Electrochemistry

Electrolysis

Transport numbers and mobilities

Galvanic cell
Transport numbers and mobilities
• The definition of transport number t is that
current carried by ion B divided by the sum of the
current of all the ions in solution, which is also
called the transference number of ion B.
I Q v nc
t    
I   I  Q  Q v  v n
I Q v na
t    
I   I  Q  Q v  v n
nc and na are the amount of substance of positive ions
migrate out from anodic region and that of negative ions
migrate out from cathodic region respectively.
Let 4F be passed through the cell; t+=3t-

Before electrolysis

On electrolysis

After electrolysis
 Mobility
• The transport numbers of ions depend on the
properties of ions and solvents, temperature,
concentration, electric field strength and the like.

• The mobility uB of an ion B is defined as its

velocity in the direction of an electric field E of
unit strength.
uB  vB / E
u u
t  t 
u  u u  u
mobilities of hydrogen and hydroxyl ions
• the mobility of hydrogen and hydroxyl ions in
aqueous solution is abnormally high.

• This is because both the H3O+ ion and hydroxyl

ion are able to transfer a proton to a neighboring
water molecule. This is explained by the fact that
the H+ and OH- ions need not migrate through a
protic solvent, but move through exchange of a
proton between neighboring solvent molecules.

• The unit of mobility is m2·V-1·s-1.

measurement of transport numbers by Hittorf method

The method of
Hittorf is based
on concentration
changes in the
anodic region
and cathodic
region in an
electrolytic cell,
caused by the
passage of
current through
the electrolyte.
measurement of transport number by the moving boundary method

Suppose the boundary moves a distant

x from AA’ to BB’ for the passage of Q
coulombs. All the ions, H+, passed
through the boundary AA’.
The amount of substances transported
is then Q/F, of which t+Q/F are carried
by the positive ion. If the volume
between the boundaries AA’ and BB’ is
V, and the concentration of HCl is c,
then
t Q / F  Vc
FVc
t 
Q
 The dependence of molar conductivity on the
concentration

Fro strong electrolytes, Kohlrausch observed

that m decreased with concentration according to
the expression

m  m  A c
conductivities and the concentrations of
electrolytes
 Law of the independent migration of ions

Kohlrausch discovered relations between the values

of  m for different electrolytes. For example

 (KCl)  0.01499 S  m  mol
m
2 -1

 m (LiCl)  0.01150 S  m 2  mol -1


 (KNO3 )  0.01450 S  m  mol
m
2 -1

 m (LiNO3 )  0.01101S  m 2  mol -1

The difference in for pairs of salts having common ion is

always approximately constant.
 m (KCl)   m (LiCl)   m (KNO3 )   m (LiNO3 )  0.00349 S  m 2  mol -1

 m (KCl)   m (KNO3 )   m (LiCl)   m (LiNO3 )  0.00049 S  m 2  mol -1

This behavior indicates that ions in an extremely dilute

solution migrate independently. There is no interaction
between different ions. Therefore

  

m

m,   
m,
For example

At 25℃，
 m (NaAc) = 91.0×10-4 S·m2·mol–1，
 m (HCl)=426.2×10-4 S·m2·mol–1，
 m (NaCl)=126.5×10-4 S·m2·mol–1，
What is the molar conductivity of HAc at 25℃?
Solution
 m (NaAc) = m (Na + ) + m (Ac  )
 m (HCl) = m (H + ) + m (Cl )
 m (NaCl) = m (Na + ) + m (Cl )
 m (HAc) = m (H + ) + m (Ac  )
= m (H + )   m (Cl )   m (Na + )   m (Ac )
  m (Na + )   m (Cl )
= m (HCl)   m (NaAc)   m (NaCl)
=(426.3 +91.0–126.5)×10–4 S·m2·mol–1
=390.7×10–4 S·m2·mol–1