Electrochemistry

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

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

ELECTROCHEMISTRY 213
(i) 1M concentration of each ion in the solution. Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu EMF = +1.1V
(ii) A temperature of 298 K. (f) If an inert electrode like platinum is involved in the
construction of the cell, it may be written along with the
(iii) 1 bar pressure for each gas.
working electrode in bracket say for example, when a zinc
8. ELECTROCHEMICAL SERIES anode is connected to a hydrogen electrode.
The half cell potential values are standard values and are Zn s | Zn 2 C1 || H C2 | H 2 | Pt s
represented as the standard reduction potential values
as shown in the table at the end which is also called 11. SALT BRIDGE
Electrochemical Series.
Salt bridge is used to maintain the charge balance and to
9. CELL POTENTIAL OR EMF OF A CELL complete the circuit by facilitating the flow of ions through it.
It contains a gel in which an inert electrolyte like Na2SO4 or
The difference between the electrode potentials of two
KNO3 etc are mixed. Negative ions flow to the anode and
half cells is called cell potential. It is known as electromotive
force (EMF) of the cell if no current is drawn from the cell. positive ions flow to the cathode through the salt bridge and
charge balance is maintained and cell keeps on functioning.
Ecell = Ecathode + Eanode
For this equation we take oxidation potential of anode and

reduction potential of cathode.
Since anode is put on left and cathode on right, it follows

therefore,
= ER + EL
For a Daniel cell, therefore
E ocell E oCu 2 / Cu EoZn / Zn 2 0.34 0.76 1.10 V
10. CELL DIAGRAM OR REPRESENTATION

OF A CELL
The following conventions or notations are applied for writing
the cell diagram in accordance with IUPAC recommendations. 12. SPONTANEITY OF A REACTION
The Daniel cell is represented as follows : 'G = – nFECELL
2+ 2+
Zn(s) | Zn (C1) || Cu (C2) | Cu (s) For a spontaneous cell reaction ΔG should be negative
(a) Anode half cell is written on the left hand side while and cell potential should be positive.
cathode half cell on right hand side. If we take standard value of cell potential in the above
(b) A single vertical line separates the metal from aqueous equation we will obtain standard value of ΔG as well.
solution of its own ions.
ΔGo = – nFE0CELL
2 2
Zn s | Zn aq ; Cu aq | Cu s
Anodic chamber Cathodic chamber
13. TYPES OF ELECTRODES
(c) A double vertical line represents salt bridge
13.1 Metal-Metal Ion electrodes
(d) The molar concentration (C) is placed in brackets after
the formula of the corresponding ion. A metal rod/plate is dipped in an electrolyte solution
containing metal ions. There is a potential difference
(e) The value of e.m.f. of the cell is written on the extreme
right of the cell. For example, between these two phases and this electrode can act as a
cathode or anode both.
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214 ELECTROCHEMISTRY
Anode: M Mn+ + ne–
Cathode: Mn+ + ne– M
13.2 Gas Electrodes
Electrode gases like H2, Cl2 etc are used with their respective
ions. For example, H2 gas is used with a dilute solution of HCl
(H+ ions). The metal should be inert so that it does not react
with the acid.
Cathode :
Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq)
Anode :
2Hg(l) + 2Cl–(aq) Hg2Cl2(s) + 2e–
This electrode is also used as another standard to measure
other potentials. Its standard form is also called Standard
Anode: H2 2H+ + 2e– Calomel Electrode (SCE).
13.5 Redox Electrode
Cathode: 2H+ + 2e– H2
In these electrodes two different oxidation states of the
The hydrogen electrode is also used as the standard to same metal are used in the same half cell. For example,
measure other electrode potentials. Its own potential is Fe2+ and Fe3+ are dissolved in the same container and an
set to 0 V as a reference. When it is used as a reference inert electrode of platinum is used for the electron transfer.
the concentration of dil HCl is taken as 1 M and the Following reactions can take place:
electrode is called “Standard Hydrogen Electrode (SHE)”. Anode: Fe2+ Fe3+ + e–
13.3 Metal-Insoluble salt electrode Cathode: Fe3+ + e– Fe2+
We use salts of some metals which are sparingly soluble 14. NERNST EQUATION
with the metal itself as electrodes. For example, if we use
AgCl with Ag there is a potential gap between these two It relates electrode potential with the concentration of ions.
phases which can be identified in the following reaction:
Thus, the reduction potential increases with the increase
in the concentration of ions. For a general electrochemical
AgCl(s) + e– Ag(s) + Cl–
reaction of the type.
This electrode is made by dipping a silver rod in a solution
containing AgCl(s) and Cl– ions. aA bB o

ne
cC dD
Nernst equation can be given as

13.4 Calomel Electrode
c d
Mercury is used with two other phases, one is a calomel RT C D
E cell E o
ln
paste (Hg2Cl2) and electrolyte containing Cl– ions. cell
nF A
a
B
b

c d concentrations and the solutions are connected through

2303 C D
E cell E o
cell RT log a b
salt bridge, such cells are known as concentration cells.
nF A B For example
H2 | H+(c1) || H+ (c2) | H2
Substituting the values of R and F we get
Cu | Cu+2 (c1) || Cu2+(c2) | Cu
c d
0.0591 C D These are of two types :
E cell o
E cell log a b
,at 298 K
n A B
16.1 Electrode concentration cells
15. APPLICATIONS OF NERNST EQUATION H2 (P1) | H+ (C) || H+ (C) | H2(P2)
15.1 Equilibrium Constant from Nernst Equation

0.059 P
Ecell = 0 – log 2
For a Daniel cell, at equilibrium n P1
ª Zn 2 º where p 2 p1 for spontaneous reaction

log ¬ 2 ¼
2.303 RT
E cell 0 E ocell
2F ª¬Cu º¼ 16.2 Electrolyte concentration cell
The EMF of concentration cell at 298 K is given by

ª Zn 2 º
log ¬ 2 ¼
o 2.303RT Zn | Zn2+ (c1) || Zn2+ (c2) | Zn
or E cell
2F ª¬Cu º¼
0.0591 c
E cell log 2 ,
n1 c1
ª¬ Zn 2 º¼
But at equilibrium, ª 2 º Kc where c2 > c1 for spontaneous reaction
¬ Cu ¼
17. CASES OF ELECTROLYSIS
2.303 RT
E ocell log K c 17.1 Electrolysis of molten sodium chloride
2F
2NaCl (l ) U 2Na+ (l ) + 2Cl– (l )
2.303 u 8.314 u 298
E ocell log K c The reactions occurring at the two electrodes may be
2 u 96500 shown as follows :
At cathode :
0.0591
log K c
2 2Na+ + 2e– o 2Na E0 = – 2.71 V
At anode :
o 0.0591
In general, E cell log K c
n 2Cl– o Cl2 + 2e– E0 = – 1.36V
Overall reaction :
n E ocell
or, log KC =
0.0591 2Na+ (l ) + 2 Cl– (l ) 2Na (l ) + Cl2 (g)
16. CONCENTRATION CELLS or 2NaCl (l ) 2Na (l ) + Cl2 (g)
If two electrodes of the same metal are dipped separately At cathode At anode
into two solutions of the same electrolyte having different
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17.2 Electrolysis of an aqueous solution of sodium chloride 18.3 Mercury cells
NaCl (aq) Na+(aq) + Cl– (aq) These are used in small equipments like watches, hearing aids.
(almost completely ionized) Anode : Zn – Hg Amalgam
H2O (l ) U H+(aq) + OH–(aq) Cathode : Paste of HgO and carbon
(only slightly ionized) Electrolyte : Paste of KOH and ZnO
At cathode : Anode : Zn (Hg) + 2OH– ZnO (s) + H2O + 2e–
2Na+ + 2e– 2Na E0 = – 2.71V Cathode : HgO (s) + H2O + 2e– Hg (l) + 2OH–
2H2O + 2e– H2 + 2OH– E0 = – 0.83V Overall Reaction : Zn (Hg) + HgO (s) ZnO (s) + Hg (l)
Thus H2 gas is evolved at cathode value Na+ ions remain The cell potential is approximately 1.35V and remains
in solution. constant during its life.
At anode : 18.4 Secondary Batteries
2H2O O2 + 4H+ + 4e– E0 = – 1.23V Secondary cells are those which can be recharged again
and again for multiple uses. e.g. lead storage battery and
2Cl– Cl2 + 2e– E0 = – 1.36V Ni – Cd battery.
Thus, Cl2 gas is evolved at the anode by over voltage 18.5 Lead Storage Battery
concept while OH– ions remain in the solution.
Anode : Lead (Pb)
18. BATTERIES
Cathode : Grid of lead packed with lead oxide (PbO2)
When Galvanic cells are connected in series to obtain a
higher voltage the arrangement is called Battery. Electrolyte : 38% solution of H2SO4
18.1 Primary Batteries Discharging Reactions

Primary cells are those which can be used so long the Anode: Pb(s) + SO42–(aq) PbSO4(s) + 2e–
active materials are present. Once they get consumed the
cell will stop functioning and cannot be re-used. Example Cathode: PbO2(s) + 4H+(aq) + SO42–(aq) + 2e–
Dry Cell or Leclanche cell and Mercury cell.
PbSO4(s) + 2H2O(l)
18.2 Dry cell
Overall Reaction : Pb(s) + PbO2(s) + 2H2SO4(aq)
Anode : Zn container
2PbSO4(s) + 2H2O(l)
Cathode : Carbon (graphite) rod surrounded by powdered
MnO2 and carbon. To recharge the cell, it is connected with a cell of higher
potential and this cell behaves as an electrolytic cell
Electrolyte : NH4Cl and ZnCl2 and the reactions are reversed. Pb(s) and PbO 2(s) are
regenerated at the respective electrodes.These cells
Reaction : deliver an almost consistent voltage.
Anode : Zn Zn2+ + 2e– Recharging Reaction : 2PbSO4(s) + 2H2O(l) Pb(s) +
Cathode : MnO2 + NH 4
e– MnO (OH) + NH3 PbO2(s) + 2H2SO4(aq)
The standard potential of this cell is 1.5 V and it falls as 19. FUEL CELLS
the cell gets discharged continuously and once used it
A fuel cell differs from an ordinary battery in the sense
cannot be recharged.
that the reactants are not contained inside the cell but are

externally supplied from an external reservoir. Fuel cell is and iron is protected. This method of protecting one metal
used in space vehicles and in this cell the two gases are by the other is also called Cathodic Protection.
supplied from external storages. In this cell carbon rods
are used as electrodes with KOH as the electrolyte.
Cathode : O2 (g) + 2H2O (l) + 4e– 4OH– (aq)
Anode : 2H2 (g) + 4OH– (aq) 4H2O (l) + 4e–
overall Reaction : 2H2(g) + O2 (g) 2H2O (l)
21. CONDUCTANCE (G)

It is the reciprocal of resistance and may be defined as the
ease with which the electric current flows through a
conductor.
1
G
R
SI unit is Siemen (S).
1 S = 1 ohm–1 (mho)
N)
22. CONDUCTIVITY (N
20. CORROSION
It is the reciprocal of resistivity (U).
It involves a redox reaction and formation of an
1 1 A A
electrochemical cell on the surface of iron or any other metal. N u Gu
U R A A
At one location oxidation of iron takes place (anode) and
Now if A = 1 cm and A = 1 cm2, then N = G..
at another location reduction of oxygen to form water takes
place (cathode). First Fe gets oxidised to Fe2+ and then in Hence, conductivity of an electrolytic solution may be
the presence of oxygen it forms Fe3+ which then reacts defined as the conductance of a solution of 1 cm length
with water to form rust which is represented by Fe2O3.xH2O. with area of cross-section equal to 1 cm2.
Anode : 2Fe (s) o 2 Fe2+ + 4e– Eº = + 0.44 V 23. FACTORS AFFECTING ELECTROLYTIC
Cathode : O2 (g) + 4H + 4e o 2H2O (l) Eº = 1.23 V
+ –
CONDUCTANCE
Overall R × N :
23.1 Electrolyte
2Fe (s) + O2 (q) + 4H+ o 2Fe2+ + + 2H2O Eºcell = 1.67 M
An electrolyte is a substance that dissociates in solution to
produce ions and hence conducts electricity in dissolved
or molten state.
Examples : HCl, NaOH, KCl (Strong electrolytes).
CH3–COOH, NH4OH (Weak electrolytes).
The conductance of electricity by ions present in the

solutions is called electrolytic or ionic conductance. The
Rusting of iron can be avoided by painting it or by coating following factors govern the flow of electricity through a
it with some other metals like Zinc. The latter process is
solution of electrolyte.
known as Galvanisation. As the tendency of Zn to get
oxidised is more than iron it gets oxidised in preference
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(i) Nature of electrolyte or interionic attractions : Lesser 25. MOLAR CONDUCTIVITY (/m)
the solute-solute interactions, greater will be the freedom
of movement of ions and higher will be the conductance. It may be defined as the conducting power of all the ions
produced by dissolving one mole of an electrolyte placed
(ii) Solvation of Ions : Larger the magnitude of solute-solvent
between two large electrodes at one centimeter apart.
interactions, greater is the extent of solvation and lower
will be the electrical conductance. Mathematically,
N u1000
(iii) The nature of solvent and its viscosity : Larger the solvent- /m N u V, / m
solvent interactions, larger will be viscosity and more will C
be the resistance offered by the solvent to flow of ions where, V is the volume of solution in cm3 containing 1
and hence lesser will be the electrical conductance. mole of electrolyte and C is the molar concentration.
(iv) Temperature : As the temperature of electrolytic solution N u 1000 S cm 1

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

1 A It is conducting power of one equivalent of electrolyte
As we know, N u The value of Ncould be known,
R A placed between two large electrodes at one centimeter apart.
if we measure l, A and R. The value of the resistance of Mathematically :
the solution R between two parallel electrodes is
determined by using ‘Wheatstones’ bridge method / eq Nu v
(Fig.)
N u1000
/ eq
N
Where, v is the volume of solution in cm3 containing

1 equivalent of electrolyte and N is normality.
Units :
N u1000
/ eq
N
S cm1 Ohm1 cm 2 equivalent 1
equivalent cm 3 or S cm 2 equivalent 1
27. VARIATION OF CONDUCTIVITY AND MOLAR

It consists of two fixed resistance R3 and R4, a variable CONDUCTIVITY WITH DILUTION
resistance R1 and the conductivity cell having the unknown
resistance R2. The bridge is balanced when no current Conductivity decreases with decrease in concentration,
passes through the detector. Under these conditions, this is because the number of ions per unit volume that
carry the current in the solution decreases on dilution.
R1 R3 R 1R 4
or R2
R2 R4 R3
Molar conductivity / m N u V increases with decrease
in concentration. This is because the total volume V of
solution containing one mole of electrolyte also increases.

It has been found that the decrease in Non dilution of a Here, O o and Oo are the limiting molar conductivities of
solution is more than compensated by increases in its cations and anions respectively.
volume.
30. APPLICATIONS OF KOHLRAUSCH’S LAW
Graphic representation of the variation of / m vs c
30.1 (i) Calculation of molar conductivities of weak
electrolyte at infinite dilution
For example, molar conductivity of acetic acid at infinite

dilution can be obtained from the knowledge of molar
conductivities at infinite dilution of strong electrolyte like
HCl, CH3COONa and NaCl as illustrated below.
ªO o OoNa º ¬ª OHo O Cl ¼º ¬ªOoNa OCl

o
º
¬ CH 3 COO ¼ ¼
i.e. / m CH3 COOH / om CH3 COONa / om HCl / om NaCl

o
28. LIMITING MOLAR CONDUCTIVITY (/m) 30.2 (ii) Determination of Degree of Dissociation
The value of molar conductivity when the concentration of Weak Electrolytes
approaches zero is known as limiting molar conductivity or
molar conductivity at infinite dilution. It is possible to / cm
determine the molar conductivity at infinite dilution / m in
o Degree of dissociation D
/ om
case of strong electrolyte by extrapolation of curve of
/ m vs c. On contrary, the value of molar conductivity of 30.3 (iii) Determination of Dissociation Constant
weak electrolyte at infinite dilution cannot be determined (K) of Weak Electrolytes:
by extapolation of the curve as the curve becomes almost
parallel to y-axis when concentration approaches to zero. cD2
K
1 D
The mathematical relationship between / m and / om for
strong electrolyte was developed by Debye, Huckel and / cm
Onsagar. In simplified form the equation can be given as also D
/ fm
/m / fm b c1/ 2 2 2
c / cm / / fm C / cm
where / f
is the molar conductivity at infinite dilution ? K
m
1 / cm / / fm / fm / fm / cm
and b is a constant which depends on the nature of the
solvent and temperature. 31. USE OF 'G IN RELATING EMF VALUES OF
HALF CELL REACTIONS
29. KOHLRAUSCH’S LAW
When we have two half cell reactions such that on adding
It states that the limiting molar conductivity of an electrolyte
them we obtain another half cell reaction then their emfs
can be represented as the sum of the individual contributions
cannot be added directly. But in any case thermodynamic
of the anion and cation of the electrolyte. In general, if an
functions like 'G can be added and emf values can be related
electrolyte on dissociation gives v+ cations and v– anions
through them. Consider the following three half cell reactions:
then its limiting molar conductivity is given by
Fe2+ + 2e– o Fe E1
/ fm v Oo v Oo
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Fe3+ + 3e– o Fe E2 / cm
5. D
Fe3+ + e– o Fe2+ E3 / fm
We can easily observe that the third reaction can be where, D = Degree of dissociation
obtained by subtracting the first reaction from the second.
But the same relation does not apply on the emf values. /cm = Molar conductivity at a given
That is, E3 z E2 – E1. But the 'G values can be related concentration
according to the reactions. That is, 6. For a weak binary electrolyte AB
'G3 = 'G2 – 'G1 c / cm
2
cD 2
K
– n3FE3 = – n2FE2 + n1FE1 1 D / fm / fm / mc
– E3 = – 3E2 + 2E1 where, K = Dissociation constant
E3 = 3E2 – 2E1 Eocell E ocathode E oanode
= Eo Right + Eo left
NOTE 7. Nernst equation for a general electrochemical reaction

We should always remember that emf values are additive aA + bB
ne
o cC + dD
only when two half cell reactions are added to give a c d
complete balanced cell reaction. In any other case we RT C D
E cell E o
In
will be using 'G values to obtain relations between emf cell
nF A
a
B
b
values. c d
2.303RT C D
E cell E o
cell log a b
32. FORMULAE nF A B
§A· A B
a b
1. R U ¨ ¸ Uu Cell constant E cell E o

0.059
log at 298 K
©A¹ cell
n c
C D
d
where, R = Resistance
n
A = Area of cross-section of the electrodes. 8. log Kc = E ocell
0.0591
U= Resistivity
where, Kc = Equilibrium constant.
1 9. 'rGo nFE ocell (Creterion of spontaneity)
2. N u cell constant
R
'rGo 2.303RT log K c
where, N = Conductivity or specific conductance
where, 'rGo = Standard Gibbs energy of the reaction.
N u1000
3. /m 10. Q=I×t
M
where Q = Quantity of charge in coulombs
where, / m = Molar conductivity I = Current in amperes
M = Molarity of the solution. t = Time in seconds
11. m=Z×I×t
4. / fm (Ax By) = x / fm (Ay+) + y / fm (Bx–)
where m = mass of the substance liberated at the
f
where, / = Molar conductivity at infinite dilution x and y electrodes
m
are the number of cations and anions produced by one Z = Electrochemical equivalent.
formula unit of the electrolyte on complete dissociation. where E = Equivalent weight = E/96500
STANDARD REDUCTION POTENTIALS AT 298 K.

IN ELECTROCHEMICAL ORDER
H4XeO6 + 2H+ + 2e– o XeO3 + 3H2O + 3.0 Hg 2SO 4 2e o 2Hg SO 24 + 0.62
F2 + 2e– o 2F– + 2.87
MnO 24 2H 2 O 2e o MnO 2 4OH + 0.60
O3 + 2H+ + 2e– o O2 + H2O + 2.07
S2O 82 2e o 2SO 24 + 2.05 MnO 4 e o MnO24 + 0.56
Ag2+ + e– o Ag+ + 1.98 I2 + 2e o 2I

– –
+ 0.54
Co3+ + e– o Co2+ + 1.81 Cu+ + e– o Cu + 0.52
H2O2 + 2H + 2e o 2H2O
+ –
+ 1.78 I 3 2e o 3I + 0.53
Au + e o Au
+ –
+ 1.69 NiOOH + H2O + e o Ni(OH)2 + OH – –
+ 0.49
Pb4+ + 2e– o Pb2+ + 1.67
Ag 2 CrO 4 2e o 2Ag CrO 24 + 0.45
2HClO + 2H+ + 2e– o Cl2 + 2H2O + 1.63
O2 + 2H2O + 4e o 4OH – –
+ 0.40
Ce4+ + e– o Ce3+ + 1.61
2HBrO + 2H+ + 2e– o Br2 + 2H2O + 1.60 ClO4 H 2 O 2e o ClO3 2OH + 0.36
MnO 4 8H 5e o Mn 2 4H 2 O + 1.51 [Fe(CN)6]3– + e– o [Fe(CN)6]4– + 0.36

Cu + 2e o Cu
2+ –
+ 0.34
Mn3+ + e– o Mn2+ + 1.51
Hg2Cl2 + 2e o 2Hg + 2Cl
– –
+ 0.27
Au3+ + 3e– o Au + 1.40
AgCl + e o Ag + Cl– –
+ 0.22
Cl2 + 2e– o 2Cl– + 1.36
Bi + 3e o Bi
–
+ 0.20
Cr2 O 27 14H 6e o 2Cr 3 7H 2 O + 1.33
Cu + e o Cu
2+ – +
+ 0.16
O3 + H2O + 2e– o O2 + 2OH– + 1.24 Sn + 2e o Sn
4+ – 2+
+ 0.15
O2 + 4H+ 4e– o 2H2O + 1.23 AgBr + e o Ag + Br– –
+ 0.07
ClO4 2H 2e
o ClO3 H2O + 1.23 Ti + e o Ti
4+ – 3+
0.00
MNO2 + 4H + 2e o Mn + 2H2O
+ – 2+
+ 1.23 2H + 2e o H2
+ –
0, by definition
Br2 + 2e o 2Br
– –
+ 1.09 Fe + 3e o Fe
3+ –
– 0.04
Pu4+ + e– o Pu3+ + 0.97 O2 H2O + 2e– o HO 2 OH – 0.08
NO3 4H 3e o NO 2H 2 O + 0.96 Pb2+ + 2e– o Pb – 0.13
In + e o In
+ –
– 0.14
2Hg 2 2e o Hg 22 + 0.92
Sn + 2e o Sn
2+ –
– 0.14
ClO– + H2O + 2e– o Cl– + 2OH– + 0.89
AgI + e– o Ag + I– – 0.15
Hg2+ + 2e– o Hg + 0.86
Ni + 2e o Ni
2+ –
– 0.23
NO3 2H e o NO 2 H 2 O + 0.80
Co + 2e o Co
2+ –
– 0.28
Ag+ + e– o Ag + 0.80 In + 3e o In
3+ –
– 0.34
Hg 22
2e o 2Hg + 0.79 Tl e o Tl
+ –
– 0.34
Fe3+ + e– o Fe2+ + 0.77 PbSO4 + 2e– o Pb + SO 24 – 0.36
BrO + H2O + 2e o Br + 2OH
– – – –
+ 0.76
Ti3+ + e– o Ti2+ – 0.37 V2+ + 2e– o V – 1.19
Cd2+ + 2e– o Cd – 0.40 Ti + 2e o Ti

2+ –
– 1.63
In2+ + e– o In+ – 0.40 Al3+ + 3e– o Al – 1.66
Cr3+ + e– o Cr2+ – 0.41 U + 3e o U

3+ –
– 1.79
Fe2+ + 2e– o Fe – 0.44 Sc + 3e o Sc

3+ –
– 2.09
In3+ + 2e– o In+ – 0.44 Mg + 2e o Mg

2+ –
– 2.36
S + 2e– o S2– – 0.48 Ce + 3e o Ce

3+ –
– 2.48
In3+ + e– o In2+ – 0.49 La3+ + 3e– o La – 2.52
U4+ + e– o U3+ – 0.61 Na + e o Na

+ –
– 2.71
Cr3+ + 3e– o Cr – 0.74 Ca + 2e o Ca

2+ –
– 2.87
Zn2+ + 2e– o Zn – 0.76 Sr + 2e o Sr

2+ –
– 2.89
Cd(OH)2 + 2e– o Cd + 2OH– – 0.81 Ba + 2e o Ba

2+ –
– 2.91
2H2O + 2e– o H2 + 2OH– – 0.83 Ra2+ + 2e– o Ra – 2.92
Cr2+ + 2e– o Cr – 0.91 Cs + e o Cs

+ –
– 2.92
Mn2+ + 2e– o Mn – 1.18 Rb + e o Rb

+ –
– 2.93
K +e oK
+ –
– 2.93
Li + e o Li
+ –
– 3.05
REDUCTION
POTENTIALS IN ALPHABETICAL ORDER
Ag+ + e– o Ag + 0.80 Ca2+ + 2e– o Ca – 2.87

Ag + e o Ag
2+ – +
+ 1.98 Cd(OH)2 + 2e o Cd + 2OH – –
– 0.81
AgBr + e o Ag + Br
– –
+ 0.0713 Cd2+ + 2e– o Cd – 0.40
AgCl + e o Ag + Cl
– –
+ 0.22 Ce + 3e o Ce
3+ –
– 2.48
Ag2CrO4 + 2e– o 2Ag + CrO 24 + 0.45 Ce4+ + e– o Ce3+ + 1.61

Cl2 + 2e o 2Cl – –
+ 1.36
AgF + e– o Ag + F– + 0.78
ClO– + H2O + 2e– o Cl– + 2OH– + 0.89
AgI + e– o Ag + I– – 0.15
Al3+ + 3e– oAl – 1.66 ClO4 2H 2e o ClO3 H 2 O + 1.23
Au+ + e– o Au + 1.69 ClO4 H 2 O 2e o ClO3 2OH + 0.36

Au3+ + 3e– oAu + 1.40
Co2+ + 2e– o Co – 0.28
Ba + 2e o Ba
2+ –
+ 2.91
Co3+ + e– o Co2+ + 1.81
Be2+ + 2e– o Be – 1.85
Cr + 2e o Cr
2+ –
– 0.91
Bi3+ + 3e– o Bi + 0.20
Cr2 O 72 14H 6e o 2Cr 3 7 H 2 O + 1.33
Br2 + 2e– o 2Br– + 1.09
BrO– + H2O + 2e– o Br– + 2OH– + 0.76 Cr3+ + 3e– o Cr – 0.74
Cr + e o Cr
3+ – 2+
– 0.41
Cs+ e– o Cs – 2.92 MnO4 2H 2O 2e o MnO2 4OH + 0.60

Cu + e o Cu
+ –
+ 0.52 Na+ + e– o Na – 2.71
Cu + 2e o Cu
2+ –
+ 0.34 Ni + 2e o Ni
2+ –
– 0.23
Cu2+ + e– o Cu+ + 0.16 NiOOH + H2O + e o Ni(OH)2 + OH – –
+ 0.49
F2 + 2e– o 2F– + 2.87
NO3 2H e o NO 2 H 2O – 0.80
Fe2+ + 2e– o Fe – 0.44
Fe3+ + 3e– o Fe – 0.04 NO3 4H 3e o NO 2H 2 O + 0.96
Fe3+ + e– o Fe2+ + 0.77 NO3 H 2 O 2e o NO 2 2OH + 0.10

[Fe(CN)6] + e o [Fe(CN)6]
3– – 4–
+ 0.36 O2 + 2H2O + 4e– o 4OH– + 0.40
2H + 2e o H2
+ –
0, by definition O2 + 4H + 4e o 2H2O
+ –
+ 1.23
2H2O + 2e– o H2 + 2OH– – 0.83
O 2 e o O 2 – 0.56
2HBrO + 2H+ + 2e– o Br2 + 2H2O + 1.60
2HClO + 2H+ + 2e– o Cl2 + 2H2O + 1.63 O2 + H2O + 2e– o HO 2 + OH– – 0.08
H2O2 + 2H+ + 2e– o 2H2O + 1.78 O3 + 2H+ + 2e– o O2 + H2O + 2.07

H4XeO6 + 2H+ + 2e– o XeO3 + 3H2O + 3.0 O3 + H2O + 2e o O2 + 2OH – –
+ 1.24
Pb + 2e o Pb
2+ –
– 0.13
Hg 22 2e o 2Hg + 0.79
Pb + 2e o Pb
4+ – 2+
+ 1.67
Hg2Cl2 + 2e– o 2Hg + 2Cl– + 0.27
Hg2+ + 2e– o Hg + 0.86 PbSO4 + 2e– o Pb + SO 24 – 0.36
Pt2+ + 2e– o Pt + 1.20
2Hg2+ + 2e– o Hg 22 + 0.92
Pu + e o Pu
4+ – 3+
+ 0.97
Hg2SO4 + 2e– o 2Hg + SO 24 + 0.62 Ra + 2e o Ra
2+ –
– 2.92
I2 + 2e– o 2I– + 0.54 Rb + e o Rb
+ –
– 2.93
I 3 S + 2e o S
– 2–
2e o 3I + 0.53 – 0.48
In+ + e– o In – 0.14 S2 O82 2e o 2SO 24 + 2.05
In + e o In
2+ – +
– 0.40 SC + 3e o Sc
3+ –
– 2.09
In + 2e o In
3+ – +
– 0.44 Sn + 2e o Sn
2+ –
– 0.14
In + 3e o In
3+ –
– 0.34 Sn + 2e o Sn
4+ – 2+
+ 0.15
In + e o In
3+ – 2+
– 0.49 Sr + 2e o Sr
2+ –
– 2.89
K +e oK
+ –
– 2.93 Ti + 2e o Ti
2+ –
– 1.63
La3+ + 3e– o La – 2.52 Ti + e o Ti
3+ – 2+
– 0.37
Li+ e– o Li – 3.05 Ti + e o Ti
4+ – 3+
0.00
Mg2+ + 2e– o Mg – 2.36 Tl + e o Tl
+ –
– 0.34
Mn2+ + 2e– o Mn – 1.18 U + 3e o U
3+ –
– 1.79
Mn3+ + e– o Mn2+ + 1.51 U +e oU
4+ – 3+
– 0.61
MnO2 + 4H+ + 2e– o Mn2+ + 2H2O + 1.23 V + 2e o V
2+ –
– 1.19
V +e oV
3+ – 2+
– 0.26
MnO 4 8H 5e o Mn 2 4H 2 O + 1.51
Zn + 2e– o Zn
2+
– 0.76
MnO 4 e o MnO24 + 0.56
ELECTROCHEMISTRY
224 224
ELECTROCHEMISTRY
SOLVED EXAMPLES
Example – 1 Example – 6
Give the relationship between equivalent and molar Write the chemical equations for all the steps involved in the
conductance ? rusting of iron, Give any one method to prevent rusting of iron.
1000 1000 Sol. o Fe 2 aq 2e , E Fe

Anode: Fe s
o
2
/ Fe
0.44 V
Sol. /m Nu and / eq Nu
Molarity Normality

Cathode : O 2 g 4H aq 4e
o 2H 2O,
/m Normality E oH / O 1.23V

? 2 / H2 O
/ eq Molarity Overall reaction
Example – 2 Fe(s)
o Fe2+ (aq) + 2e– ] × 2
Can nickel spatula be used to stir a copper sulphate solution ? O2(g) + 4H+ + 4e–
o 2H2O
Support your answer with a reason
E oNi2 / Ni 0.25 V, E oCu 2 / Cu 0.34 V. 2Fe + O2 + 4H+(aq)

o 2Fe2+ + 2 H2O E ocell 1.67V
Sol. E ocell o
E cathode E oanode
Further 4Fe2+(aq) + O2(g) + 4H2O(l)
o
E ocell o
E Cu 2
/ Cu
EoNi2 / Ni 0.34 V 0.25 0.59 V
2Fe2O3 + 8H+(aq)
As E ocell is +ve, 'G = – ve, because 'G = – nEo F, i.e, Fe2O3 + xH2O
o
reaction will take place. Therefore, we cannot stir a Fe2O3 . xH2O
copper sulphate solution with nickel spatula. Hydrated ferric oxide (Rust)
Example – 3 Galvanisation is used to prevent rusting of iron.
State two advantages of H2—O2 fuel cell over ordinary cell. Example – 7
Sol. The two advantages of H2—O2 fuel cell over ordinary The following chemical reaction is occurring in an
cell are : electrochemical cell.
(i) They do not cause any pollution. Mg(s) + 2 Ag+ (0.0001 M)

o Mg2+ (0.10M) + 2Ag(s)
(ii) They have high efficiency of 60-70%. The Eo electrode values are
Example – 4 Mg2+ / Mg = – 2.36 V
What is galvanisation ? Ag+ / Ag = 0.81 V
Sol. The process of coating zinc over iron is called For this cell calculate/write
galvanisation. (a) (i) Eo value for the electrode 2Ag+/2Ag.
Example – 5 (ii) Standard cell potential E ocell .
Which type of a metal can be used in cathodic protection
(b) Cell potential (E)cell
of iron against rusting ?
(c) (i) Symbolic representation of the above cell.
Sol. A metal which is more electropositive than iron such as
(ii) Will the above cell reaction be spontaneous ?
Al, Zn, Mg can be used in cathode protection of iron
against rusting. Sol. (a) (i) E oAg / Ag 0.81V

(ii) E ocell o
E cathode E anode
o Cathode : Ag+ (aq) + e–
o Ag s
E oAg / Ag E Mg
o
/ Mg 2
0.81 2.36 (c) Ag electrodes
Anode : Ag(s)
o Ag+ (aq) + e–
E ocell 3.17 V
Cathode : Ag+ (aq) + e–
o Ag(s)
(b) At anode : Mg
o Mg2+ + 2e–
Example – 9
A cathode : Ag+ + e–
o Ag ]×2
Explain Kohlrausch’s law of independent migration of ions.
Mg + 2Ag+
o Mg2+ + 2Ag Mention one application of Kohlrausch’s law.
Sol. Kohlrausch’s law of independent migration of ions: The

ª Mg 2 º¼
log ¬
0.059 molar conductivity of an electrolyte at infinite dilution
Ecell =E o
cell 2
n ª¬ Ag º¼ is the sum of the individual contributions of the anion
and cation of the electrolyte.
0.059 0.1
3.17 log 2 /0 v O0 v O 0
2 104
where, O 0 and O 0 are the limiting molar
7
= 3.17 – 0.0295 log 10 conductivities of the cation and anion respectively
= 3.17 – 0.0295 × 7 = 3.17 – 0.21 and v+ and v– are the number of cations and anions
formed from a formula unit of the electrolyte. For
Ecell = 2.96 V example, one formula unit of Al2(SO4)3 gives two Al3+
(c) (i) Mg | Mg2+ (0.1 M) || Ag+ (0.0001M) | Ag ions and three sulphate ions. Therefore,
(ii) Yes, as the cell potential is positive. / om Al2 (SO4 3
2O oAl3 3O oSO2
4
Example – 8 Application : It can be used to determine molar

conductivity of weak electrolytes at infinite dilution :
(a) Current of 1.50 A was passed through an electrolytic
Consider acetic acid as the example of a weak electrolyte.
cell containing AgNO3 solution with inert electrodes.
The weight of Ag deposited was 1.50g. How long did / om CH3 COONa O oCH COO O oNa
3
the current flow ?

/ om HCl O oH O oCl
(b) Write the reactions taking place at the anode and
cathode in the above cell if inert electrodes are used. / om NaCl O oNa O Cl
o

(c) Give reactions taking place at the two electrodes if From (i) + (ii) – (iii) we get
these are made up of Ag.
O oCH COO O oNa O oH O Cl
o
O
o
Na
O Cl
o

3
Sol. (a) According to Faraday’s first law, charge required to
deposit 1.50 g. O CH
o
COO
O oH / oCH3 COOH
3
96500 Example – 10
Ag u1.50 1331.70 coulombs
108
The electrical resistance of a column of 0.05 mol L–1 NaOH
solution of diameter 1 cm and length 50 cm is 5.55 × 103
1331.70 ohm. Calculate its resistivity, conductivity and molar
Time taken 893.5s
1.50 conductivity.
(b) Inert electrodes Sol. A = Sr2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2,
l = 50 cm = 0.5 m
Anode: o O2 g 4H aq 4e
2H 2 O A
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UA RA 5.55 u103 : u 0.785

R or U Example – 13
A A 50 cm
= 87.135 :cm The conductivity of 0.0011028 mol L–1 acetic acid is
4.95 × 10–5 S cm–1. Calculate its dissociation constant if / om
1 § 1 · 1
Conductivity = N ¨ ¸ S cm 0.01148 S cm 1
U © 87.135 ¹ for acetic acid is 390.5 S cm2 mol–1.
N u1000 N 4.95 u 10 5 Scm 1 1000 cm3

Molar conductivity, / m Sol. /m u
c c 0.001028 mol L1 L
0.01148 S cm 1 u 1000 cm3 L1
= 229.6 S cm2 mol–1 = 44.88 S cm2 mol–1
0.05 mol L1
Example – 11
/m 44.88 Scm 2 mol 1
The measured resistance of a conductance cell containing D 0.115
/ om 390.5 Scm 2 mol1
7.5 × 10–3 M solution of KCl at 25oC was 1005 ohms. Calculate
(a) specific conductance (b) molar conductance of the
0.001028 mol L1 u 0.115
2
solution. Cell constant = 1.25 cm–1. cD 2
K
1 D 0.115
1
Sol. Specific conductance N u cell constant
R
= 1.65 × 10–5 mol L–1
1
u 1.25 cm 1 0.001244 :1 cm 1 Example – 14
1005 :
A cell is prepared by dipping copper rod in 1 M copper
N u1000
Molar conductance / m sulphate solution and zinc rod in 1 M zinc sulphate solution.
Molarity
The standard reduction potentials of copper and zinc are
0.001244 :1 cm 1 u 1000 cm3 L1 0.34 V and – 0.76 V respectively.
7.5 u 103 mol L1 (i) What will be the cell reaction?
165.87 : 1 cm 2 mol 1 . (ii) What will be the standard electromotive force (EMF)
of the cell ?
Example – 12 (iii) Which electrode will be positive ?

(iv) How will the cell be represented ?
/ m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2
Sol. (i) The cell reaction can be
mol–1 respectively. Calculate / 0m for HAc.
Zn Cu 2
o Zn 2 Cu
Sol. / 0m HAc OoH O Ac

o
OHo O oCl O Ac
o
O
o
O Cl
o
O
o or Cu Zn 2 o Cu 2 Zn
Na Na
The EMF comes out to be positive for the 1st reaction.
/ om HCl / om NaAc / om NaCl Hence, the cell reaction is
Zn Cu 2
o Zn 2 Cu
2 –1
= (425.9 + 91.0 – 126.4) S cm mol
= 390.5 S cm2 mol–1.
o
(ii) E cell
o
E cathode E oanode o
E Cu 2
/ Cu
E oZn / Zn 2
= 0.34 + 0.76 = 1.10 V

(iii) reduction takes place on copper electrode. Hence
it is positive
(iv) Zn | Zn2+ (1 M) || Cu2+ (1 M) | Cu

Example – 15 Example – 17
Represent the cell in which the following reaction takes place Calculate the potential (emf) of the cell
Mg (s) + 2Ag+ (0.0001 M) o Mg2+ (0.130 M) + 2 Ag 9 (s) Cd | Cd2+ (0.10 M) || H+ (0.20 M) | Pt, H2 (0.5 atm)
o
Calculate its E(cell) if E cell = 3.17 V.. (Given Eo for Cd2+ / Cd = – 0.403 V, R = 8.14 JK–1 mol–1, F =
96,500 C mol–1).
Sol. The cell can be written as Mg | Mg2+ (0.130 M) || Ag+
Sol. The cell reaction is
(0.0001 M) | Ag
Cd + 2H+ (0.20 M) o Cd2+ (0.10 M) + H2 (0.5 atm)
ª Mg 2 º¼ ª Mg 2 º¼
In ¬ log ¬
RT 2.303RT
E cell Eocell E ocell E ocell E oH /1/ 2H E Cd
o
0 –(– 0.403) = 0.403 V
nF ª¬Ag º¼
2
2F ª¬ Ag º¼ 2
2
/ Cd
Applying Nernst equation to the cell reaction,

0.059 V 0.130 ªCd º¼ u PH2 2
3.17 V log
log ¬
2.303 RT
2 0.0001
2
E cell E ocell 2
nF ª¬ H º¼
= 3.17 V – 0.21 V = 2.96 V
2.303 u 8.314 u 298 0.1u 0.5
Example – 16 0.403 log
2 u 96, 500 0.2
2
A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is = 0.403 – 0.003 = 0.400 V
95% dissociated at this dilution at 298 K. Calculate the
Example – 18
o
electrode potential E Zn 2 / Zn 0.76 V .
Calculate the equilibrium constant of the reaction
Sol. The electrode reaction written as reduction reaction is
Cu (s) + 2Ag+ (aq) o Cu2+ (aq) + 2Ag(s) E ocell 0.46 V
Zn2+ + 2e– o Zn (n = 2)
Applying Nernst equation, we get 0.059 V

Sol. E ocell log K c 0.46 V
2
0.0591 1
E Zn 2 / Zn E oZn 2 / Zn log 0.46 V u 2
2 ª¬ Zn 2 º¼ or log K c 15.6 Kc = Antilog 15.6
0.059 V
Kc = 3.92 × 1015
As 0.1 M ZnSO4 solution is 95% dissociated, this means
that in the solution, Example – 19
95 Calculate the standard free energy change and maximum

ª¬ Zn 2 º¼ u 0.1M 0.095 M
100 work obtainable for the reaction occurring in the cell :
0.0591 1 (Daniell cell).
? E Zn2 / Zn 0.76 log Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
2 0.095
= – 0.76 – 0.02955 (log 1000 – log 95) [Given E oZn 2 / Zn 0.76 V, E oCu 2 / Cu
= – 0.76 – 0.02955 (3 – 1.9777) 0.34 V, F 96, 500 C mol 1 ]

= – 0.76 – 0.03021 Also calculate the equilibrium constant for the reaction.
= – 0.79021 V
Sol. (i) E ocell o
E Cu 2
/ Cu
E oZn / Zn 2 0.34 0.76
= 1.10 V
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The reaction taking place in the Daniell cell is (ii) 52 g of Cr is deposited by electricity = 6 × 96500 C
ZZX Cu(s) + Zn2+ (aq)

Zn(s) + Cu2+ (aq) YZZ 6 u 96500
?1.5 g require electricity u1.5 C 16071C
52
For this reaction, n = 2
?Time for which the current is required to be passed
'Go = – nFE ocell
16071.9
= – 2 × 96500 C mol–1 × 1.10 V 1336 s.
12.5 A
= – 212300 CV mol–1
= – 212300 J mol–1 (1 CV = 1 J) Example – 22
= – 212.300 kJ mol–1 (a) Calculate the equilibrium constant for the reaction
Thus, the maximum work that can be obtained from
Cd2+ (aq) + Zn(s)
o Zn2+ (aq) + Cd(s)
the Daniel cell = 212.3 kJ.
(ii) 'Go = – RT In Kc = – 2.303 RT log Kc If E oCd 2 / Cd 0.403 V
? –212300 = – 2.303 × 8.14 × 298 × log Kc
E oZn 2 / Zn 0.763 V
212300
or log K c 37.2704
2.303 u 8.314 u 298
(b) When a current of 0.75A is passed through a CuSO4
? Kc = Antilog 37.2074 = 1.6 ×1037
solution for 25 min, 0.369 g of copper is deposited at
Example – 20 the cathode. Calculate the atomic mass of copper.
Calculate the equilibrium constant, Kc for the reaction. (c) Tarnished silver contains Ag2S. Can this tarnish be
3Sn4+ + 2Cr o3Sn2+ + 2Cr3+ removed by placing tarnished silver ware in an
aluminium pan containing an inert electrolytic solution
Given Eo = 0.885 V.
such as NaCl. The standard electrode potential for
half reaction:
0.059
Sol. E ocell log K c , n 6
n Ag2S(s) + 2e–
o 2Ag (s) + S2– is –0.71V
0.059
0.885 log K c and forAl3+ + 3e–
o 2Al (s) is – 1.66 V
6
Sol. (a) E ocell E oc E oa 0.403 0.763 0.360 V
6 u 0.885
log K c
0.059
§ nE o cell · § 2 u 0.360 ·
90 As log Kc = ¨ ¸ ¨ ¸
Kc = Antilog 90 = 1 × 10 © 0.059 ¹ © 0.059 ¹
Example – 21
§ 0.720 ·
Chromium metal can be plated out from an acidic solution ¨ ¸ 12.20
© 0.059 ¹
containing CrO3 according to the following equation:
CrO3 (aq) + 6H+ (aq) + 6e– oCr (s) + 3H2O Kc = antilog (12.20) = 1.585 × 1012
Calculate (i) how many grams of chromium will be plated
(b) M = Z I t
out by 24,000 coulombs and (ii) how long will it take to
plate out 1.5 g of chromium by using 12.5 amp current ? (At.
x
mass of Cr = 52). 0.369 u 0.75 u 25 u 60
2 u 96500
Sol. (i) 6 × 96, 500 coulomb deposit Cr = 1 mole = 52 g
(x = molar mass of copper)
52 u 24000
?24,000 coulomb deposit Cr g 2.1554 g
6 u 965000 x = 63.3 g/mol

(c) E ocell for reaction of tarnished silver ware with Example – 24
aluminium pan is (– 0.71 V) + 1.66 V i.e., + 0.95 V (a) Depict the galvanic cell in which the following reaction
Tarnished silver ware, therefore, can be cleaned by takes place :
placing it in an aluminium pan as Eocell is positive.

Zn (s) + 2Ag+ (aq)
o Zn2+ (aq) + 2Ag (s)
Example – 23 Also indicate that in this cell
(i) which electrode is negatively charged.
(a) Calculate the standard free energy change for the
following reaction at 25oC. (ii) what are the carrier of the current in the cell.
(iii) what is the individual reaction at each electrode.
Au (s) + Ca2+ (aq, 1M)
o Au3+ (aq, 1M) + Ca(s)
(b) Write the Nernst equation and determine the e.m.f. of
the following cell at 298 K:
E oAu3 / Au 1.50 V, E Ca
o
2
/ Ca
2.87 V
Mg (s) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu (s)
Predict whether the reaction will be spontaneous or (Given : E o Mg 2 2.375 V, E oCu2 / Cu 0.34 V )
/ Mg
not at 25oC. Which of the above two half cells will act
as an oxidizing agent and which one will be a reducing Sol. (a) Zn | Zn2+ (conc.) || Ag+ (conc) | Ag
agent?
(i) Zn electrode is negatively charged.
(b) The conductivity of 0.001 M acetic acid is 4 × 10–5 S/cm. (ii) Current carriers of cell are
Calculate the dissociation constant of acetic acid, if - electrons in external wire
/ mo for acetic acid is 390. 5 S cm2/mol. - Zn2+ ions in anodic half cell.
Sol. (a) Eocell = (– 2.87 V) – (1.50 V) = – 4.37 V - Ag+ ions in cathodic half cell.
- Ions of salt bridge, i.e., K+ and Cl–.
'Gocell = – 6 × 96500 × – 4.37 V = + 2530.230 kJ/mol
o Zn 2 2e
(iii) At anode Zn
Since 'r Go is positive, reaction is non-spontaneous.
At cathode 2Ag e
o 2Ag
3+ 2+
Au /Au half cell will be a reducing agent, Ca /Ca half
cell will be an oxidising agent. o Mg 2 2e
(b) Mg
Cu 2 2e
o Cu
1000
(b) / c
m Ku
molarity
Mg Cu 2
o Cu Mg 2
K = Specific conductance
Nernst equation
4 u10 5 S / cm u 1000 2 1
40S cm mol
0.001 2
E cell E o

0.059
log ¬ª Mg ¼º
cell
n ª¬ Cu 2 º¼
/m 40
D 0.103
/ om 390.5
ª Mg º
log ¬ 2 ¼
0.059
E cell Eo Cu 2 / Cu E o Mg / Mg2
CD 2 0.001u 0.103
2 2 ª¬Cu º¼
Kc 1.19 u 105
1 D 1 0.103
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For strong electrolytes, the number of ions do not

0.059 103 increase appreciably on dilution and only mobility or
0.34 2.375 log 4
2 10 ions increases due to decrease in interionic attractions.
Therefore, / m increases a little as shown in graph by a
= 0.34 + 2.375 – 0.0295 log 10 straight line.
Ecell = 2.6855 V For weak electrolytes, the number of ions as well as
mobility of ions increases on dilution which results in a
Ecell = 2.685 V very large increase in molar conducvity especially near
Example – 25 infinite dilutuion as shown by curve in the figure.
(a) Define molar conductivity of a substance and describe At anode : Cu(s)

o Cu2+ (aq) + 2e
how weak and strong electrolytes’ molar conductivity
At cathode : 2Ag+ (aq) + 2e
o 2Ag(s)
changes with concentration of solute. How is such
change explained ?
(b) A voltaic cell is set up at 25 oC with the following half Cu s 2Ag aq

o Cu 2 aq 2Ag s
cells:
Ag+ (0.001 M) | Ag and Cu2+ (0.10 M) | Cu

ª Cu 2 º¼
log ¬
0.0591
What would be the voltage of this cell ? Here, E cell o
E cell 2
n ª¬ Ag º¼
(Eocell = 0.46 V)
Here, E ocell 0.46 V, n 2
Sol. Molar Conductivity / m : It may be defined as the
[Ag+] = 0.001M = 1 × 10–3 M, [Cu2+] = 0.1 M
conductance of a solution containing 1 mole of
electrolyte such that the entire solution is placed in 0.0591 0.1
E cell 0.46 log 2
between two electrodes one centimetre apart. 2 103
0.0591 0.0591
E cell 0.46 log 105 0.46 × 5 log 10
2 2
Ecell = 0.46 – 0.0591 × 2.5 × 1 = 0.46 – 0.14775 = 0.31225V
Ecell = 0.312 V
Example – 26
(a) State the relationship amongst cell constant of cell,
resistance of the solution in the cell and conductivity
of the solution. How is molar conductivity of a solute
related to conductivity of its solution ?
(b) A voltaic cell is set up at 25oC with the following half-
/m kuv cells:
or Al | Ag3+ (0.001 M) and Ni | Ni2+ (0.50 M)
Calculate the cell voltage
k u1000
/m
M ª E o 2 0.25 V, E o Al3 |Al 1.66 V º
¬ Ni |Ni ¼
Molar conductivity increases with decrease in
concentration or increase in dilution as number of ions
1 §l ·
as well as mobility of ions increased with dilution. (a) N u
R ¨© A ¸¹
Sol.

where, N Conductivity Example – 27
(a) What type of a cell is the lead storage battery ? Write

1
= Cell constant the anode and the cathode reactions and the overall
A
reaction occurring in a lead storage battery while
R = Resistance operating.
(b) A voltaic cell is set up at 25oC with the half-cells Al |

N u1000 Al3+ (0.001 M) and Ni | Ni2+ (0.50 M). Write the equation
/m
M for the reaction that occurs when the cell genrates an
electric current and determine the cell potential.
where, / m = Molar conductivity (Given :E oNi 2 | Ni 0.25V, E Al
o
1.66V).
3
| Al
N = Conductivity Sol. (a) The lead storage battery is a secondary cell.

M = Molarity of Solution The cell reactions when the battery is in use are
given below
(b) At anode : o Al3 aq 3e] u 2
Al s
At anode: Pb s SO24 aq
o PbSO 4 s 2e
At cathode : Ni2+ (aq) + 2e
o Ni s ] u 3
At cathode: PbO 2 s SO 42 aq 4H aq 2e

o PbSO4 s 2H 2 O A
2Al (s) + 3Ni2+ (aq)
o 2Al3+ (aq) + Ni(s)
Overall cell reaction: Pb(s) + 2H2SO4(aq)
o
PbSO4(s) + 2H2O( A )
3 2
ª Al º¼ (b) 2Al (s) + 3Ni+2 (aq) o 3Ni (s) + 2Al+3 (aq)
log ¬
0.0591
E cell o
E cell 3
n ª¬ Ni 2 º¼
E ocell = 1.41 V
Here, n = 6, [Al3+] = 0.001 M = 1 × 10–3 M,

0.0591 ª (10 3 )2 º
[Ni2+] = 0.5M E cell 1.41 log « 3 »
6 ¬ (0.5) ¼
E ocell 1.41V
= 1.46 V
2
0.0591 103 0.0591 106
E ocell 1.41V log 1.41 log Example – 28
3
6 0.5 6 0.125
(a) Express the relationship amongst cell constant,
0.0591 0.0591 resistance of the solution in the cell and conductivity
1.41 log 106 u 8 1.41 log10 6 log 23
6 6 of the solution. How is molar conductivity of a solute
related to conductivity of its solution.
0.0591 0.0591
1.41 6 log10 3log 2 1.41 6 3 u 0.3010
6 6 (b) Calculate the equilibrium constant for the reaction.
0.0591 0.3012 Fe s Cd 2 aq YZZ

ZZX Fe2 aq Cd s
1.41 5.097 1.41
6 6
(Given :E o Cd 2 |Cd 0.40 V, E Fe
o
2
|Fe
0.44 V).
= 1.41 + 0.0502 = 1.4602V
Ecell = 1.46 V 1
Sol. (a) Conductivity N u Cell constant (G)
Resistance R
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At cathode : Ag+(aq) + e–
o Ag(s)] × 2
N u1000
/m , where, / m = Molar conductivity
M Zn(s) + 2Ag+ (aq)
o Zn + 2Ag(s)
2+
ZZX Fe2+ (aq) + Cd(s)

(b) Fe(s) + Cd2+ (aq) YZZ 0.0591 [Zn 2 ]
E cell E ocell log 2
E ocell
n ª¬ Ag º¼
log k c n
0.059 Here, n = 2, [Zn2+] = 1 M
Here, n = 2
Eocell = E Ag / Ag E Zn / Zn 2 0.80V 0.76V
o o
E o
cell E o
cathode E o
anode
Eocell = 1.56 V
E o Cd 2 / Cd E o Fe / Fe2
0.0591 1
= – 0.4 + 0.44 1.48 1.56 log 2
2 ª¬ Ag º¼
E ocell 0.04 V
2 u 0.04 0.08 0.0591 1

log k c 0.08 log 2
0.059 0.059 2 ª¬ Ag º¼
log k c 1.3536
1 0.16
kc = Antilog 1.3536 log 2
2.7072 2.7072

ª¬Ag º¼ 0.0591
kc = 22.57
2
Example – 29 log1 log ª¬ Ag º¼ 2.7072
(a) Define the term molar conductivity. How is it related

0 2 log ª¬ Ag º¼ 2.7072
to conductivity of the related solution?
(b) One half-cell in a voltaic cell is constructed from a log ª¬ Ag º¼ 1.3536 2.6464
silver wire dipped in silver nitrate solution of unknown
concentration. Its other half-cell consists of zinc ª¬ Ag º¼ Anti log 2.6464 4.43 u 10 2 M
electrode dipping in 1.0 M solution of Zn(NO3)2. A
voltage of 1.48 V is measured for this cell. Use this ª¬ Ag º¼ 0.044 M
information to calculate the concentration of silver Example – 30
nitrate solution used.
(a) Corrosion is essentially an electrochemical
(E o
0.76 V, E o
0.80 V) phenomenon. Explain the reactions occurring during
Zn 2 / Zn Ag2 / Ag
corrosion of iron kept in an open atmosphere.
Sol. (b) Calculate the equilibrium constant for the equilibrium
reaction.
(a) Molar conductivity / m : It may be defined as the
Fe s Cd 2 aq YZZ
ZZX Fe2 aq Cd s
conductivity of one molar electrolytic solution placed
between two electrodes one centimetre apart and have (Given : E oCd2 / Cd 0.40 V, E oFe2 / Fe 0.44V)
enough area of cross section to hold entire volume.
N Sol. (a) At anode : Oxidation of Fe atoms takes place
/m
c
Fe
o Fe2+ + 2e– E o Fe2 / Fe 0.44 V
where, N = Conductivity
c = Concentration of solution in mol L–1 At cathode : Reduction of oxygenin the presence of H+
ions. The H+ ions are produced by either H2O or H2CO3
o Zn 2 aq 2e
(b) At anode : Zn s (formed by dissolution of CO2 in moisture)

2H aq 2e
o 2H Example – 31
1 Two half cell reactions of an electrochemical cell are given
2H O2 g
o H2O
2 below :
Net reaction at cathodic area MnO4 aq 8H aq 5e o Mn 2
1
2H aq O 2 2e
o H2O aq 4H 2 O A , E o 1.51V
2
Sn2+ (aq) o Sn4+ (aq) + 2e–, Eo = + 0.15 V
o
E H / O2 / H 2 O
1.23 V
Construct the redox equation from the two half cell reactions
The overall reaction and predict if this reaction favours formation of reactants
or product shown in the quation
1
Fe s 2H aq O 2 g
o Fe 2 aq H 2 O A
2 Sol. At cathode : MnO 4 aq 8H 5e
o Mn 2
E o cell 1.67 V aq 4H 2 O A ] u 2 Eo 1.15V
The ferrous ions are further oxidised by atmospheric o Sn 4 aq 2e ] u 5 Eo = + 0.15 V

At anode: Sn2+
oxygen to ferric ions which come out as rust in the form
Overall reaction :
of hydrated ferric oxide (Fe2O3 . xH2O).
2MnO4 aq 5Sn 2 aq 16H aq
o 2Mn 2
ZZX Fe2+ (aq) + Cd(s)
(b) Fe(s) + Cd2+ (aq) YZZ (aq) + 5Sn4 (aq) + 8H2O A
o
E Sn 4
/ Sn 2
ESn
o
2
/ Sn 4
0.15V
o
E cell
log kc = n E ocell E ocathode E oanode E oMnO / Mn 2 E Sn
o
4
/ Sn 2
0.059 4
= 1.51 – (– 0.15)
Here, n = 2 E ocell 1.66 V
E ocell E ocathode — E o anode As E ocell is +ve therefore the reaction will take place in
forward direction, i.e., favours the formation of products.
E o Cd2 / Cd E o Fe 2 / Fe 40 0.44 Example – 32
(a) Account for the following
Eocell = 0.04V
(i) Alkaline medium inhibits the rusting of iron
(ii) Iron does not rust even if the zinc coating is broken
2 u 0.04 0.08
log k c in a galvanized iron pipe.
0.059 0.059
(b) Cu2+ + 2e– o Cu ; Eo = + 0.34 V
log kc = 1.3536 Ag+ + e– o Ag; Eo = + 0.80 V
kc = Antilog 1.3536 (i) Construct a galvanic cell using the above data.
(ii) For what concentration of Ag+ ions will the emf of
kc = 22.57 the cell be zero at 25oC, if the concentration of Cu2+
is 0.01 M? [log 3.919 = 0.593]
Sol. (a) (i) The alkalinity of the solution prevents the

availability of H+ ions.
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(ii) Zinc is more electropositive than iron. 3. These cells are light in weight as compared
Therefore, zinc coating acts anode and the to electrical generators to produce
exposed iron portions act as cathode. If zinc corresponding quantity of power.
coating is broken, zinc undergoes corrosion, 4. It is a continuous source of energy if the
protecting iron from rusting. No attack supply of gases is maintained.
occurs on iron till all the zinc is corroded.
(b) Mass of silver deposited
(b) At anode Cu o Cu2+ + 2e–
m = z I t.
At cathode [Ag+ + e– o Ag] × 2
108
u 0.5 u 2 u 3600
96500
Cu + 2 Ag+ oCu2+ + 2Ag
m = 4.029 g
Cell representation m m
d v
Cu | Cu2+ (conc.) || Ag+ (conc.) | Ag v d
4.029
ª¬ Cu 2 º¼ V 0.3837 cm3
0.059 10.5
E cell Ecell
o
log 2
n ª¬ Ag º¼ Let the thickness of silver deposited be x cm.
? V =A× x
0.059 ª 0.01 º V
O = (0.80 – 0.34) log « 2 » x
2 ¬ x ¼ A
0.3837
x
§ 0.01 · 500
15.59 log ¨ 2 ¸
© x ¹ ? x = 7.67 × 10–4 cm.
Example – 34
x = 1.597 × 10 –9 M
(a) Give reasons for the following:
[Ag+] = 1.597 × 10–9M
(i) Rusting of iron is quicker in saline water than in
Example – 33
ordinary water.
(a) State advantages of H2-O2 fuel cell over ordinary
(ii) Resistance of a conductivity cell filled with 0.1 M
cell.
KCl solution is 100 ohm.If the resistance of the same
(b) Silver is electrodeposited on a metallic vessel of total cell when filled with 0.02 M KCl solution is 520
surface area 500 cm2 by passing a current of 0.5 amp ohms, calculate the conductivity and molar
for two hours. Calculate the thickness of silver conductivity of 0.02 M KCl solution.
deposited.
(Conductivity of 0.1 M KCl solution is 1.29 Sm–1).
–3
[Given: Density of silver = 10.5 g cm , Atomic mass of
silver = 108 amu, F = 9,500 C mol–1] Sol. (a) (i) It is because in saline water, there is more H+ ions.
Greater the number of H+ ions, quicker the rusting.
Sol. (a) Advantages Fuels Cells:
(ii) Due to higher reduction potential of hydrogen
1. It is a pollution-free device since no harmful we get hydrogen at cathode.
products are formed. 1
(b) N u cell constant
2. This is very efficient cell. Its efficiency is R
about 75% which is considerably higher than cell constant = Nu R
conventional cells. = 1.29 Sm–1 × 100 ohm
= 129 m–1 = 1.29 cm–1
For second solution E ocell = E ocathode + E oanode

1
N u cell constant
R = 0.76 – 0.40 = 0.36 V
1
N u 1.29 2.48 u 10 3 S cm 1 0.0591
520 E = E ocell log Q
n
N u1000
/m
M
0.0591 ª Zn 2 º
2.48 u 103 u 1000 248 0.36 log « 2 »
2 ¬ Cd ¼
0.02 2
/m 124 S cm 2 mol 1
0.0591 ª 0.1 º
Example – 35 0.36 log « » = 0.33V
2 ¬ 0.01 ¼
(a) Explain why electrolysis of aqueous solution of NaCl
gives H2 at cathode and Cl2 at anode. Write overall Example – 36
reaction.
Three iron sheets have been coated separately with three
(E
o
Na / Na
2.71 V; E o
H2 O / H2 0.83 V, E o
Cl 2 / 2Cl
metals A, B and C whose standards reduction potentials
are given below.
1.36 V; E oH O / H2O
1.23 V) metal A B C iron
2
(b) Calculate the emf of the cell of Zn / Zn2+ (0.1 M) || Cd2+ E oValue – 0.46 V –0.66V –0.20V –0.44V
(0.01 M) / Cd at 298 K,
Identify in which case rusting will take place faster when
[ Given E oZn 2 / Zn 0.76 V and E oCd2 / Cd – 0.40 V] coating is damaged.
Sol. As iron (–0.44V) has lower standard reduction potential

Sol. (a) Because of higher reduction potential of water, water
than C (– 0.20V) only therefore when coating is broken,
is reduced in preference to sodium at therefore instea of
rusting will take place faster.
deposition of sodium metal, hydrogen is discharged at
cathode.
H 2 O A 2e
o H 2 g 2OH
2Cl
o Cl2 g
H 2 O A 2Cl
o H2 g Cl2 g 2OH
At anode Cl2 gas is liberated because of overpotential

of oxygen.
Zn o Zn 2 2e ½°
2 ¾ Half cell reactions
(b) Cd 2e o Cd °¿
Zn + Cd2+ o Zn2+ + Cd} cell reaction

ELECTROCHEMISTRY
236 236
ELECTROCHEMISTRY
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Basics of electrochemical Cell 7. Adding powdered Pb and Fe to a solution containing 1.0 M
2+ 2+
1. Which of the following has been universally accepted as a is each of Pb and Fe ions would result into the formation
+2 +2
reference electrode at all temperatures and has been of (Eº Pb /Pb = – 0.13V, Eº Fe /Fe = –0.44V)
assigned a value of zero volt ? (a) More of Pb and Fe ions
2+
(a) platinum electrode (b) copper electrode (b) More of Fe and Pb ions
2+
(c) graphite electrode (d) standard hydrogen electrode (c) More of Fe and Pb
2+ 2+
(d) More of Fe and Pb ions
+ –
2. The reaction 1/2H2(g) + AgCl(s) = H (aq) + Cl (aq) + Ag(s) 8. Strongest reducing agent is :
occurs in the galvanic cell :
(a) K (b) Mg
(a) Ag | AgCl(s) | KCl(sol.) || AgNO3) (sol.) | Ag
(c) Al (d) I
(b) Pt | H2(g) | HCl(sol. || AgNO3 (sol) | Ag
9. Zn can not displace following ions from their aqueous
(c) Pt | H2(g) | HCl (sol.) || AgCl(s) | Ag solution :
(d) Pt | H2 (g) | KCl (sol.) || AgCl(s) | Ag (a) Ag
+
(b) Cu
2+
3. The equation representing the process by which standard (c) Fe

2+
(d) Na
+
reduction potential of zinc can be defined is :

10. Which of the following displacement does not occur :
(a) Zn (s) + 2e
o Zn
2+ –
+ 2+
(a) Zn + 2H o Zn + H2 n
(b) Zn (g)
o Zn2+(g) + 2e–
+ 2+
(b) Fe + 2Ag o Fe + Ag p
(c) Zn (g) + 2e
o Zn
2+ –
2+ 2+
(d) Zn (aq.) + 2e
2+ –
o Zn (s) (c) Cu + Fe o Cu + Fe p
2+ 2+
4. Which of the following statement is wrong about galvanic (d) Zn + Pb o Zn + Pb p
cell ?
11. The oxidation potential of Zn, Cu, Ag, H2 and Ni are 0.76,
(a) cathode is positive charged –0.34, – 0.80, 0, 0.55 volt respectively. Which of the following
(b) anode is negatively charged reaction will provide maximum voltage ?
(c) reduction takes place at the anode (a) Zn + Cu

2+

o Cu + Zn2+
(d) reduction takes place at the cathode
(b) Zn + 2Ag
o 2Ag + Zn2+
+
5. Which are used as secondary reference electrodes ?

o 2H + Cu
2+ +
(a) Calomel electrode (b) Ag/AgCl electrode (c) H2 + Cu

o 2H + Ni
2+ +
(c) Hg/Hg2Cl2 – KCl electrode (d) H2 + Ni
(d) All of the above 12. The position of some metals in the electrochemical series in
decreasing electropositive character is given as
Applications of Electrochemical Series
Mg > Al > Zn > Cu > Ag. What will happen if a copper
6. The standard electrode potentials (reduction) of spoon is used to stir a solution of aluminium nitrate ?
3+ 2+ 4+ 2+
Pt/Fe , Fe and Pt/Sn , Sn are + 0.77 V and 0.15 V
(a) The spoon will get coated with aluminium
respectively at 25°C. The standard EMF of the reaction
Sn + 2Fe o Sn2+ + 2Fe3+ is
4+ 2+
(b) An alloy of copper and aluminium is formed
(a) – 0.62 V (b) – 0.92 V (c) The solution becomes blue
(c) + 0.31 V (d) + 0.85 V (d) There is no reaction

13. The standard reduction electrode potential values of the Relationship between emf and gibb’s free energy
element A, B and C are + 0.68, –2.50, and –0.50 V respectively.
change
The order of their reducing power is :
18. The standard free energy change for the following reaction
(a) A > B > C (b) A > C > B is – 210 kJ. What is the standard cell potential ?
(c) C > B > A (d) B > C > A 2H2O2 (aq)
o 2H2O(l) + O2(g)
14. A metal having negative reduction potential when dipped (a) + 0.752 (b) + 1.09
in the solution of its own ions, has a tendency :
(c) + 0.420 (d) + 0.640
(a) to pass into the solution
19. Calculate the standard free energy change for the reaction,
(b) to be deposited from the solution +
2 Ag + 2H o H2 + 2 Ag ,
+
+ –
(c) to become electrically positive E° for Ag + e o Ag is 0.80 V
(d) to remain neutral (a) + 154.4 kJ (b) + 308.8 kJ
(c) –154.4 kJ (d) –308.8 kJ
15. E° for the half cell reactions are as,
20. The standard EMF of Daniell cell is 1.10 volt. The maximum
2+
(a) Zn = Zn + 2e ; E° = + 0.76 V electrical work obtained from the Daniell cell is
2+
(b) Fe = Fe + 2e ; E° = + 0.41 V (a) 212.3 kJ (b) 175.4 kJ
The E° for half cell reaction, (c) 106.15 kJ (d) 53.07 kJ
2+ 2+
21. What is the free energy change for the half reaction
Fe + Zn
o Zn + Fe is : + –
Li + e o Li?
–1
(a) – 0.35 V (b) + 0.35 V Given EqLi
/Li
3.0V, F = 96500 C mol and T = 298 K.
(c) + 1.17 V (d) – 0.17 V (a) 289.5 kJ mol
–1
(b) –298.5 kJ mol
–1
3+ 2+ –1 –1 –1
16. An aqueous solution containing 1 M each of Au , Cu , (c) 32.166 CV mol (d) –289500 CV mol
+ +
Ag , Li is being electrolysed by using inert electrodes. The 22. The emf of Daniell cell is 1.1 volt. If the value of Faraday is
value of standard potentials are : 96500 coulombs per mole, the change in free energy in kJ is
EqAg = 0.80 V, EqCu / Cu = 0.34 V and EqAu 3 / Au = 1.50 V, (a) 212.30 (b) –212.30

/ Ag
(c) 106.15 (d) –106.15
EqLi / Li = – 3.03 V Nernst Equation
with increasing voltage, the sequence of deposition of metals 23. Which of the following represents the potential of silver
wire dipped in to 0.1 M AgNO3 solution at 25°C ?
on the cathode will be :
(a) Li, Cu, Ag, Au (b) Cu, Ag, Au (a) E°red (b) (E°red + 0.059)
(c) Au, Ag, Cu (d) Au, Ag, Cu, Li (c) (E°ox – 0.059) (d) (E°red – 0.059)
17. The standard electrode potential for the reaction H 2 (Pt) H 3O (aq) Ag
24. Consider the cell Ag. The measured
+
Ag (aq) + e
o Ag(s)
– 1atm pH 5.5 x M
EMF of the cell is 1.023 V. What is the value of x ?
Sn (aq) + 2e
o Sn(s)
2+ –
at 25°C are 0.80 volt and – 0.14 volt, respectively. The emf of E 0 Ag , Ag = + 0.799 V [T = 25°C]
the cell.
–2 –3
2+ + (a) 2 × 10 M (b) 2 × 10 M
Sn | Sn (1 M) | | Ag (1M) | Ag is
–3 –2
(c) 1.5 × 10 M (d) 1.5 × 10 M
(a) 0.66 volt (b) 0.80 volt
(c) 1.08 volt (d) 0.94 volt
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25. The emf of the cell 32. The hydrogen electrode is dipped in a solution of pH = 3 at
+ 2+
Ti/Ti (0.0001 M) | | Cu (0.01 M)/Cu is 0.83 V 25°C. The potential of the cell would be (the value of 2.303
RT/F is 0.059 V)
The emf of this cell will be increased by :
(a) 0.177 V (b) 0.087 V
++
(a) Increase the concentration of Cu ions (c) –0.177 V (d) 0.059 V
+
(b) Decreasing the concentration of Ti Relating half cell potential using dG
33. When two half-cells of electrode potential of E1 and E2 are
(c) Increasing the concentration of both
combined to form a cell of electrode potential E3, then (when
(d) (a) and (b) both n1, n2 and n3 are no. of electrons exchanged in first, second
2+ 2+ and combined half-cells) :
26. Co | Co (C2) || Co (C1) | Co for this cell, 'G is negative if :
(a) C2 > C1 (b) C1 > C2 E 1 n1 E 2 n 2
(a) E3 = E2 – E1 (b) E3 =
n3
(c) C1 = C2 (d) unpredictable
27. What will be the emf for the given cell ?
E1 n1 E 2 n 2
+
Pt | H2 (g, P1) | H (aq) || H2 (g, P2) | Pt (c) E3 = n 32 (d) E3 = E1 + E2
RT P1 RT P1
(a) F ln P (b) 2F ln P 34. If EqAu / Au is 1.69 V and EqAu3 / Au is 1.40 V, then EqAu / Au3
2 2
(a) 0.19 V (b) 2.945 V

RT P2
(c) 2F ln P (d) None of these (c) 1.255 V (d) None of these
1
Electroytic cell
28. If the pressure of hydrogen gas is increased from 1 atm. to
35. Which reaction occur at cathode during electrolysis is fused
100 atm., keeping the hydrogen ion concentration constant
lead bromide ?
at 1 M, the voltage of the hydrogen half-cell is at 25°C will
be (a) Pb
o Pb2+ + 2e– (b) Br + e
–
o Br
–
(a) 0.059 V (b) –0.059 V

(c) Br
o Br + e– (d) Pb + 2e
o Pb
– 2+ –
(c) 0.295 V (d) 0.118 V.
29. The EMF of the cell 36. By the electrolysis of aqueous solution of CuSO4, the
2+ 2+ products obtained at both the electrodes are
Mg | Mg (0.01 M)| |Sn (0.1M)| Sn at 298 K is (Given
EqMg 2 2.34 V, EqSn 2 0.14 V ) (a) O2 at anode and H2 at cathode
,Mg , Sn
(b) H2 at anode and Cu at cathode

(a) 2.17 V (b) 2.23 V
(c) 2.51 V (d) 2.45 V (c) O2 at anode and Cu at cathode
30. The potential of the cell containing two hydrogen electrodes (d) H2S2O8 at anode and O2 at cathode
as represented below
+ –6 + –4 37. During the electrolysis of fused NaCl, the reaction that
Pt, H2(g) | H (10 M) | |H (10 M)| H2(g), Pt at 298 K is
occurs at the anode is :
(a) –0.118 V (b) –0.0591 V
(a) Chloride ions are oxidized
(c) 0.118 V (d) 0.0591 V
+ +
31. The emf of the cell H2(1 atm) Pt | H (a = x) | | H (a = 1) | (b) Chloride ions are reduced
H2(1 atm) Pt at 25°C is 0.59 V. The pH of the solution is (c) Sodium ions are oxidized
(a) 1 (b) 4
(d) Sodium ions are reduced
(c) 7 (d) 10

38. In electroplating the article to be electroplated is made : 46. When the same electric current is passed through the
(a) cathode (b) anode solution of different elecrolytes in series the amounts of
elements deposited on the electrodes are in the ratio of their:
(c) either cathode or anode
(d) simply suspended in the electrolytic bath. (a) atomic number (b) atomic masses
39. On electrolysing a solution of dilute H2SO4 between platinum (c) specific gravities (d) equivalent masses
electrodes, the gas evolved at the anode is 47. 13.5 g of Al get deposited when electricity is passed through
(a) SO2 (b) SO3 the solution of AlCl3. The number of faradays used are :
(c) O2 (d) H2. (a) 0.50 (b) 1.00
40. A spoon to be electroplated with gold should be : (c) 1.50 (d) 2.00
(a) cathode (b) anode 48. The ratio of weights of hydrogen and magnesium deposited
by the same amount of electricity from aqueous H2SO4 and
(c) electrolyte (d) none of these
fused MgSO4 are :
Faraday’s Laws (a) 1 : 8 (b) 1 : 12
41. Three faradays of electricity was passed through an aqueous (c) 1 : 16 (d) None of these
solution of iron (II) bromide. The mass of iron metal (at.
mass 56) deposited at the cathode is - 49. A current of 2 ampere was passed through solutions of
CuSO4 and AgNO3 in series. 0.635 g of copper was deposited.
(a) 56 g (b) 84 g
Then the weight of silver deposited will be :
(c) 112 g (d) 168 g (a) 0.59 g (b) 3.24 g
42. The electric charge for electrode deposition of one gram (c) 1.08 g (d) 2.16 g
equivalent of a substance is : 20
50. An ion is reduced to the element when it absorbs 6 × 10
(a) one amp/sec (b) 96,500 C/sec electrons. The number of equivalents of the ion is :
(c) one amp/hour (d) 96,500 C (a) 0.10 (b) 0.01
43. Number of electrons involved in the electrodeposition of (c) 0.001 (d) 0.0001
63.5 g of Cu from a solution of CuSO4 is :
51. Electrolysis can be used to determine atomic masses. A
23 23
(a) 6.022 × 10 (b) 3.011 × 10 current of 0.550 A deposits 0.55 g of a certain metal in 100
23 22 minutes. Calculate the atomic mass of the metal if n = 3 :
(c) 12.044 × 10 (d) 6.022 × 10
(a) 100 (b) 45.0
44. When one coulomb of electricity is passed through an
electrolytic solution the mass deposited on the electrode is (c) 48.25 (d) 144.75
equal to : 52. How many minutes will it take to plate out 0.50 g of Cr from
a Cr2(SO4)3 solution using a current of 1.50 A ? (Atomic
(a) equivalent weight (b) molecular weight
weight : Cr = 52.0)
(c) electrochemical equivalent
(a) 254 (b) 30
(d) one gram
(c) 152 (d) 103
45. W g of copper deposited in a copper voltameter when an
53. An electrolysis of a oxytungsten complex ion using 1.10 A
electric current of 2 ampere is passed for 2 hours. If one
for 40 min produces 0.838 g of tungsten. What is the charge
ampere of electric current is passed for 4 hours in the same of tungsten in the material ? (Atomic weight : W = 184)
voltameter, copper deposited will be :
(a) 6 (b) 2
(a) W (b) W/2
(c) 4 (d) 1
(c) W/4 (d) 2W
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54. When molten lithium chloride (LiCl) is electrolyzed, lithium 62. A current of 9.65 amp. flowing for 10 minute deposits 3.0 g
metal is formed at the cathode. If current efficiency is 75% of a metal. The equivalent wt. of the metal is :
then how many grams of lithium are liberated when 1930 C
(a) 10 (b) 30
of charge pass through the cell : (Atomic weight : Li = 7)
(a) 0.105 (b) 0.120 (c) 50 (d) 96.5
(c) 0.28 (d) 0.240 63. 108 g fairly concentrate solution of AgNO3 is electrolyzed
using 0.1 F of electricity. The weight or resulting solution is:
55. The weight ratio of Al and Ag deposited using the same
quantity of current is : (a) 94 g (b) 11.6 g
(a) 9 : 108 (b) 2 : 12 (c) 96.4 g (d) None
(c) 108 : 9 (d) 3 : 8 Batteries, Fuel Cells and Corrosion
56. The weight of silver (eq. wt. = 108) displaced by that quantity 64. When a lead storage battery is discharged
of current which displaced 5600 mL of hydrogen at STP is :
(a) PbSO4 is formed (b) Pb is formed
(a) 54 g (b) 108 g
(c) SO2 is consumed (d) H2SO4 is formed
(c) 5.4 g (d) None of these
65. A fuel cell is :
57. A current of 9.65 ampere is passed through the aqueous
(a) The voltaic cells in which continuous supply of fuels are
solution NaCl using suitable electrodes for 1000 s. The
send at anode to give oxidation
amount of NaOH formed during electrolysis is
(b) The votalic cell in which fuels such as : CH4, H2, CO are
(a) 2.0 g (b) 4.0 g used up at anode
(c) 6.0 g (d) 8.0 g (c) It involves the reactions of H2 – O2 fuel cell such as :
58. How many electrons are delivered at the cathode during
Anode : 2H2 + 4OH
o 4H2O(l) + 4e
–
electrolysis by a current of 1A in 60 seconds ?

–
(a) 3.74 × 10
20
(b) 6.0 × 10
23 Cathode : O2 + 2H2O(l) + 4e
o 4OH
(c) 7.48 × 10
21
(d) 6.0 × 10
20 (d) All of the above
66. Reaction that takes place at anode in dry cell is
59. The moles of electrons required to deposit 1 gm equivalent 2+ – 2+ –
aluminium (at. wt. = 27) from a solution of aluminium chloride (a) Zn + 2e o Zn(s) (b) Zn(s) o Zn + 2e
2+ –
will be (c) Mn + 2e o Mn(s)
+ –
(d) Mn(s) o Mn + e + 1.5 V.
(a) 3 (b) 1
67. As lead storage battery is charged
(c) 4 (d) 2
(a) lead dioxide dissolves
60. Time required to deposit one millimole of aluminium metal (b) sulphuric acid is regenerated
by the passage of 9.65 amperes through aqueous solution (c) lead electrode becomes coated with lead sulphate
of aluminium ion is :
(d) the concentration of sulphuric acid decreases.
(a) 30 s (b) 10 s Conductance of Solutions
(c) 30,000 s (d) 10,000 s 68. The specific conductance of a N/10 KCl at 25°C is 0.0112
–1 –1
ohm cm . The resistance of cell containing solution at the
61. How many coulomb of electricity are consumed when 100 same temperature was found to be 55 ohms. The cell constant
mA current is passed through a solution of AgNO3 for 30 will be
minute during an electrolysis experiment. –1 –1
(a) 6.16 cm (b) 0.616 cm
(a) 108 (b) 18000 –1 –1
(c) 0.0616 cm (d) 616 cm
(c) 180 (d) 3000
–1
69. The specific conductance of a salt of 0.01 M concentration 75. The conductivity of 0.1 N NaOH solution is 0.022 S cm .
–4
is 1.061 × 10 , molar conductance of the same solution will When equal volume of 0.1 N HCl solution is added, the
be : conductivity of resultant solution is decreases to 0.0055 S-
–1 2 –1
(a) 1.061 × 10
–4
(b) 1.061 cm . The equivalent conductivity in S cm equivalent of
NaCl solution is
(c) 10.61 (d) 106.1
(a) 0.0055 (b) 0.11
70. Which of the following solutions of NaCl will have the
highest specific conductance ? (c) 110 (d) none
(a) 0.001 N (b) 0.1 N 76. The specific conductivity of a saturated solution of AgCl is
3.40 × 10 ohm cm at 25 °C. If O Ag = 62.3 ohm cm mol
–6 –1 –1 –1 2 –1

(c) 0.01 N (d) 1.0 N
–1 2 –1
71. The molar conductance at infinite dilution of AgNO3, AgCl & O Cl = 67.7 ohm cm mol , the solubility of AgCl at 25°C
and NaCl are 116.5, 121.6 and 110.3 respectively. The molar is :
conductances of NaNO3 is : –5 –3
(a) 2.6 × 10 M (b) 4.5 × 10 M
(a) 111.4 (b) 105.2 –5 –3
(c) 3.6 × 10 M (d) 3.6 × 10 M
(c) 130.6 (d) 150.2 –1 2 –1
77. Molar conductance of 0.1 M acetic acid is 7 ohm cm mol .
–1
72. If x specific resistance (in S cm) of the electrolyte solution If the molar cond. of acetic acid at infinite dilution is 380.8
2 –1 –1 2 –1
and y is the molarity of the solution, then m (in S cm mol ) ohm cm mol , the value of dissociation constant will be
–5 –3 –3 –1
is given by : (a) 226 × 10 mol dm (b) 1.66 × 10 mol dm
–2 –3 –5 –3
(c) 1.66 × 10 mol dm (d) 3.442 × 10 mol dm
1000x x
(a) y (b) 1000 y 78. At infinite dilution, the eq. conductances of CH3COONa,
2
HCl and CH3COOH are 91, 426 and 391 mho cm respectively
at 25°C, The eq. conductance of NaCl at infinite dilution will
1000 xy
(c) xy (d) be :
1000
(a) 126 (b) 209
73. Resistance of 0.1 M KCl solution in a conductance cell is
–1 (c) 391 (d) 908
300 ohm and conductivity is 0.013 Scm . The value of cell
constant is : 79. The equivalent conductivity of 0.1 N CH3COOH at 25°C is
–1 –1 80 and at infinite dilution 400. The degree of dissociation of
(a) 3.9 cm (b) 39 m
CH3COOH is
–1
(c) 3.9 m (d) None of these
(a) 1 (b) 0.2
74. The specific conductance of a saturated solution of silver
–1 + (c) 0.1 (d) 0.5
bromide is k S cm . The limiting ionic conductivity of Ag
–1
and Br ions are x and y, respectively. The solubility of
–1
silver bromide in gL is : (molar mass of AgBr = 188)
k u1000 k
(a) xy (b) x y u188
k u1000 u188 x y 1000

(c) (d) u
xy k 188
ELECTROCHEMISTRY
242 242
ELECTROCHEMISTRY
EXERCISE - 2 : PREVIOUS YEAR COMPETITION QUESTIONS

(TOPIC1) 6. How many coulombs are required to deposit 50g of
aluminium when the electrode reaction is [RPMT]
ELECTROLYTES AND ELECTROLYTIC CONDUCTANCE
Al3 3e o Al
2011
(a) 536111 C (b) 536.111C
1. A current is passed through two cells connected in series.
The first cell contains X(NO3)3 (aq) and the second cell (c) 96500 C (d) 38600 C
contains Y (NO3)2(aq). The relative atomic mases of X 7. The resistance of 1 N solution of acetic acid is 250 : ,
and Y are in the ratio 1:2. What is the ratio of liberated when measured in a cell having a cell constant of 1.15
mass of X to that of Y? [Kerala CEE] cm–1. The equivalent conductance (in ohm–1 cm2 equiv–1)
(a) 3:2 (b) 1:2 of 1 N acetic acid is [Guj. CET]
(c) 1:3 (d) 3:1 (a) 2.3 (b) 4.6
2. Two different electrolytic cells filled with molten Cu(NO3)2 (c) 9.2 (d) 18.4
and molten Al(NO3)3 respectively are connected in series. 8. The conductivity of 0.20 M KCl solution at 298 K is
When electricity is passed 2.7 g Al is deposited on 0.0248 S cm–1. What will be its molar conductivity?
electrode. Calculate the weight of Cu deposited on [Haryana PMT]
cathode. [Cu = 63.5; Al = 27.0 g mol–1] [Guj. CET]
(a) 124 S cm2 (b) 124 cm–1
(a) 190.5 g (b) 9.525 g
(c) 124 ohm–1cm2 equiv–1 (d) 124 S cm2 mol–1
(c) 63.5 g (d) 31.75 g
9. When same quantity of electricity is passed for half an
2010 hour, an amount of Cu and Cr deposited are respectively
3. An increase in equivalent conductance of a strong 0.375 g and 0.30 g . Ratio of electrochemical equivalent
electrolyte with dilution is mainly due to [CBSE AIPMT] of Cu and Cr is [OJEE]
(a) increase in number of ions. (a) 0.8 (b) 1.25
(b) increase in ionic mobility of ions. (c) 2.5 (d) 1.62
(c) 100% ionisation of electrolyte at normal dilution. 10. In electrolysis of dil. H2SO4 using platinum electrodes
[BVP]
(d) increase in both i.e., number of ions and ionic mobility
of ions. (a) H2 is evolved at cathode.
4. The compound exhibiting maximum value of equivalent (b) SO2 is produced at anode.
conductance in a fused state is` [AMU] (c) O2 is obtained at cathode.
(a) SrCl2 (b) CaCl2 (d) SO2 is produced at cathode.
(c) MgCl2 (d) BeCl2 2009
o + –
5. At 18 C, the conductance of H and CH3COO at infinite 11. Al2O3 is reduced by electrolysis at low potentials and
dilution are 315 and 35 mho cm2 eq–1 respectively. The high current. If 4.0 ×104 amperes of current is passed
equivalent conductivity of CH3COOH at infinite dilution through molten Al2O3 for 6 h, what mass of aluminium is
is ................. mho cm2 eq–1. [AFMC] produced? (Assume 100% current efficiency, at. wt. of
(a) 350 (b) 280 Al=27) [CBSE AIPMT]
(c) 30 (d) 315 (a) 9.0×103 g (b) 8.1×104 g

(c) 2.4×103 g (d) 1.3×104 g

18. 4.5 g of aluminium (at. mass 27 u) is deposited at cathode

M
12. The equivalent conductance of solution of a weak from a molten electrolyte containing Al3+ ions by a certain
32 quantity of electric charge. The volume of hydrogen
monobasic acid is 8.0 mho cm2 and at infinite dilution is produced at STP from H+ ions in a solution by the same
400 mho cm2.The dissolution constant of this acid is quantity of electric charge will be [Manipal]
[CBSE AIPMT]
(a) 44.8 L (b) 11.2 L
(a) 1.25×10–5 (b) 1.25×10–6
(c) 22.4 L (d) 5.6 L
(c) 6.25×10–4 (d) 1.25×10–4
19. How many coulombs of electricity are required for the
13. Assertion On dilution, the equivalent as well as molar reduction of 1 mole of MnO4– to Mn2+ ? [Manipal]
conductivity of solution increases.
(a) 96500 C (b) 9.65×106 C
Reason With dilution, the number of current carrying
(c) 4.83×105 C (d) 1.93×105 C
particles per cm3 increases. [AIIMS]
20. The correct expression in SI system relating the
(a) Both Assertion and Reason are true and Reason is
correct explanation of the Assertion. equivalent conductance ( / C ), specific conductance (N)
(b) Both Assertion and Reason are true and Reason is and equivalent concentration (C) is
not the correct explanation of the Assertion. (where, C is the number of gram equivalents in one litre
(c) Assertion is true but Reason is false. of the solution). [J&K CET]
(d) Both Assertion and Reason are false. N N u 1000

(a) /C (b) / C
14. An aqueous solution containing 6.5 g of NaCl of 90% C C
purity was subjected to electrolysis. After the complete
electrolys is, the solution was evaporated to get solid N u103 N u106
(c) / C (d) / C
NaOH. The volume of 1 M acetic acid required to C C
neutralise NaOH obtained above is [KCET]
2008
(a) 2000 cm3 (b) 100 cm3
21. Kohlraush’s law states that at [CBSE AIPMT]
(c) 200 cm3 (d) 1000 cm3
(a) finite dilution, each ion makes definite contribution
15. In the electrolysis of acidulated water, it is desired to to the equivalent conductance of an electrolyte,
obtained 1.12 cc of hydrogen per second under STP whatever be the nature of the other ion of the
condition. The current to be passed is [KCET] electrolyte.
(a) 9.65 A (b) 19.3 A (b) infinite dilution, each ion makes definite contribution
(c) 0.965 A (d) 1.93 A to equivalent conductance of an electrolyte
depending on the nature of the other ion of the
16. The one which decreases with dilution is [KCET] electrolyte.
(a) conductance (c) infinite dilution, each ion makes definite contribution
(b) specific conductance to conductance of an electrolyte whatever be the
nature of the other ion of the electrolyte.
(c) equivalent conductance
(d) infinite dilution, each ion makes definite contribution
(d) molar conductance
to equivalent conductance of an electrolyte,
17. At 25oC, the molar conductances at infinite dilution for whatever be the nature of the other ion of the
the strong electrolytes NaOH, NaCl and BaCl2 are electrolyte.
248×10–4, 126×10–4 and 280×10–4 S.m2.mol–1 respectively
O 0m Ba(OH) 2 in S.m2.mol–1 [EAMCET]
(a) 52.4×10–4 (b) 524×10–4

(c) 402×10–4 (d) 262×10–4
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22. What is the time (in sec) required for depositing all the (a) Both Assertion and Reason are true and Reason is
silver present in 125 mL of 1M AgNO3 solution by passing correct explanation of the Assertion.
a current of 241.25 A? (1 F=96500 C) [AFMC]
(b) Both Assertion and Reason are true and Reason is
(a) 10 (b) 50 not the correct explanation of the Assertion.
(c) 1000 (d) 100 (c) Assertion is true but Reason is false.
23. Which of the following does not conduct electricity? (d) Both Assertion and Reason are false.
[AFMC]
30. The resistance of N/10 solution is found to be
(a) Fused NaCl (b) Solid NaCl 2.5 × 103 :.The equivalent conductance of the solution
(c) Brine solution (d) Copper is (cell constant=1.25 cm–1) [Kerala CEE]
24. Which of the following electrolytic solutions has the (a) 2.5 :–1 cm–2 equiv–1 (b) 5.0 :–1 cm–2 equiv–1
least specific conductance? [KCET] (c) 2.5 :–1 cm–2 equiv–1 (d) 50 :–1 cm–2 equiv–1
(a) 0.02 N (b) 0.2 N 31. When 3.86 A current is passed through an electrolyte
(c) 2 N (d) 0.002 N for 50 min, 2.4 g of a divalent metal is deposited. The
gram atomic weight of the metal (in gram) is [EAMCET]
25. A direct current deposits 54 g of silver (atomic mass=108)
during the electrolysis reaction. How much aluminium (a) 24 (b) 12
(atomic mass = 27) would be deposited from aluminium (c) 64 (d) 40
chloride solution by the same amount of electricity?
[Kerala CEE] 32. How many atoms of calcium will be deposited from a
solution of CaCl2 by a current of 25 mA flowing for 60 s ?
(a) 4.5 g (b) 5.4 g
[MP PMT]
(c) 54 g (d) 2.7 g
(a) 4.68×1018 (b) 4.68×1015
26. What will be the proportion of moles of metal (Cu:Ni:Ag)
(c) 4.68×1012 (d) 4.68×109
at cathode according to the second law of Faraday?
[Guj. CET] 33. The specific conductance (N) of an electrolyte of 0.1 N
(a) 1 : 2 : 1 (b) 2 : 2 : 1 concentration is related to equivalent conductance ( / )
by the following formula [J&K CET]
(c) 1 : 2 : 2 (d) 1 : 1: 2
(a) / = N (b) / = 10 N
2007
(c) / = 100 N (d) / = 10000 N
27. Which of the following is not a non-electrolyte ?
[AFMC] 34. Pure water does not conduct electricity because it is
(a) Acetic acid (b) Glucose [J&K CET]
(c) Ethanol (d) Urea (a) basic (b) almost not ionised
28. A current of 96.5 A is passed for 18 min between nickel (c) decomposed easily (d) acidic
electrodes in 500 mL solution of 2M Ni(NO3)2. The
2006
molarity of solution after electrolysis would be[AIIMS]
35. In the electrolysis of water, one faraday of electrical
(a) 0.46 M (b) 0.92 M
energy would evolve [AMU]
(c) 0.625 M (d) 1.25 M
(a) one mole of oxygen
29. Assertion According to Kohlrausch’s law the molar
conductivity of a strong electrolyte at infinite dilution is (b) one gram atom of oxygen
sum of molar conductivities of its ions. (c) 8 g of oxygen
Reason The current carried by cation and anion is always (d) 22.4 L of oxygen
equal. [AIIMS]

36. If the aqueous solution of the following salts are slolution was (molar mass of Cu=63.5, Faraday constant
electrolysed for 1 h with 10 A current, which solution will =96500 C/mol) [AMU]
deposit the maximum mass of the metal at the cathode? (a) 0.2 N (b) 0.01N
The atomic weights are Fe2+=56, Zn2+=65, Ag+=108,
Hf3+=178 and W3+=184 [Kerala CEE] (c) 0.1 N (d) 0.02 N
(a) ZnSO4 (b) FeCl3 43. An electric current is passed through silver voltameter
connected to a water voltameter. The cathode of the
(c) HfCl4 (d) AgNO3 silver voltameter weighed 0.108g more at the end of the
electrolysis. The volume of oxygen evolved at STP is
37. The ionic conductance of Ba2+ and Cl– are respectively
[Kerala CEE]
127 and 76:–1 cm2 eq–1 at infinite dilution. The equivalent
conductance (in :–1 cm2) of BaCl2 at infinite dilution will (a) 56 cm3 (b) 550 cm3
be [MHT CET] (c) 5.6 cm3 (d) 11.2 cm3
(a) 139.5 (b) 203
TOPIC 2
(c) 279 (d) 101.5
ELECTROCHEMICAL SERIES, ELECTRODE
38. The charge required to liberate one gram equivalent of
an element is [BCECE] POTENTIAL AND EMF
(a) 96500 F (b) 1F 2011
(c) 1C (d) None of these
44. If the E ocell for a given reaction has a negative value, then
2005 which of the following gives the correct relationships
39. A current of strength 2.5 A was passed through CuSO4 for the values of 'Go and Keq ? [CBSE AIPMT]
solution for 6 min 26 s. The amount of copper deposited (a) 'Go >0; Keq < 1 (b) 'Go >0; Keq > 1
is (Atomic weight of Cu=63.5, 1F= 96500 C)
[Punjab PMET] (c) 'Go <0; Keq > 1 (d) 'Go <0; Keq < 1
(a) 0.3175 g (b) 3.175 g 45. The electrode potentials for
(c) 0.635 g (d) 6.35 g
Cu 2+ (aq) e o Cu (aq) and Cu + (aq) e o Cu(s)
40. What is the electrochemical equivalent (in g-C–1) of silver? are +0.15 V and + 0.50 V respectively. The value of
(Ag=108, F=Faraday) [EAMCET]
E oCu 2 / Cu will be [CBSE AIPMT]
108
(a) 108 F (b) (a) 0.150 V (b) 0.500 V
F
(c) 0.325 V (d) 0.650 V
F 1
(c) (d) 46. Standard electrode potential of three metals X, Y and Z
108 108F
are –1.2 V, +0.5 V and –3.0 V respectively. The reducing
2004 power of these metals will be [CBSE AIPMT]
41. At 25oC the specific conductivity of a normal solution of (a) X>Y>Z (b) Y>Z>X
KCl is 0.002765 mho. The resistance of cell is 400:.The
cell constant is [Punjab PMET] (c) Y>X>Z (d) Z>X>Y
(a) 0.815 (b) 1.016 47. Standard electrode potential for Sn4+/Sn2+ couple is +0.15
V and that for the Cr3+/Cr couple is –0.74 V. These two
(c) 1.106 (d) 2.016
couples in their standard state are connected to make a
2003 cell. The cell potential will be [CBSE AIPMT]
42. On passing electric current of one ampere for 16 min and (a) +1.83 V (b) +1.19 V
5 s through one litre solution of CuCl2, all copper of
(c) +0.89 V (d) +0.18 V
solution was deposited at cathode.The strength of CuCl2
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48. Given the following reactions involving, A, B, C and D (a) 12.5 (b) 21.5
(i) C B o C B (c) 37.9 (d) 47.2

53. If the half cell reactions are given as
(ii) A D o No reaction
(i) Fe 2 (aq) 2e o Fe(s); Eo 0.44V
(iii) C+ +A o No reaction
1
(iv) D+B+ o D B (ii) 2H (aq) O2 (g) 2e o H 2O(A) E o =+1.23V
2
The correct arrangement of A, B, C, D in order of their
The Eo for the reaction
decreasing ability as reducing agent [DPMT]
(a) D > B > C > A (b) A > C > D > B 1
Fe(s) 2H O 2 o Fe2 (aq) H 2 O(A) [AMU]
2
(c) C > A > B > D (d) C >A > D > B
49. The standard emf of a galvanic cell involving 2 moles of (a) +1.67 V (b) –1.67 V
electrons in its redox reaction is 0.59 V. The equilibrium (c) +0.79 V (d) –0.79 V
constant for the redox reaction of the cell is [KCET]
54. Given for Sn4+/Sn2+, standard reduction potential is 0.15
20 5
(a) 10 (b) 10 V and for Au3+/Au, standard reduction potential is 1.5 V.
(c) 10 (d) 1010 For the reaction,
50. E1, E2 and E3 are the emfs of the following three galvanic 3Sn 2 2Au 3 o 3Sn 4 2Au
cells respectively
the value of E ocell is [MHT CET]
2 2
(i) Zn(s) | Zn (0.1M) || Cu (1M) | Cu(s)
(a) +1.35 (b) +2.55
2 2
(ii) Zn(s) | Zn (1M) || Cu (1M) | Cu(s) (c) –1.35 (d) –2.55
o
(iii) Zn(s) | Zn 2 (1M) || Cu 2 (0.1M) | Cu(s) 55. The E M3 / M2 values for Cr, Mn, Fe and Co are –0.41,
+1.57, +0.77, and +1.97 V respectively. For which one of
Which one of the following is true? [KCET]
these metals the change in oxidation state from +2 to +3
(a) E2>E1>E3 (b) E1>E2>E3 is easiest? [Manipal]
(c) E3>E1>E2 (d) E3>E2>E1 (a) Cr (b) Mn
(c) Fe (d) Co
2010
56. At 25 oC temperature, the cell potential of a given
51. For the reduction of silver ions with copper metals, the electrochemical cell is 1.92 V. Find the value of x.
standard cell potential was found to be +0.46 V at 25oC.
The value of standard Gibbs energy, 'Go will be (F=96500 Mg(s) | Mg 2 (aq) x M || Fe 2 (aq) 0.01M | Fe(s)
C mol–1) [CBSE AIPMT]
E o Mg / Mg 2 (aq) 2.37V; E o Fe / Fe 2 (aq) 0.45 V
(a) –98.0kJ (b) –89.0 kJ
[Guj. CET]
(c) –89.0 J (d) –44.5 kJ
(a) x=0.01M (b) x<0.01 M
52. The logarithm of the equilibrium constant of the cell
reaction corresponding to the cell X(s) | X2+ (aq) || Y+(aq)| (c) x>0.01M (d) x cannot be predicted
Y(s) with standard cell potential, E oCell =1.12 V is given

by [AMU]

57. The potential of a hydrogen electrode at pH=10 is (a) Zn reduces Fe2+ (b) Zn reduces Mg2+
[WB JEE] (c) Mg oxidises Fe (d) Zn oxidises Fe
(a) 0.59 V (b) 0.00V 64. The standard elecrode potential for the half cell reactions
are
(c) –0.59V (d) –0.059 V
2009 Zn 2 2e o Zn; Eo 0.76V
58. Given : (i) Cu2+ + 2e– o Cu; Eo=0.337 V Fe 2 2e o Fe; Eo 0.44V

(ii) Cu + e o Cu ;
2+ – + o
E =0.153V The emf of the cell reaction
Electrode potential, Eo for the reaction, Cu+ + e– o Cu,
will be Fe2 Zn o Zn 2 Fe [KCET]
[CBSEAIPMT,AMU] (a) –1.20 V (b) +1.20 V
(a) 0.52 V (b) 0.90 V (c) +0.32 V (d) –0.32 V
(c) 0.30 V (d) 0.38 V 65. A solution of nickel sulphate in which nickel rod is dipped
59. 2+ 2+
Given , Pb /Pb=–0.126 V; Zn /Zn=–0.763 V Find the is diluted 10 times. The reduction potential of Ni at 298
emf of the following cell Zn | Zn2+ (0.1 M)|| Pb2+ (1M) | Pb. K [Kerala CEE]
[AFMC] (a) decreases by 60mV (b) decrease by 30 mV
(a) –0.637 (b) +0.637 (c) decreases by 30 V (d) increases by 30 mV
(c) >0.637 (d) +0.889 66. The standard reduction potentials for Cu 2+ /Cu;
60. The reduction potential at pH=14 for the Cu /Cu 2+ Zn2+/Zn; Li+/Li; Ag+/Ag and H+/H2 are +0.34 V, –0.762 V,
couples is –3.05 V, +0.80 V and 0.00 V respectively. Choose the
strongest reducing agent among the following.
o
[Given, E Cu2 / Cu =0.34V; Ksp[Cu(OH)2=1 ×10–19] [Kerala CEE]
[AIIMS]
(a) Zn (b) H2
(a) 0.34 V (b) –0.34V
(c) Ag (d) Li
(c) 0.22 V (d) –0.22V
67. The standard emf of a cell involving one electron charge
61. A gas X at 1 atm is bubbled through a solution containing is found to be 0.591 V at 25oC. The equilibrium constant
a mixture of 1MY– and 1 MZ– at 25oC. If the reduction of the reaction is (1F=96500 C mol–1, R=8.314 JK–1mol–1)
potential of Z > Y > X, then [AIIMS] [Manipal]
(a) Y will oxidise X but not Z. (a) 1.0×101 (b) 1.0×1030
(b) Y will oxidise both X and Z. (c) 1.0×1010 (d) 1.0×105
(c) Y will oxidise Z but not X.
2008
(d) Y will reduce both X and Z.
68. On the basis of the following Eo values, the strongest
62. The potential of standard hydrogen electrode is zero. oxidising agent is
This implies that [AMU]
[Fe(CN)6 ]4 o [Fe(CN)6 ]3 e ; E o 0.35V
(a) 'G (H , aq)=0
o
f
+
(b) 'H (H , aq) = 0
o
f
+
Fe 2 o Fe3 e ; E o 0.77V [CBSE AIPMT]

(c) 'G (H , aq) < 0
o
f
+
(d) 'G (H , aq) > 0
o
f
+
(a) [Fe(CN)6]4– (b) Fe2+

o 2+ 2+
63. E for Mg /Mg = –2.37 V, Zn /Zn = –0.76 V, and
(c) Fe3+ (d) [Fe(CN)6]3–
Fe2+/Fe = –0.44 V. Which statement is correct?
[CPMT]
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69. What is the electrode potential (in volt) of the following 2007
electrode at 25oC?
74. Zn gives H2 gas with H2SO4 and HCl but not with HNO3
Ni2+ (0.1 M) | Ni(s) [Punjab PMET]
(Standard reduction potential of Ni2+/Ni is –0.25 V, (a) Zn act as oxidising agent when react with HNO3.
2.303RT (b) HNO3 is weaker acid than H2SO4 and HCl.
0.06 ) [Punjab PMET]
F (c) in electrochemical series Zn is above hydrogen.
(a) –0.28V (b) –0.34 V (d) NO3– is reduced in preference to hydronium ion.
(c) –0.82 V (d) –0.22V 75. EMF of hydrogen electrode in terms of pH is (at 1 atm
pressure) [MHT CET]
70. Hydrogen gas is not liberated when the following metal
is added to dil HCl [KCET]
RT RT 1
(a) Ag (b) Zn (a) E H2 pH (b) E H2 F pH
F
(c) Mg (d) Sn
2.303RT
71. The equilibrium constant for the following redox reaction (c) E H 2 pH (d) E H2 0.0591pH
F
at 298 K of 1×108.
76. The standard electrode potential of hydrogen electrode
2Fe3 (aq) 2I (aq) YZZ
ZZX 2Fe2 (aq) I2 (s) at 1 M concentration and hydrogen gas at 1 atm pressure
is [J&K CET]
If the standard reduction potential of iodine becoming
iodide is +0.54 V, what is the standard reduction potential (a) 1 V (b) 6 V
of Fe3+/Fe2+ ? [Kerala CEE] (c) 8 V (d) 0 V
(a) +1.006 V (b) –1.006 V 2006
(c) +0.77 V (d) –0.77V 77. A hypothetical electrochemical cell is shown below
72. The cell potential of the following cell at 25oC (in volts) A | A+ (xM) ||B+(yM) | B
is
The emf measured is +0.20V. The cell reaction is
2 o [CBSE AIPMT]
(pt) H 2 | H ||Cu |Cu(E Cu 2 / Cu
0.337V) [EAMCET]
(1atm) (0.01M) (0.1 M)
(a) A B o A B
(a) 0.308 (b) 0.427
(b) A e o A; B e o B
(c) –0.308 (d) 0.337
73. Cu +(aq) is unstable in solution and undergoes (c) the cell reaction cannot be predicted
simultaneous oxidation and reduction, according to the
(d) A B o A B
reaction
78. Assertion E o for Mn3+ /Mn2+ is more positive than
2Cu (aq) YZZ
ZZX Cu 2 (aq) Cu(s) Cr3+/Cr2+.
choose the correct Eo for the above reaction if Reason The third ionisation energy of Mn is larger than
that of Cr.
o
E Cu 2
|Cu = 0.34 V and
E oCu 2 |Cu = 0.15 V [MHT CET] [AIIMS]
(a) –0.38 V (b) +0.49V correct explanation of the Assertion.
(c) +0.38V (d) –0.19 V (b) Both Assertion and Reason are true and Reason is
not the correct explanation of the Assertion.
(c) Assertion is true but Reason is false.
(d) Both Assertion and Reason are false.

79. For the electrochemical cell, M | M+ || X– | X, Eo(M+/ 86. Reduction potentials of A, B, C and D are 0.8 V, 0.79 V,
M)=0.44V and Eo(X/X–)=0.33V, From this data one can 0.34 V and –2.37 V respectively. Which element displaces
deduce that [BHU] all the other three elements? [MHT CET]
(a) M X o M X is the spontaneous reaction (a) B (b) A

(c) D (d) C
(b) M X o M X is the spontaneous reaction
87. The standard emf of Daniell cell is 1.10 V. The maximum
(c) E cell 0.77V electrical work obtained from the cell is[Haryana PMT]
(a) 212.3 kJ (b) 175.4 kJ
(d) E cell 0.77V
(c) 106.15 kJ (d) 350.8 kJ
80. The reduction electrode potential, E of 0.1 M solution of
88. For cell reaction
M+ ions ( E oRP 2.36V ) is [MHT CET]
Zn Cu 2 o Zn 2 Cu
(a) –4.82V (b) –2.41 V
cell representation is [BCECE]
(c) +2.41V (d) None of these
(a) Zn | Zn 2 || Cu 2 | Cu
RT
81. Eo ln K eq
nF (b) Cu | Cu 2 || Zn 2 | Zn
This equation is called [MP PMT]
(c) Cu | Zn 2 || Zn | Cu 2
(a) Gibbs equation (b) Nernst equation
(c) Gibbs-Helmholtz equation (d) Cu 2 | Zn || Zn 2 | Cu
(d) van der Waals’ equation 89. Alkali metals have high oxidation potential and hence,
they behave as [JCECE]
82. During electrochemical process [Guj. CET]
(a) oxidising agents (b) Lewis bases
(a) Gibbs free energy increases.
(c) reducing agents (d) electrolytes
(b) Gibbs free energy remains constant.
90. What is the potential of platinum wire dipped into a
(c) no prediction can be about Gibbs free energy.
solution of 0.1 M in Sn2+ and 0.01 M in Sn4+? [JCECE]
(d) Gibbs free energy decreases.
(a) E o (b) E o 0.059
2005
83. If hydrogen electrode dipped in two solutions of pH=3 0.059 0.059
(c) E (d) E
o o
and pH=6 and salt bridge is connected, the emf of 2 2

resulting cell is [DUMET]
2004
(a) 0.177 V (b) 0.3 V
91. Assertion Copper metal gets readily corroded in an acidic
(c) 0.052 V (d) 0.104 V aqueous solution.
84. The standard electrode potential is measured by[KCET] Reason Free energy change for this process is positive.
(a) electrometer (b) voltmeter [AIIMS]
(c) pyrometer (d) galvanometer (a) Both Assertion and Reason are true and Reason is
correct explanation of the Assertion.
85. Na is used in reduction of Zn salt because [MHT CET]
(a) E o
Zn(oxi) !E o
Na (oxi) (b) E o
Zn(red) E o
Na (red )
not the correct explanation of the Assertion.
(c) E oZn(oxi) E oNa (oxi) (d) Both (a) and (b)
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92. Aluminium displaces hydrogen from dilute HCl whereas TOPIC 3

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

p1 p2
99. When iron is rusted, it is [MP PMT]
emf is given by [MHT CET]
(a) reduced (b) decomposed
RT p1 RT p1
(a) F log e p (b) 2F log e p (c) oxidised
2 2
(d) changed in the fine powder
RT p2 RT p2
(c) F loge p (d) 2F log e p 100. Which of the following statements is true for the
1 1 electrochemical Daniel cell? [Manipal]
95. For the cell, (a) Electrons flow from copper electrode to zinc electrode
2
Tl | Tl (0.001M) || Cu (0.1)M | Cu (b) Current flows from zinc electrode to copper electrode.
E cell at 25oC is 0.83 V. E cell can be increased (c) Cations move toward copper electrode.
[Haryana PMT] (d) Cations move toward zinc electrode.
2+ 2+
(a) by decreasing [Cu ] (b) by increasing [Cu ] 101. Chemical formula of rust is [OJEE]
+
(c) by increasing [Tl ] (d) None of these
(a) Fe 2 O 3 .H 2 O (b) Fe 2 O3 .5H 2 O
2003
96. On the basis of information available from the reaction (c) Fe 2 O3 .xH 2 O (d) None of these
4 2 102. When lead storage battery discharges [VMMC]

Al O 2 o Al2 O3 , 'G 827 kJ mol1
3 3 (a) SO2 is evolved (b) PbSO4is consumed
of O 2, the minimum emf required to carry out an (c) Lead is formed (d) H2SO4 is consumed
electrolysis of Al2O3, is (F=96500 C mol–1)
E ocell and 'G are related as
o
[CBSE AIPMT] 103. [VMMC]
(a) 6.42 V (b) 8.56 V
(a) 'G o nFEocell (b) 'G nFE ocell
(c) 2.14 V (d) 4.28 V
97. If the standard electrode potential of Cu 2 / Cu electrode (c) 'G o nFE ocell (d) 'G o o
nFE cell 0
is 0.34 V, what is the electrode potential at 0.01 M
concentration of Cu2+? (T = 298 K) [EAMCET]
(a) 0.399 V (b) 0.281 V
(c) 0.222 V (d) 0.176 V

104. The rusting of iron is catalysed by 110. When lead storage battery is charge [AFMC]
[CG PMT, Haryana PMT] (a) lead dioxide dissolves.
(b) sulphuric acid is regenerated.
(a) Fe (b) O2
(c) the lead electrode becomes coated with lead sulphate.
(c) H+ (d) Zn
(d) the amount of sulphuric acid decreases.
105. Standard solution of KNO3 is used to make salt bridge 111. Anode in the galvanic cell, is [RPMT]
because [CG PMT, Haryana PMT]
(a) negative electrode (b) positive electrode
(a) velocity of K+ is greater than 12 . (c) neutral electrode (d) None of these
2006
(b) velocity of 12 is greater than K+.
112. What is the cell reaction occuring in Daniell cell (Galvanic
cell)? [J&K CET]
(c) velocity of K+ and 12 are same.
(a) Cu(s) ZnSO 4 (aq) o CuSO 4 (aq) Zn(s)
(d) KNO3 is highly soluble in water.
(b) Zn(s) CuSO 4 (aq) o Cu(s) ZnSO 4 (aq)
2008
106. Standard free energies of formation (in kJ/mol) at 298 K (c) Ni(s) ZnSO 4 (aq) o NiSO 4 (aq) Zn(s)
are –237.2, –394.4 and –8.2 for H2O( A ), CO2(g) and
(d) 2Na(s) CdSO 4 (aq) o Na 2SO 4 (aq) Cd(s)
pentane (g), respectively. The value of E ocell for the
pentane-oxygen fuel cell is [CBSE AIPMT] 2005
(a) 1.968 V (b) 2.0968 V 113. When an acid cell is charged then [AFMC]
(c) 1.0968 V (d) 0.0968 V (a) voltage of cell increases
107. Assertion The cell potential of mercury cell is 1.35 V, (b) electrolyte of cell dilutes
which remains constant. (c) resistance of cell increases
Reason In mercury cell, the electrolyte is a paste of KOH (d) None of the above
and ZnO. [AIIMS] 114. The chemical reaction,
correct explanation of the Assertion. 2AgCl(s) H 2 (g) o 2HCl(aq) 2Ag(s)
(b) Both Assertion and Reason are true and Reason is taking place in a galvanic cell is represented by the
not the correct explanation of the Assertion. notation [AIIMS]
(c) Assertion is true but Reason is false. (a) Pt(s) | H 2 (g),1bar | 1M KCl(aq) | AgCl(s) | Ag(s)
(b) Pt(s) | H2 (g),1bar |1M HCl(aq) |1MAg (aq) | Ag(s)
108. Galvanic cell is a device in which [CBSE AIPMT]
(a) chemical energy is converted into electrical energy. (c) Pt(s) | H 2 (g),1bar | 1M HCl(aq) | AgCl(s) | Ag(s)
(b) electrical energy is converted into chemical energy. (d) Pt(s) | H 2 (g),1bar | 1M HCl(aq) | Ag(s) | AgCl(s)
(c) chemical energy is seen in the form of heat.
115. Assertion Galvanised iron does not rust.
(d) thermal energy from an outside source is used to
Reason Zinc has a more negative electrode potential
drive the cell reaction.
than iron [AIIMS]
2007 (a) Both Assertion and Reason are true and Reason is
109. The eficiency of a fuel cell is given by [CBSE AIPMT] correct explanation of the Assertion.
'H 'G
(a) (b) not the correct explanation of the Assertion.
'G 'S
'G 'S (d) Both Assertion and Reason are false.
(c) (d)
'H 'G
2004
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116. Iron pipes, lying in acidic soil, are often attached to the 120. Which cell convert electrical energy into chemical
blocks of magnesium for their protection from rusting energy? [Punjab PMET]
because magnesium [BHU, DUMET]
(a) Voltaic cell (b) Electrolytic cell
(a) is lighter than iron
(c) Galvanic cell (d) Electrochemical cell
(b) is readily converted into positive ion
121. The cell reaction of the galvanic cell
(c) forms a corrosion–resistant alloy with iron Cu(s) | Cu 2 (aq) || Hg 2 (aq) | Hg(A) is [EAMCET]
(d) prevents air from reaching the surface of iron.
(a) Hg Cu 2 o Hg 2 Cu
117. Which of the following statements is true for fuel cells?
[Punjab PMET]
(b) Hg Cu 2 o Cu Hg
(a) They run till the reactant are active
(c) Cu Hg o CuHg
(b) They are free from pollution.
(c) They are more efficient. (d) Cu Hg 2 o Cu 2 Hg
(d) All of the above. 122. Which one of the following metal is used in
118. In a hydrogen-oxygen fuel cell, combustion of hydrogen galvanisation? [RPMT]
occurs to [DUMET] (a) Cu (b) Ag
(a) generate heat. (c) Zn (d) Fe
(b) create potential difference between the two
electrodes.
(c) produce high purity water
(d) remove adsorbed oxygen from electrode surfaces.
2003
119. Which of the following reaction is used to make a fuel
cell? [AIIMS]
(a) Cd(s) 2Ni(OH)3 (s) o CdO(s)

2Ni(OH)2 (s) H 2O(A)
(b) Pb(s) PbO 2 (s) 2H 2SO 4 (aq) o 2PbSO4 (s)

2H 2 O(A)
(c) 2H 2 (g) O 2 (g) o 2H 2 O(A )
(d) 2Fe(s) O 2 (g) 2H (aq) o 2Fe 2 (aq) 2H 2 O(A )

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

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

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

3. TYPES 6. ELECTRODE POTENTIAL

Mahesh Tutorials Science

For this equation we take oxidation potential of anode and

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

For a Daniel cell, therefore

E ocell E oCu 2 / Cu  EoZn / Zn 2 0.34  0.76 1.10 V

10. CELL DIAGRAM OR REPRESENTATION

Anode: M Mn+ + ne–

Cathode: Mn+ + ne– M

13.2 Gas Electrodes

13.3 Metal-Insoluble salt electrode Cathode: Fe3+ + e– Fe2+

containing AgCl(s) and Cl– ions. aA  bB o

Nernst equation can be given as

Mahesh Tutorials Science

c d concentrations and the solutions are connected through

15. APPLICATIONS OF NERNST EQUATION H2 (P1) | H+ (C) || H+ (C) | H2(P2)

15.1 Equilibrium Constant from Nernst Equation

ª Zn 2  º where p 2  p1 for spontaneous reaction

The EMF of concentration cell at 298 K is given by

16. CONCENTRATION CELLS or 2NaCl (l ) 2Na (l ) + Cl2 (g)

17.2 Electrolysis of an aqueous solution of sodium chloride 18.3 Mercury cells

(almost completely ionized) Anode : Zn – Hg Amalgam

H2O (l ) U H+(aq) + OH–(aq) Cathode : Paste of HgO and carbon

(only slightly ionized) Electrolyte : Paste of KOH and ZnO

At cathode : Anode : Zn (Hg) + 2OH– ZnO (s) + H2O + 2e–

At anode : 18.4 Secondary Batteries

18.1 Primary Batteries Discharging Reactions

Mahesh Tutorials Science

Cathode : O2 (g) + 2H2O (l) + 4e– 4OH– (aq)

Anode : 2H2 (g) + 4OH– (aq) 4H2O (l) + 4e–

overall Reaction : 2H2(g) + O2 (g) 2H2O (l)

21. CONDUCTANCE (G)

Examples : HCl, NaOH, KCl (Strong electrolytes).

CH3–COOH, NH4OH (Weak electrolytes).

The conductance of electricity by ions present in the

(iv) Temperature : As the temperature of electrolytic solution N u 1000 S cm 1

24. MEASUREMENT OF CONDUCTANCE 26. EQUIVALENT CONDUCTIVITY (/eq)

Where, v is the volume of solution in cm3 containing

27. VARIATION OF CONDUCTIVITY AND MOLAR

Mahesh Tutorials Science

For example, molar conductivity of acetic acid at infinite

ªO o  OoNa º  ¬ª OHo   O Cl ¼º  ¬ªOoNa  OCl

i.e. / m CH3  COOH / om CH3  COONa  / om HCl  / om NaCl

STANDARD REDUCTION POTENTIALS AT 298 K.

S2O 82  2e  o 2SO 24 + 2.05 MnO 4  e  o MnO24 + 0.56

Ag2+ + e– o Ag+ + 1.98 I2 + 2e o 2I

MnO 4  8H   5e  o Mn 2  4H 2 O + 1.51 [Fe(CN)6]3– + e– o [Fe(CN)6]4– + 0.36

Ti3+ + e– o Ti2+ – 0.37 V2+ + 2e– o V – 1.19

Cd2+ + 2e– o Cd – 0.40 Ti + 2e o Ti

In2+ + e– o In+ – 0.40 Al3+ + 3e– o Al – 1.66

Cr3+ + e– o Cr2+ – 0.41 U + 3e o U

Fe2+ + 2e– o Fe – 0.44 Sc + 3e o Sc

In3+ + 2e– o In+ – 0.44 Mg + 2e o Mg

S + 2e– o S2– – 0.48 Ce + 3e o Ce

In3+ + e– o In2+ – 0.49 La3+ + 3e– o La – 2.52

U4+ + e– o U3+ – 0.61 Na + e o Na

Cr3+ + 3e– o Cr – 0.74 Ca + 2e o Ca

Zn2+ + 2e– o Zn – 0.76 Sr + 2e o Sr

Cd(OH)2 + 2e– o Cd + 2OH– – 0.81 Ba + 2e o Ba

2H2O + 2e– o H2 + 2OH– – 0.83 Ra2+ + 2e– o Ra – 2.92

Cr2+ + 2e– o Cr – 0.91 Cs + e o Cs

Mn2+ + 2e– o Mn – 1.18 Rb + e o Rb

E ocell E oCu 2 / Cu EoZn / Zn 2 0.34 0.76 1.10 V

containing AgCl(s) and Cl– ions. aA bB o

ª Zn 2 º where p 2 p1 for spontaneous reaction

(iv) Temperature : As the temperature of electrolytic solution N u 1000 S cm 1

ªO o OoNa º ¬ª OHo O Cl ¼º ¬ªOoNa OCl

i.e. / m CH3 COOH / om CH3 COONa / om HCl / om NaCl

S2O 82 2e o 2SO 24 + 2.05 MnO 4 e o MnO24 + 0.56

MnO 4 8H 5e o Mn 2 4H 2 O + 1.51 [Fe(CN)6]3– + e– o [Fe(CN)6]4– + 0.36

Ag2CrO4 + 2e– o 2Ag + CrO 24 + 0.45 Ce4+ + e– o Ce3+ + 1.61

Au+ + e– o Au + 1.69 ClO4 H 2 O 2e o ClO3 2OH + 0.36

Cs+ e– o Cs – 2.92 MnO4 2H 2O 2e o MnO2 4OH + 0.60

Fe3+ + e– o Fe2+ + 0.77 NO3 H 2 O 2e o NO 2 2OH + 0.10

1000 1000 Sol. o Fe 2 aq 2e , E Fe

/m Normality E oH / O 1.23V

E oNi2 / Ni 0.25 V, E oCu 2 / Cu 0.34 V. 2Fe + O2 + 4H+(aq)

(i) They do not cause any pollution. Mg(s) + 2 Ag+ (0.0001 M)

N u1000 N 4.95 u 10 5 Scm 1 1000 cm3

Sol. / 0m HAc OoH O Ac

= – 0.76 – 0.02955 (3 – 1.9777) 0.34 V, F 96, 500 C mol 1 ]

(a) Define molar conductivity of a substance and describe At anode : Cu(s)

(b) A voltaic cell is set up at 25 oC with the following half Cu s 2Ag aq

0.0591 0.3012 Fe s Cd 2 aq YZZ

E o cell 1.67 V aq 4H 2 O A ] u 2 Eo 1.15V

The ferrous ions are further oxidised by atmospheric o Sn 4 aq 2e ] u 5 Eo = + 0.15 V

k u1000 u188 x y 1000