ELECTROCHEMISTRY

F.G. QUEZON
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: MARCH 13, 2013
INSTRUCTORS NAME: IRINA DIANE CASTANOS

CALCULATIONS
Cell Notation

Anode Reaction

Cathode
Reaction
Cu2+ + 2e Cu

Cell Reaction

Cu|Cu2+ (0.01M) ||
Cu2+ (0.1M)| Cu

CuCu2+ + 2e

Zn|Zn2+ (0.1M) ||
[Cu(NH3)4] 2+
(0.033M),
NH3(0.533M)| Cu

ZnZn2+ + 2e

[Cu(NH3)4] 2+ + 2e
4NH3 + Cu

[Cu(NH3)4] 2+ + Zn
4NH3 + Cu +
Zn2+

Zn|Zn2+ (0.1M) ||
OH- (0.7M),
Cu(OH)2| Cu

ZnZn2+ + 2e

Cu(OH)2 + 2e Cu
+ 2OH-

Cu(OH)2 + Zn
Zn2+ + Cu + 2OH-

Cu|Cu2+ (0.1M) ||
Cl- (0.1M), Cl2| C

CuCu2+ + 2e

Cl2 + 2e 2Cl-

Cl2 +CuCu2+
+2Cl-

Cu|Cu2+ (0.1M) ||
Br- (0.1M), Br2| C

CuCu2+ + 2e

Br2 + 2e 2Br-

Br2 +CuCu2+
+2Br-

Cu|Cu2+ (0.1M) || I(0.1M), I2| C

CuCu2+ + 2e

I2 + 2e 2I-

I2 +CuCu2+ +2I-

Cu|Cu2+ (0.1M) ||
Zn2+ (0.1M)| Zn

CuCu2+ + 2e

Zn2+ + 2e Zn

Zn2+ + Cu Zn +
Cu2+

Cu|Cu2+ (0.1M) ||
Fe2+ (0.1M), Fe3+
(0.1M)| C

CuCu2+ + 2e

Fe3+ + e Fe2+

Fe3+ + Cu Cu2+
+Fe2+

Cu2+

CuCu2+
Cu

Determination of X2 concentration from electrolysis:

2X- X2 + 2e
=
[X 2] = It +
1 mol X2
[Cl 2] =
F
(2 mol e) V
[Br 2] = (0.15)(60) +
1 mol Br2
=

96500
(2 mol e) 0.03
0.0016 M
(0.0342)(60) +
1 mol Cl2
96500
(2 mol e) 0.03
0.00035 M

Determination of Eocell
Eocell = Ecell + 2.303RT logQ
nF
Cu|Cu2+ (0.01M) || Cu2+ (0.1M)| Cu
Eocell = 0.02 + 2.303(8.314)(298)
log10
2(96500)
=0.03
Zn|Zn2+ (0.1M) || [Cu(NH3)4] 2+
(0.033M), NH3(0.533M)| Cu
Eocell = 0.5 + 2.303(8.314)(298)
log3.03
2(96500)
=0.51
Zn|Zn2+ (0.1M) || OH- (0.7M), Cu(OH)2|
Cu
Eocell = 0.53 + 2.303(8.314)(298)
log0.049
2(96500)
=0.49

Cu|Cu2+ (0.1M) || Br- (0.1M), Br2| C

Eocell = 0.60 + 2.303(8.314)(298)
log0.625
2(96500)
=0.59
Cu|Cu2+ (0.1M) || I- (0.1M), I2| C
Eocell = 0.84 + 2.303(8.314)(298)
log2.86
2(96500)
=0.85
Cu|Cu2+ (0.1M) ||Zn2+ (0.1M)| Zn
Eocell = 1.04 + 2.303(8.314)(298) log1
2(96500)
=1.04
Cu|Cu2+ (0.1M) || Fe2+ (0.1M), Fe3+
(0.1M)| C
Eocell = -0.39 + 2.303(8.314)(298)
log0.1
2(96500)
=0.85

Determination of standard reduction potentials

Eocell = Eocathode - Eoanode
Cu|Cu2+ (0.01M) || Cu2+ (0.1M)| Cu
Eocathode = 0.03 + 0.34
= 0.37
%error = 8.82%
Zn|Zn2+ (0.1M) || [Cu(NH3)4] 2+
(0.033M), NH3(0.533M)| Cu
Eocathode = 0.51 + -0.763
= -0.253
%error = 533%
Zn|Zn2+ (0.1M) || OH- (0.7M), Cu(OH)2|
Cu
Eocathode = 0.49 + -0.763
= -0.27
%error = 9.43%
Cu|Cu2+ (0.1M) || Br- (0.1M), Br2| C

Eocathode = 0.59 + 0.34

= 0.93
%error = 12.68%

Cu|Cu2+ (0.1M) || I- (0.1M), I2| C

Eocathode = 0.85 + 0.34
= 1.19
%error = 122%
Cu|Cu2+ (0.1M) ||Zn2+ (0.1M)| Zn
Eoanode = -0.34 1.04
= -0.7
%error = 8.26%

Cu|Cu2+ (0.1M) || Fe2+ (0.1M), Fe3+

(0.1M)| C
Eocathode = 0.41 + 0.34

= 0.75
%error = 2.72%

Application of Electrochemical Cell

G = - nFEcell = -RTln Keq
Keq = e

(nFEcell/ RT)

[Cu(NH3)4]2+:

Cu(OH)2:

Kf = e[(2)(96485)(0.46)/ (8.314)(298)]

K=e

= 3.63 x1015

Ksp = 1/K = 1/1.72 x1016 = 5.80 x10-17

%error = 7160%

% error = 263 536 %

[(2)(96485)(0.46)/ (8.314)(298)]

= 1.72 x1016

ANSWERS TO QUESTIONS
1.

a.
Anode, positive terminal
b.
OH- is formed in the cathode part of the electrolytic cell, the net ionic
equation is:
2H2O + 2e- H2 + 2OHc.
60s x 0.001C x 1 mol e x 2 mol Cl- = 6.21x 10-7
1s
96500C
2 mol e
-7
6.21 X 10 mol Cl used. The obtained quantity is very small compared to 1M.
2.
a. Because it is a redox reaction involving the transfer of electrons, thus it can
conduct electricity.
3.

a.

i. Ecell = 1.51 1.36

= 0.15 V
Ecell = 0.15 (8.314)(298) ln 1x1010
10(96500)
ii. G = - (10)(96500)(0.0909)
= -87,718.5 J/mol
i. Greater
ii. Lesser

= 0.0909V

iii. Greater

c. 16H+ + 2MnO4- + 10Cl- 5Cl2 +2Mn2+ + 8H2O

Ecell = 0.15 (8.314)(298) ln 1x10-6
10(96500)
=0.48V
REFERENCES
Petrucci R. et al. General Chemistry: Principles and Modern Applications, 10th ed.;
Pearson Education South Asia: Singapore, 2010.
Institute of Chemistry. General Chemistry II Laboratory Manual.

Silberberg, M.S. Principles of General Chemisty, 2 ed.; McGraw-Hill, 2010.