Chapter 11

Electrochemistry & Electron Transfer

1. Define the oxidation and reduction processes.
Oxidation is the loss of electrons and reduction is the gain of electrons. Oxidation results in an increase in an
atom’s oxidation state and reduction results in a lowering (reduction) of the oxidation state.
3. Distinguish between donor and acceptor orbitals. Which orbital is on the oxidizing agent?
Transferred electrons move from the donor to the acceptor orbital in a redox reaction. The donor orbital is on
the reducing agent and the acceptor orbital is on the oxidizing agent.
5. What change in potential does an electron experience when it moves from a potential of +0.5 V to one at -0.3 V? Is
this a spontaneous process?
Change in potential = final potential – initial potential = -0.3 – 0.5 = -0.8 V. An electron’s free energy is greater
at the more positive potential, so moving from high potential to low potential is moving from low free energy to
high. ΔG > 0, so the process is not spontaneous.
7. The A/A1+ couple is 0.5 V above the B/B2+ couple. Which of the four species is the best oxidizing agent? Which is
the best reducing agent. Write the balanced chemical equation for the spontaneous process that occurs when the
two couples are connected in a galvanic cell.
1+
The A/A couple is at the higher potential, so it is at lower free energy. The direction of spontaneous electron
2+ 2+
flow is “downhill” in free energy, i.e., A → B . Consequently, A is the best reducing agent and B is the best
2+ 1+
oxidizing agent. The spontaneous reaction occurring when the couples are connected is 2A + B → 2A +
B.
9. The energy level diagrams for elements V and W are shown in the text. Assume that the redox orbital energies are
the dominant term in ΔG.
a) Write the standard reduction half-reactions for V, W, V2+ and W2+ and order them from most negative at top
to most positive at the bottom.
1- 2-
W + 2e U W highest energy redox orbital
1- 2-
V + 2e U V
2+ 1-
V + 2e U V
2+ 1-
W + 2e U W lowest energy redox orbital

b) Of the species, V2+, W2+, V, W, V2-, W2-, which is the best oxidizing agent? Which is the best reducing agent?
The best oxidizing agent is W2+, lowest unfilled orbital.
2-
The best reducing agent is W , highest occupied orbital.
c) Indicate whether each of the following electron transfer reactions would be extensive:
i) V + W2+ U V2+ + W Yes, electron transfer is to lower energy.

ii) V2- + W U V + W2- No, electron transfer is to higher energy.

iii) W2- + V2+ U W + V Yes

iv) W2+ + V2- U W + V Yes

v) V + W2- U V2- + W Yes

11. Determine the oxidation state of carbon in each of the following compounds:
a) CH4 (-4) b) CH2O (0) c) CO2 (+4) d) CH3F (-2) e) CH3OH (-2)
13. Indicate whether each of the following chemical conversions requires an oxididant, a reductant, or neither:
a) CO → CO2 Oxidizing agent required to take C from +2 to +4

b) BaSO4 → Ba Reducing agent required to take Ba from +2 to 0

c) Hg2Cl2 → HgCl2 Oxidizing agent required to take Hg from +1 to +2

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Electrochemistry & Electron Transfer
15. Determine the oxidant, the reductant, and the number of electrons transferred in each of the following reactions:
Oxidizing Reducing Electrons
Agent Agent Tansferred
a) 3C2H5OH + 2Cr2O72- + 16H1+ → 3CH3COOH + 4Cr3+ + 11H2O Cr2O72- C2H5OH 12

b) 4NH3 + 6NO → 5N2 + 6H2O NO NH3 12

c) 5Pb + 2MnO41- + 16H1+ → 5Pb2+ + 2Mn2+ + 8H2O MnO41- Pb 10

d) C8H16 + 12O2 → 8CO2 + 8H2O O2 C8H16 48

17. The following processes are all spontaneous:
a) 2Y+Z2+ → 2Y1++Z b) 3Y+W3+ → 3Y1++W c) X+Z2+ → X2++Z d) 2W+3X2+ → 2W3++3X
List the four redox couples that are involved in the above reactions in order of their standard reduction potentials
in a manner similar to Table 11.1, i.e., the most negative at the top.
The couple that is reduced is at the higher potential in each case, i.e., lower on the table. Reactions a and b
1+ 2+ 3+ 2+ 2+
indicate that Y /Y is above both Z /Z and W /W. Reactions c and d show that X /X is above Z /Z but
3+
below W /W. In order decreasing potential,
1+ 3+ 2+ 2+
(top) Y /Y < W /W < X /X < Z /Z (bottom)
2+
Y is the best reducing agent and Z is the best oxidizing agent.

19. What is the difference between an anode and a cathode?

The anode is the electrode at which oxidation occurs, while the cathode is the electrode at which reduction
occurs.
21. The standard reduction potentials for U3+ and In3+ are determined by measuring the voltage of the cell made by
connecting a standard Ni2+/Ni half-cell to the “Lo” terminal of a voltmeter and a standard U3+/U half-cell or
standard In3+/In half-cell to the “hi” terminal.
a) If the voltmeter reading was -1.43 V when the U3+/U half-cell was attached, what is the standard reduction
potential of uranium(III)? Write the spontaneous cell reaction between the U3+/U and the Ni2+/Ni half-cells.
o o
E Lo = E ANODE = E NI = -0.23 V (see Table 11.1)
o o o
E CELL = E Hi - E Lo = E CATHODE - E ANODE = -1.43 V
o o o
Solving for E Hi, E Hi = E CATHODE = E CELL + E Lo = -1.43 - 0.23 = -1.66 V = E U
The standard reduction potential of U(III) is -1.66 V
Since the cell potential is negative, the spontaneous half-reactions are the opposite of those used above.
Consequently, the nickel half-reaction occurs at the cathode not the anode and the uranium half-reaction
2+ 3+
occurs at the anode not the cathode. 2U(s) + 3Ni (aq) U 2 U (aq) + 3Ni(s)

b) If the voltmeter reading was -0.11 V when the In3+/In half-cell was attached, what is the standard reduction
potential of indium(III)? Write the spontaneous cell reaction between the In3+/In and the Ni2+/Ni half-cells.
o o o
E CELL = E Hi - E Lo = E CATHODE - E ANODE = -0.11 V
o o o
Solving for EHi, EHi = E CATHODE = E CELL + ELo = -0.11 - 0.23 = -0.34 V = E In
The standard reduction potential of In(III) is -0.34 V. The cell potential is negative, so the spontaneous half-
reactions are the opposite of those used above. Consequently, the nickel half-reaction occurs at the cathode
not the anode and the indium half-reaction occurs at the anode not the cathode:
2+ 3+
2 In(s) + 3 Ni (aq) U 2 In (aq) + 3 Ni(s)
c) An In3+/In half-cell and a U3+/U half-cell are connected as a galvanic cell. Which compartment is the anode,
and what is the cell voltage?
The cathode of a galvanic cell is always the half-reaction with the more positive standard reduction potential
(less negative in this case). Thus, we may write
3+ 1- o
Cathode: In (aq) + 3e U In(s) E = -0.34 V
3+ 1- o
Anode: U(s) U U (aq) + 3e E = -1.66 V
o o o
E CELL =E CATHODE - E ANODE = -0.34 -(-1.66) = +1.32 V

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 Electrochemistry & Electron Transfer
23. In the following pairs of metals, one is used to protect the other by galvanization. Indicate which metal would be
sacrificed.
a) Fe and Mg b) Ni and Cu c) Fe and Pb
Note that the metal with the more negative standard reduction potential is sacrificed.
25. Indicate whether each of the following cell reactions, run at standard conditions, would take place in a galvanic or
an electrolytic cell.
o
a) H2O(l) → H2(g) + 1/2 O2(g) E = -0.44 - 0.88 < 0 ⇒ electrolytic
o
b) Zn2+(aq) + 2 I1-(aq) → Zn(s) + I2(s) E = -0.76 - 0.54 < 0 ⇒ electrolytic
o
c) Cu2+(aq) + Sn(s) → Cu(s) + Sn2+(aq) E = +0.34 + 0.14 > 0 ⇒ galvanic
o
d) 2 Fe3+(aq) + Cu → 2 Fe2+(aq) + Cu2+(aq) E = +0.77 - 0.34 > 0 ⇒ galvanic
27. Write net equations or “no appreciable reaction” for the following:
a) An aluminum bar is placed in 1 M HCl.
1+ 3+
2Al(s) + 6H (aq) → 2Al (aq) + 3H2(g)

b) Aqueous bromine is added to a solution of Fe2+.

2+ 1- 3+
Br2(aq) + 2Fe (aq) → 2Br (aq) + 2Fe (aq)

c) A lead bar is placed in water.

Pb(s) + H2O(l) → no appreciable reaction

d) KBr is dissolved in an acidified solution of Cr2O72-.

1- 2- 1+ 3+
6Br (aq) + Cr2O7 (aq) +14H (aq) → 3Br2(aq) + 2Cr (aq) + 7H2O(l)

e) KF is dissolved in an aqueous bromine solution.

no appreciable reaction
f) Steel wool is placed into a solution of NiSO4.
2+ 2+
Fe(s) + Ni (aq) → Fe (aq) + Ni(s)

29. Lead acid batteries indicate that there should be no smoking during recharge because of the possibility of
dangerous gases being released. Suggest what gas might be generated in the recharge cycle of a lead acid battery.
(Hint: the gas reacts explosively with oxygen.) Write the half-reaction for its production.
1+
As the name suggests, lead acid batteries contain acid, H , and under an applied voltage, the following reaction
1+ 1-
can be initiated, 2H + 2e → H2(g). Hydrogen can react explosively with oxygen in the presence of a fire.

31. The following redox couples are combined to make galvanic cells; in each case, indicate which couple is the anode
and which is the cathode:
The couple with the more negative standard reduction potential is the anode.
Anode Cathode
1- 1-
a) Br2/Br and Cl2/Cl Br2/Br1- Cl2/Cl1-
2+ 1+
b) Sn /Sn and Ag /Ag Sn2+/Sn Ag1+/Ag
1- 2+ 2+
c) I2/I and Ni /Ni Ni /Ni I2/I1-
2+ 3+ 2+
d) Zn /Zn and Fe /Fe Zn2+/Zn Fe3+/Fe2+
o
33. Write the cell reaction and determine E for the galvanic cells constructed from the following redox couples:
1- 1- o
a) Br2(l)/Br (aq) and Cl2(g)/Cl (aq) Cl2(g) + 2Br1-(aq) → 2Cl1-(aq) + Br2(l) E = 0.27 V
2+ 1+ o
b) Sn (aq)/Sn(s) and Ag (aq)/Ag(s) Sn(s) + 2Ag1+(aq) → Sn2+(aq) + 2Ag(s) E = 0.94 V
1- 2+ o
c) I2(s)/I (aq) and Ni (aq)/Ni(s) Ni(s) + I2(s) → Ni2+(aq) + 2I1-(aq) E = 0.77 V
2+ 3+ 2+ o
d) Zn (aq)/Zn(s) and Fe (aq)/Fe (aq) Zn(s) + 2Fe3+(aq) → Zn2+(aq) + 2Fe2+(aq) E = 1.53 V

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Electrochemistry & Electron Transfer
35. Determine how many moles of electrons and how many coulombs are must be transferred for each of the following
processes:
a) reduction of 1.3 mol Al3+ to Al
3+ 1-
The half-reaction is Al + 3e → Al, so 3 moles of electrons are required for each mole of Al.
3 mol e1- 1- 5
1.3 mol Al3+ × = 3.9 mol e1- ; 3.9 mol e x 96,500 C/mol = 3.8 x 10 C
1 mol Al3+

b) oxidation of 3.4 mol Br1- to Br2

1- 1- 1- 1-
The half-reaction is 2Br → Br2 + 2e , so 2 mol e are transferred for each mole of Br ions.
2 mol e1- 1- 5
3.4 mol Br1- × = 6.8 mol e1- ; 6.8 mol e x 96,500 C/mol = 6.6 x 10 C
1 mol Br1-

c) oxidize 2.8 g of copper to Cu2+

2+ 1- 1-
The half-reaction is Cu → Cu + 2e , so 2 mol e are transferred for each mole of copper.
1 mol Cu 2 mol e1- 1- 3
2.8 g Cu2+ × × = 0.088 mol e1- ; 0.088 mol e x 96,500 C/mol = 8.5 x 10 C
63.5 g Cu 1 mol Cu

37. A standard galvanic cell, constructed with Ag1+/Ag and Zn2+/Zn couples, is discharged until 3.3 g of Ag forms.
a) What are the overall cell reaction and the standard cell potential?
1+ 2+
2Ag + Zn → 2Ag + Zn
o o o o 1+ o 2+
E = E cathode - E anode = E (Ag /Ag) - E (Zn /Zn) = +0.80 – (-0.76) = 1.56 V

b) How many moles of electrons flow through the circuit during the discharge?
1+ 1+ 1- 1-
The Ag /Ag half-reaction is Ag + 1e → Ag, so 1 mol e are transferred for each mole of silver(I) ions that
are reduced.
1 mol Ag 1 mol e1-
3.3 g Ag × × = 0.031 mol e1-
108 g Ag 1 mol Ag

c) How many coulombs of charge flow through the circuit?

1- 3
0.031 mol e x 96,500C/mol = 2.9 x 10 C
(Note that the calculator answer to part a (0.03556) not 0.031 was used in the calculation.
d) What is the maximum work that could be done by the electrons during the discharge?
The maximum work is –ΔG, which can be determined with Equation 11.3:
o 96,500 C 1.56 J 1 kJ
w = -ΔG = nFE = 0.031 mol e1- × × × = 4.6 kJ
mol e1- C 1000 J
(See note to part c.)

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