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Finals Phychem

This document discusses two methods for determining transport number or transference number of an ion: 1) Hittorf's method which uses electrolysis in a three compartment cell to measure concentration changes and determine transport numbers, and 2) the moving boundary method which directly observes ion migration under an electric field using different electrolyte speeds. It also defines a coulometer as an instrument that determines the amount of a substance released in electrolysis by measuring the quantity of electricity used, and discusses controlled-potential and controlled-current coulometry and its applications including determination of total anti-oxidants and pollutants.

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327 views3 pages

Finals Phychem

This document discusses two methods for determining transport number or transference number of an ion: 1) Hittorf's method which uses electrolysis in a three compartment cell to measure concentration changes and determine transport numbers, and 2) the moving boundary method which directly observes ion migration under an electric field using different electrolyte speeds. It also defines a coulometer as an instrument that determines the amount of a substance released in electrolysis by measuring the quantity of electricity used, and discusses controlled-potential and controlled-current coulometry and its applications including determination of total anti-oxidants and pollutants.

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niezajanepatna
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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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Nieza Jane L.

Patna
BSChE -5

There are two methods for the determination of transport number or transference
number of an ion.
1. HITTORF’S METHOD
This method is based on the principle that the concentration changes occur around the
electrodes due to the migration of ions. In the Hittorf method, electrolysis is carried out
in a cell with three compartments: anode, central, and cathode. Measurement of the
concentration changes in the anode and cathode compartments determines the
transport numbers. The apparatus used consists of a U-shaped tube, connected on one
side to the “anode limb” and on the other side to the “cathode limb”. The anode is
made of silver and cathode is
made of platinum metal. The
U-tube, the anode limb and
cathode limb are filled with a
standard solution of Ag NO3.
The apparatus is connected in
series to a silver voltmeter. A
steady current of about 0.01
amperes is passed for about
two to three hours. After that,
the stopcocks S1 and S2 are
closed. The whole of the
solution from anode limb is
taken out through stopcock
S3 in a weighed flask. The
silver content of this solution
is determined by Volhard’s method. The weight of silver deposited in the silver
voltameter is also determined.

2. MOVING BOUNDARY METHOD


This method was developed by British physicists Oliver Lodge in 1886 and William Cecil
Dampier in 1893. It is based on the direct observation of the migration of ions under
the influence of an applied electric field. Let us consider Hydrochloric acid and the
transport numbers of H+ and CI ions present in HCI have to be determined. The
hydrochloric acid is called the principal or experimental electrolyte. Another electrolyte
containing a common ion (Cl-) called the indicator electrolyte is selected. The speed of
the cation of the indicator electrolyte is selected. The speed of the cation of the
indicator electrolyte should be less than that of the cation of the experimental
electrolyte. For example: CdCl2 can be selected as the indicator electrolyte as the speed
of Cd++ ion is less than that of H+ ions. A concentrated solution of CdCl2 is used, so
that HCI solution can float on it.

Solving for the transference number using moving boundary method:

What is a Coulometer?
A coulometer is an instrument of chemical analysis that determines the amount
of a substance released in electrolysis by measurement of the quantity of electricity
used. Coulometry is based on an exhaustive electrolysis of the analyte. By exhaustive
we mean that the analyte is completely oxidized or reduced at the working electrode or
that it reacts completely with a reagent generated at the working electrode. There are
two forms of coulometry: controlled-potential coulometry, in which we apply a constant
potential to the electrochemical cell, and controlled-current coulometry, in which we
pass a constant current through the electrochemical cell.

Coulometric methods of analysis are based on the measurement of quantity of


electrical charge that passes through a solution during an electrochemical reaction.
There is exhaustive electrolysis of the analyte: that is quantitative reduction or oxidation
of the analyte at the working electrode or the analyte reacts quantitatively with a
reagent generated at the working electrode. The principle is governed by Faraday’s
laws of electrolysis.
Application of coulometers include: determination of the total anti-oxidant
capacity of the anti-oxidants, determination of the total carbon in ferrous and non-
ferrous metals, determination of the picric acid, separation of the nickel and cobalt,
analysis of the radioactive materials, determination n-values of the organic compounds
and determination of the environment pollutants.

References:

https://latestcontents.com/methods-for-determination-of-transport-number/
http://rxpharmaworld.blogspot.com/2016/12/coulometry.html

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