Unit 4 - 1

UNIT - IV

ELECTRO CHEMISTRY

Introduction
Electrochemistry deals with chemical applications of electricity. Chemical reactions
produced by passing electric current through an electrolyte.
Material which allows free flow of electricity is called conductors.
Eg. - All metals graphite, fused salts, solution of electrolytes.
Materials which cannot conduct electrical current is called non-conductors.
Eg. – Wood, Plastic, Glass, Most of non-metals.

Electrodes
Electrodes are classified in to two types. They are classified as
1. Reference Electrode.
2. Indicator Electrode.
1. Reference Electrode.
The electrodes which has a construct EMF (or) constant potential and that can be used in the
measurement of the potential of a given test electrode.

[E.M.F – Electromotive force]

Electricity can flow from one electrode to another electrode in an electrochemical call which
indicates that the two electrodes have difference various potentials. The difference of potential
which causes flow of current from one electrode (higher potentials) to author (lower potential)
is called electromotive force (E.M.F). ]
There are two types of reference electrodes

They are

1. Primary electrodes :- Standard Hydrogen Electrode (SHE) (or) normal Hydrogen

Electrode (NHE).
2. Secondary Electrode :- Standard calomel electrode, quinhydrone electrode, silver – silver
chloride electrode etc.,

2. Indicator Electrode
The electrode where potential changes with change in concentration of electrolyte is known
is indicator electrode.
Ex.
1. Glass electrode 2. Inert metal like Pt, Ag, electrodes etc
 Unit 4 - 2

Electrode potential
The measure of tendency of a metallic electrode to lose (or) gain electrons. when it is in
contact with its own ions in solution is called Electrode Potential.
The Tendency of the electrode to lose is called oxidation potential and gain electrons is called
reduction potential .
Standard Hydrogen Electrode (SHE)

(or)

Normal Hydrogen Electrode (NHE)

Standard Hydrogen Electrode is a primary electrode

because. Its potential is arbitrarily taken as zero volts.
Set up :- SHE can be constructed by digging a platinum wire
with a platinum foil in a HCL solution of IM concentration.

Though it hydrogen gas is passed at l atmosphere

pressure under standard conditions the current
developed in SHF is taken as zero volts.

Anodic half call representation

H+IM / H2(l atm) pt

Cathodic half cell representation

(pt) H2( l atm) / H+ (1m)

Cell reaction
H2 → 2H+ + 2e- (oxidation)

2H+ + 2e- → H2 (reduction)

When the test electrode is connected with SHE through a potentiometer the potential
indicated in the potentiometer is will be the single electrode potential of the test electrode. SHE
can be act anode and cathode.

Determination of pH using SHE

Consider a cell
(pt) H2(l atm) / H+ (1m) | | H+ (c=?) / H2(l atm) (pt)

SHE Test cell

The cell reaction

 Unit 4 - 3

H+ + e-  ½ H2

Eo cell = Eo right - Eo left

According the Nernst Equation
E = Eo + 0.0591/n log[m n+]

Ecell = ─

Ecell = ─

Ecell =

Ecell =

Ecell = [ ]

This rth only one e- is involved so n=1 then the equation becomes

Ecell =

Multiply by -1 on both sides.

-[ ]=-

We know that pH = -

So the above equvation becomes, pH =

In other words pH =
Thus, using SHE, pH of a solution can be determined.

Standard Calomel Electrode

It is widely used secondary reference electrode because its potential is determined with
reference to SHE.
 Unit 4 - 4

Standard calomel electrode consists of a glass tube with a narrow side tube. It is filled with
mercury and solid (paste) calomel (Hg2cl2). The
apparatus is filled with 1M KCl solution. A pt
wire is dipped in these chemicals.

The side tube acts as a salt bridge.

The half call rep. is

Cl- (IM) / Hg2 cl2 , Hg

The half cell reaction is

-
Hg2cl2 + 2 e  2Hg + 2Cl-
The potential of calomel electrode depends on the conc. of KCl electrolyte.
Conc. Of Kcl(M) Potential

0.1 + 0.0338

1 + 0.2800

Saturated + 0.2422

Standard calomel electrode also used to find out the single electrode potential

Zn | Znso4 | | Cl -(IM) | Hg2cl2 , Hg

The potential of the cell is given by

= -

1.040 = 0.2800 ─ Eo Zn
2+
/ Zn

Eo Zn
2+
/ Zn = 0.2800 ─ 1.040

Eo Zn
2+
/ Zn = - 0.76 v

[ =Standard Potential]

Determination of pH using SCE

= ─
 Unit 4 - 5

= 0.2422 +0.0591 v pH

0.0591 v pH = ─ 0.2422 v

pH =

Quinhydrone Electrode
The quinhydrone electrode consists of a platinum electrode dipping into the test solution
containing equimolar quinine Q and hydro quinone QH2.
1. Construction
It can be very easily setup by adding a pinch of quinhydrone powder to the experimental
solution with stirring until the solution is saturated and slight
excess of it remain undissolved.

Then indicator electrode, generally, bright platinum is inserted

in it.
For determining PH value, this half call is combined with
any other reference electrode usually SCE and the emf of the
cell is determined potentiometrically.

The complete cell represented is

Pt | QH2, Q, H+ (unknown) | | KCl(satured), Hg2cl2(s) | Hg+

The quin hydrone system involves the following ryn

OH OH

 + 2H+ +2e-

O OH

Q + 2H+ + 2e- QH2

The potential developed on platinum electrode is given by
 Unit 4 - 6

EQ = Eo -
[R = Gas constant 8.314 J/k/mol]

= Eo -

= Eo +

= Eo + +

= 2

= Eo + + 2x

= Eo + +  (1)

Quinone is hydro quinone are usually taken is equal molar conentration.

i.e., [Q] = [QH2] and the quantity [Q] / [QH2] is unity.

Hence the equation (1) becomes

= Eo + +
[

= Eo +  (2)
Substitute the values for R, T and F is the equation (2)

= Eo + 0.0591 at 25 C  (3)

PH = -

Eo  Standard electrode potential for quinhydrone electrode = 0.6996 V.

 Unit 4 - 7

So, the Equation (3) becomes

H
EQ = 0..6996 V - 0.05912 V P

2. Determination of PH of a solution using quinhydrone electrode

The PH of a solution is determined by connecting the quinhydrone electrode with a standard
calomel electrode.
The cell represent is

Pt | QH2, Q, || , Hg2 cl2(s) |

= -

= ─

= 0.2422 V ─ (0.6996V + 0.0591 V PH)

─ 0.2422 V + 0.6996 V = 0.0591 V PH

PH =

3. Advantages :
1. Used in titration of an acid by an alkali

2. Equilibrium is rapidly attained.

3. Used in the presence of the ions of many metals which is generally affect the hydrogen
electrode.

4. Disadvantages :
1. it can’t be used in solution containing redox systems which will react with either quinone
(or) hydro quinone.
2. The potential of quinhydrone electrode is altered by a change in ionic strength of the
solution.
 Unit 4 - 8

3. It gives very good result, in solution only when PH is less than 8. In more alkaline solution
the equilibrium between Q and QH2 is disturbed.
[Salt Bridge :- it consists of a U-tube containing a saturated solution of KCl (or) (NH4)2NO3 in
agar –agar gel.]

Fuel Cell (Reversible Cell)

A cell works reversibly in the thermodynamic conditions. i.e., during the measurement of
emf no current flows through the cell and no chemical reaction takes place such cells are called
as reversible cells. (or) Fuel cell.
Ex:- Daniel Cell.
Secondary batteries like lead-acid battery and Ni-cd battery.
In order to find out if a given cell is reversible or not, it is connected to an external source of
Emf acting in the opposite direction. The cell will be reversible if it satisfies the following
conditions.
1. If the external E.M.F is exactly equal to that of the cell itself, then no current is given out by
the cell and no chemical reaction takes place in the cell.
2. If the external E.M.F is infinitely smaller than that of the cell itself, an extremely small
amount of current is given out by the cell and correspondingly chemical reaction takes place in
the cell.
3. If the external E.M.F is infinitely greater than that of the cell itself, an extremely small
amount of current flows. Thro’ the cell in the opposite direction and a small unit of the
chemical reaction takes place in the reverse direction.
Since the secondary batteries like lead-acid battery, ni- cd battery obey these conditions,
they can be recharged and are called
rechargeable batteries.

When a metal (anode) is placed is an

electrolyte, e-s and metal ions are liberated
from anode. This rxn is known as oxidation
rxn (above fig)
M → Mn+ + ne-(oxidation)
When a metal (cathode) is placed is an
electrolytic solution, metal ions take e-s and then reduced to metal. They deposited on the
cathode.
Mn+ + ne- → M (reduction)
The potential developed in a cell is related to free energy change (ΔG)
ΔG = - n FE
 Unit 4 - 9

Where
n – Number of e-s

F– Faraday 96500 Coulomb

e – Energy of the cell

The negative sign means the decrease in the free energy.

Fuel cells
Oxidation – reduction reaction takes place in voltail
cell. All ordinary combustion reactions are redox
reactions.
When fuel is burned, the e- exchange takes place only
when the atoms of the oxidizing agent (02 in air) come in
direct contact with the atom of the substance being
oxidized (the fuel).
The energy is released principally as heat. In a fuel cell
(fig) the electric, energy is obtained without combustion
from oxygen and a gas than can be oxidized.
Hence, a fuel cell converts the chemical energy of the fuels directly to electricity.
Fuel + Oxygen → oxidation products + electricity
One of the simplest fuel cell is hydrogen-oxygen fuel cell.
It consists of an electrolytic solution such as a KOH and two direct porous electrodes.
Hydrogen and oxygen gases are bubbled thro’ the anode and cathode compartment
respectively.
The following chemical reaction takes place
Anode: 2 H2(g) + 4OH- (aq) → 4 H2O (l) + 4e-
Cathode: O2(g) + 2H2O+4e- (l) → 4OH- (aq)
Overall : 2H2 (g) + O2 (g) → 2H2O (l)

In a actual practice, the emf of cell produced is 0.8 V to 1.0V the only product discharged by
the cell is water. A large number of these cells are stacked together in series to make a battery
is called fuel cell battery (or) fuel cell.

(i) Lead – Acid storage battery

In a reversible cell, the chemical energy can be converted to electrical energy and vice-versa.
Ex: Daniel cell, head acid storage battery
 Unit 4 - 10

It contains 3 to 6 sets of anodes and cathode they are connected in series one anode and one
cathode is called as a cell and it can
generate 2V.
The anode is made up of spongy lead.
The cathode is made up of lead oxide
(Pb02) or a grid made of lead packed with
Pb02. The anodes and cathodes are
separated from this adjacent ones by
insulators like rubber (or) glass fiber sheets.
All electrodes are immersed in dil. H2S04
having a density of 1.30 g/ml.
The cell representation of this cell is

Pb / Pb 2+ // H2S04 / Pb02 / Pb

Working
When the battery operates, at the anode lead oxidizes to Pb 2+ ions and releases e-s. Pb02 also
forms Pb 2+ ions which form lead sulphate.

At anode
Pb → Pb 2+ + 2e-

Pb 2+ + S04 2- → Pb S04

Pb + S04 2- → Pb S04 + 2e-

At cathode
Pb 02 + 4H+ + 2e- → Pb 2+ + 2H20

Pb 2+ + S04 2- → PbS04

Pb02 + 4H+ + S04 2- + 2 e- → PbSO4 + 2H20

Overall reaction
Pb + Pb02 + 2H2S04 → 2 PbS04 + 2H20 + Energy.
From the above cell reaction it is clear that PbS04 formed from the anode and cathodes are
deposited. So, the concentration of dil-sulphuric acid is decreased. The density of H2S04 falls
below 1.2 g/ml. So the battery needs recharging.
Recharging:
By passing electric current from an external source in the opposite direction, the cell can be
charged. As the result lead sulphate gives lead and oxide. Pb is deposited on anode and Pb02 is
deposited on the cathode
2PbSO4 + 2H2O + 2e- → Pb + PbO2 +4H+ +2SO4 2-
 Unit 4 - 11

Uses:
It is used to supply current to automobiles. It is also used in engine ignition, telephone
exchange, UPS, power stations etc.

(ii) Ni – CD battery
The anode is made up of spongy cadmium and the cathode is made up of a metal grid
containing Ni02. The electrolyte is NaoH (or) KoH. The cell representation is

Cd / Cd(OH)2 // KOH (aq) / NiO2 /Ni

Working (Discharging)
On discharging, the cadmium at anode oxidized to give Cd 2+ ions and electrons.
The Cd 2+ ions react with OH- ions to give insoluble Cd(OH)2.
Cd(s) + 2OH- → Cd(OH)2 + 2e- (oxidation)
Electrons are gained by Nio2. Ni undergoes reduction from Ni 4+ to Ni 2+. This Ni 2+ ions
combine with OH- ions to give Ni (OH)2.
NiO2 + 2H2O + 2e- → Ni(OH)2 + 2OH- (reduction)
The overall reaction is
Cd(s) + NiO2 + 2H2O → Cd(OH)2 + Ni(OH)2 + energy.
The cell provides energy of 1.4 V constantly, since there is no gaseous product are formed, it
can be recharged.

Recharging
The recharging process is similar to lead acid batter. When the current is passed from an
external source, reaction takes place in reverse direction. As a result Cd is deposited on anode
Nio2 is deposited on cathode.
The reverse reaction (overall)
Cd(OH)2 + Ni(OH)2 + energy → Cd(s) + NiO2 + 2H2O
Advantages:-
 It has longer life

 It provides 1.4V constantly

 It is smaller and lighter

 It can be made in any form

 Unit 4 - 12

Disadvantages:-
It is more expensive Uses:
Used in cellphones, calculators, transistors, cordless appliance etc.

(iii) Lithium battery

It is a solid state battery since a solid
electrolyte is used instead of a liquid
(or) a paste. (Fig).
It has a lithium anode at one end and a
TiS2 (Titanium sulphide) at another
end. (Cathode).
A solid electrolyte, normally a
conductive polymer is packed in
between the 2 electrodes. This solid
electrolyte allows the ions to pass through it but it does not allow e-s to pass.
Working

When the anode is connected to cathode, lithium ions move from anode to cathode. The
anode is elemental lithium which is a source of lithium ions and e-s.
The cathode is a material capable of receiving the lithium ions and e-s.
At anode: Li (s) → Li+ + e-
At cathode: TiS2 + e- → TiS2-
Overall reaction

Li (s) + TIS2 → Li + + TiS2- → LiTiS2

Recharging the battery

The lithium battery can be recharged by supplying an external current, which drives the
lithium ions back to the anode. The overall reaction is
LiTiS2 → Li+ + TiS2-
This cell is rechargeable and produces a cell voltage 3.0V.
Advantages:
 It is smaller and lighter
 It has longer life
 It produces 3V constantly
 No chances for leakages of electrolyte
 The battery can be made in any size and any shape
Uses:

Used in ipods, cell, PC’s, laptops, watches digital cameras.

 Unit 4 - 13

Conductometric titrations
Principle:
Conductometric titration is a volumetric method based on the measurement of conductance
of the solution during the titration.
The conductance of a solution depends on

(i) The number and charge on the free ions, and

(ii) The mobility of the ions.

Types of conductometric titrations

a) Acid – base titrations

b) Precipitation titrations

c) Replacement titrations

d) Redox (oxidation-reduction) titrations

e) Complexometric titrations

Acid Base titration

Acids can be titrated against base. The conductometer readings are noted and plotted without
the addition of indicators, the end points are calculated by graphical method.
When the conductance is plotted against volume of base added, it will give a graph. The
point of meeting is the endpoint.
There are five types of acid-base titration:
(i) Strong acid – strong base

(ii) Strong acid – weak base

(iii) Weak acid – strong base

(iv) Weak acid – weak base

(v) Mixture of acids

Strong acid (vs) Strong base [Hcl (vs) Na0H]

Known amount of a strong acid (Hcl) is taken in the conductivity cell.
Strong base (Na0H) is taken in a burette initial conductance of the acid is measured. The
point is denoted as ‘A’. As Na0H is added to the conductivity
cell, it reacts with Hcl to form Nacl and water.
The conductance starts to fall gradually up to the point ‘B’.
 Unit 4 - 14

This is due to the replacement of fast moving H+ ions by OH -ions.

H+ Cl - + Na+ OH → Na+ cl - + H20

Further addition of even a small amount of Na0H will introduce the fast moving free OH- ions.
So the conductance starts to increase gradually. It is indicated by the line Bc. fig.
When the conductance is plotted against volume of NaOH, two lines are obtained. They are
intersecting at the point ‘B’. It is the endpoint the corresponding volume is the amount of
NaOH required to neutralize the Hcl solution.

Potentiometric titration
Potentiometric titrations fall into the
following three categories.
1) Precipitation titrations

2) Redox titrations

3) Acid – base titrations

Precipitation titration (AgN03 vs Nacl)

Known amount of the AgNo3 solution is
taken in a beaker and the indicator
electrode (silver – silver ion electrode) is placed in it. It is then connected to a reference
electrode (calomel electrode) to form a galvanic cell. The cell is then connected the
potentiometer and its fall is determined.
When the AgNo3 solution is titrated against the standard Nacl solution, taken in the burette,
the emf is going on decreasing as the Ag+ ion concentration decreases.
AgNo3 + NaCl → AgCl +NaNo3
At the end point, emf is suddenly decreases after the endpoint there is no noticeable change in
the potential.

When the emf is plotted against the volume of Nacl added a curve of the type shown in fig is
obtained. The endpoint is the point, where the slope of the curve is maximum.
The graph ∆E/∆V [vs] volume of Nacl – is plotted as above, to get the accurate endpoint.
 Unit 4 - 15

Redox titration (Feso4 vs K2 Cr2 07)

Known amount of Feso4 solution is taken is a beaker and the indicator electrode (platinum
electrode) is inserted in it. It is then connected to a reference electrode (calomel electrode) to
form a galvanic cell. The cell is then connected to the potentiometer and its Ecell is determined.

When it is titrated against the standard

K2 Cr2 07 solution taken in the burette,
the emf is going on increasing as the
concentration of Fe 3+ increases due
to the following reaction.

Fe 2+ → Fe 3+ + e-
At the endpoint the emf is suddenly
increases. After the endpoint there is no
charge in the potential.
When the emf is plotted against the
volume of K2 Cr2 07 added a cure of the
type shown in fig is obtained. The
endpoint is the point where the slope of the curve is maximum.
A more sensitive and satisfactory method of detecting the endpoint will be the graph of
∆E/∆V against volume of K2 Cr2 07 the resulting curve rises to a maximum at the equivalent
point, which is the end point.

GLASS ELECTRODE
[Internal reference electrode]

Construction
A glass electrode consists of thin-walled glass bulb (the glass is a special type having low
melting point and high electrical conductivity) containing a Pt wire in 0.1M Hcl (fig). The glass
electrode is represented as

Pt, 0.1M HCl / Glass

Hcl in the bulb furnishes a constant H+ ion concentration.

Glass electrode is used as the “Internal reference
electrode”. The PH of the solutions, especially coloured
solutions containing oxidizing (or) reducing agents can be
determined. The thin walled glass bulb called glass
membrane functions as an ion – exchange resin, and an
equilibrium is set up between the Na+ ions of glass and H+
ions in solution. The potential difference varies with the H+
ion concentration and its emf is given by the expression.
 Unit 4 - 16

EG = EG
0
─ 0.0592 log [H+]aq
EG = EG0 + 0.0592 PH [PH = ─ log[H+]

From the equation it is clear that the PH of solution is a direct measure of emf of a glass
electrode.

Determination of PH of a solution using glass electrode

The glass electrode is placed in the solution under test and is coupled with saturated calomel
electrode as shown in the fig.
The emf of the cell is measured. From the
emf, the PH of the solution is calculated as
follows.

Ecell = Eright ─ Eleft

Ecell = E calomel ─ Eglass

Ecell = E calomel ─ (EG0 +0.0592PH)

= E calomel ─ EG0 ─ 0.0592PH

PH = Ecal ─ EG0 ─Ecell / 0.0592

P H
= o,2422─ EG0 ─Ecell / 0.0592

Advantages of glass electrode

(i) It can be easily constructed and readily used

(ii) The results are accurate

(iii) It is not easily poisoned

(iv) Equilibrium his rapidly achieved

Disadvantages [Limitations]
(i) Since the resistance is quite high, special electronic potentiometers are employed for
measurement.
(ii) The glass electrode can be used in solutions only with PH range of 0 to 10. However
above the PH 12[high alkalinity]. Cations of the solution affect the glass and make the electrode
useless.