ELECTRO CHEMISTRY ii) Non conductor

The substances which do not passage electric

Redox Reaction current through it, is called as a non-conductor.
The chemical reaction which involves both This is also called as insulators. The insulators are
reduction and oxidation is called as redox reaction. up to two types.
a) Non-metals
Note: - b) Non-electrolyte
 In an oxidation reaction involves loss of an a) Non-metals: -
electron. All non-metals are non-conductor carbon in the
 In a reduction reaction involves gain of an form of graphite is an exception.
electron. b) Non-electrolytic: -
LOGR-loss in oxidation gain in reduction. The substances which do not allow the electric
current to pass through their aqueous solution are
Example: - called as non-electrolyte.
Zn(s) + CuSO (aq) ⟶ ZnSO (aq) + Cu(s) e.g. Cane sugar, Urea, Benzene etc.
Zn(s) + Cu (aq) ⟶ Zn (aq) + Cu(s)
iii) Strong electrolyte
Zn(s) ⟶ Zn (aq) + 2e (𝐨𝐱𝐢𝐝𝐚𝐭𝐢𝐨𝐧)
The substance which gets completely ionized in
Cu (aq) + 2e ⟶ Cu(s) (𝐑𝐞𝐝𝐮𝐜𝐭𝐢𝐨𝐧) solution are called strong electrolyte.
Here Zn is oxidized to Zn and Cu is reduces to e.g. NaCl, HCl, Mg(OH)2 etc.
Cu.
iv) Weak electrolyte
Reducing Agent The substance which gets partially ionized are
The substance which gets oxidized itself and called weak electrolyte.
reduces other substances is called reducing agent. e.g. CH3COOH, NH4OH etc.

Oxidizing Agent Factor effecting electrolyte conduction

The substance which gets reduced itself and 1. Inter ionic interaction: -
oxidized other substances is called oxidizing agent. These interactions are also called solute-
solute interaction. If such interaction is high, then
Electro Chemistry degree of ionization will be less. Due to this reason
“It is defined as the branch of chemistry which weak electrolyte are partially dissociate and strong
deals with the relationship between electrical electrolytes are completely dissociating.
energy & chemical energy taking place in a redox
chemical reaction.” 2. Solvation of ions
These are called solute-solvent interaction. In
Terminology case solute-solvent interaction is large then ions
i) Conductor: - will be highly solvated and electrical conductivity
The substance which allows the passage of will be low.
electric current through it are called conductor. The
conductors are up to two types. 3. Viscosity of solvent
a) Metallic conductor Viscosity of solvent is due to solvent-solvent
b) Electrolytic conductor interactions. Larger the value of viscosity, lower
a) Metallic conductor: will be its electrical conductivity.
The substance which transfers electric current by
the transfer of electrons without transfer of any 4. Temperature
matter are known as metallic conductor. On increase the temperature, the dissociation
e.g. Cu, Ag, Fe etc. increases and hence conduction increases.
b) Electrolytic conductor: - Note: -
The substance which allows electricity to pass Degree of dissociation(α)
through its aqueous solution or in the fused state is The fraction of the total number of
called as an electrolytic conductor. molecules of the electrolyte which ionizes in the
solution is called degree of ionization. It is
denoted as ‘𝛼’.
ELECTROCHEMISTRY 1
Electrolysis Note
The process of chemical decomposition of an The flow of electrons occurs in a direction
electrolyte in solution or in the fused state by opposite to that current.
passage of electric current is known as
electrolysis.” Application of electrolysis
Electrolysis plays an important role in
industry and a large number of chemicals are
manufacture using the process of electrolysis.
e.g. (i) sodium hydroxide and chlorine gas are
manufactured by the electrolysis of solution
chloride solution.

ii) Metals like sodium, magnesium and

aluminums are extracted by using the process of
electrolysis.

iii) By the help of electrolysis, electroplating is

carried out.
Process of electrolysis
i) The process of electrolytic is carried out in a Faraday law of electrolysis
vessel known as electrolytic tank, which is made Michael Faraday enunciated two simple laws
up of with insulating material such as, glass, as a result of his large numbers of experiment on
stone. electrolysis. The laws are called as Faradays
laws of electrolysis.
ii) In electrolytic tank, fused electrolyte or an i) Faradays first law of electrolysis
aqueous solution of the electrolyte is taken and Statement: -
two metal plates are dipped in the electrolytic It states that, “The amount of any
solution. The metal plates are known as substance deposited or liberated at any
electrodes. The electrodes are connected with electrode is directly proportional to the quantity
the poles of battery. of electricity passed through the electrolytic
solution.”
iii) The anode is connected with the positive Explanation
pole of battery and cathode is connected with the Let ‘W’gm of substance is deposited at the
negative poles of battery. electrode on passing Q coulomb of electricity.
Then according to Faradays first laws of
iv) Current enters in the electrolyte through electrolysis.
anode and leaves through cathode. W∝Q
Or, W = Z × Q ……… (i)
v) When electrolytes are dissolved in water they Where, Z is a constant of proportionality known as
split into ions. The cation moves towards the electrochemical equivalent (ECE) but,
cathodes and anions moves towards the anode. We know that,
Q = It
vi) The movement of ion towards oppositely Where, I = Current in ampere
changed electrodes is called electrolytic t = Time in second
conduction. Putting the value of Q in equation (i) we get,
W = Z × It
vii) The oxidation takes place at anode and the If, I = 1 amp t = 1 sec.
reduction takes place at cathode. Then, W = Z
So, electrochemical equivalent of a substance can
viii) The conversion of ion into neutral species is be defined as the mass of substance deposited when
called primary change and where the neutral 1coulomb of electricity is passed through the
species combined to from secondary product. electrolytic solution for 1 sec.

ELECTROCHEMISTRY 2
 ii) Faraday’s second law of electrolysis Example :-
Statement: - Consider an electrolytic solution containing
It is states that “when same quantity of CuSO4 and AgNO3 connected in series. So,
electricity is passed through different according to Faraday second laws of electrolysis,
electrolytic solution connected in series, the
substances produced at the electrodes are
=
directly proportional to their equivalent
weight”.
⇒ =
Explanation

⇒ =

Or, =

Remember: -
 Q=I×t
 1 coulomb = 1 ampere × 1 sec
 1 Faraday = 96500 coulomb

 1st law of electrolysis

Solution – A Solution – B W = Z × It
 nd
2 law of electrolysis
Let, same quantity of electricity (Q) is passed W E
through two electrolytic solutions A and B =
W E
respectively connected in series.
According to first law of electrolysis for the  Z × 96500 = 1 gm equivalent
solution – A
W ∝Q  Z=
Or, W = Z Q …..(i)
For solution – B Electrical resistance & conductance
W ∝Q Every substance offers resistance to the flow of
Or, W = Z Q …….. (ii) electricity to a small or large extent, the law that
Taking the ratio of equation (i) and (ii) we get, gives the exact value of resistance is known as
ohm’s law.
=
Ohm’s law
Or, =
× It states that, “the strength of the current (I)
× passing through a conductor varies directly to the
potential difference (E) applied across the
Or, = conductor and inversely to the resistance (R) of
the conductor”.
Where 𝐖𝐀 and 𝐖𝐁 are the weight of Thus, according to ohm’s law
substance deposited at electrode in solution A and 𝐼=
B respectively. This law governs the passage of electricity
E and E are the equivalent mass of the through the conductor.
respective electrodes. The SI unit of electric resistance (R) is ohm.
It is represented as ‘Ω’.
Note:- At a given temperature, the electric resistance of
1 Faraday = 96500 coulomb a uniform conductor is directly proportional to the
Equivalent mass = Z × 96500
ELECTROCHEMISTRY 3
length (l) and inversely proportional to its area of Equivalent conductance (𝚲𝐞𝐪)
cross section (a). “It is defined as the conducting power of all
Thus, 𝑅 ∝ 𝑙 ……. (i) the ions produced by dissolving one gm equivalent
𝑅 ∝ ……. (ii) of electrolyte in solution. It is represented as
Combining equation (i) and (ii) we get, (𝜦𝒆𝒒).
Unit
𝑅∝ Λeq = /
∙
Or, 𝑅 = 𝜌 ……. (iii) =
Where,
𝜌 = Proportionality constant is called specific Λeq = ohm cm (gm)
resistance.
The Specific resistance (𝜌) of a conductor is
equal to the resistance offered to the passage of Relationship between equivalent conductance
electricity by a unit cube of conductor. and specific conductance
If l = 1cm , a = 1 cm2 then the specific If 1𝑐𝑚 of a solution containing 1 gm
resistance (𝜌) has a unit Ω cm. the SI unit is Ω m. equivalent of electrolyte dissolve in it, the
conductance of the solution is,
Conductance Specific conductance = equivalent conductance
 It is the reciprocal of resistance of a If Vcc of the solution containing one-gram
conductor. equivalent electrolyte present in it then.
Conductance = Eq. conductance = specific conductance × V
Or, G = …….. (iv) Or, Λeq = k × V ………… (i)
Where V is the volume of the solution in cubic cm
 It has a unit of 𝑜ℎ𝑚 or mho or Ω .
which containing 1 gm equivalent of electrolyte.
 The SI unit is called Siemen’s. it is
Suppose ‘C’gm equivalent of electrolyte is
represented as ‘S’.
present per liter of solution
i.e. Normality = C
Specific conductance The volume of the solution in cubic cm
From equation (iii) & (iv) we get, containing ‘C’ gm equivalent electrolyte
G= ∴ V=
Or, G = ∙ Putting the value of v in equation (i) we get ,
×
Λeq =
×
Or, G=k Λeq =

Where k = (kappa) specific conductance. k = ohm cm

 The specific conductance is defined as the Normality = gm equivalent × cm .
conductance of solution of electrolyte
placed in between two electrodes having an  The unit of specific conductance is
area of 1 cm2 & separated by a distance of 1 𝐨𝐡𝐦 𝟏 𝐜𝐦 𝟏 .
cm.  The unit of normality is
 The specific conductance of an electrolyte gm equivalent × 𝐜𝐦 𝟑 .
is the conductance of all the ions present in
1 cm2 solution. Molar conductance (𝚲𝐦)
 Specific conductance (k) = G ∙ It is defined as the conducting power of all
where is called as cell constant. the ions produced from 1 mole electrolyte in
aqueous solution.
 Specific conductance has unit
𝐨𝐡𝐦 𝟏 ∙ 𝐜𝐦 𝟏 or 𝐦𝐡𝐨 𝐜𝐦 𝟏 .
Note
 The unit of cell constant is 𝑐𝑚 or 𝑚 .

ELECTROCHEMISTRY 4
Relationship between molar conductance and Factor affecting the conductance
specific conductance The concentration of an electrolyte depends
If 1𝑐𝑚 of a solution containing 1 mole of up on following factors.
electrolyte dissolve in it, the conductance of the i) Nature of electrolyte
solution is, The conductance of a solution depends upon the
Specific conductance = molar conductance number of ions present in solution. Greater the
If Vm cm3 of the solution containing one mole number of ions, greater will be the conductance of
electrolyte present in it then. the solution. Strong electrolyte like HCl, NaCl


molar conductance = specific conductance × V produce large number of ions in solution, so that
Or, Λm = k × V ………… (i) it’s conductance will be high. But in case of weak
Where Vm the volume of the solution in cubic cm electrolyte like CH3COOH, NH4OH etc. less ions
which containing 1 mole of electrolyte. will be produced in solution & its conductivity is
Suppose ‘Cm’ moles of electrolyte is present per very poor.
liter of solution
i.e. Molarity = C ii) Concentration of solution
The volume of the solution in cubic cm The equivalent as well as molar conductance of
containing Cm mole electrolyte electrolyte depends upon the concentration of the
solution.
∴ 𝑉 =
With increase in dilution the molar conductivity
Putting the value of V in equation (i) we get , will be increases because on dilution the
×
Λ = dissociation of electrolyte goes on increasing.
× The molar conductance of strong electrolyte &
Λ = weak electrolyte with dilution discus below.

Unit of Λm is ohm cm mol .

a) Variation of molar conductance with dilution
Relationship between equivalent conductance of strong electrolyte
and molar conductance →Strong electrolyte ionizes almost completely &
We know that, the solution of such electrolyte have high
× concentration.
Λeq =
→The conductance increases slightly on dilution
×
Or 𝑘= ……….. (i) when the dilution is infinite. The molar
× conductance of the solution approaches a limiting
Λm = value.
Or 𝑘 =
×
………… (ii) →When the concentration approaches zero
(infinite dilution) its conductance is called molar
Where,
conductance at infinite dilution (Λ° 𝑚).
k = specific conductance
→The molar conductivity of strong electrolyte is
from equation (i) & (ii) we get
varying with concentration is given by the
× × following equation.
= Λ 𝑚 = Λ° 𝑚 − 𝑏√𝑐
Where,
b = constant & its value depends upon the
⇒ Λeq × Normality = Λm × molarity nature of solvent & temperature.
⇒ = =x Λ° 𝑚 = molar conductance of infinite
dilution.
c = concentration.
Where, x = acidity of a base or basicity of an acid
The above equation is also called
or total valency of metal atom in salt.
“Debye – Huckle – Onsagar” equation.

ELECTROCHEMISTRY 5
b) Variation of molar conductance with dilution strong electrolytes like NaCl, CH COONa and HCl
in weak electrolyte as by Kohlrausch’s law.
A weak electrolyte dissociates to a very small
extent in solution. Thus, the molar conductance of Λ° = λ° + λ°
weak electrolyte is much lower than a strong Λ° =λ °
+ λ°
electrolyte at the same concentration. Λ° = λ° + λ°

iii) Temperature Λ° + λ°
The conductance of solution varies with
temperature the conducting power increases near = λ° + λ° + (λ° + λ° )
about 2% with every degree rise in temperature. − (λ° + λ° )

Kohlrausch’s law Λ° = Λ° + Λ° − Λ°
This law state that, “At infinite dilution, when
dissociation is complete each ion makes a definite Cell
contribution towards molar or equivalent A cell is a device in which an electro-chemical
conductance irrespective of the nature of the change in system is brought about.
other ion in which it is associated and the value of Depending upon the type of electro-
the equivalent conductance is equal to the sum of chemical change occurring in a cell the cell are up
the contributions of cation and anions.” to two types.
i) Electrolyte cell
Mathematically, ii) Electro-chemical cell (Galvanic cell)
Kohlrausch’s law can be represented as i) Electrolyte cell
follows, It is a device in which the electrical energy is
Λ° = 𝑥. 𝜆° + 𝑦 𝜆° converted into chemical energy resulting in a
Where, chemical reaction.
Λ° = equivalent conductance of electrolyte
CA at infinite dilution. In electrolyte cell
𝜆° = Equivalent conductance of cation (𝐶 ) i) The two electrodes are dipped in the solution of
at infinite dilution. an electrolyte and are connected to the external
𝜆° = Equivalent conductance of cation (𝐴 ) source by the help of connecting metallic wires.
at infinite dilution. ii) The current is carried by connecting metallic
x and y are the number of cation and anion wires by electrons where as it is carried through the
produce for formulae unit. solution of ions.
iii) The electrode which is connected to the
negative terminal of battery is called cathode and
Applications of Kohlrausch’s law
that of which connected to positive terminal of
Calculation of molar conductivity at infinite
battery called anode.
dilution (𝚲° 𝒎) for weak electrolyte: -
iv) the passage of electricity through the electrolyte
Generally, the molar conductivity of a weak
carries the redox reaction which is otherwise non-
electrolyte cannot be determined at infinite dilution
spontaneous in nature.
because its conductance is low in solution and the
v) In electrolytic cell the process of electrolysis is
dissociation is not complete at very high dilution.
take place.
The molar conductivity of such an electrolyte at
infinite dilution can be calculated by using Electrolyte + Electrode ⎯⎯⎯⎯⎯⎯ Electrolysis.
Kohlrausch’s law.
Let us consider the molar conductivity of ii) Galvanic cell
CH3COOH as a weak electrolyte. It is an electrochemical cell that converts
By applying Kohlrausch’s law the chemical energy of a spontaneous redox
reaction into electrical energy. A galvanic cell is
Λ° = λ° + λ° also called as voltaic cell.

The above equation can be arrived by knowing

the molar conductivity at infinite dilution for the

ELECTROCHEMISTRY 6
Electrochemical cell 𝐂𝐮𝟐 (𝐚𝐪) + 𝟐𝐞 → 𝐂𝐮(𝐬)
The cell which can convert chemical → The copper half-cell at which reduction takes
energy into the electrical energy by means of redox place is called cathode and the Zn half-cell at
reaction is known as electrochemical cell. which oxidation takes place is called anode.
OR → since electron flow from the Zn rode towards
Electrochemical cell is a device in which the copper rode. The electrical energy is produced the
redox reaction takes place indirectly and the current is flow from the opposite direction of
decrease of free energy appears in the form of electron flow i.e., beaker B to A.
electrical energy. → The neutrality of the two solution is maintained
Let us consider 𝑍𝑛 − 𝐶𝑢𝑆𝑂 Reaction in a cell. by the salt bridge.
→ The overall cell reaction is
Construction 𝐙𝐧(𝐬) ⟶ 𝐙𝐧𝟐 (𝐚𝐪) + 𝟐𝐞
The apparatus consists of two beakers, a cupper 𝐂𝐮𝟐 (𝐚𝐪) + 𝟐𝐞 ⟶ 𝐂𝐮(𝐬)
rode, a galvanometer, salt bridge & insulated
cupper wire. The different components are 𝐙𝐧(𝐬) + 𝐂𝐮𝟐 (𝐚𝐪) ⟶ 𝐙𝐧𝟐 (𝐚𝐪) + 𝐂𝐮(𝐬)
connected are showing below
→ The cell can be represented as
𝐙𝐧(𝐬)/𝐙𝐧𝟐 (𝐚𝐪) || 𝐂𝐮𝟐 (𝐚𝐪)/𝐂𝐮(𝐬)
Salt bridge
→ It is a which keeps internal continuity between
two half cells of an electrochemical cell by means
of inert electrolyte solution placed in ‘U’ tube.
→ Commonly used inert electrolyte are KCl,
KNO3 etc.
→ These are the electrolyte whose ions are not
involved in the electrochemical change and also do
not react with the electrolyte electrically connected
with them.
i) 0.1.M ZnSO solution is taken in beaker ‘A’ &
Zn rod put on this solution. It is called Zn-half cell. Function of the salt bridge
ii) 0.1.M CuSO solution is taken in the beaker ‘B’  It connects the solution in the half cell &
& Cu rode put on this solution is called cupper completes the cell circuit.
half-cell.  The electrolyte present on the salt bridge is
iii) Both electrodes are connected to terminal of split into ionic form.
galvanometer by means of insulated cupper wire to  The positive ion form in the oxidation half-
detect the flow of current. cell is neutralized by the negative ion
iv) The two solutions are rejoined by a ‘U’ shaped present on the salt bridge.
tube known as salt bridge. The salt bridge contains  The negative ion form in the reduction half-
an inert electrolyte & end of the ‘U’ tube have cell is neutralized by positive ion present in
porous plug. the salt bridge.
 So overall the salt bridge is used to
maintain the electrically neutrality of
Function solution and helps to continue the flow of
→ On connecting the two rods, in Zn rod dissolves
electricity.
to form 𝑍𝑛 ion. Thus, oxidation takes place at
the Zn rode. It is also called oxidation half cell. Electrode potential
𝐙𝐧 ⟶ 𝐙𝐧𝟐 + 𝟐𝐞 The tendency of an electrode to loss or gain
→ The electron produced in the oxidation half-cell electrons is called electrode potential.
flow towards the cupper rode with the half of If oxidation takes place at the electrode is
conducting wire & are taken up by 𝐶𝑢 to give called its oxidation potential. If reduction takes
cupper metal. It causes an increase in the mass of place at the electrode is called its reduction
copper plate. Thus, reduction takes place at the potential.
copper half cell it is also called reduction half cell.

ELECTROCHEMISTRY 7
Standard electrode potential → Depending upon the type of reaction taking
If in the half cell, the metal rode is suspended place, the hydrogen electrode can act as anode or
in a solution of 1 molar concentration and the cathode in an electrochemical cell.
temperature kept at 298 k, the electrode potential is → The standard electron potential of NHE is ‘o’.
called standard electrode potential. so, the potential of all other electrodes are found by
It is represented as ‘E°’. coupling NHE by the help of salt bridge.

Cell potential (emf of cell) Limitation of SHE

“It is defined as the force which causes the i) It is difficult to maintain unit molar concentration
flow of electron from one electrode to the other and of H ions & also 1 atm pressure uniformly for a
results in the flow of current”. long time.
ii) The hydrogen electrode get poison in presence
Cell Potential = O.P + R.P of impurity.

Cell Potential = O.P at anode – O.P at Cathode Electro chemical series

→The arrangement of different electrodes in an
Cell Potential = R.P at cathode – R.P at anode increasing order of their standard reduction
potential is called as electrochemical series.
→It is also known as activity series.
Note Note
i) Cell potential in terms of oxidation potential. The value of oxidation potential of an electrode can
Ecell = Eanode – Ecathode be obtained by reversing the sign of the reduction
ii) Cell potential in terms of reduction potential. potential for that electrode.
Ecell = Ecathode – Eanode
Nernst equation (Dependence of emf on conc. Of
electrolyte and temperature)
Standard hydrogen electrode (SHE/NHE)
→Standard electrode potential can be measured
→ The NHE consist of a platinum foil coated with
when concentration of electrolyte is one mole(m)
finely divided platinum, called platinum black.
& temperature at 298 k.
Dipping in a solution of an acid generating
→But if the concentration of electrolyte &
hydrogen ion.
temperatures is changed, then the electrode
→ One molar concentration of the acid solution
potential has a different value.
will be taken.
→The value of electrode potential at different
→ Hydrogen gas at a pressure of one atm bubbled
concentration & temperature can be obtained by
continuously into solution & temperature is
using Nernst equation.
maintained at 298 k.
→Nernst gave a relationship between reduction
potential of an electrode and concentration of the
ions in the electrode reaction.
M + ne ⟶ M(s)
. [ ]
E = E° − log [ ]
As the concentration of pure solid & pure
liquid is one. The Nernst equation can be written
as,
.
E = E° + log[M (aq)]
Where, R = Gas constant = 8.314 J. mol 𝐾
T = Temperature in Kelvin i.e. 298 K.
n = Number of electrons transfer the half-
cell reaction.
F = Faraday constant (96500).
The following reaction occurs at the surface of E = E° +
.
log[M (aq)]
the ‘Pt’ foil.
H (g) ⟶ 2H + 2e Substituting the value of R, T & F we get
2H (aq)+ 2e ⟶ H (g)
ELECTROCHEMISTRY 8
 . × . × Relationship between free energy, cell potential
E = E° + ×
log[M (aq)]
& equilibrium constant.
.
E = E° + log[M (aq)]
We know that,
∆G° = −nFE ° ………… (i)
𝟎.𝟎𝟓𝟗𝟏
𝐄𝐌𝐧 = 𝐄° 𝐌𝐧 + 𝐧
𝐥𝐨𝐠[𝐌𝐧 (𝐚𝐪)] 𝐯𝐨𝐥𝐭 Also, we know that,
𝐌 𝐌 ∆G° = −2.303RT log K ……….. (ii)
Comparing equation (i) and (ii) we get
(coulomb × volt = Joule)
−nFE ° = −2.303RT log K
This is known as Nernst equation.
°
𝐧𝐅𝐄𝐜𝐞𝐥𝐥
Application of Nernst equation Or 𝐥𝐨𝐠 𝐊 𝐜 =
Nernst equation can be applied in the following 𝟐.𝟑𝟎𝟑𝐑𝐓
sections.
i) Measurement of pressure of a gas or
concentration of solution. Commercial cell (Batteries)
ii) Measurement of PH of a solution.  It is an arrangement of electrochemical cell
used as an energy source.
 It should be compact and portable.
Relation between Gibb’s energy change & emf  It should have reasonably long time
of a cell whether in use or not in use.
→ It is known that; Gibb’s energy is a measure of  The drop in voltage should be steady & not
maximum useful work that is available in a sudden.
chemical reaction. We can write
∆G = Maximum work Types of commercial cell
→If the potential of two electrodes differs by Ecell, According to their construction & function
then the maximum work done is given as batteries are up to three types which are as follows.
Maximum work = nF. Ecell a) Primary cell
Where n is the number of molars of electron  These are the galvanic cell which cannot be
transferred, F is the Faraday constant. recharged. The cell reaction in the primary
In a Daniel cell, the work is done on the cell can’t be reversed.
surrounding because electrical energy goes through Dry cell
the external circuit so the work is given a negative
sign.
−nFE = ∆G
Where,
∆Gr = Maximum work
For standard electrode potential 𝐸 ° . The above
equation can be written as,

∆𝐆𝐫 ° = −𝐧𝐅𝐄°𝐜𝐞𝐥𝐥

Where,
∆G ° = the standard free energy change of a Construction
reaction.  It consists of a cylindrical zinc vessel which
If ∆G ° = negative (Reactions becomes is filled with a paste of NH4Cl in which
spontaneous/ feasible) ZnCl2 is added.
 The zinc cylinder act as anode and cathode
Significance is a graphite rod which is surrounded by
 The above reaction is used to predict MnO2 + C (power).
feasibility of a reaction. If ∆G° is negative  The cell has an outer insulation of
the reaction is spontaneous or feasible. cardboard.

ELECTROCHEMISTRY 9
Working b) Secondary cell
 For leak proof cell there is an outer  The secondary cell can be recharged these
covering of steel because zinc case are called storage cell or accumulators.
develops holes from which the material Example- Leads storage cell which is also
leaks. known as leads accumulator are used in
The following reaction takes place in dry cell. automobiles.
At anode
Zn (s) ⟶ Zn + 2e i. Lead storage battery (Lead accumulator)
At cathode  It consists of six such cells & their
2(𝑁𝐻 (𝑎𝑞) + 𝑀𝑛𝑂 (𝑠) + 𝑒 ⟶ MnO(OH) combined voltage is 6-12 volt.
+NH )  In each cell, anode is a lead grid packed
Net reaction with finely divided spongy lead & cathode
Zn (s) + 2NH (aq) + 2MnO (s) ⟶ Zn is lead grid coated with PbO2.
+2MnO(OH) + 2NH  The electrolyte is 38% by mass of H2SO4
In this cell, Zn is oxidized to Zn at cathode & with density1.3 𝑔𝑚𝐿 .
manganese is reduced from + 4 to + 3 states. The
NH liberated from a complex with Zn ions.
It gives a voltage in between 1.2 to 1.5 v.
Limitation
 Once the cell become dead it can’t be
recharged or used again.
 The electrolyte used NH4Cl, being acidic &
damaged the anode.

Mercury Cell :
Mercury cell consists of zinc-mercury amalgam as Following reaction takes place in the lead storage
anode and a paste of mercuric oxide (HgO) and cell.
carbon as the cathode. The paste of ZnO and KOH At anode :-
is used as electrolyte Pb(s) ⟶ Pb (aq) + 2e
Pb (aq) + SO (aq) ⟶ PbSO (s)

Net anode reaction

Pb(s) + SO (aq) ⟶ PbSO (s) + + 2e …(i)

At cathode
PbO + 4H + 2e ⟶ Pb (aq) + 2H O
Pb + SO (aq) ⟶ PbSO (s)
.
The cell reactions are Net cathode reaction:-
Anode: Zn(Hg) + 2OH- ⟶ ZnO + H2O + 2e- PbO (s) + 4H + SO + 2e ⟶
Cathode: HgO + H2O + 2e- ⟶ Hg + 2OH- PbSO (s) + 2H O … (ii)
Net Reaction: Zn(Hg) + HgO ⟶ ZnO + 2OH-
The cell potential is approximately 1.35 volt. From the equation (i) & (ii) the cell reaction
The cell potential is remains constant during its life becomes
as the overall reaction does not involve any ion in Pb(s) + PbO (s) + 2H SO
solution whose concentration can change during its ⟶ 2PbSO (s) + 2H O
use. Mercury cell is suitable for low current device Cell notation
like hearing aids, watches, etc. Pb, PbSO / H SO (aq) / PbO , Pb
From the net cell reaction, we can say that
when the cell works, the concentration of H SO
decreases and its concentration also fall. Battery is
recharge when the density falls below 1.2 gmML .

ELECTROCHEMISTRY 10
Recharging: - Palladium (Pd) or cobalt oxide (CoO) are added to
When suitable voltage of electric current is porous carbon electrode.
passed in the opposite direction the cell reaction is The catalyst accelerates the reaction &
reversed. electrolytic solution KOH is placed between the
2PbSO + 2H O ⟶ Pb(s) + PbO (s) + 2H SO electrode. Here KOH act. as an electrolyte.
 Hydrogen & oxygen are bubbled through
ii. Nickel-Cadmium cell: the porous electrode under pressure into the
It consists of a Cd anode, Ni(OH)3 as cathode and electrolyte.
NaOH or KOH acts as electrolyte.  Both H2 & O2 are continuously supply to
the fuel cell.
 The reaction which takes place on the cell
are
At anode
𝟐𝐇𝟐 + 𝟒𝐎𝐇 (𝐚𝐪) ⟶ 𝟒𝐇𝟐 𝐎 + 𝟒𝐞
At cathode
𝐎𝟐 (𝐠) + 𝟐𝐇𝟐 𝐎(𝒍) + 𝟒𝐞 ⟶ 𝟒𝐎𝐇 (𝐚𝐪)
Over all cell reaction is
𝟐𝐇𝟐 (𝐠) + 𝐎𝟐 (𝐠) ⟶ 𝟐𝐇𝟐 𝐎(𝒍)

Advantage of Fuel Cell

Cell reaction during use of battery i) Due to continuous supply of fuel these cells do
Anode : Cd + 2OH- ⟶ CdO + H2O + 2e- not become dead. These cells do not cause
Cathode: 2Ni(OH)3 + 2e- ⟶ 2Ni(OH)2 +2OH- pollution.
Net: Cd + 2Ni(OH)3 ⟶ CdO + 2Ni(OH)2 + H2O ii) It has a good efficiency power (60 – 70%).

The reverse reaction takes place during recharging. Corrosion

CdO + 2Ni(OH)2 + H2O ⟶ Cd + 2Ni(OH)3 →It is an electro-chemical process in which the
This battery gives constant potential during its life surface of the metal is slowly eaten away when it
because the net cell reaction does not involve any comes in contact with the atmosphere. Corrosion
ion whose concentration can change during its life may also be called weeping of metal.
time. OR
→The process of coating of surfaces of metallic
FUEL CELL: - objects with oxides or other salts of the metal is
These are the electrical cell which are design to called corrosion.
convert the energy from the combination of fuel
like𝐻 , methanol (CH3OH) and some hydrocarbon Examples: Rusting of irons, Tarnishing of silver
directly into electrical energy without using any objects and development of green coating on
thermal devices like boiler, turbine etc. copper or bronze etc.

Disadvantages of corrosion
Formation of unstable coating on the surface
destroys the metal objects. It causes enormous
damage to the objects made of metal especially
iron objects.

Mechanism of corrosion
Corrosion is an electrochemical phenomenon. In
corrosion metal is oxidized by loss of electrons to
oxygen of air forming oxides. This is why
corrosion occurs in presence of water and air.

The cell consists of porous carbon electrode &

finely divided catalyst like Platinum (Pt).

ELECTROCHEMISTRY 11
Example:
In rusting of iron at a particular spot of the metal
oxidation takes place. This spot behaves as anode.
2Fe(s) → 2Fe2+ + 4e- , Eo = -0.44V
Electrons releases at anodic spot move through the
metal and go to another spot on the metal and
reduce oxygen in presence of H+ ion. This spot
behaves as cathode.
O2(g) + 4H+ (aq) + 4e- → 2H2O (l) ; Eo = 1.23V
Hydrogen ion is available from the acids formed by
dissolution of CO2 or other oxides from air into
water.
H2O + CO2 → H2CO3
H2CO3 → H+ + HCO3-

The overall cell reaction is

2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+ (aq) + 2H2O(l)
E°cell = 1.67V
The ferrous ions are further oxidized by
atmospheric oxygen to ferric ions.

4Fe2+ + O2 + 4H+ → 4Fe3+ +2H2O

Ferric ions form hydrated ferric oxide and produce
H+ ion which accelerate the reaction further
2 Fe3+ +x.H2O → Fe2O3 x.H2O + 6H+
Prevention of corrosion
→Corrosion can be prevented by preventing the
surface of the metallic objects to come in contact
with atmosphere. For this process metal surface is
covered with paints or by some chemical like
bisphenols.

→ By covering the metal surface by other metals

that are either inert or non-react with atmosphere
and save the object.



ELECTROCHEMISTRY 12