Electro Chemistry

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CHEMISTRY
Reconstruct Your Chemistry With Prince Sir
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CHEMISTRY
The branch of chemistry which deals with the study of relationship between
electrical energy
and chemical energy and interconversion of one form of energy into an-
other is called
electrochemistry.
Conductors :- The substances which allow the passage of electricity through
them are called conductors.
Insulators / Non-conductors :- The substances which donot allow the
passage of electricity through them are called insulators.
Conductors are broadly of 2 types
(a) Metallic conductors :- These are the metallic substances which allow the
passage of electricity through them without undergoing any chemical change.
e.g. copper, silver, aluminium etc. Besides metals,
(b) Electrolytes :- These are the substances which allow the passage of
electricity through their molten state or through their aqueous sol.s and also
undergo chemical decomposition at the same time.
Some minerals & non-metal graphite also show conduction due to the movement
of electrons. They are collectively called electronic conductors.
Factors affecting electrolytic conduction
(i ) The inter - ionic attraction :- These are the attractive interactions between
the ions furnished by the electrolyte in solution and are referred to as solute
solute interaction. Larger the interionic attraction lesser is freedom of movement
and smaller will be the electrical conductivity.
(i i ) Solvation of ions :-These are the attractive interactions between the ions
of the electrolyte and molecules of the solvent and called as solute solvent
interactions. Larger the solute solvent interactions greater is the extent of solvation
and lower will be the electrical conductivity of the solution.
CHEMI STRY
ELECTRO CHEMI STRY
THEORY SHEET
I I T
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CHEMISTRY
(ii i) Viscosity of solvent :- It refers to the attractive interactions between the
solvent molecules called as solvent solvent interactions. Larger the solvent - solvent
interactions larger will be the viscosity and more will be the hinderance to the
movement of ions and hence lower will be the electrical conductivity.
(iv) Temp. :- As the temp. of electrolyte solution is increased, the effect of above
factors diminishes and kinetic energy of the ions increases. Thus electrical
conductance of electrolytic solution increases.
Terms related to electrical conductivity
1. Resistance :- Every conducting material offers some obstruction to the flow
of electricity which is called resistance. Ohms law relates resistance (R) to the
current strength.
Ohms law :- It is obeyed by metallic as well as electrolytic conductors. It states
that
the potential difference across the conductors is directly proportional to
the current flowing through it
i.e. Potential difference current
or
Potential difference
Current
= Constant
Mathematically :-
V
I
= R or I =
V
R
2. Resistivity :- Resistance (R) of any conductor is directly proportional to the
length (l) of the conductor and inversely proportional to its area (a) of cross
section :-
R
l
a
or R =

l
a
units W cm.
Where

(rho) is the constant of proportionality & called as specific resistance or
resistivity. It is given as
=
Ra
l
. If l = 1 cm., a = 1 cm
2
then R =

and
hence Resistivity may be defined as resistance offered by the conductor of 1 cm
length with area of cross section equal to 1 cm
2
.
3. Conductance (G) :- It is the measure of the ease with which current flows
through the conductor . It may be defined as the reciprocal of resistance. It is
denoted by G.
R R
R
1 4
3
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CHEMISTRY
G =
1
R
unit O
1
or mho.
4. Specific conductance or conductivity (k) :- It is the reciprocal of specific
resistance. It may also be defined as the conductance of one centimeter cube of
the conductor. It is represented by Greek letter Kappa (k)
k =
1 1
=
R
l
a
unit O
1
cm
1
.
5. Molar conductivity ( A
m
) :- It may be defined as the conductance of a solution
containing 1g molecule or 1 mol of electrolyte such that the entire solution is
placed between two electrodes one centimeter apart. It is denoted by the symbol
A
m
. It is related to conductivity (k) as
A
m
= kV or A
m
=
K
C
V :- Vol. , C :- conc.
If C of sol is in mol L
1
then 1 g mol of electrolyte is present in
1000
C
cm
3
of sol.
Thus A
m
= k Units :- Ohm
1
cm
2
mol
1
/ s cm
2
mol
1
.
Experimental Measurement of electrical conductivity
Arrangement of Wheatstone bridge :-
As conductance is reciprocal of its resistance, if resistance of solution is
known, its conductance can be easily calculated. Resistance can be measured
with the help of wheatstone bridge. The resistances R
1
, R
3
& R
4
are so adjusted
that a null point is obtained. The null point is indicated by detector
At null point
R
2
=
3
4 1
R
R R
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CHEMISTRY
Knowing R
1
, R
4
& R
3
, R
2
can be calculated & its reciprocal gives the conductance
of the solution
Note:- D.C. current can not be used inthe experiment because -
(i) Change in the concentration of the solution occurs due to electrolysis which
will change the resistaance.
(ii) Polaristaion of the electrodes which also changes the resistanxce.
Thus an A.C. current is used.
Variation of conductivity and Molar conductivity with concentration
1. Variation of (K) with conc. :- K (conductivity) refers to the conductance of
one centimeter cube of the electrolyte. With the |se in dilution, the no. of ions
present in one cm
3
of the sol. !ses. Thus conductivity of the electrolytic solution
also !ses as the dilution |ses.
2. Variation of molar conductivity with conc. :-
(a) Strong Electrolyte :- These are completely ionised in their aqueous
solution e.g. KCl, NaOH etc.
(b) Weak Electrolytes :- They ionise in aqueous sol. to the smaller extent or
we can say they have low degree of ionisation, but |ses with dilution e.g.
NH
4
OH, CH
3
COOH etc.
1. Molar conductivity of electrolytes generally |ses with dilution.
2. Relative : |se in the value of A
m
for strong electrolyte is quite small as
compared to that for weak electrolytes.
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CHEMISTRY
As shown in the graph, molar conductivity of strong electrolytes attains a definite
limiting value when the conc. approaches zero or dilution approaches . It is
denoted by A
m
& can be obtained from graph. In case of weak electrolytes such

as CH
3
COOH, molar conductivity at dilution cannot be obtained. It can
however be obtained by using Kohlrauschs law.
Explanation :-
1. For weak electrolytes :- On dilution, the degree of ionisation of the weak
electrolyte ses, there by sing the value of A
m
. Thus when limiting value of
molar conductivity is reached, the degree of ionisation of weak electrolytes approaches
unity i.e. whole of solute dissociate into ions. Thus a (degree of dissociation)
Ostwald dilution law.
= =
A
A
m
m
Molar conductivity at given conc.
Molar conductivity at dilution
2. For strong electrolyte :- For strong electrolyte, the no. of ions in the sol. donot
|ses because these are almost completely ionised in sol. at all concs. However
in conc. sol. of strong electrolytes, inter ionic interactions are quite strong which
reduce the speed of ions and hence A
m
.
Thus on |sing the dilution, ions move apart and inter ionic interactions
!ses and A
m
|ses. A
m
& A
m
for strong electrolytes are related by Debye Huckel

Onsager eq.
A
m
= A
m
b c
b = const. which depends upon viscosity & dielectric const of solvent
c = conc. of sol.
Kohlrauschs law
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CHEMISTRY
It states that at infinite dilution, when the dissociation of electrolyte is
complete, each ion makes a definite contribution towards the molar conductivity
of electrolyte, irrespective of the nature of the other ion with which it is associated.
Molar conductivity at

dilution can be expressed as the sum of the
contribution of its individual ion. If
&
-
represent the molar

conductivity of cation & anion respectively at dilution,
A
m
v v
- -
+
&
represent the no. of +ve and ve ions furnished by electrolyte.

Applications :-
1. Calculation of molar conductivities A
m
of weak electrolytes at dilution.

2. Calculation of degree of dissociation of weak electrolytes
o =
A
A
M
c
m
3. Calculation of dissociation constant of weak electrolytes

K =
Co
o
2
1 -
Also o =
A
A
A A
A A
m
c
m
m
c
m
m
c
m
k
C
=
-
( / )
/
2
1
Thus K =
C m
c
m m
c
m
A
A A A
2

- ( )
4. Determination of the solubility of sparingly soluble salts
A
m
=
K
Molarity
1000
A
m
=
K
Solubility
1000
or Solubility =
k
m
1000
A
Ionic salts like AgCl, BaSO
4
etc. dissolve in H
2
O to a very small extent. They are
sparingly soluble salts.
5. Calculation of Ionic Product of H
2
O
K
o
=
-
[ ][ ] H OH
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CHEMISTRY
It is found that ionic conductances H
+
and OH
at dilution are

H H
cm cm
0
O
= =
- -
349 8 198 5
1 2 1 2
. , . O O
By Kohlrauschs Law
A
H
H
OH
2
0
0 0 0
= -
= 349.8 + 198.5 = 548.7
O
-1 2
cm
Specific conductance of pure water at 298 K is found to be K = 5.54 10
8
W
1
cm
1
Applying the formula
A
m
o
K =
1000
Molarity
Molarity i.e. [H
+
] = [OH
-
]
Example1- The specific conductivity of 0.02M KCl solution at 25
0
C is
2.768 x 10
-3
ohm
-1
cm
-1
. The resistance th of this solution at 25
0
C when
measured with a particular cell was 250.2 ohm. The resistance of 0.01M CuSO
4
solution at 25
0
C measured with same cell was 8331 ohm. Calculate the molar
conductivity of CuSO
4
solution.
Solu.- Cell constant = sp. conductance of KCl/ conductance of KCl
= = 0.692
Now for 0.01M CuSO4 solution
Sp. conductivity = cell constant x Conductance = 0.692 = 8.312 x10
-5
Molar conductivity = sp. conductivity = 8.312 x 10
-5
= 8.312 x 10
-5
ohm
-
1
cm
2
mol
-1
Ex2- The conductivity of a saturated solution of AgCl is found to be
1.86x 10
-6
ohm
- 1
cm
-1
and that of water is 610
-8
ohm
-1
cm
-1
.Calculate the
solubility of AgCl if ohm
-1
cm
2
eq
-1
.
Sol u. k
AgCl
= k
AgCl(solution)
- k
Water
= 1.86 10
-6
- 610
-8
= 1.8 10
-6
S
AgCl
1000
0
= A
0
1000
AgCl
S
A
=

= 1.31 10
-5
M
Practice Exercise
Q. 1. The equivalent conductance of an infinitely dilute solution of NH
4
Cl is
150 and the ionic conductances of OH
-
and Cl
-
ions are 198 and 76
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CHEMISTRY
respectively. What will be the equivalent conductance of the solution of NH
4
OH
at infinite dilution.If the equivalent conductance of a 0.01N solution is 9.6,
what will be its degree of dissociation?
Ans- 0.0353
Q. 2. Given the equivalent conductance of sodium butyrate, sodium chloride
and hydrogen chloride as 83, 127 and 426 mho cm
2
at 25
0
C respectively.
Calculate the equivalent conductance of butyric acid at infinite dilution.
Ans- 382mho cm
2
Q. 3. The molar conductivity of 0.0250 M HCOOH(aq) is 4.61 mS m
2
mol
-1
.
D e t e r m i n e t h e pKa of the acid. Ans- 3.44
Q. 4. At 18
0
C, the mobilities of NH
4
+
and ClO
4
-
ions are 6.6 10
-4
and
5.7 10
-4
cm
2
volt
-1
sec
-1
at infinite dilution. Calculate the equivalent conductance
of ammonium chlorate solution. Ans- 118.69 mho cm
2
eq
-1
ELECTROCHEMICAL CELL
(a) It is the device in which the decrease in free energy during the spontaneous
redox reaction is made to convert chemical energy into electrical energy is
called as electrochemical cell.
(b) Galvanic and voltaic developed such devices and therefore these cells are
also known as Galvanic cells or voltaic cells or redox cells.
(c) The Daniel cell is a typical galvanic cell. It is designed to Make use of the
spontaneous redox reaction between zinc and cupric ion to produce an electric
current.
(d) The Daniel cell reaction represented as
Zn
(S)
+ Cu
+2
(aq)
Zn
+2
(aq)
+ Cu(s)
(e) The Daniel cell can be conventionally represented as
Zn(s) | Zn SO
4
(aq) | salt bridge | CuSO
4
(aq.) | Cu (s) ,
Salt Bridge - It is an invert U-shaded tube filled with concentration
solution of inert electrolytes such as KCl, KNO
3
, NH
4
NO
3
. It filled with inert
electrolytes because for the flow of electric current to give unbroken coutaces
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CHEMISTRY
all over the circuit. It prevents mechanical flow of solution but it provided free
path for migration of ions to maintain an electric current through the
electrolyte solution. It prevents the accumulation of charges.
Galvanic cells : The device in which chemical energy is converted into
electrical energy is called galvanic cell or electrochemical cell or voltaic cell.
In electrochemical cell
Anode (ve terminal) Oxidation occurs at Anode
Cathode (+ve terminal) Reduction occurs at cathode
Working of Cell
a. Zinc undergoes oxidation to form zinc ions.
Zn (s) Zn
+2
(aq.) + 2e
(oxidation)
b. The liberated electrons move towards Cu strip.
c. Cu
+2
ions from electrolytic solution move towards Cu strip, pick up the e
s
and get reduced to Cu atoms which are deposited at the Cu strip
Cu
+2
(aq.) + 2e
Cu (s) (Reduction)
Thus Zn is Anode and Cu is cathode.
Salt Bridge & its Function
Salt Bridge is a U-shaped tube containing a semisolid paste of some inert
electrolyte like KCl, KNO
3
, NH
4
Cl etc. in agar - agar & gelatine. An inert
electrolyte is one which
a. does not react chemically with the sol. in either of the compartment.
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CHEMISTRY
b. does not interfere with the net cell reaction.
Functions of salt Bridge
(i)It allows the flow of current by completing the circuit.
(ii) It maintains electrical neutrality.
(iii) It prevents accumulation of charges on electrodes & maintain flow of current.
(iv) It prevents liquid junction potential i.e. the potential difference which arises
between the two solutiuons when in contact with each other.
Note:- EMF is applied to an electrolytic cell whereas EMF is generated by
a galvanic cell.
Representation of Galvanic cell
Let M represent the element and M
n+
its cation. Thus oxidation half cell is
represented as M/M
n+
(C) [C molar conc. of ions]
Reduction half cell is represented as M
n+
(c) / M.
A cell is represented by writing the cathode on the RHS and anode on LHS.
The two vertical lines are put between the two half cells which indicates salt
bridge. The molar concentration is written in brackets after the ion.
for eg.
Z
n
Conventional current
Electron flow
Z Cu
n
2
1
( ) / /
( )
1M Saturated / Cu
KCl
M
+2
Anode () Cathode (+)
Salt Bridge Reduction Half. Oxidation Half
L LHS
O Oxidation
A Anode
N -ve terminal
ELECTRODE POTENTIAL
When a metal is placed in a solution of its ions, the metal acquires either a
positive or negative charge with respect to the solution on account of this a
definite potential difference is developed between the metal and the solution.
This potential difference is called electrode potential. .
Example - If a Zn plate is placed in a solution having Zn
+2
ions, it becomes
negatively charged with respect to solution and thus a potential difference is
set up between Zn plate and the solution.
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CHEMISTRY
(i) The conversion of metal atoms into metal ions by the attractive force of
polar water molecules.
M M
n+
+ ne
The metal ions go into the solution and electrons remains on the metal
making it negatively charged.
The tendency of the metal to change into ions is known as
electrolytic solution pressure
(ii) Metal ions start depositing on the metal surface leading to a positivecharge
on the metal. This tendency of the ion is termed osmotic pressure
The potential difference between the elctrode and the elctrolytic solu-
tion, when the electrode is in contact with the solution is called Electrode
potential.
The magnitude of electrode potential depends on-
(i) Nature of the elctrode
(ii) Concentration of the ions in solution
(iii) Temperature
Electrode potenial is of two types-
1. Oxidation Potential(E
ox
) 2. Reduction Potential (E
red
)
E
ox
= - E
red
EMF of the cell
It may be defined as the potential difference between the two terminals of the
cell when either no or very little current is drawn from it. It is measured by
potentiometer or by vaccum tube voltmeter.
EMF = E
cathode
E
anode
Standard Electrode Potential
It is not possible to measure the absolute value of the single elctrode potential
directly.
The common reference electrode used for
this purpose is standard hydrogen electrode
(SHE) or normal hydrogen electrode (NHE)
whose electrode potential is arbitrarily taken
to be zero. SHE have zero standard potential at all temps.
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CHEMISTRY
It consists of a platinum foil coated with platinum
black (finely divided platinum) dipping partially
into an aqueous sol. in which the activity of
hydrogen ion is unity and hydrogen gas is bubbled
through the sol. at 1 bar press & 298 K.
It can act as anode as well as cathode.
If SHE acts as anode then oxidation occurs as :
H
2
(g) 2H
+
(aq.) + 2e
If SHE acts as cathode than reduction occurs as :-

2H
+
(aq.) + 2e
H
2
(g)
The electrode potentials of other electrodes are
determined by coupling them with SHE.
Difference between EMF and Potential Difference- P.D. is the difference between
the elctrode potentials of the two elctrodes under any condition while EMF is the
potential generated by cell when it draws no current. EMF is the mximum voltage
that a cell can deliver.
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CHEMISTRY
Nernst Eq. for Electrode potential
For a general reaction such as
m
1
A + m
2
B + . . . . n
1
X + n
2
Y + . . . .
Gibbs free energy change can be given by the equation
AG = AG
0
+ 2.303 RT log
10
....
....
2 1
2 1
m m
n n
B A
Y X
-nFE = -nFE
0
+ 2.303 RT
Reactants
Products
log
10
E = E
0
-
nF
RT 303 . 2
log
10
Q at 25
0
C.
(This equation can be used for any single electrode)
M
n+
(aq.) + ne
M (s)
The potential of the electrode at any conc. measured with respect to standard
hydrogen electrode can be represented by
E = E
RT
nF
M
M
n
ln
Converting natural logarithm to the base 10,

we get E = E
0

2.303 RT
nF
log
[M]
[M
n 1
]
putting R = 8.314 JK
1
mole
1
, T = 298 K and F = 96500 coulombs, in above
eq. we get
E = E
00591 1 .
log
n M
n
[ Since molar conc. of solid is taken as unity [M] = 1 ]
For a general electrochemical reaction
aA + bB
ne
-

cC + dD.
Nernst eq. may be written as :-
E = E
RT
nF
C D
A B
c d
a b
ln
E = E
0

c
Q
nF
RT
log
303 . 2
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CHEMISTRY
Note :- If Q is inreased by 10 than EMF decreases by 59.2 mV and if Q is
decreased by 10 than EMF increases by 59.2 mV.
Nenst Equation and Equilibrium Conditions
at equilibrium E = 0 and Q
c
= K
c
E =
2 303 .
log
RT
n F
K
c
Electrochemical Series :-
By measuring the potential of various electrode versus hydrogen electrode
(SHE) a series of standard electrode potentials has been established.
When the electrode (metal and non-metal) in contact with their ions are ar-
ranged on the basis of the values of their standard reduction potentials or
standard oxidation potentials. The resulting series is called the electrochemi-
cal or electromotive or activity series, of the elements.
S.NO. Reduction half cell reaction E in volts at 25C
1. F
2
+ 2e
2F
+ 2.65
2.
- 2
8 2
O S + 2e

- 2
4
SO 2 + 2.01
3. Co
3+
+ e
Co
2+
+ 1.82
4. PbO
2
+ 4H
+
+
- 2
4
SO + 2e
PbSO
4
+ 2H
2
O + 1.65
5.
-
4
MnO + 8H
+
+ 5e
Mn
2+
+ 4H
2
O + 1.52
6. Au
3+
+ 3e
Au + 1.50
7. Cl
2
+ 2e
2Cl
+ 1.36
8.
- 2
7 2
O Cr + 14H
+
+ 6e
2Cr
3+
+ 7H
2
O + 1.33
9. O
2
+ 4H
+
+ 4e
2H
2
O + 1.229
10. Br
2
+ 2e
2Br
+ 1.07
11.
-
3
NO + 4H
+
+3e NO + 2H
2
O + 0.96
12. 2Hg
2+
+ 2e

2
2
Hg + 0.92
13. Cu
2+
+ I
+ e
CuI + 0.86
14. Ag
+
+ e
Ag + 0.799
15.
2
2
Hg + 2e
2 Hg + 0.79
16. Fe
3+
+ e
Fe
2+
+ 0.77
17. I
2
+ 2e
2I
+ 0.535
18. Cu
+
+ e
Cu + 0.53
19. Cu
2+
+ 2e
Cu + 0.34
20. Hg
2
Cl
2
+ 2e
2Hg + 2Cl
+ 0.27
21. AgCl + e
Ag + Cl
+ 0.222
22. Cu
2+
+ e
Cu
+
+ 0.15
23. Sn
4+
+ 2e
Sn
2+
+ 0.13
24. 2H
+
+ 2e
H
2
0.00
25. Fe
3+
+ 3e
Fe 0.036
26. Pb
2+
+ 2e
Pb 0.126
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CHEMISTRY
27. Sn
2+
+ 2e
Sn 0.14
28. AgI + e
Ag + I
0.151
29. Ni
2+
+ 2e
Ni 0.25
30. Co
2+
+ 2e
Co 0.28
31. Cd
2+
+ 2e
Cd 0.403
32. Cr
3+
+ e
Cr
2+
- 0.41
33. Fe
2+
+ 2e
Fe -0.44
34. Cr
3+
+ 3e
Cr 0.74
35. Zn
2+
+ 2e
Zn 0.762
36. 2 H
2
O + 2e
H
2
+ 2OH
0.828
37. Mn
2+
+ 2e
Mn 1.18
38. Al
3+
+ 3e
Al 1.66
39. H
2
+ 2e
2H
2.25
40. Mg
2+
+ 2e
Mg 2.37
41. Na
+
+ e
Na 2.71
42. Ca
2+
+ e
Ca 2.87
43. Ba
2+
+ 2e
Ba 2.90
44. Cs
+
+ e
Cs 2.92
45. K
+
+ e
K 2.93
46. Li
+
+ e
Li 3.03
Applications of Electrochemical Series
1. Relative oxidising and reducing powers of various substances :-
Substances with higher reduction potentials have more tendency to accept
electrons so they are strong oxidising agents while substancess with lower
reduction potentials are strong reducing agents.
2. Calculation of standard EMF of the cell
E
cell
= E
cathode
E
anode
3. Predicting feasibility of redox reaction
For a cell reaction to be spontaneous or feasible the E
cell
is +ve reaction is
feasible otherwise not.
Ex. Peroxod sulphate salts (e.g. Na
2
S
2
O
8
) are strong oxidising agents used as
bleaching agents for fats, oils and fabrics. Can oxygen gas oxidisesulphate
ion to peroxodisulphate ion (S
2
O
8
2
) in acidic solution, with the O
2
(g) being
reduced to water
Given O
2
(g) + 4H
+
(aq) + 4e
2H
2
O E = 1.23 V
S
2
O
8
2
(aq) + 2e
2SO
4
2
(aq) E = 2.01 V
Sol . We want oxidation of SO
4
2
by O
2
(g) which in turn is reduced to H
2
O in
acidic medium.
Oxdn. 2SO
4
2
S
2
O
8
2
+ 2e E = 2.01 V
Redn. O
2
(g) + 4H
+
+ 4e
2H
2
O E = +1.23 V
Net. 4SO
4
2
+ O
2
(g) + 4H
+
2S
2
O
8
2
+ 2H
2
O E
cell
= 0.78 V
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CHEMISTRY
The large negative values of E
cell
indicates that O
2
(g) will not oxidise SO
4
2
to S
2
O
8
2
to any significant extent.
4. Predicting the capability of metal to displace H
2
gas from acid
All metals lying above H
2
in electrochemical series can liberate H
2
gas by
reaction with acids while the metal lying below hydrogen in the electrochemical
series cannot undergo such a reaction.
Reaction between metal m & acid to liberate H
2
gas is as follows :-
M + n H
+
(aq.) M
n+
(aq.) +
n
2
H
2
.
5. Thermal stability of metal oxides
The thermal stability of metal oxide depends on its electropositive nature, as
the elctropositive nature decreases from top to bottom in the electrochemical series
the thermal stability of oxides decreases . Thus the oxide of metal having high
positive reduction potential are not stable towards heat.
6. Products of electrolysis
Electrolysis :- It may be defined as a process of decomposition of an electrolyte by
the passage of electricity through its aqueous solution or molten state.
Electrolysis is conducted in an electrolytic cell which consist of two metal
rods dipped in electrolytic solution. The electrode where reduction takes place is
called cathode while electrode where oxidation takes place is called anode.
Some of the electrolysis processes
1. Electrolysis of molten sodium chloride (NaCl) :-
Electrolytic reaction
NaCl (l) Na
+
(aq.) + Cl
(aq.)
Cathode :-
Na
+
+ e
Na (Reduction)
Anode :-
Cl
Cl (oxidation) + e
-
Cl + Cl Cl
2
or 2Cl
Cl
2
. + 2e
Overall Reaction :-
2Na
+
(aq.) + 2Cl
(aq.) 2Na (l) + Cl

2
(g)
(molten state)
Thus Cl
2
gas is liberated at anode.
18
CHEMISTRY
2. Electrolysis of an aqueous sol. of NaCl
NaCl (aq.) Na
+
(aq.) + Cl
(aq.)
H
2
O (l) H
+
(aq.) + OH
(aq.)
At cathode (ve electrode) :- Both Na
+
and H
+
move towards cathode but as
discharge potential of H
+
ions is lower than that of Na
+
ions, therefore H
+
ions
will be discharged at cathode
H
+
+ e
H
H + H H
2
(g)
At anode (+ve electrode ) :- Both Cl
and OH
move towards anode but as discharge

potential of Cl
ions is lower than that of OH
ions therefore Cl
must be
discharged at anode.
Cl
Cl
Cl + Cl Cl
2
(g)
Thus H
2
gas is liberated at cathode, while Cl
2
gas is liberated at anode & NaOH
remains in the sol.
3. Electrolysis of aqueous CuSO4 sol. (Pt Inert electrodes) :-
CuSO
4
(aq) Cu
+2
(aq.) + SO
4
2
(aq.)
H
2
O (l) H
+
(aq.) + OH
(aq.)
At cathode :- Both Cu
+2
and H
+
ions move towards cathode but as discharge potential
of Cu
+2
ions is lower than that of H
+
ions, therefore, Cu
+2
ions are discharged at
cathode.
Cu
+2
+ 2e
Cu
At anode :- Both SO
4
2
and OH
ions are present near anode but as discharge potential

of OH
ions is lower than that of SO

4
2
ions therefore OH
ions are discharged at

anode.
4OH
4OH + 4e
4OH 2H
2
O (l) + O
2
(g)
.
Prediction for the occurence of a redox reaction:-
For a reaction to be spontaneous AG
0
< 0,
since, AG
0
= - nFE
0
, so for the a redox reaction to occur E
0
cell
> 0
i.e. EMF of the cell must be positive.
19
CHEMISTRY
Question Using the standard values, predict the reaction will occur or not?
(i)Fe
3+
(aq) & I
-
(aq) (ii)Ag+(aq) & Cu(s)
(iii) Ag(s) & Fe
3+
(aq) (iv) Br
2
(aq) & Fe
2+
(aq)
Given - V E
Fe Fe
77 . 0
0
/
2 3 = ,
V E
I I
54 . 0
0
/
2
= - ,
V E
Ag Ag
80 . 0
0
/
= ,
V E
Cu Cu
34 . 0
0
/
2 = ,
V E
Br Br
08 . 1
0
/
2
= -
Practice Exercise
Q. 1. Will Fe be oxidised to Fe
2+
by reaction with 1M HCl ? V E
Fe Fe
44 . 0
0
/
2
=
.
Q. 2.
) ( ) 10 1 ( ) 2 . 0 ( ) (
3 2
s Ag Ag M Mg s Mg
-

V E
Ag Ag
8 . 0
0
/
=
,
V E
Mg Mg
37 . 2
0
/
2
- =
What will be the effect on EMF if concentration of Mg

2+
is decreased to 0.1M.
Q. 3. Reactions of tollens reagent are as follows
Ag
+
+ e
-
Ag V E
red
8 . 0
0
=
C
6
H
12
O
6
+ H
2
O C
6
H
12
O
7
+ 2H
+
+ 2e
-
V E
Oxd
05 . 0
0
- =
Ag(NH
3
)
2
+
+ e
-
Ag + 2NH
3
V E
red
373 . 0
0
=
(i) The value of lnK for
2Ag
+
+ C
6
H
12
O
6
+ H
2
O 2Ag + C
6
H
12
O
7
+ 2H
+
will be?
(ii) If on addition of NH
3
, pH of solution rises to 11, then which of the following
electrode is affected by change in pH.
(a) E
ox
increase over E
0
by 0.65V.
(b) E
red
increase over E
0
by 0.65V.
(c) E
ox
decrease over E
0
by 0.65V.
(d) E
red
decrease over E
0
by 0.65V.
Q. 4. The EMF of the cells obtained by combining Zn & Cu electrodes of deniel
cell
with calomel elctrodes are 1.083V and -0.018V respectively at 25
0
C. If reduction
potential of normal calomel electrode is 0.28V, find EMF of daniel cell.
Q. 5. Consider the following cell
) 2 ( ) 1 ( / ) 1 ( , ) 1 (
3 4 2 3
Pt a Ce Ce a Fe Fe Pt = =

V E
Fe Fe
77 . 0
0
/
2 3
=
, V E
Ce Ce
61 . 1
0
/
3 4
=

20
CHEMISTRY
If an ammeter is connected between the two Pt electrodes predict the direction
of flow of current. Ans- Pt(1) to Pt(2).
Q. 6. Two students use same stock solution of ZnSO
4
and a solution of CuSO
4
.
The EMF of one cell is 0.03V higher than that of other. The concentration of
CuSO
4
in the cell with higher EMF value is 0.5 M. Find out the concentration of
CuSO
4
in the other cell.
Q. 7. An excess of granular Zn was added to 500 ml of 1 M Nickel nitrate till
equillibrium was established. Find out the concentration of Ni at equillibrium.
Given V E
Zn Zn
75 . 0
0
/
2 - = , V E
Ni Ni
24 . 0
0
/
2 - =
Thermodynamic Treatment Of Nernst Equation
(1) Gibbs Free energy and cell Potential
Electrical work done = - nF Ecell.
We know that electrical work done on the system is equal to the increase in free
energy of the system.
Hence : AG = - nF Ecell
AG = nFE
As Ecell =
RT
nF
ln K
c
.
Putting Ecell value in above eq.
AG =
nF
RT
nF
ln K
c
AG = RT ln K
c
.
or AG = 2.303 RT log K
c
.
(2) Heat of the reaction in the cell
According to Gibbs Helmholtz equation
AG = AH + T
P
T
G
|
'
c
A c
-nFE = AH + T
P
T
nFE
|
'
c
- c ) (
21
CHEMISTRY
AH = -nFE + nFT
P
T
E
|
'
c
c
Where
P
T
E
|
'
c
c
is called the temperature coefficient of the cell
(i) If
P
T
E
|
'
c
c
>0, than process inside the cell is endothermic.
(ii) If
P
T
E
|
'
c
c
<0, than process inside the cell is exothermic.
(3) Entropy change in the cell
AG = AH - TAS . . . . .(1)
AG = AH + T
P
T
G
|
'
c
A c
. . . . .(2)
On comparing the two equations
-TAS = T
P
T
G
|
'
c
A c
AS = -
P
T
G
|
'
c
A c
AS = nF
P
T
E
|
'
c
c
DIFFERENT TYPE OF HALF CELLS
(1) Gas Ion Half Cell:- In this half cell, an inert electrode such as Pt or graphite is
in contact with gas and a solution containing specified ions. for example
Hydrogen-gas-hydrogen cell
In this cell purified H
2
gas at a constant pressure is passed over Pt
electrode which is in contact with an acid solution.
The half cell can act as both cathode and anode
As Cathode: H
+
(aq.) + e
-
1/2H
2
(g)
As Anode : 1/2 H
2
(g) H
+
(aq.) + e
-
According to Nerns equation
E
cell
=
] [
) (
log
1
0591 . 0
+
2
1
10
2
H
p
H
22
CHEMISTRY
(2) Metal insoluble salt-anion half cell:- In this cell a metal coated with its
insoluble salt in contact with a solution containing the anion of the insoluble salt.
Follwing are some comman examples:
(i) Ag / AgCl/ Cl
-
(ii) Hg- Hg
2
Cl
2
- Cl
-
(iii) Hg - HgO - OH
-
(iv) Hg- HgSO
4
- SO
4
2-
(v) Pb - PbSO
4
- SO
4
2-
Rpresentation of Metal insoluble salt-anion half cell :-
Reduction potential - E
anion / insoluble salt / metal
Oxidation potential - E
metal / insoluble salt / anion
(i) Ag-AgCl half cell:-
AS CATHODE AgCl(s) + e
-
Ag(s) + Cl
-
(aq)
AS ANODE Ag(S) + Cl
-
(aq.) AgCl(s) + e
-
Illustration. The SRP of Ag
+
/Ag electrode at 298 is 0.799 volt. K
sp
of AgI is
8.7 10
-17
. Evaluate the potential of the Ag
+
/Ag electrode in a standard solution
of AgI. Also calculate the SRP of I
-
/AgI/Ag electrode.
SOLUTION- The point that must be noted that here a half cell is formed by coupling
Ag+/Ag electrode with AgI solution, so we need to calculate the SRP of a new half
cell.
Reaction at cathode AgI + e
-
Ag + I
-
Reaction at anode Ag Ag + e
-
net reaction AgI Ag + I
-
Now
] [Ag log
1
0.0591
0
/ /
- =
Ag Ag Ag Ag
E E
Ksp = [Ag
+
] [I
-
] = [Ag
+
]
2
= 8.7 10
-17
So, [Ag
+
] = 9.3 10
-9
] [Ag log
1
0.0591
0
/ /
- =
Ag Ag Ag Ag
E E
= 0.799 - 0.0591 log (9.310
-9
)
= 0.324 volt
Now, volt 0.95 - = log
1
0.0591
=
sp
0
K E
cell
23
CHEMISTRY
E
0
cell
= E
C
- E
A
-0.95 =
Ag AgI I
E
/ /
- - 0.799
Ag AgI I
E
/ /
- = -0.151 Volt
(ii) Hg - Hg
2
Cl
2
- Cl
-
(Calomel electrode):-
Hg
2
Cl
2
+ 2e- 2Hg (l) + Cl
-
(aq.)
2
/ /
o
/ /
] log[
2
0.0591
- E
2 2
2 2
-
-
-
= Cl E Hg Cl Hg Cl
Hg Cl Hg Cl
(iii) Pb - PbCl
2
- Cl
-
electrode:-
PbCl
2
+ 2e
-
Pb(s) + 2Cl
-
(aq.)
Illustration 2. Given E
0
= -0.268 V for Cl
-
/PbCl
2
/Pb couple and -0.126V
for the Pb
2+
/Pb couple determine K
sp
of PbCl
2
at 25
0
C.
Solution:- First half cell PbCl
2
(s) + 2e
-
Pb(s) + 2Cl
-
Second half cell Pb
2+
+ 2e
-
Pb(s)
] [
1
log
2
0.0591
- E E
2
/
o
/
2 2

=
Pb
Pb Pb Pb Pb
E
cell
=
Pb Pb Pb PbCl Cl
E E
/
2
/
2
/
-
-
sp
/ /
o
/ Pb
o
2 - 2
/ /
o
/ Pb
o
2 2
/ /
o
/ Pb
o
2
/ /
o
2
/ Pb
o
cell
K log
2
0.0591
) -E - (E
] ][Cl log[Pb
2
0.0591
) -E - (E
] log[
2
0.0591
] log[Pb
2
0.0591
) -E - (E
) ] log[
2
0.0591
- (E -
] [Pb
1
log
2
0.0591
- E E
2
2
2
2
2
2
2
2
=
=
=
=
-
-
-
-
-
-
Pb PbCl Cl Pb
Pb PbCl Cl Pb
Pb PbCl Cl Pb
Pb PbCl Cl Pb
Cl
Cl
E
cell
= 0 , so,
-0.146 =
sp
K log
2
0.0591
K
sp
= 1.56 x 10
-5
24
CHEMISTRY
(3) Concentration Cells:- The cells in which electrical current is produced due to
transport of a substance from higher to lower concentration. There are two types of
concentration cells-
(i) Electrode gas concentration cell:-
Pt, H
2
(P
1
) H
+
(C) H
2
(P
2
) ,Pt
Here, the gas is bubbled at two different partial pressures at electrode dipped
in the solution of same electrolyte.
Cell process
(Cathode) ) (
2
1
e H
2 2
-

P H
(Anode) e H ) (
2
1
-
1 2

P H
reaction) (Net ) (
2
1
) (P H
2
1
2 2 1 2
P H
From Nernst equation
2
1
log
2
0.0591
P
P
E =
For spontaniety P
1
>P
2
Illustration The cell
) ( ) 1 (
2
x pH H atm H Pt =
Normal calomel elctrode

has an EMF of 0.67 V at 25
0
C. Calculate the pH of the solution. The oxidation
potential of the calomel elctrode on hydrogen scale is -0.28 V.
ANS- Applying Nernst equation for the given cell
reactants
Products
log
0591 . 0
0
n
E E
cell cell
- =
anode cathode
o
cell
E E E - = = 028 - 0.0
598 . 6
0591 . 0
28 . 0 67 . 0
] [
log
1
0591 . 0
28 . 0 67 . 0
2
=
-
=
- =
pH
pH
H
A (ii) Electrolyte concentration cell :- Here the concentration difference
creates the potential diffrence at the two electrodes.
Zn(s) | ZnSO
4
(C
1
) || ZnSO
4
(C
2
) | Zn(s)
In such cells, concentration gradient arise in electrolyte solutions. Cell process
may be given as,
25
CHEMISTRY
, ) , ) e 2 C Zn s Zn
1
2

(Anodic process)
) C ( Zn ) C ( Zn
) s ( Zn e 2 ) C ( Zn
1
2
2
2
2
2

(Over all process)
From Nernst equation, we have
- =
2
1
C
C
log
F 2
RT 303 . 2
0 E
or
]
=
1
2
C
C
log
F 2
RT 303 . 2
E
For spontanity of such cell reaction, C
2
> C
1
) ( ), ( .) ( .), ( ), ( ) (
2 2 1 2
s Pt Patm g H C aq H C aq H atm P g H s Pt

2
1
C
C
log
0591 . 0
n
E
cell
- =
(iii) Metal - ion - metal amalgum half cell :-
In this half cell electrode metal amalgam is placed in contact with a
solution containing metal ion. Electrical contact is made by a platinum wire
dipped into amalgam pool .
M
n+
(aq.)(C
2
) + 2e
-
M(Hg) (C
1
)
2
1 0
) ( / ) ( /
C
C
log
0591 . 0
n
E E
Hg M M Hg M M
n n
- =

Note:- Concentration of amalgam is represented as mass of metal per unit
mass of mercury.
26
CHEMISTRY
ELECTROLYSI S
The decomposition of electrolyte solution by passage of electric current,
resulting into deposition of metals or liberation of gases at electrodes is known
as electrolysis.
ELECTROLYTIC CELL
This cell converts electrical energy into chemical energy.
The entire assembly except that of the external battery is
known as the electrolytic cell
ELECTRODES
The metal strip at which positive current enters is called anode; anode is
positively charged in electrolytic cell.
On the other hand, the electrode at which current leaves is called cathode.
Cathodes are negatively charged.
Anode Positive Loss of electron
or oxidation current
takes place enters
Cathode Negative Gain of electron Current
or reduction leaves
takes place
FARADAYS LAWS OF ELECTROLYSIS
1. Faradays First Law:-
According to this law amount of substance deposited on an electrode during
electrolysis is directy proportional to quantity of the electrical charge passed
through the electrolytic solution.
If W is the mass deposited by passing Q coloumb of charge , then
W a Q
or W = ZQ = Z It
Where, Z is known as electrochemical equivalent and is a characteristic of
compound deposited.
Z =
96500
E
So, W =
96500
EIt
Note:- One Faraday is the charge carried by 1 mole of electrons.
27
CHEMISTRY
2. Faradays Second Law :- When same quantity of charge is passed through
different electrolytes, then the masses of different substances deposited are
in the ratio of their equivalent masses.
Al of mass eq.
dep osited Al of
Ca of mass eq.
dep osited Ca of
.
dep osited Na of mass mass
Na of mass eq
mass
= =
llustrations
Q. 1. A current of 3.7 ampere is passed for 6 hours between platinum electrodes in
0.5 litre of a 2M solution of Ni(NO
3
)
2
. What will be the molarity of the solution
at the end of electrolysis? What will be the molarity if Nickel electrodes are used .
Solution:- The electrode reaction is Ni
2+
+ 2e
-
Ni
amount of Ni(NO
3
)
2
decomposed = amount of Ni deposited W=
96500
EIt
For Ni(NO
3
)
2
equivalent mass E =
105
2
210
=
So, W =
95 . 86
96500
3600 6 7 . 3 105
=

Moles of Ni (NO
3
)
2
deposited =
414 . 0
210
95 . 86
=
So, number of moles of Ni (NO
3
)
2
left = 0.52 - 0.414 = 0.586
Molarity =
M 72 . 1
5 . 0
586 . 0
=
When nickel electrodes are used anode will dissolve and get deposited at
cathode, so the molarity of the solution remain unaffected.
Q. 2. An aqueous solution of NaCl on electrolysis gives H
2
(g), Cl
2
(g) and NaOH
according to the reaction:
2 Cl- (aq.) + 2H
2
O 2OH-(aq.) + H
2
(g) + Cl
2
(g)
A direct current of 25 ampere with a current efficiency 62% is passed
through 20 L of NaCl solution (20% by mass). Write down the reactions
28
CHEMISTRY
taking place at the anode and cathode . How long will it take to produce 1
Kg of Cl
2
?What will be the molarity of the solution with respect to hydroxide
ion?
Solution: At anode : 2Cl
-
Cl
2
+ 2e
-
At cathode: 2H
2
O + 2e
-
H
2
+ 2OH
-
effective current = 0.62 25 = 15.5 Amp
mass of chlorine to be deposited = 1 Kg
using W =
96500
EIt
hr
I E
t 71 . 48 . sec 82 . 175374
5 . 15 5 . 35
96500 1000 96500 W
= =
=
For each mole of Cl
2
, 2 moles of OH- are produced, so
OH- produce = 2 moles of Cl
2
= 2 14.08 = 28.16
Molarity =
20
16 . 28
=
Volume
Mole
STORAGE CELLS AND BATTERIES
Batteries can be classified as primary and secondary. Primary batteries can
not be returned to their original state by recharging, so when the reactants are
consumed, the battery is "dead" and must be discarded. Secondary batteries are
often called storage batteries or rechargeable batteries. The reactions in these batter-
ies can be reversed; thus, the batteries can be recharged.
PRIMARY BATTERIES
DRY CELLS AND ALKALINE BATTERIES
Zinc serves as the anode, and the cathode is a graphite rod placed down the
center of the device. These cells are often called "dry cells" because there is no
visible liquid phase.the cell contains a moist paste of NH
4
Cl, ZnCl
2
and MnO
2
.
The moisture is necessary because the ions present must be in a medium in
which they can migrate from one electrode to the other. The cell generates a
potential of 1.5 V using the following half-reactions:
Cathode, reductions: 2NH
4
+
(aq) + 2e
2NH
3
(g) + H
2
(g)
Anode, Oxidation : Zn (s) Zn
2+
(aq) + 2 e
29
CHEMISTRY
MERCURY CELLS
Mercury cell, suitable for low current devices like hearing aids, watches, etc.
consists of zinc mercury amalgam as anode and a paste of HgO and carbon
as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode reactions
for the cell are given below:
Anode: Zn(Hg) + 2OH
ZnO(s) + H
2
O + 2e
Cathode: HgO + H
2
O + 2e
Hg(l ) + 2OH
The overall reaction is represented by

Zn(Hg) + HgO(s) ZnO(s) + Hg(l )
The cell potential is approximately 1.35 V and remains constant during its
life as the overall reaction does not involve any ion in solution whose
concentration can change during its life time.
SECONDARY BATTERIES
A secondary cell after use can be recharged by passing current through it in
the opposite direction so that it can be used again. A good secondary cell
can undergo a large number of discharging and charging cycles. The most
important secondary cell is the lead storage battery.
LEAD STORAGE BATTERY
It is commonly used in automobiles and invertors. It consists of a lead anode
and a grid of lead packed with lead dioxide (PbO2 ) as cathode. A 38%
solution of sulphuric acid is used as an electrolyte.
Reactions when Discharging
The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO
4
2
(aq) PbSO
4
(s) + 2e
Cathode: PbO
2
(s) + SO
4
2
(aq) + 4H+(aq) + 2e PbSO
4
(s)+2H
2
O(l )
i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s)+PbO
2
(s)+2H
2
SO
4
(aq) 2PbSO
4
(s) + 2H
2
O(l)
Reactions when charging
On charging the battery the reaction is reversed and PbSO4(s) on anode and
cathode is converted into Pb and PbO2, respectively.
30
CHEMISTRY
NICKEL-CADMIUM CELL
nickel - cadmium cell which has longer life than the lead storage cell but
more expensive to manufacture.
The chemistry of the cell utilizes the oxidation of cadmium and the
reduction of nickel (III) oxide under basic conditions.
Cathode, reduction :Ni(OH)
3
(s) + H
2
O(l) + e
Ni(OH)
2
(s) + OH
(aq)
Anode, Oxidation: Cd(s) + 2 OH
Cd(OH)
2
(s) + 2e
The overall reaction during discharge is:

Cd (s)+2Ni(OH)
3
(s) CdO (s) +2Ni(OH)
2
(s) +H
2
O(l )
FUEL CELL
Galvanic cells that are designed to convert the energy of combustion of fuels
like hydrogen, methane,methanol, etc. directly into electrical energy are
called fuel cells.
One of the most successful fuel cells uses the reaction of hydrogen with
oxygen to form water . The cell was used for providing electrical power in the
Apollo space programme. The water vapours produced during the reaction
were condensed and added to the drinking water supply for the astronauts.
n the cell,
hydrogen and oxygen are bubbled through porous carbon electrodes into
concentrated aqueous sodium hydroxide solution. Catalysts like finely
divided platinum or palladium metal are incorporated into the electrodes for
increasing the rate of electrode reactions. The electrode reactions are given
below:
Cathode: O
2
(g) + 2H
2
O(l ) + 4e
4OH(aq)
Anode: 2H
2
(g) + 4OH(aq) 4H
2
O(l) + 4e
Overall reaction being:

2H
2
(g) + O
2
(g) 2 H
2
O(l )
The cell runs continuously as long as the reactants are supplied. Fuel cells
produce electricity with an efficiency of about 70 %.
CHEMI STRY
(ELECTROCHEMI STRY)
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P
R
I
N
C
E

S
I
R
Q1. The cell reaction for thegiven cell is spontaneous if- Pt(H
2
, P
1
) H
+
(1M) | | H
+
(1M) | Pt(H
2
, P
2
)
(A) P
1
> P
2
(B) P
1
< P
2
(C) P
1
= P
2
(D) P
2
= 1 atm
Q.2. The standard electrode potentials (reduction) of
2
/
4 2
/
3
0 0
and Sn Sn Fe Fe E E
are 0.77 and 0.15 V Resp ectively at 25 C. The standard EMF of the
reaction
Sn
4+
+ 2Fe
2+
Sn
2+
+ 2Fe
3+
is -
(A) 0.62 V (B) 0.92 V (C) +0.31 V (D) + 0.85 V
Q.3. F
2
gas cant be obtained by the electrolysis of any F
salt because-
(A) Fluorine is the strongest reducing agent
(B) Fluorine is the strongest oxidising agent
(C) Fluorine easily combine with atmospheric O
2
(D) All of these
Q.4. Reverse potential is the potential applied at which-
(A) Electrolytic cell converts into galvenic cell (B) Galvenic cell converts into electrolytic cell
(C) Cell reaction stops (D) EMF becomes zero
Q.5. Calculate the quantity of electricity (i.e. charge) delivered by a Daniel cell initially containing 1L each
of IM Cu
2+
ion and 1M Zn
2+
, which is operated until its potential drops to 1V. (Given :
E 0.76V; E 0.34 V
Zn
2
/ Zn
0
Cu
2
/ Cu
0

=- =
)
(A) 0.029 10
5
C. (B) 2.239 10
5
C
(C) 1.92 10
5
C. (D) 3.123 10
5
C
Q.6. Some half cell reaction & their standard potentials are given. Which combination would result in a
cell with the largest potential ?
(i) A + e
E
0
= 0.24 V
(ii) B
+ e
B
2
E
0
= 1.25 V
(iii) C
+ 2e
C
3
E
0
= 1.25 V
(iv) D + 2e
D
2
E
0
= 0.06 V
(v) E + 4e
E
4
E
0
= 0.38 V
(A) i and ii (B) ii and iii (C) iv and v (D) ii and v
B
Y

P
R
I
N
C
E

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R
Q.7. A hydrogen electrode is immersed in a solution with pH = 0 (HCI). By how much will the potential
(reduction) change if an equivalent amount of NaOH is added to the solution. (Take p
H
2
= 1 atm)
T = 298 K.
(A) Increases by 0.41 V (B) Increases by 59 mV
(C) Decreases by 0.41 V (D) decreases by 59 mV
Q.8. The solubility product of silver iodide is 8.3 10
17
and the standard potential (reduction) of Ag, Ag
+
electrode is + 0.800 volts at 25C. The standard potential of Ag, AgI/I
electrode (reduction) from

this data is-
(A) 0.30 V (B) + 0.15 V (C) + 0.10V (D) 0.15 V
Q.9. EMF is an
(A) Intensive property (B) Extensive property (C) None of these (D) Cant say
Q.10. The standard redox potentials E of the following systems are-
System E (volts)
(i) MnO
4
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O 1.51
(ii) Sn
4+
+ 2e Sn
2+
0.15
(iii) Cr
2
O
7
2
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O 1.33
(iv) Ce
4+
+ e Ce
3+
1.61
The oxidising power of the various species decreases in the order
(A) Ce
4+
> Cr2O
7
2
> Sn
4+
> MnO
4
(B) Ce
4+
> MnO
4
> Cr
2
O
7
2
> Sn
4+
(C) Cr
2
O
7
2
> Sn
4+
> Ce
4+
+ MnO
4
(D) MnO
4
> Ce
4+
> Sn
4+
> Cr
2
O
7
2
Q.11. Calculate the maximum work that can be obtained from the Daniell cell given below -
Zn(s) | Zn
2+
(aq) | Cu(s). Cu
2+
(aq)
Given E 0.76Vand E 0.34 V
Zn
2
/ Zn
0
Cu
2
/ Cu
0

=- =
(A) 212300 J (B) 202100 J (C) 513100 J (D) 232120 J
Q.12. Which is wrong about EMF ?
(A) It is the difference between electrode potential of two electrodes in an open circuit
(B) It is determined by means of a simple voltmeter
(C) The work calculated from EMF is the maximum work obtainable from a cell
(D) All are correct
Q.13. The standard reduction p otentials, E, for the half reactions are as Zn Zn
2+
+ 2e; E = + 0.76 V
and Fe Fe
2+
+ 2e; E = + 0.41 V; the e.m.f. for the cell reaction. Fe
2+
+ Zn Zn
2+
+ Fe is-
(A) 0.35 V (B) + 0.35 V (C) + 1.17 V (D) 1.17 V
Q.14. Which of following cell can produce more electrical work ?
(A) Pt, H
2
| 0.1M NH
4
Cl | | 0.1 M CH
3
COOH | H
2
, Pt
(B) Pt, H
2
| 0.1 M HCl | | 0.1 M NaOH | H
2
, Pt
(C) Pt, H
2
| 0.1 M HCl | | 0.1 M CH
3
COOK | H
2
, Pt
(D) Pt, H
2
| 0.1 M CH
3
COOK | | 0.1 M HC1|H
2
, Pt
Q.15. Zn amalgam is prepared by electrolysis of aqueous ZnCl
2
using Hg cathode (9gm). How much current
is to be passed through ZnCl
2
solution for 1000 seconds to prepare a Zn Amalgam with 25% Zn by
wt. (Zn = 65.4)
(A) 5.6 amp (B) 7.2 amp (C) 8.85 amp (D) 11.2 amp
Q.16. Zn | Zn
2+
(C1) | | Zn
2+
(C
2
) | Zn. For this cell AG is negative if :
(A) C
1
= C
2
(B) C
1
< C
2
(C) C
2
< C
1
(D) None of these
Q.17. The standard oxidation p otentials of Cu/Cu
2+
and Cu
+
/ Cu
2+
are 0.34 V and 0.16 V respectively.
The standard electrode potential of Cu
+
/ Cu would be :
(A) 0.18 V (B) 0.52 V (C) 0.82 V (D) 0.49 V
Q.18. The specific conductivity of solution depends upon :
(A) Number of ions as well as mobility of ions (B) Number of ions per c.c solution
(C) Number of ions per cc as well as mobilities of ions (D) Mobilities of ions only
Q.19. Number of electrons involved in the electrodeposition of 63.5g of Cu from a solution of CuSO
4
is -
(A) 6.022 10
23
(B) 3.011 10
23
(C) 12.044 10
23
(D) 6.022 10
22
Q.20. Which of the following statements is correct with regard toAG of cell reaction and EMF of the cell
(E) in which thereaction occurs ?
(A) Both AG and E are extensive properties
(B) AG is an intensive property but E is an extensive propery
(C) AG is an extensive property and E is an intensive property
(D) Both AG and E are intensive properties.
Q.21. The tempreature coefficient of the emf for the cell deg
1
. Calculate the entropy change AS
298K
, for
the cell reaction, Cd + 2AgCl Cd
++
+ 2Cl
O
+ 2Ag
(A) 105.5 JK
1
(B) 150.2 JK
1
(C) 75.5 JK
1
(D) 125.5 JK
1
Q.22. The cell Pt (H
2
) (1 atm) | H
(p H = ?) | | I
O
(a = 1) | AgI (s), Ag has emf, E
298
= 0. The electrode
potential for the reaction AgI + e
Ag + I
O
is 0.151 volt. Calculate the pH value.
(A) 3.37 (B) 5.26 (C) 2.56 (D) 4.62
Q.23. The reduction potential of a hlaf-cell consisting of a Pt electrode immersed in 1.5 M Fe
2+
and 0.015M
Fe
3+
solution at 25 C is (
E 0.770 V
Fe
3
/ Fe
2
=
)
(A) 0.652 V (B) 0.88 V (C) 0.710 V (D) 0.850 V
Q.24. In a concentration cell, Zn/Zn
2+
(1.0 M) | | Zn
2+
(0.15 M)/ Zn as the cell discharges,
(A) Reaction proceeds to the right
(B) The two solutions approcah each other in concentration
(C) No reaction takes place
(D) Water gets decomposed
B
Y

P
R
I
N
C
E

S
I
R
Q.25. In a half-cell containing [Tl
3+
] = 0.1 M and [Tl
+
] = 0.01 M, the cell potential is 1.2496 V for the
reaction Tl
+

Tl
3+
+ 2e
. The standard reduction potential of the Tl

+
/Tl
3+
couple at 25 C is
(A) 1.44 V (B) 0.61 V (C) 2.44 V (D) 1.22 V
Q.26. In the following electrochemical cell, M|M
+
| |X
| X, the standard reduction potentials are and

E 0.42 V
X/ X
0
-
=
at 25 C. Which one of the following statements is correct ?
(A) M + X M
+
+ X
is sp ontaneous (B) M
+
+ X
M + X is sp ontaneous
(E) E
cell
= 0.77 V (D) E
cell
= 0.77 V
Q.27. The volume of gases liberated at STP when a charge of 2F is passed through aqueous solution of
sodium phosphate- is :
(A) 11.2L (B) 44.8L (C) 33.6L (D) 22.4L
Q.28. The temperature coefficient of a standard Cd cell is( 1.5 10
5
)VK
1
. The EMF of the cell at
25
0
C is 1.018 V. During the cell operation, the temperature will -
(A) Increase (B) Decrease
(C) May increase or deacrease (D) remains constant
Q.29.
ClO
3
Cl
0.54 V
ClO
0.45 V 1
2
Cl
2
1.07 V
1.71 V
E
0
The E
0
in the given diagram is,
(A) 0.5 (B) 0.6 (C) 0.7 (D) 0.8
Q.30. Calculate the useful work of the reaction
Ag(s) + 1/2Cl
2
(g) AgCl(s)
Given
E 1.36V, E 0.22V
Cl
2
/ Cl
0
AgCl / Ag, Cl
0
- -
= =
If P
Cl
2
= 1 atm and T = 298 K
(A) 110 kJ/mol (B)220 kJ/mol (C) 55 kJ/mol (D) 1000 kJ/mol
Q.31. Acetic acid has K
a
= 1.8 10
5
while fromic acid has K
a
= 2.1 10
4
. What would be the
magnitude of the emf of the cell
Pt (H
2
)
0.1Maceticacid
0.1Msodiumacetate
0.1Mformicacid
0.1Msodiumformate
Pt (H
2
) at 25 C ?
(A) 0.0315 volt (B) 0.0629 volt (C) 0.0455 volt (D) 0.0545 volt
Q.32. With t taken in seconds and I taken in Amp, the variation of I follows the equation : t
2
+ I
2
= 25
What amount of Ag will be electrodeposited with this current flowing in the interval 05 second ?
(Ag 108)
(A) 22 mg (B) 66 mg (C) 77 mg (D) 88 mg
B
Y

P
R
I
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C
E

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Q.33. Following cell has EMF 0.7995 V
Pt | H
2
( 1 atm) | HNO
3
(1 M) | | AgNO
3
( 1 M) | Ag
If we add enough KCl to the Ag cell so that the final Cl
is 1 M. Now the meacured emf of the cell is

0.222 V. The Ksp of AgCl would be :
(A) 1 10
9.8
(B) 1 10
19.6
(C) 2 10
10
(D) 2.64 10
14
Q.34. A flashlight cell has the cathodic reaction
2MnO
2
(s) + Zn
+2
+ 2e
Zn Mn
2
O
4
(S)
If the flashlight cell is to give out 4.825 mA, how long could it run if initially 8.7 g of the limiting reagent
MnO
2
is p resent ? [Mn = 55, O = 16]
(A) 2 10
6
sec (B) 4 10
6
sec (C) 6 10
6
sec (D) 8 10
6
sec
Q.35. A current of 0.1A was passed for 2hr through a solution of suprocyanide and 0.3745 g of cop per was
deposited on the cathode. Calculate the current efficiency for the copper deposition. (Cu 63.5)
(A) 79% (B) 39.5% (C) 63.25% (D) 6
Q.36. Which of the following changes will increase the EMF of the cell,
Co(s) CoCl
2
(M
1
) HCl(M
2
) Pt (H
2
, g)
(A) Increase in the volume of the CoCl
2
solution from 100 ml to 200 ml
(B) Increasing the pressure of H
2
(g) from 1 atm to 2 atm
(C) Increasing M
2
from 0.01 to 0.5 M
(D) Increasing M
1
from 0.01 to 0.5 M
Q.37. 100 ml of a buffer of 1 M NH
3
(aq) and 1M NH
4
+
(aq) are placed in two voltaic cells seperately. A
current of 1.5 A is passed through both cells for 20 minutes. If only electrolysis of water takes place,
then pH of the :
(A) Left half cell will increase (B) Right half cell will increase
(C) both half cells will increase (D) bothe half cells will decrease
Q.38. A hydrogen electrode placed in a buffer solution of CH
3
COONa and acetic acid in the ratios x : y and
y: x has electrode potential values E
1
and E
2
resp ectively at 25
0
C. The pKa value of acetic acid is (E
1
and E
2
are oxidation potentials)
(A)
118 . 0
2 1
E E
(B)
118 . 0
1 2
E E -
(C)
118 . 0
2 1
E E
-
(D)
118 . 0
2 1
E E -
Q.39. A solution containing 4.5 mM of Cr
2
O
7
2 -
and 15 mM of Cr
3+
shows a pH of 2. calculate the potential
of half reaction. Standard potential of reactionCr
2
O
7
2 -
Cr
3+
is 1.33 V)
(A) 2.4 V (B) 1.8 V (C) 1.07 V (D) 1.1V
Q.40. The EMF of the cell
Zn Zn
2+
(0.01 M) Fe2+ (0.001 M) Fe at 298 K is 0.2905 then the value of equilibrium
constant for the cell reaction is -
(A)
0295 . 0
32 . 0
e
(B)
0295 . 0
32 . 0
10
(C)
0295 . 0
26 . 0
10
(D)
0591 . 0
32 . 0
10
Q.41. 0.04 N solution of a weak acid has specific conductance 4.23 10
-4
mho cm
-1
. if the degree of
dissociation of acid at this dilution is0.0612, then the equivalent conductivity at infinite dilution is
.....mho cm
2
eq
-1
(A) 172.8 (B) 180 (C) 190 (D) 160
Multiple Choice Questions
Q.42. Consider the following graph find out the ncorrect option(s)
(A) The cell reaction is spontaneous at point C.
(B) The cell reaction is not spontaneous at A.
(C) At B cell potential is zero.
(D) The cell reaction is spontaneous at A.
Q.43 During discharging of lead storage battery, which of the following is/are true ?
(A) H
2
SO
4
is p roduced (B) H
2
O is consumed
(C) PbSO
4
is formed at both electrodes (D) Density of electrolytic solution decreases
Q.44 Which of the following arrangement will produce oxygen at anode during electrolysis ?
(A) Dilute H
2
SO
4
solution with Cu electrodes.
(B) Dilute H
2
SO
4
solution with inert electrodes.
(C) Fused NaOH with inert electrodes.
(D) Dilute NaCl solution with inert electrodes.
Q.45 If 270.0 g of water is electrolysed during an experiment performed by miss Abhilasha with 75% current
efficiency then
(A) 168 L of O
2
(g) will be evolved at anode at 1 atm & 273 K
(B) Total 504 L gases will be p roduced at 1 atm & 273 K.
(C) 336 L of H
2
(g) will be evolved at anode at 1 atm & 273 K
(D) 45 F electricity will be consumed
Q.46 Pick out the correct statements among the following from inspection of standard reduction potentials
(Assume standard state conditions).
2
Cl (aq.) + 2e l 2Cl
(aq.)
o
Cl / Cl
2
E
- = + 1.36 volt
Br
2
(aq.) + 2e l 2Br
(aq.)
o
Br / Br
2
E
- = + 1.09 volt
I
2
(s) + 2e l 2I
(aq.)
o
I / I
2
E
- = + 0.54 volt
- 2
8 2
O S (aq.) + 2e l
- 2
4
SO 2
(aq.)
o
SO / O S
2
4
2
8 2
E
- -
= + 2.00 volt
(A) Cl
2
can oxidise
- 2
4
SO
from solution
(B) Cl
2
can oxidise Br
and I
from aqueous solution

(C)
- 2
8 2
O S can oxidise Cl
, Br
and I
from aqueous solution

(D) S
2
O
8
2
is added slowly, Br
can be reduce in p resence of Cl
A
B
C
AG
e x t e n t o f r e a c t i o n
FUNDAMENTALS
GALVANIC CELL :
Representation of Cell diagrams, complete and half cell reactions :
Q.1 Write cell reaction of the following cells :
(a) Ag | Ag
+
(aq) | | Cu
2+
(aq) | Cu
(b) Pt | Fe
2+
, Fe
3+
| |
-
4
MnO , Mn
2+
, H
+
| Pt
(c) P t , C l
2
| Cl
(aq) | | Ag
+
(aq) | Ag
(d) Pt, H
2
| H
+
(aq) | | Cd
2+
(aq) | Cd
Q.2 Write cell representation for following cells.
(a) Cd
2+
(aq) + Zn (s) Zn
2+
(aq) + Cd (s)
(b) 2Ag
+
(aq) + H
2
(g) 2H
+
(aq) + 2Ag (s)
(c)
- 2
7 2
O Cr (aq.) + 14H
+
(aq) + 6Fe
2+
(aq) 6Fe
3+
(aq) + 2Cr
3+
(aq) + 7H
2
O (l)
Q.3 Write half cells of each cell with following cell reactions :
(a) Zn (s) + 2H
+
(aq) Zn
2+
(aq) + H
2
(g)
(b) 2Fe
3+
(aq) + Sn
2+
(aq) 2Fe
2+
(aq) + Sn
4+
(aq)
(c)
-
4
MnO (aq) + 8H
+
(aq) + 5Fe
2+
(aq) 2Fe
3+
(aq) + Mn
2+
(aq) + 4H
2
O (l)
(d) Pb (s) + Br
2
(l) Pb
2+
(aq) + 2Br
(aq)
(e) Hg
2
Cl
2
(s) + Cu (s) Cu
2+
(aq) + 2Cl
(aq) + 2Hg (l)

Electrode potential and standard electrode potential :
Q.4 For the cell reaction 2Ce
4+
+ Co 2Ce
3+
+ Co
2+
o
cell
E is 1.89 V. If
o
Co | Co
2
E

is 0.28 V, what is the value of
o
3
Ce |
4
Ce
E

?
Q.5 Determine the standard reduction potential for the half reaction :
Cl
2
+ 2e
2Cl
Given Pt
2+
+ 2Cl
Pt + Cl
2
,
o
Cell
E = 0.15 V
Pt
2+
+ 2e
Pt E = 1.20 V
Q.6 What is
o
Cell
E if
2Cr + 3H
2
O + 3OCl
2Cr
3+
+ 3Cl
+ 6OH
2Cr
3+
+ 3e
Cr, E = 0.74 V
OCl
+ H
2
O + 2e
Cl
+ 2OH
, E = 0.94 V
Q.7 Is 1.0 M H
+
solution under H
2
SO
4
at 1.0 atm capable of oxidising silver metal in the presence of 1.0 M
Ag
+
ion?
o
Ag | Ag
E
= 0.80 V,
o
) Pt ( H | H
2
E
= 0.0 VV
Q.8 If for the half cell reactions Cu
2+
+ e
Cu
+
E = 0.15 V
Cu
2+
+ 2e
Cu E = 0.34 V
Calculate E of the half cell reaction
Cu
+
+ e
Cu
also predict whether Cu
+
undergoes disproportionation or not.
Q.9 If
o
Fe |
2
Fe
E

= 0.44 V,
o
2
Fe |
3
Fe
E

= 0.77 V. Calculate
o
Fe |
3
Fe
E

.
Q.10 Calculate the EMF of a Daniel cell when the concentration of ZnSO
4
and CuSO
4
are 0.001 M and
0.1M respectively. The standard potential of the cell is 1.1V.
Q.11 For a cell Mg(s) | Mg
2+
(aq) || Ag
+
(aq) | Ag, Calculate the equilibrium constant at 25C. Also find the
maximum work per mole Mg that can be obtained by operating the cell.
E
0
(Mg
2+
/Mg) = -2.37V, E
0
(Ag
+
/Ag) = 0.8 V.
Q.12 The EMF of the cell M | M
n+
(0.02M) || H
+
(1M) | H
2
(g) (1 atm), Pt at 25C is 0.81V. Calculate the
valency of the metal if the standard oxidation of the metal is 0.76V.
Q.13 Equinormal Solutions of two weak acids, HA (pK
a
= 3) and HB (pK
a
= 5) are each p laced in contact
with equal pressure of hydrogen electrode at 25C. When a cell is constructed by interconnecting them
through a salt bridge, find the emf of the cell.
Q.14 In two vessels each containing 500ml water, 0.5m mol of aniline (K
b
= 10
-9
) and 25mmol of HCl are
added separately. Two hydrogen electrodes are constructed using these solutions. Calculate the emf of
cell made by connecting them appropriately.
Q.15 Calculate E
0
and E for the cell Sn | Sn
2+
(1M) || Pb
2+
(10
-3
M) | Pb, E
0
(Sn
2+
| Sn) = -0.14V,
E
0
(Pb
2+
| Pb) = -0.13V. Is cell rep resentation is correct?
Q.16 At what concentration of Cu
2+
in a solution of CuSO
4
will the electrode potential be zero at 25C?
Given : E
0
(Cu | Cu
2+
) = -0.34 V.
Q.17 A zinc electrode is placed in a 0.1M solution at 25C. Assuming that the salt is 20% dissociated at this
dilutions calculate the electrode potential. E
0
(Zn
2+
| Zn) = -0.76V.
Q.18 From the standard potentials shown in the following diagram, calculate the potentials

1
E and

2
E .
CONCENTRATION CELLS :
Q.19 Calculate the EMF of the following cell
Zn | Zn
2+
(0.01M) || Zn
2+
(0.1 M) | Zn
at 298 K.
Q.20 Calculate the EMF of the cell,
Zn Hg(c
1
M) | Zn
2+
(aq)| Hg Zn(c
2
M)
at 25C, if the concentrations of the zinc amalgam are: c
1
= 10g p er 100g of mercury and
c
2
= 1g p er100 g of mercury.
Q.21 Calculate pH using the following cell :
Pt (H
2
) | H
+
(x M) | | H
+
(1 M) | Pt (H
2
) if E
cell
= 0.2364 V.
1 atm 1 atm
Q.22 Calculate the EMF of following cells at 25C.
(i) Fe | Fe
2+
(a
1
= 0.3) || Sn
2+
(a
2
= 0.1) | Sn E
0
(Fe
2+
/Fe) = 0.44 V
(ii) Pt, H
2
(2atm) | HCl |H
2
(10 atm), Pt. E
0
(Sn
2+
/Sn) = -0.14 V
Q.23 EMF of the cell Zn | ZnSO
4
(a
1
= 0.2) || ZnSO
4
(a
2
) | Zn is -0.0088V at 25C. Calculate the value of a
2
.
Q.24 Calculate the equilibrium constant for the reaction
Fe
2+
+Ce
4+
l Fe
3+
+ Ce
3+
, [given :
V 68 . 0 E ; V 44 . 1 E
2 3 3 4
Fe / Fe
0
Ce / Ce
0
= =

]
Q.25 Calculate the equilibrium constant for the reaction Fe + CuSO
4
l FeSO
4
+ Cu at 25C.
Given E
0
(Fe/Fe
2+
) = 0.44V, E
0
(Cu/Cu
2+
) = -0.337V.
Q.26 The standard reduction potential at 25C for the reduction of water
2H
2
O + 2e
-
l H
2
+ 2OH
-
is -0.8277 volt. Calculate the equilibrium constant for the reaction
2H
2
O l H
3
O
+
+ OH
-
at 25C.
Q.27 At 25
0
C the value of K for the equilibrium Fe
3+
+ Ag l Fe
2+
+ Ag
+
is 0.531mol/litre. The standard
electrode p otential for Ag
+
+ e
l Ag is 0.799V. What is the standard p otential for

Fe
3+
+ e
l Fe
2+
?
Q.28 For the reaction, 4Al(s) + 3O
2
(g) + 6H
2
O + 4 OH
l 4 [Al(OH)
4
] ;

cell
E
= 2.73 V. If
) OH ( G
f
-
A = 157 kJ mol
1
and ) O H ( G
2 f
A = 237.2 kJ mol
1
, determine

A
f
G
[Al (OH)
4
].
ELECTROLYTIC CELL :
Q.29 Calculate the no. of electrons lost or gained during electrolysis of
(a) 3.55 gm of Cl
ions (b) 1 gm Cu
2+
ions (c) 2.7 gm of Al
3+
ions
Q.30 How many faradays of electricity are involved in each of the case
(a) 0.25 mole Al
3+
is converted to Al.
(b) 27.6 gm of SO
3
is convered to
- 2
3
SO
(c) The Cu
2+
in 1100 ml of 0.5 M Cu
2+
is converted to Cu.
Q.31 0.5 mole of electron is passed through two electrolytic cells in series. One contains silver ions, and the
other zinc ions. Assume that only cathode reaction in each cell is the reduction of the ion to the metal.
How many gm of each metals will be deposited.
Q.32 The electrosynthesis of MnO
2
is carried out from a solution of MnSO
4
in H
2
SO
4
(aq). If a current of
25.5 ampere is used with a current efficiency of 85%, how long would it take to produce 1 kg of MnO
2
?
Q . 3 3 A c o n s t a n t c u r r e n t o f 3 0 A i s p a s s e d t h r o u g h a n a q u e o u s s o l u t i o n o f N a C l f o r a t i m e o f 1 . 0 h r . H o w m a n y
g r a m s o f N a O H a r e p r o d u c e d ? W h a t i s v o l u m e o f C l
2
gas at S.T.P. p roduced?
Q.34 If 0.224 litre of H
2
gas is formed at the cathode, how much O
2
gas is formed at the anode under identical
conditions?
Q.35 If 0.224 litre of H
2
gas is formed at the cathode of one cell at S.T.P., how much of Mg is formed at the
cathode of the other electrolytic cell.
Q.36 Assume 96500 C as one unit of electricity. If cost of electricity of producing x gm Al is Rs x, what is the
cost of electricity of producing x gm Mg?
Q . 3 7 C h r o m i u m m e t a l c a n b e p l a t e d o u t f r o m a n a c i d i c s o l u t i o n c o n t a i n i n g C r O
3
according to following equation:
CrO
3
(aq) + 6H
+
(aq) + 6e
Cr(s) + 3H
2
O
Calculate :
(i) How many grams of chromium will be plated out by 24000 coulombs and
(ii) How long will it take to plate out 1.5 gm of chromium by using 12.5 ampere current
Q.38 Calculate the quantity of electricity that would be required to reduce 12.3 g of nitrobenzene to aniline, if
the current efficiency for the process is 50 percent. If the potential drop across the cell is 3.0 volts, how
much energy will be consumed?
Q.39 How long a current of 2A has to be p assed through a solution of AgNO
3
to coat a metal surface of
80cm
2
with 5m thick layer? Density of silver = 10.8g/cm
3
.
Q.40 3A current was passed through an aqueous solution of an unknown salt of Pd for 1Hr. 2.977g of Pd
+n
was deposited at cathode. Find n.
Q.41 50mL of 0.1M CuSO
4
solution is electrolyzed with a current of 0.965 A for a p eriod of
200 sec. The reactions at electrodes are:
Cathode : Cu
2+
+ 2e
-
Cu(s) Anode : 2H
2
O O
2
+ 4H
+
+ 4e.
Assuming no change in volume during electrolysis, calculate the molar concentration of Cu
2+
, H
+
and
SO
4
2-
at the end of electrolysis.
Q.42 A metal is known to form fluoride MF
2
. When 10A of electricity is passed through a molten salt for 330
sec., 1.95g of metal is deposited. Find the atomic weight of M. What will be the quantity of electricity
required to deposit the same mass of Cu from CuSO
4
?
Q.43 10g solution of CuSO
4
is electrolyzed using 0.01F of electricity. Calculate:
(a)The weight of resulting solution (b)Equivalents of acid or alkali in the solution.
Q.44 Cadmium amalgam is prepared by electrolysis of a solution of CdCl
2
using a mercury cathode. How
long should a current of 5A be passed in order to prepare 12% Cd-Hg amalgam on a cathode of 2gm
Hg (Cd=112.4)
Q.45 After electrolysis of NaCl solution with inert electrodes for a certain p eriod of time. 600 mL of the
solution was left. Which was found to be 1N in NaOH. During the same time, 31.75 g of Cu was
deposited in the copper voltameter in series with the electrolytic cell. Calculate the percentage yield of
NaOH obtained.
Q.46 Three electrolytic cells A, B, C containing solution of ZnSO
4
, AgNO
3
and CuSO
4
, resp ectively are
connected in series. A steady current of 2 amp ere was p assed through them until 1.08 g of silver
dep osited at the cathode of cell B. How long did the current flow? What mass of copp er and of zinc
were deposited?
Q.47 A solution of Ni(NO
3
)
2
is electrolysed between platinum electrodes using a current of 5 ampere for
20 mintue. What mass of Ni is deposited at the cathode?
Q.48 A current of 3.7A is p assed for 6hrs. between Ni electrodes in 0.5L of 2M solution of Ni(NO
3
)
2
.
What will be the molarity of solution at the end of electrolysis?
CONDUCTANCE
Conductivities and cell constant:
Q.49 The resistance of a conductivity cell filled with 0.01N solution of NaCl is 210 ohm at18
o
C.Calculate
the equivalent conductivity of the solution. The cell constant of the conductivity cell is 0.88 cm
-1
.
Q.50 The molar conductivity of 0.1 M CH
3
COOH solution is 4.6 S cm
2
mole
-1
. What is the sp ecific
conductivity and resistivity of the solution ?
Q.51 The conductivity of p ure water in a conductivity cell with electrodes of cross sectional area 4 cm
2
and 2 cm ap art is 8 10
-7
S cm
-1
.
(i) What is resistance of conductivity cell ?
(ii) What current would flow through the cell under an ap p lied p otential difference of 1 volt?
Q.52 Resistivity of 0.1M KCl solution is 213 ohm cm in a conductivity cell. Calculate the cell constant
if its resistance is 330 ohm.
Q.53 Resistance of a 0.1M KCl solution in a conductance cell is 300 ohm and sp ecific conductance of
0.1M KCl is 1.29 10
-2
ohm
-1
cm
-1
. The resistance of 0.1M NaCl solution in the same cell is 380
ohm. Calculate the equivalent conductance of the 0.1M NaCl solution.
Q.54 For 0.01N KCl, the resistivity 709.22 mho cm. Calculate the conductivity and equivalent
conductance.
Q.55 A solution containing 2.08 g of anhydrous barium chloride is 400 CC of water has a sp ecific
conductivity 0.0058 ohm
1
cm
1
. What are molar and equivalent conductivities of this solution.
Application of Kohlrausch's law:
Q.56 Equivalent conductance of 0.01 N Na
2
SO
4
solution is 112.4 ohm
1
cm
2
eq
1
. The equivalent
conductance at infinite dilution is 129.9 ohm
1
cm
2
eq
1
. What is the degree of dissociation in 0.01
N Na
2
SO
4
solution?
Q.57 Sp ecific conductance of a saturated solution of AgBr is 8.48610
7
ohm
1
cm
1
at 25
0
C. Sp ecific
conductance of p ure water at 25C is 0.75 10
6
ohm
1
cm
2
.

A
m
for KBr , AgNO
3
and KNO
3
are 137.4 , 133 , 131 ( S cm
2
mol
1
) resp ectively. Calculate the solubility of AgBr in gm/litre.
Q.58 Saturated solution of AgCl at 25C has sp ecific conductance of 1.1210
6
ohm
1
cm
1
. The
Ag
+
and
Cl
are 54.3 and 65.5 ohm

1
cm
2
/ equi. resp ectively. Calculate the solubility p roduct
of AgCl at 25C.
Q.59 Hydrofluoric acid is weak acid. At 25C, the molar conductivity of 0.002M HF is
176.2 ohm
1
cm
2
mole
1
. If its

A
m
= 405.2 ohm
1
cm
2
mole
1
, calculate its degree of dissociation
and equilibrium constant at the given concentration.
Q.60 The value of

A
m
for HCl, NaCl and CH
3
CO
2
Na are 426.1, 126.5 and 91 S cm
2
mol
1
respectively. .
Calculate the value of

A
m
for acetic acid. If the equivalent conductivity of the given acetic acid is 48.15
at 25 C, calculate its degree of dissociation.
Q.61 Calculate the sp ecific conductance of a 0.1 M aqueous solution of NaCl at room temp erature,
given that the mobilities of Na
+
and Cl
ions at this temp erature are 4.2610

8
and
6.8010
8
m
2
v
1
s
1
, resp ectively.
Q.62 For the strong electroytes NaOH, NaCl and BaCl
2
the molar ionic conductivities at infinite dilution
are 248.110
4
, 126.5 10
4
and 280.0 10
-4
mho cm
2
mol
1
resp ectively. Calculate the molar
conductivity of Ba(OH)
2
at infinite dilution.
Q.63 At 25C,
(H
+
) = 3.4982 10
2
S m
2
mol
1
and
(OH
) = 1.98 10
2
S m
2
mol
1
.
Given: Sp . conductnace = 5.7 10
6
S m
1
for H
2
O, determine pH and K
w
.
APPLICATION
Q.1 The standard reduction p otential values, E
0
(Bi
3+
|Bi) and E
0
(Cu
2+
|Cu) are 0.226V and 0.344V
respectively. A mixture of salts of bismuth and copper at unit concentration each is electrolysed at 25C.
to what value can [Cu
2+
] be brought down before bismuth starts to deposit, in electrolysis.
Q.2 The cell Pt, H
2
(1 atm) | H
+
(pH=x) || Normal calomel Electrode has an EMF of 0.67V at 25C. Calculate
the pH of the solution. The oxidation potential of the calomel electrode on hydrogen scale is -0.28 V.
Q.3 Voltage of the cell Pt, H
2
(1 atm)|HOCN (1.3 10
-3
M)||Ag
+
(0.8 M)|Ag(s) is 0.982 V . Calculate
the K
a
for HOCN . Neglect [H
+
] because of oxidation of H
2
(g) .
Ag
+
+ e Ag(s) = 0.8 V.
Q.4 Calculate the potential of an indicator electrode versus the standard hydrogen electrode, which originally
contained 0.1M MnO
4
-
and 0.8M H
+
and which was treated with 90% of the Fe
2+
necessary to reduce
all the MnO
4
-
to Mn
+2
.
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O, E
0
= 1.51V
Q.5 Calculate the emf of the cell
Pt, H
2
(1.0 atm) | CH
3
COOH (0.1M) || NH
3
(aq, 0.01M) | H
2
(1.0 atm),
Pt K
a
(CH
3
COOH) = 1.8 10
-5
, K
b
(NH
3
) = 1.8 10
-5
.
Q.6 The Edison storage cell is rep resented as Fe(s) | FeO(s) | KOH(aq) | Ni
2
O
3
(s) | Ni(s) The half-cell
reaction are
Ni
2
O
3
(s) + H
2
O(i) + 2e
-
l 2NiO(s) + 2OH
-
, E
0
= + 0.40V
FeO(s) + H
2
O(l) + 2e
-
l Fe(s) + 2OH
-
, E
0
= - 0.87V
(i) What is the cell reaction?
(ii) What is the cell e.m.f.? How does it depend on the concentration of KOH?
(iii) What is the maximum amount of electrical energy that can be obtained from one mole of Ni
2
O
3
?
Q.7 The standard reduction p otential for Cu
2+
/ Cu is 0.34 V. Calculate the reduction p otential at
p H = 14 for the above coup le. K
sp
of Cu(OH)
2
is 1 10
-19
.
Q.8 Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/32 solution of
salt at 298 K from the following cell data at 298 K.
Pt | H
2
(1 atm) | H
+
(1M) || M/32 C
6
H
5
NH
3
Cl | H
2
(1 atm) | Pt ; E
cell
= 0.188 V.
Q.9 The emf of the cell, Pt | H
2
(1 atm), | H
+
(0.1 M, 30 ml) || Ag
+
(0.8 M) | Ag is 0.9 V. Calculate the emf
when 40 ml of 0.05 M NaOH is added.
Q.10 The emf of the cell Ag|AgI|KI(0.05M) || AgNO
3
(0.05M) |Ag is 0.788V. Calculate the solubility product
of AgI.
Q.11 Consider the cell Ag|AgBr(s)|Br
-
||AgCl(s), Ag | Cl
-
at 25 C . The solubility product constants of AgBr
& AgCl are respectively 5 10
-13
& 1 10
-10
. For what ratio of the concentrations of Br
-
& Cl
-
ions
would the emf of the cell be zero ?
Q.12 The pK
sp
of Agl is 16.07 . If the E value for Ag
+
, Ag is 0.7991 V . Find the E for the half cell reaction
AgI (s) + e
-
Ag + I
-
.
Q.13 For the galvanic cell : Ag|AgCl(s)| KCl (0.2M) || K Br (0.001 M)| AgBr(s) | Ag,
Calculate the EMF generated and assign correct polarity to each electrode for a spontaneous process
after taking into account the cell reaction at 25
0
C.
] 10 3 . 3 K ; 10 8 . 2 K [
13
) AgBr ( sp
10
) AgCl ( sp
- -
= =
Q.14 Given, E = 0.268 V for the Cl
| PbCl
2
| Pb couple and 0.126 V for the Pb
2+
| Pb couple, determine
K
sp
for PbCl
2
at 25C?
Q.15 Calculate the voltage, E, of the cell at 25 C
Mn(s) | Mn(OH)
2
(s) | Mn
2+
(x M), OH
(1.00 x 10
4
M) || Cu
2+
(0.675M) | Cu(s)
given that K
sp
= 1.9 10
13
for Mn(OH)
2
(s) E
0
(Mn
2+
/Mn) = 1.18 V
Q.16 Calculate the voltage, E, of the cell
Ag(s) | AgIO
3
(s) | Ag
+
(x M), HIO
3
(0.300M) || Zn
2+
(0.175M) | Zn(s)
if K
sp
= 3.02 10
8
for AgIO
3
(s) and K
a
= 0.162 for HIO
3
.
Q.17 The voltage of the cell
Pb(s) | PbSO
4
(s) | NaHSO
4
(0.600M) || Pb
2+
(2.50 x 10
5
M) | Pb(s)
is E = +0.061 V. Calculate K
2
= [H
+
] [SO
4
2
] / [HSO
4
], the dissociation constant for

-
4
HSO
.
Given : Pb (s) + SO
4
2
(aq) l PbSO
4
(s) + 2e
(E
0
= 0.356) E
0
(Pb
2+
/Pb) = 0.126 V
Q.18 The voltage of the cell
Zn(s) | Zn(CN)
4
2
(0.450M), CN
(2.65 10
3
M) || Zn
2+
(3.84 10
4
M) | Zn(s)
is E = +0.099 V. Calculate the constant K
f
for Zn
2+
+ 4CN
l Zn(CN)
4
2
, the only
Zn
2+
+ CN
complexation reaction of importance.

Q.19 Given the standard reduction p otentials Tl
+
+ e
-
TI, E
0
= -0.34V and
TI
3+
+ 2e
-
TI
+
, E
0
= 1.25V. Examine the spontaneity of the reaction, 3TI
+
2TI + TI
3+
. Also find
E
0
for this disproportionation.
Q.20 Estimate the cell potential of a Daniel cell having 1 M Zn
++
& originally having 1M Cu
++
after sufficient
NH
3
has been added to the cathode comp artment to make NH
3
concentration 2M.
K
f
for [Cu(NH
3
)
4
]
2+
= 1 10
12
, E
0
for the reaction,
Zn + Cu
2+
Zn
2+
+ Cu is 1.1 V.
Q.21 The normal oxidation potential of Zn referred to SHE is 0.76V and that of Cu is -0.34V at 25C. When
excess of Zn is added to CuSO
4
, Zn displaces Cu
2+
till equilibrium is reached. What is the ratio of Zn
2+
to Cu
2+
ions at equilibrium?
Q.22 K
d
for comp lete dissociation of [Ag(NH
3
)
2
]
+
into Ag
+
and 2NH
3
is 6 10
-8
. Calculate E
0
for the
following half reaction; Ag(NH
3
)
2
+
+ e
-
Ag + 2NH
3
Ag
+
+ e
-
Ag, E
0
= 0.799 V
Q.23 The overall formation constant for the reaction of 6 mol of CN
-
with cobalt (II) is
1 10
19
. The standard reduction potential for the reaction
[Co(CN)
6
]
3-
+ e
-
Co(CN)
6
4-
is -0.83 V. Calculate the formation constant of [Co(CN)
6
]
3-
Given Co
3+
+ e
-
Co
2+
; E
0
= 1.82 V
Q.24 Calculate E for the following reactions at 298 K,
2 3
) NH ( Ag + e
l Ag + 2NH
3
-
2
) CN ( Ag
+ e
l Ag + 2CN
Given: ] ) NH ( Ag [ K , V 7991 . 0 E
2 3 Ins
Ag | Ag

=
= 6.02 10
8
and ] ) CN ( Ag [ K
2 Ins
-
= 1.995 10
19
Q.25 Calculate the equilibrium constant for the reaction:
3Sn(s) + 2Cr
2
O
7
2
+ 28H
+
3Sn
4+
+ 4Cr
3+
+ 14H
2
O
E
0
for Sn/Sn
2+
= 0.136 V E
0
for Sn
2+
/Sn
4+
= 0.154 V
E
0
for Cr
2
O
7
2
/Cr
3+
= 1.33 V
Q.26 Calculate the equlibrium concentrations of all ions in an ideal solution prepared by mixing 25.00 mL of
0.100M Tl
+
with 25.00mL of 0.200M Co
3+
.
E
0
( Tl
+
/Tl
3+
)= 1.25 V ; E
0
(Co
3+
/Co
2+
) = 1.84 V
Q.27 Same quantity of electricity is being used to liberate iodine (at anode) and a metal x (at cathode). The
mass of x dep osited is 0.617g and the iodine is comp letely reduced by 46.3 cc of 0.124M sodium
thiosulphate. Find the equivalent mass of x.
Q.28 In a fuel cell, H
2
& O
2
react to produce electricity. In the process, H
2
gas is oxidized at the anode & O
2
at the cathode . If 67.2 litre of H
2
at STP react in 15 minutes, what is the average current produced ? If
the entire current is used for electrode deposition of Cu from Cu (II) solution, how many grams of Cu
will be deposited?
Anode : H
2
+ 2OH
-
2H
2
O + 2 e
Cathode : O
2
+ 2 H
2
O + 4e
-
4 OH
Q.29 One of the methods of prep aration of per disulphuric acid, H

2
S
2
O
8
, involve electrolytic oxidation of
H
2
SO
4
at anode (2H
2
SO
4
H
2
S
2
O
8
+ 2H
+
+ 2e
-
) with oxygen and hydrogen as
by-p roducts. In such an electrolysis, 9.722 L of H
2
and 2.35 L of O
2
were generated at STP. What is
the weight of H
2
S
2
O
8
formed?
Q.30 During the discharge of a lead storage battery the density of sulp huric acid fell from 1.294 to
1.139 g.ml
-1
. H
2
SO
4
of density 1.294 g mL
-1
is 39% and that of density 1.139 g mL
-1
is 20% by
weight. The battery holds 3.5L of acid and the volume practically remains constant during the discharge.
Calculate the number of ampere hours for which the battery must have been used. The discharging
reactions are:
Pb + SO
4
2-
PbSO
4
+ 2e
-
(anode)
PbO
2
+ 4H
+
+ SO
4
2-
+ 2e
-
PbSO
4
+ 2H
2
O (cathode)
Q.31 A current of 3 amp was passed for 2 hour through a solution of CuSO
4
,3 g of Cu
2+
ions were deposited
as Cu at cathode. Calculate percentage current efficiency of the process.
Q.32 An acidic solution of Cu
2+
salt containing 0.4 g of Cu
2+
is electrolyzed until all the copper is deposited.
The electrolysis is continued for seven more minutes with the volume of solution kept at 100 ml and the
current at 1.2 amp. Calculate the volume of gases evolved at NTP during the entire electrolysis.
Q.33 In the refining of silver by electrolytic method what will be the weight of 100 gm Ag anode if
5 ampere current is passed for 2 hours? Purity of silver is 95% by weight.
Q.34 Dal lake has water 8.2 10
12
litre approximately. A power reactor produces electricity at the rate of
1.510
6
coulomb per second at an appropriate voltage.How manyyears would it take to electrolyse the
lake?
Q.35 A lead storage cell is discharged which causes the H
2
SO
4
electrolyte to change from a concentration of
34.6 % by weight (density 1.261g ml
1
at 25C) to 27 % by weight. The original volume of electrolyte
is one litre. Calculate the total charge released at anode of the battery. Note that the water is produced
by the cell reaction as H
2
SO
4
is used up. Over all reaction is
Pb(s) + PbO
2
(s) + 2H
2
SO
4
(l) 2PbSO
4
(s) + 2H
2
O(l)
Q.36 100ml CuSO
4
(aq) was electrolyzed using inert electrodes by passing 0.965 A till the pH of the resulting
solution was 1. The solution after electrolysis was neutralized, treated with excess KI and titrated with
0.04M Na
2
S
2
O
3
. Volume of Na
2
S
2
O
3
required was 35 ml. Assuming no volume change during
electrolysis, calculate:
(a) duration of electrolysis if current efficiency is 80% (b) initial concentration (M) of CuSO
4
.
Q.37 An external current source giving a current of 5.0 A was joined with Daniel cell and removed after
10 hrs. Before passing the current the LHE and RHE contained 1L each of 1M Zn
2+
and Cu
2+
respectively.
Find the EMF supplied by the Daniel cell after removal of the external current source. E
0
of Zn
2+
/Zn and
Cu
2+
/Cu at 25C is -0.76 and +0.34V resp ectively.
Q.38 Determine at 298 for cell
Pt | Q, QH
2
, H
+
|| 1M KCl | Hg
2
Cl
2
(s) | Hg(l) | Pt
(a) it's emf when pH = 5.0
(b) the p H when E
cell
= 0
(c) the positive electrode when pH = 7.5
given E
0
RP(RHS)
= 0.28, E
0
RP(LHS)
= 0.699
Q.39 At 25C, AH
f
(H
2
O,l) = 56700 cal / mol and energy of ionization of H
2
O (l) = 19050 cal/mol. What
will be the reversible EMF at 25C of the cell,
Pt | H
2
(g) (1 atm) | H
+
|| OH
| O
2
(g) (1 atm) | Pt, if at 26C the emf increas by 0.001158 V.
Q.40 Calculate the cell potential of a cell having reaction: Ag
2
S + 2e
l 2Ag + S
2
in a solution buffered at
pH = 3 and which is also saturated with 0.1 M H
2
S.
For H
2
S : K
1
= 10
8
and K
2
= 1.1 10
13
, K
sp
(Ag
2
S) = 2 10
49
, . 8 . 0 E
Ag / Ag
=
Q.41 The equivalent conductance of 0.10 N solution of MgCl

2
is 97.1 mho cm
2
equi
1
at 25C. a cell
with electrode that are 1.5 cm
2
in surface area and 0.5 cm ap art is filled with 0.1 N MgCl
2
solution.
How much current will flow when p otential difference between the electrodes is 5 volt.
Q.42 A dilute aqueous solution of KCl was p laced between two electrodes 10 cm ap art, across which a
p otential of 6 volt was ap p lied. How far would the K
+
ion move in 2 hours at 25C? Ionic
conductance of K
+
ion at infinite dilution at 25C is 73.52 ohm
1
cm
2
mole
1
?
Q.43 When a solution of sp ecific conductance 1.342 ohm
1
metre
1
was p laced in a conductivity cell
with p arallel electrodes, the resistance was found to be 170.5 ohm. Area of electrodes is
1.8610
4
m
2
. Calculate sep aration of electrodes.
Q.44 The sp ecific conductance at 25C of a saturated solution of SrSO
4
is 1.48210
4
ohm
1
cm
1
while
that of water used is 1.510
6
mho cm
1
. Determine at 25C the solubility in gm p er litre of SrSO
4
in water. Molar ionic conductance of Sr
2+
and SO
4
2
ions at infinite dilution are 59.46 and
79.8 ohm
1
cm
2
mole
1
resp ectively. [ Sr = 87.6 , S = 32 , O = 16 ]
Q.45 Calculate the solubility and solubility p roduct of Co
2
[Fe(CN)
6
] in water at 25
0
C from the following
data:
Conductivity of a saturated solution of Co
2
[Fe(CN)
6
] is 2.06 10
6
O
1
cm
1
and that of water used
4.1 10
7
O
1
cm
1
. The ionic molar conductivities of Co
2+
and Fe(CN)
6
4
are 86.0 O
1
cm
2
mol
1
and 444.0 O
1
cm
1
mol
1
.
Q.46 A sample of water from a large swimming pool has a resistance of 9200 O at 25C when p laced in a
certain conductance cell. When filled with 0.02 M KCl solution, the cell has a resistance of 85O at
25C. 500 gm of NaCl were dissolved in the pool, which was throughly stirred. A sample of this solution
gave a resistance of 7600 O. Calculate the volume of water in the pool.
Given : Molar conductance of NaCl at that concentration is 126.5 O
1
cm
2
mol
1
and molar conductivity
of KCl at 0.02 M is 138 O
1
cm
2
mol
1
.
FEEL THE HEAT
Q.1 Calculate the equilibrium constant for the reaction, 2Fe
3+
+ 3I
-
l 2Fe
2+
+ I
3
-
. The standard
reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe
3+
/ Fe
2+
and I
3
-
/ I
-
couples. [JEE 1998]
Q.2 Find the solubility p roduct of a saturated solution of Ag
2
CrO
4
in water at 298 K if the emf of the cell
Ag|Ag
+
(satd.Ag
2
CrO
4
soln.) || Ag
+
(0.1 M) | Ag is 0.164 V at 298K. [JEE 1998]
Q.3 A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M Y and 1 M Z at 25C. If the
reduction potential of Z > Y > X, then
(A) Y will oxidise X and not Z (B) Y will oxidise Z and X
(C) Y will oxidise both X and Z (D) Y will reduce both X and Z. [JEE 1999]
Q.4 For the electrochemical cell, M | M
+
|| X
| X, E (M
+
/M) = 0.44 V and E (X/X
) = 0.33V. From this

data , one can deduce that
(A) M + X M
+
+ X
is the spontaneous reaction

(B) M
+
+ X
M + X is the sp ontaneous reaction

(C) E
cell
= 0.77 V
(D) E
cell
= 0.77 V [JEE 2000]
Q.5 Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper cathode. A
constant current of 2 mA was passed for 16 mintue. It was found that after electrolysis, the absorbance
(concentration) of the solution was reduced to 50% of its original value. Calculate the concentration of
copper sulphate in the solution to begin with. [JEE 2000]
Q.6 The following electrochemical cell has been set up
Pt
(I)
| Fe
3+
, Fe
2+
(a = 1) || Ce
4+
, Ce
3+
(a = 1) | Pt
(II)
2 3
Fe / Fe
E = 0.77 V and

3 4
Ce / Ce
E = 1.61 V
If an ammetter is connected between the two platinum electrodes. predict the direction of flow of current.
Will the current increase or decrease with time? [JEE 2000]
Q.7 The reaction, [JEE 2001]
3ClO
(aq)
-
3
ClO (aq) + 2Cl
(aq)
is an example of
(A) Oxidation reaction
(B) Reduction reaction
(C) Disproportionation reaction
(D) Decomposition reaction
Q.8 The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KCl is
(A) LiCl > NaCl > KCl [JEE 2001]
(B) KCl > NaCl > LiCl
(C) NaCl > KCl > LiCl
(D) LiCl > KCl > NaCl
Q.9 Saturated solution of KNO
3
is used to make salt bridge because
(A) velocity of K
+
is greater than that of
-
3
NO
(B) velocity of
-
3
NO is greater than that of K
+
(C) velocities of both K
+
and
-
3
NO are nearly the same
(D) KNO
3
is highly soluble in water [JEE 2001]
Q.10 The standard potential of the following cell is 0.23 V at 15 C & 0.21 V at 35 C
Pt | H
2
(g) | HCl (aq) | AgCl(s) | Ag(s)
(i) Write the cell reaction.
(ii) CalculateAH
0
,AS
0
for the cell reaction by assuming that these quantities remain unchanged in the range
15C to 35C.
(iii) Calculate the solubility of AgCl in water at 25C. Given standard reduction p otential of the
Ag
+
/Ag coup le is 0.80 V at 25C. [JEE 2001]
Q.11 Standard electrode potential data are useful for understanding the suitablilty of an oxidant in a redox
titration. Some half cell reactions and their standard potentials are given below:
-
4
MnO (aq) + 8H
+
(aq) + 5e
Mn
2+
(aq) + 4H
2
O (l); E = 1.51 V
- 2
7 2
O Cr (aq) + 14 H
+
(aq) + 6e
2Cr
3+
(aq) +7H
2
O (l); E = 1.38 V
Fe
3+
(aq) + e
Fe
2+
(aq); E = 0.77 V
Cl
2
(g) + 2e
2Cl
(aq); E = 1.40 V
Identify the only incorrect statement regarding quantitative estimation of aqueous Fe(NO
3
)
2
(A)
-
4
MnO can be used in aqueous HCl (B)
- 2
7 2
O Cr can be used in aqueous HCl
(C)
-
4
MnO can be used in aqueous H
2
SO
4
(D)
- 2
7 2
O Cr can be used in aqueous H
2
SO
4
[JEE 2002]
Q.12 In the electrolytic cell, flow of electrons is from:
(A) Cathode to anode in solution (B) Cathode to anode through external supply
(C) Cathode to anode through internal supply (D) Anode to cathode through internal supply.
[JEE 2003]
Q.13 Two students use same stock solution of ZnSO
4
and a solution of CuSO
4
. The e.m.f of one cell is
0.03 V higher than the other. The conc. of CuSO
4
in the cell with higher e.m.f value is 0.5 M. Find out
the conc. of CuSO
4
in the other cell |
'
= 06 . 0
F
RT 303 . 2
. [JEE 2003]
Q.14 Zn | Zn
2+
(a = 0.1M) || Fe
2+
(a = 0.01M)|Fe. The emf of the above cell is 0.2905 V. Equilibrium
constant for the cell reaction is
(A) 10
0.32/0.0591
(B) 10
0.32/0.0295
(C) 10
0.26/0.0295
(D) e
0.32/0.295
[JEE 2004]
Q.15 Find the equilibrium constant at 298 K for the reaction,
Cu
2+
(aq) + In
2+
(aq) l Cu
+
(aq) + In
3+
(aq)
Given that
V 15 . 0 E
Cu | Cu
2
=
,
V 42 . 0 E
In | In
3
- =
,
V 40 . 0 E
In | In
2
- =
[JEE 2004]
Q.16 The half cell reactions for rusting of iron are: [JEE 2005]
2H
+
+
2
1
O
2
+ 2e
H
2
O; E
0
= + 1.23 V, Fe
2+
+ 2e
Fe; E
0
= 0.44 VV
AG
0
(in kJ) for the reaction is:
(A) 76 (B) 322
(C) 122 (D) 176
Q.17
(a) Calculate
0
G
f
A
of the following reaction
) aq ( Ag
+
) aq ( Cl
-
AgCl(s)
Given :
0
G
f
A
(AgCl) = 109 kJ/mole,
0
G
f
A
(Cl
) = 129 kJ/mole,
0
G
f
A
(Ag
+
) = 77 kJ/mole
Represent the above reaction in form of a cell
Calculate E
0
of the cell. Find log
10
K
SP
of AgCl
(b) 6.539 10
2
g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of AgCl.
Calculate log
10
2
2
] Ag [
] Zn [
,
given that
Ag
+
+ e
Ag E
0
= 0.80 V ; Zn
2+
+ 2e
Zn E
0
= 0.76V
Also find how many moles of Ag will be formed? [JEE 2005]
Question No. 18 to 20 (3 questions)
Tollens reagent is used for the detection of aldehyde when a solution of AgNO
3
is added to glucose with
NH
4
OH then gluconic acid is formed
Ag
+
+ e
Ag ;
0
red
E = 0.8 V
C
6
H
12
O
6
+ H
2
O C
6
H
12
O
7
(Gluconic acid) + 2H
+
+ 2e
;
0
red
E = 0.05 V
2 3
) NH ( Ag + e
Ag(s) + 2NH
3
;
0
E
= 0.337 V
[Use 2.303
F
RT
= 0.0592 and
RT
F
= 38.92 at 298 K] [JEE 2006]
Q.18 2Ag
+
+ C
6
H
12
O
6
+ H
2
O 2Ag(s) + C
6
H
12
O
7
+ 2H
+
Find ln K of this reaction
(A) 66.13 (B) 58.38 (C) 28.30 (D) 46.29
Q.19 When ammonia is added to the solution, pH is raised to 11. Which half-cell reaction is affected by pH
and by how much?
(A) E
oxd
will increase by a factor of 0.65 from
0
oxd
E
(B) E
oxd
will decrease by a factor of 0.65 from
0
oxd
E
(C) E
red
will increase by a factor of 0.65 from
0
red
E
(D) E
red
will decrease by a factor of 0.65 from
0
red
E
Q.20 Ammonia is always is added in this reaction. Which of the following must be incorrect?
(A) NH
3
combines with Ag
+
to form a complex.
(B)

2 3
) NH ( Ag is a weaker oxidising reagent than Ag
+
.
(C) In absence of NH
3
silver salt of gluconic acid is formed.
(D) NH
3
has affected the standard reduction potential of glucose/gluconic acid electrode.
Q.21 We have taken a saturated solution of AgBr.K
sp
of AgBr is 12 10
14
. If 10
7
mole of AgNO
3
are
added to 1 litre of this solution find conductivity (specific conductance) of this solution in terms of 10
7
S m
1
mol
1
.
Given :
0
) Ag (

= 6 10
3
S m
2
mol
1
;
0
) Br (
-
= 8 10
3
S m
2
mol
1
;
0
) NO (
3
-
= 710
3
S m
2
mol
1
[JEE 2006]
Paragraph for Question Nos. 22 to 24 (3 questions)
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 10
23
) are present in a few grams of any chemical compound varying with their
atomic/molecular masses. To handle such large numbers conveniently, the mole concept was introduced.
This concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry
and radiochemistry. The following example illustrates a typical case, involving chemical/ electrochemical
reaction, which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads
to the evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23,
Hg = 200; 1 Faraday = 96500 coulombs) [JEE 2007]
Q.22 The total number of moles of chlorine gas evolved is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
Q.23 If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is
(A) 200 (B) 225 (C) 400 (D) 446
Q.24 The total charge (coulombs) required for complete electrolysis is
(A) 24125 (B) 48250 (C) 96500 (D) 193000
Paragraph for Question Nos. 25 & 26 (2 questions)
Redox reactions play a pivoted role in chemistry and biology. The values of standard redox potential
(E) of two half-cell reactions decide which way the reaction is expected to proceed. A simple example
is a Daniel cell in which zinc goes into solution and copp er gets deposited. Given below are a set of
half-cell reactions (acidic medium) along with their E (V with respect to normal hydrogen electrode)
values. Using this data obtain the correct explanations to Questions 14-16.
I
2
+ 2e
2I
E = 0.54
Cl
2
+ 2e
2Cl
E = 1.36
Mn
3+
+ e
Mn
2+
E = 1.50
Fe
3+
+ e
Fe
2+
E = 0.77
O
2
+ 4H
+
+ 4e
2H
2
O E = 1.23 [JEE 2007]
Q.25 Among the following, identify the correct statement.
(A) Chloride ion is oxidised by O
2
(B) Fe
2+
is oxidised by iodine
(C) Iodine ion is oxidised by chlorine (D) Mn
2+
is oxidised by chlorine
Q.26 While Fe
3+
is stable, Mn
3+
is not stable in acid solution because
(A) O
2
oxidises Mn
2+
to Mn
3+
(B) O
2
oxidises both Mn
2+
to Mn
3+
and Fe
2+
to Fe
3+
(C) Fe
3+
oxidises H
2
O to O
2
(D) Mn
3+
oxidises H
2
O to O
2
Q.27 Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of H
2
gas at the cathode is (1 Faraday = 96500 C mol
1
)
(A) 9.65 10
4
sec (B) 19.3 10
4
sec
(C) 28.95 10
4
sec (D) 38.6 10
4
sec [JEE 2008]
Q.28 For the reaction of NO
3
ion in an aqueous solution, E is +0.96 V. Values of E for some metal ions are
given below
V
2+
(aq) + 2e V E = 1.19 V
Fe
3+
(aq) + 3e Fe E = 0.04 V
Au
3+
(aq) + 3e Au E = + 1.40 V
Hg
2+
(aq) + 2e Hg E = + 0.86 V
The pair(s) of metal that is(are) oxidised by NO
3
in aqueous solution is(are) [JEE 2009]
(A) V and Hg (B) Hg and Fe
(C) Fe and Au (D) Fe and V
Q.29.. AgNO
3
(aq.) was added to an aqueous KCl solution gradually and the conductivity of the solution was
measured. The measured p lot of conductance(A) versus the volume of AgNO
3
[JEE 2011]
(A) (P) (B) (Q) (C) (R) (D) (S)
ANSWER KEY
Boost your basics
1.A 2.A 3. B 4. B 5.C 6. B 7.A 8.D 9.A 10.B 11.A 12.B 13.B
14B. 15C. 16.B 17.B 18.C 19.C 20.C 21.D 22.B 23.A 24.B 25.D 26.A
27D. 28A. 29 B 30 A 31 A 32 A 33 B
Multiple Choice Questions
42. A,B Q.43 C,D Q.44 B,C,D Q.45 A,B Q.46 B,C
FUNDAMENTALS
Q.1 (a) 2Ag + Cu
2+
2Ag
+
+ Cu, (b)
-
4
MnO + 5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
(c) 2Cl
+ 2Ag
+
2Ag + Cl
2
, (d) H
2
+ Cd
2+
Cd + 2H
+
Q.2 (a) Zn | Zn
2+
| | Cd
2+
| Cd, (b) Pt, H
2
| H
+
| | Ag
+
| Ag ,
(c) Pt | Fe
2+
, Fe
3+
| |
- 2
7 2
O Cr , H
+
, Cr
3+
| Pt
Q.3 Anode Cathode
(a) Zn | Zn
2+
H
+
, H
2
| Pt
(b) Pt | Sn
2+
, Sn
4+
Fe
3+
, Fe
2+
| Pt
(c) Pt | Fe
2+
, Fe
3+
-
4
MnO , H
+
, Mn
2+
| Pt
(d) Pb | Pb
2+
Br
2
, Br
| Pt
(e) Cu | Cu
2+
| | Cl
| Hg
2
Cl
2
| Hg]
Q.4 1.61 V Q.5 1.35 V
Q.6 1.68 V Q.7 0.80 V, NO
Q.8 0.53 V, disproportionation Q.9 0.0367 V
Q.10 E = 1.159V Q.11 K
c
= 1.864 10
107
, AG
0
= 611.8 kJ
Q.12 n = 2 Q.13 E = 0.059
Q.14 E = 0.395 V
Q.15 E
0
cell
= +0.01V, E
cell
= -0.0785V, correct rep resentation is Pb|Pb
2+
(10
-3
M)||Sn
2+
(1M)|Sn
Q.16 [Cu
2+
] = 2.97 10
-12
M for E = 0 Q.17 E = -0.81 V
Q.18 0.52 V, 0.61 V Q.19 0.0295 V
Q.20 0.0295 V Q.21 p H = 4
Q.22 (i) E = 0.286V; (ii) E = -0.0206V Q.23 a
2
= 0.1006 M
Q.24 K
c
= 7.6 10
12
Q.25 K
c
= 1.96 10
26
Q.26 K
w
~ 10
-14
Q.27 E
0
= 0.7826 V
Q.28 1.30 10
3
kJ mol
1
Q.29 (a) 6.02 10
22
electrons lost, (b) 1.89 10
22
electrons gained, (c) (b) 1.80 10
23
electrons gained
Q.30 (a) 0.75 F, (b) 0.69 F, (c)1.1 F Q.31 (i) 54 gm, (ii) 16.35 gm
Q.32 1.023 10
5
sec Q.33 1.12 mol, 12.535 litre
Q.34 0.112 litre Q.35 0.24 gms
Q.36 Rs. 0.75 x Q.37 (i) 2.1554 gm ; (ii) 1336. 15 sec
Q.38 115800C, 347.4 kJ Q.39 t = 193 sec
Q.40 n = 4 Q.41 Cu
2+
= 0.08M, H
+
= 0.04M, SO
2-
4
= 0.1M
Q.42 A = 114, Q = 5926.8C Q.43 Final weight = 9.6g, 0.01 Eq of acid
Q.44 t = 93.65 sec. Q.45 60 %
Q.46 (i) 482.5 sec (ii) 0.3175 gm (iii) 0.327 gm Q.47 1.825 g
Q.48 2M Q.49 419 S cm
2
equivalent
1
Q.50 0.00046 S cm
-1
; 2174 ohm cm Q.51 (i) 6.25 10
5
ohm, (ii) 1.6 10
-6
amp
Q.52 1.549 cm
1
Q.53 101.8 ohm
1
cm
2
/ gm equivalent
Q.54 0.0141 mho g equiv
1
m
2
, 0.141 mho m
1
Q.55 (i) 232 Mho cm
2
mol
1
, (ii) 116 Mho cm
2
equivalent
1
Q.56 0.865 Q.57 1.33 10
4
gm/litre
Q.58 8.74 10
11
mole
2
/litre
2
Q.59 o = 0.435 , k = 6.710
4
Q.60 (i) 390.6 S cm
2
mol
1
(ii) 12.32% Q.61 1.067 S m
1
Q.62 523.2 10
4
mho cm
2
mol
1
Q.63 (i) 6.98 (ii) 1.08 10
14
APPLICATION
Q.1 [Cu
2+
] = 10
-4
M Q.2 p H = 6.61
Q.3 K
a
= 6.74 10
-4
Q.4 1.39V
Q.5 0.46 V Q.6 (ii). 1.27 V, (iii) 245.1 kJ
Q.7 E
0
= -0.22 V Q.8 h = 2.12 10
2
, K
h
= 1.43 10
5
M
Q.9 0.95 V Q.10 K
sp
= 1.1 10
-16
Q.11 [Br
-
] : [Cl
-
] = 1 : 200 Q.12 E
0
= -0.1511V
Q.13 0.037 V Q.14 1.536 10
5
M
3
Q.15 1.66V Q.16 1.188V
Q.17 10
2
Q.18 5.24 10
16
Q.19 E = -1.59V, non-spontaneous Q.20 E
0
= 0.71V
Q.21 [Zn
2+
]/[Cu
2+
] = 1.941 10
37
Q.22 0.373V
Q.23 K
f
= 8.227 10
63
Q.24 0.372 V , 0.307 V
Q.25 K = 10
268
Q.26 Tl
+
= 10
8
; Co
3+
= 2 10
8
Q.27 Eq. wt. = 107.3 Q.28 643.33amp,190.5g
Q.29 43.456g Q.30 265 Amp. hr.
Q.31 42.2 %
Q.32 V(O
2
) = 99.68 mL, V(H
2
) = 58.46 mL, Total vol. = 158.1 mL
Q.33 57.5894 gm Q.34 1.9 million year
Q.35 1.21 10
5
coulomb Q.36 1250 s, 0.064 M
Q.37 1.143V Q.38 (a) 0.124 V, (b) 7.1, (c) calomel electrode
Q.39 0.4414 V Q.40 0.167 V
Q.41 0.1456 amp ere Q.42 3.29 cm
Q.43 4.2510
2
metre Q.44 0.1934 gm/litre
Q.45 K
SP
= 7.682 10
17
Q.46 2 10
5
dm
3
FEEL THE HEAT
Q.1 K
C
= 6.26 10
7
Q.2 K
sp
= 2.287 10
-12
Q.3 A Q.4 B
Q.5 7.95 10
5
M Q.6 decrease with time
Q.7 C Q.8 B
Q.9 C Q.10 AH
0
= 49987 Jmol
1
, AS
0
= 96.5 J mol
1
K
1
, s = 1.47 10
5
M
Q.11 A Q.12 C Q.13 0.05 M Q.14 B Q.15 K
C
= 10
10
Q.16 B
Q.17 (a) E
0
= 0.59 V, log
10
K
SP
= 10 (b) 52.8, 10
6
moles
Q.18 A Q.19 A Q.20 D Q.21 55 S m
1
Q.22 B Q.23 D
Q.24 D Q.25 C Q.26 D Q.27 B Q.28 A,B,D Q.29. D

Electro Chemistry

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1

& can be obtained from graph. In case of weak electrolytes such

for strong electrolytes are related by Debye Huckel

represent the molar

represent the no. of +ve and ve ions furnished by electrolyte.

of weak electrolytes at dilution.

3. Calculation of dissociation constant of weak electrolytes

If SHE acts as cathode than reduction occurs as :-

Converting natural logarithm to the base 10,

(aq.) 2Na (l) + Cl

move towards anode but as discharge

ions is lower than that of OH

ions are present near anode but as discharge potential

ions is lower than that of SO

ions are discharged at

What will be the effect on EMF if concentration of Mg

Normal calomel elctrode

(Over all process)

From Nernst equation, we have

The overall reaction is represented by

The overall reaction during discharge is:

Overall reaction being:

electrode (reduction) from

. The standard reduction potential of the Tl

| X, the standard reduction potentials are and

is 1 M. Now the meacured emf of the cell is

from aqueous solution

from aqueous solution

can be reduce in p resence of Cl

(aq) + 2Hg (l)

l Ag is 0.799V. What is the standard p otential for

are 54.3 and 65.5 ohm

ions at this temp erature are 4.2610

], the dissociation constant for

complexation reaction of importance.

Q.29 One of the methods of prep aration of per disulphuric acid, H

Q.41 The equivalent conductance of 0.10 N solution of MgCl

) = 0.33V. From this

is the spontaneous reaction

M + X is the sp ontaneous reaction

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