CONTENTS:

 Electrochemistry:
 Nernst Equation and Applications
 Relation of e.m.f. with Thermodynamic Functions (∆H, ∆F and ∆S)
 Lead Storage Battery.

 Corrosion:
 Causes, effects and its prevention

 Phase Rule: and its application to water system

 Electrochemistry deals with the relationship between
electrical energy and chemical energy and their inter
conversion into one another.

Electrical Energy Chemical Energy

 (i) Electrolytic cell: Device in which electrical energy is
converted to chemical energy through electrolysis. For Ex.
Electrolysis of NaCl produces Na metal and Cl2 gas.

 (ii) Electrochemical cells/Galvanic cells: Device in which

chemical energy is converted to electrical energy. For Ex.
Daniel cell

 (iii) Concentration cells: Device in which electrical energy

is produced due to the difference in concentrations of the
same substance in the two half cells.
Galvanic Cell
ELECTROCHEMICAL CELLS/GALVANIC CELLS
A device in which chemical energy is converted into
electrical energy.
This conversion is due to redox reactions taking place in
the cell. For ex. In Daniel cell.

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

 The oxidation and reduction occur in separate containers

called as half cells and because the redox reaction is
taking place, the electricity is produced.
 The resulting cell has voltage of 1.1 V.
 The metallic rods (Zn and Cu) are called as
electrodes (anode and cathode).

 In electrochemical cells, oxidation occurs on

anode while reduction on cathode.

 Electrons flows from anode to cathode through

external circuit. Therefore oxidation occurs at
anode (Zn rod) and reduction at cathode (Cu
rod).
At Anode; Zn (s) → Zn2+ + 2e- (oxidation)
At Cathode; Cu2+ + 2e- → Cu (s) (reduction)
 The concentration of Zn2+ ions increases while that of
Cu2+ ions decreases.

 Zn rod (anode) loses its weight while Cu metal gets

deposited on cathode.

 By convention, anode is kept at left and cathode at

right hand side.
 Salt bridge ad its Functions
 Salt bridge is an inverted U-tube which connects the
two half cells and it contains saturated solution of
electrolytes like KCl, KNO3 etc. in agar-agar jelly or
gelatin.
 Salt bridge is used to maintain the electrical neutrality.
 It connects the solutions of the two half cells and
completes the circuit.
 It prevents the intermixing of the solutions of both the
half cells.
 Cell Representation

Metal / Electrolyte (with conc.) //Electrolyte (with conc.) / Metal

(Anode half-cell) (Salt Bridge) (Cathode half-cell)
Oxidation Reduction

Zn / Zn2+ (1M) // Cu2+ (1M) / Cu

 The electrical potential difference set up between the metal and
its solution is called as electrode potential.
 It is of two types:
i. Oxidation Potential: It is the measure of the tendency
of a metallic electrode to lose electrons or to get oxidised.
eg.
Zn (s) Zn2+ (aq) + 2e-
ii. Reduction Potential: It is the measure of the tendency
of a metallic electrode to gain electrons or to get reduced.
Cu2+ (aq) + 2e- Cu (s)
 Oxidation potential is the reverse of reduction
potential and vice versa. For e.g.

reduction potential of Zn = - 0.76 V

oxidation potential of Zn = + 0.76 V
 The half-cell reactions are always written as reduction half
reactions and their potentials are represented as reduction
potentials. For ex.
Zn2+ + 2e- Zn (s) [E0 = - 0.76 V]
 The electrode potential depends upon:
1. The nature of the metal and its ions
2. Concentration of the ions in the solution
3. Temperature
 The difference between the electrode potentials of the
two electrodes constituting an electrochemical cell is
known as electromotive force (EMF) or cell potential
of a cell (ECell).
 This acts as a driving force for the cell reaction (it
causes the flow of current from the electrode having
higher potential to the electrode having lower
potential and flow of electrons in reverse direction).
 It is expressed in volts.
EMF = Reduction potential of cathode – Reduction potential of anode

OR

Ecell = E(cathode) – E(anode)

OR

Ecell = E(right) – E(left)

 It is impossible to measure absolute value of single
electrode potential as neither oxidation nor
reduction takes place independently, the electrode
potential is measured with the help of a reference
electrode.

 For this purpose a reference electrode is used. For

ex. Standard Hydrogen Electrode (SHE)
 It consists of a platinum wire or foil coated with
platinum black dipped in 1 M solution of H+ ions.
 Hydrogen gas at 1 atm Pressure is continuously passed
through it at 298 K Temp.
 In a cell when the standard hydrogen electrode acts as
anode, the electrode reaction can be written:
H2 (g) 2H+ + 2 e‒ (Oxidation )

 When the standard hydrogen electrode acts as

cathode, the electrode reaction can be written
as:
+ ‒
2H + 2e H2 (g) (Reduction )

The SHE can act as a cathode or an anode depending

upon the nature of another electrode to which it is
connected. Thus, SHE is also known as reversible
electrode.
 The electrode potential (E0) of SHE is zero.

 The electrode potential of any electrode can be

determined by connecting its half-cell with SHE.
 When E.P. of a metal electrode is determined with
respect to SHE, it is called as Standard Electrode
Potential (E0).

 The electrode at which reduction occurs with

respect to SHE has +ve reduction potential while
the electrode at which oxidation occurs with
respect to SHE has –ve reduction potential.
 A series which represents an arrangement of
various electrodes in the increasing order of their
standard electrode potential (E0).

 It is also known as Activity series.

1. Oxidizing & reducing properties:
All the metals having higher value of reduction potential (E0) appearing on the top of the series behave as a good
reducing agents and at the bottom as good oxidizing agents. For e.g. Li, K; best reducing agents, F2 ; very
powerful oxidizing agents.

2. Comparison of reactivity of metals:

Metals having lesser E0 values can displace the metals from their solutions which are having comparatively higher
E0 values. For e.g. Cu displaces Ag from AgNO3 solution as E0Cu = + 0.34 V and E0Ag = + 0.80 V
Cu + 2 AgNO3 → Cu(NO3)2 + 2 Ag (s)

3. Calculation of EMF of the cell: E°Cell = E°R - E°L

4. Predicting the feasibility of a redox reaction:
Cu2+ (aq) + 2 Ag (s) → Cu (s) + Ag+ (aq)
From series we know; Cu2+ + 2 e- → Cu (s); E0 Cu2+ /Cu = + 0.34 V
Ag+ + e- → Ag (s); E0 Ag+ /Ag = + 0.80 V
Higher the E0, higher the tendency to get reduced, therefore Ag+ should be reduced to Ag (s). So, this reaction
is not feasible. But to make it feasible the reaction should be reversed.

5. Hydrogen displacement behaviour of Metals:

It Any metal above hydrogen in the electrochemical series can liberate H2 from an acid solution.
For example: Zn lying above hydrogen in the electrochemical series reacts with dilute H2SO4 to liberate H2.

Zn + H2SO4 → ZnSO4 + H2↑

6. Corrosion tendency: The anodic or more active metals with high negative electrode
potential in the series are more prone to corrosion. The cathodic or more noble metals with less negative
electrode potential are less prone to corrosion
 NERNST EQUATION:
Dependence of electrode potential and cell potential on
concentration
If the concentration of the electrolyte solution is 1
Mol/L (1M) and the temperature is 298 K (25 0C), the
electrode potential of the given electrode is called
Standard Electrode Potential (E0).
However, if the concentration of the electrolyte solution
is different from 1M, the electrode potential of the
electrode has different value from that of standard
electrode potential, E0.
This value can be calculated with the help of Nernst
Equation. For this purpose, the electrode reaction is
always written as reduction reaction.

Nernst Equation for this electrode:
Dividing (3) by –n F, we get

Since, Molar concentration of pure solids is taken as unity; [M(s)]

=1

This is the Nernst Equation for this electrode.

Where, E = Electrode Potential
E0 = Standard Electrode Potential (for a 1M solution of metal ions)
F = Faraday of electricity (96,500 C)
T = Temperature (K)
R = Gas Constant (8.314 JK-1 mol-1)
n = No. of electrons involved in the electrode reduction reaction
[Mn+(aq)] = Molar concentration of metal ions
At T = 298 K, Putting the value of R and F, we get:
Nernst Equation for a Cell:
Nernst equation can also be applied to any cell reaction such as:
aA + bB → cC + dD

For e.g. For Galvanic cell;

Zn (s) + Cu2+ (aq) ↔ Zn2+ (aq) + Cu (s)

[Zn (s)] and [Cu (s)] = 1

It can be concluded from the Nernst Equation that,

(a) E increases as [Mn+] increases.
(b) E decreases as temperature increases.
The change in thermodynamic properties such as Gibbs
function, enthalpy and entropy can be calculated from
cell potential measurements.
 The electrical energy produced by a galvanic cell is
given by the product of its electromotive force (E)
and the quantity of electricity (Q) which passes
through it.
 The net electrical work performed by a reaction is
the product of electromotive force (E) and the
quantity of electricity (Q).

i.e. Net electrical work done = E Q -----(1)

[If E is measured in Volts and Q in Coulombs, the

electrical energy obtained is in Volt-Coulomb or Joules
(1 Volt-Coulomb = 1 Joule)].
Also in accordance with Faraday’s Law,
Quantity of electricity produced (Q):

Q=nF ……(2)
Where, n = number of electrons involved
and F = Faraday of electricity (charge on 1 mole
electrons) i.e. 96,500 C

According to Gibbs and Helmhotz, the electrical energy

(nFE) of a reversible cell is given by the decrease in free
energy (-∆G) of the cell reaction.
As electrical energy produced by the cell = n F E
Hence, -∆G = n F E ……..(3)
In the cell reaction, if the substances involved are in their
standard states i.e. at 1 atm pressure and 298 K temp,
then
∆G0 = - n F E0 ………(4)

According to Gibbs-Helmholtz equation,

∆G = ∆H – T ∆S ……..(5)

At constant pressure, Entropy change


NOTE
 When , ∆G = -ve, or E = +ve, the reaction is
spontaneous.

 If ∆G = +ve, or ∆E = -ve, the reaction is non-

spontaneous.

 If, ∆G= 0, ∆E = 0, the reaction is in
equilibrium.


Ans: Half cell reactions are:
Zn (s) = Zn2+ (aq) + 2e- ; E0(Zn2+/Zn) = - 0.76 V
Ag+ (aq) + e- = Ag (s) ] x 2 E0(Ag+/Ag) = 0.8 V

Zn (s) + 2 Ag+ (aq) → Zn2+ (aq) + 2 Ag (s)

Cell representation : Zn / Zn2+ (aq) // Ag+ (aq) / Ag (s)
E0cell = E0cathode – E0anode
= 0.8 - ( - 0.76) =1.56 V







Solution: We know,
∆G = - n F E
= - 2 x 96,500 x 0.9647
= - 2 x 96,500 x 0.9647 J
= - 186,187.1J
∆G = - 1.86 x 105 J







A battery is a combination of electrochemical
cells connected in series , that can be used as a
direct current.
Types of Cells (Battery):
1. Primary Cells
2. Secondary Cells (Storage Cells)
 PRIMARY CELLS:
• In these cells, the electrode reactions
cannot be reversed by external electric
energy source.
• Reaction occurs only once and after use
they become dead.
• They are not chargeable.
• e.g. Dry cell, Mercury cell.
SECONDARY CELLS (STORAGE CELLS):
• In these cells the reactions can
be reversed by external electric
energy source.
• They are chargeable cells.
• e.g. Lead Storage Cell and Nickel-
Cadmium storage cell
Lead Storage Battery
 LEAD STORAGE BATTERY
• It is a secondary cell and can be
recharged and used again and again as a
source of electric current.
• It is used in cars, trucks and buses etc.
• In lead storage battery, a number of
voltaic cells are connected in series.
• 3-6 such cells are generally combined to
get 6-12 V battery.
In each cell:
 Anode: A grid of lead packed with finely divided spongy
lead
 Cathode: A grid of lead packed with PbO2
 Electrolyte: Aq. H2SO4 (38%) having density 1.30 g/mL
 Reaction during Discharging (usage) of Cell
At Anode: Pb (s) + SO42-(aq) PbSO4(s) + 2e- (oxidation)
At Cathode: PbO2 (s) + 4H+ + SO42-(aq) + 2e- PbSO4(s) + 2H2O (reduction)

Overall: Pb (s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O

 Thus, at anode Pb is oxidised and at cathode PbO2 is reduced.

 PbSO4 is formed at each electrode and sulphuric acid is used up.
 As a result, concentration of sulphuric acid decreases and the
density of the solution also decreases.
 When both anode and cathode become covered with PbSO4
and the density of acid falls below 1.2 g/mL, the battery
needs recharging.
 Recharging the battery
 The cell can be charged by passing electric current of a suitable
voltage in the opposite direction.
 The electrode reaction gets reversed.
 As a result, Pb is deposited on anode and PbO2 on cathode.
 The density of acid also increases.
 The reaction is written as:

At Anode: PbSO4(s) + 2e- Pb (s) + SO42-(aq) (reduction)

At Cathode: PbSO4(s) + 2H2O PbO2 (s) + 4H+ (aq) + SO42-(aq) + 2e-
(oxidation)

Overall: 2PbSO4(s) + 2H2O Pb (s) + PbO2 (s) + 2H2SO4(aq)

It may be noted that storage battery acts as
voltaic cell as well as electrolytic cell. For ex.

 When it is used to start the engine, it acts as a

voltaic cell and produces electric energy.

 During recharging, it acts as an electrolytic

cell.