CHAPTER 12

ELECTROCHEMISTRY

12.1 (a) Cr reduced from 6+ to 3+; C oxidized from 2- to 1-;

(b) C 2 H 5 OH(aq) → C 2 H 4 O(aq) + 2 H + (aq) + 2 e − ;

(c) Cr2 O 7 2− (aq) + 14 H + (aq) + 6 e − → 2 Cr 3+ (aq) + 7 H 2 O(l) ;

(d) 8 H + (aq) + Cr2 O7 2− (aq) + 3 C2 H5 OH(aq) →

2 Cr 3+ (aq) + 3 C2 H 4 O(aq) + 7 H 2 O(l)

12.3 In each case, first obtain the balanced half-reactions. Multiply the
oxidation and reduction half-reactions by appropriate factors that will
result in the same number of electrons being present in both half-reactions.
Then add the half-reactions, canceling electrons in the process, to obtain
the balanced equation for the whole reaction. Check to see that the final
equation is balanced.
(a) 4[Cl 2 (g) + 2 e − → 2 Cl− (aq)]

1[S2 O3 2− (aq) + 5 H 2 O(l) → 2 SO 4 2− (aq) + 10 H + (aq) + 8 e − ]

4 Cl2 (g) + S2 O3 2− (aq) + 5 H 2 O(l) + 8 e − →
8 Cl− (aq) + 2 SO 4 2− (aq) + 10 H + (aq) + 8 e −
4 Cl2 (g) + S2 O3 2− (aq) + 5 H 2 O(l) → 8 Cl− (aq) + 2 SO 4 2− (aq) + 10 H + (aq)
Cl2 is the oxidizing agent and S2 O 32− is the reducing agent.

(b) 2[MnO 4 − (aq) + 8 H + (aq) + 5 e − → Mn 2+ (aq) + 4 H 2 O(l)]

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 5[H 2 SO3 (aq) + H 2 O(l) → HSO 4 − (aq) + 3 H + (aq) + 2 e − ]
2 MnO 4 − (aq) + 16 H + (aq) + 5 H 2 SO3 (aq) + 5 H 2 O(l) + 10 e − →
2 Mn 2 + (aq) + 8 H 2 O(l) + 5 HSO 4 − (aq) + 15 H + (aq) + 10 e−
2 MnO 4 − (aq) + H + (aq) + 5 H 2SO3 (aq) →
2 Mn 2+ (aq) + 3 H 2 O(l) + 5 HSO4 − (aq)

MnO 4 − is the oxidizing agent and H 2 SO3 is the reducing agent.

(c) Cl 2 (g) + 2 e − → 2 Cl− (aq)

H 2 S(aq) → S(s) + 2 H + (aq) + 2 e −

Cl2 (g) + H 2 S(aq) + 2 e − → 2 Cl− (aq) + S(s) + 2 H + (aq) + 2 e −
Cl2 (g) + H 2 S(aq) → 2 Cl− (aq) + S(s) + 2 H + (aq)

Cl2 is the oxidizing agent and H 2 S is the reducing agent.

(d) Cl 2 (g) + 2 e − → 2 Cl− (aq)

2 H 2 O(l) + Cl2 (g) → 2 HOCl(aq) + 2 H + (aq) + 2 e −

2 H 2 O(l) + Cl2 (g) + 2 e− → 2 HOCl(aq) + 2 H + (aq) + 2 Cl− (aq) + 2 e−

or H 2 O(l) + Cl2 (g) → HOCl(aq) + H + (aq) + Cl− (aq)

Cl2 is both the oxidizing and the reducing agent.

12.5 (a) O3 (g) → O 2 (g)

O3 (g) → O 2 (g) + H 2 O(l) (balances O’s)

2 H 2 O(l) + O3 (g) → O 2 (g) + H 2 O(l) + 2 OH − (aq) (balances H’s)

H 2 O(l) + O3 (g) → O 2 (g) + 2 OH − (aq) (cancels H 2 O )

H 2 O(l) + O3 (g) + 2 e − → O 2 (g) + 2 OH − (aq) (balances charge);

Br − (aq) → BrO3− (aq)

3 H 2 O(l) + Br − (aq) → BrO3− (aq) (balances O’s)

6 OH − (aq) + 3 H 2 O(l) + Br − (aq) → BrO3 − (aq) + 6 H 2 O(l) (balances H’s)

6 OH − (aq) + 3 H 2 O(l) + Br − (aq) → BrO3 − (aq) + 6 H 2 O(l) + 6 e −

(balances charge)

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Combining half-reactions yields
3[H 2 O(l) + O3 (g) + 2 e − → O 2 (g) + 2 OH − (aq)]

6 OH − (aq) + 3 H 2 O(l) + Br − (aq) → BrO3 − (aq) + 6 H 2 O(l) + 6 e−

6 H 2 O(l) + 3 O3 (g) + 6 OH − (aq) + Br − (aq) + 6 e− →
3 O 2 (g) + 6 OH − (aq) + BrO3 − (aq) + 6 H 2 O(l) + 6 e−
and 3 O3 (g) + Br − (aq) → 3 O 2 (g) + BrO3 − (aq)

O3 is the oxidizing agent and Br − is the reducing agent.

(b) Br2 (l) + 2 e − → 2 Br − (aq) (balanced reduction half-reaction)

Br2 (l) + 6 H 2 O(l) → 2 BrO3− (aq) (O’s balanced); then

Br2 (l) + 6 H 2 O(l) + 12 OH − (aq) → 2 BrO 3 − (aq) + 12 H 2 O(l) (H’s balanced);

and Br2 (l) + 12 OH − (aq) → 2 BrO3− (aq) + 6 H 2 O(l) + 10 e − (electrons
balanced)
Combining half-reactions yields
5[Br2 (l) + 2 e− → 2 Br − (aq)]
1[Br2 (l) + 12 OH − (aq) → 2 BrO3 − (aq) + 6 H 2 O(l) + 10 e− ]
6 Br2 (l) + 12 OH − (aq) + 10 e − →
10 Br − (aq) + 2 BrO3 − (aq) + 6 H 2 O(l) + 10 e −
6 Br2 (l) + 12 OH − (aq) → 10 Br − (aq) + 2 BrO3 − (aq) + 6 H 2 O(l)
Dividing by 2 gives
3 Br2 (l) + 6 OH − (aq) → 5 Br − (aq) + BrO3− (aq) + 3 H 2 O(l)

Br2 is both the oxidizing agent and the reducing agent.

(c) Cr 3+ (aq) + 4 H 2 O(l) → CrO 4 2 − (aq) (O’s balanced); then

Cr 3+ (aq) + 4 H 2 O(l) + 8 OH − (aq) → CrO 4 2− (aq) + 8 H 2 O(l) (H’s

balanced); and
Cr 3+ (aq) + 8 OH − (aq) → CrO 4 2− (aq) + 4 H 2 O(l) + 3 e − (charge
balanced)
MnO 2 (s) → Mn 2+ (aq) + 2H 2 O(l); then

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 MnO 2 (s) + 4 H 2 O(l) → Mn 2 + (aq) + 2 H 2 O(l) + 4 OH − (aq) (H’s
balanced); and
MnO 2 (s) + 2 H 2 O(l) + 2 e − → Mn 2+ (aq) + 4 OH − (aq) (charge
balanced)
Combining half-reactions yields
2[Cr 3+ (aq) + 8 OH − (aq) → CrO 4 2− (aq) + 4 H 2 O(l) + 3 e− ]
3[MnO 2 (s) + 2 H 2 O(l) + 2 e − → Mn 2+ (aq) + 4 OH − (aq)]
2 Cr 3+ (aq) + 16 OH − (aq) + 3 MnO 2 (s) + 6 H 2 O(l) + 6 e − →
2 CrO 4 2− (aq) + 8 H 2 O(l) + 3 Mn 2+ (aq) + 12 OH − (aq) + 6 e−
2 Cr 3+ (aq) + 4 OH − (aq) + 3 MnO 2 (s) →
2 CrO 4 2− (aq) + 2 H 2 O(l) + 3 Mn 2+ (aq)
Cr 3+ is the reducing agent and MnO 2 is the oxidizing agent.

(d) 3[P4 (s) + 8 OH − (aq) → 4 H 2 PO 2 − (aq) + 4 e − ]

P4 (s) + 12 H 2 O(l) + 12 e − → 4 PH 3 (g) + 12 OH − (aq)

4 P4 (s) + 12 H 2 O(l) + 24 OH − (aq) + 12 e − →
12 H 2 PO 2 − (aq) + 4 PH 3 (g) + 12 OH − (aq) + 12 e −
4 P4 (s) + 12 H 2 O(l) + 12 OH − (aq) → 12 H 2 PO2 − (aq) + 4 PH 3 (g)
or P4 (s) + 3 H 2 O(l) + 3 OH − (aq) → 3 H 2 PO 2 − (aq) + PH 3 (g)

P4 (s) is both the oxidizing and the reducing agent.

12.7 P4 S3 (aq) → H 3 PO 4 (aq) + SO 4 2− (aq)

For the oxidation of P4 S3 , both the P and S atoms are oxidized. The
assignment of oxidation states to the P and S atoms is complicated by the
presence of P—P bonds in the molecule, which leads to non-integral
values. As long as we are consistent in our assignments, the end result
should be the same. We will assume that S in P4 S3 is 2 − and, therefore,

loses 8 electrons on going to S6 + in the sulfate ion. Because P4 S3 is a

neutral molecule and, if S has an oxidation number of − 2, then each

phosphorus atom will have an oxidation number of +1.5. Phosphorus in

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 phosphoric acid has an oxidation number of +5. so each P atom of P4 S3
must lose 3.5 electrons. The total number of electrons lost is
(4 × 3.5) + (3 × 8) = 38.

P4 S3 (aq) → 4 H 3 PO 4 (aq) + 3 SO 4 2− (aq) + 38 e −

We balance the charge by adding H + in an acidic solution:

P4 S3 (aq) → 4 H 3 PO 4 (aq) + 3 SO 4 2 − (aq) + 44 H + (aq) + 38 e −

The final balance is achieved by adding water to provide the oxygen and
hydrogen atoms:
P4 S3 (aq) + 28 H 2 O(l) → 4 H 3 PO 4 (aq) + 3 SO 4 2− (aq) + 44 H + (aq) + 38 e −

The other half-reaction is simpler.

NO3 − (aq) → NO(g)

N has an oxidation number of +5 in the nitrate ion and + 2 in nitric oxide.

Each nitrogen atom gains three electrons in the course of the reaction.
NO3 − (aq) + 3 e − → NO(g)

Charge balance is again achieved by adding H + :

NO3 − (aq) + 4 H + (aq) + 3 e − → NO(g)

The number of hydrogen and oxygen atoms is completed by the addition

of water:
NO3 − (aq) + 4 H + (aq) + 3 e − → NO(aq) + 2 H 2 O(l)

Combining the two half-reactions gives

38 [NO3 − (aq) + 4 H + (aq) + 3 e − → NO(g) + 2 H 2 O(l)]
+3 [P4 S3 (aq) + 28 H 2 O(l) →
4 H 3 PO 4 (aq) + 3 SO 4 2− (aq) + 44 H + (aq) + 38 e− ]
3 P4 S3 (aq) + 38 NO3 − (aq) + 20 H + (aq) + 8 H 2 O(l) →
12 H3 PO 4 (aq) + 9 SO 4 2 − (aq) + 38 NO(g)

12.9 (a) Ag + (aq) + e − → Ag(s) E°(cathode) = + 0.80 V

Ni 2+ (aq) + 2 e− → Ni(s) E°(anode) = −0.23 V

Reversing the anode half-reaction yields

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Ni(s) → Ni 2+ (aq) + 2 e −
and the cell reaction is, upon addition of the half-reactions,
2 Ag + (aq) + Ni(s) → Ag(s) + Ni 2+ (aq) E °cell = + 0.80 V − (−0.23) V
= +1.03 V

(b) 2 H + (aq) + 2 e − → H 2 (g) E°(anode) = 0.00 V

Cl 2 (g) + 2 e − → 2 Cl− (aq) E°(cathode) = +1.36 V

Therefore, at the anode, after reversal,

H 2 (g) → 2 H + (aq) + 2 e −

and, the cell reaction is, upon addition of the half-reactions,

Cl2 (g) + H 2 (g) → 2 H + (aq) + 2 Cl− (aq) E °cell = +1.36 V − 0.00 V
= +1.36 V

(c) Cu 2+ (aq) + 2 e− → Cu(s) E°(anode) = + 0.34 V

Ce 4+ (aq) + e − → Ce3+ (aq) E°(cathode) = +1.61 V

Therefore, at the anode, after reversal,
Cu(s) → Cu 2+ (aq) + 2 e−
and, the cell reaction is, upon addition of the half-reactions,
2 Ce4+ (aq) + Cu(s) → Cu 2+ (aq) + 2 Ce3+ (aq) E °cell = 1.61 V − (0.34 V)
= +1.27 V

(d) O 2 (g) + 2 H 2 O(l) + 4 e − → 4 OH − (aq) E°(cathode) = 0.40 V

O 2 (g) + 4 H + (aq) + 4 e − → 2 H 2 O(l) E°(anode) = 1.23 V

Reversing the anode half-reaction yields

2 H 2 O(l) → O 2 (g) + 4 H + (aq) + 4 e −

and the cell reaction is, upon addition of the half-reactions,

4 H 2 O(l) → 4 H + (aq) + 4 OH − (aq) E °cell = 0.40 V − 1.23 V = −0.83 V

or, H 2 O(l) → H + (aq) + OH − (aq)

Note: This balanced equation corresponds to the cell notation given. The
spontaneous process is the reverse of this reaction.
(e) Sn 4+ (aq) + 2 e− → Sn 2+ (aq) E°(anode) = + 0.15 V

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 Hg 2 Cl 2 (s) + 2 e − → 2 Hg(l) + 2 Cl− (aq) E°(cathode) = + 0.27 V

Therefore, at the anode, after reversal,

Sn 2+ (aq) → Sn 4+ (aq) + 2 e−
and the cell reaction is, upon addition of the half-reactions,
Sn 2+ (aq) + Hg 2 Cl 2 (s) → 2 Hg(l) + 2 Cl− (aq) + Sn 4+ (aq)

E °cell = 0.27 V − 0.15 V = 0.12 V

12.11 (a) Ni 2+ (aq) + 2 e− → Ni(s) E°(cathode) = −0.23 V

Zn 2+ (aq) + 2 e− → Zn(s) E°(anode) = −0.76 V

Reversing the anode reaction yields
Zn(s) → Zn 2+ (aq) + 2 e − (at anode); then, upon addition,

Ni 2+ (aq) + Zn(s) → Ni(s) + Zn 2+ (aq) (overall cell)

E °cell = −0.23 V − (−0.76 V) = + 0.53 V

and Zn(s) | Zn 2+ (aq) || Ni 2+ (aq) | Ni(s)

(b) 2[Ce4+ (aq) + e − → Ce3+ (aq)] E°(cathode) = +1.61 V

I 2 (s) + 2 e − → 2 I − (aq) E°(anode) = + 0.54 V

Reversing the anode reaction yields

2 I − (aq) → 2 e − + I 2 (s) (at anode); then, upon addition,

2 I − (aq) + 2 Ce 4 + (aq) → 2 Ce3+ (aq) + I2 (s) (overall cell)

E °cell = +1.61 V − 0.54 V = +1.07 V

and Pt(s) | I − (aq) | I 2 (s) || Ce 4+ (aq), Ce3+ (aq) | Pt(s)

An inert electrode such as Pt is necessary when both oxidized and reduced
species are in the same solution.
(c) Cl 2 (g) + 2 e − → 2 Cl − (aq) E °(cathode) = +1.36 V

2 H + (aq) + 2 e − → H 2 (g) E °(anode) = 0.00 V

Reversing the anode reaction yields

H 2 (g) → 2 H + (aq) + 2 e − (at anode); then, upon addition,

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 H 2 (g) + Cl2 (g) → 2 HCl(aq) (overall cell) E °cell = +1.36 V − 0.00 V
= +1.36 V

and Pt(s) | H 2 (g) | H + (aq) || Cl − (aq) | Cl 2 (g) | Pt(s)

An inert electrode such as Pt is necessary for gas/ion electrode reactions.
(d) 3[Au + (aq) + e − → Au(s)] E °(cathode) = +1.69 V

Au 3+ (aq) + 3 e− → Au(s) E °(anode) = +1.40 V

Reversing the anode reaction yields
Au(s) → Au 3+ (aq) + 3 e− then, upon addition (anode),

3 Au + (aq) →
(overall cell) E °cell = +1.69 V − 1.40 V
2 Au(s) + Au 3+ (aq)
= + 0.29 V

and Au(s) | Au 3+ (aq) || Au + (aq) | Au(s)

12.13 (a) Ag + (aq) + e − → Ag(s) E °(cathode) = + 0.80 V

AgBr(s) + e − → Ag(s) + Br − (aq) E °(anode) = + 0.07 V

Reversing the anode reaction yields
Ag(s) + Br − (aq) → AgBr(s) + e − then, upon addition,

Ag + (aq) + Br − (aq) → AgBr(s) (overall cell) E °cell = + 0.80 V − 0.07 V

= + 0.73 V
This is the direction of the spontaneous standard cell reaction that could be
used to study the reverse of the given solubility equilibrium. A cell
diagram for this favorable process is
Ag(s) |AgBr(s) | Br − (aq) || Ag + (aq) | Ag(s)
(b) To conform to the notation of this chapter, the neutralization is
rewritten as
H + (aq) + OH − → H 2 O(l)

O 2 (g) + 4 H + (aq) + 4 e − → 2 H 2 O(l) E °(cathode) = +1.23 V

O 2 (g) + 2 H 2 O(l) + 4 e − → 4 OH − (aq) E °(anode) = + 0.40 V

Reversing the anode reaction yields

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 4 OH − (aq) → O 2 (g) + 2 H 2 O(l) + 4 e − ; then, upon addition,

4 H + (aq) + 4 OH − (aq) → 4 H 2 O(l)

or H + (aq) + OH − (aq) → H 2 O(l) (overall cell) E ° = +1.23 V − 0.40 V

= + 0.83 V

and Pt(s) |O 2 (g) |OH − (aq) || H + (aq) |O 2 (g) |Pt(s)

(c) Cd(OH) 2 (s) + 2 e − → Cd(s) + 2 OH − (aq) E°(anode) = − 0.81 V

Ni(OH)3 (s) + e − → Ni(OH) 2 (s) + OH − (aq) E °(cathode) = + 0.49 V

Reversing the anode reaction and multiplying the cathode reaction by 2

yields
Cd(s) + 2 OH − (aq) → Cd(OH) 2 (s) + 2 e −

2 Ni(OH)3 + 2 e − → 2 Ni(OH) 2 (s) + 2 OH − (aq) then,upon addition,

2 Ni(OH) 2 (s) + Cd(s) → Cd(OH) 2 (s) + 2 Ni(OH) 2 (s)

overall cell E° = +1.30 V

and Cd(s) | Cd(OH) 2 (s) | KOH(aq) || Ni(OH)3 (s) | Ni(OH) 2 (s) | Ni(s)

12.15 (a) MnO 4 − (aq) + 8 H + (aq) + 5 e − → Mn 2+ (aq) + 4 H 2 O(l) (cathode half-

reaction)
5[Fe3+ (aq) + e − → Fe 2+ (aq)] (anode half-reaction)
(b) Reversing the anode reaction and adding the two equations yields
MnO 4 − (aq) + 5 Fe 2+ (aq) + 8 H + (aq) → Mn 2+ (aq) + 5 Fe3+ (aq)+ 4 H 2 O(l)

The cell diagram is

Pt(s) | Fe3+ (aq), Fe 2 + (aq) || H + (aq), MnO 4 − (aq) , Mn 2+ (aq) | Pt(s)

12.17 A galvanic cell has a positive potential difference; therefore, identify as

cathode and anode the electrodes that make E° (cell) positive upon
calculating
E °(cell) = E °(cathode) − E °(anode)

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 There are only two possibilities: If your first guess gives a negative
E° (cell), switch your identification.
(a) Cu 2+ (aq) + 2 e − → Cu(s) E °(cathode) = + 0.34 V

Cr 3+ (aq) + e− → Cr 2+ (aq) E °(anode) = −0.41 V

E °(cell) = + 0.34 V − ( −0.41 V) = + 0.75 V

(b) AgCl(s) + e − → Ag(s) + Cl− (aq) E °(cathode) = + 0.22 V

AgI(s) + e − → Ag(s) + I − (aq) E °(anode) = −0.15 V

E °(cell) = + 0.22 V − ( − 0.15 V) = + 0.37 V

(c) Hg 2 2 + (aq) + 2 e − → 2 Hg(l) E °(cathode) = + 0.79 V

Hg 2 Cl2 (s) + 2 e− → 2 Hg(l) + 2 Cl− (aq) E °(anode) = + 0.27 V

E °(cell) = + 0.79 V − (+ 0.27 V) = + 0.52 V

(d) Pb 4+ (aq) + 2 e− → Pb 2+ (aq) E °(cathode) = +1.67 V

Sn 4+ (aq) + 2 e − → Sn 2+ (aq) E °(anode) = + 0.15 V

E °(cell) = +1.67 V − (+0.15 V) = +1.52 V

12.19 See Exercise 12.17 solutions for E° (cell) values. In each case,
∆G°r = − nFE °.

1 V = 1 J ⋅ C−1 . n is determined by balancing the equation for the cell

reaction constructed from the half-reactions given in Exercise 12.17.
(a) Cu 2+ (aq) + 2 Cr 2+ (aq) → Cu(s) + 2 Cr 3+ (aq), n = 2
E °cell = + 0.75 V and ∆G°r = − nFE °
= −(2) (9.6485 × 104 C ⋅ mol−1 ) (0.75 J ⋅ C−1 )
= −145 kJ ⋅ mol−1

(b) AgCl(s) + I − (aq) → AgI(s) + Cl− (aq), n = 1

E °cell = + 0.37 V and ∆G°r = − nFE °
= −1 × 9.6485 × 104 C ⋅ mol−1 × 0.37 J ⋅ C−1 = −36 kJ ⋅ mol−1

(c) Hg 2 2+ (aq) + 2 Cl − (aq) → Hg 2 Cl2 (s), n = 2

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 E °cell = + 0.52 V and ∆G°r = − nFE °
= −(2) (9.6485 × 104 C ⋅ mol−1 ) (0.52 J ⋅ C −1 )
= −100 kJ ⋅ mol−1

(d) Pb 4+ (aq) + Sn 2+ (aq) → Pb 2+ (aq) + Sn 4+ (aq), n = 2

E °cell = +1.52 V and ∆G°r = − nFE °
= −(2) (9.6485 × 104 C ⋅ mol−1 ) (1.52 J ⋅ C−1 )
= − 293 kJ ⋅ mol−1

12.21 The cell, as written Cu(s) | Cu 2+ (aq) || M 2+ (aq) | M(s), makes the Cu/Cu 2+
electrode the anode, because this is where oxidation is occurring; the
M 2+ /M electrode is the cathode. The calculation is
E ° = E °(cathode) − E °(anode)
0.689 V = E °(cathode) − (+ 0.34 V)
E °(cathode) = + 1.03 V

12.23 Refer to Appendix 2B. The more negative (less positive) the standard
reduction potential, the stronger is the metal as a reducing agent.
(a) Cu < Fe < Zn < Cr
(b) Mg < Na < K < Li
(c) V < Ti < Al < U
(d) Au < Ag < Sn < Ni

12.25 In each case, identify the couple with the more positive reduction
potential. This will be the couple at which reduction occurs, and therefore
which contains the oxidizing agent. The other couple contains the
reducing agent.
(a) Co 2+ /Co E ° = −0.28 V, Co 2+ is the oxidizing agent (cathode)

Ti3+ /Ti 2+ E ° = −0.37 V, Ti 2+ is the reducing agent (anode)

Pt(s) | Ti 2+ (aq), Ti3+ (aq) || Co 2+ (aq) | Co(s)
E °cell = E °(cathode) − E °(anode) = −0.28 V − (−0.37 V) = + 0.09 V

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 (b) U 3+ /U E ° = −1.79 V, U 3+ is the oxidizing agent (cathode)

La 3+ /La E ° = − 2.52 V, La is the reducing agent (anode)

La(s) | La 3+ (aq) || U 3+ (aq) | U(s)
E °cell = −1.79 V − ( − 2.52 V) = + 0.73 V

(c) Fe3+ /Fe2+ E ° = + 0.77 V, Fe3+ is the oxdizing agent (cathode)

H + /H 2 E ° = 0.00 V, H 2 is the reducing agent (anode)

Pt(s) | H 2 (g) | H + (aq) || Fe 2+ (aq), Fe3+ (aq) | Pt(s)
E °cell = + 0.77 V − 0.00 V = + 0.77 V

(d) O3 /O 2 ,OH − E ° = +1.24 V, O3 is the oxidizing agent (cathode)

Ag + /Ag E ° = + 0.80 V, Ag is the reducing agent (anode)

Ag(s) | Ag + (aq) || OH − (aq) | O3 (g), O 2 (g) | Pt(s)
E °cell = +1.24 V − 0.80 V = + 0.44 V

12.27 (a) E °(Cl 2 , Cl − ) = +1.36 V (cathode)

E °(Br2 , Br − ) = +1.09 V (anode)

Because E °(Cl2 , Cl− ) > E °(Br2 , Br − ) the reaction favors products.

E°cell = +1.36 V − 1.09 V = + 0.27 V

Cl2 (g) is the oxidizing agent.

(b) E °(Ce4+ /Ce3+ ) = +1.61 V (anode)

E °(MnO 4 − /Mn 2 + ) = +1.51 V (cathode)

Because E °(Ce 4+ /Ce3+ ) > E °(MnO 4 − /Mn 2+ ), the reaction does not favor
products.
(c) E °(Pb 4+ /Pb 2+ ) = +1.67 V (anode)

E °(Pb 2+ /Pb) = −0.13 V (cathode)

Because E °(Pb 4+ /Pb 2+ ) > E °(Pb 2 + /Pb), the reaction does not favor
products.
(d) E °(NO3 − / NO 2 /H + ) = + 0.80 V (cathode)

E °(Zn 2+ /Zn) = −0.76 V (anode)

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 Because E °(NO3 − / NO 2 /H + ) > E °(Zn 2+ /Zn), the reaction favors
products.
E°cell = + 0.80 V − (−0.76 V) = +1.56 V

NO 3 − is the oxidizing agent.

12.29 (a) 3 Au + (aq) → 2 Au (s) + Au 3+ (aq)

(b) Au + (aq) + e− → Au(s) E° = + 1.69 V

Au 3+ (aq) + 3 e − → Au(s) E° = + 1.40 V

Multiplying the first equation by three and subtracting the second equation
gives the net equation desired. The potential is given simply be subtracting
the second from the first:
E° = 1.69 V − 1.40 V = + 0.29 V
Because E° is positive, the process should be spontaneous for standard
state conditions.

12.31 The appropriate half-reactions are:

U 4 + + e − → U 3+ E° = − 0.61 (A)

U 3+ + 3 e − → U E° = −1.79 (B)
(A) and (B) add to give the desired half-reaction (C):
U 4+ + 4 e− → U E° = ? (C)
In order to calculate the potential of a half-reaction, we need to convert
the E° values into ∆G° values:
∆G°(A) = − nFE °(A) = −1F ( −0.61 V)
∆G°(B) = − nFE °(B) = −3F ( −1.79 V)
∆G°(C) = − nFE °(C) = − 4 FE °(C)
∆G°(C) = ∆G°(A) + ∆G°(B)
− 4 FE °(C) = −1F (−0.61 V) + [−3F ( − 1.79 V)]
The constant F will cancel from both sides, leaving:
− 4 E °(C) = − 1(−0.61 V) − 3(−1.79 V)
E °(C) = −[0.61 V + 5.37 V] /4 = −1.50 V

SM-366
12.33 (a) E °cell = E °(cathode) − E °(anode) = 0.34 V − (− 0.41 V) = 0.75 V, and

nFE ° nE ° (2) (0.75 V)

ln K = at 25°C = ln K = = 58 and
RT 0.025 69 V 0.025 69 V

K = 10 25
(b) Ti 2+ (aq) + 2 e− → Ti(s) E°(cathode) = −1.63 V

Mn 2+ (aq) + 2 e − → Mn(s) E°(anode) = −1.18 V

Note: These equations represent the cathode and anode half-reactions for
the overall reaction as written. The spontaneous direction of this reaction
under standard conditions is the opposite of that given.
E °cell = E °(cathode) − E °(anode) = −1.63 V − (−1.18 V) = −0.45 V , and

nFE ° nE ° (2) (−0.45 V)

ln K = at 25°C = ln K = = −35
RT 0.025 69 V 0.025 69 V and
K = 10−15

12.35 (a) Pb 4+ (aq) + 2 e− → Pb 2 + (aq) E °(cathode) = +1.67 V

Sn 2+ (aq) → Sn 4+ (aq) + 2e − E °(anode) = + 0.15 V

Pb 4+ (aq) + Sn 2+ (aq) → Pb 2+ (aq) + Sn 4+ (aq) E °cell

= 1.67 V − (0.15 V) = +1.52 V

⎛ 0.025 693 V ⎞ ⎛ 0.025 693 V ⎞

Then, E = E ° − ⎜ ⎟ ln Q; 1.33 V = 1.52 V − ⎜ ⎟ ln Q
⎝ n ⎠ ⎝ 2 ⎠
1.52 V − 1.33 V 0.19 V
ln Q = = = 15 Q = 106
0.0129 V 0.0129 V
2[Cr2 O7 2− (aq) + 14 H + (aq) + 6 e− →
(b)
2 Cr 3+ (aq) + 7 H 2 O(l)] E °(cathode) = 1.33 V

3[2 H 2 O(l) → O 2 (g) + 4 H + (aq) + 4 e − ] E °(anode) = +1.23 V

2 Cr2 O7 2− (aq) + 16 H + (aq) → 4 Cr 3+ (aq) + 8 H 2 O(l) + 3 O 2 (g) E °cell

= 0.10 V

SM-367
 ⎛ 0.0257 V ⎞ ⎛ 0.0257 V ⎞
Then, E = E ° − ⎜ ⎟ ln Q; 0.10 V = + 0.10 V − ⎜ ⎟ ln Q
⎝ n ⎠ ⎝ 12 ⎠
ln Q = 0.00 Q = 1.0

12.37 (a) Cu 2+ (aq, 0.010 M) + 2 e− → Cu(s) (cathode)

Cu 2+ (aq, 0.0010 M) + 2 e− → Cu(s) (anode)

Cu 2+ (aq,0.010 M) → Cu 2+ (aq, 0.0010 M) , n=2

E °cell = E °(cathode) − E °(anode) = 0 V

⎛ RT ⎞ ⎛ 0.025 693 V ⎞
Ecell = E °cell − ⎜ ⎟ ln Q = −⎜ ⎟ ln Q at 25°C
⎝ nF ⎠ ⎝ 2 ⎠
⎛ 0.025 693 V ⎞ ⎛ 0.0010 M ⎞
Ecell = − ⎜ ⎟ ln ⎜ ⎟ = + 0.030 V
⎝ 2 ⎠ ⎝ 0.010 M ⎠

(b) at pH = 3.0, [H + ] = 1 × 10−3 M

at pH = 4.0, [H + ] = 1 × 10−4 M

Cell reaction is H + (aq, 1 × 10−3 M) → H + (aq, 1 × 10−4 M), n=1

⎛ 0.025 693 V ⎞ ⎛ 1 × 10 ⎞
−4
⎛ RT ⎞
E °cell = 0 V Ecell = E °cell − ⎜ ⎟ ln Q = − ⎜ ⎟ ln ⎜ −3 ⎟
⎝ nF ⎠ ⎝ 1 ⎠ ⎝ 1 × 10 ⎠
= + 6 × 10−2 V

12.39 In each case, E °cell = E °(cathode) − E °(anode). Recall that the values for
E° at the electrodes refer to the electrode potential for the half-reaction
written as a reduction reaction. In balancing the cell reaction, the half-
reaction at the anode is reversed. However, this does not reverse the sign
of electrode potential used at the anode, because the value always refers to
the reduction potential.
(a) 2 H + (aq, 1.0 M) + 2 e − → H 2 (g, 1 atm) E °(cathode) = 0.00 V

H 2 (g, 1 atm) → 2 H + (aq,0.075 M) + 2 e− E °(anode) = 0.00 V

2 H + (aq, 1.0 M) + H 2 (g, 1 atm) → 2 H + (aq, 0.075 M) + H 2 (g, 1 atm)

SM-368
E °cell = 0.00 V
⎛ 0.025 693 V ⎞ ⎛ [H , 0.075 M] PH2 ⎞
+ 2

Then, E = E ° − ⎜ ⎟ ln ⎜⎜ ⎟
⎝ n + 2
⎠ ⎝ [H , 1.0 M] PH 2 ⎟
⎠
⎛ 0.025 693 V ⎞ ⎛ 0.075 M) × 1 atm ⎞
2
E = 0.00 V − ⎜ ln
⎟ ⎜ ⎟
⎠ ⎝ (1.0 M) × 1 atm ⎠
2
⎝ 2
E = − 0.0129 V ln (0.075) 2 = + 0.067 V

(b) Ni 2+ (aq) + 2 e − → Ni(s) E °(cathode) = −0.23 V

Zn(s) → Zn 2+ (aq) + 2 e − E °(anode) = −0.76 V

Ni 2+ (aq) + Zn(s) → Ni(s) + Zn 2+ (aq) E °cell = + 0.53 V

⎛ 0.025 693 V ⎞ ⎛ [Zn ] ⎞

2+
Then, E = E ° − ⎜ ln
⎟ ⎜ 2+ ⎟
⎝ n ⎠ ⎝ [Ni ] ⎠
⎛ 0.025 693 V ⎞ ⎛ 0.37 ⎞
E = 0.53 V − ⎜ ⎟ ln ⎜ ⎟ = 0.53 V − 0.02 V = 0.51 V
⎝ 2 ⎠ ⎝ 0.059 ⎠
(c) 2 H + (aq) + 2 e − → H 2 (g) E °(cathode) = 0.00 V

2 Cl − (aq) → Cl2 (g) + 2 e − E °(anode) = +1.36 V

2 H + (aq) + 2 Cl − (aq) → H 2 (g) + Cl 2 (g) E °cell = −1.36 V

Then,
⎛ 0.025 693 V ⎞ ⎛ PH2 PCl2 ⎞
E = E° − ⎜ ⎟ ln ⎜ + 2 − 2 ⎟
⎝ n ⎠ ⎝ [H ] [Cl ] ⎠
⎛ ⎛ 125 ⎞ ⎛ 250 ⎞ ⎞
⎜⎜ ⎟⎜ ⎟⎟
⎛ 0.025 693 V ⎞ ⎜ ⎝ 760 ⎠ ⎝ 760 ⎠ ⎟
E = −1.36 V − ⎜ ⎟ ln (1.01325) 2
⎠ ⎜ (0.85) (1.0) ⎟
2 2
⎝ 2
⎜ ⎟
⎝ ⎠
E = −1.36 V + 0.03 V
= −1.33 V

(d) Sn 4+ (aq, 0.867 M) + 2 e− → Sn 2+ (aq, 0.55 M)

E°(cathode) = + 0.15 V

Sn(s) → Sn 2+ (aq, 0.277 M) + 2 e − E °(anode) = − 0.14 V

Sn 4+ (aq, 0.867 M) + Sn(s) → Sn 2+ (aq, 0.55) + Sn 2+ (aq, 0.277 M)

SM-369
 E °cell = 0.29 V
⎛ 0.025 693 V ⎞ ⎛ (0.55) (0.277) ⎞
E = E° − ⎜ ⎟ ln ⎜ ⎟
⎝ 2 ⎠ ⎝ (0.867) ⎠
E = 0.29 V + 0.02 V = 0.31 V

12.41 In each case, obtain the balanced equation for the cell reaction from the
half-cell reactions at the electrodes, by reversing the reduction equation
for the half-reaction at the anode, multiplying the half-reaction equations
by an appropriate factor to balance the number of electrons, and then
adding the half-reactions. Calculate E °cell = E °(cathode) − E °(anode).
Then write the Nernst equation for the cell reaction and solve for the
unknown.
(a) Hg 2 Cl 2 (s) + 2 e − → 2 Hg(l) + 2 Cl− (aq) E °(cathode) = + 0.27 V

H 2 (g) → 2 H + (aq) + 2 e − E °(anode) = 0.00 V

H 2 (g) + Hg 2 Cl2 (s) → 2 H + (aq) + 2 Hg(l) + 2 Cl− (aq) E °cell = + 0.27 V

⎛ 0.025 693 V ⎞ ⎛ [H ] [Cl ] ⎞

+ 2 − 2
E = E° − ⎜ ln
⎟ ⎜ ⎟
⎝ n ⎠ ⎝ [H 2 ] ⎠
⎛ 0.025 693 V ⎞ ⎛ [H ] (1) ⎞
+ 2 2
0.33 V = 0.27 V − ⎜ ⎟ ⎜ln ⎟
⎝ 2 ⎠ ⎝ (1) ⎠
+ 2
= 0.27 V − (0.0129 V) ln [H ]
0.06 V = − 0.0257 V ln [H + ] = − 0.0257 V × (2.303 log [H + ])
0.06 V
pH = = 1.0
(2.303) (0.025 693 V)

2[MnO 4 − (aq) + 8 H + (aq) + 5 e − →

(b)
Mn 2+ (aq) + 4 H 2 O(l)] E °(cathode) = +1.51 V

5[2 Cl − (aq) → Cl 2 (g) + 2 e − ] E °(anode) = +1.36 V

2 MnO4 − (aq) + 16 H + (aq) + 10 Cl− (aq) →

5 Cl2 (g) + 2 Mn 2+ (aq) + 8 H 2 O(l) E °cell = + 0.15 V

⎛ 0.0257 V ⎞ ⎛ [Cl2 ]5 [Mn 2+ ]2 ⎞

E = E° − ⎜ ⎟ ln ⎜ 2 + 16 − 10 ⎟
⎝ n ⎠ ⎝ [MnO 4 ] [H ] [Cl ] ⎠

SM-370
 ⎛ 0.0257 V ⎞ ⎛ (1)5 (0.10) 2 ⎞
−0.30 V = + 0.15 V − ⎜ ⎟ ln ⎜ −4 16 − 10 ⎟
⎠ ⎝ (0.010) (1 × 10 ) (Cl ) ⎠
2
⎝ 10
⎛ 1 × 10−2 ⎞
−0.45 V = −(0.002 5693 V) log ⎜ −4 −64 − 10 ⎟
⎝ (1 × 10 ) (1 × 10 ) [Cl ] ⎠
⎡ ⎛ 1 ⎞⎤
= −0.002 5693 V ⎢ ln (1 × 1066 ) + ln ⎜ − 10 ⎟ ⎥
⎣ ⎝ [Cl ] ⎠ ⎦
= −0.390 V + (0.0025 693 V) ln [Cl− ]10
−0.0594 V = 0.002 5693 V ln[Cl− ]10
= (0.025 693 V) ln[Cl− ]
−0.06 V
ln[Cl− ] = =−2
0.025 693 V
[Cl− ] = 10−1 mol ⋅ L−1

12.43 Since the reduction potential of tin(II) is negative relative to the S.H.E.,
we will assume the tin electrode to be the anode such that the standard cell
potential would be positive. Then we can use the Nernst equation to solve
for the hydrogen ion activity in order to calculate the pH. The cell
reaction is Sn(s) + 2 H + → Sn 2 + + H 2 (g) .

⎛ 0.025 693 V ⎞ ⎛ [Sn ] pH2 ⎞

2+

E = E° − ⎜ ⎟ ⎜⎜
ln ⎟
⎝ n ⎠ ⎝ [H ]
+ 2 ⎟
⎠
⎛ 0.025 693 V ⎞ ⎛ [0.015][1] ⎞
0.061 V = 0.14 V − ⎜ ⎟ ln ⎜ + 2 ⎟
⎝ 2 ⎠ ⎝ [H ] ⎠
= 0.14 V − (0.01284 V) (ln(0.015) − ln [H + ]2 )
0.079 V
= ln(0.015) − 2 ln [H + ]
0.01284 V
−10.352 = 2 ln [H + ]
ln[H + ] = −5.176, [H + ] = 5.650 × 10−3
pH = − log(5.650 × 10−3 ) = 2.25

12.45 To calculate this value, we need to determine the E° value for the
solubility reaction:

SM-371
 Hg 2 Cl2 (s) → Hg 2 2+ (aq) + 2 Cl− (aq) E° = ?
The relationship ∆G° = − nRT ln K = − nFE ° can be used to calculate the
value of K sp .

The equations that will add to give the net equation we want are
Hg 2 Cl2 (s) + 2 e− → 2 Hg(l) + 2 Cl− (aq) E ° = + 0.27 V
2+ −
2 Hg(l) → Hg 2 (aq) + 2 e E ° = 0.79 V
Notice that the second equation is reversed from the reduction reaction
given in the Appendix, and consequently the E° value is changed in sign.
Adding these two equations together gives the desired net reaction, and
summing the E° values will give the E° value for that process:
E ° = (+ 0.29 V) + ( −0.79 V) = −0.50 V
nFE ° (2) (9.65 × 104 C ⋅ mol−1 ) ( −0.50 V)
ln K sp = = = −38.95
RT (8.314 J ⋅ K −1 ⋅ mol−1 ) (298 K)
K sp = 1.2 × 10−17

(b) This value is a factor of 10 greater than the value in Table

11.6 (1.3 × 10−18 ).

12.47 This cell uses two silver electrodes, so E° = 0 and E is determined by the
ratio of [Ag + ]anode to [Ag + ]cathode . Since [Ag + ]anode < [Ag + ]cathode , the ratio
is less than 1 and E > 0, so the cell can do work because
∆G=wmax = − nFE .

⎛ 0.025 693 V ⎞ ⎛ [Ag ]anode ⎞

+
⎛ 0.025 693 V ⎞ ⎛ 5.0 × 10 ⎞
−3
E =−⎜ ln
⎟ ⎜ + ⎟ = − ⎜ ln
⎟ ⎜ 0.15 ⎟
⎝ n ⎠ ⎝ [Ag ]cathode ⎠ ⎝ 1 ⎠ ⎝ ⎠
= 0.0874 V
∆G=wmax = − nFE = −(1 mol)(96 485 J V -1 mol-1 )(0.0874 V)
=-8.4 kJ

12.49 For the standard calomel electrode, E° = + 0.27 V. If this were set equal to
0, all other potentials would also be decreased by 0.27 V. (a) Therefore,
the standard hydrogen electrode’s standard reduction potential would be

SM-372
 0.00 V − 0.27 V or − 0.27 V. (b) The standard reduction potential for

Cu 2+ /Cu would be 0.34 V − 0.27 V or + 0.07 V.

12.51 The strategy is to consider the possible competing cathode and anode
reactions. At the cathode, choose the reduction reaction with the most
positive (least negative) standard reduction potential ( E° value). At the
anode, choose the oxidation reaction with the least positive (most
negative) standard reduction potential ( E° value, as given in the table).
Then calculate E °cell = E °(cathode) − E °(anode). The negative of this
value is the minimum potential that must be supplied.
(a) cathode: Ni 2+ (aq) + 2 e− → Ni(s) E° = − 0.23 V

(rather than 2 H 2 O(l) + 2 e − → H 2 (g) + 2 OH − (aq) E° = −0.83 V)

(b) anode: 2 H 2 O(l) → O 2 (g) + 4 H + (aq) + 4 e − E° = +1.23 V

(the SO 4 2− ion will not oxidize)

(c) E °cell = E °(cathode) − E °(anode) = −0.23 V − (+1.23 V) = −1.46 V

Therefore E (supplied) must be > +1.46 V (1.46 V is the minimum).

12.53 In each case, compare the reduction potential of the ion to the reduction
potential of water ( E° = − 0.42 V) and choose the process with the least
negative E° value.
(a) Mn 2+ (aq) + 2 e− → Mn(s) E° = −1.18 V

(b) Al3+ (aq) + 3 e− → Al(s) E° = −1.66 V

The reactions in (a) and (b) evolve hydrogen rather than yield a metallic
deposit because water is reduced, according to
2 H 2 O(l) + 2 e − → H 2 (g) + 2 OH − (aq) ( E° = − 0.42 V, at pH = 7)

(c) Ni 2+ (aq) + 2 e− → Ni(s) E° = − 0.23 V

(d) Au 3+ (aq) + 3 e − → Au(s) E° = +1.69 V

In (c) and (d) the metal ion will be reduced.

SM-373
12.55 4500 C ÷ 9.65 × 104 C ⋅ F−1 = 0.047 F = 0.047 mol e −

(0.047 ÷ 3) mol Bi3+ + 0.047 mol e− →

(a)
(0.047 ÷ 3) mol Bi, or 0.016 mol Bi = 3.3 g

(b) 0.047 mol H + + 0.047 mol e − → (0.047 ÷ 2) mol H 2

0.024 mol H 2 × 24.45 L ⋅ mol −1 (at 298 K) = 0.59 L

(0.047 ÷ 3) mol Co3+ + 0.047 mol e− →

(c)
(0.047 ÷ 3) mol Co = 0.016 mol Co or 0.94 g

12.57 (a) Ag + (aq) + e − → Ag(s)

⎛ 1 mol Ag ⎞ ⎛ 1 mol e − ⎞
time = (1.50 g Ag) ⎜ ⎟⎜ ⎟
⎝ 107.98 g Ag ⎠⎝ 1 mol Ag ⎠

⎛ 9.65 × 104 C ⎞⎛ 1 A ⋅ s ⎞ ⎛ 1 ⎞
⎟ = 9.9 × 10 s or 27 h
4
⎜ − ⎟⎜ ⎟⎜
⎝ 1 mol e ⎠ ⎝ 1 C ⎠ ⎝ 0.0136 ⎠
(b) Cu 2+ (aq) + 2 e− → Cu(s)

⎛ 1 C ⎞ ⎛ 1 mol e− ⎞
mass Cu = (9.9 × 104 s) (0.0136 A) ⎜ ⎟⎜ ⎟
⎝ 1 A ⋅ s ⎠⎝ 9.65 × 10 C ⎠
4

⎛ 0.50 mol Cu ⎞⎛ 63.5 g Cu ⎞

⎜ − ⎟⎜ ⎟ = 0.44 g Cu
⎝ 1 mol e ⎠ ⎝ 1 mol Cu ⎠

12.59 (a) Cr(VI) + 6 e − → Cr(s)

charge
current =
time
⎛ 1 mol Cr ⎞ ⎛ 6 mol e − ⎞ ⎛ 9.65 × 104 C ⎞
2.5 g Cr ⎜ ⎟⎜ ⎟⎜ − ⎟
⎝ 52.00 g Cr ⎠ ⎝ 1 mol Cr ⎠ ⎝ 1 mol e ⎠
=
12 h × 3600 s ⋅ h −1
= 0.64 C ⋅ s −1 = 0.64 A

(b) Na + + e− → Na(s)

SM-374
 ⎛ 1 mol Na ⎞ ⎛ 1 mol e− ⎞⎛ 9.65 × 104 C ⎞
2.5 g Na ⎜ ⎟⎜ ⎟⎜ − ⎟
= ⎝ 22.99 g Na ⎠ ⎝ 1 mol Na ⎠⎝ 1 mol e ⎠
current
12 h × 3600 s ⋅ h −1
= 0.24 C ⋅ s −1 = 0.24 A

12.61 Ru n + (aq) + n e− → Ru(s); solve for n

⎛ 1 mol ⎞ −4
moles of Ru = (0.0310 g Ru) ⎜ ⎟ = 3.07 × 10 mol
⎝ 101.07 g Ru ⎠

⎛ 10−3 A ⎞⎛ 1 C ⋅ s −1 ⎞
total charge = (500 s) (120 mA) ⎜ ⎟⎜ ⎟ = 60 C
⎝ 1 mA ⎠⎝ 1 A ⎠

⎛ 1 mol e − ⎞
moles of e− = (60 C) ⎜ −4
⎟ = 6.2 × 10 mol e
−

⎝ 96 500 C ⎠
6.2 × 10−4 mol e − 2 mol charge
n= =
3.07 × 10−4 mol 1 mol

Therefore, oxidation number of Ru 2+ is + 2.

12.63 Hf n + + n e− → Hf(s); solve for n.

charge consumed = 15.0 C ⋅ s −1 × 2.00 h × 3600 s ⋅ h −1 = 1.08 × 105 C

⎛ 1 mol e− ⎞ −
moles of charge consumed = (1.08 × 105 C) ⎜ ⎟ = 1.12 mol e
⎝ 9.65 × 10 C ⎠
4

⎛ 1 mol Hf ⎞
moles of Hf plated = (50.0 g Hf ) ⎜ ⎟ = 0.280 mol Hf
⎝ 178.49 g Hf ⎠
1.12 mol e−
Then, n = = 4.00 mol e − /mol Hf
0.280 mol Hf

Therefore, the oxidation number is 4, that is, Hf 4 + .

12.65 MCl3 → M 3+ + 3 Cl− M 3+ + 3 e − → M(s)

First, determine the number of moles of electrons consumed; the number

of moles of M 3+ reduced is one-third of this number.

SM-375
 ⎛ 3600 s ⎞⎛ 0.700 C ⎞
charge used = (6.63 h) ⎜ ⎟⎜ ⎟ = 1.67 × 10 C
4

⎝ 1 h ⎠⎝ 1 s ⎠

⎛ 1 mol e− ⎞
number of moles of e− = (1.67 × 104 C) ⎜ ⎟ = 0.173
⎝ 9.65 × 10 C ⎠
4

1 mol M 3+
number of moles of M 3+ (and M) = 0.173 mol e − ×
3 mol e−
= 0.0577
3.00 g
molar mass M = = 52.0 g ⋅ mol−1 (Cr)
0.0577 mol

12.67 Assuming all the energy comes from reduction of oxygen focuses
attention on this half reaction:
O 2 (g) + 4 H + (aq) + 4 e - → 2 H 2 O(l) E °=+1.23 V

Body conditions are far from standard state values, so the actual value of
E would be reduced by about 0.5 V if we take pH, pO2 and T into

account. However, we are only estimating an average current to one

significant digit, so E =1.23 ± 0.5 V ≈ 1 V is adequate. With these
approximations in mind, we can calculate the current.
∆G
It = nF = or
−E
∆G (−10 × 106 J) 1 V⋅C
I= = ⋅ = 115 A ≈ 100 A
− Et −(1 V)(24 h)(3600 s ⋅ h ) 1 J
-1

12.69 (a) The electrolyte is KOH(aq)/HgO(s), which will have the consistency
of a moist paste.
(b) The oxidizing agent is HgO(s).
(c) HgO(s) + Zn(s) → Hg(l) + ZnO(s)

12.71 See Table 12.1.

SM-376
 The anode reaction is Zn(s) → Zn 2+ (aq) + 2 e− ; this reaction supplies the
electrons to the external circuit. The cathode reaction is
MnO 2 (s) + H 2 O(l) + e − → MnO(OH) 2 (s) + OH − (aq). The OH − (aq)

produced reacts with NH 4 + (aq) from the NH 4 Cl(aq) present:

NH 4 + (aq) + OH − (aq) → H 2 O(l) + NH 3 (g). The NH 3 (g) produced

complexes with the Zn 2+ (aq) produced in the anode reaction

Zn 2+ (aq) + 4 NH 3 (g) → [Zn(NH 3 ) 4 ]2+ (aq).

The overall reaction is complicated.

12.73 See Table 12.1 (a) KOH(aq) (b) In the charging process, the cell
reaction is the reverse of what occurs in discharge. Therefore, at the
anode, 2 Ni(OH)2 (s) + 2 OH − (aq) → 2 Ni(OH)3 + 2 e− .

12.75 Fe3+ (aq) + 3 e− → Fe(s) E° = − 0.04 V

Cr 3+ (aq) + 3 e − → Cr(s) E° = − 0.74 V

Fe2+ (aq) + 2 e− → Fe(s) E° = − 0.44 V

Cr 2+ (aq) + 2 e− → Cr(s) E° = − 0.91 V

Comparison of the reduction potentials shows that Cr is more easily
oxidized than Fe, so the presence of Cr retards the rusting of Fe. At the
position of the scratch, the gap is filled with oxidation products of Cr,
thereby preventing contact of air and water with the iron.

It (3.5 A)(395.0 s)
12.77 (a) ne− = nAg + = = = 1.43 × 10−2 mol Ag
F (96 485 C ⋅ mol-1 )

⎛ 107.87 g Ag ⎞
1.43 × 10−2 mol Ag ⎜ ⎟ = 1.55 g Ag
⎝ mol Ag ⎠
1.55 g
× 100 = 57.4% Ag
2.69 g
(b) 2.69 g-1.55 g=1.14 g X

SM-377
 Since the salt is 1:1 Ag:X, the molar mass of X is
1.14 g
= 79.7 g ⋅ mol-1
1.43 × 10 mol
-2

This molar mass is closest to bromine, so the formula is AgBr.

12.79 (a) Fe2 O3 ⋅ H 2 O (b) H 2 O and O 2 jointly oxidize iron. (c) Water is
more highly conducting if it contains dissolved ions, so the rate of rusting
is increased.

12.81 (a) aluminum or magnesium; both are below titanium in the

electrochemical series.
(b) cost, availability, and toxicity of products in the environment
(c) Cu 2+ + 2 e − → Cu(s) E° = + 0.34 V

Cu + + e − → Cu(s) E° = + 0.52 V

Fe3+ + 3 e− → Fe(s) E° = − 0.04 V

Fe2+ + 2 e − → Fe(s) E° = − 0.44 V

Fe could act as the anode of an electrochemical cell if Cu 2+ or Cu + were

present; therefore, it could be oxidized at the point of contact. Water with
dissolved ions would act as the electrolyte.

12.83 2[Zn 2+ (aq) + 2 e− → Zn(s)] E °(cathode) = − 0.76 V

M(s) → M 4+ (aq) + 4 e − E °(anode) = x

M(s) + 2 Zn 2+ (aq) → 2 Zn(s) + M 4+ (aq) E °cell = 0.16 V

E °cell = E °(cathode) − E °(anode)

+ 0.16 V = − 0.76 V − ( x )

x = − 0.92 V = E °(M 4+ /M)

12.85 The strategy is to find the E° value for the solubility reaction and then
find appropriate half-reactions that add to give that solubility reaction.

SM-378
 One of these half-reactions is our unknown, the other is obtained from
Appendix 2B:
Cu(IO3 ) 2 (s) + 2 e − → Cu(s) + 2 IO3 − (aq) E° = ? (A)

Cu(s) → Cu 2+ (aq) + 2 e− E° = −0.34 V (B)

RT ln K sp
Cu(IO3 ) 2 (s) + → Cu 2+ (aq) + 2 IO3− (aq) E° = (C)
nF
RT ln K sp
E° =
nF
(8.314 J ⋅ K −1 ⋅ mol−1 ) (298.2 K) ln (1.4 × 10−7 )
=
2(9.65 × 104 C ⋅ mol−1 )
= − 0.20 V
− 0.20 V = E °(A) + (− 0.34 V)
E°(A) = + 0.14 V

12.87 (a) In acidic solution, the relevant reactions are

O2 + 4 H + + 4 e− → 2 H 2 O E° = + 1.23 V

Ag → Ag + + e− E ° = − 0.80 V
Overall reaction:
O 2 + 4 H + + 4 Ag → 4 Ag + + 2 H 2 O E ° = + 0.43 V

Because the potential is positive, the reaction should be spontaneous and

would be expected to occur. We should also consider the conditions;
because air is only 20.95% O 2 , the potential may be different from that
calculated for standard conditions. If air is the source of oxygen, then it
will be present at 0.2095 × 1.013 25 bar = 0.2123 bar.

0.0592 [Ag + ]4
E = E° − log
4 PO2 [H + ]4
0.0592 [1.0]4
= + 0.43 V − log
4 (0.2123)[1.0]4

SM-379
 0.0592 1
= + 0.43 V − log
4 0.2123
= + 0.43 V − 0.010 V
= + 0.42 V
The potential is still positive and the reaction is expected to be
spontaneous.
(b) In basic solution, the relevant reactions are
O 2 + 2 H 2 O + 4 e − → 4 OH − E° = + 0.40 V

Ag → Ag + + e − E° = −0.80 V
Overall reaction:
O 2 + 2 H 2 O + 4 Ag → 4 Ag + + 4 OH − E° = − 0.40 V

This process as written is nonspontaneous and is not predicted to occur.

However, AgOH forms an insoluble precipitate, changing the nature of the
reaction. The K sp value for AgOH is 1.5 × 10−8. We use the Nernst

equation to calculate the potential under these conditions:

0.0592 [Ag + ]4 [OH − ]4
E = E° − log
4 PO2
4
0.0592 K sp
= −0.40 V − log
4 PO2
0.0592 (1.5 × 10−8 ) 4
= −0.40 V − log
4 0.2132
= −0.40 V + 0.45 V
= + 0.05 V
Under these conditions, the potential is slightly positive and the oxidation
should be spontaneous.

12.89 In each case, determine the cathode and anode half-reactions

corresponding to the reactions as written. Look up the standard reduction
potentials for these half-reactions and then
calculate E °cell = E °(cathode) − E °(anode). If E °cell is positive, the
reaction is spontaneous under standard conditions.

SM-380
 (a) E °cell = E °(cathode) − E °(anode) = + 0.96 V − (+ 0.79 V) = + 0.17 V .
Therefore, spontaneous galvanic cell:
Hg(l) | Hg 2 2+ (aq) || NO3− (aq), H + (aq) | NO(g) | Pt(s)
∆G°r = − nFE ° = −(6) (9.65 × 104 C ⋅ mol−1 ) (+ 0.17 J ⋅ C−1 ) = −98 kJ ⋅ mol−1

(b) E °cell = E °(cathode) − E °(anode) = + 0.92 V − (+1.09 V) = −0.17 V

Therefore, not spontaneous.
(c) E °cell = E °(cathode) − E °(anode) = +1.33 V − (+ 0.97 V) = + 0.36 V
Therefore, spontaneous galvanic cell.
Pt(s) | Pu 3+ (aq), Pu 4+ (aq) || Cr2 O7 2− (aq),Cr 3+ (aq), H − (aq) | Pt(s)
∆G°r = − nFE ° = −(6) (9.65 × 104 C ⋅ mol−1 ) (0.36 J ⋅ C−1 ) = − 208 kJ ⋅ mol−1

12.91 (a) M Ag + VAg + = M I − VI −

M I − VI − (0.015 M)(16.7 mL)

M Ag + = =
VAg + (25.0 mL)
= 1.0 × 10−2 M
(b) We can find [Ag + ] by using the Nernst equation appropriately.

⎛ 0.025 693 V ⎞ ⎛ 1 ⎞
E = E° − ⎜ ⎟ ln ⎜ + ⎟
⎝ n ⎠ ⎝ [Ag ] ⎠
Since the standard reduction potential of silver(I) is +0.80 V, it will be the
reduction half reaction versus the S.H.E., so [Ag + ] appears in the
denominator of Q. In addition, n = 1 and E° = 0.080 V .

⎛ 0.025 693 V ⎞ ⎛ 1 ⎞
0.325 V = 0.80 V − ⎜ ⎟ ln ⎜ + ⎟
⎝ 1 ⎠ ⎝ [Ag ] ⎠
−0.475 V=( − 2.567 × 10−2 V)(ln 1 − ln[Ag + ])
−18.50 = ln[Ag + ]
[Ag + ] = 9.23 × 10−9 M

Recalling that K sp = [Ag + ][I− ] , and assuming [Ag + ]=[I − ] at the

stoichiometric point of the titration,

K sp = [Ag + ][I− ]=(9.23 × 10-9 )2 = 8.5 × 10−17

SM-381
12.93 F2 (g) + 2 e − → 2 F− (aq) E °(cathode) = + 2.87 V

2 HF(aq) → F2 (g) + 2 H + (aq) + 2 e − E °(anode) = +3.03 V

2 HF(aq) → 2 H + (aq) + 2 F− (aq)

E °cell = E °(cathode)-E °(anode) = +2.87 V − (+3.03 V) = −0.16 V

[H + ]2 [F− ]2 nFE °
For the above reaction, K = 2
and ln K =
[HF] RT
nE ° (2) ( −0.16 V)
at 25°C = = = −12
0.025 69 V 0.025 69 V

K = 10−5
K a = K = 10−5 = 10−3

12.95 The wording of this exercise suggests that K + ions participate in an

electrolyte concentration cell reaction. Therefore, E°cell = 0.00 V, because
the two half cells would be identical under standard conditions.
Then,

⎛ 0.0257 V ⎞ ⎛ [K out ] ⎞
+
⎛ 0.0257 V ⎞ ⎛ 1 ⎞
E = E° − ⎜ ⎟ ln ⎜ + ⎟
= 0.00 V − ⎜ ⎟ ln ⎜ ⎟
⎝ n ⎠ ⎝ [K in ] ⎠ ⎝ 1 ⎠ ⎝ 30 ⎠
= + 0.09 V

⎛ 0.0257 V ⎞ ⎛ 1 ⎞
and E = 0.00 V − ⎜ ⎟ ln ⎜ ⎟ = + 0.08 V
⎝ 1 ⎠ ⎝ 20 ⎠
The range of potentials is 0.08 V to 0.09 V.

12.97 Ag + (aq) + e− → Ag E °(cathode) = + 0.80 V

Fe2+ (aq) → Fe3+ (aq) + e − E °(anode) = + 0.77 V

Ag + (aq) + Fe 2+ (aq) → Fe3+ (aq) + Ag(s) E °cell = + 0.03 V

⎛ 0.0257 V ⎞ ⎛ [Fe ] ⎞
3+
Ecell = E °cell − ⎜ ln
⎟ ⎜ + 2+ ⎟
⎝ n ⎠ ⎝ [Ag ][Fe ] ⎠

SM-382
 ⎛ 1 ⎞
= 0.03 V − (0.0257 V) ln ⎜ ⎟ = 0.03 V − 0.30 V
⎝ (0.010) (0.0010) ⎠
= −0.27 V
Comment: The cell changes from spontaneous to nonspontaneous as a
function of concentration.

12.99 Since the number of electrons transferred in each half-reaction is

different, the Gibbs free energy relationship must be used rather than just
the reduction potentials themselves (see Example 12.6).
∆G3D = ∆G1D + ∆G2D
(− n3 FE3D ) = (− n1 FE1D ) + (− n2 FE2D )
n3 E3D = n1 E1D + n2 E2D
(1)(−0.256 V) + (2)(−1.175 V)
E3D =
3
= −0.869 V

12.101 buffer system =HA → H + + A −

(H + ) (A − )
Q=
(HA)

Note: (H + ) , as opposed to [H + ] , indicates a nonequilibrium molarity.

Because in a buffer system (A) ≈ (HA) , we can write

Q = (H + )
RT
Ecell = E °cell − ln (H + )
nF
⎛ 0.025 693 ⎞ +
0.060 V = E °cell − ⎜ ⎟ (2.303) (log(H ))
⎝ 1 ⎠
Because log (H + ) = − [−log(H + )] = − pH, we have
0.060 V = E °cell − 0.0592 × (− pH)

0.060 V = E °cell + 0.0592 × pH

0.060 V = E °cell + 0.0592 × 9.40

SM-383
 0.060 V = E °cell + 0.556 V
E° = 0.060 V − 0.556 V = − 0.496 V
Similarly, 0.22 V = − 0.496 V + 0.0592 V × pH
0.22 V + 0.496 V
pH = = 12
0.0592 V

12.103 (A) ClO 4 − + 2 H + + 2 e − → ClO3− + H 2 O E° = +1.23 V

(B) ClO 4 − + H 2 O + 2 e − → ClO3− + 2 OH − E° = + 0.36 V

(a) The Nernst equation can be used to derive the potential as a function
of pH:
RT
E⭈= E ° − ln Q
nF
0.059 16 [ClO3 − ]
For (A), E⭈(A) = 1.23 V − log
2 [ClO 4 − ][H + ]2

We are only interested in varying [H + ],so the [ClO3 − ] and [ClO 4 − ] will
be left at the standard values of 1 M.
0.059 16 1
E⭈(A) = +1.23 V − log + 2
2 [H ]
0.059 16 1
= +1.23 V − × 2 log +
2 [H ]

= +1.23 V − 0.059 16 (−log [H + ])

= +1.23 V − 0.059 16 pH
Similarly, for (B):
0.059 16 [ClO3 − ][OH − ]2
E⭈(B) = + 0.36 V − log
2 [ClO 4 − ]
As above, we are only interested in varying
[OH − ], so [ClO3 − ] and [ClO 4 − ] will be left at the standard value of 1 M.

SM-384
 0.059 16
E⭈(B) = + 0.36 V − log [OH − ]2
2
0.059 16
= + 0.36 V − × 2 log [OH − ]
2
= + 0.36 V − 0.059 16 × log [OH − ]
= + 0.36 V + 0.059 16 pOH
Because pOH + pH = pK w = 14.00, we can write:
pOH = 14.00 − pH
E⭈(B) = + 0.36 V + 0.059 16[14.00 − pH]
= + 0.36 V + 0.83 V − 0.059 16 pH
= +1.19 V − 0.059 16 pH
If we compare this to E°(A) , we find that the equations are essentially the
same. They should be identical, the difference being due to the limitation
of the number of significant figures available for the calculations.
(b) From the discussion above, we can see that the potential in neutral
solution should be the same, regardless of which half-reaction we use to
calculate the value.
Using E°(A) = +1.23 V − 0.059 16 pH = +1.23 V − 0.059 16 (7.00) = 0.82
Using E⭈(B) = + 0.36 V + 0.059 16 pOH = + 0.36 + 0.059 16 (7.00) = 0.77
Although these numbers differ slightly, they should be identical; again the
difference lies in the limitation of the number of significant figures.

12.105 (a) Fe2+ + 2 e− → Fe E ° = −0.44 V

2+ −
Mn + 2 e → Mn E ° = −1.18
Because these are reduction reactions, we need a corresponding oxidation.
The nitrate ion contains N in its highest oxidation state so it cannot be
oxidized further. The logical choice is the oxidation of water. The
appropriate reduction potential is
O 2 + 4 H + + 4 e − → 2 H 2 O E° = +1.23 V

The two overall reactions will be:

SM-385
2 Fe 2+ + 2 H 2 O → 2 Fe + O2 + 4 H + E ° = −0.44 V − 1.23 V
= −1.67 V

2 Mn 2+ + 2 H 2 O → 2 Mn + O 2 + 4 H + E ° = −1.18 V − 1.23 V
= − 2.41 V
(b) The actual potentials, however, will differ from these standard
potentials because the concentrations of the metal ions and hydrogen ions
are not 1 M, and the pressure of O2 is not 1 bar. To calculate the actual
values, the Nernst equation is used.

0.059 16 PO2 [H + ]4
For the Fe reaction: E = −1.67 V − log
4 [Fe 2+ ]2
In an open beaker, with the metal ions dissolved in water with pH = 5.00,
the pressure of O 2 will be 0.2095 × 1.00 atm × 0.987 bar ⋅ atm −1 = 0.207
bar. Substituting the specific values will give
0.059 16 (0.207) (1.00 × 10−5 ) 4
E = − 1.67 V − log
4 (0.0950) 2
= −1.67 V + 0.276 V = −1.39 V
For the Mn reaction:
0.059 16 (0.207) (1.00 × 10−5 ) 4
E = − 2.41 V − log
4 (0.115) 2
= −2.41 V + 0.278 V = − 2.13 V
In order to plate out iron from this mixture, 1.39 V must be applied, and
2.13 V must be applied to cause the reduction of Mn 2+ .
(c) Because the potential for reducing iron(II) is more positive than the
potential for reducing manganese(II), the iron will plate out first.
(d) The answer to this question is obtained from the Nernst equation by
determining the concentration of Fe 2 + when the applied potential reaches
2.13 V:

SM-386
 0.059 16 (0.207)[H + ]4
−2.13 V = −1.67 V − log
4 [Fe 2+ ]2
0.059 16 (0.207)[H + ]
−0.46 V = − log
4 [Fe2+ ]2

[H + ]4
31.10 = log 0.207 + log
[Fe2+ ]2
[H + ]4
31.78 = log
[Fe2+ ]2

[H + ]4
2+ 2
= 6.0 × 1031
[Fe ]
[H + ]2
2+
= 7.7 × 1015
[Fe ]

For the last ratio to be 7.7 × 1015 , essentially all of the Fe 2 + must be

converted to Fe(s). This means that [H + ] will essentially be 0.190

−1.
mol ⋅ L−1 . Substituting this number gives [Fe2+ ] = 5 × 10−18 mol ⋅ L . We
can say that the iron is quantitatively precipitated by this point.
We might note, however, that the potential of 2.13 V is now no longer the
potential at which Mn 2+ will begin to be reduced. Because the reduction
of Fe 2 + has produced a considerable amount of acid, the original reduction
of Mn 2+ should be recalculated:
0.059 16 (0.207) (0.190) 4
E = −2.41 V − log = − 2.39 V
4 (0.115) 2
Thus, even less iron will remain in solution.

12.107 (a) Addition of an electron to any molecule should have the electron enter
the molecule’s lowest unoccupied molecular orbital (LUMO) first. (b)
For CH3 X, one would predict that the LUMO would be antibonding
between C and one of the atoms attached to it. Because the C—H bond
strength (412 kJ ⋅ mol−1 ) is greater than all of the C—X bond strengths

given (C—Cl, 338 kJ ⋅ mol−1 ; C—Br, 276 kJ ⋅ mol−1 ; C—I, 238

SM-387
 kJ ⋅ mol−1 ) we would expect the LUMO to be the antibonding orbital for
the C—X bond. Adding an electron to this orbital should then result in a
weakening of the C—X bond. The result is the elimination of X − and the
formation of a CH 3 radical:

CH 3 X + e − → CH 3 + X −

(c) We would expect this reduction process to follow the C—X bond
strengths so that the formation of X − and generation of CH 3 radicals
would be easiest for X = I, followed by Br, and then Cl.

12.109 In order to determine the current applied, we need to find the number of
moles of electrons transferred. The electrolysis of water to produce
gaseous oxygen and hydrogen,
2 H 2 O(l) → O2 (g) + 2 H 2 (g) , transfers 4 moles of electrons for each mole

of oxygen gas produced: 4 OH − (aq) → O 2 (g) + 2 H 2 O(l) + 4 e − . We can

determine the number of moles of oxygen from its volume, partial
pressure, and temperature.
pO2 V ( ptot − pH2O )V
nO2 = =
RT RT
(722 Torr-19.83 Torr)(25.0 mL) 1L 1 atm
= ⋅ ⋅
(0.08206 L ⋅ atm ⋅ K ⋅ mol )(295 K) 1000 mL 760 Torr
-1 -1

= 9.542 × 10−4 mol O 2 produced

4 mol e − 4 mol e −
ne− = nO2 × = 9.542 × 10−4 mol O 2 ×
mol O 2 mol O 2
= 3.817 × 10−3 mol e −

It = nF
nF (3.817 × 10−3 mol e− ) ⎛ C ⎞
I= = ⋅ ⎜ 96 485 ⎟
t (30.0 min)(60 s ⋅ min ) ⎝
-1
mol e− ⎠
= 0.205 A

SM-388
12.111 The strategy for working this problem is to create a set of equations that
will add to the desired equilibrium reaction:
HBrO(aq) + H 2 O(l) → H 3 O + (aq) + BrO − (aq)

From Appendix 2B, we find

2 HBrO + 2 H + + 2 e − → Br2 + 2 H 2 O E° = +1.60 V

BrO − + H 2 O + 2 e − → Br − + 2 OH − E° = +0.76
On examination of these equations, it is clear that we will also need a half-
reaction that, when combined with the two above, will eliminate
Br2 and Br − . The obvious choice is

Br2 + 2 e − → 2 Br − E° = +1.09
We combine these by adding twice the reverse reaction to the other two:
2 HBrO + 2 H + + 2 e − → Br2 + 2 H 2 O
2(Br − + 2 OH − → BrO − + H 2 O + 2 e − )
Br2 + 2 e − → 2 Br −

2 HBrO + 2 H + + 4 OH − → 2 BrO − + 4 H 2 O

Caution: We must be careful here in adding the E° values—we have

created essentially a new half-reaction by summing these reactions, which
requires that we convert to ∆G values. Whenever one sums more than
two half-reactions, it is necessary to convert to the ∆G values using
∆G ° = nFE °, in order to work the problem:

2 HBrO + 2 H + + 2 e − → Br2 + 2 H 2 O
∆G° = −2(9.65 × 104 C ⋅ mol−1 )(+1.60 V) = −309 kJ ⋅ mol−1
BrO− + H 2 O + 2 e− → Br − + 2 OH −
∆G° = −2(9.65 × 104 C ⋅ mol−1 )(+0.76 V) = −147 kJ ⋅ mol−1
Br2 − + 2 e− → 2 Br −
∆G° = −2(9.65 × 104 C ⋅ mol−1 )(+1.09 V) = −210 kJ ⋅ mol−1
For 2 HBrO + 2 H + + 4 OH − → 2 BrO − + 4 H 2 O
∆G° = −309 kJ + 2(+147 kJ) − 210 kJ = −225 kJ ⋅ mol−1
We now see that we will need to eliminate OH − from the left side of the
equation. This can be done in one of two ways: we can use the Kw value

SM-389
for the autoprotolysis of water or, equivalently, we can use appropriate
half-reactions that sum to the autoprotolysis of water. The appropriate
half-reactions are
2 H 2 O → O2 + 4 H + + 4 e− E° = −1.23 V

O 2 + 2 H 2 O + 4 e − → 4 OH − E° = +0.40 V

These sum to give

4 H 2 O → 4 H + + 4 OH − E° = −0.83 V

This is a 4 e− reaction. Alternatively, one can write the 1 e− process that

will have the same E° value.
H 2 O → H + + OH − E° = −0.83 V

∆G° = −(1)(9.65 × 104 C ⋅ mol−1 )(−0.83 V) = +80 kJ ⋅ mol−1

2 HBrO + 2 H + + 4 OH − → 2 BrO − + 4 H 2 O ∆G° = −225 kJ ⋅ mol−1

4(H 2 O → H + + OH − ) 4(∆G° = +80 kJ ⋅ mol−1 )

2 HBrO → 2 H + + 2 BrO − ∆G° = −225 kJ ⋅ mol−1 + 4(+80 kJ ⋅ mol−1 )

= +95 kJ ⋅ mol−1

The desired reaction is half of this, for which ∆G° = +48 kJ ⋅ mol−1 .

Using ∆G° = − RT ln K , we obtain K = 4 × 10−9 , which is in reasonable

agreement for this type of calculation with the value of 2 × 10−9 given in
Table 10.1.

SM-390