YAB 2063 Tutorial 1: Electroanalytical Chemistry

(1) What is the difference between:

(I) Amperometry and coulometry

Amperometry - measure current at constant cell potential
Coulometry - measure charge

(ii) Polarography and differential pulse polarography

Polarography - voltage is increased linearly with time
Differential pulsed polarography - voltage is increased in a pulsed manner over time

(iii) Polarography and hydrodynamic voltammetry

Polarography - voltammetry with dropping Hg electrode
Hydrodynamic voltammetry - linear sweep voltammety in which the solution is
stirred or the electrode is rotated

(iv) Residual and diffusion current

Residual current - current produced due to matrix
Diffusion current - current produced due to diffusion process

(2) A solution containing 75.0 mg of copper was electrolyzed at a constant current of

0.250 A, causing metallic copper to deposit on a platinum cathode. What was the
percentage of copper remaining in the solution after 15.0 min?

Q = it = 0.250 A x 15.0 min x 60 min/s = 225 C

Amount Cu = 225 C/96,485 C/eq = 2.33 x 10-3 eq
Electrode rxn is Cu2+ + 2e Cu(s)
Wt copper deposited = 2.33 x 10-3 eq x 63.5 g Cu/mol Cu x 1 mol Cu/2 eq Cu =
0.0740 g
Wt Cu remaining = (75.0 - 74.0) mg = 1.0 mg
% Cu remaining = 1.0 mg/75.0 mg x 100 = 1.3 %

(3) How many hours are required to add 0.0100 mol of electrons to a solution in a
coulometric experiment using a constant-current power supply delivering 100 mA?

Q = it ; n = Q/nF
Coulombs required = 96.485 C/mol e x 0.0100 mol e = 964.85 C
t = Q/i = 964.85 C/ 0.100 A = 9648.5 s = 9648.5/[60 s/min x 60 min/h] =
2.68 h

(4) The diffusion coefficient of O2 in dilute aqueous solution is 2.6 x 10-5 cm2/s. A
0.25 mM solution of O2 in an appropriate supporting electrolyte gives a
polarographic wave with a diffusion current of 5.8 µA. The dropping mercury
electrode constants are: m = 1.85 mg/s; t = 4.09 s. Calculate the value of n. To
which product, hydrogen peroxide or water, is O2 reduced under these conditions?

Ilkovic equation: id = 607 n D1/2 C m2/3 t1/6

5.8 = 607 n (2.6 x 10-5)1/2 0.25 (1.85)2/3 (4.09)1/6
n = 3.93 closest integer is 4
Product is water: O2 + 4H+ + 4e = 2H2O
Reduction to H2O2 is a 2e process: O2 + 2H+ + 2e = H2O2

(5) The Fe(III) in a 0.8202-g sample was determined by coulometric reduction to

Fe(II) at a platinum cathode. Calculate the percentage of Fe2(SO4)3 (MW, 399.88
g/mol) in the sample if 103.2775 C were required for the reduction.

One mol Fe2(SO4)3 consumes 2 mol electrons

mol Fe2(SO4)3 = 103.2775 C/(2 mol e/mol Fe2(SO4)3 x 96,485 C/mol e)
= 5.3520 x 10-4
Mass of Fe2(SO4)3 = 5.3520 x 10-4 x 399.88 g = 0.21401 g
% Fe2(SO4)3 = 0.21401/0.8202 x 100 = 26.09%