Electrochemistry

General Introduction
Redox reactions

Oxidation and reduction

Property Oxidation Reduction

1 Hydrogen Loss Gain
2 Oxygen Gain Loss
3 Electron Loss Gain
4 Oxidation No. Increase Decrease

Oxidising agent or oxidant Reducing agent or reductant

1 Under goes reduction Undergoes oxidation

2 Gain electrons Donates electrons
3 Oxidation no. of its atoms increases Oxidation no. of its atoms decreases

For example, consider the reaction

Zn(s)  CuSO4 (aq)  ZnSO4 (aq)  Cu(s)
Or Zn(s)  Cu2 (aq)  Zn2 (aq)  Cu(s) ……(i) Concept Ladder
Zn is oxidized on Zn2+ ions while Cu2+ has been
Displacement reactions
reduced to Cu.
can and can't be
Similarly in the reaction redox reactions. Single
Cu(s)  2 AgNO3 (aq)  Cu(NO3 )2 (aq)  2 Ag(s) displacement reactions
 2
Or Cu(s)  2 Ag  Cu (aq)  2 Ag(s) ……(ii) are redox reactions where
Electrochemistry

Cu has been oxidized to Cu2+ ions while Ag+ has as double displacement
reactions are not redox
been reduced to Ag.
reactions.

1.
 Again in the reaction
Zn(s)  H2 SO4 (aq)  ZnSO4 (aq)  H2 (g)
Previous Year’s Question
Or Zn(s)  2 H (aq)  Zn2 (aq)  H2 (g) ……(iii)
Zn has been oxidized to Zn2+ whereas H+ In acidic medium H2O2 changes
ions have been reduced to H2 gas. Cr2O72- to CrO5 which has two
The substance which gets reduced (—O—O—) bonds. Oxidation state

oxidizes the other substance and is called of Cr in CrO5 is [NEET-2014]

oxidizing agent or oxidant while the substance (1) +5 (2) +3 (3) +6 (4) -10
which gets oxidized reduces the other substance
and is called reducing agent or reductant. Thus,
oxidizing agent is a substance which gains Concept Ladder
electrons while reducing agent is a substance
According to classical
which loses electrons.
concept, oxidation is an
A redox reaction may be considered to addition of oxygen [or
be made up of two half reactions, one involving electronegative radical/
oxidation, i.e. loss of electrons and the other element] or removal of
hydrogen [or electropositive
involving reduction, i.e., gain of electrons.
radical/element
These are known as oxidation half-reaction
and reduction half-reaction. For example, the
reaction (i) may be split into two half reactions
as under:
Rack your Brain

All redox reactions are

exothermic. Why?

Electrochemistry
Electrochemistry is defined as the branch
of chemistry, i.e., chemical energy produced in a Definition
redox reaction can be converted into electrical Electrochemistry deals with
energy or how electrical energy can be used to relationship between electrical
Electrochemistry

and chemical energy

bring about a redox reaction which is otherwise
non-spontaneous.

2.
3.
Electrochemistry
 • Electro chemical cell concept came from the study of redox reaction

• This reaction happens by its own. Therefore

its Gibb’s free energy is negative.
Definition
DG < 0 DG > O
The device in which
(spontaneous) (Non spontaneous
chemical energy is converted
• Work done by the system in electrochemical into electrical energy by
Electrochemistry

process Work done = –DG spontaneous redox reaction is

• Electrical work = Charge × potential called Galvanic cell Or Voltaic
Difference cell

4.
Galvanic Cell Or Voltaic Cell

In the above cell, the zinc ion solution

begins to build up a positive charge. Similarly,
Concept Ladder
as copper ions plate on as copper, the solution
builds up a negative charge. The half cell reactions In a galvanic cell, reduction
will stop unless positive ions can move from the potential of reduction half
zinc half-cell to the copper half cell, and negative cell reaction is always
greater than oxidation half
ions from the copper half-cell can move to the
cell reaction.
zinc half-cell. It is necessary that these ion flow
Electrochemistry

occur without mixing of the zinc ion and copper

ion solutions. If copper ion comes in contact with
the zinc metal.

5.
 Types of Conductors
Electronic conductors or Metallic conductors Electrolytic Conductors or Solution Conductors

1 Passage of current by movement of electrons in Passage of current by ions in molten state or in

the metallic lattice, e.g., Cu, Ag, etc. aqueous solution of electrolytes, e.g., NaCl(aq)

or NaCl (fused).
2 Passage of current brings in only physical Passage of current brings in physical as well as

changes. chemical changes.

3 It generally shows no transfer of matter. It involves transfer of matter in form of ions.
4 It generally shows an increase in resistance It generally shows a decrease in resistance due

during the passage of current due to increase in to decrease in viscosity of the medium and

temperature. Thermal motion of metal ions which degree of hydration of ions with increase in

results in hindrance in the flow of electrons temperature.

increases with increase in temperature.

5 The conducting power of metal is usually high. The conducting power of electrolytic conductors

is relatively low.

Electrolytes and Electrolysis

(1) Definition : “The substances whose aqueous Rack your Brain
solution undergo decomposition into ions
when electric current is passed through An aqueous solution and
them are known as electrolytes and the copper sulfate is electrolysed
using platinum electrodes in
whole process is known as electrolysis
another case. Will the products
or electrolytic decomposition.” Solutions of electrolysis be same of
of acids, bases, salts in water and fused different?
salts etc. are the examples of electrolytes.
Electrolytes may be weak or strong.
Concept Ladder
Solutions of cane sugar, glycerine, alcohol
etc., are examples of non-electrolytes. Higher is the value of
Strong and Weak Electrolytes dissociation constant
Electrochemistry

(i) The extent or degree of dissociation of greater is the degree of

different electrolytes in solution is different. dissociation and stronger
is the electrolyte.

6.
(ii) Substances which are largely dissociated
and form a highly conducting liquid in water Rack your Brain
are strong electrolytes. e.g., All salt (except
CdBr2, hgCl2), mineral acids like HCl, H2SO4, Mineral acids have covalent
NHO3, etc., and bases like NaOH, KOH, bond, still they are strong
etc., are strong electrolytes. The strong electrolytes. Why?
electrolytes are almost 100% ionized at
normal dilution.
(iii) Substances which dissociate only to a small
extent in aqueous solution forming low
conducting liquid are weak electrolytes,
e.g., All organic acids (except sulphonic
acids), inorganic acids like HCN, H3BO3, etc.,
and bases like NH3, amines etc., are weak Concept Ladder
electrolytes.
Factors Influencing Degree of Dissociation Dilution of solute follows
The degree of dissociation (a) of an electrolyte in ostwald's law of dilution
solution is given by: for weak electrolytes.
Mole dissoicated at any time

Total mole present at t = 0 or dissolved initially
The variation of ‘a’ of an electrolyte is governed
by
(i) Nature of solute : All ionic compounds,
i.e., strong electrolytes have a≈1 at
normal dilution. Most of the polar covalent
compounds, i.e. weeak electrolytes have
Rack your Brain
a<<1.
(ii) Nature of solvent : Solvent having high A solution of NaCl is initially
dielectric constants are themselves feebly at 50°C and temperature is
ionized but an electrolyte in high dielectric increased to 100°C. would there
constant solvent (say water) show higher be change in ionisation?
degree of dissociation than in a solvent of
low dielectric constant (say methanol).
Electrochemistry

(iii) Dilution : The extent of dissociation of

an electrolyte increases with dilution of
solution.

7.
 (iv) Temperature : the extent of dissocation
of an electrolyte also increases with an
increase in temperature.
(v) Addition of other species : Addition of Concept Ladder
another solute having an ion common to
Common ion effect involves
that of weak electrolyte shows a decrease the presence of similer
in degree of dissociation of weak electrolyte type of ions in two different
(see common ion effect). compound present in the
same solution only for
Electrical energy 
Electrolysis
 Chemical energy weak electrolytes. Example
Chemical energy 
Electromotive
 Electrical energy may insicde the soltuion of
Chemistry
CH3COOH and CH3COONa
(2) Electrolytic cell or Voltameter : The device
in which the process of electrolysis or
electrolytic decomposition is carried out is
known as electrolytic cell or voltameter.
(i) Voltameter convert electrical energy
into chemical energy.
(ii) The electrode on which oxidation takes Concept Ladder
place is called anode (or +ve pole) and
During Faraday's time,
the electrode on which reduction takes there were no devices
place is called cathode (or –ve pole) available which could
(iii) During electrolysis in voltameter supply constant current
Hence, the quantity of
cations are discharged on cathode and
electrochemistry passed
anions on anode.
was measured by putting
(iv) In voltameter, outside the electrolyte an apparatus called
electrons flow from anode to cathode coulometer (Coulomb
and current flow from cathode to measures) in the cirrcuit
which is simply a standard
anode.
Flow of electrons
electrolytic cell.

Anode 
Flow of current

 Cathode
For voltameter, Ecell = -ve and ΔG = +ve.
(v) The anions on reaching the anode give
Electrochemistry

up their electrons and converted into

the neutral atoms.

8.
 At Anode :
A  
 A  e (Oxidation) Concept Ladder
(vi) On the other hand cations on reaching Voltage (v) supplied in an
the cathode take up electrons supplied electrical circuit is obtained
by battery and converted to the neutral from the equation of emf.
atoms. E = V + Ir
= V = E - Ir
At Cathode :
Where E = emf of cell
B  e 
 B (Reduction) r = Internal resistance
This overall change is known as primary
change and products formed is known as primary
products.
The primary products may be collected as
such or they undergo further change to form
molecules or compounds. These are called
secondary products and the change is known as Rack your Brain
secondary change.
On Electrolysis of brine, NaOH,
(3) Preferential discharge theory : According to
H2 and Cl2 are obtained. H2 is
this theory “If more than one type of ion obtained at cathode and Cl2 at
is attracted towards a particular electrode, anode. Why Na is not obtained
then the ion is discharged one which at cathode?
requires least energy or ions with lower
discharge potential or which occur low in
the electrochemical series”.
The potential at which the ion is
discharged or deposited on the appropriate
electrode is termed the discharge or
Concept Ladder
deposition potential, (D.P.). The values
of discharge potential are different for To obtained the products of
different ions. electrolysis from aqueous
solution, the process is
The decreasing order of discharge
for more complicated
potential or the increasing order of
in comparison to the
Electrochemistry

deposition of some of the ions is given electrolysis products from

below, molten state.

9.
 For cations :
Li+ , K + , Na + , Ca 2+ , Mg 2+ , Al 3+ , Zn2+ ,
Concept Ladder
Fe2+ , Ni2+ , H+ , Cu2+ ,Hg 2+ , Ag + , Au3+
Compounds like NaOH,
For Anion :
KOH, Na2CO3, KClO3
SO24− , NO3− , OH− , Cl − , Br − , I−
white lead, KMnO4 etc.
are synthesised by
(4) Application of electrolysis : Electrolysis has
electrosynthesis method.
wide applications in industries. Some of the
important applications are, as follows,
(i) Production of hydrogen by electrolysis
of water.
(ii) Manufacture of heavy water (D2O). Rack your Brain
(iii) The metals like Na, K, Mg, Al, etc.,
When will be the conducting
are obtained by electrolysis of fused
power of strong electrolyte
electrolytes. greater than weak electrolyte?
(iv) Non-metals like hydrogen, fluorine,
chlorine are obtained by electrolysis.
(v) In this method pure metal is deposited
at cathode from a solution containing
the metal ions Ag, Cu etc. Concept Ladder
(vi) Electroplating : The process of coating
The techanique of
an inferior metal with a superior metal by
electrolysis is used in the
electrolysis is known as electroplating.
refining of Cu. The impure
The aim of electroplating is, to prevent
Cu(95%) is made anode
the inferior metal from corrosion and to
and thin a sheet of pure
make it more attractive in appearance.
Cu is made cathode, and
The object to be plated is made the
electrolysis is carried
cathode of an electrolytic cell that
out to get pure Cu. The
contains a solution of ions of the metal
electrolyte is CuSO4
to be deposited.
solution acidified with
dilute H2SO4. Impurities fall
Electrochemistry

down as anode mud.

10.
Faraday's laws of electrolysis
The laws, which govern the deposition of Rack your Brain
substances (In the form of ions) on electrodes
Mass of substance is deposited
during the process of electrolysis, is called
at electrode. Can this method
Faraday's laws of electrolysis. These laws be used to address corrosion?
given by Michael Faraday in 1833.
(1) Faraday's first law : It states that, “The mass
of any substance deposited or liberated at
any electrode is directly proportional to the
quantity of electricity passed.” i.e., W ∝ Q
Where, W = Mass of ions liberated in gm,
Q = Quantity of electricity passed in
Concept Ladder

Coulombs Electr chemical Equivalent

= Current in Amperes (I) × Time in second (t) = Weight deposited by 1
\ W ∝ I × t or W = Z × I × t colomb
Eq.wt of subs tan ce
In case current efficiency ( η ) is given, then =
96500

W  Z I t 
100
where, Z = constant, known as
electrochemical equivalent (ECE) of the ion
deposited.
When a current of 1 Ampere is passed for 1
Previous Year’s Question
second (i.e., Q = 1), then, W = Z
Thus, electrochemical equivalent (ECE) may Calculate the quantity of electricity
be defined as “the mass of the ion deposited that would be required to reduce
by passing a current of one Ampere for 12.3 gram of nitrobenzene to online
if the current efficiency for the
one second (i.e., by passing Coulomb of
process is 50 percent. If the process
electricity)”. It's unit is gram per coulomb. drop across the cell is 3 volts, how
Coulomb is the unit of electrical charge.
much energy will be consumed?
96500 Coulombs 6.023 × 1023
electrons = 1 mole electrons [NEET-2014]
6.023  1023
Electrochemistry

1 coulomb   6.28  1818 electrons (1) 347kJ (2) 447kJ

96500 (3) 397kJ (4) 497kJ
or 1 electronic charge = 1.6 × 10-19 Coulomb

11.
 (2) Faraday's second law : It states that, “When
the same quantity of electricity is passed
Concept Ladder
through different electrolytes, the masses
of different ions liberated at the electrodes Magnitude of charge carried
by 1 mole of electrons is
are directly proportional to their chemical
96487 C(6 × 1023 × 1.6 × 10-19
equivalents (Equivalent weights).” i.e = 96487C). It is also known
W1 E1 Z It E1 Z E as one faraday, i.e., 1F =
= = or 1 or 1 = 1
W2 E2 Z2It E2 Z2 E2 96500C.
Thus the electrochemical equivalent (Z) of
an element is directly proportional to its
equivalent weight (E), i.e.,
E ∝ Z or E = FZ or E = 96500 × Z
where,
F = Faraday constant = 96500 C mol-1
1F = Charge on an electron × Avogadro's
number.
Rack your Brain
If  e  N  (1.602  1019 c)  (6.023  1023 mol 1 )
Number of Faraday Why oxidation potential of H2O
Number of electrons passed is greater than fluoride ion?
=
6.023 × 1023

(3) Faraday's law for gaseous electrolytic

product For the gases, we use
It Ve
v=
96500
where, V = Volume of gas evolved at S.T.P. at
an electrode
Ve = Equivalent volume = Volume of gas Concept Ladder
evolved at an electrode at S.T.P. by 1 Faraday Reduction potential of H2O
charge > (×) Reduction potential of
cations of 1, 2 and 13 groups
of periodic table, e.g., Na+,
K+, Ca2+, Mg2+, Al3+, etc. so
Electrochemistry

reduction of H2O occurs at

cathode.

12.
Electrical Resistance and Conductance
• Resistance (R) :-

V
R= is expressed in ohms.
I
Previous Year’s Question
• Conductance (G) :-
Zinc can be coated on iron to
It is the property by virtue of which it favours produce galvanised iron but
flow of current. the reverse is not possible. It is
1 becasue. [NEET 2016]
G=
R (1) Zinc is lighter than iron
(2) Zinc has lower melting point
[unit of G is mho or ohm–1 or Siemens (S)]
than iron
• Specific resistance/Resistivity (r) :- (3) Znc has lower negative
The resistance (R) of a conductor is directly electrode potential than iron
proportional to its length(l) and inversely (4) Zinc has higher electrode
proportional to its area of cross section (A). potential than iron

R∝
A

R
A

A
Electrochemistry

  R.

If l = 1 cm, A= 1 cm2, therefore r = R

13.
 \ V = A × l = 1 cm3
Therefore resistance offered by 1 cm3
electrolytic solution is known as resistivity.
Previous Year’s Question
[Unit of r → ohm cm–1]
(d) Specific conductance/ Conductivity (k) :- An increase in equivalent
conductance of a strong
It is defined as the reciprocal of specific electrolyte with dilution is mainly
1 due to
resistance,   [NEET 2010]

(1) Increase in both i.e. number
 1 1  of ions and ionic mobility of
R  .
A  R A ions
(2) Increase in ionic mobility of
k = G×G*
ions
Specific conductance = Conductance × Cell
(3) 100% ionisation of electrolyte
constant [Unit of K is ohm–1 cm–1] at normal dilution.
Hence specific conductivity of a solution (4) increase in number of ions
is defined as the conductance offered by 1
cm3 of electrolytic solution.
Cell constant :

G* = : its unit is cm–1
A
(e) Molar conductivity or Molar conductance :
Lm = k × V
  1000 Concept Ladder
m 
M
Resistivity is the measure of
[Unit → ohm–1 cm2 mol–1]
resisting power of a speci-
(f) Equivalent conductivity or Equivalent
fied material to the flow of
conductance (Leq or leq) an electric current. It only
Leq = k × V depends only on nature of
material
  1000
 eq 
N
Relation between Leq and Lm
Electrochemistry

  1000 and   1000

m   eq 
M N

14.
Q.1 1.0 N solution of a salt surrounding two platinum electrodes 2.1 cm apart and
4.2 sq cm in area was found to offer a resistance of 50 ohm. Calculate the
equivalent conductivity of the solution.

A.1 Given l = 2.1 cm, a = 4.2 sq. cm, R = 50 ohm

Specific conductance,
l 1
Specific conductance,   .
a R
2.1 1
Or     0.01 ohm1
4.2 50

Equivalent conductivity = k × V
V = the volume containing 1 g equivalent = 1000 ml
So Equivalent conductivity = 0.01 × 1000 = 10 ohm–1 cm2 equiv–1

Q.2 At 298 K
1
KCl is field in a cell of Its specific conductance is 0.001735 ohm–1
50N

cm–1 and resistance is 100 ohm then calculate

(i) Cell const.
(ii) Molar conductivity (or) Molar conductance

A.2 (i) K=
1 l
. = 0.001735 =
1
×
100 ohm A
l
= 5 cm-1
R A
l
= = 0.1735 cm–1
A
 
N  Mnf 
K × 1000 0.001735 × 1000  
(ii) Lm = = n  1 
m 1 f
 1 
50 M  
 50 
= 86.75 S cm2 mol–1
Electrochemistry

15.
 Q.3 Specific conductance of an electrolyte is 3.825 S cm–1. If limiting molar
conductivity is 425 S cm2mol–1, then calculate molarity of electrolyte of it is 90%
dissociated :

A.3 K = 3.825 S cm–1

Limiting molar conductivity =
425

  
3.825  1000   m  Previous Year’s Question
m  m
0
M  
Molar conductivites (L0m) at
0.4 × 425 = Lm infinite dilution of NaCl, HCl and
= 382.5 S cm2 mol–1 CH3COONa are 126.4, 425.9 and
91.0 S cm2 mol-1 respectively for
3.825 × 100 CH3COOH will be
382.5 =
M [NEET 2012]
Molarity = 10 M (1) 425.5 S cm mol
2 -1

(2) 180.5 S cm2 mol-1

DETERMINATION OF L0m OR L0
(3) 290.8 S cm2 mol-1
A plot of Lm vs C as found experimentally is as (4) 390.5 S cm2 mol-1
shown below graphically.

Concept Ladder
There is avery large increase
in conductance with dilu-
tion especially near infinite
Debye Huckel Onsager equation - delution. As concentration
Lm =  m  b C [only for strong electrolyte] of the weak electrolyte is
• Lm values are then plotted against C when Reduced, more of it ionizes.
a straight line is obtained. This is the
Electrochemistry

extrapolated to zero concentration. The

point where the straight line intersects L0m
axis is of the strong electrolyte.

16.
• But the plot in the case of weak electrolyte
being non linear, shooting up suddenly at Previous Year’s Question
some low concentration and assuming
the shape of a straight line parallel to Lm Which of the following expression
correctly represent the equivalent
axis. Hence extrapolation in this case is
+ Conductance at of inite dilution
not possible. Thus, LO of a weak electrolyte of Al2(SO4)?
cannot be determined experimentally. It Given that  SO and  SO2 are the
2
4 4

can, however, be done with the help of equivalent conductances at

Kohlrausch's law to be discussed later. infitite dilution of respective ions
Kohlrausch's Law of Independent Migration of [NEET 2010 ]
(1) 2  Al3 3  SO2
 
Ions 4

At infinite dilution when dissociation (2)    SO2

Al 3
is complete, every ion makes some definite 4

contribution towards molar conductance of the

electrolyte irrespective of the nature of the other
(3)  Al 3
  SO2  6
4

ion which with it is associated and that the molar
1  1
(4)  Al3   SO2
conduction at infinite dilution for any electrolyte 3 2 4

is given by the sum of the contribution of the

two ions. m0
 0  0 , 0 the contribution of the

cation   is the contribution of the anion
0

APPLICATION OF KOHLRAUSCH'S LAW

• Determination of ∧m
0
of a weak electrolyte:

CH3 COOH  HCl   m

0
CH3 COONa 
 m
0
NaCl  Concept Ladder
• Determination of degree of dissociation (a) Ionic mobility is defined as
No. of molecules ionised the speed of the ion cm/sec

Total number of molecules dissolved at infinite dilution under a
m potential gradient of 1 volt/
 cm.
m
0

• Determination of solubility of sparingly Ionic Mobility =

Ionic conduc tan ce
96500
soluble salt
1000K
m
0

Electrochemistry

C
where C is the molarity of solution and
hence the solubility

17.
 Q.4 Compare the conductance in following
Cl3 C CH2 COOH CH3CH2COOH
(a) (b)

A.4 a > b → degree of dissociation of a > degree of dissociation of b

Q.5 Calculate solubility product of BaSO4 If its conductivity and molar conductance
at saturation are 3.06 × 10–6 S cm–1 and 153 S cm2 mol–1 respectively.

A.5 BaSO4  Ba 2  SO24

s s
KSP = s2
K  1000  3.06  106  1000 
s= =  2 1 
m0
 153 S cm mol 

Ksp = (2 × 10–5)2 = 2 × 10–5 mol/lit = 4 × 10–10

Q.6 The equivalent conductances of sodium chloride, hydrochloric acid and sodium
acetate at infinite dilution are 126.45, 426.16 and 91.0 ohm–1 cm2 equiv–1, respectively
at 25°C. Calculate the equivalent conductance of acetic acid at infinite dilution.

A.6 According to Kohlrausch’s law

 CH COONa  CH COO  Na  91.0 .....1 .
3 3

 HCl  H  Cl  426.16 ......2

 NaCl  Na  Cl  126.45 .....3

Adding equations (1) and (2) and Subtracting (3)

CH COO  Na  H  Cl   Na  Cl   91.0  426.16  126.45
3

CH COO  H   CH3COOH  390.7 ohm1cm2 equiv 1

3
Electrochemistry

18.
FACTORS AFFECTING ELECTROLYTIC
CONDUCTANCE
Rack your Brain
• Inter ionic attraction :-
inter ionic attraction between ions of solute Conductivity of solution
is more, then the conductance will be less. dependes upon the polarity of
• Polarity of solvent :- solvent. Would the solution of
If solvent has high-dielectric constant then benzene and toluene conduct
electrolysis?
the ionization and conductance will be
higher.
• Viscosity of medium :-
On increasing the viscosity of medium, the
conductance decreases.
• Temperature :-
As the temperature of electrolytic
solution is increased, the conductance
Concept Ladder
increases
Transport number is the
• Hydrated size : Due to hydration of ions
fraction of current carried
conductance decreases. by ion.
• Dilution :- Transport number =
(i) On increasing the dilution conductance Current carried by ion
(G) increases. Total current carried
For strong electrolyte on dilution
interionic force of attraction decreases
therefore conductance increases. For
weak electrolyte with dilution degree
of dissociation (a) increases therefore
conductance increases.
(ii) On dilution specific conductance
Rack your Brain
decreases because on dilution number
of ions in 1 ml solution decreases.
Is there any relationship between
(iii) On dilution equivalent and molar
molar conductance and dilution?
Electrochemistry

conductance increases because

with dilution normality or molarity
decreases.

19.
 Representation of a cell
Concept Ladder

In a galvanic cell, cathode

is positive with respect to
anode.

Net reaction

Q.7 Give the cell reaction from the cell notation

Zn(s) | Zn2+ (aq) || Fe3+ (aq)|, Fe2+(aq)| Pt

A.7 The half cell reactions are

Anode
Zn(s) → Zn2+ (aq) + 2e–
Cathode
Fe3+(aq) + e- → Fe2+(aq)
and the cell reaction is :
Zn(s) + 2Fe3+(aq) → Zn2+(aq) + 2Fe2+(aq)

Electrode potential Concept Ladder

When a metal is placed in a solution of
Decreasing order of metal-
its ions. it acquires either a positive or negative
lic character is given below:
charge with respect to the solution. on account of
K > Na > Ba > Ca > Mg > Al
this a definite potential is developed between the > Zn > Fe > Ni > Sn
metal and the solution. this potential difference H > Cu > Hg > Ag > Au > Pt
is called electrode potential. It depends on the
nature of electrode, concentration of ions, and
temperature.
Electrochemistry

20.
Condition in which the circuit stops working

• No current will flow. In this situation salt Rack your Brain

bridge is introduced.
Salt bridge construction : On what criteria the sign
1. It is inverted U–shaped tube convention of electrodes is
decided ?
2. Contains inert electrolyte like KCl, KNO3,
NH4,Cl etc. in agar–agar gel & gelatin.
3. Ions of electrolyte do not react with ions of Concept Ladder
electrode solution.
Another function of salt
Salt bridge functions : bridge is that it prevents
1. To complete circuit. liquid-liquid junction
2. To maintain electrical neutrality. potential i.e., the poten-
tial difference that arises
Electrochemistry

between the two solutions

when they are directly in
contact with each other

21.
 Standard Reduction Potential :
Rack your Brain
Conditions:
Concentration = 1 M
Why current drops to zero
For gases pressure = 1 atm when salt bridge is pulled
Temperature = 298 K out?

According to the IUPAC conventions,

Standard electrode potential = Standard
reduction potential Concept Ladder
Cell potential Or emf of the cell (Ecell)
Electrode an which
The difference between electrode potential
oxidation occurs is called
of two half cells is known as cell potential anode (-ve pole)
Ecell  EOP A  ERP c Electrode on which
Electrochemistry

reduction occurs is called

Ecell  ERP C  ER P A cathode (+ve pole)

22.
 Q.8 For the cell reaction 2Ce4+ + Co → 2Ce3+ + Co2+, E0cell is 1.89 V
0
E0CO2+ |CO is 0.28 V, what is the value of ECe4+ |Ce3+

A.8 E0cell  E0Ce4  |Ce3   E0CO2  |CO

Rack your Brain
1.89 = E0 4+ 3+ – (–.28)
Ce |Ce
E0Ce4+ |Ce3+ = 1.61 V Which electrode of a galvanic
cell corresponds to the higher
potential energy.

Q.9 Which of the following metal displaces hydrogen from H2SO4 solution or acidified
water?
(1) Mg (2) Al
(3) Fe (4) All of these

A.9 (4)

Previous Year’s Question

Relationship between Gibb’s free energy change
and emf of cell
The pressure of H2 required to
Work done = Decrease in free energy change make the potential of H2 elctrode
Charge on 1 mole e– = NA  e is zero in pure water at 298K is
= 6.023 × 1023 × 1.6 × 10–19 (1) 10-10 atm (2) 10-4 atm
= 96500 = 1 Faraday (3) 10-14 atm (4) 10-12 atm

[1 Faraday = charge on 1 mole of electron]

Charge of n moles of electron Concept Ladder
q = nF
Electron flow from anode
Work done = charge × cell potential to cathode in the external
DG = –nFEcell circuit. Inner circuit is
Reactions DG E completed by the flow
of ions through the salt
Electrochemistry

Spontaneous (–) (+) bridge.

Non- spontaneous (+) (–)
Equilibrium 0 0

23.
 Electrochemical Series
The elements arranged in the decreasing order of reduction potential, the series
attained is known as Electrochemical series
Electrochemistry

24.
 Q.10 If E0 for Au+ + e- → Au (s) is 1.69 V & E0 for 3e- + Au+3 → Au is 1.40 V, then E0
will Qbe
(1) 0.19 V (2) 2.945 V
(3) 1.255 V (4) none

A.10 (3)
Au+ + e– → Au(s) E° = 1.69 V ..(1); DG1
Au3+ + 3e– → Au(s) E° = 1.40 V ..(2); DG 2 G 3  G 2  G1
–2 × F × E° = –3 × F × 1.40 + 1 × 1.69 × F
E° = 1.255 V
Concept Ladder
Nernst equation:
When the concentration is not equal to 1 Molar. ERP ↑ = Reduction tendency ↑
Then we use Nernst equation EOP ↑ = Oxidation tendency ↑
If nothing is given
According to thermodynamics,
E°RP ↑ = Reduction tendency ↑
DG = DG° + RT ln Q E°OP ↑ = Oxidation tendency ↑
(\–DG = nFE and –DG° = nFE°)

–nFE = –nFE° + RT lnQ

2.303RT
Ecell = E0cell − log Q
nF
where E0 = standard electrode potential,
R = gas constant, T = temperature (in K)
F = Faraday (96500 coulomb mol–1),
Previous Year’s Question
n = number of moles of e– gained lost or
transferred in balanced equation. If the E0Cell for a given reaction
has a negative value, which of
At 25°C, above equation may be written as
the following gives the correct
Ecell = E0cell − 0.0591 log Q relationship for the value of DG0
n
and Keq?
0.0591 [P] [NEET 2016]
Ecell = E0cell − log
n [R] (1) DG > 0; Keq < 1
0

(2) DG0 > 0; Keq > 1

Electrochemistry

(3) DG0 < 0; Keq > 1

(4) DG0 < 0; Keq < 1

25.
 Q.11 Calculate the EMF of a Daniel cell when the concentration of ZnSO4 and CuSO4
are 0.001 M and 0.1 M respectively. The standard EMF of the cell is 1.1V

A.11 E = 1.159 V
Zn(S) + CuSO4 → ZnSO4 + Cu
0.0591  Zn2  0.0591 10 3
Ecell  E0cell  log  2   1.1  log 7  1.159 V
2  Cu  2 10

Q.12 Calculate E0 and E for the cell Sn | Sn2+ (1M) || Pb2+(10-3M) | Pb, E0 (Sn2+| Sn)
= -0.14V, E0 (Pb2+| Pb) = -0.13V. Is cell reaction is feasible?

A.12 No, Ecell = -0.078V

0.059  Sn2+  0.059
Ecell = -E0Sn2+ /Sn + EPb
0
2+ - log  2+  = +0.14 - 0.13 - log1013
/Pb
2  Pb  2

0.059 Previous Year’s Question

Take  0.01    0.078 V
2
APPLICATIONS OF NERNST EQUATION Consider the half-cell reduction
reaction
(i) Calculation of electrode potential
(ERP or EOP) Mn2+ + 2e- → Mn, E0 = -1.18V
Mn2+ → Mn3+ + e-, E0 = -1.51V
0.0591 1 The E0 for the reaction,
ERP = E RP 
0
log
n [M  n ]
3Mn2+ → Mn0 + 2Mn+3
If [M+n] increases, then ERP increases and possibility of the forward
reaction are respectively?
(ii) Calculation of electrode potential and pH of
[NEET 2016]
hydrogen electrode - (1) -4.18 V and yes
2H+ + 2e– → H2(g) (2) +0.33 V and Yes
(3) +2.69 V and No
0.0591 PH
ERP = E RP  (4) -2.69 V and No
0
log 2 2
2 [H ]
0.0591 1
\ E 0RP = 0 ; ERP = E RP 
0
log  2
2 [H ] Rack your Brain

[ PH is taken 1 atm]
Electrochemistry

2 Why Cu2+ dispropostionates in

ERP = 0.0591 log [H ] +
aqueous solution?
ERP = –0.0591pH EOP = +0.0591 pH

26.
(iii) Calculation of equilibrium constant (Keq)
Previous Year’s Question
and DG°
From Nernst equation – In the electrochemical cell;
Zn | ZnSO4 (0.01M) || CuSO4(1.0M)
0.0591 [P]
Ecell = E Cell − log | Cu the emf of this Daniell cell
n [R ]
is E1 when the concentration of
[P] ZnSO4 is changed to 1.0M and
At equilibrium, Ecell = 0 and = Keq
[R ] that of CuSO4 changed to 0.01
0.0591 M the emf changes to E0. From
E Cell = logK eq
n the followings, which one is the
2.303RT relationship between E1 and E2?
E Cell = log K eq
nF [NEET 2017]

(1) E1 < E2
nF E Cell = 2.303 RT logKeq (2) E1 > E2
DG° = –2.303 RT logKeq (3) E2 = 0 ≠ E2
(4) E1 = E2

Q.13 Calculate the equilibrium constant for the reaction

 2  Ce4  Fe3  Ce3  ,[E0Ce4 /Ce3  1.44V; EFe
Fe 0
3
/Fe2
 0.68V]

2.303 RT
= 0.06 at 25° C, log 4.68 = 0.67
F

A.13 Kc = 4.68 × 1012

Fe2+ + Ce4+  Fe3+ + Ce3+
0.06
E0  1.44  0.68  0.76 V  log KC
1
Kc  4.64  1012

CONCENTRATION CELL ( E°Cell = 0)

Rack your Brain
• Electrode Gas concentration cell :
Pt, H2 (P1) | H+ (C) | H2 (P2 ), Pt
Will change in tempature affect
At 25° C, E0Cell?
[For spontaneity of such cell reaction, p1
>p2]
Electrochemistry

27.
 Q.14 Pt | Cl2 (g, P2 ) | Cl– (aq,C) || Cl– (aq, C) | Cl2 (g, P1 ) | Pt EMF of cell is positive if
(1) P1 > P2 (2) P2 > P1
(3) P1 = P2 (4) We cannot predict

A.14 for spontaneous reaction P1 > P2

Anode half cell

0.0591 P .....(1)
EOX  EOx
0
 log 2
2 C Rack your Brain
Cathode half cell
Why Pt electrodes are used with
0.0591 C

Ered  Ered  log ......  2  the combination of the gas when
2 P1
oxidised or reduced part is a gas?
Ecell  EOX  Ered
  0.0591 P C
 EOX  Ered  log 2 .
2 C P1
0.0591 P
Ecell  log 1
2 P2

• Electrolyte concentration cells

Zn(s) | ZnSO4 (C1) || ZnSO4 (C2 ) | Zn(s)

Concept Ladder
2.303RT C 
E log  1 
2F A potential difference
 C2 
develops across the bound-
ary of two solutions which
[For spontaneity of such cell reaction,C2> is known has liquid junc-
C1] tion potential of diffusion
potential.
Electrochemistry

28.
Electrolytic cell

Concept Ladder

NaCl(molten) → Na+ + Cl– The minimum voltage

Reactions at Anode (oxidation) required for discharge of
ions is called discharge
Cathode (reduction)
potential
2Cl– → Cl2 (g) + 2e–
2Na+ + 2e– → 2Na(l)

Q.15 By electrolysis of aq. MgSO4 with the help of inert electrode calculate ratio of
moler of substance deposited at cathode and anode
(1) 1 : 4 (2) 1 : 2 (3) 2 : 1 (4) 4 : 1

A.15 At cathode At anode

1
2H2O + 2e– → H2 + 2H– H2O → O2  2H  2e
2
nf =2 nf =2
Electrochemistry

gm eq. H2 = mol H2 × 2 gm eq. H2 = mol × 4

mol H2 4 2
= =
mol O2 2 1

29.
 Q.16 Aq. Na2SO4 is electrolysed then after electrolysis pH will be
(1) increased (2) decreased
(3) unchanged (4) None of these

A.16 (3)
Quantitative aspects of Electrolysis
Fe+2 + 2e–1 → Fe Previous Year’s Question

2 mole of e– → 1 mol Fe On electrolysis of dil. sulphuric

1 mole of e –
→ 1/2 mol Fe acid using platinum (Pt)
electrode, the product obtained
Molecular weight at anode will be :
Equivalent weight of Fe2+ =
2 [NEET–2020]
1 Faraday will discharge 1 Equivalent. (1) Hydrogen gas
Faraday’s law (2) Oxygen gas
(3) H2S gas
(a) First law of electrolysis :
(4) SO2 gas
Amount of substance deposited or liberated
at an electrode is directly proportional
to amount of, charge passed through the
solution. Rack your Brain
W ∝Q
W = ZQ where Z = electrochemical equivalent Electrolysis of water is often
done with a small amount of
then W = Z (when Q = 1 coulomb)
sulphuric acid added to water.
Amount of substance deposited or Why?
liberated by 1 coulomb charge is called
electrochemical equivalent.
Let I ampere current is passed till 't' seconds
Q = It
Previous Year’s Question
W = ZIt.
1 Faraday = 96500 coulomb = Charge on The weight of silver (at. wt =
one mole electrons 108) displaced by a quantity
of electricity which displaces
Let 'E' is equivalent weight then 'E' gram
5600mL O8O2 at STP will be
will be liberated by 96500 coulombs. [NEET–2014]
Electrochemistry

E (1) 5.4 g (2) 10.8 g

\ 1 Coulomb will liberate gram;
96500 (3) 54.0 g (4) 108.0 g

30.
 E EIt
Z = 96500 \W =
96500
W It
= = number of g eq = number of
E 96500

faraday’s

Q.17 How long a current of 2 A has to be passed through a solution of AgNO3 to coat
a metal surface of 80 cm2 with 5 mm thick layer? Density of silver = 10.8 g/cm3.

A.17 d=
M M
⇒ 10.8 = 80 ×5 × 10-4 ⇒ M = 10.8 × 400 × 10–4
V
E ×I× t 108 × 2 × t
W= ⇒ 10.8 × 400 ×10–4 = ⇒ t = 193 s
96500 96500

(b) Second law of electrolysis:

When same amount of charge is passed
Concept Ladder
through different electrolyte solutions
connected in series then weight of Amount of substance
deposited
substances deposited or liberated at
electrodes are in ratio of their respective  Eq. wt Q 
 
equivalent weights.  96500 
W1 E1
i.e. =
W2 E2

Q.18 One ampere current for how much time should be passed through Aq. Soln of 2
molar, 200 ml AgNO3 , so that 1 mol of Ag can be deposited

A.18 AgNO3  Ag +

w i.t W 1 t 1 t
= molarity    10 3  1 
E 96500 E 9600 96500
Electrochemistry

T= 96.5 sec

31.
 Q.19 When 1 M 2L Aq. AgNO3 and 1 M, 2L aq NaCl are connected in units If 10.8 gm
Ag deposited on cathode, then calculated volume of Cl2 (at NTP) collected at
anode

A.19 gm aq. Of Ag = gm aq. Of Cl2

Previous Year’s Question
w VSTP
  nf
E 22.4 When 0.1 mole MnO42- is oxidised
the quantity of electricity
concept (Z) =
Eq.wt
96500 AgNO3 + e– = Ag = 1
required to completely oxidise
10.8 VSTP MnO42- to MnO4- is
 2
108 22.4 [NEET–2014]
1 (1) 96500 C (2) 2×96500C
(3) 9650C (4) 96.50C
2NaCl → Cl2 + 2e– = nf = 2

Deniell cell
Deniell cell converts chemical energy
liberated during the redox reaction to electrical Concept Ladder
energy and has an electrical potential equal to
Electrochemical equivalent
1.1V when the concentration or activity of Zn2+
and Cu2+ ions is unity (1 mol dm-3). Eq.wt
(Z) =
Zn(s) + Cu2+ (aq)  96500
 Zn2+(aq) + Cu(s)
Electrochemistry

32.
PRIMARY BATTERIES
(Dry cells and alkaline batteries)

Cathode, reductions: Rack your Brain

2NH4  aq  2e  2NH3  g   H2  g 
What is the most common
Anode Oxidation : Primary Battery?

Zn  s   Zn2  aq  2e

The two gases formed at the cathode will build

up pressure and could cause the cell to rupture.
Concept Ladder
Zn2
aq  2NH3  g   2Cl aq  Zn NH3 2 Cl 2  s 

Mecury cell suitable for low
current devices like hearing
2MnO2  s   H2  g   Mn2O3  s   H2O l 
acids, watches, etc. con-
sists of zinc-mercury amal-
gam as anode and a paste
Electrochemistry

of HgO and carbon as the

cathode.

33.
 SECONDARY OR RECHARGABLE BATTERIES
Concept Ladder
The lead storage battery –
Discharging reaction : The discharging process of
the storage cell is based on
Pb(s)  PbO2 (s)  2 H2 SO4  PbSO4 (s)  2 H2 O the principles of electro-
Cathode reduction : chemical cell, whereas the
2MnO2  s   H2  g   Mn2O3  s   H2O l  charging process is based
upon the principles of elec-
Anode Oxidation trolytic cells.

PbO2  s   4H  aq  SO42  aq  2e  PbSO4  s   2H2 O l 

Net Cell reaction

Pb  s   SO24 aq  PbSO4  s   2e

Charging reaction is reverse of discharging Rack your Brain

reaction with the reaction on anode will be
Electrochemistry

What is end life of the battery?

written on cathode and vice versa

34.
Nickel - Cadmium ("Ni - Cad") batteries
Cathode (Reduction) :
NiO2 + 2H2O + 2e– → Ni(OH)2 + 2OH–
Anode (Oxidation): Concept Ladder
Cd + 2OH– → Cd(OH)2 + 2e–
Discharge potential of
Net cell reaction : negative ions is as follows
NiO2(OH) + Cd + H2O → 2Ni(OH)2 + Cd(OH)2 SO24  NO3  OH  Br   I
Electrochemistry

35.
 Fuel Cell

Concept Ladder
Cathode, reduction :
O2(g) + 2 H2O(l) + 4e– → 4OH– (aq) Efficiency of a Fuel Cell
E° = 1.23 V
G nFE
Anode, Oxidation :  
H H
H2 (g) → 2H+ (aq) + 2e–
E° = 0 V
CORROSION CELLS AND REACTIONS
Previous Year’s Question
A corrosion system can be regarded as a short-
circuited electrochemical cell in which the anodic A device that converts energy
process is something like of combustion of fuels like
Fe(s) → Fe2+(aq) + 2e– hydrogen and methane, directly
into electrical energy is known as
and the cathodic steps can be given as
[2015, Cancelled]
O2 + 2H2O + 4e– → 4OH– (1) Dynamo
Electrochemistry

2H+ + 2e– → H2 (g) (2) Ni-Cd cell

M2+ + 2e– → M(s) (3) Fuel cell
(4) Electrolytic cell

36.
CONTROL OF CORROSION
• Sacrificial coatings
One way of supplying this negative charge is
to apply a coating of a more active metal.

CATHODIC PROTECTION
A more sophisticated strategy is to
maintain a continual negative electrical charge
on a metal, so that its dissolution as positive ions
Concept Ladder
is inhibited.
In a galvanic cell, cathode
is positive with respect to
anode.
Electrochemistry

37.
 Q.20 Compare the conductance in following Colour of KI solution containing starch
turns blue when Cl2 water is added. Explain.

A.20 Chlorine placed below iodine in electrochemical series having more reduction
potential and thus shows reduction whereas I– undergoes oxidation. The I2 so
formed get absorbed in starch to give blue colour.
2I 
 2e
Cl 2  2e  2Cl 
Cl   2I 
 I2  2Cl 

Q.21 How many moles of electrons are needed for the reduction of 20 mL of 0.5M
solution of KMnO4 in acid medium ?

A.21 Moles of KMnO4 = M × V (L) = 0.5 × 20 × 10–3 = 10–2 [ Mn7+ + 5e­ → Mn2+]
 1 mol KMnO4 required = 5 mol e–
\ 10–2 mol KMnO4 required = 5 × 10–2 mol e–

Q.22 Given the standard electrode potentials ; K+/K = –2.93 V, Ag+/Ag = 0.80 V, Hg2+/Hg
= 0.79 V, Mg2+/Mg = – 2.37 V, Cr3+/Cr = –0.74V.
Arrange these metals in their increasing order of reducing power.

A.22 More is E°RP, more is the tendency to get reduced or more is the oxidising power
or lesser is reducing power. Ag < Hg < Cr < Mg < K

Q.23 An aqueous solution of NaCl is electrolysed with inert electrodes. Write the
equations for the reactions taking place at cathode and anode. What happens if
NaNO3(aq.) is used instead of NaCl ?

A.23 For NaCl(aq.)anode : 2Cl– → Cl2 + 2e–

cathode : 2H+ + 2e– → H2
Electrochemistry

For NaNO3 (aq.) anode : 2OH– → H2O + 1/2 O2 + 2e–

cathode : 2H+ + 2e– → H2

38.
Q.24 
The value of  for NH4Cl, NaOH and NaCl are 129.8, 248.1 and 126.4 ohm–1 cm2

mol–1 respectively. Calculate  for NH4OH solution.

A.24  NH4OH   NH4 Cl   NaOH   NaCl  129.8 + 248.1 - 126.4 = 251.5 ohm-1cm2mol-1

Q.25 Given the standard electrode potentials ; K+/K = –2.93 V, Ag+/Ag = 0.80 V,
Hg2+/Hg = 0.79 V, Mg2+/Mg = –2.37 V, Cr3+/Cr = –0.74V.
Arrange these metals in their increasing order of reducing power.

A.25 More is E°RP, more is the tendency to get reduced or more is the oxidising
power or lesser is reducing power. Ag < Hg < Cr < Mg < K

Q.26 Iron does not rust even if zinc coating on its surface is broken but the same is
not true when coating is of tin.

A.26 The zinc is more reactive than iron. This means that if a crack appears on
the surface of iron coated with zinc even then zinc will take part in the redox
reaction and not iron. In other words, zinc will be corroded in preference to
iron. But same is not in the case with tin. it is less reactive than iron. If a
crack appears on the surface of iron coated with tin, then iron will take part
in the redox reaction and not tin. Therefore, iron will be corroded under these
circumstances.

Q.27 How will show that Faraday's second law of electrolysis is simply corollary of
the first law.

A.27 According to Faraday's first law of electrolysis. w = Z × Q If same quantity of

electricity is passed through two electrolytes, i.e., Q1 = Q2 = Q, then In case of
Electrochemistry

first electrolyte,
w1 = Z1 × Q and In case of second electrolyte, w2 = Z2 × Q

39.
 w1 Z1 E1 / 96500 E1
On diving = = =
w2 Z2 E2 / 96500 E2
Where E1 and E2 are their equivalent masses

Q.28
Calculate the equilibrium constant for the reaction at 298 K
Zn  s   Cu  aq   Zn  aq  Cu  s 


2 2


 0.76V and ECu2  /Cu  0.34V

0
Given E0 2 
zn /Zn

nE0Cell
A.29 We know that log =
0.0591

E0cell  E0cathode  E0anode  = [(+0.34 V) – (– 0.76 V)] = 1.10 V, n =2,

2   1.10 V 
log Kc =  37.29  Kc = Antilog 37.29 = 1.95 × 1037
0.0591 V 

Q.30 Given that, Co3+ + e– 

 Co2+ E° = + 1.82V
2H2O 
 O2 + 4H+ + 4e– ; E° = –1.23V.
Explain why Co3+ is not stable in aqueous solutions

A.30 The can be calculated as follows :

4 [Co+3 + e– 
 Co2+] ; E° = + 1.82V
2H2O 
 O2 + 4H+ + 4e– ; E° = – 1.23 V
Since is positive, the cell reaction is spontaneous. This means that Co3+ ions will
take part in the reaction. Therefore, Co3+ is not stable.
Electrochemistry

40.
Q.31 The measured e.m.f. at 25°C for the cell reaction,
Zn (s) + Cu2+ (1.0M) 
 Cu (s) + Zn2+ (0.1 M)
is 1.3 volt Calculate E° for the cell reaction.

A.31 Using Nernst equation (at 298 K),

0.0591 V Zn2  aq 
Ecell  E  0
log
Cu2  aq 
cell
2
Substituting the values
1.3V  E0  0.0591V log 0.1  1.3V  E0  0.02955 V log 101
cell cell
2 1.0

1.3V  Ecell  0.02955 V log 10  Ecell  1.3 V  0.02955  1.27 V

0 0

Q.32 The resistance of a 0.01 N solution of an electrolyte was found to 210 ohm at 298
K using a conductivity cell with a cell constant of 0.88 cm–1. Calculate specific
conductance and equivalent conductance of solution

A.32 Given for 0.01 N solution. R = 210 ohm

  0.88 cm1
A
1  1 3 1
 K  R  A  K  210  0.88  4.19  10 mho cm

k  1000 4.19  103  1000

eq   eq   eq  419 mho cm2 eq1
N 0.01 Electrochemistry

41.
 Chapter Summary

Š An electrochemical cell consists of two electrodes (metallic conductors) in

contact with an electrolyte.
An electrode and its electrolyte comprise an Electrode Compartment.
Electrochemical Cells can be classified as:
(i) Electrolytic Cells in which a non-spontaneous reaction is driven by an
external source of current.
(ii) Galvanic Cells which produce electricity as a result of a spontaneous cell
reaction
Š A voltaic or galvanic cell is an electrochemical cell in which a spontaneous reaction
generates an electric current.
In a galvanic cell, cathode is positive with respect to anode.
The salt-bridge contains solution of strong ionic salts like NaCl, NaNO3, KNO3, KCl
etc., which is soaked in a colloidal solution of agar-agar gel which permits the
movement of ions of salts only.
REPRESENTATION OF A CELL (IUPAC CONVENTIONS)
Anodic half-cell is written on left and cathodic half-cell on right hand side.
Zn(s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
The net reaction that occurs in the voltaic cell, it is called the cell reaction.
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)
Š A definite potential difference is developed between the metal and the solution.
This potential difference is called electrode potential.
(i) Oxidation potential : When electrode is negatively charged with respect to
solution, i.e., it acts as anode. Oxidation occurs. M Mn+ + ne–
(ii) Reduction potential : When electrode is positively charged with respect to
solution. i.e., it acts as cathode. Reduction occurs. Mn+ + ne– M
Š The magnitude of potential depends on the following factors :
(i) Nature of the electrode
(ii) Concentration of the ion in solution
(iii) Temperature
Š Concept of Electromotive force (EMF) of a Cell
ECell = R.P. (Cathode) – R.P. (Anode)
= R.P. (Cathode) + O.P (Anode)
Š Electrolytic Cell : This cell converts electrical energy into chemical energy. The
entire assembly except that of the external battery is known as the electrolytic
Electrochemistry

cell.
Electrolysis of molten sodium Chloride
NaCl(molten) Na+ + Cl–

42.
 Reactions at anode (oxidation) : cathode (reduction)
2Cl– Cl2 (g) + 2e– : 2Na+ + 2e– 2Na(l)
Š Relationship Between DG & Electrode Potential
Reactions DG E
1 Spontaneous (-) (+)
2 Non-spontaneous (+) (-)
3 Equilibrium 0 0
Š Nernst Equation :
aA + bB cC + dD,

Š Concentration Cell :
For such cell, E°Cell = 0.
Electrode Gas concentration cell :
For spontaneity of such cell reaction, p1>p2
Electrolyte concentration cells:
For spontaneity of such cell reaction, C2>C1
Š Commercial Voltaic Cells :
Primary batteries cannot be returned to their original state by recharging, so
when the reactants are consumed, the battery is "dead" and must be discarded.
Secondary batteries are often called storage batteries or rechargeable batteries.
The reactions in these batteries can be reversed; thus, the batteries can be
recharged.
Š The discharging process of the storage cell is based on the principles of
electrochemical cell, whereas the charging process is based upon the principles
of electrolytic cells.
Š Faraday’s laws of Electrolysis :
Š First law of electrolysis : Amount of substance deposited or liberated at an
electrode is directly proportional to amount of charge passed (utilized) through
the solution.
Š Second law of electrolysis : When same amount of charge is passed through
different electrolyte solutions connected in series then weight of substances
deposited or dissolved at anode or cathode are in ratio of their equivalent weights.
Š i.e. w1 /w2 = E1 /E2
Š Conductance
Electrochemistry

Reciprocal of resistance is called as conductance and reciprocal of specific

resistance is called as specific conductance.

43.
 E0
cell

Š Equivalent Conductance

E0CO2+ |CO

Molar Conductance

E0Ce4+ |Ce3+

Relation between

0
E
Š Kohlrausch's Law of Independent Migration of Ions
E0CO2+ |CO

cell
Electrochemistry

44.