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half-cell (cathode). The potentials of these half-cells are always different. On account of this difference in
electrode potentials, the electric current moves from the electrode at higher potential to the electrode at lower
potential, i.e., from cathode to anode. The direction of the flow of electrons is from anode to cathode.
The difference in potentials of the two half-cells is known as the electromotive force (EMF) of the cell or cell
potential.
The emf of the cell or cell potential can be calculated from the values of electrode potentials of the two half-cells
constituting the cell. The following three methods are in use:
When oxidation potential of anode and reduction potential of cathode are taken into account:
ECello = Oxidation potential of anode + Reduction potential of cathode
ECello = Eoxo (anode) + Eredo (cathode)
S.No.
EMF
Potential Difference
circuit.
operation.
deliver.
deliver.
in the cell.
the cell.
Nernst Equation
The electrode potential and the emf of the cell depend upon the nature of the electrode, temperature and the
activities (concentrations) of the ions in solution. The variation of electrode and cell potentials with concentration
of ions in solution can be obtained from thermodynamic considerations. For a general reaction such as
where
'a' represents the activities of reactants and products under a given set of conditions and
?Go refers to free energy change for the reaction when the various reactants and products are present at
standard conditions.
The free energy change of a cell reaction is related to the electrical work that can be obtained from the cell, i.e.,
T = 298 K and
F=96500 C,
where Eox is the oxidation potential of the electrode (anode), is the standard oxidation potential of the electrode.
Let us consider a Daniell cell to explain the above equations. The concentrations of the electrolytes are not 1 M.
Zn(s)+Cu2+(aq)
Zn2+(aq) + Cu(s)
All the EMFs that have been used are reduction potentials in volts. Whatever be the value of reduction potentials,
substitute them as such, taking into account the signs.
Zn2+(aq)+Cu(s)
Let n faraday charge be taken out of a cell of emf E; then work done by the cell will be calculated as:
Work = Charge x Potential = nFE
Work done by the cell is equal to decrease in free energy.
-?G = nFE
Similarly, maximum obtainable work from the cell will be
Wmax = nFE
where, Eo = standard emf or standard cell potential.
-?G = nFE
...... (i)
...... (ii)
The emf of the following cell was 0.2699 V at 293 K and 0.2669V at 303 K
Pt | H2 | HCl (aq) || Hg2Cl2 | Hg
Calculate (i) temperature coefficient
(ii) dG, dH and dS at 293 K
Solution:
(i) Temperature coefficient = dEcell/dT =(0.2669-0.2669)/(303-293) VK-1 = -3
VK1
(ii) at 293 K
dG = nFEcell [Q Ecell at 293 K = 0.2699 volt]
=2
96,500
0.2699 J = 52.09 kJ
dH293K = nF[T(dE/dT)-Ecell]
=2
96,500 [293
-3
96,500
104 VK1 = -3
10
Question 1:
Which of the following expressions for cell potential is incorrect?
a. ECello = Oxidation potential of anode + Reduction potential of cathode
b. ECello = Eo (anode) + Eo (cathode)
c. ECello = Erighto- Elefto
d.
Question 2:
Consider the reaction,
2Ag+ + Cd 2Ag + Cd2+
The standard electrode potentials for Ag+ Ag and Cd2+ Cd couples are 0.80 volt and -0.40 volt, respectively.
What is the standard potential Eo for this reaction?
a. 1.20 V
b. 12.0 V
c. 120 V
d. 0.12 V
Question 3:
Eo = 0.350 volt
Eo = -0.763 volt
a. 1.113 V
b. 12.43 V
c. 1.92 V
d. 5.324 V
Question 4:
What will be the electrode potential at a copper electrode dipped in a 0.1 M solution of copper sulphate at 25 oC?
The standard electrode potential of Cu2+/Cu system is 0.34 volt at 298 K.
a. 10.113 V
b. 0.31045 V
c. 11.92 V
d. 9.324 V
Q.1
Q.2
Q.3
Q.4