Electrochemistry Practice Problems

F = 96,500 coulombs • mole–1 R = 8.314 joules • mole–1 • K–1

⎛ nFE ⎞
0

0
∆G = − nFE = − RT ln K ⎜ ⎟
⎝ 2.3 RT ⎠
K = 10
RT ⎛ products ⎞ 0.059 products ⎞
E cell = E 0 − ln⎜ 0
⎟=E − log10 ⎛⎜ ⎟
nF ⎝ reactants ⎠ n ⎝ reactants ⎠

1. Calculate E° and K for the following reactions:

A) Mg (s) + Cl2 (g) ↔ Mg2+ + 2 Cl–

Mg(s) ↔ Mg2+ + 2e- +2.360 volts

Cl2(g) + 2e- ↔ 2Cl- +1.360 volts

Mg (s) + Cl2 (g) ↔ Mg2+ + 2 Cl- +3.720 volts

⎡ ( 2 )( 96 , 500 )( 3.72 ) ⎤
⎢ ( 2.3)(8.314 )( 298 ) ⎥
K = 10 ⎣ ⎦
= 10126

B) 5 MnO2 (s) + 4 H+ ↔ 3 Mn2+ + 2 MnO4– + 2H2O

5 MnO2 (s) + 10 H2O ↔ 5 MnO4– + 20 H+ + 15e- -1.692 volts

3 MnO4– + 24 H+ + 15e- ↔ 3 Mn2+ + 12H2O +1.507 volts

5 MnO2 (s) + 4 H+ ↔ 3 Mn2+ + 2 MnO4– + 2H2O -0.185 volts

⎡ (15)( 96,500 )( −0.185 ) ⎤

⎢ ( 2.3)(8.314 )( 298 ) ⎥
K = 10 ⎣ ⎦
= 10 −47

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 C) I2(s) + 5Br2(aq) + 6H2O ↔ 2IO3– + 10 Br– + 12H+

5Br2(aq) + 10e- ↔ 10 Br– +1.098 volts

I2(s) + 6H2O ↔ 2IO3– + 12H+ + 10e- -1.210 volts

I2(s) + 5Br2(aq) + 6H2O ↔ 2IO3– + 10 Br– + 12H+ -0.112 volts

⎡ (10 )( 96 ,500 )( −0.112 ) ⎤

⎢ ( 2.3)(8.314 )( 298 ) ⎥
K = 10 ⎣ ⎦
= 10 −19

2. Pt(s) ⏐ Fe3+(0.1 M), Fe2+(0.01M) ⏐⏐ Cr2O72-(0.01M), Cr3+(0.2M), H+(1.0M) ⏐Pt(s)

A. Write an oxidation half reaction for the left electrode and a reduction half reaction for the right
electrode.
Fe2+ ↔ Fe3+ + e- -0.771 volts

Cr2O72- + 14H+ + 6e- ↔ 2Cr3+ + 7H2O +1.36 volts

B. Write a balanced reaction for the cell reaction.

6Fe2+ + Cr2O72- + 14H+ + ↔ 6Fe3+ + 2Cr3+ + 7H2O

C. Calculate Eo for the cell. In which direction is the reaction spontaneous; left to right or right to
left?

Eo = -0.771 + 1.36 = +0.589 volts

D. Calculate the cell potential, taking into account the concentrations listed.

= E0 −
0 .059 ⎡
log ⎢
Fe [
3+ 6
Cr 3+ 2
][ ] ⎤
⎥
][ ][ ]
E cell
n [ 6
⎢⎣ Fe 2+ Cr2 O7 2− H +
14
⎥⎦

00.059 ⎡ [0.1]6 [0.2]2 ⎤

Ecell =E − log ⎢ 14 ⎥
= +0.524volts
⎣[0.01] [0.01][1] ⎦
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6
2
3, A) Draw a diagram of the glass pH sensing electrode. Label the parts of your drawing carefully.

B) Write an equation which describes voltage as a function of pH for this electrode.

Ecell = C − 0.059( pH )

C) Describe the cause of "alkaline error", and what effect it has on pH measurements.

When [H+] is very low and [Na+] is high, the electrode responds to Na+ and the apparent pH is lower than
the true pH. This is called alkaline error.

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4, A) Draw a diagram of the silver/silver chloride reference electrode. Label the parts of your drawing
carefully.

B) What is meant by a liquid junction potential?

Whenever dissimilar electrolyte solutions are in contact, a voltage difference called the junction
potential develops at their interface. This small voltage (usually a few millivolts) is found at each end
of a salt bridge connecting two half-cells. The junction potential puts a fundamental limitation on the
accuracy of direct potentiometric measurements, because we usually do not know the contribution of
the junction to the measured voltage. To see why the junction potential occurs, consider a solution of
NaCl in contact with distilled water. Na+ and Cl− ions begin to diffuse from the NaCl solution into the
water. However, Cl− ion has a greater mobility than Na+. That is, Cl− diffuses faster than Na+. As a
result, a region rich in Cl−, with excess negative charge, develops at the front. Behind it is a positively
charged region depleted of Cl−. The result is an electric potential difference at the junction of the NaCl
and H2O phases.

C) What salt shows the least tendency to cause a liquid junction potential, and why?

Potassium chloride, KCl, because the mobilities and diffusion coefficients of potassium ion and
chloride ion are nearly identical.

4
5. Using data from the table of reduction potentials, calculate the solubility product constant (Ksp) for
lead sulfate.

Pb(s) ↔ Pb2+ + 2e- +0.126 volts

-
PbSO4(s) +2e- ↔ Pb(s) + SO4 -0.355 volts

PbSO4(s) ↔ Pb2+ + SO42- -0.229 volts

0.059
Ecell = 0 = E 0 − log K sp
n
0.059
Ecell = 0 = −0.229 − log K sp
2
log K sp = −7.763

K sp ≈ 1.73 x10−8

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6. Calculate the cell potential for the following cell:

Pt (s) ⏐ H2 (1 atm) ⏐ acetate buffer (pH = 3.50) ⏐⏐ KCl (1.00 M) ⏐AgCl (s) ⏐ Ag (s)

H2(g) ↔ 2H+ + 2e- 0.000 volts

2AgCl(s) + 2e- ↔ 2Ag(s) + 2Cl- +0.222 volts

H2(g) + 2AgCl(s) ↔ 2H+ + 2Ag(s) + 2Cl- +0.222 volts

Ecell = 0.222 −
0.059
log
H + Cl − [ ][ ] 2 2

2 [H 2 ]

Ecell = 0.222 −
0.059
log
[
3.16 x10− 4 [1]2 ]2

2 [1]

Ecell = 0.222 + 0.206 = +0.428volts