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Amina.S Ii MSC Chemistry University College TVM

Coulometric titration methods involve quantitatively converting a sample to a different oxidation state by measuring the electric charge required. They are highly accurate like conventional methods but do not require standard solutions. There are two types: potentiostatic uses constant electrode potential while coulometric titrimetry uses constant current. It is based on Faraday's law where the extent of reaction is directly proportional to current. Various reagents can be generated and used for precipitation, complex formation, neutralization or redox titrations of organic and inorganic compounds.

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53 views18 pages

Amina.S Ii MSC Chemistry University College TVM

Coulometric titration methods involve quantitatively converting a sample to a different oxidation state by measuring the electric charge required. They are highly accurate like conventional methods but do not require standard solutions. There are two types: potentiostatic uses constant electrode potential while coulometric titrimetry uses constant current. It is based on Faraday's law where the extent of reaction is directly proportional to current. Various reagents can be generated and used for precipitation, complex formation, neutralization or redox titrations of organic and inorganic compounds.

Uploaded by

Saudath Amina
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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AMINA.

S
II Msc CHEMISTRY
UNIVERSITY
COLLEGE TVM.
INTRODUCTION

Coulometric methods are performed by


measuring the quantity of electric change
required to convert a sample of analyte
quantitatively to a different oxidation state.
These method do not need burette and the
preparation and storage of standard solution.The
electrons become the primary standard and
titrant.
. Coulometric methods are as accurate as
conventional gravimetry and volumetric
procedure and are readily automated
PRINCIPLE
It is an application of Faraday first law of
electrolysis.
States that the extend of chemical reaction at an
electrode is directly proportional to the quantity
of electricity passing through the electrode.
For each mol of chemical change at an electrode
(96485n) coulombs are required.
TYPES OF COULOMETRIC
METHODS

Two types.

Potentiostatic coulometry.

Amperostatic coulometry or Coulometric


titrimetry.
POTENTIOSTATIC COULOMETRY
The potential of working electrode is maintained
at a constant level relative to reference electrode.
The electrolysis current is recorded as a function
of time.
Analysis is completed by integrating the current
time curve
The current generally decreases exponentially
with time and reaches to 0
COULOMETRIC TITRIMETRY
The analysis is based on the combing capacity of
the analyte with the standard reagent.
o Here the reagent is electron and the standard
solution is a constant current of known
magnitude.
Electrons are added to the analyte until an end
point is reached.
The amount of analyte is determined from the
magnitude of the current and the time required
to complete the titration.
REQUIREMENTS

A fundamental requirement for all coulometric


method is 100% current efficiency.

100% current effiency can be achieved without


direct participation of the analyte in electron
transfer of an electrode.
COULOMETRIC TITRATIONS

It is carried out with a constant current source


called an amperostat.

The 100% current efficiency w.r.t. the analyte can


be maintained only by having a large excess an
auxiliary reagent ,oxidised or reduced at the
electrode to give a product that react with the
analyte.
INSTRUMENTATION
CELLS FOR COULOMETRIC
TITRATIONS
ERRORS IN COULOMETRIC
TITRATION

Variation in current during electrolysis.


Departure of the process from 100% current
efficiency.
Error in the measurement of current.

Error in the measurement of time.

Titration error due to the difference between the


equivalence point and the end point.
ADVANTAGES
Standard solutions are not required , the titrant
is produced.
Very small quantities of reagent may be
determined.
Reagents difficult to store and standardise may
be used.
The titration are extremely precise.

A single constant current source provides


reagent for precipitation,complex formation
neutralization or oxidation/reduction titration.
APPLICATIONS OF
COULOMETRIC
TITRATIONS
NEUTRALISATION TITRATIONS

Both weak and strong acids can be titrated with


a high degree of accuracy using hydroxide ion.

The generation of hydroxide ion at a platinum


cathod within the solution provides the most
convenient method.

Both potentiometric and indicator end point can


be used for these titration.
PRECIPITATION AND COMPLEX
FORMATION TITRATION

o A large number of coulometric


precipitation titration are based upon
anodically generated silver ion.
C.N Reilley and W.W Proterfied have
applied coulometric method to the
titration of several cations by means of
ethylenediamine-tetra acetate ion
generated at mercury cathod.
OXIDATION REDUCTION
TITRATION

A variety of reagents can be generated


coulometrically and the analysis to which
have been applied.

The electrogenerated bromine has


provided to be particularly useful among
the oxidising agents and form the basis
for a host of methods.
ORGANIC COMPOUNDS

The controlled potential coulometric


titration procedure also offers possibilities
for the electrolytic determination of
organic compound

Eg,trichloroacetic acid and picric acid are


quantitatively reduced at a mercury
cathod whose potential is suitably
controlled.
REFERENCE

Electrochemistry - K Sharma-5th edition-


1998-GEOL Publishing House
Analytical Chemistry an introduction-

Douglus A Skoog,Donald M West,F James


Holler-6th edition -1994-Saunders College
Publishing.
Instrumental Methods of Chemical Analysis-

Gurdeep R Chatwal,Sham K.Anand-5th


edition-2002-Himalaya Publishing House.

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