CHAPTER

:ELECTROCHEMISTRY
TOPIC:Nernst Equation
The electrode 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

 
 
◦
 GIBBS FREE ENERGY AND
EMF OF A CELL
When cell does electrical work reversibly only an infinitesimal current id drawn from the
cell ,the free energy change ∆G is equal to electrical work done and we have
∆G= w electrical ( eq 1)

If∆G is negative the system does electrical work on the sourroundings. Current is
generated

If ∆G is positive no electrical work is done by the system.

No electrical current is generated.
 
Suppose cell reaction in a galvanic cell transfer n moles of electrons
Therefore total charge involved =nF coulombs
Hence welec= charge * EMF 
welec = -nF Ecell(because work done by the system is taken as negative) 
substituting this value in eq 1 we get
∆rG= -nF Ecell
Under standard conditions
∆rG= -nF E◦cell
 
FREE ENERGY CAHNGE AND EQUILLIBRIUM
CONSTANT

Substituting the value of E◦cell we have

∆rG= -nF * 0.0591/nF log10 Kc

∆rG= -0.0591 log10 Kc

Calculate the standard free energy change for the reaction occurring in the cell

Zn│Zn2+(1M) │ │ Cu2+(1M) │ Cu
E Zn2+/Zn= - 0.76

E Cu2+/Cu= +0.34
F=96500 C/mol

Solution:
E◦cell= E◦R- E◦L

=+0.34-(-0.76)

=1.10V

Cell reaction :

Zn (s)+Cu2+--------- Zn 2+ + Cu(s)
∆rG= -nF E◦cell substituting value
∆rG= -2* 96500*1.10= -212300J= 212.3kJ
EMF OF CELL AND FEASIBLITY
OF CELL REACTION
 
A spontaneous reaction occurring at constant temperature
and pressure proceeds in the direction in which free
energy of the system decreases i.e
∆G<0
Therefore a cell reaction should proceed in the
direction in which Gibbs free energy decreases.In
other words a cell reaction is feasible only if ∆G is
negative for it.
The free energy change ∆r G= - nF Ecell

If cell operates under standard conditions We have

PREDICT WHETHER THE FOLLOWING REACTIONS ARE FEASIBLE OR NOT
Ni(s) +2H+ ------------ Ni2+(aq) + H2(aq)
Given:
= E Ni2+/ Ni =-0.025 V,

Ni(s) + 2H+(aq) --------- Ni2+(aq)+ H2(g)

For this cell

E◦cell= E◦R- E◦L

E◦H+/1/2H2 - E◦ Ni2+/Ni

0-(-0.25)= +0.25 V
E◦cell is positive therefore ∆rG should be negative and
The reaction is feasible

Try aother example from book

 Electrical
INSULATORS
Conductors
The substance which conduct electricity E.g All Metals in fused
Doand
notionic
conduct
state
elctricity
E.G
E.G Plastic ,sulphur, rubber
CLASSIFICATION OF ELECTRICAL CONDUCTORS

Metallic conductors

●
Metallic conduction

Electrtolytic conductors

●
Electrolytic conduction
 Conduc
All metals
●

tion by
metals
:copper, silver
aluminium etc

Possess
●
Responsibl
mobile
elctrons
e for
conduction
METALLI Because no
●

movement of

CCONDU
No chemical
change take
place during
passage of
elctrical
matter
current
Only flow of
●

electrons

CTORS
 Posse
Resposible
●

ss for
ions
conduction

Chemic
●
Because there
al
change is movement
is there
of ions

ELECTROLYTIC ●
example sodium

CONDUCTION
Shown
by ionic chloride,
compou
nds
potassium
chloride et
OHM’s LAW

According to Ohm’s Law The potentail diffrence across a conductor is

Directly proportional to current flowing through it

Vα I
V/I= constant
V/I = R Mathematical form of Ohm’s Law

WHAT IS R
R is the resistance of a conductor which is directly proportional to its length and
Inversely proportional to its area of cross section

R αl
R α 1/A thus R α l/A or R= ϼ l/A
R= ϼ

RESISITIVITY IS a measure of the resisting

power of a specified material to the flow of
an electric current.
Low resistivity of substance= more current
SPECIFIC CONDUCTANCE(Conductivity Ϗ)
The reciprocal of specific resistance is called Specific
conductivity
It is represented by the symbol Kappa(Ϗ)

Ϗ=1/ϼ

We know that R= ϼ l/A

Substituting the value of rho from this equation to Kappa

We get
K=1/R * l/A

Ϗ= C. l/A( because C= 1/R)

If l= 1 cm A= 1cm2 We have Ϗ= C

Hence Specific conductivity may be defined as the

conductance of a conductor whose length is 1 cm and area of
cross section equal to 1 cm2