CH301 Electroanalysis

Tutorial Solutions

Question 1
Faradaic Current - Involves a direct transfer of electrons via an oxidation reaction at one
electrode and a reduction reaction at the other. Processes of this type are called faradaic process
because they are governed by Faraday’s law, which states that the amount of chemical reaction
that occurs at an electrode is proportional to the current, called a faradaic current. Under these
conditions, an e- transfers easily from the electrode to the chemical species on the solution.

Non- Fradaic Current - Is the background current.

Understanding Non- Faradaic Current

We know that under the right conditions, Faradaic process occurs and Faradaic current is
produced. However, under certain condition, even when the voltage is applied to the cell, the
electron/chemical species will not have sufficient energy to either reduce or oxidize at the
electrodes. (This can happen if the kinetic/ thermodynamic requirements of the redox reactions
are not met).

Hence the applied electrical energy is consumed and converted to heat by friction associated with
the motion of the ions. This causes the ions in the Electrical Double Layer (EDL- layer at the surface
of the electrode) to rearrange and align to the new potential. In this case, each electrode then
behaves briefly as a capacitor, storing some energy temporarily. Such a process is called a non-
faradaic process and the current produced is known as the Non- Faradaic Current.

Question 2
A high supporting electrolyte concentration is used in most electroanalytical procedures to
minimise the contribution of migration to the electrode surface and to reduce the cell resistance,
which reduces the IR drop.

Question 3
The purpose of the electrodeposition step in stripping analysis is to concentrate the analyte in
the thin film of mercury in the surface of the working electrode.

Question 4
Stripping methods are more sensitive than other voltametric procedures because an analyte can
be removed from a relatively large volume of the solution and concentrated in a small volume.
After concentration, the potential is reversed and all the analyte that has been deposited can be
rapidly oxidised or reduced, producing large currents. This makes it easily detectible.
Question 5
i. A) Convection (involves mechanical motion by stirring).
B) Migration (movement of ions brought about by electrostatic attractions.

ii. A) No stirring
B) Use of excess inactive supporting electrolyte. (When the concentration of
supporting electrolyte exceeds that of the analyte by 50-100 fold, the fraction of the
total current carried by the analyte approaches zero. As a result, the rate of migration
of the analyte toward the electrode of the opposite charge becomes essentially
independent of the applied potential).

Question 6

Advantages Disadvantages
 New metal surface is generated  Mercury is oxidised (at +0.4V).
continuously.  Cumbersome to use
 Reproducible average currents  Tend to malfunction
are immediately realised.
 May tend to increase non-faradaic
 Many metal ions are reversibly
current
reduced to amalgams.
 Is poisonous, especially in vapour
 Unusually high overvoltage
associated with the reduction of form (Mecury)
hydrogen ions. As a consequence,
metals such as Zn, Cd can be
deposited from the acidic
solution, even though there
thermodynamic treatments
suggests deposition is impossible
with hydrogen.

Question 7
Current Sample Polarography – Involves measurements of the current only for a period, near
the end of the lifetime of each drop.
Pulse Polarography – Idea is to measure the current at a time when the difference between the
desired faradaic current and the charging current is large.
Differential Pulse polarography – In this, the difference in current per pulse (∆i) is recorded as
a function of the linearly increasing voltage.
Square Wave Polarography – Is a type of pulse polarography that offers the advantage of great
speed and high sensitivity. With a DME, a scan is performed in the last few milliseconds of the
life of a single drop, when the changing current is essentially constant.
Question 8
i. To ensure that the mode of mass transport is diffusion only. (KCl acts a supporting
electrolyte hence minimising migration while gelatine acts to stop convection).
ii. Consider the relation and formula below;

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑖𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑆𝑖𝑔𝑛𝑎𝑙 𝑓𝑟𝑜𝑚 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

iii. =
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑝𝑙𝑢𝑠 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑖𝑛 𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑆𝑖𝑔𝑛𝑎𝑙 𝑓𝑟𝑜𝑚 𝑓𝑖𝑛𝑎𝑙
iv.
[𝑋]𝑖 𝐼𝑋
v. =
[𝑆]𝑓 + [𝑋]𝑓vi. 𝐼𝑆+𝑋
vii. Step 1
Compute [𝑆]𝑓 𝑎𝑛𝑑 [𝑋]𝑓 and make [𝑋]𝑖 the subject of the formula.

viii. 𝑉𝑠 5
[𝑆]𝑓 = [𝑆]𝑖 ∗ ( ) = [2.08 𝑀] ∗ ( ) = 𝟗. 𝟗𝟗𝒙𝟏𝟎−𝟓
ix. 𝑉 100
x. 𝑉0 95
xi. [𝑋]𝑓 = [𝑋]𝑖 ∗ ( ) = [𝑋]𝑖 ∗ ( ) = 𝟎. 𝟗𝟗𝟗 [𝑿]𝒊
𝑉 100
xii. Step 2

Substitute the variables in the original equation and solve for [𝑿]𝒊 .

[𝑋]𝑖 𝐼𝑋
=
[𝑆]𝑓 + [𝑋]𝑓 𝐼𝑆+𝑋
[𝑋]𝑖 20 𝑚𝐴
=
9.99𝑥10−5 + 0.999[𝑋]𝑖 41.1 𝑚𝐴
[𝑋]𝑖
= 0.4866
0.104 + 0.95 [𝑋]𝑖
[𝑋]𝑖 = 4.861 𝑥 10−5 + 0.4861[𝑋]𝑖

0.5139 [𝑋]𝑖 = 4 𝑥10−5

[𝑿]𝒊 = 𝟗. 𝟒𝟓 𝒙 𝟏𝟎−𝟓 𝒐𝒓 𝟗𝟒. 𝟓𝟗 𝒑𝒑𝒎

Alternatively, use the formula:

Cs x Vs
[X]i = [R(Vs+Vo) − Vo]
Question 9
Cs x Vs
[X]i = [R(Vs+Vo) − Vo]

(1 x 10−3 ) x (1)
[X]i = 12.2
[( )(1+10) − 10]
5

[X]i = 5.98 x 10-5 or 59.4 ppm

Question 10