Electrolytic

Conductance

B. R. Thorat
Govt of Maharashtra

ismail Yusuf Arts, Science

and
Commerce College,
Mumbai

Resistance
Resistance refers to the opposition to the flow of current.
For a conductor of uniform cross section area (a) and
length(l); Resistance R,

a
l
R l and R
a

l
R
a

Where, is called resistivity or specific resistance.

Conductance
The reciprocal of the resistance is called conductance. It is denoted by C.
C = 1/R
Conductors allows electric current to pass through them. Examples: metals,
aqueous solution of acids, bases and salts etc.
Unit of conductance is ohm-1 or mho or Siemen(S)
Insulators do not allow the electric current to pass through them.
Examples are pure water, urea, sugar etc.

Specific Conductivity
It is the reciprocal of specific resistance of an electrolyte.
Specific conductance

But = R
K

a.R

K x Conductance
a

K = C x Cell constant
l/a is known as cell constant
Unit of specific conductance is ohm1cm1
SI Unit of specific conductance is Sm1 where S is Siemen

Equivalent conductance
Equivalent conductance is defined as the conductance of all the ions produced by
one gram-equivalent of an electrolyte in a given solution OR It is specific
conductance of one gram-equivalent of electrolyte.
(To understand the manning of equivalent
conductance, imagine a rectangular trough with
two opposite sides made of metallic conductor
(acting as electrodes) exactly 1 cm apart, If 1 cm3
(1 ml) solution containing 1 gram equivalent of
an electrolyte is places in this container is
measured. )

/\ eq = v x specific conductance of
1cm3 solution (k)

/\ eq= V
/\ eq = 1000/N
1 cc

1c

Where N = normality, V = volume of

solution used.
The unit of equivalent conductance is
ohm-1 cm-2 equi-1.

1 cm

Molar conductance
The molar conductance is defined as the conductance of all the ions produced
by ionization of 1 g mole of an electrolyte when present in V mL of solution.

OR It is the specific conductance of one mole of electrolyte.

It is denoted by.
Molar conductance m = k V
Where, V is the volume in ml containing 1 g mole of the electrolyte. If c is the
concentration of the solution in g mole per litre, then

m = k 1000/M
It units are ohm- cm2 mol-1.

Relaxation or asymmetric effect.

The force exerted by the ionic atmosphere on central ion is not uniform, it is
greater behind the ion and weaker in front of it. Such unbalanced forces
decrease the speed of ions and therefore molar conductance of the solution.

+
-

+
-

+
-

+
+

In presence of external electric field

Transport Number of ions

The current flow through the solution due to migration of ions of electrolyte.
If I is total current flowing through the solution, then contribution to it by
cations is I+ and that of anions is I-.
I = I+ + I-.

e.g. NaCl solution,

INaCl = INa+ + ICl-.
For NaCl + CuSO4 solution, Isolution = INa+ + ICl- +

ICu2+ +

ISO42-.

The fraction of the total current carried by the cation/anion isf+ = I+ / I

&
f- = I- / I
f+ and f- are the fraction of total current carries by cation and anion respectively.
The fraction of the current carries by ion from total current is also called as
transport number (t) of that ion.
Transport number of cation = t+ = f+ = I+ / I
t+ = I+ / Ii. i - total number of ions
Transport number of anion = t- = f- = I- / I
t- = I- / Ii. i - total number of ions

Dependence of transport number on the velocity of the ion

The transport number of the ion will be depends on its velocity in the solution.
Suppose d is the distance between two electrodes LMNO and ABCD in
between solution of electrolyte is placed. n+ & n- are the number of cations &
anions present in the solution between two electrodes. Z+ & Z- are the charges
on cations and anions, u+ & u- are the velocities of cations and anions
respectively.
Q

M
P

u+

B
A

E
n+ are cations

q+
Cathode

q-

Anode

u-

G
n- are anions
O

The total current (I) is the quantity of charges transferred per unit time (number of
ions deposited in unit time) which will be depends on the charge carried by individual
ion & total number of ions present in the solution.
As velocity of cation is u+ & distance covered by cation in one second is q+, it means that
all cations present at distance q+ from LMNO get deposited on the cathode in one
second.

Dependence of transport number on the velocity of the ion

Total charge transferred by cation = I+ = q+ / time in second
= [Total cation deposited on cathode in 1 sec.] [charge carried by cation]
= [Total cation deposited on cathode in 1 sec.] [Z+]
[Total cation deposited on cathode in 1 sec.] = [Total cations in between LMNO & PQRS]
= [u+/d] x [total number of cations present in total volume of solution]
= [u+ n+/d]
Put equation (2) in equation (1) asI+ = [u+ n+/d] [Z+] = [u+ n+ Z+/d]
Similarly for anions,
I- = [u- n-/d] [Z-] = [u- n- Z-/d]
The total current (I) passes through the solution = I = I+ + IFrom the equation (3), (4) & (5), I = [u+ n+ Z+/d] + [u- n- Z-/d]
The solution of any electrolyte is always electrically neutral, therefore[Total charges due to cation] = [Total charges due to anions]
Z+ n+ = Z- nFrom equation (6) & (7)- I = [u+ n+ Z+/d] + [u- n+ Z+/d]
= [n+ Z+ (u+ + u-)/d]
Therefore transport number of cation = t+ = I+ /I = u+ / (u+ + u-)
Similarly, for anions is- = t- = I- /I = u- / (u- + u+)
And
I- /I+ = t-/t+ = u-/u+
Conclusions:
1.
Transport number of ions are directly proportional to its velocity, t u.
2.
Transport number is also depends on the velocity of co-ions moves in the solution.
3.
If u- = u+, then t- = t+.
4.
t- + t+ = (u- + u+) / (u- + u+) = 1; sum of transport number is one.

(1)

(2)

(3)
(4)
(5)
(6)

(7)
(8)
(9)
(10)
(11)

Hittorf Rule
The total current can be measured directly, but I- or I+ can not be
determined directly from the experiment.

When current passage through the solution causes following changes Ions of the electrolytes are migrates towards opposite charge electrodes
and thus carry the current through the solution.
Ions get discharged on the opposite charged electrodes is called
electrolysis of the solution.
Due to the electrolysis and the migration of the ions in an unstirred
solution, a net change in concentration of the electrolyte around the
electrodes was determined experimentally. This change is related to the
transport number of the ions.
This can be explain by considering following two cases.
Case I: Cations and anions are moving with equal speed [u- = u+]
Case II: Cations and anions are moving with unequal speed (u+ 3u-)

Case I: Cations and anions are moving with equal speed [u- = u+]

The electrolyte cell can be divided into three components, the

cathode, the anode and middle compartment. In absence of external
electric field, the concentration of ions in each compartment is same.
Electrolysis of HCl solution

Anodic region

Bulk solution

Cathodic region

Case I: Cations and anions are moving with equal speed [u- = u+]

Let each compartment (cathode, anode and middle) contains five equivalents of the
electrolyte before electrolysis.
Suppose four faraday of electricity be passed through the solution, causes the
electrolysis of four equivalent of cations form cathode compartment and four
equivalents of anions form the anode compartment.

+
Anode
a

+ + + + +

+ + + + +

- - - - -

- - - - -

- - - - -

+ + + + +

+ + + + +

+ + + + +

- - - - -

- - - - -

- - - - -

+ + + + +

+ + + + +

+ + +

- - - - -

- - - - -

+ + + + +

+ + +

- - - - -

- - Anode compartment

+ + + + +

A'

middle compartment

-Cathode

- - B'

Cathode compartment

In absence of external electric field

By applying external electric field

Balancing the charges or concentration

After electrolysis

To balance ionic neutrality, ions are moving with equal speed and
hence will carry the same magnitude of the current [if each having
+/- one equivalent charge].
Therefore out of four faraday of current passed through the solution
of electrolyte, two faraday will be carried by the cation and two
faraday by the anions.

This will leads the migration of two cations from anode to middle
and from middle to cathode compartment. Similarly, two
equivalents of anions will get migrated from the cathode to the
middle and from middle to anode compartment.
At the end, the concentration of the middle compartment does not
change, while that of the anode and cathode compartment is
changed but remains same, because cations and anions are moving
with equal speed.

Case II: Cations and anions are moving with unequal speed (u+ = 3u-) (u+ u-)
Suppose each compartment (cathode, anode and middle) contains five equivalent of
electrolyte and speed of the cation is three times to the speed of anions i.e. u+ = 3u-.
Suppose four faraday of electricity be passed through the solution, causes the electrolysis
of four equivalent of cations form cathode compartment and four equivalents of anions
form the anode compartment. The ions are moving with unequal speed, therefore unequal
fraction of current carries by cations & anions i.e. I+ / I- = u+/u- = 3.

+
Anode
a

+ + + + +

+ + + + +

- - - - -

- - - - -

- - - - -

+ + + + +

+ + + + +

+ + + + +

- - - - -

- - - - -

- - - - -

+ + + + +

+ + + + +

+ +

- Anode compartment

A'

+ + + + +

- - - - -

- - - - -

+ + + + +

+ + + +

- - - - -

- - - -

middle compartment

B'

-Cathode

Cathode compartment

In absence of external electric field

By applying external electric field

Balancing the charges or concentration

After electrolysis

The velocity of cations is three times to the velocity of anions; therefore,

current carries by the cation will be three times to the current carries by the
anions.
Hence, out of four faradays of electricity passed through the solution,
three faraday of electricity was conducted by cations and only one fraction
was by the anions.
This will be results the migration of three equivalents of cations from anode
compartment to the middle compartment and from middle compartment to
cathode compartment while one equivalent of anion from cathode to middle
and from middle to anode compartment.
As a result, concentration of the middle compartment does not change,
but that of the cathode and anode compartments decreases unequally.
The decrease in concentration of cathode and anode compartment is equal to
the ratio of velocities of the cations and anions.
[Lose in equivalent of electrolyte in cathode compartment]
[Lose in equivalent of electrolyte in anode compartment]

u+
u-

1
3

From these two observations, Hittorfs rule states thatThe loss in equivalents of an electrolyte in a given compartment due to migration is
proportional to the velocity of the ion migrating away from the compartment.

The moving boundary method to determine transport number

Principle:
The method used to determine the
distance covered by a boundary,
generated and maintained between
two electrolyte solutions during
electrolysis.

From that distance covered in given

time interval, transport number of the
ion can be determined
MA, MA have an (M) ion in common. The
boundary, rather difference in color,
refractivity, etc. is sharp.

Construction:
It consist of vertical glass tube fitted with two metal electrodes, one at the top and
second at the bottom. The electrode in the bottom portion of the tube is of the same
metal as the cation of the electrolyte MA which is filled at the lower portion of the
tube. This electrode is worked as anode
Pt electrode
Source

Direction of movement of cation & boundary

MA'

MA Transport number is to be determined

A

C'

B' (boundary)

M'A

following electrolyte

Anode (M')

The electrode at the top is made up of platinum and act as cathode which is surrounded
by electrolyte MA. The rest portion of the tube is filled with electrolyte MA for which
the transport number is to be determined. The cation M+ has less velocity than M+
hence the solution MA is called as following electrolyte. The boundary BB between
two electrolytes solution MA and MA can be made visible by using dye or indicator.
The position of boundary can also be determined by using refractive index
measurement (two solutions have different refractive index).

Working:
Complete the circuit as shows in above diagram. As current passage, both M+ and M+ will
be moves in the upwards direction; with M+ following M+ due to lesser velocity. So
that boundary BB will move in same direction. For the given time interval, measure the
distance covered by the boundary BB during electrolysis.

Calculation:
If l is the distance covered by the boundary & A is cross section of the tube, then
volume swept by the boundary will beV = A x l cm3 (ml)
If c is the concentration of electrolyte in gm-equivalents per lit, then V ml of
solution will contain VC/1000 ml equivalents.
The quantity of the charge transported by the cations in ml of the solution.
I+ = FVC/1000;
where F stands for Faraday = 96500 coulombs.
If Q is the total quantity of electricity passed through solution, thent+ = FVC/1000Q = FVC/1000 I.t;
where I stands for total current
passed through solution & t is time in seconds.

Example:
Let us consider Hydrochloric acid and the transport numbers of H+ and Cl- ions
present in HCl 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.
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.

( c) Mechanism of hydrogen and hydroxyl

ions transfer

Grotthus mechanism (1805)

Factor affecting transport number of electrolytes:

Transport number of ions depends on1. Concentration.
2. Temperature.
3. Nature of the co-ion.
4. Size of the ion.
5. Complex formation.

1. Concentration:
Transport number of the ion increases with decreases in the concentration of the
electrolyte. The variation of transport number with concentration can be expressed
mathematically ast = t0 - Ac.
Where, t is the transport number at the concentration c, t0 is the transport number at infinite
dilution.

2. Temperature:
As temperature increases, transport number of all ions increases and reach to the limiting
value as 0.5.

As temperature increases, velocity of the ions increases and therefore transport number.
This behaviour is observed in both cations and anions.
At elevated temperature, both cations and anions are migrates with equal speed and shows
same contribution in the transport number (each by 0.5).

3. Nature of co-ion:
The transport number of the ions will be depends on the velocity with which the ion moves
in the solution and velocity of the co-ions.
At any given temperature, a given ion will move with same velocity in all of its salt
solutions, but velocity of the co-ions is different in each case.
But at same temperature, transport numbers of anions are different in different salt solutions
of the same cation.
4. Size of the ion:
Transport number of ion depends on its velocity in the solution with which it can
moves in solution. The velocity of the ion will be depends on size. As size of ion decreases,
velocity of it increases and vice-versa. Hence transport number of the ions of same group is
used to determine their size.
Sc < Ti < V < Cr < Mn < Fe < Co < Ni < Cu < Zn
Size decreases
Transport number increases
5. Complex formation:
Transport number of the ion will be also affected by the complex formation and in some cases, it will be
negative.
e.g. In concentrated solution of cadmium iodide, cadmium exist in anionic complex [CdI4]2-, hence it
migrates towards anode. But actually cadmium ion (Cd 2+) must migrates towards cathode. As the ions
are actually migrates toward opposite direction than expected, the transport number of the cadmium is
negative under such conditions.