School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus

CHEM120R 2013

Electrochemistry - Tutorial

1.

For each of the following unbalanced equations, write the half-reactions for
oxidation and for reduction and balance the overall cell reactions.
(i)

Hg2+ + Cu Hg + Cu2+
Cu Cu2+ + 2e-

oxidation - reaction:

reduction - reaction: Hg2+ + 2e- Hg

Hg2+ + Cu Hg + Cu2+

overall:

(ii)

MnO2 + Cl- Mn2+ + Cl2

2Cl- Cl2 + 2e-

oxidation - reaction:

reduction - reaction: MnO2 + 2e- + 4H+ Mn2+ + 2H2O

overall:

(iii)

MnO2 + 2Cl- + 4H+ Mn2+ + Cl2 + 2H2O

Sn2+ + O2 Sn4+ + H2O

oxidation - reaction:

Sn2+ Sn4+ + 2e-

reduction - reaction:

O2 + 4H+ + 4e- 2H2O

overall:

2Sn2+ + O2 + 4H+ 2Sn4+ + 2H2O

x2

2. For each of the following cells :

(a)

Ag Ag+ Cd2+ Cd and

(i)

Write down the net reaction in the direction consistent with the way the
cell is written.
a) 2Ag + Cd2+ Cd + 2Ag+
b)Zn + Co2+ Co + Zn2+
1

(b)

Zn Zn2+ Co2+ Co

(ii)

Write the half-reactions for the anode and cathode processes.

anode:
a)

Ag Ag+ + e-

b)

Zn Zn2+ + 2e-

cathode:
a)

Cd2+ + 2e- Cd

b)

Co2+ + 2e- Co

c)

Find the standard cell potential at 25oC.

(a) Eocell = Eored - Eoox = -0.40 V 0.80 V = -1.20 V
(b) Eocell = Eored - Eoox = -0.28 V (- 0.76 V) = 0.48 V

d)

State whether the standard cell reaction actually occurs as given or

in the reverse direction.
(a)

reverse

(b)

foward

3. Calculate the potential associated with the following half-reaction when the
concentration of the cobalt(II) ion is 1.0 x 10-3 M.
Co(s) Co2+ + 2eEcell = -0.28 V - {(0.0592 V/2)log(1 10-3)} = -0.28 V + 0.0888 V = -0.191 V
4.

Consider the cell represented by the notation :

Zn(s) ZnCl2(aq) Cl2(g,1atm); Cl-(aq) C(s)
Calculate the Eo for the cell and calculate the E for the cell when the concentration
of the ZnCl2 is 0.15 M.
overall cell reaction: Zn + Cl2 2Cl- + Zn2+
Eocell = Eored - Eoox = 1.36 V (-0.76 V) = 2.12 V
2

Ecell = 2.12 V - {(0.0592 V/2)log(0.15)(0.30)2} = 2.12 V + 0.055 V = 2.175 V

5. Consider the electrochemical cell represented by:
Zn(s) Zn2+ Fe3+ Fe(s)
(i)

Write the ion-electron equations for the half-reactions and the overall cell
reaction.
Zn Zn2+ + 2eFe3+ + 3e- Fe
Zn + Fe3+ Zn2+ + Fe

(ii)

Determine the standard potential for the reaction.

Eo = -0.04 V - (-0.76 V) = 0.72 V
Determine E for the cell when the concentration of Fe3+ is 10.0 M and that of

(iii)

Zn2+ is 1.00 x 10-3 M.

Ecell = 0.72 V - {(0.0592 V/6)log(1 10-3)3/(10)2}
= 0.72 V + 0.109 V = 0.829 V

6.

Given the following half-cell reactions with their standard potentials:

(i)

Ag+(aq) + e- Ag(s)

Eo = +0.80 V

Cd2+(aq) + 2e- Cd(s)

Eo = -0.40 V

Write the cell notation, according to convention, for the galvanic cell
formed by coupling the above half-cells.
Cd Cd2+ Ag+ Ag

(ii)

Write the electrode reactions for this electrochemical cell

Cd Cd2+ + 2e- and Ag+ + e- Ag

(iii)

Write the overall cell reaction giving a balanced equation.

Cd + 2Ag+ Ag + Cd2+

(iv)

Calculate the e.m.f (Eocell.) of the cell.

Eo = 0.80 V (-0.40 V) = 1.20 V

(v)

Calculate the free energy change for the overall cell reaction.
3

Go = - nFEo = - 2(96485 C mol-1)(1.20 V) = - 2.32 x 105 J mol-1

(vi)

Calculate the e.m.f. of the cell (Ecell) at 25oC when [Ag+] = 0.100 M and
[Cd2+] = 0.010 M
Ecell = 1.20 V - {(0.0592 V/2)log(0.010)/(0.1)2} = 1.20 V

(vii)

Calculate the equilibrium constant, K, for the reaction at 25oC.

Go = - RTlnK,
lnK = (2.32 105 J mol-1)/(8.315 J mol-1 K-1)(298 K) = 93.63
K = 4.6 x 1040

7.

What is the potential of the cell involving this reaction?

Zn + 2Ag+ Zn2++ 2Ag
(Assume all substances in their standard states.)
Standard Reduction Potentials
Zn2+ + 2e Zn E0 = 0.76 V
Ag+ + e Ag E0 = +0.80 V
Eocell = Eored - Eoox = +0.80 V (-0.76) V = 1.56 V

8. Predict whether the following reaction will occur as written at 298 K, assuming
[Co2+] = 0.15 M and [Fe2+] = 0.68 M. Write the anode and cathode half reactions.
Co(s) + Fe2+ (aq) Co2+(aq) + Fe(s)
EoFe2+ /Fe = -0.44 V

EoCo2+/Co = -0.28 V

anode:
Co(s) Co2+ + 2ecathode:
4

Fe2+ + 2e- Fe(s)

The standard cell potential

Eocell = Eoreduction - Eooxidation = -0.44 V (-0.28 V) = -0.16 V
The reactant quotient, Q for the reaction is:
[Co2+] / [Fe2+] = (0.15/0.68) = 0.22.
E = Eo - 0.0592/n log Q = - 0.16 V (0.0592/2)log 0.22 = -0.14 V

The negative E value indicates that the reaction is not spontaneous as

written under the conditions described.

9.

Consider the following reaction at 25oC.

Sn(s) + 2Cu2+ (aq) Sn2+(aq) + 2Cu+(aq)
Eo (Sn2+/Sn) = -0.14 V

Eo (Cu2+/Cu+) = 0.15 V

(i) Write the half-reactions for the anode and cathode processes.
anode:
Sn(s) Sn2+ + 2ecathode:
2Cu2+ + 2e- 2Cu+(aq)
(ii) Find the standard cell potential at 25 oC.
Eocell = Eoreduction - Eooxidation = 0.15 V (-0.14 V) = 0.29 V
(iii) Calculate the equilibrium constant, K, for the reaction at 25 oC.
Go = - RTlnK, (determine Go)
5

lnK = (Go)/(8.315 J mol-1 K-1)(298 K)

K = 6 x 109

10.

Calculate the standard free energy change for the following reaction at 25 C.
2Au(s) + Ca2+ (aq,1M) 2Au3+(aq,1M) + Ca(s)
EoAu3+ /Au = 1.50 V

EoCa2+/Ca = -2.87 V

i) Write the half-reactions for the anode and cathode processes.

anode:
2Au(s) 2Au3+ + 6ecathode:
3Ca2+ + 6e- 3Ca
Find the standard cell potential at 25oC.

ii)

Eocell = Eoreduction - Eooxidation = -2.87 V (1.50 V) = -4.37 V

iii)

Calculate the free energy change for the overall cell reaction.
o

G = - nFEo = - 6(96485 J/V mol-1)(-4.37 V) = 2.53 106 J mol-1

= 2.53 103 kJ mol-1

11.

If the voltage of a Zn-H+ cell is 0.45 V at 25C when [Zn2+] =1.0 M and PH2 = 1.2
atm, what is the concentration of H+?

The cell reaction is

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
The standard emf is: Eocell = Eocathode - Eoanode = 0.00 V (-0.76 V) = +0.76 V
E = Eo (0.0592/n) logQ = 0.45
0.45 V = 0.76 V - 0.0592/2 log Q
log Q = (0.76 0.45)V (2/0.0592 V) = 10.47
6

Q = 3.0 x 1010
But Q = [Zn2+]PH2 / [H+]2 = (1.0)(1.2)/ [H+]2 = 3.0 x 1010
[H+]2 = (1.0 x 1.2/3.0 x 1010)
[H+] = 6.3 x 10-6 M

12.

A current of 0.452 A is passed through an electrolytic cell containing molten

CaCl2 for 1.50 h. Write the balanced half-cell reactions and calculate the amount
of product formed at the anode and the cathode.
Ca2+ + 2e- Ca (cathode reaction)
Q = I x t = (0.452 A) x (1.50h x 3600 s/ 1 h) x 1 C/1 A s-1 = 2.44 x 103 C
Moles of e- = 2.44 x 103 C x (1 mol e-/ 96 485 C) = 2.53 x 10-2 mol
Moles of Ca = 2.53 x 10-2 x (1mol Ca/2 mol e-) = 1.26 x 10-2 mol
Mass of Ca = 1.26 x 10-2 x (40.08 g mol-1 Ca/ 1mol e-) = 0.507 g
2Cl- (l) Cl2(g) + 2e- (anode reaction)
Moles of e- = 2.44 x 103 C x (1 mol e-/ 96 485 C) = 2.53 x 10-2 mol
Moles of Cl2 = 2.53 x 10-2 mol x (1mol Cl2/2 mol e-) = 1.26 x 10-2 mol
Mass of Cl2 = 1.26 x 10-2 mol x (70.90 g mol-1 Cl2 / 1mol e-) = 0.893 g

Additional Problems
Which is the direction of spontaneous change for the following reaction to the

1.

left or to the right?

2 Cr

6 Fe

?
2
2
7 H2O

Cr2O7 14 H 6 Fe

Answer
The two -reactions of interest are
Fe

e Fe

E0 = +0.77 V

2-

Cr2O7 14 H 6 e 2 Cr

7 H2O

E0 = +1.33 V

For the overall reaction equation to proceed to the right as written, the Fe3+ will be
reduced and the Cr3+ will be oxidised thus
0

2-

E E ( Fe /Fe ) - E (Cr2O7 /Cr )

0.77 V - 1.33 V
- 0.56 V

Therefore this reaction will not go spontaneously.

If the overall reaction proceeds to the left then

0

2-

E E (Cr2O7 /Cr

) - E ( Fe /Fe )

1.33 - 0.77 V
0.56 V

This means that the spontaneous reaction will be

2-

Cr2O7 14 H 6 Fe

2 Cr

6 Fe

7 H2O

i.e the dichromate ion will oxidise Fe2+ to Fe3+ and be itself reduced to Cr3+.

2.

Calculate the equilibrium constant for the reaction between MnO4 and Fe2+ in
acidic aqueous solution at 25 oC.

The reaction equation is

2+

MnO4 + 5Fe

+ 8H+ Mn2+ + 5Fe3+ + 4H2O

Answer
The number of electrons being transferred, n , equals 5.
If we look up the table of relevant Eo values we will find
Eo ( MnO4 /Mn2+) = 1.51 V
Eo (Fe3+/Fe2+) = 0.77 V

The manganese couple is

E red and the iron couple is E ox . Therefore

o

Eo = E red - E ox
= 1.51 0.77
= 0.74 V

Now we have all the information we need to calculate Kc.

ln Kc = nFE/RT
5 x 96485 C mol

8.315 J mol

0.74 V

298 K

Lets make sure we know whats happening with the units

A coloumb, C, the measurement of charge is
C = A x s
Amp x second

(from the equation: charge = current x time).

A volt, V, the measurement of Eo is

V = J s-1 A-1
from the equation: potential difference = energy/charge)

lnK C

5 x 96485 A s mol
8.315 J mol

0.74 J s

298 K

= 144
and KC = 3.7 1062

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