REVIEW QUESTIONS – SOLUTIONS

Multiple Choice
1. At 298K, Keq = 4.34×10–5 for the reaction: PH3(g) + HI(g)  PH4I(s). ∆G° for this reaction is
A) 17.6 kJ B) 24.9 kJ C) 0 kJ D) –16.7 kJ E) –30.2 kJ
STRATEGY:
An equilibrium constant can be related to the standard free energy via: ∆G° = –RT ln K
To find ∆G° simply fill in the variables and solve, i.e., ∆G° = – (8.314 J/mol K × 298K) ln 4.34×10–5
∆G° = 24.9 kJ Note: Because K < 1, ∆G° is a positive value.

2. At 298K, the reaction: H2(g) + ½ O2(g) → H2O(l) is

A) disfavoured by the enthalpy change as written.
B) favoured by the entropy change as written.
C) favoured by both the enthalpy and entropy changes as written.
D) spontaneous in the reverse direction.
E) spontaneous as written.

STRATEGY:
When given this type of question, where no values are given in the question for ∆G, ∆H or ∆S, one has to either
estimate the signs of ∆H and ∆S, based on qualitative analysis or determine the actual value based on data. Note,
since this equation contains two elements, the individual ∆G° and ∆H° values may be provided or you may need
to remember that their values are zero.
In this case, if you refer to the data provided, ∆G° and ∆H° can be determined (i.e., -237.2 and -285.8 kJ/mol,
respectively). ∆S° is negative (i.e., gases turning into a liquid is a direction of less entropy). So in this case, the
reaction is favoured by the enthalpy (negative sign) but not favoured by the entropy (negative sign). For T =
298K, the reaction does favour the products under standard conditions, since ∆G° is negative.
A. FALSE – it’s an exothermic reaction; ∆H° is negative and favourable
B. FALSE – ∆S° is negative, which is unfavourable.
C. FALSE – refer to B.
D. FALSE – ∆G° is negative
E. TRUE – refer to D.

3. The boiling point of CH3COOH(l) can be calculated to be:

A) 426°C B) 153°C C) 0.426°C D) 799°C E) –153°C
STRATEGY:
For any boiling point, the liquid is in equilibrium with its vapour, i.e., CH3COOH(l)  CH3COOH(g)
When a reaction is at equilibrium, ∆G = 0 because Q = K (i.e., ∆G = RT ln Q/K = RT ln (1) = 0).
At the normal boiling point, the vapour pressure is 1 atm, making K = 1 and ∆G° = 0. We can then use
∆G° = ∆H° – T∆S° = 0. We just need to find the values for ∆H°Rxn and ∆S°Rxn, and solve for T.
Based on the data provided, i.e., evaluate "products minus reactants": ∆H°Rxn = 52.25 kJ; ∆S°Rxn = 122.6 J/K
Tnbpt = ∆H°Rxn /∆S°Rxn ≈ 52.25 × 103 J/ 122.6 J/K = 426.2 K = 153.2°C
Watch your units!!! Note: Review the given choices to see what common errors are made.

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4. The oxidation state of P in Na2HPO4 is
A) +1 B) –1 C) +5 D) +3 E) –3

STRATEGY:
Assign oxidation numbers to the most common elements, i.e., H, O, and then use periodic trends. Since this is a
salt, Na is +1 and HPO4 will add up to -2. H is +1 and O is -2, so just solve for P:
For the whole salt, Na2HPO4: 2(+1) + 1 + x + 4(-2) = 0
OR Isolating only the polyatomic ion, HPO42-: 1 + x + 4(-2) = -2
Solving for x, x = +5

5. Given Zn(s) + Sn2+(aq) → Sn(s) + Zn2+(aq)

The standard free energy change in kJ/mol for this reaction at 298K is:
A) 1.2×102 B) –21.2 C) –60 D) –1.2×102 E) 60

STRATEGY:
The standard free energy can be related to the standard cell potential via the relationship: ∆G° = –nFE°
To solve for ∆G°, one first needs to determine E°, as well as n.
From the data given, the following SRP equations can be selected:
Zn2+ (aq) + 2e– → Zn(s); E° = – 0.76V
Sn2+(aq) + 2e– → Sn(s); E° = – 0.14V
E°(cell) = E°(SRP for cathode) – E°(SRP for anode) = – 0.14V– (–0.76V) = 0.62V; n = 2
∆G° = –nFE° = – (2 moles e– )(96485 C/mol e– )(0.62 J/C) = –119641 J = –120 kJ

6. The value of the equilibrium constant, K, for the reaction

Br2(l) + H2O(l) → H+(aq) + Br–(aq) + HOBr(aq) at 298K is:
A) 1.6×10–9 B) 2.5×104 C) 4.1×10–5 D) 6.1×108 E) 1.2×10–4

STRATEGY:
An equilibrium constant can be related to the standard cell potential via the relationship:
∆G° = –nFE° = –RT ln K ∴ E° = RT/nF ln K
Rearrange the second equation to isolate for K, i.e., K = exp{nFE°/RT}
To solve for K, one needs to determine E°, as well as n, through separating the overall equation into its two half
reactions, i.e.,
Br2(l) + 2e– → 2Br–(aq); E° = +1.06V
HOBr(aq) + H+(aq) + 2e– → Br–(aq) + H2O(l); E° = +1.32V
Based on the overall reaction, the first equation is the reduction and the second is the oxidation, i.e.,
E°(cell) = E°(SRP for cathode) – E°(SRP for anode) = +1.06V– (1.32V) = – 0.26V; n = 2
K = exp {nFE°/RT} = exp {(2 moles e– × 96485 C/mol e– × –0.26 J/C)/(8.314 J/molK × 298K)}
K = e–20.25 = 1.6 × 10–9

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7. A current is passed through a molten mixture of ZnI2 and KCl. The product at the cathode is:
A) K+ B) Cl– C) I2 D) Zn E) K
STRATEGY:
This is an electrolysis question using a molten mixture. “Molten” means the salt mixture has been heated to the
point where a liquid forms. This allows the charged particles to move and complete a circuit. Note, there is NO
water present. To determine what is formed at the cathode, one first needs to identify all the reactants present and
list all the possible reactions. The reduction reaction(s) are then isolated and the final answer is based on which
reduction has the most positive standard potential.
If ZnI2 and KCl is present, then the reactants are: Zn2+(l), I–(l), K+(l) and Cl–(l).
Possible redox reactions (placing the reactants on the reactant side of the equation):
Reduction: Zn2+(l) + 2e– → Zn(l); E° = – 0.76V
Oxidation: 2I–(l) → I2(l) + 2e–; E° = – 0.535V (equation was flipped to have reactant on correct side.)
Reduction: K+(l) + e– → K(l); E° = – 2.92V
Oxidation: 2Cl–(l) → Cl2(g) + 2e–; E° = – 1.36V (equation was flipped to have reactant on correct side.)
The reduction reaction Zn2+(l) + 2e– → Zn(l) has the most positive potential, so the product formed at the cathode
will be Zn in a molten state.

8. Use the following experimental data for NO(g) + Cl2(g) → NOCl2(g)

Trial [NO] [Cl2] Initial Rate
1 1.01×10–2 5.30×10–2 5.00×10–2
2 1.02×10–2 1.05×10–1 1.99×10–1
3 2.02×10–2 1.51×10–1 9.02×10–1
4 3.02×10–2 1.53×10–1 1.34
The order of Cl2(g) in the rate law is:
A) 1 B) none of these C) 2 D) 3 E) 0
STRATEGY:
Based on the table of results provided, choose two trials where the [NO] remains the same but the [Cl2] changes.
This will isolated the effect of only Cl2(g) on the rate of the reaction. For example, upon comparing trial #2 and
#1, the [Cl2] doubled and the rate quadrupled. This indicates second order kinetics in Cl2.

9. Tritium is radioactive and decays by a first order process with a half life of 12.5 years. If an
experiment starts with 1.00×10–6 moles of tritium then the number of moles of tritium left after
4.5 years is
A) 1.1×10–7 B) 7.8×10–7 C) 3.6×10–7 D) 4.8×10–6 E) 1.0×10–9
STRATEGY:
If you know the order and the half life, one can find the rate constant. Based on the integrated rate law, if one
knows the initial amount of material (doesn’t have to be concentration – can be moles, pressure, etc.), the rate
constant and the time, then the final amount remaining can be determined, i.e.,
Radioactive decay follows 1st order kinetics.
1st order half life equation: k = ln 2/ t½ = 0.693/12.5 years = 0.0555 years–1
1st order integrated rate law: ln A = ln A0 – kt
ln A = ln 1.00×10–6 moles – (0.0555 years–1)(4.5 years) = –14.07
A = exp {–14.07} = 7.8×10–7 moles

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10. The rate constant for a particular first order reaction at 500°C is 1.20×10–4 s–1. The rate constant
for this reaction at 600°C is 6.80×10–3 s–1. The activation energy in kJ/mol for this reaction is:
A) 27.4 B) 226 C) 318 D) 3.36 E) 33.6
STRATEGY:
The question gives two rate constants at two different temperatures. The only way to solve for the activation
energy is to use: ln(k2/k1) = (Ea/R){(T2 – T1)/(T1 × T2)} where,
k1 = 1.20×10–4 s–1 @ T1 = 500°C = 773K
k2 = 6.80×10–3 s–1 @ T2 = 600°C = 873K

∴ln(6.80×10–3/1.20×10–4) = (Ea/8.314 J/mol K){(873K – 773K)/ (773K × 873K)}

ln (56.667) = (Ea/8.314 J/mol K) × 1.482×10–4 K–1
4.037 /1.482×10–4 K–1 = Ea/8.314 J/mol K
27241 K ×8.314 J/mol K = Ea
Ea = 226 000 J/mol = 226 kJ/mol

Problem Questions:
11. Calculate the work needed to make room for products in the combustion of 2 moles of C4H10(g)
to carbon dioxide and water vapor at STP (1 L · atm = 101.325 J).
STRATEGY:
1. Write the chemical equation that represents the combustion of 2 moles of butane.
2. STP = Standard Temperature and Pressure; 1 atm and 273K
3. Since no volume change is given, instead of using w = – P∆V one should use w = –∆nRT
4. Find the change in the number moles of gas based on the balanced chemical equation.
5. Solve for the work done by the system.
Overall chemical equation: 2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g)
∆ngas = 8 + 10 – 2 – 13 = +3 moles
w = – (3)R(273) = -6.8 kJ (expansion)

12. At the normal boiling point of CH3CH2OH(l), 315.7 K, the value of the standard enthalpy of
vaporization is 38.7 kJ.mol-1. Assuming that CH3CH2OH(g) behaves as an ideal gas and that the
molar volume of CH3CH2OH(l) is negligible compared to that of CH3CH2OH(g), calculate the
values of q, w, ∆Uo, ∆So, and ∆Go for the reversible vaporization of 1 mole of CH3CH2OH(l) at
315.7 K and 1 atm.
STRATEGY:
1. Write the chemical equation that represents the boiling of CH3CH2OH(l).
2. A boiling point indicates an equilibrium between the vapour and its liquid, therefore ∆G = 0.
3. A normal boiling point indicates the vapour is at 1 atm, therefore K = 1 and ∆Go = 0.
4. ∆V = V(gas) - V(liquid) ≈ V(gas) = nRT/P
5. Since the process is happening at constant pressure, q = ∆Ho = qP
6. Since the process is reversible, ∆So = qrev/T

Overall chemical equation: CH3CH2OH(l) → CH3CH2OH(g)

q = ∆Ho = 38.7 kJ/mol w = – PV(gas) = -2.625 kJ/mol ∆Uo = q + w = 36.1 kJ/mol
∆S = 123 J/(mol K)
o
∆Go = 0 since K = 1

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13. If the Ksp of AgI is 8.5×10–17 at 298 K, calculate ∆Gr for the rxn of 5 mL of 0.20 M AgNO3(aq)
with 5 mL of 0.20 M NaI(aq) at 298 K.
STRATEGY:
1. Write the chemical equation that represents the reaction to be evaluated and compare it to Ksp.
2. To go from K to ∆G, one also needs Q and the relationship: ∆G = RT ln{Q/K}.
3. Find Q based on the concentrations given. Don't forget to correct the concentrations due to mixing.

Net Ionic Equation: Ag+(aq) + I–(aq) → AgI(s)

This is the inverse of the Ksp equation, therefore, Keq = 1/Ksp = 1.2×1016
Note: Keq is large because the product (AgI) is highly favoured (stable).
[Ag+] = [I–] = 5 mL × (0.20M/10 mL) = 0.10M
Q = 1/(0.10)2 = 100
∆G = RT ln{Q/K} = -80.32 kJ/mol Note: Since Q < K, the rxn is spontaneously moving from left to right.

14. Balance the reaction: IO3–(aq) + I–(aq) → I3–(aq) which occurs in acidic solution.
STRATEGY:
Identify the oxidation numbers for each element involved in the reaction. Based on the changes in oxidation
numbers, isolate the two half reactions. Balance each half reaction based on the presence of acid and then unite
the two half reaction to form the overall reaction, i.e.,
IO3–: O is -2 and I is (x – 6 = -1), x = +5; I in I– is -1; I3– has (3x = –1), x = –⅓
Steps Reduction Oxidation
ID two half reactions: IO3–(aq) → I3–(aq) I–(aq) → I3–(aq)
A (Balance the strange atoms): 3IO3–(aq) → I3–(aq) 3I–(aq) → I3–(aq)
E (Balance oxidation #’s with e–’s ): 3 × +5 = +15 3 × –⅓ = –1 3×-1 = – 3 3 × –⅓ = –1
3IO3–(aq) + 16e– → I3–(aq) 3I–(aq) → I3–(aq) + 2e–
I (Balance charge with H+): (3 × –1) + (16× –1) = –19 3 × –⅓ = –1 3I–(aq) → I3–(aq) + 2e–
3IO3–
(aq)
–
+ 16e + 18H +
(aq) → I3–
(aq)
Balanced!

O (Balance O’s with H2O): 3 × 3= 9 0

3IO3–(aq) + 16e– + 18H+(aq) → I3–(aq) + 9H2O(l)
U (Unite the two half reactions): 3IO3–(aq) + 16e– + 18H+(aq) → I3–(aq) + 9H2O(l) (3I–(aq) → I3–(aq) + 2e–) ×8
24I–(aq) → 8I3–(aq) + 16e–
Add the two ½-rxns together: 3IO3–(aq) + 18H+(aq) + 24I–(aq) → 9I3–(aq) + 9H2O(l)
Simplify to get final Answer: IO3–(aq) + 6H+(aq) + 8I–(aq) → 3I3–(aq) + 3H2O(l)

15. Balance the following equation in basic solution:

OCl–(aq) + SCN–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq) + Cl–(aq)
STRATEGY:
1. Identify what is oxidised and reduced and separate into two half reactions.
2. Balance each reaction individually.
3. Unite the two half reactions by matching the amount of electrons.
Note: For SCN–, start with S having same oxidation number as O (since from same group in the periodic table).
Since S is -2, then the sum of the oxidation numbers from both C and N must add up to +1.
What common oxidation numbers for C and N add up to +1? Answer: +4 and -3.
Therefore, both S (ox. #’s: -2 to +6) and N (-3 to +5) are oxidised in the same equation:
SCN–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq) + 8e– (from S) + 8e– (from N)

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 Steps
ID two half reactions:
A (Balance strange atoms):
E (Balance ox. #’s w/ e–’s ):
I (Balance charge with H+):
O (Balance O’s with H2O):
U (Unite the two ½
reactions):
Final answer: 8OCl–(aq) + SCN–(aq) + 4OH–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq) + 8Cl–(aq) + 2H2O(l)
Reduction Oxidation
OCl–(aq) → Cl–(aq) SCN–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq)
OCl–(aq) → Cl–(aq) SCN–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq)
+1 –1 -2 +4 -3 +6 +4 +5
OCl–(aq) + 2e– → Cl–(aq) SCN–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq) +16e–
–1 + (2× –1) = –3 –1 –1 -2 + -2 + -1 + (16× –1) = –21
OCl (aq) + 2e– → Cl–(aq) + 2OH–(aq)
– SCN–(aq) + 20OH–(aq)→ SO42–(aq) + CO32–(aq) + NO3–(aq) +16e–
O 2 O’s 20 O’s
OCl–(aq) + H2O(l) + 2e– → Cl–(aq) + 2OH(aq) SCN–(aq) + 20OH–(aq) 4 + 3 + 3 = 10 O’s
→ SO42–(aq) + CO32–(aq) + NO3–(aq) + 10H2O(l) +16e–
(OCl–(aq) + H2O(l) + 2e– → Cl–(aq) + 2OH–(aq))×8 SCN–(aq) + 20OH–(aq)
8OCl–(aq) + 8H2O(l) + 16e– → 8Cl–(aq) + 16OH–(aq) → SO42–(aq) + CO32–(aq) + NO3–(aq) + 10H2O(l) +16e–

16. The overall reaction in the lead storage battery is

Pb(s) + PbO2(s) + 2H+(aq) + 2HSO4–(aq) → 2PbSO4(s) + 2H2O(l); E° = 2.04V at 298K
a) Calculate E at 298K for this battery when [H+] = [HSO4–] = 4.5M
b) For the cell reaction in the lead storage battery, ∆H° = – 315.9 kJ and ∆S° = 263.5 J/K.
Calculate E° at –20°C.
c) Calculate E at –20°C when [H+] = [HSO4–] = 4.5M
STRATEGY:
In a) to calculate E, one needs to use the Nernst equation: E = E° – RT/nF ln Q. E° and values needed for Q are
given. The only value missing is n, which can be determined by identifying the two half reactions and the total
number of electrons transferred.
For b) to calculate E° based on ∆H° and ∆S°, one first needs to determine ∆G° at –20°C (253 K) and then convert
to E°, or just use the relationships: ∆G° = ∆H° – T∆S° = –nFE° and solve for E° directly.
For c), again the Nernst equation is used, only this time the new E° value and the new temperature are used.
(Note: one cannot use the special Nernst constant since T ≠ 298K).
a) E = E° – RT/nF ln Q, where E° = 2.04V, n = 2, Q = 1/[H+]2[HSO4–]2 = 1/ (4.5)4 = 2.44×10–3
E = 2.04V – (8.314 J/mol K × 298K)/(2 × 96485 C/mol) ln 2.44×10–3
E = 2.12 V (3 sig figs due to the subtraction at the end of the calculation)
b) ∆G° = ∆H° – T∆S° = –nFE°
–315.9×103 J – (253 K × 263.5 J/K) = –(2 moles × 96 485 C/mol)E°
–382600 J = – 192970 C × E°
E° = 1.98 V @ –20°C
c) E = 1.98V – (8.314 J/mol K × 253K)/(2 × 96485 C/mol) ln 2.44×10–3 = 2.05 V @ –20°C

17. Consider a voltaic cell based on the following half reaction

VO2+(aq) + 2H+(aq) + e– → VO2+(aq) + H2O(l) ; E° = 1.00V
Zn2+(aq) + 2e– → Zn(s); E° = –0.76V
a) Write the overall cell reaction which is spontaneous under standard conditions and determine
E° for this cell at T = 298K.
b) Determine the cell potential, E, at T = 298K if [VO2+] = 2.0M, [H+] = 0.50M,
[VO2+] = 1.10×10–2 M and [Zn2+] = 1.0×10–1 M

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STRATEGY:
Based on the two half reactions given, determine which is the oxidation (more negative standard potential) and
flip the equation (and its potential) to determine the overall cell reaction and the standard cell potential. To find
the cell potential in b), use the Nernst equation.
a) VO2+(aq) + 2H+(aq) + e– → VO2+(aq) + H2O(l); E° = 1.00V(need to multiple equation by 2 to match e– ’s)
Zn2+(aq) + 2e– → Zn(s); E° = –0.76V (need to flip equation & voltage to form oxidation rxn)

2VO2+(aq) + 4H+(aq) + 2e– → 2VO2+(aq) + 2H2O(l); E° = +1.00V (voltage does not double!)
Zn(s) → Zn2+(aq) + 2e–; E° = +0.76V
2VO2+(aq) + 4H+(aq) + Zn(s) → 2VO2+(aq) + 2H2O(l) + Zn2+(aq); E° = +1.76V

b) E = E° – RT/nF ln Q, where E° = 1.76V, n = 2, Q = [VO2+]2[Zn2+]/[VO2+]2[H+]4

Q = [1.10×10–2]2[1.0×10–1]/[2.0]2[0.50]4 = 4.84×10–5
E = 1.76V – (8.314 J/mol K × 298K)/(2 × 96485 C/mol) ln 4.84×10–5
E = 1.89 V

18. The standard voltage of the cell: Pt(s)Hg(l) Hg2Cl2(s) Cl–(aq) || Hg22+(aq)Hg(l)Pt(s)
is +0.529 V at 25oC. Calculate the Ksp of Hg2Cl2.

STRATEGY:
1. To find the Ksp for Hg2Cl2, we need the chemical equation: Hg2Cl2(s) → Hg22+(aq) + 2Cl–(aq)
2. To solve for K, one needs to use the relationship: K = exp{nFEo/RT}
3. Find Eo. In this case it is given in the question (i.e., +0.529V).
4. Determine the total number of electrons for the overall reaction.
5. Check that the overall reaction for the cell matches the direction of the equation we want.
6. Plug everything in and solve for K.
7. Overall Reaction: Hg22+(aq) + 2Cl–(aq) → Hg2Cl2(s) – reaction is going in the wrong direction for Ksp!
Therefore we either need to change the sign of Eo (to reverse the reaction) or take the inverse of the K that is
determined at the end of the calculation. Note: Ksp is always a very small number!
n = 2 moles of electrons
Eo(for cell) = +0.529V; Eo(for reaction we want) = -0.529 V
K = exp{ (2 × 96485 × 0.529)/(8.314 × 298)} OR Ksp = exp{ (2 × 96485 × -0.529)/(8.314 × 298)}
K = e41.2 = 7.8 × 1017 = 1/Ksp OR Ksp = e–41.2 = 1 × 10–18

19. Consider a voltaic cell at 298K with the net cell equation:
H2(g) + 2AgCl(s) → 2H+(aq) + 2Cl–(aq) + 2Ag(s)
a) Write the appropriate half reactions and calculate the cell potential under standard conditions.
b) With [Cl–] = 1.0M, P(H2) = 1.00 atm and the measured cell voltage +0.340V, calculate pH.

STRATEGY:
Dissect the overall equation into the two half reaction and solve for E°. Based on the overall equation, formulate
the proper form of the Nernst equation and then solve for [H+] and pH. In this case, one could use the log form of
the Nernst equation to save a few extra steps on the calculation.

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 a) Two half reactions:
H2(g) → 2H+(aq) + 2e– E° = 0.00 V (set to zero by def’n) Oxidation
AgCl(s) + e– → Cl–(aq) + Ag(s) E° = +0.222 V Reduction
H2(g) + 2AgCl(s) → 2H+(aq) + 2Cl–(aq) + 2Ag(s); E° = 0.222 V

b) E = E° – 2.303RT/nF log Q, where E = +0.340V, E° = 0.222V, n = 2, Q = [H+]2[Cl–]2/P(H2) = [H+]2

0.340 = 0.222V – (2.303 × 8.314 J/mol K × 298K)/(2 × 96485 C/mol) log [H+]2
0.340 – 0.222 = – 0.0591/2 log [H+]2
0.118 = – 0.591/2 log [H+]2
Note: An exponent within a log term, can be brought outside of the log as a number, which gives:
0.118 = – (2 × 0.0591/2) log [H+] = – 0.5914 log [H+]
Note: pH = – log [H+], so we can substitute pH into our expression as: 0.118 = 0.0591 × pH OR pH = 2.00

20. When 1 M NiBr2(aq) is electrolyzed at pH = 7, what is the product formed at the anode (or
cathode)? Assume that no overpotential is present and standard conditions are used. If one were
to assume an overpotential of 0.50 V in the production of any gases, does your answer change?
STRATEGY:
1. List all the appropriate equations based on the reactants present in the solution.
2. Take into account the effect of the pH on the end potentials for the water equations.
3. Compare all the oxidation equations and choose the most positive standard oxidation potential
(i.e., since the equation is flipped, you take the negative of the SRP value).
4. If asked for the cathode reaction, compare all the reduction equations and choose the most positive reduction
potential to be the reaction at the cathode.
5. Apply the 0.50 V in the production of any gases and re-evaluate your answer.

Step 1: Based on Ni2+, Br- and H2O:

Ni2+(aq) + 2e- → Ni(s); Eo = -0.24V
2Br–(aq) → Br2(l) + 2e–; Eo = -1.07 V (this is NOT the SRP)
H2O(l) + 2e– → H2(g) + 2OH–(aq); Eo = -0.83V
H2O(l) → O2(g) + 4H+(aq) + 4e-; Eo = -1.23V (this is NOT the SRP)

Step 2: Based on pH = 7, we are no longer at standard conditions for [H+] or [OH–] (i.e., 1M). Therefore, we need
to find E for the two water equations by using the Nernst equation (or refer to tables that refer to pH = 7
conditions). If you do this, you will arrive at the following values:
H2O(l) + 2e– → H2(g) + 2OH–(aq); E = -0.42V at pH = 7
H2O(l) → O2(g) + 4H+(aq) + 4e–; E = -0.82V at pH = 7 (this is NOT the SRP)
Aside: To correct the 1st eq’n, E° = -0.83V, n = 2, [OH–] = 10–7 M & Q = P(H2) × [OH–]2 = 1 atm × (10–7 M)2 = 10–14
RT 8.314 × 298
E = E° – ln Q = −0.83V − ln 10 –14 =
−0.83 + 0.41 =
−0.42V
nF 2 × 96485
8.314 × 298
For the 2nd equation: E =
−1.23V − ln (1 × 10 –7 ) 4 =
−1.23 + 0.41 =
−0.82V
4 × 96485

Step 3: Compare the equations and determine which is the anode reaction (with no overpotential):
Oxidations:
2Br–(aq) → Br2(l) + 2e–; Eo = -1.09V (this is NOT the SRP; it’s the SOP)
H2O(l) → O2(g) + 4H+(aq) + 4e–; E = -0.82V at pH = 7 (this is the std. oxidation potential at pH = 7)
Due to the effect of pH, O2 will be produced as the anode (now much most positive) not Br2.

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 Step 4: Compare the equations and determine which reaction occurs at the cathode (no overpotential):
Reductions:
Ni2+(aq) + 2e- → Ni(s); Eo = -0.24V
H2O(l) + 2e → H2(g) + 2OH (aq);
– –
E = -0.42V at pH = 7
At the cathode, Ni(s) will be produced.

Step 5: Compare equations and determine which is the anode/cathode reaction with 0.50V overpotential:
Oxidations:
2Br–(aq) → Br2(l) + 2e–; Eo = -1.09V (SOP)
H2O(l) → O2(g) + 4H (aq) + 4e ;
+ –
E = -0.82V – 0.50V = -1.32 V at pH = 7 (oxidation potential)
Due to overpotential associated with the production of O2, Br2 will be produced at the anode (more easily oxidized).
Reductions:
Ni2+(aq) + 2e- → Ni(s); Eo = -0.24V
H2O(l) + 2e– → H2(g) + 2OH–(aq); E = -0.42V – 0.50V = -0.92V at pH = 7
At the cathode, Ni(s) is still produced (more easily reduced).

21. Sodium metal is produced commercially by the electrolysis of molten sodium chloride. Calculate
the mass of sodium and the volume of chlorine gas measured at 1 atm and 25°C produced by a
current of 20.0 amperes in 1.00 hour.

STRATEGY:
1. Determine the number of coulombs supplied based on the current (C/s) and time (s): Q = It.
2. Convert coulombs to moles of electrons using Faradays constant (i.e., F = 96485 C/moles of electrons).
3. a) Convert to moles of sodium produced based on the stoichiometry of the sodium chemical equation.
Convert moles to mass using molar mass.
b) Convert the moles of electrons to the number of moles of chlorine gas produced based on the
stoichiometry. Convert moles to volume using the ideal gas law.

Q = 72 000 C
# moles of electrons supplied = 0.746 moles
Equations: Na+(l) + e- → Na(l)
2Cl–(l) + 2e- → Cl2(g)
# moles of Na(l) = 0.746 moles (1:1 ratio); Mass of Na(l) = 17.2 g
# moles of Cl2(g) = 0.373 moles (2:1 ratio); Volume Cl2(g) = 9.13 L

22. How many moles of O2(g) are produced by electrolysis of Na2SO4(aq) if 0.240 A is passed
through the solution for 65.0 minutes?

STRATEGY:
1. Determine the number of coulombs supplied based on the current (C/s) and time (s): Q = It.
2. Convert coulombs to moles of electrons using Faradays constant (i.e., F = 96485 C/moles of electrons).
3. Convert to moles of oxygen based on the stoichiometry of the chemical equation.
Q = 0.240 C/s × 65 min × 60 sec/min = 936 C
# moles of electrons supplied = 9.70×10-3 moles
Equation: 2H2O(l) → O2(g) + 4H+(aq) + 4e– (1:4 ratio) (Note: This rxn is found based on analyzing the
# moles of O2(g) = 2.43×10-3 moles possible rxns for the electrolysis of Na2SO4(aq))

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23. A proposed mechanism for the gas phase reaction of bromine with bromoform is:
Br2(g)  2Br(g) K1, fast equilibrium
Br(g) + CHBr3(g) → HBr(g) + CBr3(g) k2, slow
CBr3(g) + Br(g) → CBr4(g) k3, fast
Write the overall reaction and find an expression for the rate law.
STRATEGY:
Find the overall reaction by adding all the elementary reaction together and cancelling out any intermediate(s) or
catalyst(s). The rate is based on the slowest step in the mechanism (i.e., rate determining step). Write a rate law
based on the molecularity of the reactants in the slowest elementary reaction. Check to see that no intermediates
are in the rate law. If so, then form a substitution for the intermediate based on the equilibrium reaction.

Overall Rxn: Br2(g) + CHBr3(g) → HBr(g) + CBr4(g)

Note: Br(g) and CBr3(g) are both intermediates in this mechanism. There is no catalyst present.
Rate law for slowest step: Rate = k2[Br][CHBr3] – need to find a substitution for Br
Based on the fast equilibrium: K1 = [Br]2/[Br2]; [Br] = K1½ [Br2]½ (OR alternatively: [Br] = (k1/k-1)½ [Br2]½ )
Rate = K1½ k2 [Br2]½[CHBr3] = (k1/k-1)½ k2 [Br2]½[CHBr3] = kobs[Br2]½[CHBr3] (units of k = M– ½  time– 1 )

24. Plot the energy profiles (and identify Ea, forward) for the following reaction mechanisms:
(i) a slow step followed by a fast step (overall endothermic reaction )
(ii) a fast step followed by a slow step (exothermic reaction)

STRATEGY:
1. Slow steps are slow because they have greater activation energy than a fast step.
2. If a reaction is endothermic, the reactants have lower energy than the products.
3. Energy profiles outline the process of the reaction through plotting the change in energy as reactants move
towards products. For every step in a mechanism, there will be "peak" to profile the reactant(s), transition
state and product(s).

Below is an example for a reaction that is
endothermic and has a mechanism with a slow
step, followed by a fast step. The Ea, forward for the
overall reaction is equivalent to Ea for the first,
slow step.
Ea, fwd
Below is an example for a reaction that is exothermic
and has a mechanism with a fast step, followed by a
slow step. The Ea, fwd for the overall reaction is
measured from the reactants (at the very beginning of
the plot) to the top of the second peak.
Ea, fwd

Note: There is a Final Exam Review Quiz on CourseLink for further practice.

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