Transport Number

Electrochemistry
(Transport Number, Hittorfs

Method, Moving Boundary
Method)
Dr.S.SURESH
Assistant Professor
Email:[email protected]
m
Transport number
During electrolysis, the current carried by the anions and
cations, and the amount carried by each is proportional to its
speed.
If u and v represents the speed of migration of the cation and
u fraction of current carried
anion, then
represents the
uv
by the cation, and
represent
the fraction
of current
v
u v
carried by the anion, and is called its transport
number or
Hittorfs number. It is denoted by symbols like t+ and t
Hence,
Transport number of cation (t+) =
Transport number of the cation (t+) =Current carried by the cation
Total current
u
u v
Transport number
Transport number of cation (t +)
u
t
u v
Similarly, the transport number of anion (t_ ) is given by
v
t-
u v
The fraction of the total current carried by the ions is

directly proportional to their velocities (Hittorfs rule).
t + t + = 1
Determination of Transport Number

The are two methods for determination of
transport number
Hittorfs Method
2. Moving Boundary Method
1.
Relative speed of ions during

electrolysis
Let us consider a electrolytic vessel containing two
metal
electrodes A and B. The vessel is divided into three
compartments AC, CD and DB, termed as anodic, central
and cathodic compartments respectively.

electrolysis
Before
electrolysis, the position of the solution is

represented as (1st) in the diagram. Now, suppose that on
applying potential, only two of the cations move towards
the cathode. This condition will be as represented in the
diagram in 2nd. There will be two unpaired cations in the
cathodic compartment. There will also be two unpaired
anions left in the anodic compartment. As unpaired ions
always get discharged at the respective electrodes (by the
gain or loss of electrons as the case may be), two cations
will be discharged at the cathode and two anions will be
discharged at the anode.

electrolysis
Now suppose that if two cations move towards
the
cathode and two anions will move towards the anode
in the same time as represented by 3rd. Now four
cations and four anions will be discharged at the
respective electrodes.
Finally, If cations and anions move with different
velocities so that two cations move towards the
cathode, and three anions move towards the anode. In
this case, five unpaired cations and five unpaired
anions (i.e the same number) will be discharged at the
respective electrodes as shown at 4th in the diagram.
Thus, Even if only cations are moving, the same
number of cations and anions will be discharged, at the
respective electrodes.
Hittorfs Rule
It is based on the fact that during electrolysis the loss in
amount of electrolyte around any electrode is
proportional to the speed of the ion moving away from it
loss around cathode speed of anion
v
loss around anode

speed of cation
u
Adding 1 to both sides we get
1 + loss around cathode 1 v
loss around anode
u
loss around anode loss around cathode
uv
loss around anode

u
Taking the reciprocal, we get
loss around anode

u
t
Total loss
uv
Hittorfs Method (Experimental

procedure)
Hittorfs
apparatus consists of a two limbed vessel,

connected by a narrow U-tube in the middle. Both limbs
as well as the U-tube are provided with stop-cocks at the
bottom for the withdrawal of the solution.
The two limbs are provided with Pt electrodes. To
determine the transport numbers of Ag+ in AgNO3 the
electrodes are either of Pt or pure Ag.
The apparatus is filled with a standard solution of
AgNO3 (usually 0.1N) and the cell is connected in series
with a source of direct current (like battery).
Hittorfs Method
Hittorfs
Method
After the electrolysis, the solutions from anodic as well as
central compartments are withdrawn separately by opening
stop-cocks at the bottom and analysed by titration with
standard ammoniuim thiocyanate (NH4CNS) solution.
The change in amount of electrolyte in the anode
compartment is thus obtained.
The amount of solution withdrawn from anode for analysis
should include all the solution, whose composition has
changed. This can be checked by withdrawing a further
portion of solution from the anode limb, and finding whether
it has the same composition as the original AgNO 3 solution
or not.
Thus, solution left after withdrawal from it must be of
starting (or initial) concentration.
The moving boundary

method
This
method is based on the

direct observation of migration
of ions in an electric field. The
conductivity cell, in this
method consists of a vertical
tube filled with cadmium
chloride and hydrochloric acid.
HCl is the principal electrolyte,
and CdCl2 serves as the
indicator electrolyte to enable
formation of a boundary.
The moving boundary method

The
concentrations of the solutions are so

adjusted that hydrochloric acid floats over
cadmium chloride, since HCl is lighter than
the cadmium chloride solution.
A sharp boundary appears between the two
solutions. The selection of the indicator
electrolyte is done carefully, so that its cation
do not move faster than the cation whose
transport number is to be determined, and it
should have the same anion as the principal
electrolyte; cadmium chloride fulfills both the
requirements.
The mobility of cadmium ions is less than that
of hydrogen ions and it has a common anion
with hydrochloric acid.
The moving boundary

method
The
anode is a stick of cadmium metal inserted at the

bottom, while the cathode at the top is a platinum foil.
When
a small current is made to flow through the

conductivity cell, the anions (chloride ions) move
towards the anode while, cations (hydrogen ions
followed by cadmium ions) move towards the cathode.
The
boundary separating the two solutions also moves

upwards and if the boundary moves through a distance
lcm (say, from AA to BB) then the volume of the liquid
that has moved up is lA cm2. Let the concentration of
the acid be C gram equivalents per litre
Then
the number of gram equivalents of H+ ions carried

towards the cathode = l A C
1000
Thank you

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Electrochemistry

(Transport Number, Hittorfs

The fraction of the total current carried by the ions is

Determination of Transport Number

Relative speed of ions during

Relative speed of ions during

electrolysis, the position of the solution is

Relative speed of ions during

loss around anode

loss around anode

loss around anode

Hittorfs Method (Experimental

apparatus consists of a two limbed vessel,

The moving boundary

method is based on the

The moving boundary method

concentrations of the solutions are so

The moving boundary

anode is a stick of cadmium metal inserted at the

a small current is made to flow through the

boundary separating the two solutions also moves

the number of gram equivalents of H+ ions carried

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