CM4011 – Advanced Analytical Chemistry
Topic 3 – Electrolytic Methods
Question 1
(a) With reference to the reduction of protons (H+) at an electrode surface, explain the kinetic
polarization effect.
In kinetic polarization, the magnitude of the current is limited by the rate of the electrode reactions.
The affect is most pronounced for reactions that produce gaseous products, because the kinetics of
the gas reactions are involved. For example, the reduction of protons goes through an adsorption
and desorption step, which varies depending on the electrode surface. On Pt the
adsorption/desorption step is fast, while on Hg it is relatively slow.
2H+(aq) + 2e– ⇌ 2H.(ads)
H.(ads) + H.(ads) ⇌ H2(g) Rate determining step
(b) What are the reasons that supporting electrolyte is added to solutions for voltammetric
measurements?
(1) To improve the conductivity of the solution (reduce IR drop)
(2) To reduce the effects of migration.
(c) An electrochemical cell has a cell potential (Ecell) equal to –0.650 V. What applied potential is
needed to develop a current of –10.00 mA, when the cell resistance is 50 ohms?
Eapplied = Ecell + IR
= –0.65 V + (–0.010 A x 50 Ω)
= –1.15 V
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Question 2
Polarization observed in voltammetric measurements occurs via two main mechanisms;
concentration polarization and kinetic polarization. Describe the main features of each mechanism
and how they affect the appearance of the voltammograms.
Concentration polarization occurs via three main mechanisms that affect the transfer of the analyte
to the electrode surface. These are diffusion, migration and convection.
The effect of concentration polarization is to introduce an overpotential () that must be applied in
order to achieve the desired current.
Eapplied = Ecell + IR +
Diffusion - When there is a concentration difference between two regions of a solution, ions or
molecules move from the more concentrated region to the more dilute – leads to disappearance of
the concentration gradient.
The rate of diffusion and the current become correspondingly larger until the surface concentration
falls to zero and a maximum or limiting current is reached.
Migration is the primary cause of mass transfer in the bulk solution. Migration causes anions to be
attracted to the positive electrode and cations to the negative electrode. Migration can be minimized
by having a high concentration of an inert electrolyte, called a supporting electrolyte, present in
the cell.
Forced convection, such as stirring, tends to a decrease the thickness of the diffusion layer at the
surface of an electrode, and thus decreases concentration polarization. Natural convection which
results from temperature or density differences contributes to the transfer of molecules and ions.
In kinetic polarization, the magnitude of the current is limited by the rate of one or both of the
electrode reactions (between the reactants and electrodes). Called a heterogeneous rate constant.
Kinetic polarization is most pronounced for electrode reactions that produce gaseous products
because the kinetics of the gas reactions are involved.
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Question 3
(a) Sulfuric acid was reduced at negative potentials at a platinum electrode to form hydrogen gas.
The reaction that simultaneously occurred at the zinc anode was the oxidation of Zn metal to
produce zinc sulfate. If a constant current of 0.5 A was applied between the electrodes for 10
minutes, what mass of H2(g) and ZnSO4 would be produced?
[M (H2) = 2.02 g mol–1; M (ZnSO4) = 161.47 g mol–1]
Cathode: 2H+ + 2 e– ⇌ H2(g)
Anode: Zn ⇌ Zn2+ + 2 e–
Zn2+(aq) + SO42–(aq) ⇌ ZnSO4(aq)
The charge (Q) equals the current (A) × time (s);
Q = it = 0.5 A × (60 s × 10) = 300 C
NA = Q/nF
N(H2) = N(ZnSO4) = 300 C/(2 × 96485 C mol–1) = 1.555 × 10–3 mols
Mass (H2) = 1.555 × 10–3 mols × 2.02 g mol–1 = 3.14 × 10–3 g
Mass (ZnSO4) = 1.555 × 10–3 mols × 161.47 g mol–1 = 0.251 g
(b) If you are interested in making hydrogen gas from the electrolysis of acid solutions, why is it
preferable to use a platinum electrode surface rather than an alternative metallic surface?
The reason mainly relates to kinetic polarization. In kinetic polarization, the magnitude of the
current is limited by the rate of the electrode reactions (see question 1 above).
In addition, Pt is an inert metal and so is stable in the presence of strong acids.
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Question 4
The Karl Fischer (KF) coulometric titration is a very important method for determining the water
content of samples and utilises the following reactions.
ROH + SO2 + RN → (RNH)•SO3R
(RNH)•SO3R + 2 RN + I2 + H2O → (RNH)•SO4R + 2 (RNH)I
(a) Draw and label the main components of a KF titrator.
See lecture notes (a simple schematic diagram is fine).
(b) Explain how the iodine is generated and how it is related to the amount of water present.
In KF coulometric titrations, the I2 is generated electrochemically by the oxidation of iodide.
2 I− → I2 + 2e−
2 mol of electrons is produced for every mol of water that reacts with iodine. Therefore, 2 x 96485
coulombs (C) are produced for 1 mol of water.
(c) Describe how the end point of the reaction is measured and how the water content is thus
determined.
The end point of the “titration” is measured by a change in voltage across two indicator electrodes
due to the presence of free iodine.
As soon as free iodine is produced, “ionic conduction” occurs and a much lower voltage is needed
(50 – 100 mV) for the polarisation current.
With “ionic conduction”, the iodine takes up 2 electrons at the negatively charged pin and is thereby
reduced to 2 mols of iodide. The iodide, which is present in excess in the anolyte solution, then
releases the electron again at the positively charged platinum pin and is again oxidised to iodine.
(d) List the most common sources of error that can occur in KF coulometric titrations in
determining the correct water content.
There is a minimum charge that can be accurately measured by the coulometer, meaning that low
concentrations of water require higher masses of the analyte to achieve the greatest accuracy.
In some situations the charge measured during the oxidation of iodide is not necessarily selective
for water because other oxidisable species are present, or in some media the reaction between H2O
and I2 does not occur in a 1 : 1 ratio.
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Question 5
A Karl Fischer coulometric titration was performed on a liquid sample of 0.94933 g of the organic
solvent acetonitrile (CH3CN) to determine the trace water content. If the number of coulombs
measured during the coulometric titration was found to be 0.67364 C, what is the amount of water
in the CH3CN, measured in both, (i) parts per million (ppm) and, (ii) in mol L−1?
(Molecular weight H2O = 18.02 g mol−1; Molecular weight CH3CN = 41.05 g mol−1; Density
CH3CN = 0.786 g mL−1).
2 I− → I2 + 2e−
(RNH)•SO3R + 2 RN + I2 + H2O → (RNH)•SO4R + 2 (RNH)I
NA = Q/nF
NA(Iodine) = 0.67364 C / (2 × 96485 C mol−1) = 3.4909 × 10−6 mols
NA(H2O) = NA(Iodine) = 3.4909 × 10−6 mols
mass(H2O) = n x mw = 3.4909 × 10−6 mols × 18.02 g mol−1 = 6.2906 × 10−5 g = 62.906 g
(i) Concentration (in ppm)
62.906 g / 0.94933 g = 66.26 ppm
(ii) Concentration (in mol L−1)
0.94933g / 0.786 g mL−1 = 1.2078 mL = 1.2078 × 10−3 L
3.4909 × 10−6 mols / 1.2078 × 10−3 L = 2.89 × 10−3 mol L−1
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Question 6
Explain what a suppressor is used for in ion-chromatography measurements and why it is needed.
For anion chromatography the eluent ions are either carbonate/bicarbonate or hydroxide. In IC, the
analyte ions of interest travel through the column along with the eluent ions, which prevent the
analyte ions from irreversibly sticking to the column.
Because there is a much higher concentration of eluent ions compared to analyte ions, it is
important to remove the conductivity of the eluent to improve the detection limits and stability of
the detector. The purpose of the suppressor is thus to remove the conductivity of the eluent ions
before the analytes reach the conductivity detector.