Chapter 9

Electrochemistry
Chapter Contents
z Metallic / Electrolytic METALLIC / ELECTROLYTIC CONDUCTORS
Conductors
z Equivalent Conductivity
Conductors
Substances which allow electric current to flow through them are called
z Molar Conductivity conductors while those which do not permit the flow of electric current
z Variation of Molar are called insulators. There are two types of conductors namely
Conductivity with (i) metallic conductors and (ii) electrolytic conductors.
Concentration Differences between Metallic and Electrolytic Conduction
z Kohlrausch Law of Metallic conduction Electrolytic conduction
Independent Migration of Ions
1. Metallic conduction is Electrolytic conduction is
z Electrolysis carried by the movement of carried by the movement of
electrons. ions.
z Quantitative Aspects of
Electrolysis and Faraday's 2. It involves no change in the It involves the decomposition of
Laws chemical properties of the the electrolyte as a result of the
conductor. chemical reaction.
z Electrode Potential and EMF
of a Cell 3. It does not involve the It involves the transfer of matter
transfer of any matter. as ions.
z Nernst Equation
4. Metallic conduction Electrolytic conduction
z Commercial Cells decreases with increase in increases with increase in
temperature. temperature.
z Corrosion
Factors affecting electrolytic conduction
a. Nature of the electrolyte : Conductivity  extent of ionization
b. Size of the ions produced and their solvation : Greater the size of
the ions or greater the solvation of the ions, lesser is the
conductance.
c. Nature of the solvent and its viscosity : Greater the polarity of the
solvent, greater is the ionization and hence greater is the
conductance. Similarly, greater is the viscosity of a solvent, lesser
is the conductance.
d. Concentration of the solution : Higher the conc. of the solution lesser
is the conduction.
e. Temperature Conductance  Temperature.

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Conductance (G) : The reciprocal of resistance is called as conductance i.e.

1
G
R

It measures the ease with which current flows through a conductor.

1
Units. G  ohm1 or mho or siemen (S) (1S = 1–1) (S.I. unit : siemen (S))
ohm

Resistivity (Specific Resistance)

The resistance of a conductor is
(i) Directly proportional to its length
Rl
(ii) Inversely proportional to its area of cross section.
1
R
a
Combining equations (i) and (ii)

l l
R or R  
a a

where  = Constant of proportionality known as resistivity or specific resistance.

If l = 1 cm; a = 1 cm2 then R = 
Thus resistivity may be defined as,
"The resistance offered by a conductor of unit length with unit area of cross-section."
In other words, specific resistance is the resistance offered by all the ions present in 1 cm3 of an electrolytic
solution.

l Ra ohm cm2
Units : R  or l = Ra or    = ohm - cm
a l cm

Specific Conductance (Conductivity)

The reciprocal of the specific resistance is called as specific conductance. It is denoted by  (Kappa)
1 Ra
 We know,  
 l
1 l 1 1
 l   Now G
Ra a R R
l
  G
a
If l = 1 cm, a = 1 cm2, then  = G
Hence conductivity or specific conductance of a solution may be defined as the conductance of a conductor
of unit length with unity area of cross section.
It may be defined as conducting power of all the ions present in 1 cm3 of an electrolytic solution.

1 1
Units :    ohm1cm1
 ohm  cm
S.I. units : Conductivity : Sm–1.

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Cell Constant
For a particular cell, l/a is constant and this constant is called Cell constant,
l = distance between two electrodes
a = area of cross section of the electrodes
 Specific conductivity () = Conductance × Cell constant

EQUIVALENT CONDUCTIVITY
Equivalent conductivity (eq) of an electrolyte in solution is defined as the conductance of a solution containing
one gram equivalent of an electrolyte. If V ml is the volume of a solution containing 1 gm equivalent of an
electrolyte and  is its conductivity in S cm–1, then equivalent conductance (eq) of the electrolyte is given by

  1000
eq =  × V or  eq  Scm2 equiv.1
Normality
The SI unit of equivalent conductivity is S m2 equiv–1.

MOLAR CONDUCTIVITY
It is defined as, "the conducting power of all the ions produced by dissolving one gram mole of an electrolyte
in solution". It is expressed as m and is defined as
 1000
m 
M
where M is the concentration in moles per litre.
Units : Molar conductance has unit ohm–1 cm2 mol–1 or S cm2 mol–1.
z Affecting parameters of molar conductivity
1. Nature of electrolyte
2. Concentration of the solution
3. Temperature
z Relation of m and eq
m = eq × n-factor

Example 1 : The conductivity of 0.25 M solution of KCl at 300 K is 0.0275 S cm–1. Calculate molar
conductivity.

Conductivity  1000
Solution : Molar conductivity 
Molarity

0.0275  1000
m   110 S cm2 mol1
0.25

Example 2 : The resistance of conductivity cell containing 0.001 M KCl solution at 298 K is 1500 ohm. What
is the cell constant if the conductivity of 0.001 M KCl solution at 298 K is
0.146 × 10–3 S cm–1?

Solution : Cell constant = Conductivity × Resistance

= 0.146 × 10–3 × 1500

= 0.219 cm–1

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VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION

The values of both conductivity and molar conductivity of an electrolyte in solution change with the concentration
of the electrolyte. Conductivity of all electrolytes always decreases with decrease in concentration because
it is the conductance of all the ions present in unit volume and the number of ions per unit volume decreases
with the decrease in concentration.

Molar conductivity of an electrolyte not only depends on the nature of electrolyte but also on its concentration.
Depending upon the values of molar conductivity, the electrolytes can be divided into two groups, namely
(i) strong electrolytes and (ii) weak electrolytes. For the same concentration, the molar conductivity of a strong
electrolyte is higher than that of weak electrolyte because a strong electrolyte is completely ionised at all
concentrations and a weak electrolyte is partially ionised in the high concentration region. As concentration
of an electrolyte decreases the molar conductivity of a strong electrolyte marginally increases whereas it
increases appreciably in case of a weak electrolyte. The former is due to increase in interionic distance on
dilution which reduces the influence of cation on anion and vice versa whereas the latter is due to increase
in the extent of ionisation of weak electrolytes on dilution. The plot of a graph between molar conductivity
(m) vs conc. for a strong electrolyte and a weak electrolyte is shown in the figure.

Strong electrolyte
m m
Weak electrolyte

conc. conc.

Molar conductivity of a strong electrolyte varies linearly with concentration . It can be extrapolated when
concentration approaches zero. The molar conductivity at infinite dilution is known as limiting molar conductivity
o 
and is represented by m or m . It can be experimentally determined for strong electrolytes only because
m slowly increases linearly with dilution and can be represented as

o
m  m A C

o
The intercept of the plot along Y-axis is m and slope equal to (–A). The magnitude of slope for a given solvent
and temperature depends on the charges on cations and anions produced on dissociation of the electrolyte
in the solution. Thus, all electrolytes having same type of charges have same value for A.
Explanation for the Variation of Molar Conductivity with Concentration
Conductance Behaviour of Weak Electrolytes
z The variation of  with dilution can be explained on the basis of number of ions in solution.
z The number of ions furnished by the electrolyte in solution depends upon the degree of dissociation with
dilution.
z With the increase in dilution, the degree of dissociation increases and as a result molar conductance
increases.
z The limiting value of molar conductance (m ) corresponds to degree of dissociation equal to 1 i.e., the
whole of the electrolyte dissociates.

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z Thus, the degree of dissociation can be calculated at any concentration as :
C
m
 
m
C
where  is the degree of dissociation, Λm , is the molar conductance at concentration C and m is the
molar conductance at infinite dilution.
Conductance Behaviour of Strong Electrolytes
z For strong electrolytes, there is no increase in the number of ions with dilution because strong electrolytes
are completely ionised in solution at all concentrations (by definition).
z If in concentrated solutions of strong electrolytes there are strong forces of attraction between the ions
of opposite charges called inter-ionic forces. Due to these interionic forces the conducting ability of the
ions is less in concentrated solutions.
z With dilution, the ions become far apart from one another and interionic forces decreases.

KOHLRAUSCH LAW OF INDEPENDENT MIGRATION OF IONS

z This law states that at infinite dilution when the dissociation is complete, each ion makes a definite
contribution towards molar conductance of the electrolyte irrespective of the nature of the other ion with
which it is associated.
z If molar conductivity of the cation is denoted by + and that of anion by – , then the law of independent
migration of ions is :

m  v     v –  –

where v+ and v– are the number of cations and anions per formula units of electrolyte (e.g., v+ = v– =1 for
HCl, v+ = 1 and v– = 2 for MgCl2).  and  are also called molar ionic conductances at infinite dilution.
z For example,
For NaCl m (NaCl) =  (Na+) + (Cl–)
For KNO3 m (KNO3) =  (K+) + (NO3–)
For MgCl2 m (MgCl2) =  (Mg2+) + (Cl–)
For Al2(SO4)3 m (Al2(SO4)3) =  (Al3+) + (SO42–)

o o
Example 3 : Calculate m for NH4OH given that values of m for Ba(OH)2, BaCl2 and NH4Cl as 523.28,
280.0 and 129.8 S cm2 mol–1 respectively.

Solution : o
m o
(NH4OH)  m (NH4 )  m
o
(OH )

Now,

1 o 1 o
o
m o
(NH4 OH)   m (NH4 )   m
o
(OH )   m (Ba2 )   m (Ba2 )   m
o
(Cl )   m
o
(Cl )
2 2

o 1 o 1 o
 m (NH4Cl)  m (Ba(OH)2 )  m (BaCl2 )
2 2

1
 129.8  (523.28  280.0)  251.44 Scm2 mol1
2

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Example 4 : The resistance of 0.01 M CH3COOH solution is found to be 2220 ohm when measured in a
o
cell of cell constant 0.366 cm –1 . Given that m (H ) and m
o
(CH3COO ) as 349.1 and
2 –1
40.9 S cm mol . Calculate
(a) Conductivity (b) Molar conductivity
(c) Degree of dissociation (d) Dissociation constant
Solution : o
m o
(CH 3COOH)  m (H )  m
o
(CH3COO )
= 349.1 + 40.9 = 390.0 S cm2 mol–1

Cell constant 0.366

(a) Conductivity    1.648  10 4 S cm1
Resistance 2220
Conductivity  1000 1.648  10 4  1000
(b) m    16.48 S cm2 mol1
Molarity 0.01
m 16.48
(c)  o
  0.0422
m 390

C 2
(d) Ka   C 2  0.01(0.0422)2  1.78  10 5
1 

Electrolytic Cells & Galvanic Cells

The chemical changes which involve the flow of the electric current are called electrochemical changes. These
are broadly of two types
(1) The changes in which electrical energy causes chemical reaction to occur. This phenomenon is called
electrolysis and the devices or cells used to carry out electrolysis is called electrolytic cell. These
reactions are non-spontaneous and are forced to occur by the passage of electricity.
(2) The change in which electrical energy is produced as a result of chemical change. The devices used to
produce electrical energy (or electric current) from chemical reactions are called galvanic cells (e.g. cells
or batteries). These reactions are spontaneous and the system can do work (e.g. it can run a motor).
Electrolytic Cells
(D.C.)
–
e
–
e

Anode Cathode

(1) The instrument used to bring about electrolysis is called electrolytic cell.
(2) In such a cell electrolyte is in the form of an aqueous solution or in the molten state is taken.
(3) Two metal rods are dipped into it and are connected to a source of electricity. These rods are called
electrodes; the anode is the electrode at which oxidation takes place, in electrolytic cell it is
positively charged. While the electrode at which reduction takes place is known as cathode and
in electrolytic cell it is negatively charged.

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ELECTROLYSIS
It is a process in which an electrolyte is broken down into simple substance by passing electric current through
it in molten state or in aqueous solution.

Product of Electrolysis
Ions having lower discharge potentials are discharged in preference to those having high discharge potentials.
(i) Electrolysis of molten lead bromide
PbBr2 +2
Pb + 2Br
At cathode
Pb+2(l) + 2e–  Pb(l)
At anode
Br–  Br + e–
Br + Br  Br2(g)
(ii) Electrolysis of an aqueous solution of sodium chloride
NaCl and H2O ionize as under
NaCl(aq)  Na+(aq) + Cl–(aq)


  
 H (aq)  OH (aq)
H2O(l) 

At cathode
Discharge potential of H ions is lower than that of Na ions. Therefore, H ions are discharged in
preference to Na ions.
H+ + e–  H (Primary change)
H + H  H2(g) (Secondary change)
H2 gas is evolved at the cathode while Na ions remain in the solution.
At anode
Discharge potential of Cl– ion is lower than that of OH ions, therefore, Cl ions are discharged in
preference to OH ions.
Cl–  Cl + e– (Primary change)
Cl + Cl  Cl2(g) (Secondary change)
Cl2 gas is evolved at the anode while OH ions remain in the solution.

QUANTITATIVE ASPECTS OF ELECTROLYSIS AND FARADAY'S LAWS

Faraday's First Law of Electrolysis
Amount of a substance deposited or liberated at any electrode is directly proportional to the charge passed.
W(g)  Q where, Q is amount of charge flowing in the circuit
W = Z  Q or W = Z  i  t, i = current, t = time
Z = electrochemical equivalent of the substance deposited
Eq. wt. of the substance

96500

Faraday's Second Law of Electrolysis

When the same quantity of electricity is passed through solutions of different electrolytes connected in se-
ries, the weights of the substances produced at the electrodes are directly proportional to their equivalent
weights.

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Example : For AgNO3 solution and CuSO4 solution connected in series if the same quantity of electricity is
passed.

WAg Eq. wt. of Ag


WCu Eq. wt. of Cu

Note : (i) 1F = 1eq

= 96500 coulombs
= 6.02 × 1023 electrons

volume of gas given at STP

(ii) Eq. of gas =
volume of 1eq. of gas at STP
(iii) q = nF
n is number of electrons transferred

Example 5 : How much copper is deposited on the cathode if a current of 3A is passed through aqueous CuSO4
solution for 15 minutes ?
Solution : Quantity of electricity passed = Current in amperes × time in seconds
Q = 3 × 15 × 60 = 2700 C
Cu2+ + 2e–  Cu
Two mole electrons or 2F charge can deposit 1 mole copper i.e., 63.5 g and so 2700 C will deposit

2700  63.5
 0.889 g
2  96500

Example 6 : How much time would be needed to deposit 0.25g of metallic nickel (Atomic mass = 58.5) on a
metal object using a current of 1A during electroplating?
Solution : Ni2+ + 2e–  Ni
2F or 2 × 96500 C of electricity is required to deposit 58.5 g of Ni.
58.5g of Ni requires 2 × 96500 C
2  96500  0.25
0.25g of Ni requires = = 824.8 C
58.5
Amount of electricity = Current in amperes × time in seconds
Amount of electricity
Time in seconds =
Current in amperes
824.8
= = 824.8 sec = 13.74 minutes
1

Example 7 : Exactly 0.2 mole electrons passed through two electrolytic cells in series containing CuSO4 and
ZnSO4 respectively. How many grams of each metal will be deposited on the respective cathodes
in the two cells?
63.5
Solution : Gram equivalent mass of copper =  31.75g
2
65.0
Gram equivalent mass of zinc=  32.50g
2

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Now 1.0 mole of electrons deposit copper = 31.75 g
31.75  0.2
0.2 mole of electrons deposit copper = = 6.35 g
1.0
Similarly, 1.0 mole of electrons deposit zinc = 32.50 g
32.5  0.2
0.2 mole of electrons deposit zinc = = 6.50 g
1.0

EXERCISE

1. Electrolysis of dil. H2SO4 liberates gases at anode and cathode respectively

(1) O2, SO2 (2) SO2, O2
(3) O2, H2 (4) H2, SO2
2. When aqueous solution of KCl is electrolysed, resultant solution has
(1) pH > 7 (2) pH < 7
(3) pH = 7 (4) Initially less than 7 then increases
3. Ionic conductance of H+ and SO42 – are x and yS cm2 mol–1. Hence, equivalent conductivity of H2SO4 is
y y
(1) 2x + (2) x +
2 2
x x y
(3) +y (4) 
2 2 2
4. Specific conductivity of 0.01 N H2SO4 solution is 6 × 10–3 S cm–1. Its molar conductivity is
(1) 1200 S cm2 mol–1 (2) 600 S cm2 mol–1
(3) 60 S cm2 mol–1 (4) 2400 S cm2 mol–1
5. Which relation is correct?
(1) Molar conductance = conductivity × concentration
Conductivity
(2) Equivalent conductance =
Volume
Conductivity
(3) Cell constant =
Conductance
(4) Conductance = specific conductivity × cell constant
6. From the following molar conductivities at infinite dilution,
o
m for Al2(SO4)3 = 858 S cm2 mol–1
o
m for NH4OH = 238.3 S cm2 mol–1
o
m for (NH4)2SO4 = 238.4 S cm2 mol–1
o
Calculate m for Al(OH)3
(1) 715.2 S cm2 mol–1 (2) 1575.6 S cm2 mol–1
(3) 786.3 S cm2 mol–1 (4) 157.56 S cm2 mol–1

7. Four faradays of electricity were passed through AgNO3 () , CdSO4 ( ) , AlCl3 () and PbCl4 ( ) kept in four
vessels using inert electrodes. The ratio of moles of Ag, Cd, Al and Pb deposited will be
(1) 12 : 4 : 6 : 3 (2) 1 : 2 : 3 : 4
(3) 12 : 6 : 4 : 3 (4) 4 : 3 : 2 : 1

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Galvanic cells : “A device employed to convert the chemical energy of a redox reaction into electrical energy” is
called an electrochemical cell or simple chemical cell. The most common example is that of Daniel cell. It consist
of two beakers one containing solution of ZnSO4 (say 0.1 M) and Zinc plate is dipped in it. The other beaker
contains CuSO4 solution (say 0.1 M) and a copper plate is dipped in it. The two solutions are connected by a salt
bridge containing concentrated solution of an inert electrolyte like KCl, KNO3 etc.On connecting the two electrodes
by a wire, the redox reaction takes place and the electron flow from Zn to the Cu. This flow of electrons constitute
electric current. The electrode (Zn) at which oxidation takes place i.e., electrons are lost, is called anode and the
electrode (Cu) at which reduction takes place i.e., electrons are gained, is known as cathode.

V
–
e flow
current
Zinc Salt bridge
electrode Copper
electrode

ZnSO4 CuSO4
solution solution
Half-cell Half-cell
DANIEL CELL

The net reaction is the sum of two half-cell reactions.

At anode : Zn(s)  Zn2 (aq)  2e

At cathode : Cu2 (aq)  2e  Cu(s)
Net reaction : Zn(s)  Cu2  Zn2 (aq)  Cu(s)

Schematic Representation : Zn | Zn+2 || Cu+2 | Cu

ELECTRODE POTENTIAL AND EMF OF A CELL

z When an electrode is kept in contact with a solution of its ions, the metal tends to lose electrons and
thus passes into the solution in the form of metal ions or the metal ions tend to gain electron from metal
electrode and deposit on electrode.
M  Mn+(aq) + ne– or Mn+(aq) + ne–  M
z Thus, an electrical potential difference is set up between metal and its solution. This is known as half
cell electrode potential.
z If the electrons are released during the process, this is called oxidation potential and if the electrons
are accepted, this is called reduction potential.
z Separately, these are known as single electrode potentials.
z The electrode potential is a measure of tendency of an electrode in a half cell to lose or gain electrons.
z According to the present convention the half reactions are always written as reduction half reactions
and their potentials are represented as reduction potentials.
Electromotive Force or Cell Potential :
z The difference between the electrode potentials of two electrodes constituting an electrochemical cell is
called electromotive force (EMF) or cell potential of a cell.
z It is expressed as:

Standard reduction  Standard reduction 

E°cell =   —  
potential of cathode  potential of anode 
or E°cell = E° (cathode) – E° (anode)

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Standard Electrode Potential
z The absolute value of the electrode potential cannot be determined experimentally because neither the
oxidation nor the reduction reaction can occur by itself.
z The electrode potentials are always determined with respect to a standard hydrogen electrode.
Standard Hydrogen Electrode :
z It consists of platinum wire sealed in a glass tube and has a platinum foil attached to it. The foil is coated
with finely divided platinum and acts as platinum electrode. It is dipped into an acid solution containing
H+ ions in 1 M concentration (1 M HCl). Pure hydrogen gas at 1 bar pressure is constantly bubbled into
the solution at constant temperature of 298 K. The following reaction occurs in this half cell depending
upon whether it acts as an anode or as a cathode.
If S.H.E. acts as anode
H2 (g) 2H+ + 2e–
If S.H.E. acts as cathode
2H+ + 2e– H2 (g)
z The standard hydrogen electrode is also regarded as reversible electrode.
H2 (g) 2H+ + 2e—
z The electrode potential of an electrode can be determined by connecting that with a standard hydrogen
electrode. The electrode potential of the standard hydrogen electrode is taken as zero. The electrode
potential of a metal electrode as determined with respect to a standard or normal hydrogen electrode is
called standard electrode potential (E°).
Voltmeter
– –
e e

0.34 V

Copper + Salt bridge

+ – –
(cathode) Na NO3
H2(g) (1 atm)

+
– H
NO 3 Standard hydrogen
2+
(1 M)
Cu – electrode (anode)
NO 3
(1 M)
–
NO 3
2+ – + –
Cu (aq) + 2e  Cu(s) H 2(g)  2H (aq) + 2e
Electrochemical Series
Table in which the reduction potentials of various electrodes have been arranged in the increasing order is called
electrochemical series or activity series or electromotive series.
Electrode Electrode reaction E°(volts)

Li+/Li Li+ + e– = Li –3.045 (Lowest)

Zn2+/Zn Zn2+ + 2e– = Zn –0.763

H+/H2, Pt 2H+ + 2e– = H2 0.0 Standard

Cu2+/Cu Cu2+ + 2e– = Cu +0.334

– –
F2/F , Pt F2 + 2e– = 2F +2.887 (Highest)

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Applications of Electrochemical Series

The important applications of electrochemical series are:
z Relative strength of oxidising and reducing agents. In the series, the metals are arranged in the
increasing order of reduction potentials or decreasing order of oxidation potentials. Therefore, the elements
at the top are good reducing agents while those at the bottom are good oxidising agents.
z Calculating e.m.f. of the cell : The e.m.f. of the cell can be determined by knowing the standard electrode
potentials from the series as:
E°cell = E° (right) – E° (left) (If standard reduction potential are given)
z Predicting feasibility of a redox reaction. In general, a redox reaction is feasible only if the species
which has higher reduction potential is reduced i.e., accepts the electrons and the species which has lower
reduction potential is oxidised i.e., loses the electrons. Otherwise, a redox reaction is not feasible. In other
words, the species to release electrons must have lesser reduction potential as compared to the species
which is to accept electrons.
z To predict whether a metal can liberate hydrogen from acid or not. The metals which have negative reduction
potentials can only liberate hydrogen from the acids.
z Metals which have low S.R.P. value have greater rate of corrosion.
z Cations having higher S.R.P. value will discharge first at cathode and anions having low S.R.P. value
discharge first at onode
(i) K+ < Ca2+ < Na+ < Mg2+ < Al3+ < Zn2+ < Fe2+ < H+ < Cu2+ < Ag+ < Au3+ (order of discharging at cathode)

(ii) SO24  OH  Cl  Br   I (order of discharging at anode).

Example 8 : Write each half cell reaction as well as redox reaction for the following electrochemical cell
 2
A( s ) | A(31M ) || B( 1M ) | B( s )
Solution : Oxidation half cell reaction: A(s)   A3+ + 3e–] × 2
Reduction half cell reaction: B2+ + 2e–   B(s) ] × 3
___________________________________________________
Net redox reaction: 2A(s) + 3B2+   2A3+ + 3B(s)

Example 9 : Write the cell reaction that occurs when the following half cells are combined
I2 + 2e–   2I– ; E° = + 0.54 V
Br2 + 2e – 
 2Br– ; E° = + 1.08 V
Solution : The half cell reaction with lesser value of E° takes place at the anode while the other takes place
at cathode. Thus,
At anode: 2I–   I2 + 2e–
At cathode: Br2 + 2e–   2Br–
___________________________________
Cell reaction: 2I– + Br2   I2 + 2Br
–

EMFCell = E°c – E°a

= 1.08 – 0.54 = 0.54 V

NERNST EQUATION
It is used when concentration of ions in which electrode is dipped is not equal to 1M.
Mn+ + ne–  M.
2.303 RT 1
EMn /M  EMn /M  log n
nF [M ]

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NEET Electrochemistry 79
R = 8.314 JK–1 mol–1, F = 96500C, T = 298 K. 'n' is no. of electrons involved in balanced half cell reactions.
After substituting these values we get :

0.05916 1
EMn /M = EMn /M – log
n [Mn ]
For Example :
Cl2 + 2e–  2Cl–

0.0591 [Cl– ]2
ECl – = ECl2 /Cl– – log [p ] where p Cl 2 is partial pressure of Cl2 (g), [Cl–] is molar conc. of
2 /Cl
2 Cl2
Cl–.
In general
2.303RT
Ecell = E°cell – log Q (Q is the reaction quotient)
nF

Example 10 : Calculate the emf of the cell in which the following reaction takes place
Ni(s) + 2Ag+(0.002M)  2+
 Ni (0.160M) + 2Ag(s)
Given: E°cell = 1.05 V
Solution : At anode: Ni(s)   Ni2+ + 2e–
At cathode: 2Ag+ + 2e–   2Ag
____________________________________________
The net reactions: Ni(s) + 2Ag+  2+
 Ni + 2Ag(s)
 0.0591 [Anode]
Ecell  Ecell  log
n [Cathode]

0.0591 [Ni2  ]
Ecell  1.05  log
2 [Ag ]2
0.0591 0.16
 1.05  log
2 (0.002)2 = 0.914 V

Example 11 : Calcualte the electrode potential of given electrode

Pt, Cl2(1.5 bar) | 2Cl–(0.01M) ; EClº / 2Cl 

 1.36 V
2

Solution : The reaction of electrode is

Cl2 (g) 2e   2Cl 

1.5 bar 0.01M

0.0591 [Cl ]2 0.0591 (0.01)2

E = E  log  1.36  log = 1.483 V
n PCl 2 1.5
2

Equilibrium Constant and emf

At equilibrium E(Cell) = 0, so
2.303 RT
E°(Cell) = log KC
nF
At 298 K it may be written as
0.0591
E°(Cell) = log KC
n

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80 Electrochemistry NEET

Example 12 : Calculate the equilibrium constant for the cell reaction

4Br – + O2 + 4H+ 
 2Br2 + 2H2O ; E°cell = 0.16 V

n Ecell
Solution : log K c 
0.0591

E°cell = 0.16 V, n=4

4  0.16
log K c   10.8
0.0591

Kc = antilog 10.8 = 6.31 × 1010

Concentration Cell
When same metal electrodes are dipped in same electrolyte having different conc. in two half cells, such a

cell is called concentration cell. For concentration cell, Eocell = 0 but Ecell  0.

2.303RT C
Ecell = – log 1 , C1 is concentrations of electrolyte in which anode is dipped, C2 is concentrations
nF C2

of electrolyte in which cathode is dipped. Reaction is spontaneous, when Ecell > 0 i.e., C2 > C1.

Electrochemical Cell and Free Energy

–G = WElec

= nFEcell

G = –nFEcell

G° = 0 only when equilibrium constant (K) = 1

∵ G° = –2.303 RT log K

Example 13 : Find out work done for the given cell

Cr Cr+3 Fe+2 Fe
o o
ECr/Cr = 0.74 V ; EFe
3+ 2+
/Fe
= –0.44 V

Solution :  
E cell 
E Cathode  
E Anode
(Reduction potential) (Reduction potential)

= –0.44V + 0.74V = 0.30 V Since cell reaction 

 2 3 
W = nFE° 2Cr  3Fe  2Cr  3Fe 
n  6 mol electron 
= 6 × 96500 × 0.30  
 W = 173700 J

 W = 173.7 kJ

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NEET Electrochemistry 81

Example 14 : Calculate G° for the given reaction occuring in fuel cell

(i) O2 + 4H+ + 4e–  2H2O ; E° = 1.229 volt

(ii) 2H2  4H+ + 4e– ; E° = 0 volt

Solution : E°Cell = E°cathode – E°Anode

= 1.229 – 0.0

= 1.229 V

G° = –nFE°

= – 4 × 96500 × 1.229

= 474.4 kJ

EXERCISE
8. Half cell reactions for some electrodes are given below :

I. A + e–  A– ; E° = 0.96 V

II. B– + e–  B2– ; E° = – 0.12 V

III. C+ + e–  C ; E° = + 0.18 V

IV. D2+ + 2e–  D ; E° = – 1.12 V

Largest potential will be generated in which cell?
(1) A– | A || B– | B2– (2) D | D2+ || A | A–
(3) B2– | B– || C+ | C (4) D | D2+ || C+ | C
9. Select correct statement.
(1) If salt bridge is removed, potential falls to zero
(2) KCl cannot be used as electrolyte in salt bridge in case of silver electrode
(3) Cell reaction is spontaneous if emf is positive
(4) All of these



10. The measured potential for Mg2+ + 2e– 
 Mg (s) does not depend upon
(1) Raising the temperature
(2) Increasing the concentration of Mg2+ ion
(3) Making the magnesium plate bigger
(4) Decreasing the concentration of Mg2+ ion
11. Which of the following metal do not evolve H2 gas from dil. acid?


(1) A EoA  / A  0.25 V  
o
(2) B EB/B    0.22 V 

(3) C EoC /C   0.30 V  
o
(4) D ED/D    0.44 V 
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82 Electrochemistry NEET

12. The standard electrode potentials EIo /I , EBr

o

/Br
o
and EFe/Fe 2  are respectively + 0.54 V, – 1.09 V and 0.44 V. On
2 2
the basis of above data which of the following process is nonspontaneous?

(1) Br2 + 2I–  2Br– + I2 (2) Fe + Br2  Fe2+ + 2Br–

(3) Fe + I2  Fe2+ + 2I– (4) I2 + 2Br–  2I– + Br2

13. Pb+2 + 2e–  Pb(s), E° = – 0.13 V

Sn+2 + 2e–  Sn(s), E° = – 0.16 V
Ni+2 + 2e–  Ni(s), E° = – 0.25 V
Cr+3 + 3e–  Cr(s), E° = – 0.74 V
Based on the above data, the reducing power of Pb, Sn, Ni and Cr is in the order
(1) Pb > Sn > Ni > Cr (2) Cr > Ni > Sn > Pb
(3) Cr > Sn > Ni > Pb (4) Sn > Ni > Cr > Pb
14. Consider the following equations for a cell reaction:
A + B  C + D ; E° = x volt, G = G1
2A + 2B  2C + 2D ; E° = y volt, G = G2
Then,
(1) x = y, G1 = G2 (2) x > y, G1 > G2
(3) x = y, G2 = 2G1 (4) x < y, 2G2 = G1
2 2
15. Zn | Zn(C1)
|| Zn(C 2)
| Zn (s) . The G is –ve if

(1) C1 = C2 (2) C1 > C2

(3) C2 > C1 (4) C1 > 2C2

16. Calculate the half cell potential at 298 K for the reaction, Zn +2 + 2e –  Zn if [Zn +2 ] = 2 M,
EoZn2 /Zn = – 0.76 V
(1) – 0.90 V (2) – 0.75 V
(3) – 0.85 V (4) – 0.65 V
17. Calculate G° for the galvanic cell:
2Cr (s) + 3Cd+2 (aq)  2Cr+3 (aq) + 3Cd (s)

EoCr 3 /Cr = – 0.74 V, EoCd2 /Cd = – 0.40 V

(1) – 196.86 kJ/mol (2) – 98.43 kJ/mol
(3) – 65.62 kJ/mol (4) – 164.05 kJ/mol
18. If the standard electrode potential of Cu2+/Cu electrode is 0.34 V, what is the electrode potential of 0.1 M
concentration of Cu2+?
(1) 3.99 V (2) 0.3105 V
(3) 0.222 V (4) 0.176 V
19. For a spontaneous reaction, G, equilibrium constant K and Eºcell will be respectively
(1) –ve, > 1, +ve (2) +ve, > 1, –ve
(3) –ve, < 1, –ve (4) –ve, > 1, –ve

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NEET Electrochemistry 83
COMMERCIAL CELLS
(i) Primary Cells are those in which the redox reaction occurs only once and the cell becomes dead after
sometime e.g., dry cell, mercury cell.
(ii) Secondary Cells are those which can be recharged by passing an electric current through them and
hence can be used over and again e.g., lead storage.
(iii) Fuel Cells are those in which the energy produced from the combustion of fuels like H2, CO, CH4 etc.
is converted into electric current.
z Dry Cell : Anode : Zinc, cathode: a graphite rod, electrolyte in contact of Zn is a paste of NH4Cl and
ZnCl2. While electrolyte in contact with graphite rod is powdered MnO2 and carbon. Anode reaction Zn
 Zn++ + 2e–

Insulator

Graphite rod
(cathode)
MnO2 and carbon
black paste
NH4Cl and ZnCl2
paste (electrolyte)
Zinc metal can
(anode)

A commercial dry cell

Cathode reaction :
2MnO2 + 2NH4+ + 2e–  Mn2O3 + 2NH3 + H2O
Zn2+ + 2Cl– + 4NH3  [Zn(NH3)4]Cl2 complex.
It does not give a constant voltage. Voltage is continuously dropped as concentration of electrolyte is
decreased
z Mercury Cells: Zn as anode while carbon rod as cathode, Moist HgO mixed with KOH as electrolyte is
filled between two electrodes.
Anode reaction: Zn + 2OH–  ZnO + H2O + 2e–
Cathode reaction: HgO + H2O + 2e–  Hg + 2OH–. It gives constant potential of 1.35 V used in hearing
aids, watches etc.
z Lead Storage Battery: Anode: Lead plates, cathode: grid of lead packed with PbO2. Electrolyte: dil
H2SO4 (30% by mass, sp. gravity 1.30).
The reaction occuring during discharging.
Cathode reaction :
PbO2 + 4H+ + 2e–  Pb2+ + 2H2O (Reduction)
Pb 2+
+ SO4 2-
 PbSO4 (Precipitation)
+
Net cathode reaction = PbO2 + 4H + 2e + SO4 – 2–
 PbSO4 + 2H2O
Anodic reaction :
Pb  Pb2+ + 2e– (Oxidation)
Pb 2+
+ SO4 2–
 PbSO4 (Precipitation)
Net anodic reaction = Pb + SO4 2–
 PbSO4 + 2e –

Total cell reaction = PbO2 + Pb + 4H+ + 2SO42–  2PbSO4 + 2H2O

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84 Electrochemistry NEET

Sulphuric acid is consumed during discharging and when the conc. of H2SO4 falls to 1.20 g ml–1, it requires
recharging. In recharging current is passed from outside source to reverse the reactions of anode and
cathode till the conc. of H2SO4 again rises to 1.30 g cm–3.

H2SO4
(electrolyte)

Lead grid packed with Lead grid packed

spongy lead (anode) with PbO2 (cathode)
The lead storage battery
z Fuel Cells : Hydrogen oxygen fuel cell is one of the important fuel cells. It consists of porous carbon
electrodes containing suitable catalysts. Conc. KOH or NaOH is placed between the electrodes to act
as electrolyte. H2 and O2 gases are bubbled through the porous electrodes into KOH solution, operational
temp. 70º – 140ºC.
At anode : H2  2H, 2H + 2OH–  2H2O + 2e–
At cathode : 2H2O + 4e– + O2  4 OH–
Net cell reaction : 2H2 + O2 2H2O + energy
Its cell potential is 0.9 V. Do not cause any pollution, used in space crafts.
Anode Cathode
– +

H2 O2

Porous carbon
electrodes containing
metallic catalysts

H 2O H2O

Hot aqueous KOH

Fuel Cell

CORROSION
Process of slowly eating away of the metal due to attack of atmospheric gases, on the surface of the metal
resulting into the formation of oxides, sulphides, carbonates. Corrosion of iron is called rusting. Rust is
hydrated ferric oxide Fe2O3 . x H2O.
z Mechanism of Rusting: Electrochemical theory

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NEET Electrochemistry 85
(i) Iron in contact with the dissolved CO2 and oxygen undergoes oxidation

Fe  Fe++ + 2e– (Anode reaction);

(ii) Electrons lost by iron are taken up by the H+ ions produced on the surface of metal.

H+ + e–  H, 4H + O2  2H2O

O2 + 4H+ + 4e–  2H2O.

The dissolved oxygen may take up electron directly to form OH– ions.

O2 + 2H2O + 4e–  4OH–

(cathode)

overall reaction:

2Fe + O2 + 4H+  2Fe2+ + 2H2O, Eº = +1.67 V.

(iii) 4Fe2+ + O2 + 4H2O  2Fe2O3 + 8H+

Fe2O3 + x H2O  Fe2O3  x H2O

Air Water droplet

O2
Rust (Fe2O3  xH2O)
O2 Fe3+
O2
2+
Fe
Anode region Cathode region
Fe  Fe + 2e
2+ –
e
–
O2 + 4H+ + 4e–  2H2O

Iron metal

Corrosion of iron in atmosphere

z Factors which Promote Corrosion : Reactivity of metal, presence of impurity, presence of air and
moisture; strains in metals; presence of electrolyte.

z Prevention of Corrosion:

(i) Barrier protection: by using paints, thin film of oil, grease etc.

(ii) Sacrificial Protection covering the surface of iron with a layer of metal which is more active than
iron thus prevents the iron from losing electrons.

Galvanisation: Covering iron with more active metal like zinc. The layer of Zn on the iron surface
when comes in contact with moisture, oxygen and CO2 in air, protective invisible thin layer of basic
zinc carbonate ZnCO3. Zn(OH)2 is formed due to which the galvanised iron sheets lose their lusture
and tends to protect it from further corrosion. Iron can be coated with Cu or by Sn. Now if the coating
is broken, iron is exposed and being more reactive than Cu and Sn corrodes more rapidly.

(iii) Electrical Protection (Cathodic protection): More electropositive metals like Zn, Mg or Al may be
connected with the iron pipes burried in the moist soil, canals, storage tanks etc.

(iv) Using Anti Rust Solutions: These are alkaline phosphate and alkaline chromate solutions. The
alkaline nature of solutions prevents availability of H+ ions. On the surface of iron, a protective, insoluble
thin film of iron phosphate is formed. These are used in car radiators to prevent rusting.

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86 Electrochemistry NEET

EXERCISE
20. In the electrorefining of metals, impure metal is
(1) Cathode and oxidation takes place (2) Anode and oxidation takes place
(3) Anode and reduction takes place (4) Cathode and reduction takes place
21. Rusting on the surface of iron involves

(1) Fe (s)  Fe2+ (aq) + 2e– (at anodic site)

(2) O2 (g) + 4H+ (aq) + 4e–  2H2O (l) (at cathodic site)

(3) 4Fe2+ (aq) + O2 (g) + 4H2O (l)  2Fe2O3 (s) + 8H+
(4) All of these
22. When a lead storage battery is recharged
(1) Pb is formed (2) H2SO4 is formed
(3) H2SO4 is consumed (4) Both (1) & (2)
23. Which of the following reactions occurs at the cathode?
(1) 2OH–  H2O + O + 2e– (2) Zn  Zn2+ + 2e–
(3) Sn2+  Sn4+ + 2e– (4) Cu2+ + 2e–  Cu
24. Select the correct statement
(1) Cathode is negative terminal, both in galvanic and electrolytic cells
(2) Anode is negative terminal, both in galvanic and electrolytic cells
(3) Cathode is negative terminal in electrolytic cell and anode is negative terminal in galvanic cell
(4) Cathode and anode respectively are negative and positive terminal in galvanic and electrolytic cell
respectively

‰ ‰ ‰

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 nt
me nment
sigAnssig
Assignment
As

Assignment
7. Two different electrolytic cells are connected in
SECTION - A
series, containing aq.AgNO 3 and aq.CuSO 4
NCERT Based MCQs respectively. The mole ratio of copper to silver
1. In lead storage battery, cathode is made up of deposited at cathodes in the two cells will be
[NCERT Pg. 89] [NCERT Pg. 85]

(1) Pb grid packed with PbO2  2  1

(1)   (2)  
(2) Pd plates 1 2
(3) Platinum
 3  2
(4) Zinc plates (3)   (4)  
2 3
2. After operating the electrolytic cell for sometime, if
anode is removed then, what will happen? 8. When aqueous solution of KBr is electrolysed
[NCERT Pg. 85] using Pt electrodes, the resultant solution will have
(1) The cell will work as a capacitor [NCERT Pg. 87]

(2) Ions will start moving randomly (1) pH > 7 (2) pH < 7

(3) Current will continue to flow for sometime (3) pH = 7 (4) Any value of pH

(4) Cathode rod will start working as both anode 9. Function of salt bridge is/are
and cathode a. It completes the cell circuit
3. In a mercury cell, product at anode is b. It allows the movement of ions from one
[NCERT Pg. 88] solution to other without mixing of the two
(1) HgO(s) (2) Hg(l) solutions
(3) ZnO(s) (4) Zn(Hg) c. It maintains the electrical neutrality of the
4. How many Faraday’s of charge are required to solution in two half cells [NCERT Pg. 66]
reduce 1 mol of Cr2O72– to Cr+3? [NCERT Pg. 88] (1) a & b (2) a, b & c
(1) 6 F (2) 3 F (3) Only a (4) b & c
(3) 2 F (4) 1 F 10. The conductance of 0.01 N CH3COOH solution is
5. A solution of concentration CuSO4 is electrolysed 4.5  10–4 ohm–1 which is present in a tube having
for 965 s with a current of 20 A and 50% efficiency. length 6 cm and cross sectional area 36 cm2. The
The amount of Cu deposited at cathode will be molar conductivity of the solution is
[NCERT Pg. 86] [NCERT Pg. 81]
(1) 4.175 g (2) 3.175 g (1) 7.5 S cm2 mol–1 (2) 8.5 S cm2 mol–1
(3) 5.35 g (4) 6.35 g (3) 2.5 S cm2 mol–1 (4) 1.5 S cm2 mol–1
6. The decreasing order of standard electrode 11. If Zn2+/Zn electrode is diluted 1000 times, then the
potential is [NCERT Pg. 71] change in electrode potential is [NCERT Pg. 72]
(1) Li, Al, Zn, Ba (1) Increase of 29.5 mV
(2) Ba, Al, Zn, Li (2) Increase of 59 mV
(3) Zn, Al, Ba, Li (3) Decrease of 88.5 mV
(4) Zn, Ba, Al, Li (4) Increase of 88.5 mV

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88 Electrochemistry NEET

12. What will be the emf of the cell in which the 2. Equivalent conductance of a substance increases
following reaction takes place at 298 K? on dilution because of

Mn(s)  Cu 2+  aq   aq  Cu  s (1) Increase in number of ions per unit volume
 Mn2+
0.01 M 0.0001 M
(2) Increase in molecular attraction
(Given: Eocell  1.52 V ) [NCERT Pg. 73] (3) Increase in degree of association
(1) 1.58 V (4) Increase in degree of ionisation of the
substance
(2) 1.52 V
3. The specific conductivity of 0.5N solution is
(3) 0.059 V
0.01287 ohm–1 cm–1. What would be its equivalent
(4) 1.21 V conductance (in ohm–1 cm2 eq–1)?
13. The electrode potential of hydrogen electrode is (1) 257.4 (2) 2.574
when H 3 O + ion concentration is 10 –5 M
(3) 25.74 (4) 0.2574
(pH2 = 1 atm) [NCERT Pg. 68]
4. Deduced from the following E° values of half cells,
(1) – 0.059 V what combination of two half cells would result in
(2) – 0.295 V a cell with the largest potential?
(3) – 0.118 V (i) A3–  A2– + e–, E° = 1. 5 V
(4) – 0.59 V (ii) B2+ + e–  B+, E° = 2.1 V
14. Cell constant is maximum in case of (iii) C2+ + e–  C+, E° = +0.5 V
[NCERT Pg. 75] (iv) D D2+ + 2e–, E° = –1.5 V
(1) Wire of length 100 m and cross sectional area (1) (i) and (iii) (2) (i) and (ii)
100 m2
(3) (ii) and (iv) (4) (iii) and (iv)
(2) Wire of length 10 m and cross sectional area
5. The number of Faradays required to deposit 1g
10 m2
equivalent of aluminium (At.wt 27) from a solution
(3) One meter cube of a material of AlCl3 is
(4) Equal in all cases (1) 1 (2) 2
15. The molar conductivity of an infinitely diluted (3) 3 (4) 4
solution of NH4Cl is 150 S cm2 mol–1 and the ionic
6. The standard reduction potential of Pb and Zn
conductances of OH– and Cl– ions are 198 S cm2
electrodes are –0.126 and –0.763 volts
mol–1 and 76 S cm2 mol–1 respectively. The molar
respectively. The e.m.f. of the cell
conductivity (S cm2 mol–1) of the solution of NH4OH
at infinite dilution is [NCERT Pg. 83] Zn | Zn2+ (0.1 M) || Pb2+ (1 M) | Pb is

(1) 272 (2) 424 (1) 0.637 V (2) 0.607 V

(3) 124 (4) 226 (3) 0.667 V (4) 0.889 V

7. When dil HNO3 is electrolysed

SECTION - B (1) H2(g) is formed at anode

(2) O2 gas is formed at anode
Objective Type Questions
(3) NO2 is formed at cathode
1. Which of the following is not correct?
(4) N2 is formed at anode
(1) Molar conductance of a solution increases with
8. Three faraday of electricity is passed through three
dilution
electrolytic cells connected in series containing
(2) Equivalent conductance increases with dilution Ag+, Ca2+ and Al+3 ions respectively. The molar
(3) Specific conductance increases with dilution ratio in which the three metal ions are liberated at
the electrodes is
(4) At infinite dilution each ion (cation or anion)
(1) 1 : 2 : 3 (2) 3 : 2 : 1
plays a definite role towards electrical
conductance (3) 6 : 3 : 2 (4) 3 : 4 : 2

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NEET Electrochemistry 89
9. The quantity of electricity required to reduce 12.3 15. Electrochemical equivalent of Cu in the reaction
g of nitro benzene to aniline assuming 50% Cu2+(aq) + 2e– Cu is
current effeciency is
(1) 115800 C (2) 57900 C 63.5 63.5
(1) (2)
(3) 231600 C (4) 28950 C 96.5 96500  2

10. The EMF of a chemical cell is positive when free 63.5  2 96500
energy change of reaction (3) (4)
96500 63.5  2
(1) > 0
16. For given cell; Zn |Zn+2 (C1) || Zn+2 (C2)| Zn; G is
(2) < 0 negative if
(3) = 0 (1) C1 = C2
(4) No relationship of free energy change and (2) C1 > C2
e.m.f.
(3) C2 > C1
11. A 0.1M solution of monobasic acid has specific
resistance of ‘r’ ohm-cm, its molar conductivity is (4) None of these

(1) 10/r (2) 10r 17. For given half cell; Al 3+ + 3e – Al ; on

increasing [Al+3], the reduction electrode potential
(3) 104/r (4) 104r
(1) Increases
12. Find out the Eºcell from the given data
(2) Decreases
(a) Zn | Zn+2 || Cu+2 | Cu ; Eºcell = 1.10 V
(3) No change
(b) Cu | Cu+2 || Ag+ | Ag ; Eºcell = 0.46 V
(4) First increases then decreases
(c) Zn | Zn+2 || Ag+ | Ag ; Eºcell = ?

(Given ECu2 /Cu  0.34V ) 18. If EºFe2 |Fe is x 1, EºFe3 |Fe is x 2; then Eº 3 2
Fe |Fe
will be
(1) – 0.04 V (2) + 0.04 V
(1) 3x2 – 2x1 (2) x2 – x1
(3) + 0.30 V (4) 1.56 V
(3) x2 + x1 (4) 2x1 + 3x2
13. Consider the following equations for a cell
19. What will be the molar conductance ‘’, (in S cm2
A+B C+D; E° = x volt , Keq = K1
mol–1)if resistivity is ‘x’ for 0.1 N H2SO4 solution?
2A + 2B 2C + 2D ; E° = y volt , Keq = K2
(1)   x  1000 (2)   2  1000
Then 0.1 x  0.1
(1) x = y, K1 = K2 (2) x =2y, K12 = K2 0.5
(3)   x  1000 (4) 
(3) x = y, K12 = K2 (4) x2 = y, K12 = K2 0.5 1000 x
14. For strong electrolytes the values of molar 20. E° values of Mg+2|Mg, Zn+2|Zn and Fe+2|Fe are
conductivities at infinite dilution are given below –2.37 V, –0.76 V and –0.44 V respectively. Which
of the following is correct ?
Electrolyte 0
m (Sm2 mol1 )
(1) Mg oxidises Fe (2) Zn oxidises Fe
BaCl2 280 × 10–4
(3) Zn reduces Mg+2 (4) Zn reduces Fe+2
NaCl 126.5 × 10–4
21. The standard reduction potential value of three
NaOH 248 × 10–4 metallic cations X, Y and Z are 0.52, –3.303 and
The molar conductance at infinite dilution for –1.18 V respectively. The order of reducing power
Ba(OH)2 is of the corresponding metals is
(1) 523 × 10–4 Sm2 mol–1 (1) Y > Z > X
(2) 52.3 × 10–4 Sm2 mol–1 (2) X > Y > Z
(3) 5.23 × 10–4 Sm2 mol–1 (3) Z > Y > X
(4) 523 × 10–2 Sm2 mol–1 (4) Z > X > Y

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90 Electrochemistry NEET

22. The conductivities at infinite dilution of NH4Cl, NaOH 30. What volume of gases at STP will evolve if 1 L of
and NaCl are 130, 218, 120 ohm –1 cm 2 eq –1 . 0.01 M solution of H2SO4 is electrolysed?
N (1) 33.6 L (2) 336 ml
If equivalent conductance of solution of NH4OH
100 (3) 3.36 ml (4) 3.36 L
is 10, then degree of dissociation of NH4OH at this
31. Which of the following does not affect the value of
dilution is
Ecell?
(1) 0.005 (2) 0.044
(1) Volume of container
(3) 0.01 (4) 0.02
(2) Concentration
23. During electrolysis of aqueous solution of a salt pH
(3) Temperature
in the space near one of the electrodes is increased.
Which of the following salt solution was electrolysed? (4) All of these
(1) KCl (2) CuCl2 32. Which of the following is secondary cell?
(3) Cu(NO3)2 (4) CuSO4 (1) Dry cell
24. The oxidation potential of hydrogen electrode at (2) Mercury cell
pH = 10 and pH2  1atm (3) Lead storage battery
(4) All of these
(1) 0.51 V (2) 0.00 V
33. Find the value of ‘Z’ in the following reaction
(3) 0.59 V (4) 0.059 V
25. Faradays charge required for conversion of 1 mol 1 x volt y volt
Cl2 ClO– ClO3–
MnO4 to Mn2 , is 2
z volt
(1) 5 (2) 2.5
(3) 3 (4) 7 4x + y
(1) x + y (2)
5
26. Eº for F2 + 2e–  2F– is

1 5x + 4y x + 4y
2.8V, Eº for F2 + e–  F– is (3) (4)
2 1 5


(1) 2.8 V (2) 1.4 V 34. The value of  eq (cm2–1eq–1) of Al3+ is x and Cl–
(3) –2.8 V (4) –1.4 V 
is y then, the value of m (cm2–1mole–1) of AlCl3
27. On electrolysis, 1 mole of calcium will be
will be
deposited from its molten salt by
(1) 1 mole of electrons (2) 2 mole of electrons x
(1) y (2) 3x + 3y
(3) 3 mole of electrons (4) 4 mole of electrons 3

28. A solution of sodium sulphate in water is x y y

electrolysed using inert electrodes. The products at (3)  (4) 3x 
3 3 3
the anode and cathode respectively are
35. Which of the following can change the conductivity
(1) O2, H2 (2) H2, O2
of a electrolytic solution?
(3) O2, Na (4) Na, O2
(1) Temperature (2) Viscosity
29. In electrochemical corrosion of metals, the metal
(3) Interionic attraction (4) All of these
undergoing corrosion
36. For an electrochemical cell Ag/Ag+(0.1 M) || Ag+/Ag
(1) Acts as anode
(1M), which of the following electrolyte cannot be
(2) Acts as cathode used in salt bridge?
(3) Is reduced (1) NaNO3 (2) KCl
(4) Either of these (3) KNO3 (4) Both (2) & (3)

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NEET Electrochemistry 91
37. For an electrochemical cell Al |Al3+ (1 M) || Cu2+(1M)|Cu, –
2. The standard electrode potential E values of
it is given that EAl Al3  1.66V and ECu/Cu2   0.34V .
Al3+/Al, Ag+/Ag, K+/K and Cr3+/Cr are –1.66 V, 0.80
The value of Ecell is V, –2.93 V and –0.74 V, respectively. The correct
(1) 2.00 V (2) 3.02 V decreasing order of reducing power of the metal is

(3) 1.75 V (4) 2.25 V [NEET-2019 (Odisha)]

(1) Al > K > Ag > Cr (2) Ag > Cr > Al > K
38. CuSO4 (aq) electrolysed using platinum electrodes
A current is passed until 1.6 g of O2 liberated at (3) K > Al > Cr > Ag (4) K > Al > Ag > Cr
anode. The amount of Cu deposited at the cathode 3. For the cell reaction
during same time period
(1) 6.35 g (2) 63.5 g 2Fe3 (aq)  2I (aq)  2Fe2 (aq)  I2 (aq)
(3) 12.7 g (4) 3.2 g EΘ
cell  0.24 V at 298 K. The standard Gibbs
1 energy ( r GΘ ) of the cell reaction is :
39. For a half cell having reaction Cl2  e  Cl , if
2 [Given that Faraday constant F = 96500 C mol–1]
1MCl – solution is diluted to 100 times
[NEET-2019]
(ECl 2Cl–
 1.36V) , then ECl 2Cl
will be (Given
2 2
PCl2  1atm ) (1) – 46.32 kJ mol–1 (2) – 23.16 kJ mol–1
(3) 46.32 kJ mol–1 (4) 23.16 kJ mol–1
(1) 1.18 V (2) 1.48 V
4. For a cell involving one electron E°cell = 0.59 V at 298
(3) 1.68 V (4) 3.48 V
K, the equilibrium constant for the cell reaction is :
40. For the given reactions
 2.303 RT 
Given that  0.059 V at T  298 K 
Sn 4 
 2e  Sn 2 E  x V F 
[NEET-2019]
Sn  Sn2  2e E  y V
(1) 1.0 × 102 (2) 1.0 × 105
The value of E° for the reaction
(3) 1.0 × 1010 (4) 1.0 × 1030
Sn4   4e  Sn will be 5. Consider the change in oxidation state of Bromine
corresponding to different emf values as shown in
x  y x  y the diagram below :
(1) (2)
2 2 – 1.82 V – 1.5 V
BrO4 BrO3 HBrO
y
(3) 2x + 2y (4) 2x  –
2 Br Br2
1.0652 V 1.595 V
Then the species undergoing disproportionation is
SECTION - C [NEET-2018]
Previous Years Questions (1) BrO3 (2) BrO4
1. Following limiting molar conductivities are given as (3) HBrO (4) Br2
º 2 –1 6. In the electrochemical cell :
m (H2SO4 )  x S cm mol
Zn|ZnSO4(0.01M)||CuSO4(1.0 M)|Cu, the emf of this
º
m (K 2SO4 )  y S cm2 mol–1 Daniel cell is E 1 . When the concentration of
º ZnSO4 is changed to 1.0 M and that of CuSO4
m (CH3COOK)  z S cm2 mol–1
changed to 0.01 M, the emf changes to E2. From
º the following, which one is the relationship between
m (in S cm2 mol–1) for CH3COOH will be
E1 and E2?
[NEET-2019 (Odisha)] RT
(Given, = 0.059) [NEET-2017]
(x – y) F
(1) z (2) x – y + 2z
2 (1) E1 = E2 (2) E1 < E2
(3) x + y + z (4) x – y + z (3) E1 > E2 (4) E2 = 0 ≠ E1

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92 Electrochemistry NEET

7. If the Eºcell for a given reaction has a negative 14. A device that converts energy of combustion of
value, which of the following gives the correct fuels like hydrogen and methane, directly into
relationships for the values of G° and Keq? electrical energy is known as [AIPMT-2015]
[NEET (Phase-2) 2016] (1) Ni-Cd cell
(1) G° > 0; Keq < 1 (2) G° > 0; Keq > 1 (2) Fuel cell
(3) G° < 0; Keq > 1 (4) G° < 0; Keq < 1 (3) Electrolytic cell
8. The molar conductivity of a 0.5 mol/dm3
solution of (4) Dynamo
AgNO 3 with electrolytic conductivity of
15. When 0.1 mol MnO24 is oxidised the quantity of
5.76 × 10–3 S cm–1 at 298 K
[NEET-Phase-2-2016] electricity required to completely oxidise MnO24 to
(1) 2.88 S cm2/mol (2) 11.52 S cm2/mol MnO4 is [AIPMT-2014]
(3) 0.086 S cm2/mol (4) 28.8 S cm2/mol (1) 96500 C
9. During the electrolysis of molten sodium chloride, (2) 2 × 96500 C
the time required to produce 0.10 mol of chlorine (3) 9650 C
gas using a current of 3 amperes is
(4) 96.50 C
[NEET-Phase-2-2016]
16. The weight of silver (At. Wt. = 108) displaced by a
(1) 55 minutes (2) 110 minutes quantity of electricity which displaces 5600 mL of
(3) 220 minutes (4) 330 minutes O2 at STP will be [AIPMT-2014]
10. The number of electrons delivered at the cathode (1) 5.4 g (2) 10.8 g
during electrolysis by a current of 1 ampere in
(3) 54.0 g (4) 108.0 g
60 sec. is (charge on electron = 1.60 × 10–19 C)
17. A button cell used in watches functions as following
[NEET-Phase-2-2016]


Zn(s)  Ag2O(s)  H2O(l ) 

(1) 6 × 1023 (2) 6 × 1020
2Ag(s) + Zn2+ (aq) + 2OH– (aq)
(3) 3.75 × 1020 (4) 7.48 × 1023
If half cell potentials are
11. Zinc can be coated on iron to produce galvanized
iron but the reverse is not possible. It is because Zn2+ (aq) + 2e–  Zn(s) ; E° = –0.76 V
[NEET-Phase-2-2016] Ag2O(s) + H2O(l) + 2e–  2Ag(s) + 2OH– (aq),
(1) Zinc is lighter than iron E° = 0.34 V
(2) Zinc has lower melting point than iron The cell potential will be [NEET-2013]
(3) Zinc has lower negative electrode potential than (1) 0.42 V (2) 0.84 V
iron (3) 1.34 V (4) 1.10 V
(4) Zinc has higher negative electrode potential 18. At 25°C molar conductance of 0.1 molar aqueous
than iron solution of ammonium hydroxide is 9.54 ohm–1 cm2
12. The pressure of H2 required to make the potential mol–1 and at infinite dilution its molar conductance is
of H2 electrode zero in pure water at 298 K is 238 ohm–1 cm2 mol–1. The degree of ionisation of
ammonium hydroxide at the same concentration and
[NEET-2016]
temperature is [NEET-2013]
(1) 10–4 atm (2) 10–14 atm
(1) 20.800% (2) 4.008%
(3) 10–12 atm (4) 10–10 atm (3) 40.800% (4) 2.080%
13. Aqueous solution of which of the following 19. A hydrogen gas electrode is made by dipping
compounds is the best conductor of electric platinum wire in a solution of HCl of pH = 10 and by
current? [Re-AIPMT-2015] passing hydrogen gas around the platinum wire at
(1) Ammonia, NH3 one atm pressure. The oxidation potential of electrode
(2) Fructose, C6H12O6 would be? [NEET-2013]

(3) Acetic acid, C2H4O2 (1) 0.59 V (2) 0.118 V

(4) Hydrochloric acid, HCl (3) 1.18 V (4) 0.059 V

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NEET Electrochemistry 93
20. Limiting molar conductivity of NH 4 OH 25. Standard electrode potential for Sn4 / Sn2 couple
   is +0.15 V and that for the Cr 3 / Cr couple is
 i .e.  m (NH4 OH)  is equal to
  –0.74 V. These two couples in their standard state
[AIPMT (Prelims)-2012]
are connected to make a cell. The cell potential will
o
(1) m o
(NH4OH)  m o
(NH4Cl) – m (HCl) be [AIPMT (Prelims)-2011]
(1) + 1.83 V
(2) mo (NH4Cl)  mo (NaOH) – mo (NaCl)
(2) + 1.19 V
(3) mo (NH4Cl)  mo (NaCl) – mo (NaOH) (3) + 0.89 V
(4) + 0.18 V
(4) mo (NaOH)  mo (NaCl) – mo (NH4Cl)
21. Standard reduction potentials of the half reactions 26. If the Eocell for a given reaction has a negative
are given below value, then which of the following gives the correct
F2(g) +2e–  2F–(aq); E = +2.85 V relationships for the values of G° and Keq?

Cl2(g) + 2e–  2Cl–(aq) ; E = +1.36 V [AIPMT (Prelims)-2011]

Br2(l) + 2e–  2Br–(aq) ; E = +1.06 V (1) G  0; K eq  1

2(s) + 2e– 2–(aq) ; E = +0.53 V (2) G  0; K eq  1
The strongest oxidising and reducing agents
respectively are [AIPMT (Mains)-2012] (3) G  0; K eq  1
(1) F2 and – (2) Br2 and Cl– (4) G  0; K eq  1
(3) Cl2 and Br– (4) Cl2 and 2 27. An increase in equivalent conductance of a strong
22. Molar conductivities  
o
m
at infinite dilution of NaCl,
electrolyte with dilution is mainly due to

HCl and CH3COONa are 126.4, 425.9 and 91.0 S [AIPMT (Prelims)-2010]
o
cm2 mol–1 respectively m for CH3COOH will be (1) Increase in ionic mobility of ions
[AIPMT (Mains)-2012] (2) 100% ionisation of electrolyte at normal dilution
(1) 425.5 S cm2 mol–1 (2) 180.5 S cm2 mol–1 (3) Increase in both i.e. number of ions and ionic
(3) 290.8 S cm2 mol–1 (4) 390.5 S cm2 mol–1 mobility of ions

23. The Gibb’s energy for the decomposition of Al2O3 at (4) Increase in number of ions
500C is as follows 28. For the reduction of silver ions with copper metal,
the standard cell potential was found to be +0.46V
2 4
Al O Al+O2 ; rG = +960 kJ mol–1 at 25C. The value of standard Gibbs energy, G
3 2 3 3
will be (F = 96500 C mol–1) [AIPMT (Prelims)-2010]
The potential difference needed for the electrolytic
(1) –89.0 kJ
reduction of aluminium oxide (Al2O3) at 500C is at
least [AIPMT (Mains)-2012] (2) –89.0 J
(1) 4.5 V (2) 3.0 V (3) –44.5 kJ
(3) 2.5 V (4) 5.0 V (4) –98.0 kJ

24. The electrode potentials for Cu2  e  Cu 29. Which of the following expressions correctly
(aq) (aq) represents the equivalent conductance at infinite
o
and Cu  e  Cu are +0.15 V and +0.50 V dilution of Al2(SO4)3. Given that  oAl3 and SO24 are
(aq) (s)
the equivalent conductances at infinite dilution of the
respectively. The value of Eo will be respective ions? [AIPMT (Mains)-2010]
Cu2  /Cu
o o o o
[AIPMT (Prelims)-2011] (1) 2 Al3  3 SO24 (2)  Al3  SO24
(1) 0.150 V (2) 0.500 V 1 o 1 o
o o
(3) (  Al3   SO24 )  6 (4)  Al3   SO 2
(3) 0.325 V (4) 0.650 V 3 2 4

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94 Electrochemistry NEET

30. Consider the following relations for emf of a (3) Infinite dilution each ion makes definite
electrochemical cell contribution to equivalent conductance of an
(a) emf of cell = (Oxidation potential of anode) electrolyte depending on the nature of the other
– (Reduction potential of cathode) ion of the electrolyte

(b) emf of cell = (Oxidation potential of anode) (4) Infinite dilution, each ion makes definite
+ (Reduction potential of cathode) contribution to conductance of an electrolyte
whatever be the nature of the other ion of the
(c) emf of cell = (Reductional potential of anode) + electrolyte
(Reduction potential of cathode)
35. Standard free energies of formation (in kJ/mol) at
(d) emf of cell = (Oxidation potential of anode) 298 K are –237.2, –394.4 and –8.2 for H2O (l), CO2
– (Oxidation potential of cathode)
(g) and pentane (g) respectively. The value of Ecell
Which of the above relations are correct?
for the pentane-oxygen fuel cell is
Options: [AIPMT (Mains)-2010] [AIPMT (Prelims)-2008]
(1) (c) and (a) (2) (a) and (b) (1) 0.0968 V (2) 1.968 V
(3) (c) and (d) (4) (b) and (d) (3) 2.0968 V (4) 1.0968 V
31. Given 36. On the basis of the following E° values, the
(i) Cu2+ + 2e–  Cu, Eo = 0.337 V strongest oxidizing agent is
(ii) Cu2+ + e–  Cu+, Eo = 0.153 V [Fe(CN)6]4–  [Fe(CN)6]3– + e–1; E° = – 0.35 V
Electrode potential, Eo for the reaction, Fe2+  Fe3+ + e–1; E° = – 0.77 V
Cu+ + e–  Cu, will be [AIPMT (Prelims)-2009] [AIPMT (Prelims)-2008]

(1) 0.90 V (2) 0.30 V (1) [Fe(CN)6]3– (2) [Fe(CN)6]4–

(3) Fe2+ (4) Fe3+
(3) 0.38 V (4) 0.52 V
37. The equilibrium constant of the reaction
32. Al2O3 is reduced by electrolysis at low potentials
and high currents. If 4.0 × 104 amperes of current Cu(s) + 2Ag+ (aq)  Cu2+(aq) + 2Ag(s) ; E=0.46V
is passed through molten Al2O3 for 6 hours, what at 298 K is [AIPMT (Prelims)-2007]
mass of aluminium is produced? (Assume 100% (1) 4.0 × 1015 (2) 2.4 × 1010
current efficiency, At. mass of Al = 27 g mol–1)
(3) 2.0 × 1010 (4) 4.0 × 1010
[AIPMT (Prelims)-2009]
38. The efficiency of a fuel cell is given by
(1) 8.1 × 104 g (2) 2.4 × 105 g
[AIPMT (Prelims)-2007]
(3) 1.3 × 104 g (4) 9.0 × 103 g
S H
M (1) (2)
33. The equivalent conductance of solution of a G G
32
weak monobasic acid is 8.0 mhos cm2 and at G G
(3) (4)
infinite dilution is 400 mhos cm2. The dissociation S H
constant of this acid is [AIPMT (Prelims)-2009]
39. If E° = –0.441 V and E° = 0.771 V,
Fe2+ / Fe Fe3+ /Fe2+
(1) 1.25 × 10–6 (2) 6.25 × 10–4
the standard EMF of the reaction Fe + 2Fe3+ 
(3) 1.25 × 10–4 (4) 1.25 × 10–5
3Fe2+ will be [AIPMT (Prelims)-2006]
34. Kohlrausch's law states that at
(1) 0.330 V (2) 1.653 V
[AIPMT (Prelims)-2008]
(3) 1.212 V (4) 0.111 V
(1) Infinite dilution, each ion makes definite
40. A hypothetical electrochemical cell is shown below
contribution to equivalent conductance of an
A|A+(xM)||B +(yM)|B, the emf measured is +0.20 V.
electrolyte, whatever be the nature of the other
The cell reaction is [AIPMT (Prelims)-2006]
ion of the electrolyte
(1) A+ + B  A + B+
(2) Finite dilution, each ion makes definite
contribution to equivalent conductance of an (2) A+ + e–  A ; B+ + e–  B
electrolyte, whatever be the naure of the other (3) The cell reaction cannot be predicted
ion of the electrolyte (4) A + B+  A+ + B
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NEET Electrochemistry 95
41. 4.5 g of aluminium (at. mass 27 amu) is deposited 47. How many grams of cobalt metal will be deposited
at cathode from Al3+ solution by a certain quantity when a solution of cobalt(II) chloride is electrolyzed
of electric charge. The volume of hydrogen with a current of 10 amperes for 109 minutes?
produced at STP from H+ ions in solution by the (1 Faraday = 96,500 C; Atomic mass of Co = 59 u)
same quantity of electric charge will be (1) 0.66 (2) 4.0
[AIPMT (Prelims)-2005] (3) 20.0 (4) 40.0
(1) 22.4 L (2) 44.8 L 48. A 5 ampere current is passed through a solution of
(3) 5.6 L (4) 11.2 L zinc sulphate for 40 minutes. The amount of zinc
Questions asked Prior to Medical Ent. Exams. 2005 deposited at the cathode is
42. A solution contains Fe2+, Fe3+ and I– ions. This (1) 0.4065 g (2) 65.04 g
solution was treated with iodine at 35°C. E° for (3) 40.65 g (4) 4.065 g
Fe3+/Fe2+ is +0.77 V and E° for I2/2I– = 0.536 V. 49. The molar conductances of NaCl, HCl and
The favourable redox reaction is CH3COONa at infinite dilution are 126.45, 426.16 and
(1) I– will be oxidised to I2 91 ohm –1 cm 2 mol –1 respectively. The molar
(2) Fe2+ will be oxidised to Fe3+ conductance of CH3COOH at infinite dilution is
(3) I2 will be reduced to I– (1) 698.28 ohm–1 cm2 mol–1
(4) There will be no redox reaction (2) 540.48 ohm–1 cm2 mol–1
43. Standard reduction potentials at 25°C of Li+ / Li, (3) 201.28 ohm–1 cm2 mol–1
Ba2+ / Ba, Na+ / Na and Mg2+ / Mg are –3.05, –2.90, (4) 390.71 ohm–1 cm2 mol–1
–2.71 and –2.37 volt respectively. Which one of the
50. E° for the cell, Zn|Zn2+(aq)||Cu2+(aq)|Cu is 1.10 V at
following is the strongest oxidizing agent?
25ºC, the equilibrium constant for the reaction
(1) Ba2+ (2) Mg2+ Zn + Cu2+ (aq) Cu + Zn2+ (aq) is the order of
(3) Na+ (4) Li+ (1) 10+18 (2) 10+37
44. To protect iron against corrosion, the most suitable (3) 10–28 (4) 10–37
metal plating on it, is
51. For the cell reaction,
(1) Copper plating
Cu2+ (C1 · aq) + Zn(s) = Zn2+ (C2 · aq) + Cu(s) of an
(2) Zinc plating electrochemical cell, the change in Free Energy (G)
(3) Nickel plating at a given temperature is a function of
(4) Tin plating (1) ln (C2) (2) ln (C2/C1)
45. An electrochemical cell is set up as : (3) ln (C1) (4) ln (C1 + C2)
Pt; H2 (1 atm) |HCl (0.1 M) || CH3COOH (0.1M) | 52. The specific conductance of a 0.1 N KCl solution at
H2 (1 atm) ; Pt. The e.m.f. of this cell will not be zero, 23°C is 0.012 ohm–1 cm–1. The resistance of cell
because containing the solution at the same temperature was
found to be 55 ohm. The cell constant will be
(1) Acids used in two compartments are different
(1) 0.918 cm–1 (2) 0.66 cm–1
(2) e.m.f. depends on molarities of acids used
(3) 1.142 cm–1 (4) 1.12 cm–1
(3) The temperature is constant
53. For the disproportionation of copper 2Cu+  Cu2+ +
(4) pH of 0.1 M HCl & 0.1 M CH3COOH is not same Cu, E° is (Given E° for Cu2+/Cu is 0.34 V and E° for
46. Electrode potential for the following half-cell reactions Cu2+/Cu+ is 0.15 V)
are (1) 0.49 V (2) –0.19 V
Zn  Zn2+ + 2e–; E° = + 0.76 V; (3) 0.38 V (4) –0.38 V
Fe  Fe2+ + 2e–; E° = + 0.44 V 54. Cell reaction is spontaneous when
The EMF for the cell reaction Fe2+ + Zn  Zn2+ + Fe (1) G° is negative
will be (2) G° is positive
(1) – 0.32 V (2) + 1.20 V (3) E°Red is positive
(3) – 1.20 V (4) + 0.32 V (4) E°Red is negative

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96 Electrochemistry NEET

55. Equivalent conductances of Ba2+ and Cl– ions are 127 61. The e.m.f. of a Daniel cell at 298 K is E1
and 76 ohm–1 cm2 eq–1 respectively. Equivalent
Zn ZnSO4 CuSO4 Cu
conductance of BaCl2 at infinite dilution is (in the unit (0.01M) (1.0M)
ohm–1 cm2 eq–1)
When the concentration of ZnSO4 is 1.0 M and that
(1) 139.5 (2) 101.5 of CuSO4 is 0.01 M, the e.m.f. changed to E2. What
(3) 203 (4) 279 is the relationship between E1 and E2?
56. Standard electrode potentials are (1) E1 > E2
Fe2+/Fe ; E° = –0.44 volts (2) E1 < E2
Fe3+/Fe2+ ; E° = 0.77 volts (3) E1 = E2
Fe2+, Fe3+ and Fe blocks are kept together, then (4) E2 = 0  E1
(1) Fe3+ increases 62. The standard e.m.f. of a galvanic cell involving cell
(2) Fe3+ decreases reaction with n = 2 is found to be 0.295 V at 25°C.
The equilibrium constant of the reaction would be
(3) Fe2+/Fe3+ remains unchanged
(Given F = 96500 C mol–1, R = 8.314 J K–1 mol–1)
(4) Fe2+ decreases
(1) 2.0 × 1011 (2) 4.0 × 1012
57. PbO2  PbO ; G298 < 0
(3) 1.0 × 102 (4) 1.0 × 1010
SnO2  SnO ; G298 > 0
63. The mass of carbon anode consumed (giving only
Most probable oxidation state of Pb and Sn will be carbon dioxide) in the production of 270 kg of
(1) Pb4+, Sn4+ aluminium metal from bauxite by the Hall process is
(2) Pb4+, Sn2+ (Atomic Mass of Al = 27)
(3) Pb2+, Sn2+ (1) 270 kg (2) 540 kg
(4) Pb2+, Sn4+ (3) 90 kg (4) 180 kg
58. The most convenient method to protect the bottom 64. Consider the half-cell reduction reaction :
of ship made of iron is Mn2+ + 2e–  Mn, Eo = –1.18 V
(1) Coating it with red lead oxide Mn2+  Mn3+ + e–, Eo = –1.51 V
(2) White tin plating The Eo for the reaction 3 Mn2+  Mn0 + 2 Mn3+, and
(3) Connecting it with Mg block possibility of the forward reaction are, respectively
(4) Connecting it with Pb block (1) –2.69 V and no (2) –4.18 V and yes
59. In electrolysis of NaCl when Pt electrode is taken then (3) +0.33 V and yes (4) +2.69 V and no
H2 is liberated at cathode while with Hg cathode it
forms sodium amalgam SECTION - D
(1) Hg is more inert than Pt NEET Booster Questions
(2) More voltage is required to reduce H+ at Hg than 1. Given :
at Pt Mn2+  MnO4–; E° = – 1.51 V
(3) Na is dissolved in Hg while it does not dissolve MnO2  Mn2+; E° = 1.23 V
in Pt
What is the E° value for the reaction?
(4) Conc. of H+ ions is larger when Pt electrode is
MnO4–  MnO2
taken
(1) 1.7 V (2) 2.74 V
60. On the basis of the information available from the
reaction of O2, (3) 5.09 V (4) 1.1 V
4 2 2. For the following cell reaction :
Al  O2  Al2O3 , G  827 kJ mol1 ,
3 3 Cu(s) + 2Ag+(aq)  2Ag(s) + Cu2+(aq)
the minimum e.m.f. required to carry out electrolysis E°cell is 0.46 V at 300 K and 0.50 V at 340 K, then
of Al2O3 is (F = 96500 C mol–1) what will be entropy change?
(1) 2.14 V (2) 4.28 V (1) 386 JK–1 (2) 276 JK–1
(3) 6.42 V (4) 8.56 V (3) 96.5 JK–1 (4) 193 JK–1

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NEET Electrochemistry 97
3. The chemical species undergoing reduction in dry 11. Reactivity of metals increases as electropositivity
cell is increases, what will happen if a copper spoon is
used to stir a solution of aluminium nitrate?
(1) Zn (2) NH4
(1) The spoon will get coated with aluminium
(3) MnO2 (4) NH3 (2) An alloy of aluminium and coper is formed
4. The amount of Cu deposited when 10 A of current (3) The solution becomes blue
is passed for 10 minute through CuSO4(aq) is
(4) There is no reaction.
(1) 1.97 g (2) 2.89 g
12. Resistance of decimolar solution is 50 ohm. If
(3) 4 g (4) 3.5 g electrodes of surface area 0.0004 m2 each are
5. The volume of O2(g) released by 1 C electricity at placed at a distance of 0.02 m then conductivity of
NTP would be solution is
5.6 (1) 1 S cm–1 (2) 0.01 S cm–1
(1) 5.6 L (2) L
96500 (3) 0.001 S cm–1 (4) 10 S cm–1
13. The conductivity of a saturated solution of BaSO4
11.2 22.4 is 3.06 × 10 –6 ohm –1 cm –1 and its equivalent
(3) L (4) L
96500 96500 conductance is 1.53 ohm–1cm2eq–1. The Ksp for
6. The value of specific conductivity is maximum for BaSO4 will be

(1) 0.1 M NaCl (1) 4 × 10–12 (2) 2.5 × 10–13

(2) 0.01 M NaCl (3) 25 × 10–9 (4) 10–6
(3) 10–4 M NaCl 14. The EMF of a concentration cell consisting of two
(4) All will have equal specific conductivity M
zinc electrodes, one dipping into solution of
7. The net reaction in Ni–Cd cell is 4
(1) Cd + 2Ni(OH)3  CdO + 2Ni(OH)2 + H2O M
zinc sulphate & other into solution of the
(2) Ni(s) + 2Cd(OH)3  NiO + 2Cd(OH)2 + 16
H2O same salt at 25ºC is :-
(3) Cd + Ni2+  Cd2+ + Ni (1) 0.0125 V (2) 0.0250 V
(4) Ni + Cd2+  Ni2+ + Cd (3) 0.0178 V (4) 0.0356 V
8. The product released at anode in the electrolysis 15. The charge required for the reaction of 1 mole
of 50% concentrated H2SO4 is
Cr2O72 to Cr3+ in acidic medium is
(1) H2(g) (2) O2(g)
(3) S2O82– (4) All of these (1) 3 F (2) 6 F
9. L–1
If the electrical resistance of a column of 0.1 mol (3) 12 F (4) 2 F
NaOH solution of diameter 1 cm and length 10 cm 16. Given standard electrode potentials :-
is 5 × 10 3 ohm, what would be the molar
Fe3+ + 3e– Fe; Eº = –0.036 volt
conductivity of the solution?
Fe2+ + 2e– Fe; Eº = –0.440 volt
(1) 254.8 S cm2 mol–1
The standard electrode potential Eº for
(2) 50.96 S cm2 mol–1
Fe3+ + e– Fe2+
(3) 102.3 S cm2 mol–1
(1) –0.476 volt (2) –0.440 volt
(4) 25.48 S cm2 mol–1
(3) 0.440 volt (4) 0.772 volt
10. The emf of the cell,
17. The EMF of the cell;
Ni|Ni2+(1.0 M)||Ag+(1.0 M)|Ag (Eº of Ni2+|Ni = –0.25
volt, Eº for Ag+| Ag = 0.80 volt) Cr|Cr3+(0.1 M)|| Fe2+ (0.01 M)| Fe
(1) 0.55 volt
(2) – 1.05 volt
Given E 0
Cr 3  |Cr
 0.75 V, E0
Fe2 |Fe
 0.45 V 
(3) + 1.05 volt (1) 0.30 V (2) 0.36 V
(4) – 0.55 volt (3) 0.26 V (4) 0.22 V

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98 Electrochemistry NEET

18. Same quantity of current is passed through molten 24. The coulombic charge on one mole electron is
NaCl and molten Al 2 O 3 . If 2.3 g of Na was (1) 1.6 × 10–19 C
deposited in one cell, the mass of al deposited in
(2) 96500 C
other cells
(3) 6.02 × 10–23 C
(1) 1.8 gm (2) 0.9 gm
(4) 1.6 × 10–23 C
(3) 2.7 gm (4) 3.6 gm
25. Zn rod is placed in 100 mL of 1M CuSO4 solution
19. Standard electrode potential of some half cell
so that molarity of Cu2+ changes to 0.7 M. The
reactions are given below
molarity of SO42– at this stage will be
(i) Sn4+ + 2e–  Sn2+, Eº = + 0.15 V
(1) 0.8 M
(ii) 2Hg2+ + 2e–  Hg22 , Eº = + 0.92 V (2) 1 M
(iii) PbO2 + 4H+ + 2e–  Pb2++2H2O, Eº = + 1.45 V (3) 0.7 M
Which of the following statement is correct (4) 1.8 M
according to electrode ? 26. The time taken by the galvanic cell which operates
(1) Pb2+ is more powerful reducing agent than almost ideally under reversible conditions at a
Sn2+. current of 10–16A to deliver 1 mole of electron is

(2) Sn4+ is more powerful oxidising agent than (1) 19.30 × 1020 s (2) 4.825 × 1020 s
Pb4+. (3) 9.65 × 1020 s (4) 3.4 × 1011 s
(3) Sn2+ is more powerful reducing agent than 27. A direct current deposits 54 g of silver
Hg22+ (atomic mass = 108) during the electrolysis. The
(4) Hg2+ is more powerful oxidising agent than same quantity of electricity would deposit
Pb4+. aluminium (atomic mass = 27) from aluminium
chloride in molten state equal to
20. In a cell that utilizes the reaction
(1) 4.5 g (2) 5.4 g
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
(3) 54 g (4) 27 g
Addition of H2SO4 to cathode compartment will
28. During the electrolysis of water, 4 mol of electrons
(1) Lower the E and shift equilibrium to left. were transferred from anode to cathode. The total
(2) Lower the E and shift equilibrium to the right. volume of gases produced at STP will be
(3) Increase the E and shift equilibrium to the right. approximately
(4) Increase the E and the equilibrium to left. (1) 67.2 L (2) 22.4 L
(3) 44.8 L (4) 89.4 L
o
21. The EM3  |M2  values for Cr, Mn, Fe and Co are 29. The quantity of electricity required to reduce
–0.41, + 1.57, + 0.77 and + 1.97 respectively. For 12.3 g of nitro benzene to aniline assuming 50%
which one of these metals, the change in oxidation current effeciency is
state from +2 to +3 is easiest (1) 115800 C (2) 57900 C
(1) Cr (2) Mn (3) 231600 C (4) 28950 C
(3) Fe (4) Co 30. A 100 watt, 110 volt lamp is connected in series
22. The resistance of 0.0025 M solution of K2SO4 is with an electrolytic cell containing CdSO4 solution,
326 ohm. The specific conductance of the solution, the weight of Cd deposited by the current for
if cell constant is 4 (in ohm). 10 hrs is (At. wt. of Cd = 112.4)
(1) 4.997 × 10–4 (2) 5.997 × 10–7 (1) 19.06 g (2) 38.12 g
(3) 6.997 × 10–4 (4) 1.20 × 10–2 (3) 1.906 g (4) 3.812 g
23. The conductivity of four electrolytes P, Q, R, S in ohm– 31. The two platinum electrodes fitted in a conductance
1 cm–1 are as follows P(5 × 10–5), Q(1× 10–10), R(7 × cell are 1.5 cm apart while the cross sectional area
10–8); S(9.2 ×10–3). The one which offers highest of each electrode is 0.75 cm2. What is the cell
resistance to the passage of electric current is constant?
(1) P (2) S (1) 1.25 cm–1 (2) 0.5 cm–1
(3) R (4) Q (3) 2.0 cm–1 (4) 0.2 cm–1

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NEET Electrochemistry 99
32. A current of 2.0 A is passed for 5 hours through a 41. The hydrogen electrode is dipped in a solution of
molten metal salt deposits 22.2 g of metal pH = 3 at 25°C. The reduction potential of the
(At. mass: 177). The oxidation state of the metal in electrode would be
metal salt is (1) 0.177 V (2) 0.087 V
(1) +1 (2) +2 (3) –0.177 V (4) 0.059 V
(3) +3 (4) +4 2 2
42. Zn | Zn(aq) || Cu(aq) | Cu E° for the cell is 1.10 V at
33. A current of 0.965 ampere is passed through
500 ml of 0.2 M solution of ZnSO4 for 10 minutes. 25°C. The equilibrium constant for the cell reaction
The molarity of Zn2+ after deposition of zinc is is of the order of
(Atomic mass of Zn is 65 u) (1) 10–37 (2) 1037
(1) 0.1 M (2) 0.5 M (3) 10–17 (4) 1017
(3) 0.8 M (4) 0.194 M 43. What will be the emf of the given cell?
34. Electrolysis of H2SO4 (conc.) gives the following at 
Pt | H2(P1 ) | H(aq) | H2(P2 ) | Pt
anode
(1) H2 (2) O2 RT P1 RT P
(1) ln (2) ln 1
(3) H2S2O3 (4) H2S2O8 F P2 2F P2
35. In SHE, the pH of the acid solution should be RT P2 RT P
(3) ln (4) ln 2
(1) 7 (2) 14 F P1 2F P1
(3) 0 (4) 4 44. Which of the following can oxidise fluoride ions?
36. E.M.F. of Ni(s)|Ni2+ (aq) || Cu2+ (aq)|Cu(s) cell can (1) O3
be increased by (2) Cl2
(1) Adding NH3 in the right half-cell (3) Br2
(2) Increasing the conc. of Ni2+ ions (4) No chemical substance
(3) Adding dimethyl glyoxime into the left half-cell 45. If the standard reduction potential E° for four divalent
(4) Changing the electrolyte present in salt bridge elements X, Y, Z, W are –1.46 V, –0.36V, 0.15 V and
37. For given cell; Zn |Zn2+ (C1) || Zn2+ (C2)| Zn; G is –1.24 V respectively then
negative if (1) X will replace Z2+ from aqueous solution
(1) C1 = C2 (2) C1 > C2 (2) Y will replace Z2+ from aqueous solution
(3) C2 > C1 (4) Can't predicted (3) W will replace Z2+ from aqueous solution
38. The emf of the cell, Zn|Zn2+||Cu2+|Cu is independent (4) All statements are correct
of 46. The following facts are available
(1) The volume of Zn2+ and Cu2+ solution 2A– + B2  2B– + A2
(2) The molarity of Zn2+ ions in solution 2C– + B2  No reaction
(3) The molarity of Cu2+ ions in solution 2D– + A2  2A– + D2
(4) Temperature Which of the following statement is correct?
39. Standard cell voltage for the cell Pb/Pb2+||Sn2+/Sn
(1) Eo   Eo   Eo   Eo 
is –0.01V. If the cell is to exhibit Ecell = 0 then the C /C2 B /B2 A /A 2 D /D2
value of log [Sn2+] /[Pb2+] should be
(2) Eo   Eo   Eo   Eo 
(1) 0.33 (2) 0.5 C /C2 B /B2 A /A 2 D /D2

(3) 1.5 (4) –0.5 (3) Eo   Eo   Eo   Eo 

C /C2 B /B2 A /A 2 D /D2
40. The voltage of a cell whose half cell reactions are (4) Can’t predict
given below is
47. The specific conductance of a 0.1 N KCl solution at
Mg2  2e   Mg(s); E  –2.37 V 23°C is 0.012 ohm–1cm–1. The resistance of cell
containing the solution at the same temperature was
Cu2  2e   Cu(s); E  0.34 V found to be 55 ohm. The cell constant will be
(1) 1.02 V (2) 1.36 V (1) 0.142 cm–1 (2) 0.66 cm–1
(3) 2.71 V (4) 2.03 V (3) 0.918 cm–1 (4) 1.12 cm–1

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100 Electrochemistry NEET

48. Saturated solution of KNO3 is used to make salt 55. If equivalent conductance of 1M benzoic acid is 12.8
bridge because ohm–1 cm2 eq–1 and if the equivalent conductances
(1) Velocity of K+ is greater than that of NO3 of benzoate ion and H+ ion at infinite dilution are 42
and 288.42 ohm–1 cm2 eq–1 respectively, then its
(2) Velocity of NO3– is greater than that of K+
degree of dissociation is
(3) Velocity of both K+ and NO3– are nearly the same
(1) 39%
(4) KNO3 is highly soluble in H2O
(2) 3.9%
49. Cu 2+ + 2e –  Cu. On increasing [Cu 2+ ]
concentration, electrode potential (3) 0.35%
(1) Increases (4) 0.039%
(2) Decreases 56. Four alkali metals A, B, C & D have standard electrode
potentials –3.05, –1.66, –0.40 and 0.80 V
(3) Will remain unchanged
respectively. Which metal will be the most reactive
(4) First increases, then decreases
(1) A
50. In the electrochemical cell
(2) B
Pt | H2(g) 1atm | H+(1M) || Cu2+ (1M) | Cu(s)
(3) C
Which of the following statements is true?
(4) D
(1) H2 is cathode, Cu is anode
57. Consider the cell given below :
(2) Oxidation occurs at Cu electrode
Ag(s) / Ag+ || Cu2+/Cu(s)
(3) Reduction occurs at H2 electrode
Ag+ + e–  Ag ; E° = x
(4) H2 is anode, Cu is cathode
51. If hydrogen electrode is dipped in two solutions of Cu2+ + 2e–  Cu ; E° = y
pH = 3 and pH = 6 and salt bridge is connected, the E°Cell is
emf of resulting cell is (1) x + 2y (2) 2x + y
(1) 0.177 V (2) 0.3 V (3) y – x (4) y – 2x
(3) 0.052 V (4) 0.104 V 58. If the specific conductance of 1M H2SO4 solution is
52. The emf of the cell reaction 26 × 10–2 S cm–1, then the equivalent conductivity
Ag | Ag+(0.1M) || Ag+(1M) | Ag at 298 K is would be

(1) 0.0059 V (2) 0.059 V (1) 1.3 × 102 S cm2 eq–1

(3) 5.9 V (4) 0.59 V (2) 1.6 × 102 S cm2 eq–1

53. An electrolytic cell contains aqueous solution of (3) 13 S cm2 mol–1

Ag2SO4 and has Platinum electrodes. A current is (4) 1.3 × 103 S cm2 mol–1
passed until 1.6 g of O2 is liberated at anode. The 59. How many atoms of calcium will be deposited from
amount of silver deposited at cathode would be molten CaCl2 by a current of 25 milliamperes flowing
(1) 107.88 g (2) 1.6 g for 60 seconds?
(3) 0.8 g (4) 21.6 g (1) 4.68 × 1018 (2) 4.68 × 1015
54. E° values of Mg2+/Mg, Zn2+/Zn and Fe2+/Fe are (3) 4.68 × 1012 (4) 4.68 × 1019
–2.37 V, –0.76 V and –0.44 V respectively. Which of 60. Limiting molar conductivity of which among the
the following statements is correct following ion is maximum in water at 298 K
(1) Zn will reduce Fe2+ (2) Zn will reduce Mg2+ (1) H+ (2) Na+
(3) Mg oxidises Fe (4) Zn oxidises Fe (3) K+ (4) Ca2+

‰‰‰

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