CHAPTER

:ELECTROCHEMISTRY
TOPIC:Nernst Equation
The elctrode potential of an electrode assembly depends upon the
following factors:

1) Nature of metal and ions

2) Concentration of ions in the soultions.
3) Temperature

When the electrode assembly is in standard state i.e conc of ions 1

mol/L
T= 298K
Pgas= 1 atm
the value of electrode potential is directly calculated from
electrochemical series

But when the electrode assembly is not in standard state then

electrode potential can not be
calculated from electrochemical series. In such case Nernst equation
is used.
NERNST EQUATION
The relationship between the concentration of ions and
electrode potential is given by Nernst equation

Electrode involving process of reduction nernst eq is :

E=E◦ - RT/nF loge [reduced state]/[oxidised state]

E=reduction potential of electrode
E°= standard reduction electrode
R=gas constant
F= 1 faraday=965000 coulombs
n=number of moles of electrons lost or gain

 
 EXAMPLE:

Concentration of solid is taken as unity (1) therefore M(s) = 1

Lets solve one numerical based on
it.
Calculate the electrode potential
of following half cells at 298K.
Fe2+(0.1M) /Fe
Given : E Fe2+/Fe = -0.44V
First write the half cell equation

Fe 2+(0.1M) + 2e------------ Fe(s)

n=2 [Fe2+]=0.1M
According to nernst equation

E Fe2+/Fe=E ◦Fe2+/Fe – 0.059/n log10 1/Fe2+

Substituting the values in equations
E Fe2+/Fe= -0.44- 0.059/2 log10 1/0.1
= - 0.44 –(0.0295)
=- 0.4695 V
EMF OF A GALVANIC CELLL

The Electromotive force of a galvanic cell is defined as the difference

of electrical potential which causes the flow of current from one electrode to
another when virtually no Current is drawn from the cell.

The EMF of galvanic cell will be positive when there is a tendency of electrons to
Flow from left to right in the external circuit.

IN a cell where

OXIDATION REDUCTION

Left hand electrode Right hand electrode

Positive value of EMF

calculation of Standard EMF of Cell

E◦cell= E◦R- E◦L

E◦cell =standard emf of cell
E◦R= standard electrode
potentail(cathode,reduction electrode)
E◦L =Standard electrode potentail(oxidation,anode)
Example
Zn│Zn2+(1M) │ │ Cu2+(1M) │ Cu

E Zn2+/Zn= - 0.76

E Cu2+/Cu= +0.34

E◦cell= E◦R- E◦L

=+0.34-(-0.76)
=1.10V
 Nernst equation for EMF of cell
For a redox reaction
pA+qB↔ rC+sD

Ecell= E◦cell - RT/nF ln [C]r[D]s/[A]p[B]q

Ecell= E◦cell - 0.059/n ln10 [C]r[D]s/[A]p[B]q

Zn│Zn2+(1M) │ │ Cu2+(1M) │ Cu

Ecell= E◦cell - 0.059/nF ln10[ Zn2+( aq)][Cu ]/ [Cu2+(aq)]

[Zn(s)]

Cu=1 Zn=1(coz in solid state)

Ecell= E◦cell - 0.059/nF ln10 [ Zn2+( aq)]/[Cu2+( (aq)]

Ecell= E◦cell - 0.059/nF ln10 c1/c2

Calculate the emf of the cell
Cr│Cr3+(0.1M) │ │ Fe2+(0.01M) │Fe

E=Cr3+/Cr = -0.75 E Fe2+/Fe= -0.45V

EQUILLIBRIUM CONSTANT FROM NERNST
EQUATION
For a electrochemical cell,

Concentration of pure solids and liquids is taken as unity

Nernst equation and Kc

At equilibrium

Log 10 Kc= nE◦cell/0.059

 
 
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