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.
nc I Q v t I I Q Q v v n

na I Q v 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 t u u

u t 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 m2V-1s-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 for different electrolytes. For example m

(KCl) 0.01499 S m mol

2

-1

(LiCl) 0.01150 S m 2 mol -1 m

(KNO3 ) 0.01450 S m mol
2 m -1

(LiNO3 ) 0.01101S m 2 mol -1 m

The difference in for pairs of salts having common ion is always approximately constant.

 (KCl) (LiCl) (KNO3 ) (LiNO3 ) 0.00349 S m 2 mol -1 m m m m (KCl) (KNO3 ) (LiCl) (LiNO3 ) 0.00049 S m 2 mol -1 m m m m

This behavior indicates that ions in an extremely dilute solution migrate independently. There is no interaction between different ions. Therefore

m,

m,

For example
At 25 (NaAc) = 91.010-4 Sm2mol1 m (HCl)=426.210-4 Sm2mol1 m (NaCl)=126.510-4 Sm2mol1 m What is the molar conductivity of HAc at 25?

Solution (NaAc) = (Na + ) + (Ac ) m m m

(HCl) = (H + ) + (Cl ) m m m

(NaCl) = (Na + ) + (Cl ) m m m

(HAc) = (H + ) + (Ac ) m m m
= (H + ) (Cl ) (Na + ) (Ac ) m m m m (Na + ) (Cl ) m m = (HCl) (NaAc) (NaCl) m m m

=(426.3 +91.0126.5)104 Sm2mol1 =390.7104 Sm2mol1