Electrochemistry

7.
ELECTROCHEMISTRY
1.ELECTROCHEMISTRY the external circuit. Anode is assigned negative polarity

Electrochemistry is the study of production of and cathode is assigned positive polarity. In Daniell
electricity from the energy released during a Cell, Zn acts as the anode and Cu acts as the cathode.
spontaneous chemical reaction and the use of electrical 5.ELECTROLYTIC CELL
energy to bring about non-spontaneous chemical
transformations. These electrodes are dipped in and electrolytic solution
containing cations and anions. On supplying current the
2.ELECTROCHEMICAL CELLS ions move towards electrodes of opposite polarity and
simultaneous reduction and oxidation takes place.
A spontaneous chemical process is the one which can
take place on its own and in such a process the Gibb's 5.1Preferential Discharge of ions
energy of the system decreases. It is this energy that Where there are more than one cation or anion the
gets converted to electrical energy.The reverse process process of discharge becomes competitive in nature.
is also possible in which we can make non-spontaneous Discharge of any ion requires energy and in case of
processes occur by supplying external energy in the several ions being present the discharge of that ion will
form of electrical energy. These inter conversions are take place first which requires the energy.
carried out in equipments called Electrochemical Cells.
3.TYPES 6.ELECTRODE POTENTIAL
Electrochemical Cells are of two types: It may be defined as the tendency of an element, when it
is placed in contact with its own ions to either lose or gain
3.1 Galvanic Cells
electrons and in turn becomepositivelyor
Converts chemical energy into electrical energy negativelycharged.
3.2Electrolytic Cells The electrode potential will be named as oxidation or
reduction potential depending upon whether oxidation
Converts electrical energy into chemical energy.
or reduction has taken place.
-
M s - - �---- - � M n + aq + ne
ox ida tio n
-reduction
4.GALVANIC CELL
Cell energy is extracted from a spontaneous chemical
Mn + aq + ne - �----
re duc tio n
-oxidation
- - - �M s
process or reaction and it is converted to electric current.
For example, Daniell Cell is a Galvanic Cell in which 6.1Characteristics
Zinc
and Copper are used for the redox reaction to take
(a) Both oxidation and reduction potentials are equal in
2+ 2+
place. Zn (s) + Cu (aq) Zn (aq) + Cu(s) magnitude but opposite in sign.
Oxidation Half : Zn (s) Zn2+ (aq) + 2e (b) It is not a thermodynamic property, so values of E
are not additive.
Reduction Half : Cu2+(aq) + 2e Cu(s)
7.STANDARD ELECTRODE POTENTIAL (EO)
Zn is the reducing agent and Cu2+ is the oxidising
agent.The half cells are also known as Electrodes. The It may be defined as the electrode potential of an
oxidation half is known as Anode and the reduction half electrode determined relative to standard hydrogen
is called Cathode. Electrons flow from anode to cathode electrode under standard conditions. The standard
in conditions taken are :
Mahesh Tutorials
Science
ELECTROCHEMISTRY 213
(i) 1M concentration of each ion in the solution.

Zn(s) I Zn2+ (1 M) II Cu2+ (1 M) I Cu EMF = +1.1V
(ii)Atemperature of 298 K.
(f) If an inert electrode like platinum is involved in the
(iii) 1 bar pressure for each gas. construction of the cell, it may be written along with the
working electrode in bracket say for example, when a
8. ELECTROCHEMICAL SERIES zinc anode is connected to a hydrogen electrode.
2+ +
Zn s I Zn C II H C I H I Pt s
The half cell potential values are standard values and 1 2 2
are represented as the standard reduction potential

values as shown in the table at the end which is also 11. SALT BRIDGE
called Electrochemical Series.
Salt bridge is used to maintain the charge balance and to
9.CELL POTENTIAL OR EMF OF A CELL complete the circuit by facilitating the flow of ions
through it. It contains a gel in which an inert electrolyte
The difference between the electrode potentials of two
half cells is called cell potential. It is known as like Na2S04 or
electromotive force (EMF) of the cell if no current is KN03 etc are mixed. Negative ions flow to the anode and
drawn from the cell. positive ions flow to the cathode through the salt bridge
and charge balance is maintained and cell keeps on
Ecell = Ecathode + Eanode
functioning.
For this equation we take oxidation potential of anode
and reduction potential of cathode.
Since anode is put on left and cathode on right, it

follows therefore,
= ER + EL
For a Daniel cell, therefore

=E -E = 0.34 + 0.76 = 1.10 V
o o o
E
cell Cu2+ / Cu Zn / Zn+2
10. CELL DIAGRAM OR REPRESENTATION OF A CELL
The followingconventions or notations areapplied for

writing the cell diagramin accordance with IUPAC 12. SPONTANEITY OF A REACTION
recommendations. The Daniel cell is represented as �G = - nFECELL
follows :
For a spontaneous cell reaction �G should be negative
Zn(s) I Zn2+ (C1 ) II Cu2+ (C2 ) I Cu (s) and cell potential should be positive.
(a) Anode half cell is written on the left hand side while If we take standard value of cell potential in the above
cathode half cell on right hand side. equation we will obtain standard value of �G as well.
(b) A single vertical line separates the metal from �Go = - nFE0
aqueous solution of its own ions.
2+ 2+ CELL
Zn s I Zn aq Cu aq I Cu s
Anodic chamber Cathodic chamber
13. TYPES OF ELECTRODES
(c) A double vertical line represents salt bridge
(d) The molar concentration (C) is placed in brackets 13.1 Metal-Metal Ion electrodes
after the formula of the corresponding ion.
A metal rod/plate is dipped in an electrolyte solution
(e) The value of e.m.f. of the cell is written on the containing metal ions. There is a potential difference
extreme right of the cell. For example, between these two phases and this electrode can act as a
214 ELECTROCHEMISTRY
cathode or anode both.
Anode: M Mn+ + ne-
Cathode: Mn+ + ne- M
13.2 Gas Electrodes
Electrode gases like H2, Cl2 etc are used with their
respective ions. For example, H2 gas is used with a dilute
solution of HCl
(H+ ions). The metal should be inert so that it does not
react with the acid.
Cathode :
Hg2Cl
2
(s) + 2e- 2Hg(l) + 2Cl-
(aq) Anode :
2Hg(l) + 2Cl-(aq) Hg2Cl
2
(s) + 2e-
This electrode is also used as another standard to
measure other potentials. Its standard form is also called
Anode: 2H+ + 2e- Standard Calomel Electrode (SCE).
H2 13.5 Redox Electrode
Cathode: 2H+ + 2e- H

2 In these electrodes two different oxidation states of the
The hydrogen electrode is also used as the standard to same metal are used in the same half cell. For example,
measure other electrode potentials. Its own potential is Fe2+ and Fe3+ are dissolved in the same container and an
set to O V as a reference. When it is used as a reference inert electrode of platinum is used for the electron
the concentration of dil HCl is taken as 1 M and the
transfer. Following reactions can take place:
electrode is called "Standard Hydrogen Electrode
Anode: Fe2+ Fe3+ + e-
(SHE)".
Cathode: Fe3+ + e- Fe2+
13.3 Metal-Insoluble salt electrode
14. NERNST EQUATION
We use salts of some metals which are sparingly soluble
with the metal itself as electrodes. For example, if we It relates electrode potential with the concentration of
use AgCl with Ag there is a potential gap between these ions.
two phases which can be identified in the following
reaction: Thus, the reduction potential increases with the increase
in the concentration of ions. For a general
AgCl(s) + e- Ag(s) + Cl- electrochemical reaction of the type.
aA + bB - - - ➔ cC + dD
n e
This electrode is made by dipping a silver rod in a
solution
containing AgCl(s) and Cl ions.
Nernst equation can be given as
13.4 Calomel Electrode
o
Mercury is used with two other phases, one is a calomel E
E =
RT C
c
D
d
- In
paste (Hg Cl ) and electrolyte containing Cl ions. cell cell
nF a b
2 2 A B
c d concentrations and the solutions are connected through
E = RT log C D
salt bridge, such cells are known as concentration cells.
o
E cell -2303
cell
nF A B
a b
For example
H2I H+(c ) II H+ (c2 ) I H

Substituting the values of R and F we get 2
Cu I Cu+2 (c ) II Cu2+(c
2
) I Cu
E = c d
E
o
log C D , at 298 K These are of two types :
-0.059
cell cell
a b
n A B 16.1 Electrode concentration cells
15. APPLICATIONS OF NERNST EQUATION H2(P ) I H+ (C) II H+ (C) I 2H2 (P )
15.1 Equilibrium Constantfrom Nernst Equation P2

E = 0 - 0.059 log
cell
For a Daniel cell, at n P
equilibrium
l Zn where p2 < p for spontaneous reaction

2+
E cell = 0 = o 2.303 log lJ 16.2 Electrolyte concentration cell
cell - RT
E 2F l
2+
Cu
lJ
+ The EMF of concentration cell at 298 K is given by

2.303 RT l Zn2
Zn I Zn2+ (c ) II Zn2+ (c ) I Zn
l
o
E
or log J 2+ 2
=
cell
2F l Cu l
J
Ecell = 0.059 log c2 ,
l Zn 2+
l n c
J
But at =
lCu2 lJ
+ where c2 > c for spontaneous reaction
equilibrium,
K 17. CASES OF ELECTROLYSIS
c
E ocell = 2.303 RT log Kc 17.1 Electrolysis of molten sodium chloride

2F
2NaCI (I ) � 2Na+ (I ) + 2Cl- (I )
2.303x8.3 4 x 298 The reactions occurring at the two electrodes may be
E ocell 2 x 96500 log Kc
= shown as follows :
0.059 Atcathode :
= log K c
2 2Na+ + 2e- ➔ 2Na EO = - 2.71 V
Atanode :
In general, E cell = 0.059 log Kc
o
n 2Cl- ➔ Cl + 2e- EO = - 1.36V

2
nE
o Overall reaction :
or, log =
cell
2Na+ (I ) + 2 Cl- (I ) 2Na (I ) + CI2 (g)
KC 0.059
16. CONCENTRATION CELLS or 2NaCl (I ) 2Na (I ) + Cl2 (g)
If two electrodes of the same metal are dipped separately At cathode At anode
into two solutions of the same electrolyte having
different
17.2 Electrolysisofanaqueoussolutionofsodiumchloride 18.3 Mercury cells
NaCl (aq) Na+(aq) + Cl- (aq) These are used in small equipments like watches, hearing aids.
(almost completely ionized) Anode : Zn - Hg Amalgam
H2O (I ) � H+(aq) + OH-(aq) Cathode : Paste of HgO and carbon
(only slightly ionized) Electrolyte : Paste of KOH and ZnO
Atcathode : Anode : Zn (Hg) + 2OH- ZnO (s) + H2 O + 2e-
2Na+ + 2e- 2Na E0 = - 2.71V
Cathode : HgO (s) + H2 O + 2e- Hg (l) + 2OH-
2H2O + 2e- H 2+ 2OH- E0 = - 0.83V
Overall Reaction : Zn (Hg) + HgO (s) ZnO (s) + Hg
+
Thus H2gas is evolved at cathode value Na ions remain
(l)
in solution.
The cell potential is approximately 1.35V and remains
Atanode :
constant during its life.
2H2O O 2+ 4H+ + 4e- E0 = - 1.23V
18.4 Secondary Batteries
- - 0
2Cl Cl2 + 2e E = - 1.36V Secondary cells are those which can be recharged again
Thus, Cl2 gas is evolved at the anode by over voltage and again for multiple uses. e.g. lead storage battery and
Ni - Cd battery.
concept while OH- ions remain in the solution.
18.5 Lead Storage
18. BATTERIES
Battery Anode :
When Galvanic cells are connected in series to obtain a
higher voltage the arrangement is called Battery. Lead (Pb)
18.1 Primary Batteries
Cathode : Grid of lead packed with lead oxide (PbO2)
Primary cells are those which can be used so long the
Electrolyte : 38% solution of H2SO4
Discharging Reactions
Anode: Pb(s) + SO 2-(aq) PbSO (s) + 2e-
4 4
active materials are present. Once they get consumed the
cell will stop functioning and cannot be re-used. Cathode: PbO 2(s) + 4H (aq) + SO4 (aq) + 2e-
+ 2-
Example Dry Cell or Leclanche cell and Mercury cell.

PbSO4(s) + 2H2O(l)
18.2 Dry cell
Overall Reaction : Pb(s) + PbO2(s) + 2H2SO4(aq)
Anode : Zn container
2PbSO4(s) + 2H2O(l)
Cathode : Carbon (graphite) rod surrounded by powdered
MnO2 and carbon. To recharge the cell, it is connected with a cell of
higher potential and this cell behaves as an
Electrolyte : NH4Cl and ZnCl2 electrolytic cell
and the reactions are reversed. Pb(s) and PbO 2(s) are
Reaction : regenerated at the respective electrodes.These cells
deliver an almost consistent voltage.
Anode : Zn Zn2+ + 2e-
Recharging Reaction : 2PbSO4(s) + 2H2O(l) Pb(s) +
Cathode : MnO + NH+ + e- MnO (OH) + NH
PbO2(s)+ 2H2SO4(aq)
2 4 3
The standard potential of this cell is 1.5 V and it falls as the cell gets discharged continuously and once used it
cannot be recharged.
19. FUEL CELLS
A fuel cell differs from an ordinary battery in the sense
that the reactants are not contained inside the cell but are
externally supplied from an external reservoir. Fuel cell and iron is protected. This method of protecting one metal
is used in space vehicles and in this cell the two gases
by the other is also called Cathodic Protection.
are supplied from external storages. In this cell carbon
rods are used as electrodes with KOH as the electrolyte.
Cathode : 02 (g) + 2H
2
0 (l) + 4e-
40H- (aq)
Anode : 2H (g) + 40H- (aq) 4H 0 (l) + 4e-

2 2
overall Reaction : 2H2(g) + 02 (g) 2H20 (l)
21. CONDUCTANCE (G)

It is the reciprocal of resistance and may be defined as
the ease with which the electric current flows through
a conductor.
1
G=
R
SI unit is Siemen (S).
1 S = 1 ohm-1 (mho)
22. CONDUCTIVITY (K)
20. CORROSION
It is the reciprocal of resistivity (p).
It involves a redox reaction and formation of an 1 1 /J /J
K = = x = Gx
electrochemical cell on the surface of iron or any other p R A A
metal.
Now if /J = 1 cm and A= 1 cm2, then K = G.
At one location oxidation of iron takes place (anode) Hence, conductivity of an electrolytic solution may be
and at another location reduction of oxygen to form water defined as the conductance of a solution of 1 cm length
takes place (cathode). First Fe gets oxidised to Fe 2+ and with area of cross-section equal to 1 cm2.
then in the presence of oxygen it forms Fe3+ which then
reacts with water to form rust which is represented by 23. FACTORS AFFECTING ELECTROLY
Fe2O3.xH2O. Anode : 2Fe (s) ➔ 2 Fe + 4e E0 = + 0.44
2+ -
CONDUCTANCE
V
Cathode : O 2(g) + 4H+ + 4e- ➔ 2H2 O (I) E0 = 1.23 V
0verall R x N : preference
2Fe (s) + O (q) + 4H+ ➔ 2Fe2+ + + 2H O E0= 1.67 M

2 2 cell
Rusting of iron can be avoided by painting it or by

coating it with some other metals like Zinc. The latter
process is known as Galvanisation. As the tendency of
Zn to get oxidised is more than iron it gets oxidised in
23.1 Electrolyte CH3-COOH, NH4OH (Weak electrolytes).
An electrolyte is a substance that dissociates in The conductance of electricity by ions present in the
solution to produce ions and hence conducts solutions is called electrolytic or ionic conductance. The
electricity in dissolved or molten state. following factors govern the flow of electricity through
a solution of electrolyte.
Examples : HCl, NaOH, KCl (Strong electrolytes).
(i) Nature of electrolyte or interionic attractions : Lesser

the solute-solute interactions, greater will be the 25. MOLAR CONDUCTIVITY (Am )
freedom of movement of ions and higher will be the
It may be defined as the conducting power of all the ions
conductance.
produced by dissolving one mole of an electrolyte
(ii) Solvation of Ions : Larger the magnitude of solute- placed between two large electrodes at one centimeter
solvent interactions, greater is the extent of solvation apart.
and lower will be the electrical conductance. Mathematically,
(iii) The nature of solvent and its viscosity : Largerthe
solvent- A = Kx V, A = Kx1000
solvent interactions, larger will be viscosity and more m m
C
will be the resistance offered by the solvent to flow of
ions and hence lesser will be the electrical conductance. where, V is the volume of solution in cm3 containing 1
mole of electrolyte and C is the molar concentration.
(iv) Temperature : As the temperature of electrolytic -1

solution Kx1000 S cm
A= =
rises solute-solute, solute-solvent and solvent-solvent Units : m -3
C mol cm
interactions decreases, this results in the increase of
electrolytic conductance. = ohm-1 cm2 mol-1 or S cm2 mol-1
24. MEASUREMENT OF CONDUCTANCE 26. EQUIVALENT CONDUCTIVITY (A )

eq
1 /J It is conducting power of one equivalent of electrolyte

As we know, K = x The value of K could be known, placed between two large electrodes at one centimeter
R A apart.
if we measure I, A and R. The value of the resistance of
the solution R between two parallel electrodes is Mathematically :
determined by using 'Wheatstones' bridge method (Fig.)
Aeq = Kx v =
K x1000
A eq =
N
Where, v is the volume of solution in cm3 containing

1 equivalent of electrolyte and N is normality.
Units :
K x1000
A eq=
N -1 2 -1
-1
Ohm cm equivalent
S cm
= -3 = 2
S cm equivalent
-1
equivalent cm or
unknown resistance R2. The bridge is balanced when no
It consists of two fixed resistance R3 and R4, a variable current passes through the detector. Under these
conditions,
resistance R1 and the conductivity cell having the
R R RR
27. VARIATION OF CONDUCTIVITY AND Conductivity decreases with decrease in concentration,
MOLAR CONDUCTIVITY WITH this is because the number of ions per unit volume that
carry the current in the solution decreases on dilution.
DILUTION
1
= 3 or R = 14
2
R2 R4 R3 Molar conductivity A m = Kx V increases with decrease
in concentration. This is because the total volume V of
solution containing one mole of electrolyte also increases.
It has been found that the decrease in K on dilution of a Here, o and o are the limiting molar conductivities of
+ -
solution is more than compensated by increases in its cations and anions respectively.
volume.
Graphic representation of the variation of Am vs c 30. APPLICATIONS OF KOHLRAUSCH'S LAW
30.1 (i) Calculation of molar conductivities of
weak electrolyte at infinite dilution
For example, molar conductivity of acetic acid at

infinite dilution can be obtained from the knowledge of
molar conductivities at infinite dilution of strong
electrolyte like HCl, CH3COONa and NaCl as
illustrated below.
=l o
+ ol + l o+ l - l
o + ol
-
CH3 - COO
Na
+
J H
+
Cl
-
J +
Na Cl
-
J
o
i.e. A =A
o
+A
o
- A
o
m CH3 -COOH m CH3 -COONa m HCl m NaCl

28. LIMITING MOLAR CONDUCTIVITY (A )
The value of molar conductivity when the m concentration 30.2 (ii) Determination of Degree of Dissociation
approaches zero is known as limiting molar conductivity of Weak Electrolytes
or molar conductivity at infinite dilution. It is possible
to Am A
c
determine the molar conductivity at infinite o

in Degree of a= A m o
dilution dissociation m
case of strong electrolyte by extrapolation of curve of

Am vs c. On contrary, the value of molar conductivity of 30.3 (iii) Determination of Dissociation Constant
weak electrolyte at infinite dilution cannot be determined
(K) of Weak Electrolytes:
by extapolation of the curve as the curve becomes
almost parallel to y-axis when concentration approaches ca
2
to zero. K=
1- a
The mathematical relationship between A and Ao for
m m
strong electrolyte was developed by Debye, Huckel and Ac
Onsagar. In simplified form the equation can be given as a m
also A oo
oo =
A = A - bc
1/ 2 m
2 2
CA
c
m m
c Ac /Aoo
where
A m is the molar conductivity at infinite dilution
oo m m oom
K= 1- / oo = oo A -A
c
A
c
A A
and b is a constant which depends on the nature of the and v- anions
solvent and temperature. then its limiting molar conductivity is given by
oo
A =
o o
29. KOHLRAUSCH'S LAW

It states that the limiting molar conductivity of an
electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte. In
general, if an electrolyte on dissociation gives v+ cations
m m m m m
thermodynamic
31. USE OF �G IN RELATING EMF VALUES functions like �G can be added and emf valuescan be
OF HALF CELL REACTIONS related
through them. Consider the following three half cell
When we have two half cell reactions such that on reactions:
adding them we obtain another half cell reaction then Fe 2+ + 2e- ➔ Fe El
their emfs cannot be added directly. But in any case
m v+ + + v- -
Fe3+ + 3e- ➔ Fe E2 A cm
5. a oo
Fe3+ + e- ➔ Fe2+ E3 = Am
We can easily observe that the third reaction can be where, a = Degree of dissociation
obtained by subtracting the first reaction from the A m= Molar conductivity at a given
c
second. But the same relation does not apply on the concentration
emf values. accord 3E2 + 2El
That is, E3 1: E2 - El. But the �G values can be related ing to
the
reactio
ns.
That
is,
�
G
3
�
G
2
�
G
l
n
3
F
E
3
n
2
F
E
2
n
l
F
E
l
E
3
-
d
6. Fo electrolyte AB RT c
ra E = o
- In CA a BDb cell cell
2 2
we ca c Acm
K= = nF
ak Aoo Ammm
oo - A c
1- a
bi c d
na where, K = C D
= l
ry Dissociation E A a-2.30
Bb
32. FORMULAE 3R o
constant T g
⇒ E
o
=E
o n
R= a
A B F
b
E3 = ( / a
A p C cD d
+E
o
t
3E2 - J1 2
2El E = - 0 9
cell
= . 8
0 K
cathode 5
px 9
anode
Cell l
=E
o
leftcons
g
ues are additive only when two half cell reactions are added to give a 7. N balanced
complete tant cell reaction. In any other case we
s between emf er n
n
st where, R=
e Resistance no
E 8.
q A = Area
u c
at
of cross- Kc 0. e
section = 05 l
l
io of the
n 91
electrode
f s.
o
p= where, Kc
r
a Resistivit =
g y Equilibriu
e m
n constant.
er
K= 9 (Creterion of
al 1
. spontaneity)
el x
e
ct cel �
r l
o G
c co
o
h nst =
e
m ant -
ic R n
al F
re E
r cell o
a
ct where, K = 4.
oo
A (A B ) = x A
oo
m x y m m io Conductivity or oo
(A ) + y A (B )
y+ x-
n specific conductance oo
where, A = Molar
Kx1000
-
m
a 3. conductivity at
Am =
M infinite dilution x and
where, Am = Molar y are the number of
conductivity cations and anions
M = Molarity produced by one
of the formula unit of the
cC electrolyte on
solution.
complete
dissociation. � G = -2.303RT log K
o
r c
where, � G = Standard
o
r
Gibbs energy of the
reaction.
10. Q=Ixt
where Q
=
Qu
ant
ity
of
ch
arg
e
in
co
ulo
mb
sI
=
Cu
rre
nt
in
am
per
es
t = Time in
seconds
11. m=ZxIxt
where m = mass of
the
substan
ce
liberat
ed at
the
electro
des
Z
=
Electroche
mical
equivalent
. where E
=
Equivalen
t weight =
E/96500
STANDARD REDUCTION POTENTIALS AT 298 K. IN ELECTROCHEMICAL
H Xe0 + 2H+ + 2e- ➔ Xe0 + 3H 0 + Hg S0 + 2e- ➔ 2Hg + S02- + 0.62

3.0
4 6 3 2 2 4 4
2- -
F2 + 2e ➔ 2F + 2H 0 + 2e ➔ + 40H-
- -
+ Mn0 + 0.60
2.87 Mn0
0 + 2H+ + 2e- ➔ 0 + H 0 + 2.07 4 2 2
- -
Mn0 + e ➔
3 2 2
2- - 2- 2- + 0.56
Mn0
S208 + 2e ➔ 2S04 + 2.05 4 4
Ag + e ➔ Ag
2+ - +
+ 1.98 I2 + 2e ➔ 2I - -
+ 0.54
Co3+ + e- ➔ Co2+- + 1.81 Cu + e ➔ Cu
+ -
+ 0.52
H 0 + 2H +
+ 2e ➔ 2H 0 + - - - + 0.53
1.78
2 2 2
I3 + 2e ➔ 3I
+ -
Au + e ➔ Au + 1.69 Ni00H + H 0 + e- ➔ Ni(0H) + 0H- + 0.49
Pb4+ + 2e- ➔ Pb2+ + 1.67 2 2
2HCl0 + 2H+ + 2e- ➔ Cl + 2H 0 + Ag2Cr04 + 2e- ➔ 2Ag + + 0.45

4
1.63
2-
2 Cr0
2 0 + 2H 0 + 4e- ➔ 40H- + 0.40
Ce4+ + e- ➔ Ce3+ + 1.61 2 2
2HBr0 + 2H+ + 2e- ➔ Br + 2H 0 + Cl0-- + H 2 0 + 2e- ➔ Cl0- + + 0.36

1.60 20H
2 2 4 3
- + - 2+ [Fe(CN) ]3- + e- ➔ [Fe(CN) ]4- + 0.36
Mn04 + 8H + 5e ➔ Mn + 4H20 + 1.51 6 6
Mn3+ + e- ➔ Mn2+ + Cu2+ + 2e- ➔ Cu + 0.34

1.51
Au3+ + ➔ Au + Hg2Cl2 + 2e- ➔ 2Hg + 2Cl- + 0.27

3e- 1.40
-
Cl2 + 2e ➔
- 2Cl AgCl + e- ➔Ag + Cl- + 0.22
+ 1.36
Bi + 3e- ➔ Bi + 0.20
Cr202- +14H+ + 6e- ➔ 2Cr3+ + 7H + 1.33 2+ - +
0
7 2
Cu + e ➔ Cu + 0.16
0 + H 0 + 2e- ➔ + 20H- +
0
3 2 2
1.24 Sn4+ + 2e - ➔ + 0.15
Sn2+
0 2+ 4H 4e ➔ 2H2 0 + -
+ AgBr + ➔Ag + + 0.07
1.23 e-
Br-
Cl0- + 2H + + 2e- ➔ Cl0- + H + 1.23 Ti + e ➔ Ti3+
4+ -
0.00
0
4 3 2
MN02+ 4H+ + 2e- ➔ Mn2+ + 2H

2
0 + 1.23 2H+ + 2e- ➔ H2 0, by definition
Br2 + 2e- ➔ 2Br- + 1.09 Fe3+ + 3e- ➔ Fe - 0.04
Pu 4+
+ e ➔ Pu - 3+
+ 0 H 0 + 2e- H0- + 0H- - 0.08
➔
0.97 2 2 2
N03- + 4H + + 3e- ➔ N0 + 2 + 0.96 Pb 2+
+ 2e ➔ Pb -
- 0.13
2H 0 2Hg2+ + 2e- ➔ Hg2+ In + e ➔ In
+ -
- 0.14
2 + 0.92
Sn2+ + 2e- ➔ Sn
Cl0- + H2 0 + 2e- ➔ Cl- + 20H- + 0.89
2+ - AgI + e- ➔ Ag + I- - 0.15
Hg + 2e ➔ Hg + 0.86
Ni2+ + 2e- ➔ Ni - 0.23
N0-3 + 2H+ + e- ➔ + H2 0 + 0.80
Co2+ + - ➔ Co - 0.28
N02 2e
Ag+ + e- ➔ Ag + In3+ + 3e- ➔ In - 0.34
0.80
Hg22+ + 2e- ➔ 2Hg + 0.79 TI+ e- ➔ TI - 0.34
3+ - 2+
Fe + e ➔ Fe + 0.77 PbS04 + 2e- ➔ Pb + - 0.36
- - -
Br0 + H2 0 + 2e ➔ Br + 20H -
+ 0.76 S02-
4
Ti3+ + e- ➔ Ti2+ - 0.37 V2+ + 2e- ➔ V - 1.19

2+ 2+
TiCd+ 2e -
➔- ➔
+ 2e Ti Cd - 0.40 - 1.63
+ +3ee-- ➔Al
3+ 2+
AlIn ➔ In+ - 0.40 - 1.66
Cr3+ + e- ➔ Cr2+ - 0.41 U3+ + 3e- ➔ U - 1.79
Fe 2+
+ 2e ➔ Fe -
- 0.44 Sc + 3e ➔ Sc
3+ -
- 2.09
In3+ + 2e- ➔ In+ - 0.44 Mg + 2e ➔ Mg
2+ -
- 2.36
S + 2e- ➔ S2- - 0.48 Ce + 3e ➔ Ce
3+ -
- 2.48
In3+ + e- ➔ In2+ - 0.49 La3+ + 3e- ➔ La - 2.52
U +e ➔ U
4+ - 3+
- Na + e ➔ Na
+ -
- 2.71
0.61 Ca + 2e ➔ Ca
2+ -
- 2.87
Cr3+ + 3e- ➔ Cr - Sr2+ + 2e- ➔ Sr - 2.89
0.74 Ba + 2e ➔ Ba
2+ -
- 2.91
Zn2+ + 2e- ➔ Zn - Ra + 2e ➔ Ra
2+ -
- 2.92
0.76 Cs + e ➔ Cs
+ -
- 2.92
Cd(0H)2 + 2e- ➔ Cd + 20H- - 0.81 Rb + e ➔ Rb
+ -
- 2.93
2H2 0 + 2e- ➔ 2H + 20H- - 0.83 K+ + e- ➔ K - 2.93
Cr + 2e ➔ Cr
2+ -
- Li + e ➔ Li
+ -
- 3.05
0.91
Mn2+ + 2e- ➔ Mn -
1.18
REDUCTION
POTENTIALS IN ALPHABETICALORDER
Ag+ + e- ➔ Ag + 0.80 Ca2+ + 2e- ➔ Ca - 2.87

2+ - +
Ag + e ➔ Ag + 1.98 Cd(0H)2 + 2e- ➔ Cd + 20H- - 0.81
- -
AgBr + e ➔ Ag + Br + 0.0713 Cd + 2e ➔ Cd
2+ -
- 0.40
- -
AgCl + e ➔Ag + Cl + 0.22 Ce3+ + 3e- ➔ Ce - 2.48
Ag2Cr04 Ce4+ + e- ➔ Ce3+ + 1.61

+ 2e- ➔ 2Ag + + 0.45
Cr02-
4
AgF + Cl2 + 2e- ➔ 2Cl- + 1.36
➔ Ag + + 0.78
e- -
F
AgI + ➔ Ag + Cl0- + H 0 + 2e- ➔ Cl- + 20H- + 0.89
-
e- I- 2
0.15
Cl0- + 2H+ + 2e- ➔ Cl0- + H 0 + 1.23
Al3+ + 3e- ➔Al - 1.66 4 3 2
Au+ + e- ➔ Au + 1.69 Cl0- + H 0 + 2e- ➔ Cl0- +

20H- + 0.36
Au3+ + 3e- ➔Au + 1.40 4 2 3
2+ -
Ba2+ + 2e- ➔ Ba + 2.91 Co + 2e ➔ Co - 0.28
3+ - 2+
2+ - + 1.81
Be + 2e ➔ Be - 1.85 Co + e ➔ Co
2+ -
Bi3+ + 3e- ➔ Bi + 0.20 Cr + 2e ➔ Cr - 0.91
Br + 2e ➔ 2Br - - + 1.09 Cr202- +14H + + 6e- ➔ 2Cr3+ + 7H + 1.33
- - - -
0
Br0 + H 0 + 2e ➔ Br + 20H + 0.76 7 2
2
Cr3+ + 3e- ➔ Cr - 0.74
2
Cr3+ + e- ➔ Cr2+ - 0.41

4 Cs+ e- ➔ Cs - 2.92 Mn0- + 2H2 0 + 2e- ➔ Mn0

2 + 40H
-
+ 0.60
Cu + e ➔ Cu
+ - + 0.52 Na + e ➔ Na
+ -
- 2.71
Cu + 2e ➔ Cu
2+ - + 0.34 Ni + 2e ➔ Ni
2+ -
- 0.23
Cu + e ➔ Cu
2+ - +
+ 0.16 Ni00H + H 0 + e ➔ Ni(0H) + 0H - -
+ 0.49
F + 2e ➔ 2F - -
+ 2.87 2 2
2 2+
Fe + 2e- ➔ Fe - N0-3 + 2H+ + e- ➔ N02 + - 0.80
0.44 H20
3+ -
N0- + 4H+ + 3e- ➔ N0 + + 0.96
2H 0
Fe + 3e ➔ Fe - 0.04 3 2
Fe3+ + e- ➔ Fe2+ + N0- -+ H 0 + 2e- ➔ N0- + + 0.10
0.77 20H
3 2 2
[Fe(CN) ]3- + e- ➔ [Fe(CN) ]4- + 0 + 2H 0 + 4e- ➔ 40H- + 0.40
0.36
6 6
2H+ + 2e- ➔ 0, by definition 0 2 + 4H2+ + 4e- ➔ 2H 0 + 1.23
H 2
2 2
2H2 0 + 2e- ➔ 2H + 20H- - 0.83 - -
02 + e ➔ 02 - 0.56
2HBr0 + 2H+ + 2e- ➔ 2Br + 22H 0 + 1.60 - - -
2HCl0 + 2H+ + 2e- ➔ Cl + 2H 0 + 02 + H20 + ➔ H02 + - 0.08
1.63 2e 0H
2 2
H 0 + 2H+ + 2e- ➔ 2H 0 + 0 + 2H+ + 2e- ➔ 0 + H 0 + 2.07
1.78
2 2 2 3 2 2
-
H4 Xe06 + 2H + 2e ➔ Xe0
3 + 3H
2 0 + -
+ 0 3 + H2 0 + 2e ➔ 2 + 20H - + 1.24
3.0 0
Hg2+ + 2e- ➔ 2Hg + 0.79 Pb2+ + 2e- ➔ Pb - 0.13
2 Pb4+ + 2e- ➔ Pb2+ + 1.67
Hg2Cl2 + 2e- ➔ 2Hg + 2Cl- + 0.27 - 2-
Hg + 2e ➔ Hg
2+ -
+ PbS04 + 2e ➔ Pb + - 0.36
0.86 S04
2Hg2+ + 2e- Pt2+ + 2e- ➔ Pt + 1.20

Hg2+ + 0.92
➔ 2
Pu4+ + e- ➔ Pu3+ + 0.97
Hg2S0 + 2e- ➔ 2Hg + + 0.62
4
Ra2+ + - ➔ Ra - 2.92
2- 2e
S0 4
I2 + 2e- ➔ 2I- + Rb+ + e- ➔ Rb - 2.93

0.54
I-3 + 2e- ➔ 3I- + 0.53 S + 2e- ➔ S2- - 0.48
In+ + e- ➔ In - S 02 - + 2e- ➔ 2S02- + 2.05
0.14
2 8 4
In + e ➔ In
2+ - + - 0.40 SC + 3e ➔ Sc
3+ -
-
2.09
In3+ + 2e- ➔ In+ - 0.44 Sn2+ + 2e- ➔ Sn -
M 0.14
n0 + 5e ➔
In3+ + 3e- ➔ In - 0.34 Sn4+2 + 2e- ➔ Sn2+ +
4 Mn
+ 0.15
In3+ + e- ➔ In2+
8 - 0.49 Sr2+ + 2e- ➔ Sr -
H 2.89
K+ + e- ➔ K - 2.93 Ti2+ + 2e- ➔ Ti -
1.63
La + 3e ➔ La
3+ - - 2.52 Ti3+ + e- ➔ Ti2+ -
0.37
Li+ e- ➔Li - 3.05 Ti4+ + e- ➔ Ti3+ 0.00
Mg + 2e ➔ Mg
2+ - - 2.36 Tl + e ➔ Tl
+ -
-
0.34
+ 4H20
3+ - 2+
+ 1.51 - 0.26
4 4
2E2L4ECTROCHEMISTRY
ELECTROCHEMIST2R24Y
SOLVED EXAMPLES
Example - 1 Example - 6
Give the relationship between equivalent and molar Write the chemical equations for all the steps involved in the
conductance ? rusting of iron, Give any one method to prevent rusting of iron.
1000 1000 Sol. Anode: Fe s --➔

-
aq + 2e , E o = -0.44 V
Am = K
Molarity and Aeq = Kx Normality
2+
Fe /
Sol. +
Fe
2
Fe
x + -
Cathode : 0 g + 4H aq + 4e --➔ 2H 0,
2 2
Am E o = 1.23V
H+ / 02 / H 2 0
Normality
Aeq = Molarity 0verall reaction
Example -
Fe(s) --➔ Fe2+ (aq) + 2e- ] x 2
2
Can nickel spatula be used to stir a copper sulphate
solution ? 0 (g) + 4H+ + 4e- --➔ 2H 0
2 2
Support your answer with a reason
= -0.25 V, E = +0.34 V.
o o
E
Ni 2+
/ Ni Cu2+ / Cu 2Fe
o
+ 0 + 4H+(aq) --➔ 2Fe2+ + 2 H 0 = 1.67V
E
2 2 cell
=E - E
o o o
Sol. E
cell cathode anode
Further 4Fe2+(aq) + 0 (g) + 4H 0(I) --➔
Eo = E - = +0.34 V - = +0.59 V 2 2
o o
E -0.25
cell Cu2+ / Cu Ni2+ / Ni
2Fe2 30 + 8H+(aq)
o
As E is +ve, �G = - ve, because �G = - nEo F, i.e, Fe 0 + xH 0 --➔
cell 2 3 2
reaction will take place. Therefore, we cannot stir a Fe 0 . xH 0

2 3 2
copper sulphate solution with nickel spatula. Hydrated ferric oxide (Rust)
Example - 3 Galvanisation is used to prevent rusting of iron.
State two advantages of H2-02 fuel cell over ordinary Example - 7
cell.
Sol. The two advantages of H2-02 fuel cell over ordinary The following chemical reaction is occurring in an
cell are : electrochemical cell.
(i) They do not cause any pollution. Mg(s) + 2 Ag+ (0.0001 M) --➔ Mg2+ (0.10M) + 2Ag(s)
(ii) They have high efficiency of 60-70%. The Eo electrode values are
Example - 4 Mg2+ / Mg = - 2.36 V
What is galvanisation ? Ag+ / Ag = 0.81 V
Sol. The process of coating zinc over iron is called For this cell calculate/write
galvanisation. (a) (i) Eo value for the electrode 2Ag+/2Ag.
Example - 5
(ii) Standard cell potential Eocell
.
Which type of a metal can be used in cathodic protection
(b) Cell potential
of iron against rusting ? (E)
cell
Sol. A metal which is more electropositive than iron such as (c) (i) Symbolic representation of the above cell.
Al, Zn, Mg can be used in cathode protection of iron (ii) Will the above cell reaction be spontaneous ?
against rusting.
= 0.81V
o
Sol. (a) (i) E +
Ag / Ag
Mahesh Tutorials Science
(ii) Eo = E o +E
o
Cathode : Ag+ (aq) + e- --➔ Ag s

cell cathode anode
= Eo +
+ o = 0.81 + (c) Ag electrodes
Ag I Ag Mg I Mg+2
E 2.36
Anode : Ag(s) --➔ Ag+ (aq) + e-
E ocell = 3.17 V
Cathode : Ag+ (aq) + e- --➔ Ag(s)
(b) At anode : Mg --➔ Mg2+ + 2e-
Example - 9
A cathode : Ag+ + e- --➔ Ag ]x2
Mg + 2Ag+ --➔ Mg2+ + Explain Kohlrausch's law of independent migration of
2Ag ions. Mention one application of Kohlrausch's law.
Sol. Kohlrausch's law of independentmigrationof ions: The

l
Ecell = Eo lo 2+ molar conductivity of an electrolyte at infinite
cell -
0.059 Mg
g l l dilution is the sum of the individual contributions
n J
+
of the anion and cation of the electrolyte.
Ag
lJ 2
0.059 0.1
= 3.17 - log A =v
0 0
+v
0
2 + + - -
2 10-4 0 0
where, and are the limiting molar
+ -
= 3.17 - 0.0295 log 107 conductivities of the cation and anion respectively
= 3.17 - 0.0295 x 7 = 3.17 - and v+ and v- are the number of cations and anions
0.21 formed from a formula unit of the electrolyte. For
example, one formula unit of Al (SO ) gives two Al3+
Ecell = 2.96 V
2 43
(c) (i) Mg I Mg2+ (0.1 M) IIAg+ (0.0001M) I Ag ions and three sulphate ions. Therefore,
(ii) Yes, as the cell potential is positive. =2
A om Al2 (SO4 3 +3
o o
Al3+ SO42-
Example - 8
Application : It can be used to determine molar
(a) Current of 1.50 A was passed through an electrolytic conductivity of weak electrolytes at infinite dilution :
cell containing AgNO3 solution with inert electrodes. Consider acetic acid as the example of a weak electrolyte.
The weight of Ag deposited was 1.50g. How long did A om CH3 COONa = o
+ o
CH3COO- Na+
the current flow ?

A om = o + o
HCl H+ Cl-
(b) Write the reactions taking place at the anode and
A = +
o o o
cathode in the above cell if inert electrodes are

used.
m NaCl Na+ Cl-
(c) Give reactions taking place at the two electrodes if
From (i) + (ii) - (iii) we
these are made up of Ag. get
o
+ o
+ o
+ o
- o
- o
Sol. (a) According to Faraday's first law, charge required CH3COO- Na+ H+ Cl- Na+ Cl-
=
o
+ =A
o o
to deposit 1.50 g.
CH3COO- H+ CH3COOH
96500 Example -
Ag = x1.50 = 1331.70
coulombs 108 10
(b) Inert electrodes

1331.70
Time taken = =
893.5s
1.50
Lakshya
Educare
The electrical resistance of a resistivity, conductivity and molar conductivity.
column of 0.05 mol L-1 NaOH
solution of diameter 1 cm Sol. A = r2 = 3.14 x 0.52 cm2 = 0.785 cm2 = 0.785 x 10-4 m2,
and length 50 cm is 5.55 x I = 50 cm = 0.5 m
103 ohm. Calculate its -
Anode: 2H O /J --➔O + + aq + 4e
g 4H
2 2
Mahesh Tutorials
Science
p/J RA 5.55 x10 0 x 0.785
R= p= = 3
=
or Example - 13
A /J 50 cm
= 87.135 0
cm The conductivity of 0.0011028 mol L-1 acetic acid is
m A
o
1 ( 1 4.95 x 10-5 S cm-1. Calculate its dissociation constant if
1
- -
Conductivity = K = = S cm 1 = 0.01148 S cm 1
p 87.135 for acetic acid is 390.5 S cm2 mol-1.
Kx1000 K
-5
4.95x10 Scm
-1
1000 cm
3
A= Am = = x
Molar conductivity, m Sol -1
c c 0.001028 mol L L
-1 -1
.
0.01148 S cm x1000
3
cm L
= 0.05 mol L
-1
= 229.6 S cm2 mol-1 = 44.88 S cm2 mol-1
Example - -1
Am
2
11 44.88 Scm mol
a= = = 0.115
The measured resistance of a conductance cell containing A mo 390.5 Scm mol
2 -1
7.5 x 10-3 Msolution of KCl at 25oC was 1005 ohms.

Calculate 0.115 2
-1
(a) specific conductance (b) molar conductance of the ca2 0.001028 mol L
solution. Cell constant = 1.25 cm-1. x
K= =
1- 0.115
1
Sol. Specific conductance K = Rxcell constant a
= 1.65 x 10-5 mol L-

1
1
= -1 -1 -1
10050 x1.25 cm = 0.0012440 cm Example -
14
Molar conductance Kx1000 A cell is prepared by dipping copper rod in 1 M copper
A m = Molarity sulphate solution and zinc rod in 1 M zinc sulphate
solution. The standard reduction potentials of copper and
zinc are
-1 -1 -1
0.001244 0 cm x1000 cm L
3
0.34 V and - 0.76 V respectively.
= -3 -1
7.5x10 mol L
(i) What will be the cell reaction?
-1 -1
= 165.87 0 cm mol .
2
(ii) What will be the standard electromotive force
(EMF) of the cell ?
Example - (iii) Which electrode will be positive ?

12 (iv) How will the cell be represented ?
A m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S
Sol. (i) The cell reaction can be
cm2
mol-1 respectively. Calculate A0m for HAc. Zn + Cu --➔
2
+ Cu
+ 2+
Zn
Sol. 2+ 2+
A
0
= +
o o
= +
o o
+ +
o
-o -o or Cu + Zn --➔Cu + Zn
o
m HAc H+ Ac H+ Cl- Ac- Na+ Cl- Na+

The EMF comes out to be positive for the 1st reaction.
=A +A -A
o o o
Hence, the cell reaction is
m HCl m NaAc m NaCl
mol-1
= (425.9 + 91.0 - 126.4) S cm2
2+ 2+
Zn + Cu --➔ Zn + Cu
= 390.5 S cm2 mol-1. o
= Eo + Eo = Eo + Eo
(ii) E
cell cathode anode Cu 2+
I Cu Zn I Zn+2
= 0.34 + 0.76 = 1.10 V

(iii) reduction takes place on copper electrode. Hence
it is positive
(iv) Zn I Zn2+ (1 M) II Cu2+ (1 M) I Cu
Example - 15 Example - 17
Represent the cell in which the following reaction takes Calculate the potential (emf) of the cell
place
Mg(s) + 2Ag+ (0.0001 M) ➔ Mg2+ (0.130 M) + 2 Ag Cd ICd2+ (0.10 M) IIH+ (0.20 M) IPt,
2
H (0.5
9 (s) atm)
o
Calculate its = 3.17 (cell)
if E cell
(Given Eo for Cd2+ / Cd = - 0.403 V, R = 8.14 JK-1 mol-
E V. 1
, F = 96,500 Cmol-1).
Sol. The cell can be written as Mg I Mg2+ (0.130 M) II Ag+
Sol. The cell reaction is
(0.0001 M) IAg
Cd + 2H+ (0.20 M) ➔ Cd2+ (0.10 M) + H (0.5 atm)
2
Eo = RT 2+
E - In l =o 2.303 log l Mg E =E
o o
- E
o
=0
2+ E -
RT lJ
Mg
lJ
cell cell
nF l Ag
+
cell l Ag
+
cell H+ /1/ 2H 2 Cd2+ / Cd -(- 0.403) = 0.403 V
2F
lJ
lJ 2
0.059 V Applying Nernst equation to the cell reaction,

= 3.17 V - 0.130 2.303 RT
+
lCd2 l x P
log
E = - J
2 0.0001 2 o log H2
cell
E cell
nF +
l H lJ 2
= 3.17 V - 0.21 V = 2.96 V
2.303x8.314 x 298 0.1x
Example- 16 0.50.403 -
= log
2 x 96, 500
2
0.2
A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt
= 0.403 - 0.003 = 0.400 V
is 95% dissociated at this dilution at 298 K. Calculate the
electrode potential = -0.76 V . Example - 18
E oZn 2+
/ Zn
Sol. The electrode reaction written as reduction reaction is Calculate the equilibrium constant of the reaction
Zn + 2e ➔ Zn (n =
2+ -
Cu (s) + 2Ag+ (aq) ➔ Cu2+ (aq) + = 0.46 V
cell
2)
2Ag(s) Eo
Applying Nernst equation, we get E
Sol.
o 0.059 V = 0.46 V
cell = log Kc
2
E 2+
= 0.0591 12+ 0.46 Vx 2

Zn / Zn
o
Zn 2/ Zn - 2 loglZn l or log K = = 15.6 ⇒ K = Antilog 15.6
E J c c
0.59 V
As 0.1 M ZnSO4 solution is 95% dissociated, this Kc = 3.92 x 1015

means that in the solution,
Example - 19
+
lZn 2 l
J = 95 Calculate the standard free energy change and maximum
x 0.1M = 0.095
work obtainable for the reaction occurring in the cell
M
100
EZn 0.0591 1 (Daniell cell).
= -0.76 -
2+
/ Zn
log
2 0.095 Zn (s) I Zn2+ (1 M) II Cu2+ (1 M) I Cu (s)
= -0.76 V, E
o o
[Given E
= - 0.76 - 0.02955 (log 1000 - Zn2+ / Zn Cu2+ / Cu
log 95) -1
= + 0.34 V, F = 96, 500 C mol ]
= - 0.76 - 0.02955 (3 - 1.9777) Also calculate the equilibrium constant for the reaction.
= - 0.76 - 0.03021
= - 0.79021 V
Sol. (i) Eo = E + = 0.34 + 0.76
o o
E
cell Cu 2+
/ Cu +2
Zn / Zn
= 1.10 V
The reaction taking place in the Daniell cell (ii) 52 g of Cr is deposited by electricity = 6 x 96500 C
6 x 96500
is Zn(s) + Cu2+ (aq) �- -�- Cu(s) + 1.5 g require electricity = x1.5 C = 16071C
52
Zn2+ (aq)
Time for which the current is required to be passed
For this reaction, n = 2 16071.9
= = 1336 s.
o
�Go = - nFE
cell
=-
2x 12.5 A
965
00 E
C x
mol- a
1
x m
1.10 p
V l
e
=- -
212 2
300 2
CV
mol
-1
=-
212
300
J
mol-
1
(1
CV
=1
J)
=-
(a) Calculate the
212.300
kJ mol-1 equilibri
Thus, the um
maximum work that constant
can be obtained
for the
from the Daniel cell
= 212.3 kJ. reaction
Cd2+
(aq) +
Zn(s)
--➔
Zn2+
(aq) +
Cd(s)
= -0.403 V
o
c c (ii) �GIfo E Cd2+ / Cd
= - RT In
K=-
2.303 RT
log K
c
- 2.303 x 298
212300 = - x x log
K
o = -0.763 V S
Zn2+ / Zn E o
or log K l
212300
.
= 37.2704
c
(
2.303x a
8.314
x 298 )
E
K= (b) When a current of o
Antilog c 0.75A is passed =

37.2074 = through a CuSO4
1.6 x1037 solution for 25 E
o
min, 0.369 g +
Example - 20
of copper is
Calculate the deposited at E
o
equilibrium the cathode. =

constant, Kc for Calculate the
the reaction. -
atomic mass 0
3Sn4+ of copper. .
+ 2Cr 4
(c) Tarnished silver 0
➔ contains Ag2S. 3
3Sn2+ Can this tarnish
+
be
+ removed by 0
2Cr3+ placing .
7
Give tarnished
6
n Eo silver ware in 3
= an aluminium
0.88 =
pan containing
5 V.
an inert 0
electrolytic .
0.059 3
E = solution such 6
as NaCl. The 0
standard V
electrode cell c
log K 6
potential for a
c 0
half reaction =. (
S
o
c
n
o e n Ag S(s) + 2e- E
l
ll
l --➔ 2Ag
o
o
. g (s) + S2- is
K 1
c -0.71V
,
n (
= 2
x
6 0.
2
3
0.885 and for 6
= Al3+ + 0
0.059 3e- 1
--➔ K= = 1 21
x 10
log K 2Al (s)
c Ant Exa
6 is - 1.66 ilog mpl
c V 90 e-
As =
0 0.059
.
log Kc 0
= cell 5
9
Chromium metal ( 0.720 1

= =
can be plated out
12.20
from an acidic 0.059
solution
containing CrO3 K= c
antilog
according to the
(12.20) =
following equation 1.585 x
CrO3 (aq) + 6H+ 2 1012
(aq) + 6e- ➔ Cr
(b) M = Z I t
(s) + 3H O
Calculate (i) how
x
many grams of 0.369 = x
chromium will be 0.75x 25 x 60
plated out by 2x
24,000 coulombs 965
and (ii) how long 00
will it take to plate
(x =
out 1.5 g of molar
chromium by using mass
12.5 amp current ? of
(At. mass of Cr = copper
)
52).
x = 63.3
Sol. (i) 6 x 96, 500
g/mol
coulomb deposit Cr = 1
mole = 52 g
24,000
coulomb
deposit Cr =
52 x 24000
g=
2.1554 g
6 x 965000
(c) Example - 24
E ocell for reaction of tarnished silver ware with
aluminium pan is (- 0.71 V) + 1.66 V i.e., + 0.95 V
(a) Depict the galvanic cell in which the following
Tarnished silver ware, therefore, can be cleaned by reaction takes place
placing it in an aluminium pan as Eocell is positive. Zn (s) + 2Ag+ (aq) --➔ Zn2+ (aq) + 2Ag (s)
Also indicate that in this cell
Example - 23
(a) Calculate the standard free energy change for the (i) which electrode is negatively charged.
following reaction at 25oC.
(ii) what are the carrier of the current in the cell.
Au (s) + Ca2+ (aq, 1M) --➔ Au3+ (aq, 1M) + (iii) what is the individual reaction at each electrode.
Ca(s)
(b) Write the Nernst equation and determine the e.m.f. of
the following cell at 298 K
E oAu 3+
= +1.50 V, o = -2.87
/ Au Ca2+ / Ca
E V Mg(s) IMg2+ (0.001 M) IICu2+ (0.0001 M) ICu(s)
Predict whether the reaction will be spontaneous or
(Given Eo = -2.375 V, Eo = +0.34 V )
not at 25oC. Which of the above two half cells will Mg
2+
/ Mg
2+
Cu / Cu
act
as an oxidizing agent and which one will be a Sol. (a) Zn I Zn2+ (conc.) II Ag+ (conc) I Ag
reducing agent?
(i) Zn electrode is negatively charged.
(b) The conductivity of 0.001 Macetic acid is 4 x 10 -5
(ii) Current carriers of cell are
S/cm.
- electrons in external wire
Calculate the dissociation constant of acetic acid, if
- Zn2+ ions in anodic half cell.
A omfor acetic acid is 390. 5 S cm2/mol.
Sol. (a) Eocell = (- 2.87 V) - (1.50 V) = - 4.37 V - Ag+ ions in cathodic half cell.
- Ions of salt bridge, i.e., K+ and Cl-.
� o
cell
= - 6 x 96500 x - 4.37 V = + 2530.230
2+ -
G kJ/mol (iii) At anode Zn --➔ Zn + 2e
Since �r Go is positive, reaction is non-spontaneous. + -
At cathode 2Ag + e --➔ 2Ag
Au3+/Au half cell will be a reducing agent, Ca2+/Ca
+ -
half cell will be an oxidising agent. (b) Mg --➔ Mg 2 + 2e
2+ -
Cu + 2e --➔Cu
(b) A = K 1000
c
m
x molarity 2+ 2+
Mg + Cu --➔ Cu + Mg
K = Specific conductance
Nernst equation
-5
4 x10 S/ cmx1000 2 -1
= 0.001 = 40S cm mol +
0.059 l Mg2 l
J
Am E cell = o
- log +
a= =
cell
n l Cu2 l
E J
m 40 =
Ao 390.5 0.103
0.059 2+
l Mg l
E = E
o
+o - log J
E
+
l Cu2 l
2
Ca 0.001x 0.103 2 J
cell Cu2+ / Cu Mg / Mg+2
-5
2
Kc = 1- = 1.19 x10
= 1- a
0.103
-3 For strong electrolytes, the number of ions do not

0.059 10 increase appreciably on dilution and only mobility or
= 0.34 + 2.37 lo
5- ions increases due to
2 g decrease in
interionic
-4
attractions.
Therefore, Am
increases a little as
shown in graph by a
= 0.34 + 2.375 5
- 0.0295 log 10
E
V
c
Example - 25
e
l (a) Define molar

l
conductivity of a
substance and
describe how
= weak and strong
electrolytes' molar
conductivity
2 changes with
. concentration of
solute. How is
6
such change
8 explained ?
5
5
E
c
2
.
6
8
Cu
2+ l +l 2
l l
+
straight line. A J
log J g
For weak (E (a o
=
electrolytes, q) cell
Here, o = 0.46 V, n = 2
the number of + 0 ce
ll
ions as well as 2e .
mobility of 4
At 6
ions increases ca
on dilution V
th
which results ) E
od Sol. Molar Am It may be
in a very large
e Conductivity [Ag+] = 0.001M = 1 x 10-3
increase in defined as the
M, [Cu2+] = 0.1 M
molar 2
conductance of a
conducvity A solution containing 1 E = 0.1
especially near g+ mole of 0.46 -
infinite (a electrolyte such that 0.0591
dilutuion as q) the entire solution is
log
shown by placed in
+ cell
curve in the between two 2 2
2e 10-3
figure. electrodes one
- centimetre apart.
At
-
ano 0.0591
Ecell = 0.46 - log 10 =
5
de C ➔
0.0591
u(s) 0.46 - x 5 log 10
2 2 2
-
A Ecell = 0.46 -
-
g( 0.0591 x 2.5 x
➔ 1 = 0.46 -
s)
Cu2 0.14775 =
0.31225V
(b) A + aq aq +
voltaic Ecell = 0.312 V
2 - 2Ag
cell Example - 26
A - s
isset
A (a) State the
up at g ➔ relationshi
25 oC
+
Cu
2+ p amongst
cell
with constant of
the cell,
resistance
followi of the
ng half solution in
k x1000 the cell and
cells A= conductivit
Ag+ y of the
(0.001 solution.
M) How is
IAg molar
and2+ conductivit
Cu
(0.10 y of a
M) I solute
Cu related to
the n conductivit
W
o
Here ofcell-
voltage E = y of its
hat , ?0
this cell E solution ?
wo .
cell
0 (b) A voltaic
uld 5 cell is set
be 9 up at 25oC
1
v r the cathode
o i reactions and
l t the overall
Al IAg t
M) and Ni I Ni a e reaction
(0.50 M) g occurring in
Calculate the cell
m
e t a lead
o
= -1.66 hE = -0.25 V, storage
Ni+2 INi J
E battery while
MIAl
Vl e
operating.
l a (b) A voltaic cell
o
n is set up at
o 25oC with the
Molar
conductivity d half-cells Al
1( I e K= x
increases I Al3+ (0.001
with 1
M) and Ni
decrease in Sol. (a) a
RA INi2+ (0.50
concentration n
or increase in M). Write the
dilution as d equation
number of M for
ions as well genrates an
as mobility elec
of ions tric
increased curr
with dilution. ent
and
whe
dete
re, Example
rmi
K= - 27
ne
Con the
duc (a) W
cell
tivit ha pote
y t ntial
ty .
1
= Cell pe where, Am Solution
constant A
of = Molar
R= a
conductivit
Resistance cel
l y
K is K
x1000
A= m th =
e C
lea on
d du
sto cti
vi
ra
ty
ge
ba M
tte =
M
ry ola
? rit
W y
of
2 4
(Given w +
(aq)
Eo h
e --➔ -
= -0.25 n -
2Al3+ (aq) +
V, E ➔
t Ni(s)
= h Pb
e
-1.66V) S
. Ni2+ I Ni Al3+ I Al O4
b
s
So a
t +
l. 2
t
e H2
(a O
) r
y /J
T
he 2 4 Over
le i all
ad s
cell
st
i reacti
or
ag n on
e Pb(s)
ba u
s + 2H
tte
ry e SO
is (aq)
a a
r --
se
co e ➔
nd
ar PbSO4(s) + 2H2O( /J )
0.0591 l
y A (b) 2A +2
+3
3
ce l+
ll. l2
l I (s) + 3Ni (aq) ➔ (aq)
cell = - o
The E cell cell
reactions o 3Ni (s) +

given g 2Al
(b A- a
below aq
q Pb +-
) l - --
A s➔ Ats + ➔ 2e
J
anode
SO
t Al + 2- PbSO
s
a 3+ n
n 3
o e lNi
+
l
2
3
d ]
e x E = 1.41 V
J
2
4 4
-
At cathode Ni2+ (aq) + 2e o
--➔ Ni s ]x 3 cell
At cathode
Here, n = 6, .41
PbO- s [Al3+] = 0.001 M 0.0591
2e E
= 1 x 10-3 M, [Ni2+] ce 6
l (s) = ll
+ 0.5M =
2
A 3Ni 2
1
-3 log I l
l(10 ) l 2
( 0.5)
3 - 0.44 V).
J
o Ecell 1
= E = SK = x
1. = 1.46 V o Cell constant (G)
0.05
o
41 0. E 1 l Resistance R
0 91
= -6 Example -
V l (a) Express the .
5 0 1. 28
o lo
9 -3 4
g 2 g relationshi
= 1 1 6 p amongst (
1. 6 0- cell a
41 . 0.1 constant, )
V 5 25
-
C
3 o
= = 1.41- resistance of n
1. 0.0591 the solution d
41 log10 +
-6 in the cell u
- 3 and c
0. log 2
conductivity t
05 i
91 v
i
lo
t
g y
10
-6
K x1000
x8 A = , At cathode Ag+(aq) +
6 of e- --➔ Ag(s)] x 2
where, A
the solution. How is molar Zn(s) +
conductivity of a solute conductivity 2Ag+ (aq)
related to conductivity of m
M --➔
its solution. Zn2+ +
0.0591 2Ag(s)
= 1.41- (b) the
Calculate
-6 log10 0.0591
+ 3log 2 equilibrium
constant for
= 1.41-
the reaction. (b) Fe(s) + 2+
0.0591 [Zn
-6 + 3 x 0.3010 Cd2+ (aq) E ]
- log
6
�- - �-
=
Fe2+ (aq) +
6 Fe s
2+
Cd(s)
+ Cd cell
+
0.0 E aq l Ag lJ 2
59 log o
cell
1 k
�- -
0.3 �- n n
01 c
0.
2 2+ Here, n = 2,
Fe
He 0 [Zn2+] = 1 M
aq + re, 5
Cd s n=9
= 1.41 - -5.097 = 1.41+ 2 o E
o
+E
o
= 0.80V +
6 0.76V
o
( o E = -0.40 V, E cell = Ag+
=E
Cd 2+
ICd o
6 G E / Ag Zn /
iv +2
+E
o Zn
= e
cell
n Eo = 1.56 V
1 E cathode
.
anode
4 cell
+ = E Cd
o o
1 2+
E / Cd
Fe /
Fe+2
+
= - 0.4 + 0.44 1
1.48 it related to +
log1 - log l Ag
l
0.0591 conductivity of the
related solution? l 2 = 2.7072
2 J
A +
(b) One half-cell in a 0 - 2 log l Ag lJ
g
+ voltaic cell is = 2.7072
constructed from a +
silver wire dipped log l Ag lJ
l
in silver nitrate = -1.3536 =
J solution of 2.6464
2 unknown
o +
= 0.04 V E concentration. Its l Ag l =
= AntiJ -2
other half-cell log 4.43x10
log k = - 2.6464
consists of zinc M
2 0
x electrode dipping in l Ag l =
+
0 . J
. Exa
0 1.0 M solution of 0.044 M
4 0 mpl
= Zn(NO3)2. A voltage of e-
8
0 1.48 V is measured for 30
.
0 =
8 this cell. Use this
information to
-
0 calculate the
. concentration of silver
0 nitrate solution used.
5 (a) Corrosion is
(E = -0.76 V, o = essentially an
9
E
Zn2+ / Zn
+0 electrochemical
1 Ag
phenomenon.
S .80
V) Explain the reactions
l ol
occurring during
o .
corrosion of iron
g kept in an open
1 atmosphere.
c 2 (b) Calculate the

equilibrium constant
l Ag for the equilibrium
0.059
reaction.
0.059 (a) Molar conductivity
Fe s + aq + Cd s
log kc = Am It may be defined 2+
Cd aq
1 = 2.7072
1.3536 l =
as the �-
o l 0. = 2.7072
- �-
kc = Antilog 16
gA 0 Fe
2+
1.3536 g
+
. conductivity of one
kc = 22.57 0
l
J 5 molar electrolytic =
o
(Given E
9
-0.40 V, E =
o
2 1 solution placed
between two electrodesCd2+
/ Cd -0.44V)
Fe2+
/ Fe
Example - y
29 one centimetre apart
. Sol. (a) At anode Oxidation
and have enough area
H of Fe atoms takes place
(a) Defin of cross section to hold
o o
e the entire volume.
w
term K
molar A =
i m
condu c
s w here , Con
ctivit
2 2 3
ductivity E=
-0.4
F
4V
e2
+
/
F
e
c At cathode
Reduction
=
of oxygenin
C the
o presence of
n
c H+ ions. The
e H+ ions are
n produced
t by either H
r
a O or H CO
t (formed by
i dissolution
o
of CO2 in
n
moisture)
o
f
s
o
l
u
t
i
o
n
i
n
m
o
l
L
-
1
(b) At
anod
e
Zn s
--
➔
2+
Zn
aq +
-
2e
+ -
2H aq + 2e --➔
Example - 31
2H
1
2H + O g --➔
Two half cell reactions of an electrochemical cell are given
H O below
2 2
2
Net reaction at cathodic area MnO4 aq + 8H+ aq + 5e- ➔ Mn2+
-
+
2H 1 aq + 4H O /J , E = 1.51V
o
-
aq + O 2 + 2e --➔2 2
2 H O
Sn2+ (aq) ➔ Sn4+ (aq) + 2e-, Eo = + 0.15 V
= 1.23
o
E
Construct the redox equation from the two half cell reactions
V
H +/ O2 / H2 O
The overall reaction and predict if this reaction favours formation of reactants
1 or product shown in the quation
+ 2+
Fe s + 2H aq + O g --➔ Fe aq + H O /J
- + - 2+
2 2 2 Sol. Atcathode MnO 4 aq + 8H + 5e --➔Mn
= 1.67 V aq + 4H2 O /J ]x 2 E = +1.15V

o o
E cell
The ferrous ions are further oxidised by atmospheric At anode Sn2+ -

aq + 2e ]x 5 Eo = + 0.15 V
4+
oxygen to ferric ions which come out as rust in the --➔Sn
form Overall reaction
of hydrated ferric oxide (Fe2O3 . 2MnO4 aq + 5Sn2+ aq +16H+ aq --➔
xH2O). - 2+
2Mn
(b) Fe(s) + Cd2+ (aq) �- -�- Fe2+ (aq) +
Cd(s) (aq) + 5Sn4 (aq) + 8H2 O /J
= o
o
E Sn Sn2+ / Sn 4+ = -0.15V
o
4+
/ Sn2+ -E
E cell
log kc= n E cell = Ecathode - Eanode =
o o o o
- 2+ - o
0.059 MnO4 / Mn
E
Sn4+ / Sn 2+
E
= 1.51 - (- 0.15)
Here, n = 2
E = 1.66 V
o
cell
=E
o o o
E - As E is +ve therefore the reaction will take place in
o
E
cell cathode anode cell
forward direction, i.e., favours the formation of products.

= Eo Cd 2+
/ Cd
- Eo Fe 2+
/ Fe
= -40 - -0.44 Example - 32
(a) Account for the following
Eocell = 0.04V
(i) Alkaline medium inhibits the rusting of iron
2 x 0.04 0.08 (ii) Iron does not rust even if the zinc coating is broken
log kc = = in a galvanized iron pipe.
0.059 0.059
(b) Cu2+ + 2e- ➔ Cu ; Eo = +
0.34 V
log kc = 1.3536 Ag+ + e- ➔Ag; Eo = + 0.80 V
kc = Antilog 1.3536 (i) Construct a galvanic cell using the above data.
(ii) For what concentration of Ag+ ions will the emf
kc = 22.57 of the cell be zero at 25oC, if the concentration of
Cu2+ is
0.01
M?
[log
3.919
=
0.593]
Sol. (a) (i)

T
h
e
al
k
al
in
it
y
of
th
e
so
lu
ti
o
n
pr
e
v
e
nt
s
th
e
a
v
ai
la
bi
lit
y
of
H
+
io
ns
.
(ii) Zinc is more electropositive than iron. 3. These cells are light in weight as compared
Therefore, zinc coating acts anode and the to electrical generators to produce
exposed iron portions act as cathode. If corresponding quantity of power.
zinc coating is broken, zinc undergoes 4. It is a continuous source of energy if the
corrosion, protecting iron from rusting. supply of gases is maintained.
No attack occurs on iron till all the zinc is
(b) Mass of silver deposited
corroded.
(b) At anode Cu ➔ Cu2+ + 2e- m = z I t.
At cathode [Ag+ + e- ➔ Ag] x 2 108 x 0.5 x 2
= 96500
Cu x3600
+2
Ag+
➔
Cu2+
+
2Ag
m=
4.029
Cell g
represent
ation d= m
C
u ⇒
v
I =
m
C
v
u
2
+
V=
4.029
( =
c 0.383
o 7 cm
3
n
c
.
)
I
I
A
g
+
(
c
o
n
c
.
)
A
g
+
lCu 2 l
E =E J
o
59
-.
0 log
0
7
cell
l Let the
cell
Ag thicknes
+
n s of
l 2 x
J silver
deposite
d be x
cm. 1
Ax x 0
O= ⇒
-
(0.8 V
0- x= 9
0.34
-
)0.05
9 M
l
log
0.01
l
[
2 l I x2 A A
J
x g
1
=
5 +
0
. .
3 ]
5 8
9 3
7
5
0 =
= 0
l
1
o
g .
( 5
0 9
.
7
0
1
1
x2= 7.67 x 10-4 cm. x
- 34 x
1
sons for the following
of iron is quicker in saline water than in ordinary water. 0
= with 0.1 M KCl solution is 100 ohm.If the resistance of the same cell
ce of a conductivity cell filled - when filled with 0.02 M KCl solution is 520 ohms, c
dinary cell.
tivity of 0.1 M KCl solution is 1.29 Sm-1).
sel of total surface area 500 cm2 by passing a current of 0.5 amp for two hours. Calculate the9 thickness of silver deposited.
c mass of silver = 108 amu, F = 9,500 C mol-1]
1 M
.
9
Sol. (a) (i) It is because
in saline
Sol. (a) Advantages water, there
Fuels Cells:
is more H+
1. It is a ions. Greater
pollution- the number of
free
device H+ ions,
since no quicker the
harmful rusting.
(ii) Due to
higher
reduction
potential
of
hydrogen
we get
hydrogen
at cathode.
products K =1
are (b)
formed.
x
2.This is c
e
very l
l
efficient c
o
cell. Its n
s
t
efficiency a
n
is about t
R
75%
⇒ cell constant =
which is
Kx R
considera
= 1.29
bly higher Sm-1 x
than 100
conventio ohm
nal cells. =
129
m-1 =
1.29
cm-1
For second solution o o o

E =E +E
cell cathode anode
1
K = x cell constant
R = 0.76 - 0.40 = 0.36 V
1 -3 -1
K = x1.29 = 2.48x10 S cm 0.0591
520 E = Eo - log Q
cell
Kx1000 n
Am =
M +
0.0591 l Zn 2 l
= 0.36 -
2 log ICd +2 l
-3
2.48x10 x1000
=
248 = J
0.02 2
-1
A = 124 S cm mol
2
m 0.0591 l 0.1 l
= 0.36 -
2 log I 0.01 l = 0.33V
J
hy electrolysis of aqueous solution of NaCl gives H 2 at cathode and Cl2 at anode. Write overall
Example - 36
Three iron sheets have been coated separately with three metals A, B
o
E= -2.71 V; Eo = - 0.83 V, EoCl 2 / 2Cl- = metalABCiron
( Na+ / Na H2 0 / H2
+1.36 V; EoH+ + 02 / H20 = 1.23 V)
EoValue - 0.46 V -0.66V -0.2

(b) Calculate the emf of the cell of Zn / Zn2+ (0.1 M) II Cd2+
(0.01 M) / Cd at 298 K,
Identify in which case rusting w
[ Given EoZn2+ / Zn = -0.76 V and EoCd2+ / Cd = - 0.40 V] coating is damaged.
Sol. As iron (-0.44V) has lower standard reduction potential

Sol. (a) Because of higher reduction potential of water, water is
than C (- 0.20V) only therefore when coating is
reduced in preference to sodium at therefore instea of
broken, rusting will take place faster.
deposition of sodium metal, hydrogen is discharged at
cathode.
H20 /J - -
+ 2e g + 20H
--➔H 2
-
2Cl --➔Cl
2
g
H20 /J + 2Cl- g + Cl2 g + 20H-

--➔ H 2
At anode Cl2 gas is liberated because of overpotential

of oxygen.
2+ -
Zn --➔ Zn + 2e lI
(b) 2+ - � Half cell reactions

Cd + 2e --➔ IJ
Cd
Zn + Cd2+ ➔ Zn2+ + Cd} cell reaction

2E3L6ECTROCHEMISTRY
ELECTROCHEMIST2R36Y
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Basics of electrochemical Cell 7. Adding powdered Pb and Fe to a solution containing 1.0 M
2+ 2+
1. Which of the following has been universally accepted as a is each of Pb and Fe ions would result into the formation
+2 +2
reference electrode at all temperatures and has been of (E0 Pb /Pb = - 0.13V, E0 /Fe = -0.44V)
Fe
assigned a value of zero volt ? 2+
(a) More of Pb and Fe ions
(a) platinum electrode (b) copper electrode 2+
(b) More of Fe and Pb ions
(c) graphite electrode (d) standard hydrogen electrode 2+ 2+
+ -
(c) More of Fe and Pb (d) More of Fe and Pb ions
2. The reaction 1/2H2 (g) + AgCl(s) = H (aq) + Cl (aq) +
8. Strongest reducing agent is :
Ag(s) occurs in the galvanic cell :
(a) K (b) Mg
(a) Ag I AgCl(s) I KCl(sol.) II AgN03) (sol.) I Ag
(c) Al (d) I
(b) Pt I H2(g) I HCl(sol. IIAgN03 (sol) IAg
9. Zn can not displace following ions from their aqueous
(c) Pt I H2(g) I HCl (sol.) II AgCl(s) IAg
solution :
(d) Pt I H2 (g) I KCl (sol.) IIAgCl(s) IAg + 2+
(a) Ag (b) Cu
3. The equation representing the process by which standard 2+ +
reduction potential of zinc can be defined is : (c) Fe (d) Na
(a) Zn (s) + 2e --➔ Zn 10. Which of the following displacement does not occur :
2+ -
+ 2+
(b) Zn (g) --➔ Zn (g) + 2e (a) Zn+ 2H ➔ Zn + H t
2+ -
2
(c) Zn (g) + 2e --➔

2+ - +
(b) Fe + 2Ag ➔ + Ag t
Zn Fe
2+
(d) Zn (aq.) + 2e --➔ Zn

2+ - 2+
(c) Cu + Fe ➔ + Fe t
(s) 2+
Cu
4. Which of the following statement is wrong about (d) Zn + Pb ➔ Zn + Pb t
2+ 2+
galvanic cell ?
11. The oxidation potential of Zn, Cu, Ag, H2 and Ni are 0.76,
(a) cathode is positive charged
-0.34, - 0.80, 0, 0.55 volt respectively. Which of the
(b) anode is negatively charged following reaction will provide maximum voltage ?
(c) reduction takes place at the anode (a) Zn + Cu
2+
--➔ Cu + Zn
2+
(d) reduction takes place at the cathode

Zn + 2Ag --➔ 2Ag + Zn
+ 2+
(b)
5. Which are used as secondary reference electrodes ?

2+
(a) Calomel electrode (b) Ag/AgCl electrode (c) H2 + Cu --➔ + Cu

+
2H
(c) Hg/Hg2Cl2 - KCl electrode

--➔ 2H + Ni
2+ +
(d) H2 + Ni
(d) All of the above
12. The position of some metals in the electrochemical series
Applications of Electrochemical Series in decreasing electropositive character is given as
Mg > Al > Zn > Cu > Ag. What will happen if a copper
6. The standard electrode potentials (reduction) of
3+ 2+ 4+ 2+ spoon is used to stir a solution of aluminium nitrate ?
Pt/Fe , Fe and Pt/Sn , Sn are + 0.77 V and 0.15 V
respectively at 25°C. The standard EMF of the reaction (a) The spoon will get coated with aluminium
Sn + 2Fe --➔ Sn + 2Fe is
4+ 2+ 2+ 3+
(b) An alloy of copper and aluminium is formed
(a) - 0.62 V (b) - 0.92 V (c) The solution becomes blue
(c) + 0.31 V (d) + 0.85 V (d) There is no reaction
13. The standard reduction electrode potential values of the Relationship between emf and gibb's free energy
elementA, B and C are + 0.68,-2.50, and -0.50 V
change
respectively. The order of their reducing power is :
18. The standard free energy change for the following
(a) A> B > C (b) A> C > B reaction is - 210 kJ. What is the standard cell potential ?
(c) C > B > A (d) B > C > A 2H202 (aq) --➔ 2H20(I) + 02(g)
14. A metal having negative reduction potential when dipped (a) + 0.752 (b) + 1.09
in the solution of its own ions, has a tendency :
(c) + 0.420 (d) + 0.640
(a) to pass into the solution
19. Calculate the standard free energy change for the
+ +
(b) to be deposited from the solution reaction, 2 Ag + 2H ➔ H + 2 Ag ,
2
+ -
E° for Ag + e ➔Ag is 0.80 V
(c) to become electrically positive
(a) + 154.4 kJ (b) + 308.8 kJ
(d) to remain neutral (c) -154.4 kJ (d) -308.8 kJ
15. E° for the half cell reactions are 20. The standard EMF of Daniell cell is 1.10 volt. The
2+ maximum electrical work obtained from the Daniell cell
as, (a) Zn = Zn + 2e ; E° = +
is
2+
0.76 V (b) Fe = Fe + 2e ; E° = + (a) 212.3 kJ (b) 175.4 kJ
0.41 V The E° for half cell (c) 106.15 kJ (d) 53.07 kJ
reaction, 21. What is the free energy change for the half reaction
+ -
Li + e ➔ Li?
2+ 2+
Fe + Zn --➔ Zn + Fe is : Given E0 = -3.0V, F = 96500 C mol-1 and T = 298 K.
Li+ /Li
(a) - 0.35 V (b) + 0.35 V (a) 289.5 kJ mol
-1
(b) -298.5 kJ mol
-1
-1 -1 -1
(c) + 1.17 V (d) - 0.17 V (c) 32.166 CV mol (d) -289500 CV mol
16. An aqueous solution containing 1 M each of Au , Cu ,
3+ 2+ 22. The emf of Daniell cell is 1.1 volt. If the value of Faraday
+ + is 96500 coulombs per mole, the change in free energy in
Ag , Li is being electrolysed by using inert electrodes.
kJ is
The value of standard potentials are :
(a) 212.30 (b) -212.30
E0 = 0.80 V, E0 = 0.34 V and E0 = 1.50 V, A Cu Au
3+
g
+
+
/ Au (c) 106.15
Cu
/
Nernst Equation
A
g
+
E0
3.0
3V
L
i
/
L
i
with increasing voltage, potential for the reaction

the sequence of
deposition of metals on
the cathode will be :
(a) Li, Cu, Ag, Au
Ag, Au
(c) Au, Ag, Cu
Ag, Cu, Li
17. The standard electrode
Lakshya
Educare
23. Which of the (a) E°red
following represents
(c) (E°ox - 0.059)(d)
the potential of silver
(E°red - 0.059)
wire dipped in to 0.1
M AgN03 solution at H+ (Pt) H
25°C ? 0 (aq)
+
Ag
A 24. Cons Ag. The
ider
g the measure
+ cell
3 d
( 1atm
a
q
) pH
+ M
e
-
-
-
➔
A
g
(s
)
Sn (aq) + 2e --➔
2+ -
EMF of the cell is 1.023
Sn(s) V. What is the value of x
?
at 25°C are 0.80 volt
and - 0.14 volt,
= + 0.799 V [T =
Ag+ , Ag E0
respectively. The emf
25°C]
of the cell.
2+ + -2
Sn I Sn (1 M) I I Ag (a) 2 x 10 M
3
(1M) I Ag is M
(a) 0.66 volt (c) 1.5 x 10 M
-3
-2
(c) 1.08 volt 10 M
25. The emf of the cell 32. The hydrogen electrode is dipped in a solution of pH = 3
+ 2+
Ti/Ti (0.0001 M) I I Cu (0.01 M)/Cu is 0.83 V at 25°C. The potential of the cell would be (the value of
2.303 RT/F is 0.059 V)
The emf of this cell will be increased by :
(a) 0.177 V (b) 0.087 V
++
(a) Increase the concentration of Cu ions (c) -0.177 V (d) 0.059 V
+
(b) Decreasing the concentration of Ti Relating half cell potential using dG
(c) Increasing the concentration of both 33. When two half-cells of electrode potential of E1 and E2 are
combined to form a cell of electrode potential E3, then
(d) (a) and (b) both (when n1, n2 and n3 are no. of electrons exchanged in first,
2+ 2+
26. Co I Co (C ) II Co (C ) I Co for this cell, �G is second and combined half-cells) :
negative if :
2 1
(a) C > C (b) C > C E1n1 + E2 n 2

2 1 1 2 (a) E = E - (b) E =
E
(c) C = C (d) unpredictable 3 2 1
1 2
3
n3
27. What will be the emf for the given cell
? E1n1 - E2 n2
+ (c) E3 = n2 (d) E3 = E1 + E2
Pt I H (g, P ) I H (aq) II H (g, P ) I Pt
2 1 2 2 3
RT
(a)
ln RT
P (b)
ln 34. If E0 Au / Au
+ is 1.69 V and Au
3+
/
is 1.40 V, then +
Au / Au
3+
1 P E0
Au
E0
F P2 1
2F P2
(a) 0.19 V (b) 2.945 V
RT
(c P2 2Fln (c) 1.255 V (d) None of these
(d) None of these
P1 Electroytic cell
28. If the pressure of hydrogen gas is increased from 1 atm. 35. Which reaction occur at cathode during electrolysis is
to 100 atm., keeping the hydrogen ion concentration fused lead bromide ?
constant at 1 M, the voltage of the hydrogen half-cell is at
(a) Pb --➔ Pb + 2e (b) Br + e --➔ Br
2+ - - -
25°C will be
(a) 0.059 V (b) -0.059 V
(c) Br --➔ Br + e (d) Pb + 2e --➔ Pb
- - 2+ -
(c) 0.295 V (d) 0.118 V.

36. By the electrolysis of aqueous solution of CuS04, the
29. The EMF of the cell products obtained at both the electrodes are
2+ 2+
Mg I Mg (0.01 M)I ISn (0.1M)I Sn at 298 K is (Given (a) 02 at anode and H2 at cathode
E0Mg ,Mg = -2.34 V, E0Sn , Sn = -0.l4 V
2+ 2+
(b) H2 at anode and Cu at cathode

) (a) 2.17 V (b) 2.23 V
(c) 02 at anode and Cu at cathode
(c) 2.51 V (d) 2.45 V
30. The potential of the cell containing two hydrogen (d) H2S208 at anode and 02 at cathode
electrodes as represented below 37. During the electrolysis of fused NaCl, the reaction that
+ -6 + -4
Pt, H (g) I H (10 M) I IH (10 M)I H (g), Pt at 298 K is
2 2
occurs at the anode is :
(a) -0.118 V (b)-0.0591 V
(a) Chloride ions are oxidized
(c) 0.118 V (d) 0.0591 V
31. The emf of the cell H (12 atm) Pt I H (a = x) I I H (a = 1) I
+ +
(b) Chloride ions are reduced
H2(1 atm) Pt at 25°C is 0.59 V. The pH of the solution is (c) Sodium ions are oxidized
(a) 1 (b) 4
(d) Sodium ions are reduced
(c) 7 (d) 10
38. In electroplating the article to be electroplated is made : 46. When the same electric current is passed through the
(a) cathode (b) anode solution of different elecrolytes in series the amounts of
elements deposited on the electrodes are in the ratio of
(c) either cathode or anode
their:
(d) simply suspended in the electrolytic bath.
(a) atomic number (b) atomic masses
39. 0n electrolysing a solution of dilute H2S04 between
platinum electrodes, the gas evolved at the anode is (c) specific gravities (d) equivalent masses
(a) S02 (b) S03 47. 13.5 g of Al get deposited when electricity is passed
through the solution of AlCl3. The number of faradays
(c) 02 (d) H2.
used are :
40. A spoon to be electroplated with gold should be :
(a) 0.50 (b) 1.00
(a) cathode (b) anode
(c) 1.50 (d) 2.00
(c) electrolyte (d) none of these
48. The ratio of weights of hydrogen and magnesium
Faraday's Laws deposited by the same amount of electricity from aqueous
H2S04 and fused MgS04 are :
41. Three faradays of electricity was passed through an
aqueous solution of iron (II) bromide. The mass of iron (a) 1 : 8 (b) 1 : 12
metal (at. mass 56) deposited at the cathode is - (c) 1 : 16 (d) None of these
(a) 56 g (b) 84 g 49. A current of 2 ampere was passed through solutions of
(c) 112 g (d) 168 g CuS04 and AgN03 in series. 0.635 g of copper was
42. The electric charge for electrode deposition of one gram deposited.
Then the weight of silver deposited will be :
equivalent of a substance is :
(a) 0.59 g (b) 3.24 g
(a) one amp/sec (b) 96,500 C/sec
(c) 1.08 g (d) 2.16 g
(c) one amp/hour (d) 96,500 C
20
50. An ion is reduced to the element when it absorbs 6 x 10
43. Number of electrons involved in the electrodeposition of
electrons. The number of equivalents of the ion is :
63.5 g of Cu from a solution of CuS04 is
(a) 0.10 (b) 0.01
23
: (a) 6.022 x 10 (b) 3.011 x
(c) 0.001 (d) 0.0001
23
10 51. Electrolysis can be used to determine atomic masses. A
23 22 current of 0.550 A deposits 0.55 g of a certain metal in
(c) 12.044 x 10 (d) 6.022 x 10
100 minutes. Calculate the atomic mass of the metal if n
44. When one coulomb of electricity is passed through an =3:
electrolytic solution the mass deposited on the electrode
(a) 100 (b) 45.0
is equal to :
(c) 48.25 (d) 144.75
(a) equivalent weight (b) molecular weight
52. How many minutes will it take to plate out 0.50 g of Cr
(c) electrochemical equivalent from
(d) one gram a Cr2(S04)3 solution using a current of 1.50 A ? (Atomic
weight : Cr = 52.0)
45. W g of copper deposited in a copper voltameter when an
(a) 254 (b) 30
electric current of 2 ampere is passed for 2 hours. If one
ampere of electric current is passed for 4 hours in the (c) 152 (d) 103
same voltameter, copper deposited will be :
53. An electrolysis of a oxytungsten complex ion using 1.10
(a) W (b) W/2 A for 40 min produces 0.838 g of tungsten. What is the
charge of tungsten in the material ? (Atomic weight : W =
(c) W/4 (d) 2W
184)
(a) 6 (b) 2
Lakshya
Educare
(c) 4 (d) 1
54. When molten lithium chloride (LiCl) is electrolyzed, 62. A current of 9.65 amp. flowing for 10 minute deposits 3.0
lithium metal is formed at the cathode. If current g of a metal. The equivalent wt. of the metal is :
efficiency is 75% then how many grams of lithium are
(a) 10 (b) 30
liberated when 1930 C of charge pass through the cell :
(Atomic weight : Li = 7) (c) 50 (d) 96.5
(a) 0.105 (b) 0.120 63. 108 g fairly concentrate solution of AgN03 is electrolyzed
(c) 0.28 (d) 0.240 using 0.1 F of electricity. The weight or resulting solution
is:
55. The weight ratio of Al and Ag deposited using the same
quantity of current is : (a) 94 g (b) 11.6 g
(a) 9 : 108 (b) 2 : 12 (c) 96.4 g (d) None
(c) 108 : 9 (d) 3 : 8 Batteries, Fuel Cells and Corrosion

56. The weight of silver (eq. wt. = 108) displaced by that 64. When a lead storage battery is discharged
quantity of current which displaced 5600 mL of hydrogen
(a) PbS04 is formed (b) Pb is formed
at STP is :
(c) S02 is consumed (d) H2S04 is formed
(a) 54 g (b) 108 g
65. A fuel cell is :
(c) 5.4 g (d) None of these
(a) The voltaic cells in which continuous supply of fuels
57. A current of 9.65 ampere is passed through the aqueous are send at anode to give oxidation
solution NaCl using suitable electrodes for 1000 s. The
amount of Na0H formed during electrolysis is (b) The votalic cell in which fuels such as : CH4, H2, C0
are used up at anode
(a) 2.0 g (b) 4.0 g
(c) It involves the reactions of H2 - 02 fuel cell such as :
(c) 6.0 g (d) 8.0 g -
Anode : 2H + 40H --➔ 4H 0(I) + 4e
58. How many electrons are delivered at the cathode during electrolysis by a current of 1A in 60 seconds ?
2
20
(a) 3.74 x 10 passed through a solution
10
23 of AgN03 for 30 minute
21
during an electrolysis
(c) 7.48 x 10 experiment.
20
10
(a) 108 (b) 180
59. The moles of electrons
(c) 180 (d) 300
required to deposit 1 gm
equivalent aluminium
(at. wt.= 27) froma
solution of aluminium
chloride will be
(a) 3
(c) 4
60. Time required to deposit

one millimole of
aluminium metal by the
passage of 9.65 amperes
through aqueous
solution of aluminium
ion is :
(a) 30 s
(c) 30,000 s
61. How many coulomb of

electricity are consumed
when 100 mA current is
Cathode : 0 + 2H 0(I)
+ 4e --➔ 40H- 2 2
(d) All of the above

66. Reaction that takes
place at anode in dry
cell is
2+ -
(a) Zn + 2e ➔ Zn(s)
2+
(b) Zn(s) ➔ Zn +
-
2e
2+ -
(c) Mn + 2e ➔
Mn(s)
+ -
(d) Mn(s) ➔ Mn + e
+ 1.5 V.
67. As lead storage battery
is charged
(a) lead dioxide
dissolves
(b) sulphuric acid is
regenerated
(c) lead electrode
becomes coated with
lead sulphate
(d) the concentration of
sulphuric acid
decreases.
Conductance of
Solutions
68. The specific
conductance of a
N/10 KCl at 25°C is
-1 -1
0.0112 ohm cm .
The resistance of cell
containing solution at
the same temperature
was found to be 55
ohms. The cell
constant will be
-1
(a) 6.16 cm
-1
cm
-1
(c) 0.0616 cm
-1
cm
69. The specific conductance of a salt of 0.01 M 75. The conductivity of 0.1 N NaOH solution is 0.022 S cm .
-1
-4
concentration is 1.061 x 10 , molar conductance of the When equal volume of 0.1 N HCl solution is added, the
same solution will be : conductivity of resultant solution is decreases to 0.0055
-4 -1 2 -1
(a) 1.061 x 10 (b) 1.061 S- cm . The equivalent conductivity in S cm equivalent
of NaCl solution is
(c) 10.61 (d) 106.1
(a) 0.0055 (b) 0.11
70. Which of the following solutions of NaCl will have the
highest specific conductance ? (c) 110 (d) none
(a) 0.001 N (b) 0.1 N 76. The specific conductivity of a saturated solution of AgCl
-6 -1 -1 -1 2 -1
(c) 0.01 N (d) 1.0 N is 3.40 x 10 ohm cm at 25 °C. IfAg = 62.3 ohm cm mol +
71. The molar conductance at infinite dilution of AgNO3, -1 2 -1

& = Cl67.7 ohm cm mol , the solubility of AgCl at 25°C
AgCl and NaCl are 116.5, 121.6 and 110.3 respectively.
is :
The molar conductances of NaNO3 is :
-5 -3
(a) 111.4 (b) 105.2 (a) 2.6 x 10 M (b) 4.5 x 10 M
-5 -3
(c) 130.6 (d) 150.2 (c) 3.6 x 10 M (d) 3.6 x 10 M
-1 2
72.
-1
If x specific resistance (in S cm) of the electrolyte 77. Molar conductance of 0.1 M acetic acid is 7 ohm cm
-1
solution and y is the molarity of the solution, then /\ (in mol . If the molar cond. of acetic acid at infinite dilution
m -1 2 -1
2 -1
S cm mol ) is given by : is 380.8 ohm cm mol , the value of dissociation
constant will be
-5 -3 -3 -1
(a) 226 x 10 mol dm (b) 1.66 x 10 mol dm
-2 -3 -5 -3
(c) 1.66 x 10 mol dm (d) 3.442 x 10 mol dm
1000x x
(a) (b) 1000 y 78. At infinite dilution, the eq. conductances of CH3COONa,
y 2
HCl and CH COOH are 91, 426 and 391 mho cm
respectively 3
1000 xy
at 25°C, The eq. conductance of NaCl at infinite dilution will
(c) xy (d) be :
1000
(a) 126 (b) 209
73. Resistance of 0.1 M KCl solution in a conductance cell is
-1 (c) 391 (d) 908
300 ohm and conductivity is 0.013 Scm . The value of
cell constant is : 79. The equivalent conductivity of 0.1 N CH3COOH at 25°C
-1 -1 is 80 and at infinite dilution 400. The degree of
(a) 3.9 cm (b) 39 m dissociation of
(c) 3.9 m
-1
(d) None of these CH3COOH is
74. The specific conductance of a saturated solution of silver (a) 1 (b) 0.2
-1
bromide is k S cm . The limiting ionic conductivity of (c) 0.1 (d) 0.5
+ -1
Ag and Br ions are x and y, respectively. The solubility
-1
of silver bromide in gL is : (molar mass of AgBr = 188)
kx1000 k
(a) (b) x +x188
y
x- y
kx1000x188 (d) x + y 1000

(c)
x+ y k x188
2E4L2ECTROCHEMISTRY
ELECTROCHEMIST2R42Y
EXERCISE - 2 : PREVIOUS YEAR COMPETITION QUESTIONS

(TOPIC-1) 6. How many coulombs are required to deposit 50g of
aluminium when the electrode reaction is [RPMT]
ELECTROLYTES AND ELECTROLYTIC CONDUCTANCE
3+ -
Al + 3e ➔ Al
2011
(a) 536111 C (b) 536.111C
1. A current is passed through two cells connected in
series. The first cell contains X(NO3)3 (aq) and the (c) 96500 C (d) 38600 C
second cell 7. The resistance of 1 N solution of acetic acid is 250 0 ,
contains Y (NO3)2(aq). The relative atomic mases of X when measured in a cell having a cell constant of 1.15
and Y are in the ratio 1:2. What is the ratio of cm-1. The equivalent conductance (in ohm-1 cm2 equiv-1)
liberated mass of X to that of Y? [Kerala of 1 N acetic acid is [Guj. CET]
CEE]
(a) 2.3 (b) 4.6
(a) 3:2 (b) 1:2
(c) 9.2 (d) 18.4
(c) 1:3 (d) 3:1
8. The conductivity of 0.20 M KCl solution at 298 K is
2. Two different electrolytic cells filled with molten 0.0248 S cm-1. What will be its molar conductivity?
Cu(NO3)2 and molten Al(NO3)3 respectively are
[HaryanaPMT]
connected in series. When electricity is passed 2.7 g
Al is deposited on (a) 124 S cm2 (b) 124 cm-1
electrode. Calculate the weight of Cu deposited on
(c) 124 ohm-1cm2 equiv-1 (d) 124 S cm2 mol-1
cathode. [Cu = 63.5; Al = 27.0 g mol-1] [Guj. CET]
9. When same quantity of electricity is passed for half an
(a) 190.5 g (b) 9.525 g
hour, an amount of Cu and Cr deposited are
(c) 63.5 g (d) 31.75 g respectively
0.375 g and 0.30 g . Ratio of electrochemical
2010
equivalent of Cu and Cr is [OJEE]
3. An increase in equivalent conductance of a strong
(a) 0.8 (b) 1.25
electrolyte with dilution is mainly due to
[CBSEAIPMT] (c) 2.5 (d) 1.62
(a) increase in number of ions. 10. In electrolysis of dil. H2SO4 using platinum electrodes
[BVP]
(b) increase in ionic mobility of ions.
(a) H2 is evolved at cathode.
(c) 100% ionisation of electrolyte at normal dilution.
(b) SO2 is produced at anode.
(d) increase in both i.e., number of ions and ionic
mobility of ions.
4. The compound exhibiting maximum value of
equivalent
conductance in a fused state is' [AMU] (c) O2 is obtained at cathode.
(a) SrCl2 (b) CaCl2 (d) SO2 is produced at cathode.
(c) MgCl2 (d) BeCl2
2009
5. At 18 C, the conductance of H and CH
o +
3
COO- at
infinite dilution are 315 and 35 mho cm2 eq-1 11. Al2O3 is reduced by electrolysis at low potentials and
high current. If 4.0 x104 amperes of current is passed
respectively. The
through molten Al2O3 for 6 h, what mass of aluminium is
equivalent conductivity of CH3COOH at infinite
produced? (Assum e 00%
1 current efficiency, at. wt. of
dilution is ................. mho cm2 eq-1. [AFMC]
(a) 350 (b) 280 Al=27) [CBSEAIPMT]
(c) 30 (d) 315 (a) 9.0x103 g (b) 8.1x104 g
(c) 2.4x103 g (d) 1.3x104 g
18. 4.5 g of aluminium (at. mass 27 u) is deposited at cathode

M
12. The equivalent conductance of from a molten electrolyte containing Al3+ ions by a
solution of a weak
32 certain quantity of electric charge. The volume of
hydrogen
monobasic acid is 8.0 mho cm2 and at infinite dilution produced at STP from H+ ions in a solution by the
is same quantity of electric charge will be [Manipal]
400 mho cm2.The dissolution constant of this acid is
[CBSEATPMT] (a) 44.8 L (b) 11.2 L
(a) 1.25x10-5 (b) 1.25x10-6 (c) 22.4 L (d) 5.6 L
(c) 6.25x10-4 (d) 1.25x10-4 19. How many coulombs of electricity are required for
the reduction of 1 mole4 of MnO - to Mn2+ ?
13. Assertion On dilution, the equivalent as well as molar [Manipal]
conductivity of solution increases.
(a) 96500 C (b) 9.65x106 C
Reason With dilution, the number of current carrying
particles per cm3 increases. [ATTMS] (c) 4.83x105 C (d) 1.93x105 C
(a) Both Assertion and Reason are true and Reason is 20. The correct expression in ST system relating the
correct explanation of the Assertion. equivalent conductance ( A C ), specific conductance
(b) Both Assertion and Reason are true and Reason is (K) and equivalent concentration (C) is
not the correct explanation of the Assertion. (where, C is the number of gram equivalents in one
(c) Assertion is true but Reason is false. litre of the solution). [J&KCET]
(d) Both Assertion and Reason are false. K

(a) A = (b) Kx1000
C A C=
14. An aqueous solution containing 6.5 g of NaCl of 90% C C
purity was subjected to electrolysis. After the complete
-3 -6
electrolys is, the solution was evaporated to get solid Kx10 K x10
NaOH. The volume of 1 M acetic acid required to (c) A C (d) A C
= C = C
neutralise NaOH obtained above is [KCET]
(a) 2000 cm3 (b) 100 cm3
2008
(c) 200 cm3 (d) 1000 cm3 (c) 402x10-4 (d) 262x10-4
15. Tn the electrolysis of acidulated water, it is desired to
obtained 1.12 cc of hydrogen per second under STP
condition. The current to be passed is [KCET]
(a) 9.65 A (b) 19.3 A
(c) 0.965 A (d) 1.93 A
16. The one which decreases with dilution is [KCET]
(a) conductance
(b) specific conductance
(c) equivalent conductance
(d) molar conductance
17. At 25oC, the molar conductances at infinite dilution
for the strong electrolytes NaOH, NaCl and BaCl2 are
248x10-4, 126x10-4 and 280x10-4 S.m2.mol-1 respectively
0
m Ba(OH)2 in S.m2.mol-1 [EAMCET]
(a) 52.4x10-4 (b) 524x10-4
Lakshya
Educare
21. Kohlraush's law states that at [CBSEATPMT] (c) infinite dilution, each ion makes definite
contribution to conductance of an electrolyte
(a) finite dilution, each ion makes definite
whatever be the nature of the other ion of the
contribution to the equivalent conductance of an
electrolyte.
electrolyte, whatever be the nature of the other
ion of the electrolyte. (d) infinite dilution, each ion makes definite
contribution to equivalent conductance of an
(b) infinite dilution, each ion makes definite
electrolyte, whatever be the nature of the other
contribution to equivalent conductance of an
ion of the electrolyte.
electrolyte depending on the nature of the
other ion of the electrolyte.
22. What is the time (in sec) required for depositing all
the silver present in 125 mL of 1MAgNO3 solution by (a) Both Assertion and Reason are true and Reason is
passing a current of 241.25 A? (1 F=96500 C) [AFMC] correct explanation of the Assertion.
(a) 10 (b) 50 (b) Both Assertion and Reason are true and Reason is
not the correct explanation of the Assertion.
(c) 1000 (d) 100
(c) Assertion is true but Reason is false.
23. Which of the following does not conduct electricity?
[AFMC] (d) Both Assertion and Reason are false.
30. The resistance of N/10 solution is found to be
(a) Fused NaCl (b) Solid NaCl
2.5 x 103 0.The equivalent conductance of the solution
(c) Brine solution (d) Copper is (cell constant=1.25 cm-1) [Kerala CEE]
24. Which of the following electrolytic solutions has the (a) 2.5 0-1 cm-2 equiv-1 (b) 5.0 0-1 cm-2 equiv-1
least specific conductance? [KCET] (c) 2.5 0-1 cm-2 equiv-1 (d) 50 0-1 cm-2 equiv-1
(a) 0.02 N (b) 0.2 N 31. When 3.86 A current is passed through an electrolyte
for 50 min, 2.4 g of a divalent metal is deposited. The
(c) 2 N (d) 0.002 N gram atomic weight of the metal (in gram) is
25. A direct current deposits 54 g of silver (atomic [EAMCET]
mass=108) during the electrolysis reaction. How much (a) 24 (b) 12
aluminium (atomic mass = 27) would be deposited
from aluminium chloride solution by the same amount (c) 64 (d) 40
of electricity? 32. How many atoms of calcium will be deposited from a
[Kerala CEE] solution of CaCl2 by a current of 25 mA flowing for 60
(a) 4.5 g (b) 5.4 g s?
[MPPMT]
(c) 54 g (d) 2.7 g The molarity of solution after electrolysis would
be[ATTMS]
26. What will be the proportion of moles of metal
(Cu:Ni:Ag) at cathode according to the second law of (a) 0.46 M (b) 0.92 M
Faraday? (c) 0.625 M (d) 1.25 M
[Guj. CET]
29. Assertion According to Kohlrausch's law the molar
(a) 1 : 2 : 1 (b) 2 : 2 : 1 conductivity of a strong electrolyte at infinite dilution is
(c) 1 : 2 : 2 (d) 1 : 1: 2 sum of molar conductivities of its ions.
2007 Reason The current carried by cation and anion is

always equal. [ATTMS]
27. Which of the following is not a non-electrolyte ?
[AFMC]
(a) Acetic acid (b) Glucose
(c) Ethanol (d) Urea
28. A current of 96.5 A is passed for 18 min between
nickel electrodes in 500 mL solution of 2M Ni(NO 3)2.
Mahesh Tutorials
Science
(a) 4.68x1018 (b) 4.68x1015
(c) 4.68x1012 (d) 4.68x109
33. The specific conductance (K) of an electrolyte of 0.1
N concentration is related to equivalent conductance
( A ) by the following formula
[J&KCET]
(a) A = K (b) A = 10K

(c) A = 100K (d) A = 10000K
34. Pure water does not conduct electricity because it is
[J&KCET]
(a) basic (b) almost not ionised

(c) decomposed easily (d) acidic
2006
35. Tn the electrolysis of water, one faraday of electrical
energy would evolve
[AMU]
(a) one mole of oxygen
(b) one gram atom of oxygen
(c) 8 g of oxygen
(d) 22.4 L of oxygen
Lakshya
Educare
36. If the aqueous solution of the following salts are slolution was (molar mass of Cu=63.5, Faraday constant
electrolysed for 1 h with 10 Acurrent, which solution =96500 C/mol) [AMU]
will deposit the maximum mass of the metal at the
(a) 0.2 N (b) 0.01N
cathode? The atomic weights are Fe2+=56, Zn2+=65,
Ag+=108, Hf3+=178 and W3+=184 [Kerala CEE] (c) 0.1 N (d) 0.02 N
(a) Z 43. An
(b)FeC
n electric
l
S current is
O passed
4
through
silver
voltamet
er
connecte
d to a
water
voltamet
er. The
cathode
of the
(c) HfCl4 silver voltameter
AgNO3 weighed 0.108g more
at the end of the
37. The ionic
conductance of electrolysis. The
Ba2+ and Cl- are volume of oxygen
2
respectively evolved at STP is
127 and 760-1
cm2 eq-1 at [Keral
infinite dilution.
The equivalent (a) 56 cm3
conductance (in
0-1 cm2) of BaCl (c) 5.6 cm3
at infinite
dilution will T
be 2
(a) 139.5
0 OPIC 2
1 ELECTROCHEM
(c) 279
1
38. The charge ICAL SERIES,
required to
liberate one ELECTRODE
gram equivalent POTENT
of an element is IAL AND
[BCECE] EMF
(a) 96500 F
(c) 1C
None of these
cell
4 for a given
4. reaction has a
negative value,
th then
e
o
E
2 whi
ch
of
the
- . 3.0 V
f
o 1 5 respectively
39. A current of for the ? . eq . The
strength 2.5 A was
values of 2 V reducing
passed through [CBSEATPM
�G and T]o power of
CuSO4
V a these
K
, n metals will
solution for 6 min (a) �< 1 (b)
d be
26 s. The amount of G �G >0; K > 1
o
eq
copper deposited is o
>1 (d) +
(Atomic weight of 0 - [CBSEATP
eq
�Go <0; K < 1
Cu=63.5, 1F= 96500 > MT]
C) 0
41. At 25oC the
; specific (a) X>Y>Z
[PunjabPMET]
conductivity of a Y>Z>X
K normal
eq solution
( of KCl is (c) Y>X>Z
0.002765
eq mho. Z>X>Y
c The resistance
) of cell is 47. Standard
4000.The cell electrode
� constant is
potential for
G
o Sn4+/Sn2+ couple
(a) 0.815
is +0.15 V and
< (c) 1.106 that for the
0
Cr3+/Cr couple
; 2003
is -0.74 V.
K 42. On passing These two
electric current couples in their
(a) 0.3175 g of one ampere
45. The electrode standard state
g for 16 min and 5
potentials for are connected
s through one
(c) 0.635 g to make a cell.
Cu (aq) + e ➔
2+ - litre solution of
40. What is the + +
CuCl2, all The cell
Cu (aq) and Cu copper of
electrochemical -
potential will be
equivalent (in g-C-1) (aq) + e ➔ Cu(s) solution was
of silver? (Ag=108, are +0.15 V and + deposited at
0.50 V cathode.The (a) +1.83 V
F=Faraday)
strength of +1.19 V
[EAMCET] respectively. The
CuCl2
value of (c) +0.89 V
o
+0.18 V
(a) 108 Cu2+
will be E
/ Cu
48. Given the +B
F
following
F
reactions
(b) 0.500 V
involving, A, B,
(c) 0.325 C and D
+
(d) 0.650 (i) C + B ➔
F 1 +
C +B
+
(c) (ii) A + D ➔
2 108 46. Standard No reaction
0 electrode
108F +
(iii) C +A ➔
0 potential of
No
4 three metals X,
reaction
Y and Z are + +
(iv) D+B ➔ D
2+ -
(a) +1.67 V 0.15 V and for
(i) Fe (aq) + 2e ➔
(a) 12.5 -1.67 V Au3+/Au,
Fe(s);
(c) 37.9 (c) +0.79 V standard
+ 1 reduction
(ii) 2H (aq) + O -0.79 V
53. If the half cell -
potential is 1.5
reactions are given (g) + 2e ➔ H O(/J)
54. Given for V. For the
as Sn4+/Sn2+, reaction,
2
2
standard
2+ 3+
The correct reduction 3Sn + 2Au ➔
arrangement of A, The E for the
o
potential is 4+
3Sn + 2Au
B, C, D in order of reaction
their decreasing (i) Zn(s 2 2
the value of
o
)I E is
ability as reducing 2+
Zn
agent (0.1
(a) D > B > C > M)
+
A (b) A> C F ➔ Fe2 [ II
2
Cu
>D>B e (aq) + H A +
O(/J) M
(c) C > A> B > ( (1M
U
D )I
s ]
>B Cu(
) s)
(a) +1.35
+ +2.55
(ii) Zn
(s) (c) -1.35
I -2.55
2 Zn
2+
H
+ (1
M)
+ II
Cu
2+
1 (1
M)
I
O Cu
2 (s)
49. The standard emf of respectively (iii) Zn(s) I o

E 55. T M values for Cr,
a galvanic cell Zn
2+
3
2+
he Mn, Fe and Co are

+
involving 2 moles (1M)
-0.41,
of electrons in its II /
2+
redox reaction is Cu M
0.59 V. The (0.1M)

I Cu(s)
equilibrium constant
+1.57, +0.77,
for the redox Which one of the
and +1.97 V
reaction of the cell following is true?
respectively.
is [KCET]
For which one
(a) 1020 (a) E2>E1>E3(b) of these metals
E1>E2>E3 the change in
(c) 10 2
oxidation state
0 (c) E3>E1>E2(d)
50. E1, E2 and E3 are the from +2 to +3
emfs of the 1 E3>E2>E1 is easiest?
following three 0 cell
galvanic cells
(a) 56. At 25oC temperature,
the cell potential of a
(c) Fe given
51. For the reduction electrochemical cell is
of silver ions with 1.92 V. Find the value
copper metals, the of x.
standard cell
2+
potential was Mg(s) I Mg (aq) x M
2+
found to be +0.46 II Fe (aq) 0.01M I
Fe(s)
V at 25oC.
The value of 2+
E Mg / Mg (aq) =
o
standard Gibbs o 2+
2.37V; E Fe / Fe (aq)
energy, �Go will = 0.45 V
be (F=96500 [Guj. CET]
C mol-1)
(a) x=0.01M
M
(a) -98.0kJ
-89.0 kJ (c) x>0.01M
be predicted
(c) -89.0 J
-44.5 kJ
52. The logarithm of
the equilibrium
constant of the
cell reaction
corresponding to
the cell X(s) I X2+
(aq) II Y+(aq)I
Y(s) with standard cell potential, E o =1.12 V is given
Cell
by [AMU]
57. The potential of a hydrogen electrode at pH=10 is (a) Zn reduces Fe2+ (b) Zn reduces Mg2+
[WB JEE] (c) Mg oxidises Fe (d) Zn oxidises Fe
(a) 0.59 V (b) 0.00V 64. The standard elecrode potential for the half cell
(c) -0.59V (d) -0.059 V reactions are
2+ -
2009 Zn + 2e ➔ Zn; E = -0.76V
o
58. Given : (i) Cu2+ + 2e- ➔ Cu; Eo=0.337 V 2+ -

+ 2e ➔ Fe; E = -0.44V
o
Fe
(ii) Cu2+ + e- ➔ Cu+; Eo=0.153V
Electrode potential, E for the reaction, Cu+ + e- ➔
o The emf of the cell reaction
Cu,
will be 2+
Fe + Zn ➔ Zn + Fe
2+ [KCET]
[CBSEATPMT,AMU] (a) -1.20 V (b) +1.20
V
(a) 0.52 V (b) 0.90 V
(c) +0.32 V (d) -0.32 V
(c) 0.30 V (d) 0.38 V
65. A solution of nickel sulphate in which nickel rod is
59. Given , Pb2+/Pb=-0.126 V; Zn2+/Zn=-0.763 V Find the dipped is diluted 10 times. The reduction potential of
emf of the following cell Zn I Zn2+ (0.1 M)II Pb2+ (1M) Ni at 298 K [Kerala CEE]
I Pb.
(a) decreases by 60mV (b) decrease by 30 mV
[AFMC]
(c) decreases by 30 V (d) increases by 30 mV
(a) -0.637 (b) +0.637
66. The standard reduction potentials for Cu 2+ /Cu;
(c) >0.637 (d) +0.889
Zn2+/Zn; Li+/Li; Ag+/Ag and H+/H
2
are +0.34 V, -0.762
60. The reduction potential at pH=14 for the Cu2+/Cu V,
couples is -3.05 V, +0.80 V and 0.00 V respectively. Choose the
o strongest reducing agent among the following.
[Given, E =0.34V; K [Cu(OH) =1 x10-19]
Cu2+ / Cu sp 2 [Kerala CEE]
[ATTMS
] (a) Zn (b)
H2
(a) 0.34 V (b) -0.34V
(c) Ag (d) Li
(c) 0.22 V (d) -0.22V
67. The standard emf of a cell involving one electron
61. A gas X at 1 atm is bubbled through a solution charge is found to be 0.591 V at 25oC. The
containing a mixture of 1MY- and 1 MZ- at 25oC. If the equilibrium constant of the reaction is (1F=96500 C
reduction potential of Z > Y > X, then [ATTMS] mol-1, R=8.314 JK-1mol-1)
(a) Y will oxidise X but not Z. [Manipal]
(b) Y will oxidise both X and Z. (a) 1.0x101 (b) 1.0x1030
(c) Y will oxidise Z but not X. (c) 1.0x1010 (d) 1.0x105

(d) Y will reduce both X and Z. 2008
62. The potential of standard hydrogen electrode is zero. 68. On the basis of the following E o values, the strongest
This implies that [AMU] oxidising agent is
o o
(a) �G (H+, aq)=0 (b) �H (H+, aq) = 0 4- 3- -
[Fe(CN)6 ] ➔ [Fe(CN)6 ] + e ; E = -0.35V
o
f f
2+ 3+ -
Fe ➔ Fe + e ; E = -0.77V
o
[CBSEATPMT]
o o
(c) �Gf (H , aq) < 0 +
(d) �G (H , aq) > 0
+
(a) [Fe(CN)6 ]4- (b) Fe2+

63. E for Mg /Mg = -2.37 V, Zn /Zn = -0.76 V, and
o 2+ 2+ 2+
Fe /Fe = -0.44 V. Which statement is correct?
6
[CPMT]
(c) Fe3+ (d) [Fe(CN) ]3-
69. What is the electrode potential (in volt) of the

following electrode at 25oC? 2007
Ni2+ (0.1 M) I Ni(s) 74. Zn gives H2 gas with H2SO4 and HCl but not with HNO3
[PunjabPMET]
(Standard reduction potential of Ni2+/Ni is -0.25 V,
(a) Zn act as oxidising agent when react with HNO3.
2.303RT
= 0.06 ) [PunjabPMET] (b) HNO3 is weaker acid than H2SO4 and HCl.
F
(c) in electrochemical series Zn is above hydrogen.
(a) -0.28V (b) -0.34 V
(d) NO3 - is reduced in preference to hydronium ion.
(c) -0.82 V (d) -0.22V
75. EMF of hydrogen electrode in terms of pH is (at 1 atm
70. Hydrogen gas is not liberated when the following pressure) [MHTCET]
metal
is added to dil HCl [KCET]
EH = RT pH EH2 = RT 1
2
(a) (b)
(a) Ag (b) Zn F F pH
(c) Mg (d) Sn
71. The equilibrium constant for the following redox
(c) EH = 2.303RT pH
2
(d) EH = -0.0591pH
reaction at 298 K of 1x108. F 2
3+ - 2+
2Fe (aq) + 2I (aq) �- -�- 2Fe (aq) + I (s) 76. The standard electrode potential of hydrogen electrode
2 at 1 M concentration and hydrogen gas at 1 atm
If the standard reduction potential of iodine becoming pressure is [J&KCET]
iodide is +0.54 V, what is the standard reduction
(a) 1V (b) 6 V
potential of Fe3+/Fe2+ ? [Kerala CEE]
(c) 8 V (d) 0 V
(a) +1.006 V (b) -1.006 V
(c) +0.77 V (d) -0.77V 2006
72. The cell potential of the following cell at 25oC (in 77. A hypothetical electrochemical cell is shown
volts) is below AIA + (xM) IIB+(yM) I B
+ 2+
The emf measured is +0.20V. The cell reaction is
=
o
(pt) H I H IICu ICu(E [CBSEATPMT]
0.337V)
2
(1 atm) (0.01M) (0.1 M) Cu2+ / Cu [EAMCET]
+ +
(a) A + B➔ A+ B
(a) 0.308 (b) 0.427
+ - + -
(b) A + e ➔ A; B + e ➔ B
(c) -0.308 (d) 0.337
(c) the cell reaction cannot be predicted
73. Cu + (aq) is unstable in solution and undergoes
+ +
simultaneous oxidation and reduction, according to (d) A + B ➔ A + B
the reaction 78. Assertion Eo for Mn3+/Mn2+ is more positive than
+ 2+ Cr3+/Cr2+.
2Cu (aq) �- -�- Cu (aq) + Cu(s)
Reason The third ionisation energy of Mn is larger than
choose the correct Eo for the above reaction if that of Cr.
[ATTMS]
EoCu 2+ ICu = 0.34 V andEoCu 2+ ICu+ = 0.15 V [MHTCET]
(a) Both Assertion and Reason are true and Reason is
(a) -0.38 V (b)+0.49V correct explanation of the Assertion.
(c)+0.38V (d) -0.19 V (b) Both Assertion and Reason are true and Reason is
(d) Both Assertion and Reason are false.
79. For the electrochemical cell, M I M + II X- I X, Eo(M+/
M)=0.44V and Eo(X/X-)=0.33V, From this data one 86. Reduction potentials of A, B, C and D are 0.8 V, 0.79 V,
can deduce that [BHU] 0.34 Vand -2.37 V respectively. Which element
displaces all the other three elements? [MHTCET]
+ -
(a) M + X ➔ M + X is the spontaneous reaction
(a) B (b) A
+ -
(b) M + X ➔ M + X is the spontaneous reaction (c) D (d) C
(c) Ecell = 0.77V 87. The standard emf of Daniell cell is 1.10 V. The
maximum electrical work obtained from the cell
(d) Ecell = -0.77V
is[HaryanaPMT]
80. The reduction electrode potential, E of 0.1 M solution (a) 212.3 kJ (b) 175.4 kJ
of M+ ions ( E = -2.36V ) is
o
[MHTCET]
RP
(c) 106.15 kJ (d) 350.8 kJ
88. For cell reaction
2+ 2+
Zn + Cu ➔ Zn + Cu
(a) -4.82V (b) -2.41 V
cell representation is [BCECE]
(c)+2.41V (d) None of these
2+ 2+
RT (a) Zn I Zn II Cu I Cu
E =
o
81. ln K
2+ 2+
nF
eq
(b) Cu I Cu II Zn I Zn
This equation is called [MPPMT]

2+ 2+
(a) Gibbs equation (b) Nernst equation (c) Cu I Zn II Zn I Cu
2+ 2+
(c) Gibbs-Helmholtz equation (d) Cu I Zn II Zn I Cu
(d) van der Waals' equation 89. Alkali metals have high oxidation potential and hence,
82. During electrochemical process [Guj. CET] they behave as [JCECE]
(a) Gibbs free energy increases. (a) oxidising agents (b) Lewis bases
(b) Gibbs free energy remains constant. (c) reducing agents (d) electrolytes
(c) no prediction can be about Gibbs free energy. 90. What is the potential of platinum wire dipped into a
solution of 0.1 M in Sn2+ and 0.01 M in Sn4+? [JCECE]
(d) Gibbs free energy decreases.
2005 (a) Eo (b) Eo + 0.059
83. If hydrogen electrode dipped in two solutions of pH=3

and pH=6 and salt bridge is connected, the emf of 0.059 0.059
(c) E + (d) E -
o o
2 2
resulting cell is [DUMET]
(a) 0.177 V (b) 0.3 V 2004
91. Assertion Copper metal gets readily corroded in an
(c) 0.052 V (d) 0.104 V acidic aqueous solution.
84. The standard electrode potential is measured Reason Free energy change for this process is positive.
by[KCET] [ATTMS]
(a) electrometer (b) voltmeter (a) Both Assertion and Reason are true and Reason is
(c) pyrometer (d) galvanometer correct explanation of the Assertion.
85. Na is used in reduction of Zn salt because [MHTCET] (b) Both Assertion and Reason are true and Reason is
o o
(a) E Zn(oxi) > Na(oxi) (b) E oZn(red) < o
Na(red)
<E
o o
(c) E (d) Both (a) and (b)
Zn(oxi) Na(oxi)
(d) Both
Assertion and
Reason are
false.
92. Aluminium displaces hydrogen from dilute HCl TOPIC 3

whereas silver does not. The emf of a cell prepared by
+
ELECTROCHEMICAL CELLS, (INCLUDING FUEL
combining Al / Al3+ and Ag / Ag is 2.46 V. The CELLS), CORROSION
reduction potential of silver electrode is +0.80 V. The 2011
reduction potential of
98. Which of the following reactions is correct for a given
aluminium electrode is [KCET]
electrochemical cell at 25oC ? [Guj. CET]
(a)+1.66V (b) -3.26 V - -
Pt / Br2 (g) / Br (aq) // Cl (aq) / Cl2 (g) / Pt.
(c) 3.26 V (d) -1.66 V
- -
(a) 2Br (aq) + Cl2 (g) ➔ 2Cl (aq) + 2Br (g)
93. Standard electrode potential of cell
- -
+ + (b) Br2 (g) + 2Cl (aq) ➔ 2Br (aq) + Cl (g)
H 2/ H II Ag / Ag is (E0Ag+/Ag= 0.80V)[Kerala 2
CEE] - -
(c) Br2 (g) + Cl2 (g) ➔ 2Br (aq) + 2Cl (aq)
(a) 0.8 V (b) -0.8 V - -
(d) 2Br (aq) + 2Cl (aq) ➔ Br
2
(g) + Cl (g)
(c) -1.2 V (d) 1.2 V + +
Pt(H ) I H (aq) II Pt(H ) I H (aq) 2010
94. For the
2
following cell with
2
hydrogen electrode at two p1 p2
different pressures p1 and p2 99. When iron is rusted, it

emf is given by
is
(a) reduced
decomposed
(a) R p1 RT
Te log (c) oxidised
p 2 p1
lo (d) changed in the
p2 g 2F
(c) F p fine powder
p 2 RT
100. Which of the
R e1 log
p1 p following
T 2
2F statements is
lo true for the
g
F electrochemical
Daniel cell?
[Manipal]
95. For the cell, O , �G = -827 kJ
+ -1
Tl I Tl (0.001M) II mol
2+
Cu (0.1)M I Cu 3
2
3
23
Ecell at 25oC is 0.83 V.

Ecell can be increased
[HaryanaPMT]
(a) by decreasing
[Cu2+]
increasing [Cu2+]
(c) by increasing
[Tl+]
these
2003
96. On the basis of
information available
from the reaction
4 2
Al + O ➔ Al
(a) Electrons flow electrode. (c) velocity of K and
+
from copper - 110. When lead storage

101.3
Chemical formula of NO are same.
electrode to zinc battery is charge
rust is [OJEE] (d) KNO3 is highly [AFMC]
electrode
(a) Fe 2 O 3 .H 2 O soluble in water. (a) lead dioxide
(b) Current flows
dissolves.
from zinc Fe2 O3 .5H2O 2008
electrode to (b) sulphuric acid is
copper electrode. (c) Fe2 O3 .xH2 O 106. Standard free regenerated.
None of these energies of (c) the lead electrode
(c) Cations move formation (in kJ/mol)
toward copper E becomes coated
102. When lead storage at 298 K are -237.2, with lead sulphate.
electrode. battery discharges -394.4 and -8.2 for (d) the amount of
(d) Cations move (a) SO is evolved H2O( /J ), CO2(g)
PbSO is sulphuric acid
toward zinc consumed and decreases.
of O2, the minimum 2
111. Anode in the galvanic
emf required to carry (c) Lead is formed cell, is
out an H2SO4 is consumed (a) negative electrode
electrolysis of Al O-1 , (b) positive
is (F=96500 C mol )
2
o electrode
3 1 oand �G are related as E
cell
(c) neutral electrode
[CBSEATPMT] 0
3
. 2006
(a) 6.42 V 112. What is the cell
V (a (b) �G
) reaction occuring in
=
(c) 2.14 V Daniell cell
� -nFE
o
V (Galvanic cell)?
cell
G
(d) [J&KCET]
97. If the standard o
cell
electrode potential = �G =
o
(a) Cu(s) + ZnSO4
of Cu2+ / Cu n nFE =
o
(aq) ➔ CuSO4
electrode is 0.34 F 0
V, what is the (aq) + Zn(s)
E
electrode o (b) Zn(s) + CuSO4
cell
potential at 0.01
M concentration (aq) ➔ Cu(s) +
(c
of Cu2+? (T = 298 cell ZnSO4 (aq)
)
K) (c) Ni(s) + ZnSO4
�
(a) 0.399 V G (aq) ➔ NiSO4
0.281 V o
(aq) + Zn(s)
(c) 0.222 V =
0.176 V - (d) 2Na(s) + CdSO4
n (aq) ➔ Na2SO4
F (aq) + Cd(s)
E
o pentane (g), o
c
for the
respectively. el
(c) H+ The value of
l
104. The rusting of iron is

catalysed by 105. Standard solution of pentane-oxygen fuel Reason In mercury
KNO3 is used to cell is cell, the electrolyte is
[CG make salt bridge a paste of KOH and
because (a) 1.968 V
PMT ZnO.
Haryana PMT] V
,
(c) 1.0968 V (a) Both Assertion
Hary (a) velocity of K+ is
ana 3 - 0.0968 V and Reason are
greater than NO . true and Reason is
PMT 107. Assertion The cell
] - correct
3
(b) velocity of NO is potential of mercury explanation of the
(a) Fe (b) O2 greater than K+. cell is 1.35 V, which Assertion.
remains constant.
(b) Both Assertion 2005 (b) B alse.
and Reason are 113. When an acid cell is o th
true and Reason (d) Both Assertion and
charged then t e Reason are false.
is not the correct c
(a) voltage of cell h
explanation of
increases or
the Assertion.
(b) electrolyte of cell A re
(c) Assertion is true 200 ct
dilutes s
but Reason is 4
s e
false. (c) resistance of cell
increases e x
(d) Both Assertion pl
(d) None of the above r
and Reason are
t a
false. 114. The chemical
i n
108. Galvanic cell is a reaction, at
o
device in which 2AgCl(s) + H2 (g) ➔ io
n
2HCl(aq) + 2Ag(s) n
[CBSEATPMT]
taking place in a a of
(a) chemical energy th
is converted into galvanic cell is n
represented by the d e
electrical energy.
notation A
(b) electrical energy ss
is converted into R
(a) Pt(s) I H2 (g),1bar er
chemical energy. e
I 1M KCl(aq) I ti
(c) chemical energy AgCl(s) I Ag(s) a
o
is seen in the s
(b) Pt(s) I H (g),1bar n.
form of heat. o2
I1M HCl(aq)
+ n (c) A
(d) thermal energy I1MAg (aq) I s
from an outside Ag(s)
a s
source is used to
e
drive the cell (c) Pt(s) I H2 (g),1bar r
r
reaction. I 1M HCl(aq) I e t
AgCl(s) I Ag(s) i
2007
t o
109. The eficiency of a (d) Pt(s) I H 2 (g),1bar
r n
fuel cell is given by I 1M HCl(aq) I
Ag(s) I AgCl(s) u
[CBSEATPMT] i
e
115. Assertion Galvanised s
iron does not rust.
a
Reason Zinc has a t
n r
more negative d u
electrode potential e
than iron
R
(a) Both Assertion e b
and Reason are a u
true and t
s
Reason is R
o e
correct n a
explanation of s
the Assertion. i o
(d) s n
�H � �G
H �G
(a) (b) i
�
G �S n
s
o
�G �S t f
(c)
116. Iron pipes, lying in acidic soil, are often attached to 120. Which cell convert electrical energy into chemical
the blocks of magnesium for their protection from energy? [PunjabPMET]
rusting because magnesium [BHU,DUMET]
(a) Voltaic cell (b) Electrolytic cell
(a) is lighter than iron
(c) Galvanic cell (d) Electrochemical cell
(b) is readily converted into positive ion
121. The cell reaction of the galvanic cell
(c) forms a corrosion-resistant alloy with iron 2+ 2+
Cu(s) I Cu (aq) II Hg (aq) I Hg(/J) is [EAMCET]
(d) prevents air from reaching the surface of iron.
2+ 2+
117. Which of the following statements is true for fuel cells? (a) Hg + Cu ➔ Hg + Cu
[PunjabPMET] 2+ + +
(b) Hg + Cu ➔ Cu + Hg
(a) They run till the reactant are active
(c) Cu + Hg ➔ CuHg
(b) They are free from pollution.
2+ 2+
(d) Cu + Hg ➔ Cu + Hg
(c) They are more efficient.
(d) All of the above. 122. Which one of the following metal is used in
galvanisation? [RPMT]
118. In a hydrogen-oxygen fuel cell, combustion of
(a) Cu (b) Ag
hydrogen occurs to [DUMET]
(c) Zn (d) Fe
(a) generate heat.
(b)create potential difference between the two
electrodes.
(c) produce high purity water
(d) remove adsorbed oxygen from electrode surfaces.
2003
119. Which of the following reaction is used to make a fuel
cell? [ATTMS]
(a) Cd(s) + 2Ni(OH)3 (s) ➔ CdO(s)

+ 2Ni(OH)2 (s) + H2O(/J)
(b) Pb(s) + PbO2 (s) + 2H2SO4 (aq) ➔ 2PbSO4 (s)

+ 2H2 O(/J)
(c) 2H2 (g) + O2 (g) ➔ 2H2O(/J)

+ 2+
(d) 2Fe(s) + O2 (g) + 2H (aq) ➔ 2Fe (aq) + 2H2 O(/J)
ANSWER KEY
EXERCISE - 1 : (Basic Objective Questions)
1. (d) 2. (c) 3. (d) 4. (c) 5. (d) 6. (a) 7. (a) 8. (a) 9. (d) 10. (c)
11. (b) 12. (d) 13. (d) 14. (a) 15. (b) 16. (c) 17. (d) 18. (b) 19. (a) 20. (a)
21. (a) 22. (b) 23. (d) 24. (a) 25. (d) 26. (b) 27. (b) 28. (b) 29. (b) 30. (c)
31. (d) 32. (c) 33. (b) 34. (d) 35. (d) 36. (c) 37. (a) 38. (a) 39. (c) 40. (a)
41. (b) 42. (d) 43. (c) 44. (c) 45. (a) 46. (d) 47. (c) 48. (b) 49. (d) 50. (c)
51. (c) 52. (b) 53. (a) 54. (a) 55. (a) 56. (a) 57. (b) 58. (a) 59. (b) 60. (a)
61. (c) 62. (c) 63. (d) 64. (a) 65. (d) 66. (b) 67. (b) 68. (b) 69. (c) 70. (d)
71. (b) 72. (c) 73. (a) 74. (c) 75. (c) 76. (a) 77. (d) 78. (a) 79. (b)
EXERCISE - 2 : (Previous Year Competition Questions)

1 . (c) 2 . (b) 3. (b) 4. (a) 5. (a) 6. (a) 7. (b) 8. (d) 9. (b) 10. (a)
11. (b) 12. (a) 13. (c) 14. (b) 15. (a) 16. (b) 17. (b) 18. (d) 19. (c) 20. (c)
21. (d) 22. (b) 23. (b) 24. (d) 25. (a) 26. (d) 27. (a) 28. (b) 29. (c) 30. (b)
31. (d) 32. (a) 33. (d) 34. (b) 35. (c) 36. (d) 37. (b) 38. (b) 39. (a) 40. (b)
41. (c) 42. (b) 43. (c) 44. (a) 45. (c) 46. (d) 47. (c) 48. (d) 49. (a) 50. (b)
51. (b) 52. (c) 53. (a) 54. (a) 55. (a) 56. (a) 57. (c) 58. (a) 59. (c) 60. (d)
61. (a) 62. (a) 63. (a) 64. (c) 65. (b) 66. (d) 67. (c) 68. (c) 69. (a) 70. (a)
71. (c) 72. (b) 73. (c) 74. (d) 75. (d) 76. (d) 77. (d) 78. (b) 79. (b) 80. (b)
81. (b) 82. (d) 83. (a) 84. (b) 85. (c) 86. (c) 87. (a) 88. (a) 89. (c) 90. (d)
91. (c) 92. (d) 93. (a) 94. (b) 95. (b) 96. (c) 97. (b) 98. (a) 99. (c) 100. (c)
101. (c) 102. (d) 103. (c) 104. (c) 105. (c) 106. (c) 107. (b) 108. (a) 109. (c) 110. (b)
111. (a) 112. (b) 113. (a) 114. (c) 115. (a) 116. (b) 117. (d) 118. (b) 119. (c) 120. (b)
121. (d) 122. (c)
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7.

1.ELECTROCHEMISTRY the external circuit. Anode is assigned negative polarity

(i) 1M concentration of each ion in the solution.

are represented as the standard reduction potential

Since anode is put on left and cathode on right, it

For a Daniel cell, therefore

10. CELL DIAGRAM OR REPRESENTATION OF A CELL

The followingconventions or notations areapplied for

Cathode: Mn+ + ne- M

13.2 Gas Electrodes

Cathode: 2H+ + 2e- H

H2I H+(c ) II H+ (c2 ) I H

15. APPLICATIONS OF NERNST EQUATION H2(P ) I H+ (C) II H+ (C) I 2H2 (P )

15.1 Equilibrium Constantfrom Nernst Equation P2

l Zn where p2 < p for spontaneous reaction

+ The EMF of concentration cell at 298 K is given by

E ocell = 2.303 RT log Kc 17.1 Electrolysis of molten sodium chloride

n 2Cl- ➔ Cl + 2e- EO = - 1.36V

Example Dry Cell or Leclanche cell and Mercury cell.

Anode : 2H (g) + 40H- (aq) 4H 0 (l) + 4e-

overall Reaction : 2H2(g) + 02 (g) 2H20 (l)

21. CONDUCTANCE (G)

2Fe (s) + O (q) + 4H+ ➔ 2Fe2+ + + 2H O E0= 1.67 M

Rusting of iron can be avoided by painting it or by

(i) Nature of electrolyte or interionic attractions : Lesser

(iv) Temperature : As the temperature of electrolytic -1

24. MEASUREMENT OF CONDUCTANCE 26. EQUIVALENT CONDUCTIVITY (A )

1 /J It is conducting power of one equivalent of electrolyte

Where, v is the volume of solution in cm3 containing

For example, molar conductivity of acetic acid at

m CH3 -COOH m CH3 -COONa m HCl m NaCl

determine the molar conductivity at infinite o

case of strong electrolyte by extrapolation of curve of

29. KOHLRAUSCH'S LAW

STANDARD REDUCTION POTENTIALS AT 298 K. IN ELECTROCHEMICAL

H Xe0 + 2H+ + 2e- ➔ Xe0 + 3H 0 + Hg S0 + 2e- ➔ 2Hg + S02- + 0.62

2HCl0 + 2H+ + 2e- ➔ Cl + 2H 0 + Ag2Cr04 + 2e- ➔ 2Ag + + 0.45

2HBr0 + 2H+ + 2e- ➔ Br + 2H 0 + Cl0-- + H 2 0 + 2e- ➔ Cl0- + + 0.36

Mn3+ + e- ➔ Mn2+ + Cu2+ + 2e- ➔ Cu + 0.34

Au3+ + ➔ Au + Hg2Cl2 + 2e- ➔ 2Hg + 2Cl- + 0.27

MN02+ 4H+ + 2e- ➔ Mn2+ + 2H

Ti3+ + e- ➔ Ti2+ - 0.37 V2+ + 2e- ➔ V - 1.19

Ag+ + e- ➔ Ag + 0.80 Ca2+ + 2e- ➔ Ca - 2.87

Ag2Cr04 Ce4+ + e- ➔ Ce3+ + 1.61

Au+ + e- ➔ Au + 1.69 Cl0- + H 0 + 2e- ➔ Cl0- +

Cr3+ + e- ➔ Cr2+ - 0.41

4 Cs+ e- ➔ Cs - 2.92 Mn0- + 2H2 0 + 2e- ➔ Mn0

2Hg2+ + 2e- Pt2+ + 2e- ➔ Pt + 1.20

I2 + 2e- ➔ 2I- + Rb+ + e- ➔ Rb - 2.93

1000 1000 Sol. Anode: Fe s --➔

reaction will take place. Therefore, we cannot stir a Fe 0 . xH 0

Cathode : Ag+ (aq) + e- --➔ Ag s

Sol. Kohlrausch's law of independentmigrationof ions: The

the current flow ?

cathode in the above cell if inert electrodes are

(b) Inert electrodes

7.5 x 10-3 Msolution of KCl at 25oC was 1005 ohms.

= 1.65 x 10-5 mol L-

Example - (iii) Which electrode will be positive ?