 0.80V
Answer:
Reduction: O2(g) + 4H+(aq) + 4e- → 2H2O(l) Eo = 1.23V

Oxidation: 4Ag(s) → 4Ag+(aq) + 4e- Eo = 0.80V
o o o
E cell =E − E
(reduction process) (oxidation process)
= 1.23V − 0.80V
E o cell = 0.43V
ΔG o = − nF E o
= − 4 × 96485JV −1 mol −1 × 0.43V
= − 1.66 × 10 5 Jmol −1
= − 166kJmol −1
ΔGo is negative and Eo is positive, therefore, the reaction is spontaneous.
Nernst Equation
What happens to cell potentials as concentrations change (as reactants are used up)? Cells
with changing solution concentrations have changing potentials. Dependence of cell
potential on concentration can be obtained from free energy change.
Recall that:
ΔG = ΔGo + RT lnQ
Substituting ΔG = -nFE:
-nFE = -nFEo + RT lnQ
o RT
E=E − nF lnQ
Nernst equation is used to predict changing cell potential:

● E is reduction potential for reaction.
● Eo is standard cell potential.
● n is the number of moles of electrons transferred during reaction.
● R is universal constant (8.314JK-1mol-1)
● T is temperature (usually 298.15 K)
● F is Faraday’s constant.

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● Q is reaction quotient:
[C] c [D] d
Q= [A] a [B] b
where:
aA + bB → cC + dD
Nernst equation helps us understand why potential of galvanic cell drops as cell discharges
– as reactants are converted to products, Q increases so E decreases.
E.g. Predict whether the following reaction would spontaneously proceed at 298 K:
Co2+(aq) + Fe(s) → Co(s) + Fe2+(aq)
given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M.
Useful data:
● E°(Co2+(aq) / Co(s)) = -0.28V
● E°(Fe2+(aq) / Fe(s)) = -0.44V
Cathode (reduction): Co2+(aq) + 2e- → Co(s)

Anode (oxidation): Fe(s) → Fe2+(aq) + 2e-
o o o
E cell =E − E (oxidation process)
(reduction process)
o
E cell = − 0.28V − (− 0.44V )
E o cell = 0.16V
[F e 2+ ]
Q= [Co 2+ ]
o RT
E=E nF lnQ
−
8.314JK −1 mol −1 ×298K
= 0.16V − 2×96485 ln 0.68
0.15
E = 0.14V
E is positive, therefore, the reaction is spontaneous.
Corrosion
Corrosion is oxidation of metals by certain substances in the environment (mostly H2O and
O2). An unwanted compound, such as rust (Fe2O3.H2O), with poorer qualities may be formed
Corrosion is an electrochemical process.

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Two-half reactions of the cell use corroding metal as both the electrodes and the metal
conduct electrons.
Fe(s) can be oxidised by O2(g) because standard reduction potential for Fe2+ reduction is less
positive than for O2 reduction:
O2(g) + 4H+(aq) + 4e- → 2H2O(l) Eo = 1.23V

Fe(s) → Fe2+(aq) + 2e- Eo = -0.44V
Part of metal acts as anode. Electrons produced can migrate through metal to another part
of the surface that acts as cathode.
Fe2+ formed at anode is eventually oxidised to Fe3+ and forms rust:
2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+(aq) + 2H2Ol)
2Fe2+(aq) + ¹⁄ O2(g) + 3H2O(l) → Fe2O3.H2O(s) + 4H+(aq)
2Fe(s) + 3/2O2(g) + H2O(l) → Fe2O3.H2O(s)
Layer of rust formed does not protect metal from further oxidation because it is porous to O2.
Presence of salts enhances corrosion – conductivity of water increases and so does the rate
of corrosion.
Prevention of Corrosion
Corrosion of iron can be prevented by protecting the surface from O2 and H2O (e.g. paint).
Corrosion can also be prevented using cathodic protection: metal to be protected is made
the cathode in a cell and another metal is oxidised (sacrificial anode) Galvanised iron is iron
coated with a thin layer of zinc. Standard reduction potential for Zn2+ is more negative than
for Fe2+ so Zn is easier to oxidise than Fe:
Fe2+(aq) + 2e- → Fe(s) Eo = -0.44V

Zn2+(aq) + 2e- → Zn(s) Eo = -0.76V
E.g. Which of the following metals are suitable as sacrificial anodes to protect against the
corrosion of underground iron pipes? (a) aluminium (b) nickel
Useful data:
● E°(Fe2+/Fe) = -0.44V
● E°(Al3+/Al) = -1.66V
● E°(Ni2+/Ni) = -0.23V
Answer:
(a) Yes: E°(Al3+/Al) < E°(Fe2+/Fe), so Al will oxidise.
(b) No: E°(Ni2+/Ni) > E°(Fe2+/Fe), so Fe will oxidise.

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Electrolysis
Electrolysis is the process of forcing a non-spontaneous reaction to occur by applying an
electric current. Electrolysis is important for metal refining, recharging batteries,
electroplating objects with metals and environmental testing.
An electrolytic cell is usually constructed with inert electrodes (metal or graphite) which can
share the same compartment.
Voltage needed to drive a non-spontaneous reaction must be greater than that which would
be produced by reverse (spontaneous) reaction.
Electrolyte in the cell can be an aqueous solution or a molten

salt.
Many electrolytic applications involve isolating a metal or

non-metal from a molten salt or aqueous solution of a salt.
Electrolysis of Molten Salts

Cation will be reduced and anion will be oxidised.
E.g. What product forms at each electrode in the electrolysis of molten CaCl2?
Answer:
2Cl-(l) → Cl2(g) + 2e- anode – oxidation
Ca2+(l) + 2e- → Ca(l) cathode – reduction
Ca2+(l) + 2Cl-(l) → Ca(l) + Cl2(g) overall

Cl2(g) formed at anode and Ca(l) formed at cathode.

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Quantitative Analysis of Electrolysis

To calculate amount of product formed by an electrolytic process need:
● Electric current (I) that flowed through the cell.
● Time (t) in seconds that current flowed.
● Ratio of moles of electrons transferred to moles of product formed (given by relevant
half-equation).
Important relationships:
Q = It
● Q is charge transferred in coulombs (C) (coulomb is quantity of charge passing a

point in circuit in 1s when current is 1 ampere).
● I is current (A) that flows for t seconds.
Q
n= F
● n is moles of electrons transferred

● F is Faraday constant
Combining into one expression:
It
n= F
E.g. Calculate the number of grams of aluminium produced in 1.00 hour by the electrolysis
of molten AlCl3 if the electrical current in 10.0A.
Answer:
1.00h = 3600s
Quantity of charge:
Q = It = 10.0A x 3600s = 3.60 x 104C
Moles of electrons
n=Q/F
= 3.60 x 104C / 96485Cmol-1 = 0.373mol
Moles of substance
Al3+ + 3e- → Al

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3 mole electrons are required to form 1 mole Al

n = 0.373mol / 3 = 0.124mol
Mass of substance
m = moles x atomic mass
= 0.124mol x 27.0gmol-1
= 3.36g Al

Chemistry 2 Physical Chemistry Lecture Notes

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Chemistry 2 Physical Chemistry Lecture Notes

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Chemistry 2 - Physical Chemistry Lecture Notes

Chemistry 2 (University of Technology Sydney)

Studocu is not sponsored or endorsed by any college or university

Acid: is a proton (H+) donor (produces H+ in aqueous solutions).

Extent of dissociation (acid strength) is measured by equilibrium constant, Ka.

(Equilibrium lies to the left)

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Conjugate Acid-Base Pairs

acid + base ⇌ conjugate base + conjugate acid

● A strong acid will have a weaker conjugate base.

- Ka1 >> Ka2 (i.e. pKa1 << pKa2)

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Example Question for the pH of a Weak Polyprotic Acid

x = √0.0020 × 4.5 × 10 −7 = 3.0 × 10 −5 = [H + ]

E.g. a solution of sodium acetate (NaCH3COO) is basic:

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- Na+ is neutral, pKb = 14 − 4.76 = 9.24

K b = 10 − 9.24 = 5.75 × 10 −10

x 2 = 0.0100 × 5.75 × 10 −10

x = √0.0100 × 5.75 × 10 −10 = 2.4 × 10 −6 = [OH − ]

pOH = − log[2.4 × 10 −6 ] = 5.62

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= 4.76 + log [0.07]

Before dilution: pH = 7. After dilution:

pOH = − log[0.03333...] = 1.477

pH = 14 − 1.477 = 12.52 (increase)

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3. How much will the pH change if 10 mL of 0.1M NaOH is added to a 20mL of a

= 7.21 + log [0.006/0.02]

pH = 7.21 + log [0.007/0.03]

Acid-Base Titration Theory

● Strong Acid and Strong Base

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● Weak Acid and Strong Base

● Strong Acid and Weak Base

Diprotic acids/bases can show two

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Indicators in Acid/Base Titrations

If you look up pKa(indicator),you can estimate it will change in the range:

So, choose an indicator with pKa(Ind) close to pH of the equivalence point.

Salts that are Sparingly Soluble in Water

The Solubility of a Salt

When calcium hydroxide dissolves, it dissociates according to:

C a(OH) 2(s) ⇌ Ca 2+ (aq) + 2OH −

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The Solubility Product (Ksp) (not to be confused with solubility (s))

E.g. AgCl (s) ⇌ Ag + (aq) + Cl − (aq)

C a(OH) 2(s) ⇌ Ca 2+ (aq) + 2OH −

K sp = [Ca 2+ ][OH − ] 2 = [s][2s] 2 = 4s 2

C a 3 (P O 4 ) 2(s) ⇌ 3Ca 2+ (aq) + 2P O 4 3− (aq)

K sp = [Ca 2+ ] 3 [P O 4 3− ] 2 = [3s] 3 [2s] 2 = 108s 5 = 1.2 × 10 −29

The Ionic Product

● If Q < K, the system is undersaturated, i.e. more solid can be dissolved.

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Common Ion Effect

AgCl (s) ⇌ Ag + (aq) + Cl − (aq)

1. Determine the solubility of AgCl in pure water (Ksp = 1.9 x 10-10).

AgCl (s) ⇌ Ag + (aq) + Cl − (aq)

K sp = [Ag + ][Cl − ] = s 2 = 1.9 × 10 −10

Let solubility = [Ag+] = s:

AgCl (s) ⇌ Ag + (aq) + Cl − (aq)