Chapter 4

ELECTROCHEMISTRY
Lecture/Lession Plan -5

ELECTROCHEMISTRY

4.0.1 Determination of valency of an ion which have tendency to reduced

to pure metal.
Let us consider a metal (M) and its salt (MA) having M+n oxidation state. Now the metal ion can
be reduced to metal or the metal can be oxidised to M+n and hence the valency of the metal will
be n. Now an unknown concentration (a) of salt solution prepared for cathode and exactly 10 fold
diluted solution (a/10) prepared for anode.
So, the concentration of M+n at cathode and anode is a and a/10 respectively. If we construct a cell
from this two solution using M as electrode, then the cell representation and the reaction at cathode
and anode will look like-

M | M+n (a/10) k M+n (a) | M

M → M+n (a/10) + ne(Anode reaction)
M+n (a) + ne = M(Cathode reaction)
M+n (a) = M+n (a/10)

The Half cell potential of both electrode will be as-

For cathode:

0.0591 1
E +n = E0 +n − log
M |M(cathode) M |M n a

For Anode:

0.0591 1
E +n = E0 +n − log
M |M(anode) M |M n a/10

7
8 CHAPTER 4. ELECTROCHEMISTRY LECTURE/LESSION PLAN -5

Now the expression of complete cell EMF will look like-

Ecell = E +n − E +n
M |M(cathode) M |M(anode)
0 0.0591 1 0.0591 1
Ecell = E +n − log − E0 +n + log
M |M n a M |M n a/10
0.0591 1 0.0591 1
Ecell = − log + log
n a n a/10
0.0591 10 0.0591 1
Ecell = log − log
n a n a
0.0591
Ecell = log10
n
0.0591
Ecell =
n
0.0591
n =
Ecell

Thus from the above equation we can determine the valency of the metal (n) just from the observed
emf value of the electrochemical cell.

4.1 Determination solubility product of a sparingly soluble

salt
Let us consider a sparingly soluble salt PbSO4 and hence solubility product of this salt will be-

Ks = [Pb+2 ][SO−2
4 ]

This can be correlated with the equilibrium constant of a reaction like-

PbSO4 ® Pb+2 + SO−2

4

So, to evaluate the value of Ks we need to construct a electrochemical cell where a net above reaction
happens-

Pb | PbNO3 (soln.) k K2 SO4 (soln.), PbSO4 (s) | Pb

Pb → Pb+2 + 2e(Anode reaction)
PbSO4 (s) + 2e = Pb(s) + SO−2
4 (Cathode reaction)
PbSO4 (s) + 2e = Pb+2 + SO−2
4

Now standard EMF of the cell will be-

E0cell = E0cathode − E0anode

E0cell = E0 +2 − E0PbSO |Pb
Pb |Pb 4
4.2. DETERMINATION OF EQUILIBRIUM CONSTANT 9

As this is a precipitation reaction, observed cell potential will be zero. Hence we can write a Nernst
equation for the whole cell reaction like this-

0.0591
E0cell = E0cell − logPb+2 SO−2
4
2
0.0591
0 = E0cell − logKs
2
2E0cell
logKs =
0.0591
Thus from the above equation solubility product Ks can be determined.

4.2 Determination of equilibrium constant

For this chemical equation we have established the Nernst equation like this-

aA + bB = cC + dD
0.0591
E = E0 − logQ
n
Now at equilibrium point Q=K (equilibrium constant) and cell potential will be zero as rate of
forward recation will be equal to rate of backward rcation. So, the above equation can be written
as-

0.0591
0 = E0 − logK
n
nE0
logK =
0.0591
nE0
K = 10 0.0591

Thus equilibrium constant (K) can be determined from Nernst equation.