Ionic mobility and transference number

1) Ionic mobility

dV
dV
v
v(m / s) u
uE
dl
dl
Under unit potential gradient: dV/dl = 1
V m-1: v = u , ionic mobility

2) Transference number
I = I + + IQ = Q+ + Q-

tj

Qj
Q

The fraction of the current transported by an

ion is its transference number or transport
number

t = t + + t- = 1

3) Relation between ionic mobility and

transference number

C-, Z-, u-; C+, Z+, u+;

For time t:

Q+ = A Eu+ t C+ Z+ F
Q = A Eut C Z F

Q = Q+ + Q = AtF E( u+C+ Z+ + u C Z)

C+ Z+ = C Z
Q = AtF C+ Z+ E( u+ + u)

u
t
u u

u
t
u u

Relation between transference

number and molar conductivity
I+ = AEu+Z+C+F

I = AEuZ C F

I = I++ I = AC+Z+F E(u++ u)

AC Z FE (u u )
G
V

l AC Z FE (u u ) l
G
A
V
A
C Z FE (u u ) C Z FE (u u )

V
E
l
C Z F (u u )


m
C

C
Z
F
(
u

)
m
C

For uni-univalent
electrolyte:

m zF (u u )

u F m u F

u F

t

(u u ) F

To measure m+ or m- , either t+ and t- or u+ and u- must be determined

Measurement of transference numbers

1) Hittorf method (1853)
Electrolysis of HCl solution

Anodic region

Bulk solution

cathodic region

When 4 Faraday pass through the electrolytic cell

4 Cl- -4e- 2 Cl2

3 mol H+
1 mol Cl-

4 H+ +4e- 2 H2
3 mol H+
1 mol Cl-

For anodic region:

Cresidual = Cinitial Creact + C transfer

Hittorfs
transference cell

Example
Pt electrode, FeCl3 solution:
In cathodic compartment:
Initial: FeCl3 4.00 mol dm-3
Final: FeCl3 3.150 mol dm-3
FeCl2 1.000 mol dm-3
Calculate the transference number of Fe3+

2) The moving-boundary method

MA, MA have an ion in common. The
boundary, rather difference in color,
refractivity, etc. is sharp.

In the steady state, the two ions

move with the same velocity.

When Q coulomb passes, the

boundary moves x, the crosssectional area of the tube is A:

xACZ+F = t+Q

Factors affecting transference number

a) temperature
Table : Transference number of K+ in KCl solution
at different concentration and temperature
0.01M
0.02M
T / oC KCl(0.0001 0.005 M
M)

15

0.4928

0.4926

0.4925

0.4924

25

0.4906

0.4903

0.4902

0.4901

35

0.4889

0.4887

0.4886

0.4885

b) Co-existed ions
electrolyte

KCl

KBr

KI

KNO3

t+

0.4902

0.4833

0.4884

0.5084

electrolyte

LiCl

NaCl

KCl

HCl

0.6711

0.6080

0.5098

0.1749

u
t
u u

Sample:
When A = 1.05 10-5 m2, C(HCl) = 10.0 mol m-3, I = 0.01 A
for 200 s, x was measured to be 0.17 m. Calculate t (H+)

Solution:
t+ = 0.17 m 1.05 10-5 m2 10.0 mol m-3 1
96500 C mol-1 / 0.01 A 200 S
= 0.82

Problems
1. Make comparison between Hittorfs method and moving boundary
method.
2. Why the limiting molar conductivity of weak electrolyte can not be
obtained by extrapolating of m ~ C1/2.

3. What experimental results back up the Kohlrauschs Law of

independent ionic mobilities

4. Summarize the effect of ionic nature on limiting molar conductivity

of ions