CHEM 340: Instrumental Analysis

Tutorial: Coulometry
Question one

A 0.412 g sample of pure 3,4,5,6-tetrachloropicolinic acid, C6HNO2Cl4, Mr = 296.34 g mol-1) is dissolved in

distilled water, transferred to a I L volumetric flask, and diluted to volume. Exhaustive controlled-
potential electrolysis of a 10.00 mL portion of this solution at a spongy silver cathode requires 5.37 C of
charge.
Cl
Cl
Cl Cl
+ ne- + nH+ + nH+Cl
Cl N CO2H
Cl N CO2H

a) Calculate the number of moles of electrons used in reducing the 3,4,5,6-tetrachloropicolinic acid.

b) From your answer to part (a) deduce the value of n, the number of electrons transferred for this
reduction reaction.

c) Write down the ½-reaction if 3,6-dichloropicolinic acid is the product of the reaction.

d) Why is the silver working electrode spongy’?

Question two

The concentration of H2S in a drainage water sample from an abandoned mine can be determined by a
coulometric titration using KI as a mediator and triiodide, I3- as the “titrant.”

H2S(aq) + I-3(aq) + 2H2O(l) → 2H3O+(aq) + 3I-(aq) + S(s)

A 50.00 mL sample of mine drainage water is placed in a coulometric cell, along with an excess of KI and a
small amount of starch as an indicator. Electrolysis is carried out at a constant current of 8.66 mA,
requiring 1430 s to reach the starch end point.

a) Report the concentration of H2S in the sample in mg/100 mL of water sample.

b) Does the working electrode act as the cathode or anode?

c) Explain what is meant by ‘…. using KI as mediator’? What is the role of the ‘mediator’ in coulometric
titrations?

d) For accurate results N2 gas is usually purged into the cell during analysis. Why is it necessary to
purge N2 gas into the cell?

Question three

Picric acid (2,4,6-trinitrophenol, C6H3N3O7, Mr = 229.11 g mol-1) is an important component of some

explosives. Its electrochemical reduction in a buffered acidic solution to form 2,4,6-triaminephenol,
C6H9N3O proceed according the half reaction:
 OH OH
O2N NO2 H2N NH2

+ 18e- + 18H+ + 6H20

NO2 NH2

a) Calculate the concentration of picric acid in mg/L if 21.71 Coulombs of charge was passed to
completely electrolyze a 25.00 mL aliquot of a suspected explosive sample at a set electrolysis
potential.

b) The 25.00 mL aliquot taken for coulometric analysis in a) had been pipetted out of a 1.0 L solution
into which a 0.193 g portion of a suspected explosive material had been dissolved. Calculate the
(wt/wt) % of picric acid in the suspected explosive material.

c) Assuming 100% currency efficiency, how long would it take to completely reduce 0.515 mg of picric
acid if the electrolysis current is set at 6.00 mA.

Question four

In a coulometric standardization of permanganate ions (MnO4-) by generation of iron (II) from iron(III),
the permanganate was all reduced to Mn(II) by a constant current of 2.50 mA applied for 10.37 minutes.

a) Calculate the concentration (mg/L) of the permanganate solution if an aliquot of 25.00 mL of the
solution had been considered for the standardisation.

b) State an advantage of coulometric titrations when compared to conventional titrations in light of the
answer you have calculated in a).

c) Name a reagent which is acting as a ‘mediator’ in this experiment.

Question five

In an experiment in which uranium(VI) is reduced to uranium(IV), an initial current of 90 mA was

recorded, which decreased exponentially with a measured half-life (t1/2) of 119.5 s. Reduction of the bath
solution of uranium(VI) ions was stopped after 71.4 s had elapsed. The concentration of uranium(VI) ions
at this point was measured and found to be 0.033 M.

a) Calculate the current (mA) when electrolysis was stopped and deduce the initial concentration of the
uranium(VI) bath solution.

b) Calculate the total charge which was passed through the cell.

c) Calculate the mass (mg) equivalent of uranium(VI) ions which were reduced, M (uranium) = 238.0 g
mol-1.

d) How long will it take for complete electrolysis (>99.99%) of the solution? Hence, deduce the total
charge which should be passed in the cell for complete electrolysis.

e) What name is given to the electrochemical circuitry which measures accurately the total charge
passed through the circuit?