Electrochemical methods

Presented to: Dr. Moazzma Akbar (Rph) Presented by: Zuhaa Javaid
M.Phil Pharmaceutical Chemistry DPH-FA20-039
Pharm.D (2020-2025)
Course Code: PHARM-516 6th semester
(Group A)
Objectives

1. Electrochemical technique
2. Principle OR Basic Concept
3. Electrochemical cell
4. Electrochemical methods
• Potentiometry
• Voltammetry / Polarography
• Coulometry
• Conductometry
5. Applications
Electrochemical techniques:

Techniques in analytical chemistry that study an analyte in an

electrochemical cell and measure the potential, charge, or
current to:

I. determine an analyte's concentration

II. characterize an analyte's chemical reactivity

Five Important Concepts:

To understand electrochemistry we need to appreciate five important and interrelated concepts:

(1) the electrode’s potential determines the analyte’s form at the electrode’s surface
(2) the concentration of analyte at the electrode’s surface may not be the same as its concentration in bulk
solution
(3) in addition to an oxidation–reduction reaction, the analyte may participate in other reactions
(4) current is a measure of the rate of the analyte’s oxidation or reduction
(5) we cannot simultaneously control current and potential.
Electrochemical cell:
Electrochemical measurements are made in an electrochemical cell consisting of two or more electrodes and the
electronic circuitry for controlling and measuring the current and the potential.
The simplest electrochemical cell uses:
1. Three types of electrodes
a. Working electrode or indicator electrode
b. Reference electrode
c. Auxiliary electrode
2. Potentiometer
3. Potentiostats
4. Galvanostats
Electrochemical methods:
Potentiometry:
• Measures the potential of an electrochemical cell.
• The potential is then related to the concentration of one or
more analytes.
• Selective sensitive to the ion of interest electrodes.
e.g. glass-membrane electrode in a pH meter.
The electromotive force of the complete cell is given by the
following equation:
E cell = E reference + E indicator + E junction
Where,
E reference is the electromotive force of the reference electrode
E indicator is electromotive force of indicator electrode
E junction is the electromotive force at the junction of the liquid.
Voltammetry / Polarography:
• Measures the current as a function of a fixed or variable
potential.
• In voltammetry, a time-dependent potential is applied to an
electrochemical cell and we measure the resulting current with a
3 electrode system as a function of that potential.
• There is a minimum potential required to initiate an oxidation or
reduction reaction at an electrode.
• The change in current with the varying voltage gives the plot and
is known as uoltammogram.
Coulometry:
Measures an unknown concentration of an analyte in solution by completely
converting the analyte from one oxidation state to another.

Forms of coulometry:
i. controlled-potential __ a constant potential is applied to the electrochemical
cell.
ii. controlled-current __ a constant current pass through the electrochemical cell.

During the electrolysis, the total charge Q passing through the electrochemical cell
is proportional to the absolute amount of analyte:
According to Faraday law:
Q = nFNA
n is the number of electrons per mole of analyte,
F is Faraday’s constant (96487 C mol–1),
NA is the moles of analyte
Conductometry:

Conductometry is the measurement of electrolytic conductivity to

monitor the progress of a chemical reaction.
Conductivity of an electrolyte solution is a measure of its ability to
conduct electricity.
It is measured by determining the resistance of the solution between
two flat or cylindrical electrodes separated by a fixed distance.
Example:
Conductometric titration in which the electrolytic conductivity of a
reaction mixture is continuously monitored as one reactant is added.
 Electrochemical Analysis
Project analysis slide 2
Obtain thermo-dynamic data of reaction Analytical chemistry .

Biological sources (Blood clotting)

Trace amount of metal & organic ions Applications
Bioelectrochemistry .

Generate unstable radical ions Metallurgy .

References

David G. Watson ___ Pharmaceutical Analysis

B.K Sharma ___Instrumental methods of Chemical analysis
David Harvey ___ Analytical Chemistry 2.0
Wiley ___ Electrochemical methods (Fundamental & Applications)
Thank You