Electrochemistry 491

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Flow of electrons
Anode Cathod

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Flow of e
current

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Chemistry Page
Chapter

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12
Electrochemistry

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Electrochemistry is the branch of physical (iv) In voltameter, outside the electrolyte
chemistry which deals with the relationship between electrons flow from anode to cathode and current flow
electrical energy and chemical changes taking place in from cathode to anode.
redox reactions
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Electrolytes and Electrolysis

(1) Definition : “The substances whose aqueous For voltameter, E cell  ve and ΔG  ve.
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solution undergo decomposition into ions when electric
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(v) The anions on reaching the anode give up

current is passed through them are known as
their electrons and converted into the neutral atoms.
electrolytes and the whole process is known as
electrolysis or electrolytic decomposition.” At anode : A–  A  e  (Oxidation)
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Solutions of acids, bases, salts in water and fused (vi) On the other hand cations on reaching the
salts etc. are the examples of electrolytes. Electrolytes cathode take up electrons supplied by battery and
may be weak or strong. Solutions of cane sugar, converted to the neutral atoms.
glycerine, alcohol etc., are examples of non-
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At cathode : B  e   B (Reduction)

electrolytes.
This overall change is known as primary change
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(2) Electrolytic cell or Voltameter : The device

and products formed is known as primary products.
in which the process of electrolysis or electrolytic
The primary products may be collected as such or
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decomposition is carried out is known as electrolytic

cell or voltameter. they undergo further change to form molecules or
compounds. These are called secondary products and
(i) Voltameter convert electrical energy into the change is known as secondary change.
chemical energy.
(3) Preferential discharge theory : According to
(ii) The electrode on which oxidation takes place this theory “If more than one type of ion is attracted
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is called anode (or +ve pole) and the electrode on towards a particular electrode, then the ion is discharged
which reduction takes place is called cathode (or –ve one which requires least energy or ions with lower
pole) discharge potential or which occur low in the
(iii) During electrolysis in voltameter cations are electrochemical series”.
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discharged on cathode and anions on anode. The potential at which the ion is discharged or
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deposited on the appropriate electrode is termed the

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492 Electrochemistry
discharge or deposition potential, (D.P.). The values of For cations : Li , K  , Na  , Ca 2  , Mg 2  , Al 3  , Zn2  ,

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discharge potential are different for different ions.
Fe 2 , Ni 2  , H  , Cu 2  , Hg 2  , Ag  , Au 3  .
The decreasing order of discharge potential or the
increasing order of deposition of some of the ions is For anions : SO 42  , NO 3 , OH  , Cl  , Br  , I  .

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given below,
Table : 12.1 Products of electrolysis of some electrolytes

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Electrolyte Electrode Product at cathode Product at anode
Aqueous NaOH Pt or Graphite 2 H   2e   H 2 1
2OH   O 2  H 2 O  2e 

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2
Fused NaOH Pt or Graphite Na   e   Na 1
2 OH   O2  H 2 O  2e 
2
Aqueous NaCl Pt or Graphite 2 H   2e   H 2 2Cl   Cl 2  2e 

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Fused NaCl Pt or Graphite Na   e   Na 2Cl   Cl 2  2e 
Aqueous CuSO4 Pt or Graphite Cu 2  2e   Cu 1
2OH   O 2  H 2 O  2e 
2
Aqueous CuSO4
Dilute H2SO4 e.i om Cu electrode
Pt electrode
Cu 2  2e   Cu
2 H   2e   H 2
Cu oxidised to Cu 2  ions

2 OH  
1
2
O2  H 2 O  2e 

Conc. H2SO4 Pt electrode 2 H   2e   H 2 Peroxodisulphuric

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acid (H 2 S 2O8 )
Aqueous AgNO3 Pt electrode Ag   e   Ag 1
2 OH   O2  H 2 O  2e 
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2
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Aqueous AgNO3 Ag electrode Ag   e   Ag Ag oxidised to Ag  ions

(4) Application of electrolysis : Electrolysis has electroplati
wide applications in industries. Some of the important ng
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applications are, as follows, With copper Cu Object CuSO  dilute H 2 SO 4

4
(i) Production of hydrogen by electrolysis of
With silver Ag Object K[ Ag (CN )2 ]
water.
(ii) Manufacture of heavy water (D2O) . With nickel Ni Object Nickel
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ammonium
(iii) The metals like Na , K, Mg, Al, etc., are
sulphate
obtained by electrolysis of fused electrolytes.
With gold Au Object K[ Au (CN )2 ]
(iv) Non-metals like hydrogen, fluorine, chlorine
are obtained by electrolysis. With zinc Zn Iron ZnSO 4
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(v) In this method pure metal is deposited at objects

cathode from a solution containing the metal ions With tin Sn Iron SnSO 4
Ag, Cu etc. objects
(vi) Compounds like NaOH, KOH, Thickness of coated layer : Let the dimensions of
Na 2CO 3 , KClO 3 , white lead, KMnO 4 etc. are synthesised metal sheet to be coated be (a cm  b cm).
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by electrosynthesis method. Thickness of coated layer  c cm

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(vii) Electroplating : The process of coating an

Volume of coated layer  (a  b  c) cm 3
inferior metal with a superior metal by electrolysis is
known as electroplating. The aim of electroplating is, to Mass of the deposited substance  Volume  density
prevent the inferior metal from corrosion and to make  (a  b  c)  dg
t

it more attractive in appearance. The object to be It E

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 (a  b  c)  d 
plated is made the cathode of an electrolytic cell that 96500
contains a solution of ions of the metal to be deposited. Using above relation we may calculate the
thickness of coated layer.
For Anode Cathode Electrolyte

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Electrochemistry 493
Faraday's laws of electrolysis (3) Faraday's law for gaseous electrolytic product
For the gases, we use

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The laws, which govern the deposition of
It Ve
substances (In the form of ions) on electrodes during V
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the process of electrolysis, is called Faraday's laws of
electrolysis. These laws given by Michael Faraday in where, V  Volume of gas evolved at S.T.P. at an

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1833. electrode
(1) Faraday's first law : It states that, Ve  Equivalent volume = Volume of gas evolved at

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“The mass of any substance deposited or liberated an electrode at S.T.P. by 1 Faraday charge
at any electrode is directly proportional to the quantity (4) Quantitative aspects of electrolysis : We know
of electricity passed.”i.e., W  Q that, one Faraday (1F) of electricity is equal to the

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Where, charge carried by one mole (6.023  10 23 ) of electrons.
W = Mass of ions liberated in gm, So, in any reaction, if one mole of electrons are
Q  Quantity of electricity passed in Coulombs involved, then that reaction would consume or produce
= Current in Amperes (I) × Time in second (t) 1F of electricity. Since 1F is equal to 96,500 Coulombs,

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 W  I  t or W  Z  I  t hence 96,500 Coulombs of electricity would cause a
In case current efficiency () is given, then reaction involving one mole of electrons.
 If in any reaction, n moles of electrons are
W  ZIt involved, then the total electricity (Q ) involved in the
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where, Z  constant, known as electrochemical
equivalent (ECE) of the ion deposited.
When a current of 1 Ampere is passed for 1 second
(i.e., Q  1 ), then, W  Z
reaction is given by, Q  nF  n  96,500 C
Thus, the amount of electricity involved in any
reaction is related to,
(i) The number of moles of electrons involved in
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Thus, electrochemical equivalent (ECE) may be the reaction,
defined as “the mass of the ion deposited by passing a (ii) The amount of any substance involved in the
current of one Ampere for one second (i.e., by passing reaction.
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Coulomb of electricity)”. It's unit is gram per coulomb.
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Therefore, 1 Faraday or 96,500 C or 1 mole of

Coulomb is the unit of electrical charge. electrons will reduce,
96500 Coulombs  6 .023  10 23 electrons = 1 mole (a) 1 mole of monovalent cation,(b) 1/2mole of
electrons. divalent cation,
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6 .023  10 23 (c) 1/3 mole of trivalent cation, (d) 1/n mole of n

1 Coulomb   6 .28  10 18 electrons,
96500 valent cations.
or 1 electronic charge  1 .6  10 19 Coulomb. Metallic and Electrolytic conductors
(2) Faraday's second law : It states that,
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All substances do not conduct electrical current.

“When the same quantity of electricity is passed The substances, which allow the passage of electric
through different electrolytes, the masses of different current, are called conductors. The best metal
ions liberated at the electrodes are directly proportional conductors are such as copper, silver, tin, etc. On the
to their chemical equivalents (Equivalent weights).” i.e., other hand, the substances, which do not allow the
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W1 E Z It E Z1 E passage of electric current through them, are called

 1 or 1  1 or  1 ( W  ZIt)
W2 E2 Z 2 It E2 Z 2 E2 non-conductors or insulators. Some common examples
Thus the electrochemical equivalent (Z) of an of insulators are rubber, wood, wax, etc.
element is directly proportional to its equivalent The conductors are broadly classified into two
weight (E), i.e., types,
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E  Z or E  FZ or E  96500  Z Metallic and electrolytic conductors.

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where, F  Faraday constant  96500 C mol 1 Metallic conduction Electrolytic conduction

So, 1 Faraday = 1F =Electrical charge carried out (i) It is due to the flow of (i) It is due to the flow of
electrons. ions.
by one mole of electrons.
(ii) It is not accompanied by (ii) It is accompanied by
t

1F = Charge on an electron × Avogadro's number. decomposition of the decomposition of the

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1F = e   N  (1.602  10 19 c)  (6.023  10 23 mol 1 ). substance.(Only physical substance. (Physical as

changes occurs) well as chemical change
Number of electrons passed occur)
Number of Faraday 
6.023  10 23 (iii) It does not involve (iii) It involves transfer of

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494 Electrochemistry

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transfer of matter. matter in the form of ions. Thus, resistivity is defined as the resistance of a
(iv) Conductivity decreases (iv) Conductivity increases conductor of 1 cm length and having area of cross-

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with increase in temperature. with increases in
section equal to 1 cm 2 .
temperature and degree of
hydration due to decreases Units : The units of resistivity are
in viscosity of medium. 2
a cm

r
  R.  Ohm  Ohm. cm
The electrolyte may, therefore, be defined as the l cm

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substance whose aqueous solution or fused state Its SI units are Ohm metre ( m ). But quite often
conduct electricity accompanied by chemical
Ohm centimetre ( cm) is also used.
decomposition. The conduction of current through

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electrolyte is due to the movement of ions. (4) Conductance : It is a measure of the ease with
On the contrary, substances, which in the form of which current flows through a conductor. It is an
their solutions or in their molten state do not conduct additive property. It is expressed as G. It is reciprocal
electricity, are called non-electrolytes. of the resistance, i.e.,

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Electrolytic conduction G
1
When a voltage is applied to the electrodes dipped R
into an electrolytic solution, ions of the electrolyte Units : The units of conductance are reciprocal
move and, therefore, electric current flows through the Ohm (ohm 1 ) or mho. Ohm is also abbreviated as  so

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electrolytic solution. The power of the electrolytes to
that Ohm 1 may be written as  1 .
conduct electric current is termed conductance or
According to SI system, the units of electrical
conductivity.
(1) Ohm's law : This law states that the current conductance is Siemens, S (i.e., 1S  1  1 ).
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flowing through a conductor is directly proportional to (5) Conductivity : The inverse of resistivity is
the potential difference across it, i.e., I  V called conductivity (or specific conductance). It is
where I is the current strength (In Amperes) and V represented by the symbol,  (Greek kappa). The
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is the potential difference applied across the conductor IUPAC has recommended the use of term conductivity
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(In Volts) over specific conductance. It may be defined as, the

V conductance of a solution of 1 cm length and having 1 sq.
or I  or V  IR
R cm as the area of cross-section. In other words,
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where R is the constant of proportionality and is conductivity is the conductance of one centimetre cube of
known as resistance of the conductor. It is expressed in a solution of an electrolyte.
Ohm's and is represented as . The above equation is 1
Thus,  
known as Ohm's law. Ohm's law may also be stated as, 
“the strength of current flowing through a
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conductor is directly proportional to the potential Units : The units of conductivity are
difference applied across the conductor and inversely 1
  Ohm 1 cm–1 or  1 cm 1
proportional to the resistance of the conductor.” Ohm . cm
(2) Resistance : It measures the obstruction to
In SI units, l is expressed in m area of cross-
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the flow of current. The resistance of any conductor is

directly proportional to the length (l) and inversely section in m 2 so that the units of conductivity are
proportional to the area of cross-section (a) so that S m 1 .
l l (6) Molar conductivity or molar conductance :
R or R  ρ
a a Molar conductivity is defined as the conducting power
where  (rho) is the constant of proportionality of all the ions produced by dissolving one mole of an
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and is called specific resistance or resistivity. The electrolyte in solution.

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resistance depends upon the nature of the material. It is denoted by  (lambda). Molar conductance is
Units : The unit of resistance is ohm (). In terms related to specific conductance (  ) as,
of SI, base unit is equal to (kgm 2 ) / (s 3 A 2 ). 

t

M
(3) Resistivity or specific resistance : We know
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that resistance R is where, M is the molar concentration.

l If M is in the units of molarity i.e., moles per litre
R ; Now, if l  1 cm , a  1 cm 2 then R  
a (mol L ), the  may be expressed as,
1

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Electrochemistry 495

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  1000 determination of the conductance of a solution involves

M the measurement of its resistance.
For the solution containing 1 gm mole of (ii) Calculation of conductivity : We have seen

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electrolyte placed between two parallel electrodes of 1 that conductivity () is reciprocal of resistivity (  ) , i.e.,
sq. cm area of cross-section and one cm apart, 1 a
 and   R

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Conductanc e(G)  Conductivi ty  Molar conductivi ty()  l
But if solution contains 1 gm mole of the 1l l
electrolyte therefore, the measured conductance will be      or   G  
R a a

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the molar conductivity. Thus,
where G is the conductance of the cell, l is the
Molar conductivi ty()  100  Conductivi ty
distance of separation of two electrodes having cross
In other words, ()    V section area a cm 2 .
where V is the volume of the solution in

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l
cm 3 containing one gram mole of the electrolyte. The quantity   is called cell constant and is
a
If M is the concentration of the solution in mole per
expressed in cm 1 . Knowing the value of cell constant
litre, then
and conductance of the solution, the specific
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M mole of electrolyte is present in 1000 cm 3

1 mole of electrolyte is present in 

1000
cm 3 of
conductance can be calculated as,
  G  Cell constant
M i.e., Conductivi ty  Conductanc e  Cell constant
solution
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Factors affecting the electrolytic conductance
Thus,     Volume in cm 3 containing 1 mole of
electrolyte. In general, conductance of an electrolyte depends
upon the following factors,
n
  1000
or  
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M (1) Nature of electrolyte : The conductance of an

electrolyte depends upon the number of ions present in
Units of Molar Conductance : The units of molar
the solution. Therefore, the greater the number of ions
conductance can be derived from the formula ,
in the solution the greater is the conductance. The
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  1000
 number of ions produced by an electrolyte depends
M
upon its nature. The strong electrolytes dissociate
The units of  are S cm 1 and units of  are, almost completely into ions in solutions and, therefore,
cm 3 their solutions have high conductance. On the other
Λ  S cm 1   S cm 2 mol 1  S cm 2mol 1
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mol hand, weak electrolytes, dissociate to only small

According to SI system, molar conductance is extents and give lesser number of ions. Therefore, the
expressed as S m 2mol 1 , if concentration is expressed as solutions of weak electrolytes have low conductance.
mol m 3 . (2) Concentration of the solution : The molar
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(7) Equivalent conductivity : It is defined as the conductance of electrolytic solution varies with the
conducting power of all the ions produced by dissolving concentration of the electrolyte. In general, the molar
one gram equivalent of an electrolyte in solution. conductance of an electrolyte increases with decrease
It is expressed as  e and is related to specific in concentration or increase in dilution.
conductance as The molar conductance of strong electrolyte
  1000 1000 ( HCl, KCl, KNO 3 ) as well as weak electrolytes
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e    (M is Molarity of the
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C M
( CH 3 COOH , NH 4 OH ) increase with decrease in
solution)
where C is the concentration in gram equivalent concentration or increase in dilution. The variation is
per litre (or Normality). This term has earlier been however different for strong and weak electrolytes.
quite frequently used. Now it is replaced by molar The variation of molar conductance with
t

conductance. The units of equivalent conductance are concentration can be explained on the basis of
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Ohm 1 cm 2 (gm equiv )1 . conducting ability of ions for weak and strong
(8) Experimental measurement of conductance electrolytes.
(i) The conductance of a solution is reciprocal of For weak electrolytes the variation of  with
the resistance, therefore, the experimental dilution can be explained on the bases of number of
ions in solution. The number of ions furnished by an

Chemistry Page
 496 Electrochemistry
electrolyte in solution depends upon the degree of Loss around anode Speed of cation


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dissociation with dilution. With the increase in Loss around cathode Speed of anion
dilution, the degree of dissociation increases and as a The relation is valid only when the discharged ions
result molar conductance increases. The limiting value
do not react with atoms of the electrodes. But when the

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of molar conductance (0 ) corresponds to degree of ions combine with the material of the electrode, the
dissociation equal to 1 i.e., the whole of the electrolyte concentration around the electrode shows an increase.
dissociates. Transport number or Transference number

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Thus, the degree of dissociation can be calculated (1) Definition : “The fraction of the total current
at any concentration as, carried by an ion is known as transport number,
transference number or Hittorf number may be denoted

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c


0 by sets symbols like t+ and t– or tc and ta or nc and na”.
where  is the degree of dissociation, From this definition,

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Current carried by an anion
c is the molar conductance at concentration C ta 
Total current passed through the solution
and
Current carried by a cation
tc 
0 is the molar conductance at infinite dilution. Total current passed through the solution

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For strong electrolytes, there is no increase in evidently, ta  tc  1.
the number of ions with dilution because strong (2) Determination of transport number :
electrolytes are completely ionised in solution at all Transport number can be determined by Hittorf's
concentrations (By definition). However, in method, moving boundary method, emf method and
concentrated solutions of strong electrolytes there are
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strong forces of attraction between the ions of opposite
(3) Factors affecting transport number
charges called inter-ionic forces. Due to these inter-
ionic forces the conducting ability of the ions is less in A rise in temperature tends to bring the transport
concentrated solutions. With dilution, the ions become number of cation and anion more closer to 0.5
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far apart from one another and inter-ionic forces (4) Transport number and Ionic mobility : Ionic
decrease. As a result, molar conductivity increases with mobility or Ionic conductance is the conductivity of a
dilution. When the concentration of the solution solution containing 1 g ion, at infinite dilution, when
n
becomes very-very low, the inter-ionic attractions two sufficiently large electrodes are placed 1 cm apart.
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become negligible and the molar conductance Ionic mobilities (a or c )  speeds of ions (uaor uc )
approaches the limiting value called molar conductance
at infinite dilution. This value is characteristic of each Unit of ionic mobility is Ohm–1 cm2 or V–1S-1cm2
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electrolyte. Ionic mobility and transport number are related

(3) Temperature : The conductivity of an as,
electrolyte depends upon the temperature. With a orc  ta or tc  
increase in temperature, the conductivity of an
Absolute ionic mobility is the mobility with which
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electrolyte increases.
Migration of ions the ion moves under unit potential gradient. It's unit is
w

cm sec 1 .
Electricity is carried out through the solution of
an electrolyte by migration of ions. Therefore, Ionic mobility
Absolute ionic mobility 
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(1) Ions move toward oppositely charged 96,500

electrodes at different speeds.
Kohlrausch's law
(2) During electrolysis, ions are discharged or
liberated in equivalent amounts at the two electrodes, (1) Kohlrausch law states that, “At time infinite
no matter what their relative speed is. dilution, the molar conductivity of an electrolyte can be
(3) Concentration of the electrolyte changes expressed as the sum of the contributions from its
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around the electrode due to difference in the speed of individual ions” i.e., m         , where,   and
the ions.   are the number of cations and anions per formula
(4) Loss of concentration around any electrode is unit of electrolyte respectively and,  and  are the
proportional to the speed of the ion that moves away
molar conductivities of the cation and anion at infinite
t

from the electrode, so

dilution respectively. The use of above equation in
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Chemistry Page
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Electrochemistry 497
expressing the molar conductivity of an electrolyte is We know, that at any concentration C, the degree
illustrated as, of ionisation ( ) is given by,   cm / m

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The molar conductivity of HCl at infinite dilution
C(cm / m ) 2 C(cm ) 2
can be expressed as, Then, K  ; Thus,
[1  (cm / m )] m (m  cm )

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HCl   H  H    Cl  Cl  ; For HCl, H  1 and
knowing m and cm at any concentration, the
 Cl   1 . So, HCl  (1  H  )  (1  Cl  ) ; Hence, ionisation constant (K) of the electrolyte can be

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HCl  H   Cl  determined.
(iv) Determination of the solubility of a
(2) Applications of Kohlrausch's law : Some
sparingly soluble salt : The solubility of a sparingly

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typical applications of the Kohlrausch's law are described
soluble salt in a solvent is quite low. Even a saturated
below,
solution of such a salt is so dilute that it can be
(i) Determination of m for weak electrolytes : assumed to be at infinite dilution. Then, the molar
The molar conductivity of a weak electrolyte at infinite conductivity of a sparingly soluble salt at infinite

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dilution (m ) cannot be determined by extrapolation dilution (m ) can be obtained from the relationship,

method. However, m values for weak electrolytes can m        ........(i)
be determined by using the Kohlrausch's equation.
The conductivity of the saturated solution of the

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CH 3 COOH  CH 3 COONa  HCl  NaCl

(ii) Determination of the degree of ionisation of

sparingly soluble salt is measured. From this, the
conductivity of the salt ( salt ) can be obtained by using
the relationship,  salt   sol   water , where,  water is the
a weak electrolyte : The Kohlrausch's law can be used
for determining the degree of ionisation of a weak conductivity of the water used in the preparation of the
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electrolyte at any concentration. If  cm is the molar saturated solution of the salt.
conductivity of a weak electrolyte at any concentration 1000  salt
........(ii)
n
salt 
C and,  m is the molar conductivity of a electrolyte at Cm
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infinite dilution. Then, the degree of ionisation is given From equation (i) and (ii) ;
c cm
by, c  m  1000  salt
m (     )

Cm  , Cm is the molar concentration
ist out

(       )
Thus, knowing the value of cm , and m (From of the sparingly soluble salt in its saturated solution.
the Kohlrausch's equation), the degree of ionisation at Thus, Cm is equal to the solubility of the sparingly
any concentration ( c ) can be determined. soluble salt in the mole per litre units. The solubility of
em w.y

the salt in gram per litre units can be obtained by

(iii) Determination of the ionisation constant of multiplying Cm with the molar mass of the salt.
a weak electrolyte : Weak electrolytes in aqueous
solutions ionise to a very small extent. The extent of Electrochemical or Galvanic cell
ionisation is described in terms of the degree of
w. /ww

“Electrochemical cell or Galvanic cell is a device in

ionisation ( ). In solution, the ions are in dynamic
which a spontaneous redox reaction is used to convert
equilibrium with the unionised molecules. Such an chemical energy into electrical energy i.e. electricity can
equilibrium can be described by a constant called
be obtained with the help of oxidation and reduction
ionisation constant. For example, for a weak reaction”.
electrolyte AB, the ionisation equilibrium is, AB ⇌
(1) Characteristics of electrochemical cell :
ww ps:/

A   B  ; If C is the initial concentration of the

ch

Following are the important characteristics of

electrolyte AB in solution, then the equilibrium e–
electrochemical cell, e–
concentrations of various species in the solution are,
Voltmeter Salt bridge
[ AB ]  C(1   ), [ A  ]  C  and [B  ]  C Cu
Zn anode
cathode
t

Then, the ionisation constant of AB is given by,

ht

[ A  ][B  ] C  .C  C 2
K   Porous
[ AB ] C(1   ) (1   )
ZnSO4plug
CuSO4
Fig. 12.1

Chemistry Page
 ge
498 Electrochemistry

(4) Reversible and irreversible cells : A cell is said

pa
(i) Electrochemical cell consists of two vessels, to be reversible if the following two conditions are
two electrodes, two electrolytic solutions and a salt fulfilled
bridge. (i) The chemical reaction of the cell stops when
(ii) The two electrodes taken are made of

ry
an exactly equal external emf is applied.
different materials and usually set up in two separate
(ii) The chemical reaction of the cell is reversed
vessels.
and the current flows in opposite direction when the

ist
(iii) The electrolytes are taken in the two
external emf is slightly higher than that of the cell. Any
different vessels called as half - cells.
other cell, which does not obey the above two
(iv) The two vessels are connected by a salt
bridge/porous pot. conditions, is termed as irreversible. Daniell cell is

em
reversible but Zn| H 2 SO 4 | Ag cell is irreversible in
(v) The electrode on which oxidation takes place
is called the anode (or – ve pole) and the electrode on nature
which reduction takes place is called the cathode (or + (5) Types of electrochemical cells : Two main
ve pole). types of electrochemical cells have been reported, these

/ch
(vi) In electrochemical cell, ions are discharged are,
only on the cathode. (i) Chemical cells : The cells in which electrical
(vii) Like electrolytic cell, in electrochemical cell, energy is produced from the energy change
from outside the electrolytes electrons flow from anode accompanying a chemical reaction or a physical process
to cathode and current flow from cathode to anode.

e.i om
(viii) For electrochemical cell,
Ecell  ve, G  ve.
(ix) In a electrochemical cell, cell reaction is
are known as chemical cells. Chemical cells are of two
types,
(a) Chemical cells without transference : In this
type of chemical cells, the liquid junction potential is
exothermic. neglected or the transference number is not taken into
ag e.c
(2) Salt bridge and its significance consideration. In these cells, one electrode is reversible
(i) Salt bridge is U – shaped glass tube filled with to cations while the other is reversible to the anions of
a gelly like substance, agar – agar (plant gel) mixed
n
the electrolyte.
ryp ub

with an electrolyte like KCl, KNO3, NH4NO3 etc. (b) Chemical cells with transference : In this type
(ii) The electrolytes of the two half-cells should of chemical cells, the liquid-liquid junction potential or
be inert and should not react chemically with each
diffusion potential is developed across the boundary
other.
between the two solutions. This potential develops due
ist out

(iii) The cation as well as anion of the electrolyte

to the difference in mobilities of  ve and  ve ions of
should have same ionic mobility and almost same
transport number, viz. KCl, KNO 3 , NH 4 NO 3 etc. the electrolytes.
(6) Concentration cells : “A cell in which
(iv) The following are the functions of the salt
electrical energy is produced by the transference of a
bridge,
em .y

substance from a system of high concentration to one at

(a) It connects the solutions of two half - cells
low concentration is known as concentration cells”.
and completes the cell circuit.
w

Concentration cells are of two types.

(b) It prevent transference or diffusion of the
(i) Electrode concentration cells : In these cells,
solutions from one half cell to the other.
the potential difference is developed between two
w. /ww

(c) It keeps the solution of two half - cells

electrically neutral. electrodes at different concentrations dipped in the
same solution of the electrolyte. For example, two
(d) It prevents liquid – liquid junction potential
i.e. the potential difference which arises between two hydrogen electrodes at different gaseous pressures in
solutions when they contact with each other. the same solution of hydrogen ions constitute a cell of
(3) Representation of an electrochemical cell this type.
ww ps:/

The cell may be written by arranging each of the Pt, H 2 (pressure p1 ) H 2 (pressure p 2 ) Pt
ch

| H | ;
pair left – right, anode – cathode, oxidation – reduction, Anode Cathode
negative and positive in the alphabetical order as, 0.0591 (p )
Ecell  log 1 at 25 o C If p1  p2 , oxidation occurs
2 (p 2 )
Right at L. H. S. electrode and reduction occurs at R. H. S.
t

Left Bridge
electrode.
ht

Anode Cathode In the amalgam cells, two amalgams of the same

Reductio metal at two different concentrations are immersed in
Oxidation
n the same electrolytic solution. M (Hg C1 ) | M n | Zn(Hg C 2 )
Negative Positive

Chemistry Page
 e
Electrochemistry 499

ag
The emf of the cell is given by the expression, Some Commercial cell (Batteries)
0 .0591 C
Ecell  log 1 at 25 o C One of the main use of galvanic cells is the
n C2

yp
generation of portable electrical energy. These cells are
(ii) Electrolyte concentration cells : In these also popularly known as batteries. The term battery is
cells, electrodes are identical but these are immersed in generally used for two or more Galvanic cells
solutions of the same electrolyte of different connected in series. Thus, a battery is an arrangement

r
concentrations. The source of electrical energy in the of electrochemical cells used as an energy source. The

ist
cell is the tendency of the electrolyte to diffuse from a basis of an electrochemical cell is an oxidation –
solution of higher concentration to that of lower reduction reaction.
concentration. With the expiry of time, the two

em
Types of commercial cells : There are mainly two
concentrations tend to become equal. Thus, at the start
types of commercial cells,
the emf of the cell is maximum and it gradually falls to
zero. Such a cell is represented in the following manner (1) Primary cells : In these cells, the electrode
reactions cannot be reversed by an external electric P
( C 2 is greater then C1 ).

/ch
energy source. In these cells, reactions occur only once
M | M  n (C1 )| | M n  (C 2 )| M and after use they become dead. Therefore, they are
not chargeable. Some common example are, dry cell,
Zn | Zn2  (C1 ) Zn2  (C2 )| Zn
or || mercury cell, Daniell cell and alkaline dry cell
Anode Cathode

e.i om (i) Voltaic cellCu rod – + Zn rod

The emf of the cell is given by the following
expression,
0.0591 C Dil. H2SO4
Ecell  log 2(R. H .S ) e at 25o C
n C1(L. H .S .)
ag e.c
Local action
Cu
Polarisatio
The concentration cells are used to determine the
n Zn
solubility of sparingly soluble salts, valency of the
n
cation of the electrolyte and transition point of the two Fig. 12.2
ryp ub

allotropic forms of metal used as electrodes, etc. Cathode : Cu rod Anode : Zn rod
(7) Heat of reaction in an electrochemical cell : Electrolyte : dil. H 2SO 4 Emf : 1.08 V
Let n Faraday charge flows out of a cell of emf E, then At cathode : Cu 2   2e   Cu
ist out

G  nFE …….(i) At Anode : Zn  Zn2   2e 

Gibbs – Helmholtz equation from thermodynamics Over all reaction : Zn  Cu 2   Zn2   Cu
may be given as (ii) Daniel cell Electrons flow
e–
 G 
em w.y

e–
G  H  T   …….(ii) – Key
Ammeter Current
+
 T  P
Anode (Zn)
Salt bridge Cathode (Cu)
From equation (i) and (ii) we get,
 (nFE )   E 
 nFE  H  T    H  nFT  T 
w. /ww

Cotton Plugs
 T  P  P
Zn2+ Cu2+
 E 
H  nFE  nFT  
 T  P
1M ZnSO4 (aq) Fig. 12.3 1M CuSO4 (aq)
 E  (Depolariser)
where   = Temperature coefficient of cell
 T  P Cathode : Cu rod Anode : Zn rod
ww ps:/
ch

Electrolyte : dil. H 2SO 4 Emf : 1.1 V

 E 
Case I: When   = 0, then H  nFE At cathode : Cu 2   2e   Cu
 T  P
At Anode : Zn  Zn2   2e 
 E 
Case II: When   > 0, then nFE  H , i.e. Over all reaction : Zn  Cu 2   Zn2   Cu
t

 T 
(iii) Lechlanche cell (Dry cell)
ht

process inside the cell is endothermic.

+ Seal
 E  Graphite (cathode)
Case III: When   < 0, then nFE  H , i.e.,
 T  MnO2 +C
(Depolariser)
process inside the cell is exothermic. Paste of NH4Cl+ZnCl2

–
Zinc
Fig. 12.4 anode
 ge
500 Electrochemistry

pa
Cathode : Mercury (II) oxide Anode :
Zn rod

ry
Electrolyte : Paste of KOH  ZnO Emf :
Cathode : Graphite rod Anode : Zn pot
1.35 V
Electrolyte : Paste of NH 4 Cl  ZnCl2 in starch
At cathode : HgO(s)  H 2 O(l)  2e   Hg (l)  2OH (aq)

ist
Emf : 1.2 V to 1.5 V
At cathode : NH 4  MnO 2  2e   MnO (OH )  NH 3 At Anode : Zn(s)  20 H (aq )  ZnO (s)  H 2 O(l)  2e 
(amalgam)
At Anode : Zn  Zn2   2e  Over all reaction : Zn(s)  HgO(s)  ZnO(s)  Hg(l)

em
Over all reaction :
(2) Secondary cells : In the secondary cells, the
Zn  NH 4  MnO 2  Zn 2   MnO (OH )  NH 3
reactions can be reversed by an external electrical
(iv) Mercury cell energy source. Therefore, these cells can be recharged

/ch
by passing electric current and used again and again.
These are also celled storage cells. Examples of
secondary cells are, lead storage battery and nickel –
cadmium storage cell.

In charged
e.i om Lead storage cell Alkali cell

Ni(OH)2
+ – + –
ag e.c
Glass
Fe(OH)2
vessel
PbO2 Perforated
n
steel grid
ryp ub

Pb
KOH 20%
dil. H2SO4 + Li(OH), 1%
ist out

Positive Perforated lead plates coated with PbO2 Perforated steel plate coated with Ni(OH)4
electrode
Negative Perforated lead plates coated with pure lead Perforated steel plate coated with Fe
electrode
em .y

Electrolyte dil. H2SO4 20% solution of KOH + 1% LiOH

During charging Chemical reaction Chemical reaction
w

At anode : PbSO4 + 2H+ + 2e–  Pb + H2SO4 At anode : Ni (OH)2 + 2OH+ – 2e– 

At cathode : PbSO4 + SO4– – + 2H2O – 2e–  Ni(OH)4
w. /ww

PbO2 At cathode : Fe(OH)2 + 2K+ + 2e–  Fe +

+ 2KOH
2H2SO4 Emf of cell : When cell is fully charged
Specific gravity of H2SO4 increases and when then E = 1.36 volt
specific gravity becomes 1.25 the cell is fully
charged.
ww ps:/

Emf of cell: When cell is fully charged then E =

ch

2.2 volt
During Chemical reaction Chemical reaction
discharging At anode : Pb + SO4– – – 2e–  PbSO4 At anode : Fe + 2OH– – 2e–  Fe(OH)2
At cathode : PbO2 + 2H+ + 2e– + H2SO4  PbSO4 At cathode : Ni(OH)4 + 2K+ + 2e– 
t

+ Ni(OH)2 +
ht

2H2O 2KOH
Specific gravity of H2SO4 decreases and when Emf of cell : When emf of cell falls below
specific gravity falls below 1.18 the cell 1.1 V it requires charging.
requires recharging.

Chemistry Page
 Electrochemistry 501
Emf of cell : When emf of cell falls below 1.9
volt the cell requires recharging.

ge
Efficiency 80% 60%

Fuel cells battery. The fuel can be fed continuously to produce

pa
power. For this reason, H 2  O 2 fuel cells have been used
These are Voltaic cells in which the reactants are
continuously supplied to the electrodes. These are in space crafts.
designed to convert the energy from the combustion of (3) Pollution free working : There are no
fuels such as H 2 , CO, CH 4 , etc. directly into electrical

ry
objectionable byproducts and, therefore, they do not
energy. The common example is hydrogen-oxygen fuel cause pollution problems. Since fuel cells are efficient
cell as described below, and free from pollution, attempts are being made to get

ist
In this cell, hydrogen and oxygen are bubbled better commercially practical fuel cells.
through a porous carbon electrode into concentrated
aqueous sodium hydroxide or potassium hydroxide. Electrode Potential

em
Hydrogen (the fuel) is fed into the anode compartment (1) When a metal (M) is placed in a solution of its
where it is oxidised. The oxygen is fed into cathode ions (M++), either of the following three possibilities
compartment where it is reduced. The diffusion rates of can occurs, according to the electrode potential
the gases into the cell are carefully regulated to get
solution pressure theory of Nernst.
maximum efficiency. The net reaction is the same as

/ch
burning of hydrogen and oxygen to form water. The (i) A metal ion M n+ collides with the electrode,
reactions are and undergoes no change.
At anode : 2[H 2 (g)  2OH  ](aq)  2 H 2 O(l)  2e  (ii) A metal ion M n+ collides with the electrode,
gains n electrons and gets converted into a metal atom
At cathode : O2 (g)  2 H 2 O(l)  4 e   4 OH  (aq)
M, (i.e. the metal ion is reduced).
Overall
e.i om reaction :
M n  (aq)  ne   M (s)
2 H 2 (g)  O2 (g)  2 H 2 O(l)
(iii) A metal atom on the electrode M may lose an
Each electrode is made of porous compressed
electrons to the electrode, and enter to the solution as
carbon containing a small amount of catalyst
ag e.c

(Pt, Ag or CoO ) . This cell runs continuously as long as M n , (i.e. the metal atom is oxidised).
the reactants are fed. Fuel cells convert the energy of M (s)  M n  (aq)  ne  .
the fuel directly into electricity EMF of fuel cell is 1.23 Thus, “the electrode potential is the tendency of an
n
V. This cell has been used for electric power in the electrode to lose or gain electrons when it is in contact
ryp ub

Apollo space programme. H2OThe important advantages of

with solution of its own ions.”
fuel cells are Anode – + Cathode (2) The magnitude of electrode potential depends
on the following factors,
ist ut

Porous carbon electrode

(i) Nature of the electrode, (ii) Concentration of
the ions in solution, (iii) Temperature.
(3) Types of electrode potential : Depending on
o

the nature of the metal electrode to lose or gain

OH–
em w.y

electrons, the electrode potential may be of two types,

H2 O2
Electrolyte (i) Oxidation potential : When electrode is
Fig. 12.6 negatively charged with respect to solution, i.e., it acts
as anode. Oxidation occurs. M  M n   ne 
w. /ww

(1) High efficiency : The fuel cells convert the (ii) Reduction potential : When electrode is
energy of a fuel directly into electricity and therefore, positively charged with respect to solution, i.e. it acts
they are more efficient than the conventional methods as cathode. Reduction occurs. M n   ne   M
of generating electricity on a large scale by burning (4) Standard electrode potential : “If in the half
hydrogen, carbon fuels. Though we expect 100 % cell, the metal rod (M) is suspended in a solution of one
efficiency in fuel cells, so far 60 – 70% efficiency has
ww ps:/

molar concentration, and the temperature is kept at 298

ch

been attained. The conventional methods of production K, the electrode potential is called standard electrode
of electrical energy involve combustion of a fuel to potential, represented usually by E o ”. ‘or’
liberate heat which is then used to produce electricity.
The standard electrode potential of a metal may
The efficiency of these methods is only about 40%.
be defined as “the potential difference in volts developed
t

(2) Continuous source of energy : There is no in a cell consisting of two electrodes, the pure metal in
ht

electrode material to be replaced as in ordinary

Chemistry Page
 ge
502 Electrochemistry
contact with a molar solution of one of its ions and the couple the electrode with another electrode whose
normal hydrogen electrode (NHE)”. potential is known. This electrode is termed as

pa
Standard oxidation potential for any half - cell  – (Standard reduction potential ) reference electrode or reference half - cells. Various
Standard reduction potential for any half - cell  – (Standard reduction potential ) types of half – cells have been used to make complete
(5) Reference electrode or reference half - cells cell with spontaneous reaction in forward direction.

ry
These half – cells have been summarised in following
It is not possible to measure the absolute value of
table,
the single electrode potential directly. Only the
difference in potential between two electrodes can be

ist
measured experimentally. It is, therefore, necessary to
Table : 12.2 Various Types of Half – cells

em
Type Example Half – cell reaction Q= Reversibl Electrode Potential
e to (oxidn), E =
Gas ion half - cell Pt(H 2 )| H  (aq) 1 [H  ] H E0  0.0591log[H  ]
H 2 (g)  H  (aq)  e 
2 1 Cl 
Pt(Cl 2 )| Cl  (aq) E0  0.0591log[Cl  ]

/ch
1 [Cl  ]
Cl (aq)  Cl 2 (g)  e 

2
Metal – metal ion Ag | Ag  (aq) Ag(s)  Ag  (aq)  e  [ Ag  ] Ag  E0  0.0591log[Ag  ]
half – cell
Metal insoluble e.i om
salt anion half –
cell
Ag, AgCl | Cl  (aq) Ag(s)  Cl  (aq)  AgCl(s)  e  1
[Cl  ]
Cl  E0  0.0591log[Cl  ]

Calomel electrode Hg, Hg2Cl 2 | Cl  (aq) 2 Hg(l)  2Cl  (aq)  1 Cl  E0  0.0591log[Cl  ]

[Cl  ]2
ag e.c
Hg 2Cl 2 (s)  2e 
Metal – metal Hg, HgO | OH  (aq) Hg(l)  2OH  (aq)  1 OH  E0  0.0591log[OH  ]
oxide hydroxide  [OH  ]2
HgO(s)  H 2O(l)  2e
n
half - cell
ryp ub

Oxidation – Pt | Fe 2  , Fe 3  Fe2  (aq)  Fe3  (aq)  e  [ Fe 3  ] Fe2  , Fe3  [Fe 3  ]

(aq) (a q) E 0  0 .0591 log
reduction half – [ Fe 2  ] [Fe 2  ]
dell
ist out

Cell potential or EMF of the cell 0

Ecell  Reduction potential of cathode – Reduction potential of anode
(1) “The difference in potentials of the two half – cells 0 0 o o
 E Cathode  E Anode  Eright  Eleft
of a cell known as electromotive force (emf) of the cell or
cell potential.” (iii) When oxidation potentials of both electrodes
em w.y

The difference in potentials of the two half – cells are taken into account
of a cell arises due to the flow of electrons from anode o
Ecell  Oxidation potential of anode – Oxidation
to cathode and flow of current from cathode to anode.
potential of cathode  Eox
0 0
(anode )  Eox (cathode )
w. /ww

Flow of electrons
Anode Cathode (3) Difference between emf and potential difference
Flow of current
(2) The emf of the cell or cell potential can be Emf Potential difference
calculated from the values of electrode potentials of It is the potential It is the difference of the
two the half – cells constituting the cell. The following difference between two electrode potentials of
ww ps:/

three methods are in use : electrodes when no the two electrodes when
ch

(i) When oxidation potential of anode and current is flowing in the the cell is under
reduction potential of cathode are taken into account circuit. operation.
0
E cell  Oxidation potential of anode + Reduction It is the maximum It is always less then the
t

voltage that the cell can maximum value of

ht

potential of cathode  E ox
0 0
(anode )  E red (cathode )
deliver. voltage which the cell
(ii) When reduction potentials of both electrodes can deliver.
are taken into account

Chemistry Page
 ge
Electrochemistry 503
It is responsible for the It is not responsible for At 298 K, the Nernst equation for the M n / M

pa
steady flow of current in the steady flow of electrode can be written as,
the cell. current in the cell.
0 0 .0591 1
EM n  / M  EM n  log n
(4) Cell EMF and the spontaneity of the reaction : /M n [M (aq)]

ry
We know, G  nFEcell
For an electrode (half - cell) corresponding to the
Nature of electrode reaction,

ist
o
ΔG(or ΔG ) E cell (or E ocell )
reaction Oxidised form  ne   Reduced form
Spontaneous – + The Nernst equation for the electrode is written

em
Equilibrium 0 0 as,

Non – spontaneous + – 0 2.303 RT [Reduced form ]

Ehalf cell  Ehalf  cell  log
nF [Oxidised form]
Nernst's equation

/ch
(1) Nernst’s equation for electrode potential At 298 K, the Nernst equation can be written as,

The potential of the electrode at which the 0 0.0591 [Reduced form ]

Ehalf cell  Ehalf  cell  log
reaction, n [Oxidised form]
e.i om
M n  (aq)  ne   M (s) (2) Nernst’s equation for cell EMF
takes place is described by the equation, For a cell in which the net cell reaction involving
RT [M (s)] n electrons is, aA  bB  cC  dD
0
EM n  / M  EM  ln
ag e.c

n
/M nF [M n  (aq.)] The Nernst equation is written as,

0 RT [C]c [D]d
2.303 RT [M (s)] Ecell  Ecell  ln
or EM n  / M  0
EM  log [ A]a [B]b
n
n nF
/M nF [M n  (aq)]
ryp ub

Where, E cell
0 0
 E cathode 0
 E anode .
above eq. is called the Nernst equation.
Where, The E cell
o
is called the standard cell potential.
ist out

E M n  / M = the potential of the electrode at a given 2 . 303 RT [C ]c [D]d

or Ecell  Ecell
o
 log
nF [ A]a [B]b
concentration,
At 298 K, above eq. can be written as,
0
EM = the standard electrode potential
[C ]c [D]d
n
/M 0 . 0592
em w.y

or Ecell  Ecell
o
 log
n [ A]a [B]b
R = the universal gas constant, 8 .31 J K 1 mol 1
It may be noted here, that the concentrations of A,
T= the temperature on the absolute scale, B, C and D referred in the eqs. are the concentrations at
n = the number of electrons involved in the the time the cell emf is measured.
w. /ww

electrode reaction, (3) Nernst’s equation for Daniells cell :

Daniell’s cell consists of zinc and copper electrodes.
F = the Faraday constant : (96500 C),
The electrode reactions in Daniell’s cell are,
[M (s)] = the concentration of the deposited metal,
At anode : Zn(s)  Zn2  (aq)  2e 
[M n (aq)] = the molar concentration of the metal At cathode : Cu 2  (aq)  2e   Cu(s)
ww ps:/
ch

ion in the solution,

Net cell reaction :
The concentration of pure metal M(s) is taken as 2
Zn(s)  Cu (aq)  Cu(s)  Zn (aq) 2

unity. So, the Nernst equation for the M n / M Therefore, the Nernst equation for the Daniell’s
t

electrode is written as, cell is,

ht

2 .303 RT 1 0 2.303 RT [Cu (s)][Zn 2  (aq)]

0
EM n  / M  EM  log Ecdll  Ecell  log
[Zn(s)][Cu 2  (aq)]
n
/M nF n
[M (aq)] 2F

Chemistry Page
 504 Electrochemistry
Since, the activities of pure copper and zinc (1) The standard reduction potentials of a large
metals are taken as unity, hence the Nernst equation number of electrodes have been measured using
for the Daniell’s cell is, standard hydrogen electrode as the reference electrode.

e
These various electrodes can be arranged in increasing
2.303 RT [ Zn 2  (aq]

ag
0
Ecdll  Ecell  log or decreasing order of their reduction potentials. The
2F [Cu 2  (aq)]
arrangement of elements in order of increasing
The above eq. at 298 K is, reduction potential values is called electrochemical

yp
0.0591 [Zn2  (aq] series.It is also called activity series, of some typical
o
Ecdll  Ecell  log V electrodes.
2 [Cu 2  (aq)]
(2) Characteristics of Electrochemical series
For Daniells cell, E cell
0
 1 .1 V (i) The negative sign of standard reduction

s tr
(4) Nernst's equation and equilibrium constant potential indicates that an electrode when joined with
SHE acts as anode and oxidation occurs on this
electrode. For example, standard reduction potential of

mi
For a cell, in which the net cell reaction involving zinc is –0.76 volt, When zinc electrode is joined with
n electrons is, aA  bB  cC  dD SHE, it acts as anode (–ve electrode) i.e., oxidation
occurs on this electrode. Similarly, the +ve sign of
standard reduction potential indicates that the

he
The Nernst equation is
electrode when joined with SHE acts as cathode and
RT [C]c [D]d reduction occurs on this electrode.
0
ECell  Ecell  ln .....(i)
nF [ A]a [B]b (ii) The substances, which are stronger reducing

/c
agents than hydrogen are placed above hydrogen in the
At equilibrium, the cell cannot perform any useful series and have negative values of standard reduction
work. So at equilibrium, ECell is zero. Also at potentials. All those substances which have positive
e.i om
values of reduction potentials and placed below
equilibrium, the ratio
hydrogen in the series are weaker reducing agents than
hydrogen.
[C]c [D]d  [C]c [D]d 
   Kc (iii) The substances, which are stronger oxidising
[ A]a [B]b  [ A]a [B]b  equilibriu m
agents than H  ion are placed below hydrogen in the
ag e.c

Relationship between potential, Gibbs energy series.

and equilibrium constant (iv) The metals on the top (having high negative
n

value of standard reduction potentials) have the

The electrical work (electrical energy) is equal to
ryp ub

tendency to lose electrons readily. These are active

the product of the EMF of the cell and electrical charge
metals. The activity of metals decreases from top to
that flows through the external circuit i.e.,
bottom. The non-metals on the bottom (having high
Wmax  nFEcell ......(i)
positive values of standard reduction potentials) have
ist out

According to thermodynamics the free energy the tendency to accept electrons readily. These are
change (G) is equal to the maximum work. In the cell active non-metals. The activity of non-metals increases
work is done on the surroundings by which electrical from top to bottom.
energy flows through the external circuit, So Table : 12.3 Standard reduction electrode potentials at
em .y

Wmax,  G 298K
......(ii) Element Electrode Reaction Standard
w

(Reduction) Electrode
from eq. (i) and (ii) G  nFEcell
Reduction
w. /ww

In standard conditions G 0   nFE cell

0
potential E0,
volt
Where G 0  standard free energy change
Li Li++ e– = Li –3.05
2 .303 K K++ e– = K –2.925
But E cell
0
 RT log K c
nF Ba Ba+++ 2e = Ba –2.90

 G  nF  2 .303 RT log K c

0 Sr Sr+++ 2e = Sr –2.89
ww ps:/

nF Ca 2  –2.87
ch

Ca  2e  Ca
tendency to accept electrons Increasing

G   2.303 RT log K c or G  G  2 .303 RT log Q

0
Na Na   e   Na –2.714
rength as reducing agent Increasing

G 0   RT ln K c (2 .303 log X  ln X ) Mg Mg 2   2e   Mg –2.37

Al Al 3   3 e   Al –1.66
Electrochemical series
strength as oxidising agent
t

ndency to lose electrons

ht
 Electrochemistry 505

e
Mn Mn+++ 2e = Mn –1.18 negative like alkali metals, alkaline earth metals are

ag
Zn Zn2+ +2e–=Zn –0.7628 strongly electropositive in nature.
Cr Cr3++3 e– = Cr –0.74 (b) Moderately electropositive metals : Metals having
Fe Fe2++ 2e– = Fe –0.44 values of reduction potentials between 0.0 and about –

yp
Cd Cd2++2e– = Cd –0.403 2.0 volt are moderately electropositive Al, Zn, Fe, Ni, Co,
Co Co+++ 2e = Co –0.27
etc., belong to this group.
Ni Ni2++2e– = Ni –0.25
(c) Weakly electropositive : The metals which are
Sn Sn2++2e– = Sn –0.14

r
below hydrogen and possess positive values of reduction
Pb Pb+++ 2e = Pb –0.12

ist
potentials are weakly electropositive metals. Cu, Hg, Ag,
H2 2H++2e– = H2 0.00
Cu Cu2++ 2e– = Cu +0.337
etc., belong to this group.
I2 I2+2e– = 2I– +0.535 (iii) Displacement reactions

em
Hg Hg +2e = Hg
2+ –
+0.885 (a) To predict whether a given metal will displace
Ag Ag++ e– = Ag +0.799 another, from its salt solution: A metal higher in the
Br2 Br2+2e– = 2Br– +1.08 series will displace the metal from its solution which is
Pt Pt+++ 2e = Pt +1.20 lower in the series, i.e., The metal having low standard

/ch
Cl2 Cl2+2e– = 2Cl– +1.36 reduction potential will displace the metal from its
Au Au 3++3e– = Au +1.50 salt's solution which has higher value of standard
F2 F2+2e–= 2F– +2.87 reduction potential. A metal higher in the series has
greater tendency to provide electrons to the cations of
(3) Application of Electrochemical series

e.i om
(i) Reactivity of metals: The activity of the metal
depends on its tendency to lose electron or electrons,
i.e., tendency to form cation (M n  ) . This tendency
the metal to be precipitated.
(b) Displacement of one nonmetal from its salt
solution by another nonmetal: A non-metal higher in the
series (towards bottom side), i.e., having high value of
depends on the magnitude of standard reduction
ag e.c
reduction potential will displace another non-metal
potential. The metal which has high negative value (or with lower reduction potential, i.e., occupying position
smaller positive value) of standard reduction potential above in the series. The non-metal's which possess high
n
readily loses the electron or electrons and is converted positive reduction potentials have the tendency to
ryp ub

into cation. Such a metal is said to be chemically active. accept electrons readily. These electrons are provided
The chemical reactivity of metals decreases from top to by the ions of the nonmetal having low value of
bottom in the series. The metal higher in the series is reduction potential,. Thus, Cl 2 can displace bromine
more active than the metal lower in the series. For
ist out

and iodine from bromides and iodides.

example,
Cl2  2 KI  2 KCl  I2
(a) Alkali metals and alkaline earth metals having
high negative values of standard reduction potentials 2 I   I2  2e  .....(Oxidation)
are chemically active. These react with cold water and Cl 2  2e   2Cl  .....(Reduction)
em .y

evolve hydrogen. These readily dissolve in acids

forming corresponding salts and combine with those [The activity or electronegative character or
w

substances which accept electrons. oxidising nature of the nonmetal increases as the value
of reduction potential increases.]
(b) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a
w. /ww

(c) Displacement of hydrogen from dilute acids by

little down in the series do not react with cold water
but react with steam to evolve hydrogen. metals : The metal which can provide electrons to H 
ions present in dilute acids for reduction, evolve
(c) Metals like Cu, Ag and Au which lie below
hydrogen from dilute acids.
hydrogen are less reactive and do not evolve hydrogen
from water. Mn  Mn n  ne  .....(Oxidation)
ww ps:/

(ii) Electropositive character of metals : The  

2 H  2e  H 2
ch

electropositive character also depends on the tendency .....(Reduction)

to lose electron or electrons. Like reactivity, the
The metal having negative values of reduction
electropositive character of metals decreases from top
potential possess the property of losing electron or
to bottom in the electrochemical series. On the basis of electrons.
t

standard reduction potential values, metals are divided

Thus, the metals occupying top positions in the
ht

into three groups

electrochemical series readily liberate hydrogen from
(a) Strongly electropositive metals : Metals having
dilute acids and on descending in the series tendency to
standard reduction potential near about – 2.0 volt or more
liberate hydrogen gas from dilute acids decreases.

Chemistry Page
 e
506 Electrochemistry

ag
The metals which are below hydrogen in decreases from top to bottom, the thermal stability of
electrochemical series like Cu, Hg, Au, Pt, etc., do not the oxide also decreases from top to bottom. The oxides
evolve hydrogen from dilute acids. of metals having high positive reduction potentials are

yp
(d) Displacement of hydrogen from water : Iron not stable towards heat. The metals which come below
and the metals above iron are capable of liberating copper form unstable oxides, i.e., these are decomposed
hydrogen from water. The tendency decreases from top on heating.

r
to bottom in electrochemical series. Alkali and alkaline

ist
earth metals liberate hydrogen from cold water but Mg,  1
Ag 2 O  2 Ag  O2
Zn and Fe liberate hydrogen from hot water or steam. 2

(iv) Reducing power of metals: Reducing nature BaO 

em
depends on the tendency of losing electron or electrons.

2 HgO  2 Hg  O2 ; Na 2 O  

No decomposit ion

Al 2 O3 
More the negative reduction potential, more is the
tendency to lose electron or electrons. Thus reducing
(vii) Extraction of metals : A more
nature decreases from top to bottom in the
electropositive metal can displace a less electropositive

/ch
electrochemical series. The power of the reducing agent metal from its salt's solution. This principle is applied
increases, as the standard reduction potential becomes
for the extraction of Ag and Au by cyanide process.
more and more negative. Sodium is a stronger reducing silver from the solution containing sodium argento
agent than zinc and zinc is a stronger reducing agent cyanide, NaAg (CN )2 , can be obtained by the addition of

e.i om
than iron. (decreasing order of reducing nature)
zinc as it is more electro-positive than Ag .
Element : Na  Zn  Fe
Reduction potential :  2.71  0.76  0 .44 2 NaAg (CN )2  Zn  Na2 Zn(CN )4  2 Ag

Alkali and alkaline earth metals are strong Corrosion

ag e.c
reducing agents. (1) When metals are exposed to atmospheric
(v) Oxidising nature of non-metals : Oxidising conditions, they react with air or water in the
nature depends on the tendency to accept electron or environment to form undesirable compounds (usually
n
electrons. More the value of reduction potential, higher oxides). This process is called corrosion. Almost all
ryp ub

is the tendency to accept electron or electrons. Thus, metals except the least active metals such as gold,
oxidising nature increases from top to bottom in the platinum and palladium are attacked by environment
electrochemical series. The strength of an oxidising i.e., undergo corrosion. For example, silver tarnishes,
ist out

agent increases as the value of reduction potential copper develops a green coating, lead or stainless steel
becomes more and more positive. lose their lusture due to corrosion. Corrosion causes
F2 (Fluorine) is a stronger oxidant than Cl 2 , Br2 enormous damage to building, bridges, ships and many
other articles made of iron.
and I 2 , Cl 2 (Chlorine) is a stronger oxidant than
Thus corrosion is a process of deterioration of a
em .y

Br 2 and I 2
Element : metal as a result of its reaction with air or water
Reduction potential : (environment) surrounding it.
w

I2 Br2 Cl 2 F2 In case of iron, corrosion is called rusting.

 0 .53  1.06  1.36  2 .85 Chemically, rust is hydrated form of ferric oxide,
w. /ww


Oxidising nature increases Fe 2 O 3 . xH 2 O . Rusting of iron is generally caused by
Thus, in electrochemical series moisture, carbon dioxide and oxygen present in air. It
has been observed that rusting takes place only when
(Strongest reducing agent)
Top iron is in contact with moist air. Iron does not rust in
Highest negative reduction potential dry air and in vacuum.
Reducing
Oxidising

nature
ww ps:/
nature

or (2) Factors which affect corrosion : The main

ch

factors which affect corrosion are

(Minimum reduction potential)
More the reactivity of metal, the more will be the
(Strongest oxidising agent) possibility of the metal getting corroded.
Botto The impurities help in setting up voltaic cells,
Highest positive value of reduction potential
t

m which increase the speed of corrosion

ht

(vi) Thermal stability of metallic oxides : The Presence of electrolytes in water also increases
thermal stability of the metal oxide depends on its the rate of corrosion
electropositive nature. As the electropositivity

Chemistry Page
 ge
Electrochemistry 507
Presence of CO 2 in natural water increase rusting H 2O  H   OH  or CO 2  H 2 O  H   HCO 3

pa
of iron.
At cathode : H   e   H
(v) When the iron surface is coated with layers of
metals more active than iron, then the rate of corrosion The hydrogen atoms on the iron surface reduce

ry
is retarded. dissolved oxygen. 4 H  O2  2 H 2 O
A rise in temperature (with in a reasonable limit) Therefore, the overall reaction at cathode of

ist
increases the rate of corrosion. different electrochemical cells may be written as,
(3) Classification of corrosion process : 4 H   O2  4 e   2 H 2 O
Depending upon the nature of corrosion, and the

em
factors affecting it, the corrosion may be classified as (iii) The overall redox reaction may be written by
follows. multiplying reaction at anode by 2 and adding reaction
at cathode to equalise number of electrons lost and
(i) Chemical corrosion : Such corrosion, generally
gained i.e.
takes place when

/ch
(a) Reactive gases come in contact with metals at Oxi. half reaction : Fe(s)  Fe 2  (aq)  2e  ]  2
high temperatures e.g., corrosion in chemical industry. (E  0 . 44 V )
(b) Slow dissolution of metal takes place when Red. half reaction : 4 H   O2  4 e   2 H 2 O
kept in contact with non conducting media containing
(E  1 . 23 V )
organic acids. e.i om
(ii) Bio-chemical corrosion or Bio-corrosion: Overall cell reaction : 2 Fe (s)  4 H   O2  2 Fe 2  (aq)  2 H 2 O
This is caused by the action of microorganisms. Soils of (ECell  1 .67 V )
definite composition, stagnant water and certain
The ferrous ions are oxidised further by
ag e.c
organic products greatly favour the bio-corrosion.
(iii) Electrochemical corrosion : It occurs in a atmospheric oxygen to form rust.
gaseous atmosphere in the presence of moisture, in 4 Fe 2  (aq)  O2 (g)  4 H 2 O  2 Fe 2 O3  8 H  and
n
soils and in solutions.
ryp ub

Fe 2 O3  xH 2 O  Fe 2 O3 . xH 2 O
(4) Mechanism of rusting of iron : Rust
Electrochemical theory of rusting. It may be noted that salt water accelerates
The overall rusting involves the following steps, corrosion. This is mainly due to the fact that salt water
ist out

(i) Oxidation occurs at the anodes of each increases the electrical conduction of electrolyte
solution formed on the metal surface. Therefore,
electrochemical cell. Therefore, at each anode neutral
rusting becomes more serious problem where salt
iron atoms are oxidised to ferrous ions.
water is present.
At anode : Fe(s)  Fe 2  (aq)  2e  .
em .y

(5) Corrosion protection : Corrosion of metals

Thus, the metal atoms in the lattice pass into the can be prevented in many ways. Some commonly used
w

solution as ions, leaving electrons on the metal itself. methods are

These electrons move towards the cathode region (i) By surface coating
through the metal.
w. /ww

(a) By applying, oil, grease, paint or varnish on

Drop of the surface.
moisture
4H++O2+4e–2H2O (b) By coating/depositing a thin layer of any other
(Cathode)
Rust metal which does not corrode. For example, iron
Fe2+
surface can be protected from corrosion by depositing a
Fe
+
2e–
thin layer of zinc, nickel or chromium on it.
ww ps:/

anode Copper/brass can be protected by coating it with a thin

ch

Flow of
electron layer of tin. Tinning of brass utensils is a very common
Iron s
practice in our country.
Schematic representation of mechanism of rusting of
iron (c) By Galvanization : Prevention of corrosion of
Fig. 12.7
iron by Zn coating.
t

(ii) At the cathodes of each cell, the electrons are (ii) By connecting metal to a more
ht

taken up by hydrogen ions (reduction takes place). The electropositive metal : As long as the more
H  ions are obtained either from water or from acidic electropositive metal is there, the given metal does not
substances (e.g. CO 2 ) in water get corroded. For example, iron can be protected from
corrosion by connecting it to a block/plate of zinc or

Chemistry Page
 508 Electrochemistry
magnesium. This method of corrosion protection is
called cathodic protection.

e
(iii) By forming insoluble phosphate or

ag
chromate coating : Metal surfaces are treated with
phosphoric acid to form an insoluble phosphate.
Formation of a thin chromate layer also prevents the
corrosion of metals.

yp
(iv) Using anti – rust solutions : Solutions of
alkaline phosphates and alkaline chromates are
generally used as anti – rust solutions. For example,

r
iron articles are dipped in boiling alkaline sodium

ist
phosphate solutions, when a protective insoluble
sticking film of iron phosphate is formed.

em
/ch
 When two or more ions compete at the electrodes
then the ion with higher reduction potential gets
liberated at the cathode while the one with lower
e.i om
reduction potential at the anode.
 Cell constant is determined with the help of
conductivity bridge, where a standard solution of
KCl is used.
ag e.c

 If the external EMF is slightly more than the

actual EMF, the current will flow into the cell
and reverse reaction takes place.
n
 Identification of cathode and anode is done by
ryp ub

the use of galvanometer.

 KCl / NaCl / NH4Cl etc., can not be used in the
salt bridge of a cell containing silver salt as one
of the electrodes as Cl– ions form a ppt. of AgCl
ist out

with silver ion.

 Weston cell is a common example of standard
cell. The emf of a standard cell does not change
with temperature.
em w.y

 In Appolo moon flights, H2 – O2 fuel cell was the

source of energy and drinking water.
 Conductivity water is the highly purified water
whose on conductance is very small. It is
prepared by the demineralisation of ordinary
w. /ww

water by passing through cation and anion

exchange resins.
ww ps:/
ch
t
ht

Chemistry Page