Subject Electro-analytical Techniques

Submitted to Mam Bushra Shakoor

Submitted by Alishba Amjad

Clg Roll num 411

Uni Roll num 383810

Assignment topic Working,Principle and Instrumentation

Of Coulometry

Govt. Municipal Graduate College Jaranwala Road, Faisalabad.

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 TOPIC CONTENTS
Discovery
History
Defination
Example
Working Principle
Types of Coulometry
Instrumentation
Diagram
Applications
Limitations

Coulometry:
The name coulometry is derived from coulombs, named after Charles-Augustin
de Coulomb. He introduced the attraction and repulsion between electric charges leading to a
discovery of coulombs allowing for electrochemical research.

Discovery:
The coulometer was one of the instruments used by Michael Faraday in his early
work on electrolytic conduction. His first law states that the mass of a substance liberated at or
dissolved from an electrode is proportional to the quantity of electricity passed.
➢ Michael Faraday was born on 22 September 1791 in south London.

History:
The technique of coulometric titration was originally developed by Szebelledy and
Somogy (1) in 1938.

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Defination:
Coulometry is an electroanalytical technique used to measure the amount of
substance that is oxidized or reduced during an electrochemical reaction by measuring the total
electric charge passed through the system.
➢ The mass of a substance produced or consumed during an electrolytic reaction is directly
proportional to the amount of electricity that flows through the system.
➢ The amount of electricity passed is directly proportional to the amount of analyte,
according to Faraday's laws of electrolysis.

Faraday's law:
It's based on Faraday's law and is used to:
➢ Determine the quantity of a substance
➢ Measure charge with precision
➢ Analyze organic carbon, carbonate, and total carbon in sediments.

Working Principle:
The basic principle of coulometry is to measure the quantity Q of electricity
which can be regarded as the integral of current I, and time of passage t.
W = M X Q / 96,487n

Process:
Coulometry is an electroanalytic method where the determined compound is completely
converted into another form in a different oxidation state at the electrode.

Types of Coulometry:
Coulometry can be classified into two types:
➢ Controlled potential coulometry and
➢ Controlled current coulometry.

Controlled Potential Coulometry:

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 ➢ Controlled potential coulometry also known as potentiostatic coulometry.
➢ The electric potential is held constant during the reaction using a potentiostat.
➢ In constant potential coulometry, a constant electrical potential is applied to the solution,
and the amount of current required to produce a specific amount of product is measured.
➢ Constant potential coulometry is more commonly used than constant current coulometry,
as it allows for better control of the reaction conditions.

Controlled Current Coulometry:

➢ Controlled current coulometry also known as amperostatic coulometry and galvanostatic
coulometry.
➢ The current is kept constant using an amperostat.
➢ In constant current coulometry, a constant electrical current is passed through the
solution, and the time required to produce a specific amount of product is measured.

Example:
In the controlled-current coulometric analysis for Fe2+ using a Ce3+ mediator, the
oxidation of Fe2+ by Ce4+.

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Current efficiency:fficiency:
Coulometry requires 100% current efficiency, which means that all the current
must be used to oxidize or reduce the analyte.

Application:
➢ Karl Fischer reaction to determine water content.
➢ Determination of film thickness.
➢ Coulometry in Healthcare.
➢ Determination of Chloride Levels.
➢ Determination of Antioxidant Capacity in Human Blood.

Advantages:
Coulometry has many advantages over other analytical techniques.
➢ It is a highly accurate technique, as the amount of electricity required to complete the
reaction is directly proportional to the amount of analyte present.
➢ Coulometry is also a selective technique, as it can be used to selectively remove or
deposit one of the substances in a solution.
➢ This makes it ideal for the analysis of trace elements or impurities.
➢ Additionally, coulometry is a non-destructive technique, as the analyte can be recovered
after the analysis is complete.
Limitations:
However, there are also some limitations to coulometry.
➢ Coulometry requires a high level of skill and expertise to perform, as it is sensitive to
small variations in the reaction conditions.

Instrumentation of Coulometry:
The instrumentation for coulometry includes:
Three-electrode potentiostat: Used to set and control the potential in controlled-potential
coulometry
Working electrode: Usually made of platinum or liquid mercury
Reference electrode: A constant-potential electrode connected to the working electrode through
a high-impedance potentiometer

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Slide wire resistor: Connected to the auxiliary electrode to adjust the working electrode's
potential
Electronic integration: Used to monitor charge as a function of time in modern instruments.

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