JEE Advanced Revision Notes

Chemistry
Electrochemistry

Electrochemistry deals with

● Oxidation-reduction responses that either produce or use electrical energy
and electrochemical responses take place in cells.
● Each cell has two electrodes, operators through which electrons enter or
leave the cell.
Three effects are:
● Either oxidation or reduction occurs at each electrode.
● Electrons flow through an external captain.
● Ions flow in the electrolyte result.

There are two types of electrochemical cells: Voltaic cells and Electrolytic
cells.
● A voltaic cell derives its energy from spontaneous redox reactions, while
electrolytic cells involve non-spontaneous reactions and thus require an
external electron source like a DC battery or an AC power source.
● An electrolytic cell is an electrochemical cell in which the energy from an
external power source is used to drive a normally non-spontaneous
reaction, i.e. apply a reverse voltage to a voltaic cell.
Electric current is considered a flow of electrons. The substance which allows the
electric current to pass through it is called a conductor.

Two types of Conductors:

S.No Electronic Conductors
Conducts electricity by the flow of
1
electrons.
Electrons flow from the negative
2
end to the positive end.
3 No transfer of matter takes place.
4 In this there is no chemical change.
Electrolytic conductor
Conduct electricity by the movement
of ions.
Charge species (ions) move toward
the oppositely charged electrodes.
Transfer of matter takes place.
Chemical decomposition takes place
at the electrodes.

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 It decreases with rising It increases with the increase in
5
temperatures. temperature.
Metals, alloys, graphite, solid such Liquids of molten salt, an aqueous
6
as Silver, Copper etc. solution of salts, and acids.

Electrochemical Cells:
An electrochemical cell is a device that can induce electrical energy from the
chemical responses being in it, or use the electrical energy supplied to it to grease
chemical responses in it.
● This device is able of converting chemical energy into electrical energy, or
vice versa.
● A common illustration of an electrochemical cell is a standard 1.5- volt cell
which is used to power numerous electrical appliances similar to television
remotes and timepieces.

Daniel Cell:
● Example of a galvanic cell is the Daniel cell.
● It consists of zinc and copper half-cells.
● This cell converts the chemical energy liberated during the redox reaction.
Zn( s )  Cu 2( aq )  Zn2( aq )  Cu( s )
● Electron flow from Cu to Zn
● Zinc is deposited at the zinc electrode and Copper dissolves at copper
electrode.

Galvanic cell:
● A Galvanic cell and a voltaic cell are the same thing. There are other cells,
however, similar to an electrolytic cell.
● A Galvanic/ voltaic cell converts chemical energy into electrical energy.
An electrolytic cell uses electrical energy to drive a non-spontaneous
response i.e., converts electrical energy into chemical energy.
● Example: Zn rod is dipped in zinc sulphate solution
● Zinc undergoes oxidation, gives electrons, it is electron-rich, so
represented by a negative sign. Zn  Zn2  2e

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 ● Cu 2 present in the solution undergoes reduction on Cu rod surface. Cu rod
is electron-poor, so it is represented by a positive sign. Cu 2  2e  Cu
● Electron flow in the external circuit from Zn to Cu.
● A salt bridge is used to prevent the accumulation of charges, at the
electrodes.
● The reaction taking place in the electrochemical cell is
Zn( s )  CuSO4( aq )  ZnSO4( aq )  Cu( s )

Electromotive force of the cell:

The difference between two electrode potential present in the electrochemical cell
is the electromotive force of the cell.
Ecell = Standard electrode potential of right hand electrode-Standard electrode
potential of left hand electrode
● If the EMF of the cell is positive, the cell reaction is spontaneous or
irreversible. We can draw current from it.
● If EMF of the cell is negative, cell reaction is nonspontaneous or reversible.
We cannot draw current from it.
● If the EMF of the cell is zero, the cell reaction is at equilibrium.

Image: EMF of a cell

The reduction potential of an electrode is exactly equal in magnitude but opposite
in sign to its oxidation potential.

Electrochemical Series:
● In the IUPAC system of referring to electrode potentials, standard reducing
potentials are simply called standard potential.

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 ● In the electrochemical series, the metals are arranged in the increasing
order to reduce potential.
● Metals placed above can displace the below metal ions from their solution.
1
● Oxidation power ∝ reduction potential ∝
Oxidation potential
1
Reducing power ∝ oxidation potential ∝
reduction potential
Note: In two half-cell reaction having electrode potential E1° and E°2 are combined
to give a third half-cell reaction having an electrode potential E°3 then,
G3  G1  G2
n3 FE3  n1FE1  n2 FE2
n1E1  n2 E2
E3 
n3
If the number of electrons involved are equal E3  E1  E2

EMF of Galvanic cell -Nernst Equation:

The variation of electrode potential and cell potential with a concentration of ions
in solutions is given by Nernst equation which is derived from Vant’s Hoff
isotherm equation.
G  G   2.303RT log Q
R is the univeral gas constant 8.314 J / K / mole  .
T is the temperature in kelvin.
n= number of electrons involved in the reaction
F= Faraday =96500 coulombs
Q= reaction quotient
2.303RT  Product  ...... 1



E cell =E cell 0 log

nF  Reactants
By substituting the value of F, R and T(298 K) in the above equation(1) we get,


E cell =E cell 0
0.059
log
 Product 
n  Reactants

For Cation Electrodes:

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The Nernst equation for a single electrode potential  EM n
/M  at 298K is
M n  (aq)  ne  M ( s)
The equilibrium state EMF is given by:
M n  (aq)  ne  M ( s)
RT 1
E  Eo  ln
nF c
2.303RT 1
E  E  log
nF c
 c   M n  

 M n   is the molar concentration of the metal ion.

 
R is the univeral gas constant 8.314 J / K / mole  .
T is the temperature in kelvin.
n is the numnver of electrons involved in the reaction.
F is the faraday’s constant (96500 C/mole).
The concentration of pure liquid and solid are taken as one so, the expression will
be:
0.059
(or) E  E   log  M n  
n

Electrolytic solution resistance and conductance:

Ohm’s Law: It states the current (I) flowing through a conductor at a given
temperature is proportional to the potential difference (V) and proportional to
resistance.
Ohm’s law formula is written as:
V∝I
Thus, V = RI where R is a constant called resistance. R depends on the dimensions
of the conductor and also on the material of the conductor. Its SI unit is Ohm (Ω)

Resistance(R): It is the opposition to the flow of current offered by the

electrolytic solution. Its unit are Ohm (Ω).
The two parallel electrodes of the cell and inversely proportional to the area of
l l
cross-section(A) of electrode i.e., R OR R = .
A A

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Conductance (G):
It is the reciprocal of the electrical resistance(R).
1
G
R
It measures the ease with which the current flows through a conductor.
1
G
R
1 1 1 l
G  k k G
 l l A
A A
Where, G= Conductance.
 = Specific conductance (Conductivity).
l
= Cell Constant
A
S.I unit of conductance = Siemens(S).
The conductance or the current conducting capacity of an electrolytic solution
can be expressed in terms of
● Specific conductance (k) Kappa
● Molar conductance   m 
● Equivalent conductance   

Specific conductance (K): It is reciprocal of specific resistance   

1
k

l 1 1 l
R  . ;  .
A G k A
l
k G
A
l
G= conductance, =cell constant
A
Molar conductance   m 
It is the conducting power of all the ions produced by dissolving
k
m 
molarity

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 k ( Scm1 )  1000(cm3 / L)
 m ( Scm2mol 1 ) 
molarity (mole / L)

Equivalent Conductance:
It is the conducting power of all the ions produced by dissolving 1 gram
equivalent of an electrolyte (or) The conductance of a solution containing 1 gram
equivalent of the electrolyte placed between two parallel electrodes separated by
unit length and area large enough to contain that 1 mole is called Equivalent
conductance.

 eq   ohm1cm2eq1  

k ohm1cm1  1000 
N (eq.wts / L)

 eq   ohm
 
k sm1  103
1
m eq2 1
 N (eq.wts / L)

Factors Affecting Molar and Equivalent Conductance

● Nature of electrolyte
● Nature of the solvent
● Viscosity of solvent
● Temperature
● Concentration of electrolyte
● Size of the ions produced and their solvation

Effect of dilution: With both  eq   as well as   m  of both weak strong

electrolytes increases.
Specific conductivity (k) decreases with dilution because of the decrease in the
number of ions per cm3 of electrolyte.

 
Effect of Temperature: The conductivity  eq and   m  of all electrolytes
increases with increase in temperature.

Debye-Huckel-Onsager equation:

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  
 82.4 8.2  10 5 
c  o   1
 3
 o  C
 (DT) 2 (DT) 2 
  
Here,
D= Dielectric constant of water
T = Temperature in kelvin scale
c = Equivalent conductance at conc. ‘c’
o = equivalent conductance at almost zero concentration or infinite dilution.
 = Viscosity coefficient of solvent
c   o  b C , where b is constant and depends on the nature of the solvent and
temperature.

Electrolysis:
Non electrolyte: The substance which does not conduct electricity either in its
molten state or in aqueous solution is called non-electrolyte.
Electrolyte: A substance, that is in the molten state or in the dissolved state
containing ions and is functioning as an electrically conducting medium is called
an electrolyte.

Faraday’s Law of Electrolysis:

First Law:
The amount of the substance deposited or electrolysed is directly proportional to
the quantity of electricity passed through the electrolyte.
● The weight of the substance deposited on the electrode for 1 coulomb of
electricity is called electrochemical equivalent (Z).
● The unit for electrochemical equivalent is gram/coulomb (g/C).
● Electrochemical equivalent depends only on the nature of the electrolyte.

Second Law:
When the same quantity of electricity is passed through different electrolytes
connected in series the weights the substances deposited will be in the ratio of
their equivalent weight.
mass of the hydrogen Equivalent mass of hydrogen
=
mass of copper Equivalent mass of copper

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 ● Chemical equivalent weight of an element.
 W1 E1 
   Where,
 2
W E2
W1 and W2 are weight deposited of two elements.
E1 and E2 are the equivalent weight of two element
● 1 Faraday of electric current or 96500 coulombs of electricity or one mole
of electron, when passed through an electrolyte 1G.E.W of a substance will
be deposited.
● 1 coulomb deposited
 gram equivalent weight 
=  
 96500
E
= = e (electrochemical equivalent)
F
● 1Faraday=charge present on 6.023  1023 electrons
● 1 coulomb  6.25  1018 electrons

mass actually produced

Current Efficiency: % of current efficiency   100
mass of substance expected

Electrochemical corrosion:
The process of corrosion may be chemical (or) electrochemical in nature
● The anodic dissolution of a metal under the conditions of corrosion is
known as electrochemical corrosion
M  M n   ne

Passivity:
The phenomenon of a metal reaching a stage of non-reactive state in its reaction
with concentrated acids may called passivity.
● Iron group of metal and some other transition metals are rendered passive
with concentrated acids.
● Passivity of metal can be classified into
1. Chemical passivity
2. Mechanical passivity
3. Electro-chemical passivity

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Chemical Passivity:
● Non-reactivity of metals after initial reaction with concentrated HNO3
● Passive iron doesn’t dissolve in dill HNO3 and iron don’t displace Ag from
AgNO3

Mechanical passivity:
● In some cases, dissolution of metal stops due to visible oxide film
formation.

Electrochemical passivity:
● Metal with more -ve potential function as anode in cell.
● Generally, Fe, Ni, Co functions are anode.
● They dissolve as M  M n   ne
● At a particular stage anode stops dissolving due to formation of an invisible
metal oxide film. This phenomenon is called electro-chemical passivity.

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