KENDRIYA VIDYALAYA SANGATHAN BENGALURU REGION

CLASS XII
CHAPTER 3 : ELECTROCHEMISTRY

Types of Cells
[Link] cells (GalvanicCell)
[Link] cell.
In Galvanic cell the chemical energy of a spontaneous redox reaction is converted into
electrical work.
In Electrolytic cell electrical energy is used to carry out a non-spontaneous redox reaction.
Electrochemical cell is a device that converts the chemical energy in to electrical energy.
Standard cell Potential or electromotive force (emf): The cell potential is the difference
between the electrode potentials of the cathode and anode. E 0 cell  E 0 cathode  E 0 anode
Standard hydrogen electrode (SHE): It is assigned a value of zero for it electrode potential
and is used as reference electrode
1. Salt Bridge connects the solution of two half cells & completes the cell [Link]
prevents the transference or diffusion of the solutions from one half cell to other.

The Standard Electrode Potential for any electrode dipped in an appropriate solution is
defined with respect to standard electrode potential of hydrogen electrode taken as zero
E0 cell = E0 cathode-E0 anode
Cell reaction:
Cu(s) + 2Ag+(aq)⎯→ Cu2+(aq) + 2 Ag(s)
Half-cell reactions:
Cathode (reduction): 2Ag+(aq) + 2e– → 2Ag(s)
Anode (oxidation): Cu(s) → Cu2+(aq) + 2e–
The cell can be represented as:
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
Ecell = Eright – Eleft = EAg+⎥Ag – ECu2+⎥ Cu
The standard hydrogen electrode consists of a platinum electrode coated with platinum black.
The electrode is dipped in an acidic solution of 1M concentration and pure hydrogen gas is
bubbled through it at 1 bar pressure at 298K. It is represented as Pt(s) /H2(g) /H+(aq) . Its
Electrode potential is zer0
aA + bB→cC + dD
Nernst equation can be written as at 298 K, R= 8.314 J/K/mol, F =96500 C/mol
Ecell = E°cell – (RT/nF)

Ecell = E°cell – 0.059 Log [C]c[D]d

n [A]a[B]b

Relation between standard Gibbs energy change and standard Emf of the cell
∆rG°=-nFE0 cell
The standard potential of the cells is related to equilibrium constant.
∆rG°= -RT lnk
∆rG°=-2.303RTlogK
Concentration dependence of the potentials of the electrodes and the cells are given by Nernst
equation.
CONDUCTIVITY AND MOLAR CONDUCTIVITY
l
1. Resistance: R   ( ) Where  resistivity. Unit of resistance is ohm
A
2. The Resistivityfor a substance is its resistance when it is one metre long and its areaof
cross section is one m2.
3. Conductance : The ease with which current flows through a conductor is called its
1
conductance. It is reciprocal of the resistance G  .The SI unit is Siemens,
R
represented by the symbol‘S’ and is equal to ohm–1 .
4. Conductivity : of any conductor is the reciprocal of specific resistance or
Resistivity and is denoted by  .The SI units of conductivity are Sm–1 but quite
often, κ is expressed in S cm–1.
5. Conductivity of a materialin Sm–1 is its conductance when it is 1 m long and its area
1 1 l
of crosssection is 1 m2.  =      = GG*
 RA
6. Cell constant The quantity l/A is called cell constant denoted by the symbol, G*. It
depends on the distance between the electrodes and their area ofcross-section and has
the dimension of length–1 and can be calculatedif we know l and A.
l
G*(cell constant)=
A
7. The conductivity of a solution at any given concentration is the conductance of one
unit volume of solution kept between two platinum electrodes with unit area of cross
section and at a distanceof unit length.
8. Molar Conductivity: It is defined as the conducting power of all the ions produced
by one gram mol of an electrolyte in a solution.
  (Sm -1 )
m   m (Sm 2 mol -1 ) 
C 1000( Lm )  Molarity (molL1 )
3

 (Scm -1 )  1000( Lcm 3 )

 m (Scm 2 mol -1 ) 
Molarity (molL1 )
9. Limiting molarconductivity :When concentration approaches zero, the molar
conductivity is known as limiting molar conductivity and is represented by the symbol
0
10. Conductivity of a solution decrease with dilution because Conductance of a solution
is the conductance of ions present in a unit volume of the solution.
On dilution the number of ions per unit volume decreases. So the conductivity
decreases.
• Molar conductivity increases with decrease in concentration. This is because the
total volume, V, of solution containing one mole of electrolyte also increases. It
has been found that decrease in κ on dilution of a solution is more than
compensated by increase in its volume.

11. Variation of molar conductivity with dilution (concentration is decreased)

a) FOR STRONG ELECTROLYTES molar conductivity increases slowly
with dilution because in strong electrolytes the dissociation of the electrolyte
in to ions is almost complete however interionic forces are quite strong. Upon
dilution ionic attractions are reduced. This leads to increase in ionic
mobility thus molar conductivity increases with dilution(or decrease in
concentration)
 b) FOR WEAK ELECTROLYTES molar conductivity increases steeply with
dilution because inweak electrolytes the dissociation of electrolyte into ions is
comparatively less. Dilution helps in dissociation of electrolyte .As a result
more ions are formed and corresponding value of conductivity also increases.
This increase quite large.

Molar conductivity versus c1/2 for acetic acid (weak electrolyte) &KCl
(Strong electrolyte) in aqueous solution

12. Kohlrausch’sLaw : The law states that limiting molar conductivity of an electrolyte
can be represented as the sum of the individual contributions of the anion and cation
of the electrolyte.
(i)   CaCl 2   (Ca 2  )  2  (Cl  ) (ii)   Al 2 ( SO 4 ) 3  2 ( Al 3 )  3 ( SO 4 ) 2

13. Application ofKohlrausch’s Law

[Link] of limiting molar conductivity
2. Calculation of degree of dissociation: Degree of Dissociation is ratio of molar
conductivity at a specific concentration ‘C’ to limiting molar conductivity. It is
c
denoted by  .   0m
m
c 2 c2
3. Calculation of dissociation constant Ka =   
(1  )  (   )

ELECTROLYSIS & PRODUCTS OF ELECTROLYSIS

1. FARADAY’S FIRST LAW: The amount of substance deposited or liberated at the
electrode during electrolysis is directly proportional to quantity of electricity passed
through the electrolyte. mathematically w=ZIt ,where w=amount of substance
deposited It = quantity of electricity , I is in ampere and t is in second Z=
electrochemical equivalent W= ZIt
2. Quantity of electricity carried by n moles of electrons=nF (1F = 96500 coulombs)
3. Second Law:When same quantity of electricity is passed through different
electrolytes, the amount of different substances librated at the electrode is directly
proportional to their chemical equivalent weights.(Atomic Mass of Metal ÷ Number
w E
of electrons required to reduce the cation) 1 = 1
w2 E 2
4. PRODUCTS OF ELECTROLYSIS

[Link] Electrolysis of CATHODE ANODE

1 Aqueous solution of AgNO3 with Ag metal(Ag+ are discharged Ag+ions(Ag electrode being
reactive dissolves to produce
 silver electrodes compared to H+ , E red
o
is higher) Ag+ions)

2 Aqueous solution of AgNO3 with Ag metal(Ag+ are discharged O2 gas(OH- discharged

platinum electrodes compared to H+asits E red
o
is compared to NO3-as its E red
o
is
higher) lower)
3 Aqueous solution of CuCl2 with Copper metal Cl2 gas
platinum electrodes
4 Aqueous solution of CuCl2 with Cu Copper metal Cu2+ions
electrodes
4 Molten NaCl Sodium metal Cl2 gas
5 Aqueous sodium chloride solution H2 gas Cl2 gas
6 Dilute Sulphuric acid with Pt H2 gas O2 gas
electrodes
7 Copper sulphate using inert Copper metal O2 gas
electrodes (Pt)
8 Aqueous sodium bromide H2 gas Br2 gas

BATTERIES AND CORROSION

1. Primary Cell : In the primary batteries, the reaction occurs only once and after
useover a period of time battery becomes dead and cannot be reusedagain .The most
familiar example of this type is the dry cell
2. Dry Cell : The cell consists of a zinc container that also acts as anode and the
cathode is a carbon (graphite) rod surrounded by powdered manganesedioxide and
carbon . The space between theelectrodes is filled by a moist paste of ammonium
chloride (NH4Cl) and zinc chloride (ZnCl2). The electrode reactionsare complex, but
they can be written approximately as follows :
Anode Zn(s) → Zn2++2e-Cathode MnO2 + NH4+ + e-  MnO(OH) +NH3 It is
used commonly in our transistors and clocks. Ammonia produced in the reaction
forms a complex with Zn2+ to give [Zn(NH3)4] 2+.
3. Mercury Cell : It consists zinc-mercury amalgam as anode and a paste of HgO
and carbon as the cathode. The electrolyte is a paste of KOH & ZnO.
Cathode: HgO  H 2O  2e   Hg (1)  2OH 
Anode: Zn( Hg )  2OH   ZnO( s )  H 2O  2e 

Overall reaction Zn(Hg) +HgO(s)ZnO +Hg(l) Zn Mercury cell suitable

for low current devices like hearing aids, watches, etc
4. Secondary Batteries A secondary cell after use can be recharged by passing current
through it in the opposite direction so that it can be used again. e.g. lead storage
batteries, Nickel – cadmium storage batteries.
5. Lead Storage Battery :It consists of a lead anode and a grid of lead packed with
lead dioxide (PbO2 ) as cathode. A 38% solution of sulphuric acid is used as an
electrolyte
AnodePb(s) + SO42- (aq)PbSO4(s)+2e-
 Cathode PbO2(S) + SO42-+ 4H+(aq) +2e-  PbSO4(s)+ 2H2O(l)
Overall ReactionPb(s)+ PbO2(S)+2 H2SO4(aq) 2PbSO4(s) + 2H2O(l)
On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode
is converted into Pb and PbO2, respectively.
2PbSO4(s) + 2H2O(l)Pb(s)+ PbO2(S)+2 H2SO4(aq)
6. Nickel cadmium cell is a secondary cell which has longer life than thelead storage
cell butmore expensive [Link] overall reaction during discharge is:
Cd(s)+2Ni(OH)3(s)CdO(s)+2Ni(OH)2(s)+H2O(l)
7. Fuel Cell : Chemical energy of fossil fuels (coal, gas or oil) is first used for
converting water into high pressure steam. This is then used to run turbine to produce
electricity. To convert the energy of combustion of fuels like methane directly into
electrical energy are called fuel cells e.g. Hydrogen with oxygen to form water. In
the cell, hydrogen and oxygen are bubbled through porous carbon electrodes into
concentrated aqueous sodium hydroxide solution. Catalysts like finely divided
platinum or palladium metal are incorporated into the electrodes for increasing the
rate of electrode reactions.
Cathode : O2 ( g )  2 H 2O(l )  4e   4OH  (aq)
Anode : 2 H 2  4OH   4 H 2O  4e 
Overall Reaction 2 H 2 ( g )  O2 ( g )  2 H 2O(l )

Fuel cells are pollution free.

8. Corrosion : The slow process of eating away of metals when exposed to the
atmosphere is called corrosion. It is electro-chemical phenomenon in which metal is
oxidized by loss of electrons to form metal oxide
9. Mechanism of Corrosion :Oxidn :Fe Fe2+ + 2e-
Redn: O2 ( g )  4 H  (ag )  4e   2 H 2O(l )
Atmospheric Oxidation 2Fe2+(aq) + 2H2O(l)+1/2O2  Fe2O3(s)+4H+(aq)
10. Rusting : Corrosion of iron is called rusting formula of rust Fe2O3. xH2O
11. Prevention of Corrosion : (1). Barrier Protection, (2). Sacrificial Protection (Zn &
Mg are used for the purpose), (3). Electrical Protection, (4). Using anti-rust solution.

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