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ELECTRO CHEMISTRY

 Electronic conduction depends on


SYNOPSIS
(i) the nature and structure of the metal
Electrochemistry deals with (ii) the number of valence electrons per atom
I. The use of electrical energy for the dissociation (iii) temperature (it decreases with increase of
of chemical compounds (electrolysis) temperature)
II. The use of chemical reactions for the  Electrolytic conduction depends on
production of electrical energy (Electro- (i) the nature of the electrolyte added
chemical cells) (ii) size of the ions produced and their solvation
III. The use of electrical energy in the study and (iii) the nature of the solvent and its viscosity
preparation of chemical substances. (iv) concentration of the electrolyte
IV. The commercial power generating cells, (v) temperature (it increases with the increase
namely secondary cells (batteries & fuel cells) of temperature)
 The Basis of electro chemistry is thus a process  Non-metals which are electronically conducting
in which electrons are transferred from one Ex: Carbon-black, graphite, organic polymers
system to another like polyaniline, polypyrrole, polythiophene,
 Electric current is considered as flow of polyacetylene when exposed to vapours of
electrons or flow of electrical charges through a iodine.
conducting system.  Metals and their alloys, at very low temperatures
 The Substance which allows the electric current (0 to 15 K) were known to behave as
to pass through it, is called Electrical Conductor. superconductors.
 The electrical conductors are of two types.  Ceramic materials and mixed oxides also show
(a) Electronic Conductors superconductivity at temperatures as high as
(b) Electrolytic conductors 150K.
 Distinction between electronic conductors and  The flow of current in the case of electrolytic
electrolytic conductors: conductors (Eg.Solutions of salts in water ) is
SL. ELECTRONIC ELECTROLYTIC due to the movement of ions in the solution
NO CONDUCTORS CONDUCTORS under the influence of an applied voltage.
1
Conducts electricity by Conducts Electricity by  The movement of ions under applied voltage is
the flow of E lectrons the movement of ions called electrical migration or mobility or ionic
Electrons flow from Char ged species (ions)
negative end to positive move towardsthe
conductivity of ions.
2
end oppositely charged Electrolysis
electrodes
No transfer of matter  Non electrolyte: The substance which does
Transfer of matter takes
3
takes place place not conduct electricity either in its molten state
No chemical change Chemical change takes
or in aqueous solution is called a non–
4
takes place place at the electrodes
electrolyte.
It decreases with rise of It increases with
5
temperature  Sugar Solution, glucose solution, urea in water,
increase of temperature
6 Metals, alloys, graphite, organic solvents, non polar covalent substances,
Liquids of molten salts,
solid salts such as CdS, aqueous solution of
are non electrolytes.
CuS, etc., are examples salts, acids ( Eg ;HCl,
of electronic
 Pure water is a poor conductor of electricity.
HNO3 ,H2 SO4 ) and
conductors bases ( NaOH, KOH)  Electrolyte : A substance, that is, in the molten
are examples of state (fused state) or in the dissolved state ( in
electrolytic conductors water or any other solvent) containing ions and
is functioning as an electrically conducting
Note:i. CdS and CuS exhibit electronic conduction
medium is called an electrolyte.
due to crystal defect.
 Fused salts (in the liquid state) : ( NaCl , KCl etc) Anode(+): It is the electrode, which is connected
and fused hydrides, solid halides of Ag, Ba, Pb to the +ve terminal of the battery, and through
which the electrons leave the electrolyte.
and of some other metals.   form of Ag 2 S .
 In an electrolytic cell oxidation of anions take
 Aqueous solutions, of place at anode and reduction of cations take
NaCl , KCl , K 2 SO4 , CuSO4 , etc.; place at cathode.
HCl , H 2 SO4 , HNO3 ; NaOH , KOH etc. in  Electrons flows from anode to cathode, but
current flow from cathode to anode.
water. In general all fused liquid salts (or)
solutions which contain ions are electrolytes.  MA  M+ + A– (Lattice Breaking)
Strong electrolytes :Electrolytes, which ionize M+ + e–  M at cathode (Reduction)
– –
almost completely at moderate dilutions and A — e A at anode (Oxidation )
have high conductivity are called Strong At cathode electronation and at anode
Electrolytes. deelectronation occurs.
 Mineral acids (HCl, H2SO4,HNO3), alkali and  When a solution contains two (or) more anions
alkaline earth metallic hydroxides and most of and cations, the ion with the lower discharge
the salts are strong electrolytes in aqueous potential will deposit first.
solution.
 Decreasing order of discharge potentials for
Weak Electrolytes: Electrolytes, which various anions
ionize partially and have low conductivity are
called Weak Electrolytes. F   SO42  NO3  OH   Cl   Br   I   CO32
 Most of the organic acids, bases and salts like  Decreasing order of discharge potentials for
CH3COONH4, HgCl2, BaSO4, NH4OH, H3BO3 various cations
are weak electrolytes. + + 2+ 2+ 3+ 2+
Li   K > Na > Ca > Mg > Al > Mn >
Zn2+> Cr3+ > Fe2+ >H+ >Cu2+ > Hg+ >Ag+ > Pt2+
Mechanism of electrolysis - Its
> Au3+
Application:
 ORDER OF DEPOSITION OF ANIONS:
 The decomposition of an electrolyte at the
electrodes as a result of the passage of electric CO32  I   Br  Cl  OH  NO3  SO42
current is called electrolysis. (or)  ORDER OF DEPOSITION OF CATIONS
The process of decomposition of an electrolyte
by passing electric current is called electrolysis. Au 3  Pt 2  Ag   Hg   Cu 2  H  
 The cell in which electrolysis is carried out is Fe 3  Cr 3  Zn 2  Mn 2  Al 3  Mg 2 
called electrolytic cell.
Ca 2  Na   K   Li 
 In an electrolytic cell, electrical energy is  In some cases, the electrodes also may take part
converted into chemical energy in the electrolysis reaction. Such electrodes are
 In the electrolytic cell, a source of emf like called active electrodes.
battery is used Eg:In the electrolysis of NiCl 2(fused) using
 The medium through which the electrons enters nickel electrodes, the anode nickel dissolves
and leaves the electrolyte is called electrode. electrolytically as nickel ion.
Cathode(–): It is the electrode which is  Electrolysis of Water (to which some sulphuric
connected to the –ve terminal of the battery, and acid is added to make it good conductor)
through which the electrons enter the electrolyte between two platinum electrodes give H2(g) at
cathode and O2(g) at anode.
Electrolysis of some electrolytes  The unit for electrochemical equivalent is
gram/coulomb (g/c)
 Electrochemical equivalent depends only on the
nature of the electrolyte.
 Second Law: When the same quantity of
electricity is passed through different
electrolytes connected in series the weights of
the substances deposited will be in the ratio of
their equivalent weights.
 chemical equivalent weight of an element
atomic weight
= valency

W1 E1

W2 E2
setylortceE
l
W1 : W2= weights ratio
E1: E2 = equivalent weights ratio
 1Faraday of electric current (or) 96,500
coulombs of electricity (or) one mole of
electrons, when passed through an electrolyte
1G.E.W of a substance will be deposited.
 1 Faraday = 1 gram. eq. wt
Faraday’s Law of Electrolysis:Michel = charge on 1 mole of electrons
Faraday introduced laws of electrolysis to
 1 Faraday will deposit / Liberate (at STP)
explain the quantitative relationship between the
quantity of electricity passed into an eletrolytic a) 1.008 g / 11.2 lit of H 2
cell and the amount of substance electrolysed
b) 35.5 g / 11.2 lit of Cl2
or deposited.
 First Law: The amount of the substance c) 8 g / 5.6 lit of O2 d) 9 g of H 2O
deposited or electrolysed is directly proportional e) 9 g of Al f) 12 g of Mg
to the quantity of electricity passed through the
g) 23 g of Na h) 108 g of Ag
electrolyte
i) 31.75 g of Cu j) 32.75 g of Zn
W Q –– (1)
a) 1 mole of univalent ions  M 

W =wt.in grams  will be
Q = quantity of electricity in coulombs deposited by passing one Faraday.
Q= c x t —(2) Eg. Na  , Ag 
C= current in amperes
t= time in seconds b) 1 mole of bivalent ions  M 2  will be
w  ct ———(3)
deposited by passing Two Faradays
W  ect OR W  e Q —(4)
Mg 2 , Ca 2 , Fe2
 If c=1 ampere,t=1 second,Q=1 coulomb
 W= e c) 1 mole of trivalent ions  M 3  will be
 The weight of the substance deposited on the deposited by passing Three Faradays
electrode for 1 coulomb of electricity is called
electrochemical equivalent(e) Eg. Al 3 , Fe 3
 1 coulomb deposit W.E-3:
 gram equivalent weight  What is the ratio of weights of Ag and Al
=  96500 
  deposited at the respective cathodes when the
same current is passed for same period through
E
=  e(electrochemical equivalent )
F aqueous AgNO3 and Al2  SO4 3 solutions.
E E mass of Ag Equivalent weight of Ag
 W=
F
ct (or) W= Q
F Sol: mass of Al  Equivalent weight of Al

M M 108
 W ct (or) W  Q   12 :1
nF nF 9
W= wt of the substance deposited
Electrolytic solution resistance and
M= atomic weight of the element
conductance:
n = valency of the element
Aqueous electrolytic solutions also offer
F= 1 Faraday=96,500C resistance like metallic wires to the flow of
 1Faraday=Charge present on 6.023x10 23 current and obey Ohm’s law.
electrons  Ohm’s Law: It states that the current (I)
1 coulomb =6.25x1018 electrons flowing through a conductor at a given
temperature is proportional to the potential
W.E-1: difference (V) and inversely proportional to
resistance (R). Mathematically it can be
BaSO4 is ionic and PCl3 is covalent but a expressed as
saturated solution of BaSO4 is a weak
V  IR
electrolyte, While that of PCl3 is a strong
 Resistance (R) : It is the opposition to the flow
electrolyte. Explain? of current offered by the electrolytic solution.
Sol: BaSO4 has high lattice energy. It is very less Its units are ohm   
soluble in water, even in saturated solutions. The
 S.I base units of ohm =  kg m 2  /  S 3 A2 
ionic concentration is in the order of 105 M .
Hence it is a weak Electrolyte.  The resistance ‘R’ offered by the electrolytic
solution, taken in a conductivity cell, is directly
PCl3 is covalent. It undergoes hydrolysis in proportional to distance of separation ‘ l ’
water to give hydrochloric acid. Which is a between the two parallel electrodes of the cell
strong electrolyte. and inversely proportional to the area of cross-
section (A) of electrode i.e,
W.E-2:
l l
Solution of CuSO4 is electrolysed for 10 R or R  .
A A
minutes with a current of 1.5amperes. What is
where  = specific resistance (Resistivity).
the mass of copper deposited at the cathode?
 It can be measured with the help of wheatstone
Sol: CuSO4  Cu 2  SO42 bridge.
 Conductance (G) : It is the reciprocal of the
Ect 31.75 1.5 10  60
m  electrical resistance (R)
96500 96500
= 0.296 grams 1
G
R
 It measures the ease with which the current flows Resistance of solution is determined by the
through a conductor equation.
1 1 1 1 l l
G G  k R R
R  l/A l/A A kA
l The quantity l / A is called cell constant denoted
k  G 
A by the symbol, G*. It depends on
Where G = Conductance a) Distance between the electrodes
K  Specific conductance (Conductivity) b) Area of cross sections
l The cell constant is determined by measuring
= Constant known as cell constant G * . the resistance of the cell containing a solution
A
whose conductivity is already known.
Its units are cm-1 (or) m-1
 S.I unit of conductance = Siemens (S)
 1S = 1 ohm 1 ( or mho )
Specific Resistance (OR) Resistivity (  ) (unknown
resistance)
l l R2
 We know that R  R R1
A A
(or) R =  x cell constant Detector
Where  = Resistivity P
l = Length and A = area of cross section of the
conductor
l R4 R3
= cell constant  G * 
A
 The resistance in ohm of a conductor having
length of 1cm and area of cross - section 1cm2 is Oscillator
called resistivity (or) “The resistance offered by
1 cm3 solution of an electrolytic solution” is
RR
called resistivity (  ). Unknown resistance R 2  R
1 4

 Its units are ohm – cm 3

 S.I unit : ohm - metre  Instead of AC if DC is used it leads to


 1  m  100  cm a) Electrolysis resulting in the change of
concentration.
 1  cm  0.01  m
b) polarisation at the electrodes resulting in the
Measurement of conductivity of Ionic change of resistance.
solutions: Unknown resistance can be Specific, Molar and equivalent conductance
calculated using Wheatstone bridge. Resistance
The conductance (or) the current conducting
of ionic solution is measured by using an
capacity of an electrolytic solution can be
alternating current(AC) source of power and
expressed in terms of
specially designed vessel called conductivity
cell. a) Specific conductance (k) Kappa
Conductivity cell consists of two platinum b) Molar conductance (  m ),
electrodes coated with platinum black, whose
area of cross section equal to ‘A’ and are c) Equivalent conductance   
separated by distance ‘ l ’
 Specific conductance (k): It is the electrodes separated by a distance of unit length
reciprocal of specific resistance (  ) of 1 centimeter (in CGS system) or 1 meter (in
1 SI system) is called molar conductance (  m ).
k 
 Relation between specific conductance (k) &
l 1 1 l molar conductance (  m ) of an electrolytic
R  . ;  .
A G k A solutions, is as follows
l k  1000
k  G m 
A Molarity
Where
G = conductance k  S cm1  1000 cm3 / L
m  S cm2mol 1  
l Molarity  mol / L
= cell constant ( G * )
A
Units of  m :
l
Since : k  G  , if l = 1cm ; A  1cm2 then ohm-1.cm2 .mol-1 (in CGS system) (or)
A
mho.cm2 .mol-1 (in CGS system) (or)
k  G thus the conductance of 1cm3 of
electrolytic solution is called specific S. cm2 .mol-1 (in CGS system) (or)
conductance (k) ohm-1.m2 .mol-1 (in SI system)
(or)
1 S m 2 mol 1  104 S cm 2 mol 1
Similarly, the conductance of the electrolyte in 
the solution of volume of 1m 3 is known as  Equivalent conductance ( eq ) : It is the
specific conductance (k) Kappa conducting power of all the ions produced by
(or) dissolving 1 gram equivalent of an electrolyte
The conductance of the solution enclosed (or) The conductance of a volume of solution
between two parallel electrodes of unit area of containing 1 gram equivalent of the electrolyte
cross-section separated by a unit distance is placed between two parallel electrodes separated
called specific conductance (k) by unit length of 1 centimeter (in CGS units)
Its units are : (or) 1 meter (in SI units) is called equivalent
ohm-1 ×cm-1 (in CGS system) conductance ( eq ) .
(or) ohm-1m-1 (or)S×m-1 (in SI system) Relation between ‘k’ and  is as follows
 1 Scm 1  100 Sm 1 k  1000
Note:If l / A ( Cell constant ) = 1 then k = G  eq 
Normality
 The conductivity of solutions of different
electrolytes in the same solvent and at a given Units of  : - eq

temperature differs due to ohm-1.cm2 .equivalent -1 (or)


( i ) Charge and size of the ions in which they
dissociate. mho.cm2 .equivalent -1 (or)
( ii ) The concentrations of ions (or) ease with S.cm2 .equivalent -1 (in CGS system) (or)
which the ions move under a potential gradient.
 Molar Conductance (  m ): It is the ohm-1.m2 .equivalent -1 (in SI system)
conducting power of all the ions produced by Note:An electrolytic solution whose molarity is
dissolving equal to its normality has the same value for
1 gram mole of an electrolyte (or) molar conductance (  m )& equivalent
The conductance of a volume of solution
containing 1 gram molecular weight of the conductance (  e q )
electrolyte placed between two parallel Eg : KCl solution, NaCl solution
W.E-4: W.E-6:
Resistance of a conductivity cell filled with 0.1 The conductivity of 0.1 m KCl solution is
M KCl solution is 100 ohms. If the resistance
1.29 sm 1 . If the resistance of the cell filled with
of the same cell when filled with 0.02M KCl
solution is 520 ohms. Calculate conducivity 0.1M KCl is 100 ohm. Calculate the cell
and molar conductance of 0.02M KCl solution. constant.
–1
Conductivity of 0.1M KCl is 1.29 Sm . 1
Sol: k  G  G *  k   G
*
Sol: We know, R
Conductivity = Conductance x Cell constant 1
k = G x Cell constant G  k  R  1.29  100  129 cm .
*

1 Factors Effecting Molar & Equivalent


1.29   Cell constant
100 conductances:
Cell constant = 1.29 x 100m–1= 1.29 cm–1  Nature of electrolyte i.e, strong (or) weak
For 0.02 M KCl, R = 520 ohm  Nature of the solvent
Conductivity = Conductance x Cell constant  Viscosity of solvent
 Temperature
1
k  Cell constant  Concentration of electrolyte
R  Size of the ions produced & their solvation
1 Variation of Conductance with
  1.29  2.48  10 3 ohm 1cm 1
520 concentration: Specific conductance of a
solution increases with increase in the ionic
1000
We know,  m  k  concentration of the solution.
M
Reason :no. of ions per unit volume increases
1000
3
= 2.48  10  = 124 S cm2 mol–1  But equivalent and molar conductance decrease
0.02 with increase in concentration
W.E-5: Reason:decrease in ionic mobility and
The electrical resistance of a column of 0.05M increase in interionic attractions
NaOH solution of diameter 1 cm and length
 The specific conductance (k) or conductivity at
50 cm is 5.55x103 ohm. Calculate its resistivity,
any specified concentration of an electrolyte
conductivity and molar conductivity.
depends on the nature of the electrolyte.
Sol: Area of cross-section
 Strong electrolytes show high conductance
=  r 2  3.14  (0.5) 2 cm 2 = 0.785 cm2 while weak electrolytes show low conductance
1 at any given concentration
We know, R    The variation of equivalent conductance   
A
50 (or) molar conductance (  m ) with the
5.55  103   
0.785 concentration of the electrolyte is generally
Resistivity,   87.135 ohm cm expressed graphically, as follows.
1 1
Conductivity, k    0.01148 S cm 1
 87.135
Molar conductivity  m can be calculated as,
1000
m  k 
M
1000
 0.01148  = 229.6 S cm2 mol–1
0.05
 It indicates that the variation of  with W.E-7:
concentration depends to a great extent on the Why does the conductivity of a solution
type of the electrolyte rather than on the actual decreases with dilution?
chemical nature of it. Sol: Conductivity of an electrolyte solution depends
 Thus equivalent conductance    (or) molar on the number of ions present per unit volume.
On dilution, the number of ions present per unit
conductance (  m ) of electrolytic solution volume decreases, therefore, conductivity also
increases with decrease in concentration. decrease.
 For strong uni-univalent electrolytes (Eg. KCl),
Effect of Temperature: The conductivity
the decrease in  with increase in concentration
of all electrolytes increases with increase in
is not very large.
temperature
 If electrolyte is not uni-univalent electrolyte then
decrease in  with concentration is more Conductance Ratio   : The ratio of the
marked as the valency of the ions increases. equivalent conductance at any concentration
They behave in an intermediate manner.
 c  to that at infinite dilution   0  is called
Eg : NiSO4 ; K 2 SO4 (Uni-bivalent),
conductance ratio   .
BaCl2 (Bi-Univalent)

 Weak electrolytes  Eg : CH 3COOH , NH 4OH  exhibit c



an apparently different behaviour as they are not o
ionised completely. For weak electrolytes,  = degree of ionisation.
EFFECT OF DILUTION : Note:  is high for 0.01 M CH 3COOH
solution when compared to that of 0.1 M
 With dilution “  ” as well as “  m ” of both
CH 3COOH , because  C is high in case of 0.01
weak/strong electrolytes increases.
 Specific conductivity (k) decreases with dilution M CH 3COOH
because of decrease in no.of ions per cm 3 of Debye - Huckel Onsager Equation
electrolyte.  In the case of weak electrolytes like
 The molar (or) equivalent conductance of an CH 3COOH ,  is known as degree of
electrolyte at infinite dilution (or) zero dissociation (or) degree of ionisation of
concentration is known as limiting molar electrolyte.
conductance (or) limiting equivalent  The equivalent conductance at large dilution (or)
conductance. at very low concentration is known as equivalent
  0 value for any strong electrolyte is calculated conductance at infinite dilution     or Zero
by graphically but for weak electrolyte it is
determined by kohlrausch’s law. concentration   o 
 The magnitude of increase in molar conductance
 The equivalent conductance of an electrolytic
for weak electrolyte is much larger than that for
solution at any concentration (C) is related to
a strong electrolyte because strong electrolytes
are almost completely ionised in all  o for solutions is given by the following
concentration and increase in  eq (or)  m with Debye-Huckel - Onsager equation.
dilution is only due to decrease in interionic  82.4 8.2  10 5 
attractions. C  o     o
 C
  DT   DT 
1/ 2 3/ 2

 
Where
Io n Ionic Ion Ionic
D = Dielectric constant of water conductance conductance
T = Temperature in kelvin scale ( ( 0 )ohm 1 ( 0 )ohm 1
 C = Equivalent conductance at conc ‘c’
H 349.83 Na 50.11
 o = equivalent conductance at almost zero K 73.52 NH 4 73.40
concentration or infinite dilution. Ag  61.92 Cl  76.34
 = viscosity co-efficient of solvent.
Br  78.40 I 76.80
In short form this equation is represented
OH  198.50 NO3 71.44
as
CH 3COO  40.89
c  0  b C
Where b is constant and depends on the nature Statement of Kohlrausch’s Law :
of the solvent and temperature. “The equivalent conductance at infinite dilution
Variation of Equivalent Conductance with (   ) of an electrolyte is equal to the algebric
sum of equivalent condutances (or) mobilities
CONCENTRATION is as follows
of anion  0  and cation    of the electrolyte
 
 It is a straight line with negative slope. 0

at infinite dilution”
 0  electrolyte    0   0  ions 

1  1 
eq  c   a
n n

e.g. (i) KCl  K    Cl

1
 This is not applicable for weak electrolytes (ii) CaCl2  Ca    Cl
2
Kohlrauch’s Law of independent  1  
(iii)  AlCl3   Al3    Cl
migration of ions: Based on  (specific 3
conductance) value, electrolytes are of two ° 1 ° 1 °
types. (iv) ΛFe2 SO4  = 3 λ Fe3+ + 2 λSO2-
3 4
1) weak electrolytes: These have low ‘  ’ value In the above Λ = Equivalent Conductance.
Eg : weak acids, weak bases.
λ = Molar Conductance
2) Strong electrolytes:These have high ‘  ’ value
Eg : strong Acids, strong Bases, Salt solutions. where n and n are charge on each ion
 The conductance of an electrolyte is due to it’s furnished by electrolyte. This law is valid at any
ionisation. dilution but is applied only at infinite dilution.
 The ionisation extent reaches maximum for Whereas “molar conductivity of an electrolyte
weak electrolytes as dilution reaches maximum at infinite dilution is the sum of the ionic
conductivities of the cations and the anions each
Note: Cl. CH 2COOH has higher ‘  ’ value than multiplied by the number of ions present in one
CH 3COOH since Cl.CH 2COOH is stronger formula unit of electrolyte” e.g. A xB y
acid than CH 3COOH  M  x   A y   y   B x 

 Kohlrausch determined the  0 (equivalent   


e.g (i)  BaCl2   Ba   2 Cl
conductance at infinite dilution) for some pairs   
of strong electrolytes having common anion (or) (ii) Fe2 SO4   2Fe3   3SO2
3 4
cation
Note: Ionic conductance is more for hydrated Cs  . speed of the ion
 Ionic mobility  
than hydrated Li 
potential gradient
 Applications: Determination of  0 for weak  Potential gradient
electrolytes. Potential difference between electrodes
=
Eg : NH 4OH is a weak electrolyte its  0 is Distance between electrodes
calculated as
W.E-8:
0  NH4OH   0  NH4Cl   0  NaOH   0  NaCl 
Calculate  0m for CaCl2 and MgSO4 using
 Degree of ionisation of weak electrolyte
following data

   c 0
Ca 2
2  119 S cm mol
1
;
 0

 c =equivalent conductivity at given concentration Cl0   76.3 S cm2 mol 1


0 = limiting equivalent conductivity 0 2 1
Mg 2  106 S cm mol

 Dissociation constant of weak electrolyte K=c 2 0 2 1


SO 2  160 S cm mol

m olecular w eight
4

0 0
  m  eq  Sol: 0m CaCl2  Ca
0 0
2  2 
equivalent w eight Cl
= 119 + 2 x 76.3 = 271.6 S cm2 mol–1
0 0
Expression for K :  m  n   e q u  0m MgSO4  Mg
0
2  
0
SO 24

 Calculation of dissociation constant of weak =106+160=266 S cm2 mol–1


electrolytes.
2
W.E-9:
  The equivalent conductances of sodium
C C 
C 2  C C2
K K  0  chloride, hydrochloric acid and sodium acetate
1   C  0  0  C  at infinite dilution are 126.45, 426.16 and 91.0
1  
 0  ohm –1 cm 2 equiv –1 , respectively, at 25 0C.
Calculate the equivalent conducatance of
Solubility of sparingly soluble salts : acetic acid at infinite dilution.
ksalt 1000 k 1000  0m (HCl) = 426.16 S cm2 mol–1
0m  (or) Sin moles/lit  salt 0
solubility m
 0m (NaCl) = 126.45 S cm2 mol–1
k salt =specific conductance of sparingly soluble
 0m (CH3COONa)=91 S cm2 mol–1
salt
Sol: According to Kohlraush’s law,
Solubility product of salt can be calculated from
solubility.   CH3COONa  CH COO  Na  91.0 ---(i)
3

salt  solution  solvent   HCl  H   Cl   426.16 ---- (ii)


solution= Specific conductance of saturated
  NaCl  Na   Cl   126.45 ---- (iii)
solution
Adding eqns. (i) and (ii) and subtracting (iii),
 solvent = Specific conductance of solvent
CH 3COO   Na   H   Cl   Na   Cl 
 Ionic mobility: Ionic mobilities can be
= 91.0 + 426.16 – 126.45
   
calculated as :    ,   F  96,500 CH 3COO   H    CH 3COOH
F 96,500
= 390.7 ohm–1cm2equiv–1
W.E-10: Degree of dissociation ‘  ’ may be calculated as
The conductivity of 0.001028M acetic acid is  m HCOOH 46.1
4.95 ×10-5Scm–1. Calculate its dissociation constant    0.114
 m HCOOH 404.2
0

if  0m for acetic acid is 390.5Scm2 mol–1.


Sol: We know, Let us consider the ionisation of HCOOH.

1000 HCOOH  HCOO   H 


m  k  -----(i) t=0 C 0 0
M
teq. C–C  C C
Given : k=4.95 x 10–5 S cm–1 ; M=0.001028
Dissociation constant of formic acid may be
5 1000 calculated as,
 From (i)  m  4.95  10 
0.001028
 HCOO    H  
= 48.15 ohm cm2 mol–1 K
–1

Degree of dissociation,  HCOOH 


 Cm 48.15 C  C C 2
   0.1233  
 0m 390.5 C  C 1  
CH 3COOH  CH 3COO   H  0.025  (0.114)2 3.249 104
K  =3.667x10–4
t=0 C 0 0 1  0.114 0.886
teq. C–C  C C
Dissociation constant, Electrochemical Cells: The cell in which
CH 3COO   H  
 chemical energy is converted into electric
K energy is called electrochemical cell.
CH 3COOH   First electrochemical cell was constructed by
Volta and Galvani, so it is called as Voltaic (or)
C  C C 2
  Galvanic cell.
C  C 1  
Substituting the values of ‘C’ and ‘  ’ in above e voltmeter
equation, we get,
Anode(-) cathode(+)
0.001028  (0.1233) 2
K  1.78  105

NO 3 K

1  0.1233 ' Zn' rod 'Cu' rod

salt bridge

W.E-11:
The molar conductivity of 0.025 mol L –1
methanoic acid is 46.1 S cm2 mol–1. Calculate
cot ton plug
its degree of dissociation and dissociation
constant. ZnSO4 Soln CuSO 4 So ln

Given H0  = 349.6 S cm2 mol–1


Galavanic Cell
HCOO
0

= 54.6 S cm2 mol–1  A metal dipped in its ionic solution works as an
electrode.
Sol: We know,
 Zinc rod is dipped in zinc sulphate solution
HCOOH  H   HCOO  works as anode.
 0m HCOOH  H0   HCOO
0

 Zinc undergo oxidation, gives electrons, It is
electron rich, so represented by negative sign.
= 349.6 + 54.6
= 404.2 S cm2 mol–1 Zn  Zn   2e 
 Cu rod dipped in CuSO 4 solution acts as Reversible Cell : A voltaic cell may be
cathode. reversible or irreversible.
 Cu+2 present in the solution undergo reduction  The anodic and the cathodic reactions in a
on Cu rod surface. Cu rod is electron poor, so it reversible Galvanic cell are always in a state of
is represented by positive sign. equilibrium.
 A reversible cell shall satisfy the following
Cu 2  2e  Cu
conditions.
 Electrons flow in the external circuit from Zn a) When the cell is connected to an external
to Cu. source( a battery) , whose emf is exactly equal
 Two portions of the cell are also called half-cells to that of voltaic cell, no current flow in the
(or) redox couples. voltaic cell.
 A salt bridge is used to prevent the accumulation b) If the emf of the external battery is more than
of charges, at the electrodes the emf of the voltaic cell, current flows from
 Saltbridge is an inverted U- shaped tube, filled the battery into the voltaic cell.
with Agar–Agar gel which is saturated with an c) If the emf of the external battery is less than
electrolyte KCl (or) KNO3(or) NH4 NO3 the emf of the voltaic cell the current flows from
 The solution of KCl (or) KNO3(or)NH4NO3 acts the cell to the battery.
as inert electrolyte.
 The reaction taking place in the electrochemical Difference between Electrochemical
cell is a redox reaction. Cell and Electrolytic Cell
Zn  s   CuSO4  aq   ZnSO 4  aq   Cu  s 

 In Daniel cell instead of salt bridge, porous pot


(or) porous diaphragm is used.
e voltmeter

Anode(-) cathode(+)

' Zn' rod 'Cu' rod

Porous
draphragm

ZnSO4 Soln CuSO 4 So ln

 Daniel cell is also an electrochemical cell.


 Daniel cell(Galvanic) is a reversible cell.
 During the working of galvanic cell and with Representation of Galvanic Cells
the passage of time the following changes takes
place
(IUPAC Convention )
a) spontaneity of the cell reaction decreases  In writing the electrochemical cell, keep anode
(or) oxidation electrode in the left hand side
b) Ecell decreases and reduction electrode or cathode in the right
c) reaction quotient Q increases. hand side.
 Electrode can be represented by semicolon (or) Single Electrodes : A metal rod immersed in
single vertical line. the aqueous solution of its salt or a gaseous non-
 Double vertical line represents salt bridge. metal in contact with the aqueous solution of
Eg: Galvanic cell its anion in the form of salt (or acid or alkali)
Zn  s   CuSO4  aq   ZnSO4  aq   Cu  s  function as single electrodes.
Metal Electrodes :
Zn | Zn 2  c  || Cu 2  c  | Cu
1. Zinc electrode : Zn| ZnSO4 aqueous solution
Zn | ZnSO4  c  || CuSO4  c  | Cu
2. Copper electrode : Cu | CuSO4 aqueous solution
Zn | Zn  c  || Cu
2 2
 c  | Cu 3. Magnesium electrode: Mg | MgSO4 aqueous
 If it is Daniel cell solution
Zn; Zn 2  c  || Cu 2  c  ; Cu 4. Silver electrode: Ag | AgNO3 aqueous solution
 In case of a Galvanic cell with a non-metal 5. Iron electrode : Fe | FeSO4 aqueous solution;etc.
electrode, inert metal like Pt rod (wire) is
introduced in solution which acts as electrode. Non metal electrodes:
A Galvanic cell containing H 2 and Cl2 gases 1. Hydrogen electrode: H+(aq) / H2(g),Pt
as electrodes in an HCl solution is 2. Chlorine electrode : Pt;Cl2(g) / Claq
represented as, 3. Oxygen electrode : Pt;O2(g) / OH
Pt , H 2 g   P1 atm  | HCl aq   C mol / L  | Cl2  P2 atm , Pt 
4. Bromine electrode : Pt;Br2(g) / Br aq 
Electromotive Force of the cell (emf of  Single Electrode Potentials :A metal (or)
the cell):The difference between two electrode non–metal in contact with the solution of its ions
potentials present in the electrochemical cell is tends to develop electric potential at the metal/
called electromotive force of the cell. metal ion (or) non–metal/ non–metal ion
 EMF of the cell = Left hand electrode oxidation interface. It is called single electrode potential.
potential + Right hand electrode reduction  Electrode potential(E): The potential
potential difference developed between the electrode and
= LHE oxidation potential – RHE oxidation the electrolyte is called electrode potential.
potential
 Standard Electrode potential(E 0 ):
= RHE reduction potential – LHE reduction
according to IUPAC convention, standard
potential
reduction potentials are now called standard
= LHE oxidation potential + RHE reduction
electrode potential.
potential
 The magnitude of the potential (E) depends on
= Eright – Eleft a) Chemical nature of the metal or the non–metal
= Ecathode – Eanode b) The number of electrons transferred (n) in
 High reduction potential metal electrode works the half cell reaction namely
as right hand electrode (or) cathode or reduction Mn+ + ne–  M (M=metal)
electrode in the correct electrochemical cell. A+ne–  An– (A=non metal)
 If EMF of the cell is +ve , cell reaction is c) The concentration of the ions(c) (Mn+ or An–)
spontaneous or irreversible. We can draw current in the solution.
from it. d) The temperature of the system(T)
 If EMF of the cell is negative(–ve), cell reaction  250c (or) 298K, 1 atmosphere pressure are called
is non– spontaneous or reversible . We cannot standard conditions.
draw the current from it. The cell does not work.  standard reduction potential (E0) of the metal
 If EMF of the cell is zero, cell reaction is at measured at standard conditions, using (Mn+) as
equilibrium. unit concentration.
 The reduction potential of an electrode is other half cell as cathode gives the reduction
exactly equal in magnitude but opposite in sign potential of the other half cell (concentration of
to its oxidation potential. the oxidised and reduced species taken as unity).
 Measurement of Electrode Potential: 0
Ecell  ER0  EL0 as EL0 for SHE is zero
Single electrode potential cannot be determined
0
experimentally by taking single electrode. Ecell  E R0  0  E R0
Therefore, this single electrode is combined with Eg. The measured emf of the cell
a second single electrode and the emf of the cell
is determined by using a potentiometer. Pt( s ) H 2(1atm ) / H (1 M ) / /Cu(12M ) / Cu( s ) is
 The second electrode is an electrode of exactly 0.34 V and it is also the value of standard
known potential and is called as reference electrode potential of the half cell corresponding
electrode.
 The hydrogen electrode is the earliest reference to the reaction. Cu(12M )  2e  Cu( s )
electrode,  The positive value of standard electrode
 Hydrogen electrode consists of H2 gas at 1 potential in the above example indicates that
atmosphere pressure in contact with H+ ions of Cu+2 ions gets reduced more easily than H+ ions
unit activity
 A saturated calomel electrode Hg/Hg2Cl2(S),KCl
 Pt, H 2 (g)/ H + (aq)(C=1). The potential of
(solution) is now used as a secondary reference
hydrogen electrode is assumed as zero volts.
electrode.
 Hydrogen electrode is also called as Normal
Hydrogen Electrode (NHE) or standard  The potential of saturated calomel electrode is
Hydrogen Electrode (SHE) –0.2422 volts (SRP).
 Hydrogen electrode is a reversible electrode.
Nernst equation is applicable only for reversible
electrodes.
 Reduction Potential of Hydrogen electrode
H2  g = –0.059 x PH
 at1atm   Oxidation Potential of Hydrogen electrode
= +0.059 x PH

Electrochemical Series: In the IUPAC


H3 Oaq.
system of referring the electrode potentials,
1M standard reduction potentials are simply called
Pt black
a standard potentials.
electrode
 In the electrochemical series, the metals are
arranged in the increasing order of reduction
potentials.
 High reduction potential metal ions undergo
reduction first on cathode or it acts as cathode
 A small platinum foil coated with platinum black
in the electrochemical cell.
is used as electrode in Hydrogen electrode.
 The Pt electrode is partially immersed in the  Low reduction potential metal (high negative
solution and is partially exposed to the value) undergo oxidation (or) it acts as anode.
atmosphere of H2 gas. It is more reactive (or) more electro positive.
 At 298K the emf of the cell , standard hydrogen  In the electrochemical series metal placed
electrode || Second half cell constructed by above can displace the below metal ions from
taking SHE as anode (Reference electrode) and their solution.
ELECTROCHEMICAL SERIES(ECS) : Pt,Br2 / 2Br – +1.065
Electrode E o (V) (SRP) standard
Pt,Cl2 / 2Cl– +1.360
System Reduction potential Au+3 / Au +1.50
Li+ / Li –3.045 MnO 4 / Mn 2  +1.51
Cs+/Cs –2.95
Rb+ / Rb –2.93 H 2O2 / H 2O +1.78
K+ / K –2.925 Co 3 / Co 2 +1.81
Ba+2 / Ba –2.90 Pt,F2 / 2F– +2.87
Sr+2 / Sr –2.89
Ca+2/Ca –2.870 Useful Conclusions:A negative E0 means
Na+ / Na –2.714 that the redox couple is a stronger reducing
Mg+2 / Mg –2.375 agent than the H+/H2 couple.
Al+3 / Al –1.66  A positive E0 means that the redox couple is a
weaker reducing agent than the H+/H2 couple.
Mn+2/Mn –1.18
 The metal with higher negative potential
H 2O / H 2 –0.83 displaces a metal with lower negative potential
Zn+2/Zn –0.762 (or) positive potential (i.e. all metals below it in
Cr+3/Cr –0.74 the series ) from the aqueous salt solution of the
Fe+2/Fe –0.441 metal.
Eg: a).Zn displaces all metals underneath it in
Cd+2 / Cd –0.403
the electrochemical series from their aqueous
Co+2 / Co –0.277
salt solutions.
Ni+2 / Ni –0.250
Sn+2 / Sn –0.140 Zn  CdSO4 aq   ZnSO4 aq   Cd 
Pb+2/Pb –0.126 b) Similarly
H+ / H2, Pt  0.000 Ni  PbSO4 aq   NiSO4 aq   Pb 
AgBr/Ag +0.10
AgCl/Ag +0.22 Cd  CuSO4 aq   CdSO4 aq   Cu 
Cu+2/Cu +0.337  All metals with higher negative potentials are
Cu+/Cu +0.52 stronger reducing agents than the metals with
lower negative potentials or positive potentials.
Pt, O2 / OH  +0.401
Ex: Li  K  Ca  Zn  Fe  Cu
Pt,I2 / 2I– +0.536  The metal ion of the metal with lower negative
 potential or higher positive potential is a better
O 2 , 2H / H 2 O 2 +0.68
oxidising agent than the metal ion of the metal
Fe+3/Fe+2,Pt +0.771 with higher negative potential or less positive
Hg+ / Hg +0.790 potential.
Ag+ / Ag +0.800 Ex. Ag   Cu    Sn    Ni    Fe 3  Zn  
Hg 2  / Hg 22  +0.92  Oxidising power  reduction potential
1
NO 3 / NO +0.97 
oxidation potential
MnO 2 / Mn 2  +1.23 Reducing power  oxidation potential
O2 / H 2O +1.23 1

reduction potential
Cr2 O 72  / Cr 3 +1.33
 Fluorine with highest reduction potential is the From thermodynamic relation G   nFEcell
best oxidant. Lithium with least reduction
potential the best reductant in aqueous medium and G 0  nFEcell
0

based on the potentials.  According to the thermodynamic equation


 The more negative the reduction potential, the
more reactive the metal. G  G 0  RTlnQ
 Metals above hydrogen displace hydrogen from 0
 nFEcell   nFEcell  RTlnQ
dilute acids
RT
 M  Na , Mg , Al , Znetc   H 2  .
M M
Cu 
 M Cu , Ag , Au ,etc  aq HCl 
0
Ecell  Ecell  lnQ
 Cu does not dissolve in HCl. nF
 In nitric acid Cu is oxidised by nitrate ion and 0
Ecell = emf of the cell under standard conditions
not by hydrogen ion.
Ecell = emf of the cell at the given concentration
W.E-12: n = number of electrons involved in the reaction
Can you store copper sulphate solutions in a F = Faraday = 96500 coulombs
zinc pot? T = absolute temperature.
0
EZn 2
0
 0.76V , ECu 2  0.34V R = gas constant = 8.314 joule mole–1 K–1
/ Zn / Cu
Sol. Since the standard reduction potential of Zn is Q = reaction quotient
less than that of copper, hence zinc metal will 0 2.303RT
Ecell  Ecell  log Q
reduce Cu2+ ions present in aqueous solution of nF
copper sulphate. Thus, we can not store copper
sulphate solution in a vessel of zinc. 0 0.059  2.303RT 
Ecell  Ecell  log Q   0.059 
Zn( s )  CuSO4 (aq )  ZnSO4 (aq )  Cu
n  96500 
0
ERedox 0 0 0.059  product 
process  EReducedspecies  EOxidisedspecies
0
Ecell  Ecell  log
= + 0.34 – (–0.76) = + 1.10 V
n  reactant 
Positive value of E0 confirms that above redox (or)
process is spontaneous and hence we cannot 0.059  oxidised form 
0
store copper sulphate solution in a vessel of zinc. Ecell  Ecell  log
n  reduced form 
W.E-13: For Cation Electrodes:The Nernst equation
for single electrode potential  EM n / M  at 298
Consult the table of the standard electrode
potentials and suggest three substances that
can oxidise ferrous ion under suitable K is
conditions. M (naq )  ne  M ( s )
0
EFe3
/ Fe2
 0.77 V RT 1
E  E0  ln
Sol. Only those species can oxidise ferrous ions nF c
(Fe2+) whose standard reduction potential is
2.303 RT 1
more positive than 0.77 V. Thus, suitable E  E0  log
nF c
oxidising agents will be F2, Cl2, Br2.
0 0.059
 EE  n
log c
EMF of Galvanic Cell-Nernst Equations
 The variation of electrode potential and cell (or)
potentials with concentration of ions in solution 0 0.059
ERP  ERP  log  M n   (c=[Mn+])
is given by NERNST equation. n
For Anion Electrodes :If a non-metal / non- Current Efficiency: % of current efficiency
metal ion is present as electrode, then Nernst mass actually produced
equation for single electrode potential at 298 K
=  100
mass of substance exp ected

is Over voltage : The difference between the


voltage at which a gas is actually evolved and
2.303 RT theoretical value at which it ought to have been
E  E0  log C
nF evolved during electrolysis is called over
voltage.
0.059
E  E0  log C
n For Hydrogen Electrode :
 2H  2e  H2  g
 
0.059
E RP  E RP
0
 log  A n   (C=[A–]) Patm.  
n 0.059 PH2
0
ERP  ERP  log
EMF of a cell and free energy: n H 
2 ( E  0.059  P H )
 Relation between EMF of cell and free energy
Concentration cells: An electrochemical
G  nFEcell cell in which EMF produced is due to difference
in concentration of either electrode or
 Ecell is intensive property but G is an electrolyte.
extensive thermodynamic property and the value These are of two types :
depends on ‘n’. 1) Electrolyte concentration cell.
2) Electrode concentration cell.
Eg. Zn( s )  Cu(aq2 )  Zn(aq2 )  Cu( s ) , G  2 FEcell  Electrolyte concentration cell :
In this type of a cell electrodes in both the half
but when we represent equation as
cells are made up of same substance and
2 Zn( s )  2Cu (aq2 )  2 Zn(aq2 )  2Cu ( s ) , electrolyte is the solution of same substance but
with different concentration
G  4 FEcell Eg:1) Zn rods dipped in two half cells containing
 Standard free energy change (Concentration of ZnSO4 solution of two different concentration
reacting species taken as unity) is represented as
  C1  | Zn aq   C2  | Zn s 
 2
Zn s  | Zn2aq
G  nFE
0 0
cell

 The EMF of a chemical cell is positive, when 2) H 2 g  electrode dipped in aqueous solution
the free energy of reaction is less than zero (or) H 2 g   P atm  | HCl aq   C1  || HCl aq   C2  | H 2 g   P atm 
negative. 0.059 C
Ecell  log 2
Free energy and Equilibrium Constant n C1
Go  2.303RT log K (or) Go  RT ln K If C2  C1 , the cell is spontaneous
 Electrode concentration cell : In this type
G 0 is negative for a cell reaction to be of cell two electrodes of same substance but with
spontaneous different concentration are dipped into same
Relation Between EMF and Equilibrium solution.
constant Eg : Two H 2 g  electrodes of two different
 G 0   nFE 0cell pressures are dipped in HCl solution.
The cell is represented as
G o  2.303RT log K Pt , H 2 g   P1 atm  | H  aq   C  || H 2 g  ,  P2 atm  | Pt
0.059 P
Hence E 0cell  0.059 log K Ecell  log 1
n n P2
Thermo dynamic efficiency of the cell W.E-15:
 nFE Calculate the potential of hydrogen electrode
 in contact with a solution whose pH is 10.
H
Sol: If pH of solutions is 10 then its [H + ] ion
 If two half cell reactions having electrode
concentration will be 10–10M.
0 0
potential E1 and E2 are combined to give a third Let us consider a reduction half cell
half cell reaction having an electrode potential H+ (10–10M) | H2 (1 atm) | Pt
0 Electrode process :
E3 then
2 H  (10 10 M )  2e   H 2 (1 atm) (n  2)
G 03  G10  G 02
PH 2 1
n 3 FE30  n1FE10  n 2 FE02 or Q 2
 2
 1020
 H  
10  10

0n E 0  n 2 E 02
E  1 1
3
n3 According to Nernst equation
If number of electrons involved are equal then 0.059
EH  / H  EH0  / H  log Q
E03  E10  E02
2 2
n
 Gibbs Q vs K Cell Spontaneous  0
0.059
log1020  0.59 V
Free energy potentials direction 2
G  0 Q<K Ecell  0 Forward
W.E-16:
G  0 Q=K Ecell = 0 Equilibrium
Calculate the equilibrium constant for the
G  0 Q>K Ecell > 0 Backward reaction
Cu ( s )  2 Ag  (aq )  Cu 2  (aq )  2 Ag ( s )
W.E-14:
Represent the cell in which following reaction Ecell
0
 0.46 V
Sol. We know
takes place and Calculate Ecell if Ecell
0
 3.17V
 nE 0 
Mg (s)  2 Ag  (0.0001M )  Mg 2 (0.13M )  2 Ag (s) K=Antilog  
 0.059 
Calculate Ecell if Ecell
0
 3.17V
Sol. The cell may be represented as  2  0.46 
= Antilog 
 0.059 
= 3.92 x 1015
Mg ( s ) | Mg 2 (0.13M ) || Ag  (0.0001M ) | Ag ( s )
The cell reaction may be given as, W.E-17:
2 
Mg ( s )  Mg (0.13M )  2e The cell in which the following reaction
occurs: 2 Fe3 (aq )  2 I  (aq )  2 Fe 2 (aq )  I 2 ( s )
2 Ag  (104 M )  2e   2 Ag ( s )
has Ecell
0
 0.236 V at 298K. Calculate the
Mg ( s )  2 Ag  (104 M )  Mg 2 (0.13M )  2 Ag ( s )
standard Gibbs free energy and the equilibrium
 Mg 2   Ag 
2
0.13  1 constant of the reaction.
Q  4
 0.13  108 Sol: G 0   nFE 0
 Mg   Ag  1 (10 )2
 2

= –2 x 96500 x 0.236 J
According to Nernst equation = –45548 J = -45.548 kJ

E  E0 
0.059
log10 Q  nE 0 
n K= Antilog  
 0.059 
0.059 2  0.236
 3.17  log(0.13  108 ) = 2.96V  108
2 = Antilog
0.059
W.E-18: Secondary Cells:
In the button cells widely used in watches and  i) Electrical energy from an external source is
other devices the following reaction takes first converted into chemical energy
place: (Electrolysis ) and when the source is removed
Zn( s )  Ag 2O ( s )  H 2O ( I )  Zn 2  (aq )  2 Ag ( s ) then the cell is made to operate in the reverse
direction.
2O H  (aq )
ii) Secondary cells are those which can be
Determine G 0 and E 0 for the reaction rechargeable and used again and again.
Zn( s )  Zn 2  2e  E0 = –0.76 V iii) These are designed to convert the energy
from combustion of fuel such as
Ag 2O  H 2O  2e   2 Ag  2OH  E0 = +0.34 V
H 2 , CO, CH 4 , etc., directly into electrical
Sol. Ecell
0
 Ecathode
0
 Eanode
0
energy.
= 0.34–(–0.76) = 1.10 V iv) The common examples are hydrogen-
G 0   nFE 0 oxygen fuel cell, Hydrocarbon fuel cell Ni-Cd
= –2 x 96500 x 1.10 = –2.123 x 10–5 J cell, Lead accumulator, Li-ion battery.
v) Acid storage cell is Lead accumulator and
W.E-19: Alkali storage cell is Edison Battery
The standard electrode potential for Daniel cell  Fuel Cells: The cell (or) device that converts
is 1.1 V. Calculate the standard Gibbs free heat of combustion obtained by burning gases
energy for the reaction :
like H 2 , CH 4 , CO etc., directly into electrical
Zn( s )  Cu 2 (aq )  Zn 2 (aq )  Cu ( s )
energy.
Sol. We know,
 First fuel cell was developed by Sir William
G 0   nFE 0 ---(i)
Grove using Pt - electrodes and H2 &O2 gases .
n=2 for the given reaction
F=96500C, E0 = +1.1V  Fuel cells are more advantageous than ordinary
 from (i) batteries in the following respects;
G 0  2  96500  1.1 i) High efficiency.
= –212300 J In ' H 2  O2 ' fuel cell 60-70% efficiency has
been attained wheres as in conventional
Some Commercial Cells and Batteries methods, only 40% efficiency is attained.
i) The electrochemical cells can be used to ii) They can be used continuously. There is no
generate electricity. need to replace electrodes.
ii) The word battery is used for two (or) more iii) They don’t cause pollution problems.
galvanic cells generally connected in series.
iii) There are two types of commercial cells: Eg : in ' H 2  O2 ' fuel cell, H 2O is product
Primary Cells: iv) Silent operation.
 i) It is an electrochemical cell which acts as a  Theoretically 100% efficiency.
source of electrical energy without being  General representation of fuel cell :
previously charged up by an electric current from
Fuel/electrode/ electrolyte/ electrode / oxidant
an external source of current.
ii)In which electrode reactions cannot be
reversed by external source. W.E-20:
iii) These are not chargeable. Suggest two materials other than hydrogen
iv) Examples of this type is dry cell (or) that can be used as fuels in fuel cells.
Leclanche cell, voltaic cell. Ans.Methane, Methanol
Hydrogen-Oxygen Fuel Cell: Hydrocarbon-Oxygen Fuel Cell:
 H 2 is bubbled through electrolyte at anode. It  Hydrocarbons are burned in oxygen at high
temperature to get large amount of electrical
undergoes oxidation.
energy.
 O2 is bubbled through electrolyte at cathode. It  Air freed from impurities (or) pure oxygen is
undergoes reduction. oxidant.
 Porous graphite rods acts as electrodes. They
 KOH  aq  is used as electrolyte.
are coated with Pt, Ag (or) CoO which acts as
catalyst.  Pt electrodes are used.
 Reaction at anode :  H 3 PO4 is used as electrolyte if hydrocarbon is
2  H 2  g   2OH   aq   2H 2 O l  2e   burned. It is because the obtained CO2 in

Cathode : O2 g   2H 2Ol   4e  4OH  aq  combustion is absorbed by KOH  aq  .


 

 It is costlier.
Overall reaction : 2 H 2 g   O2 g   2 H 2Ol   Fuel cells may be liquid fuel cells (or) gas fuel
 Electrolyte is concentrated NaOH  aq  / KOH aq . cells.
 In liquid fuel cells
 Fuel cells are even used in space crafts Eg :
CH 3OH , C2 H 5OH , HCHO, N 2 H 4 are used as
Apollo gemini air ships utilised ' H 2  O2 ' fuel
cell. fuels. In gas fuel cells - H 2 , C n H 2 n  2 , CO are
 The heat of combustion is directly converted to used as fuels.
electrical energy.  Fuel cells a)working below 100°C are low
temperature cells.
b)working between 100-250°C are medium
temperature cells .
c) working above 500°C are high temperature
cells.
 O2 , air, H 2O2 , HNO3 are used as oxidants.
 Pt, Porous PVC, PTFE coated with Ag are used
as electrodes.
 In biochemical cells organic compounds
disintegrated by micro organisms. These are in
use now a days.
G0m
Note:Efficiency of fuel cell =
H0m
Corrosion: The natural tendency of
conversion of a metal into its mineral compound
form on interaction with the environment
(Polluted air, water, associated other Metals etc)
is known as corrosion.
Ex : Iron converts itself into its oxide ( Fe2O3 -
haematite).
Copper converts itself into its carbonate
( CaCO 3 .Cu  OH 2 - Malachite).
Silver converts itself into its sulphide ( Ag 2 S -
horn silver).
 Corrosion of iron by conversion into iron oxide W.E-21.
is known as rusting. Explain how the rusting of iron is envisaged
 Corrosion of silver by conversion into its as setting up of an electrochemical cell.
sulphide is known as tarnishing. Sol. Formation of carbonic acid takes place on the
Mechanism: surface of iron:
H 2O (l )  CO2 ( g )  H 2CO3  2 H   CO32 
In presence of H+ ion, oxidation of iron takes
place Fe( s )  Fe 2 (aq)  2e 
The electrons are used at other spot where
reduction takes place :
O2 ( g )  4 H  ( aq )  4e   2 H 2O (l )
Overall reaction is :
2 Fe( s )  O2 ( g )  4 H  ( aq )  2 Fe 2 ( aq )  2 H 2O (l )
Thus, an electrochemical cell is established on
the surface.
In corrosion, a metal is oxidised by loss of
eletrons to oxygen and formation of oxides. Electrochemical corrosion:
Corrosion of iron (commonly known as rusting)  The process of corrosion may be chemical (or)
occurs in presence of water and air. At a electrochemical in nature
particular spot (figure given above) of an object  The anodic dissolution of a metal under the
made of iron, oxidation takes place and that spot conditions of corrosion is known as
behaves as anode and we can write the reaction. electrochemical corrosion
M  M n   ne 
Anode: 2Fe  s   2Fe  4e E  Fe
2  0
 0.44V
2
 / Fe  Corrosion occurs if the environmental
Electrons released at anodic spot move through conditions of the metal favour the formation of
the metal and go to another spot on the metal an voltaic cell with the metal acting as anode
and reduce oxygen in presence of H  , which is  Electrochemical corrosion is basically of two
types
believed to be available from H 2 CO3 formed 1) Hydrogen evolution type
due to dissolution of carbondioxide from air into 2) Differential oxygenation type
water. Hydrogen ion in water may also be
available due to dissolution of other acidic Hydrogen Evolution type :
oxides from the atmosphere. This spot behaves  This type of corrosion is exhibited by metals
as cathode with the reaction. which can displace H 2 gas from aqueous
solution.
O 2  g   4H   aq   4e   2H 2 O 1
 This happens if the electrode potential of the
Cathode: E 0  1.23V metal under the conditions of corrosion is more

H /O 2 /H 2 O
negative than that of the hydrogen electode
The overall reaction being : under the given conditions.
2Fe  s   O 2  g   4H   aq   This type of corrosion depends upon
1) P H of the medium
 2Fe 2  aq   2H 2 O 1 E 0cell  1.67 V
2) chemical nature of the metal under going
The ferrous ions are further oxidised by corrosion
atmospheric oxygen to ferric ions which come  Pure zinc does not corrode in salt solutions but
out as rust in the form of hydrated ferric oxide in the presence of Cu as impurity Zn corrodes.
 Zn corrodes in 2M acid but not in neutral salt
 Fe2O3 .x H 2O  . solution
Differential Oxygenation type Passivity: The phenomenon of a metal
 This type of corrosion occurs if O2 reaching a stage of non-reactive state in its
concentration is not uniformly distributed on the reaction with concentrated acids may be called
surface of the metal passivity.
 Corrosion of the metal generally occurs at the  Iron group of metals and some other transition
metals are rendered passive with concentrated
point where O2 concentration is less acids.
 The portion of the metal with access to high  Passivity of a metal can be classified into
concentration of O2 functions as cathode and a) chemical passivity
with access to low concentration of O2 functions b) Mechanical passivity
c) Electro - chemical passivity
as anode.
Hence, the metal with differential oxygenation Chemical Passivity: Non-reactivity of
acts as a galvanic cell metals after initial reaction with conc HNO3 is
Eg : When an iron rod is immersed in NaCl
called chemical passivity
solution the immersed part is corroded due to
less oxygenation of the surface of the metal. Eg : If iron is dipped in conc HNO3 (sp gravity
Factors that promote electrochemical corrosion 1.25) it is attacked for some time and after
 The nature of the impurity metal with which the becomes inactive
metal under consideration is associated  Passive iron don’t dissolve in dil HNO3 and iron
For Ex : Cu favours corrosion of Zn. because
Zn is more anodic than copper don’t displace Ag from AgNO3
Zn disfavours corrosion of ‘Fe’(Galvanization)  Co,Ni, Cr can also become passive
 The concentration of O2 in contact with the  Air can also cause passivity to Fe, Cr, Mo, W&V
surface of the metal Mechanical Passivity: In some cases
 For Ex : Metal rod half immersed in aqueous dissolution of metal stops due to visible oxide
salt solution gets corroded at the surface not film formation. This is mechanical passivity Eg
exposed to O2 , i.e., the immersed part of the : PbO2 on Pb
Metal gets easily corroded Fe, Co, Ni, Mn also exhibit this type of passivity
 Highly conducting solutions favour rapid
corrosion Electrochemical passivity : Metal with
more -ve potential functions as anode in cell.
Prevention of Corrosion: The main  Generally Fe, Ni, Co functions as anode
principle underlying the methods of prevention
 They dissolve as M  M  n  ne 
of corrosion is to separate the metal (or) isolate
the metal from the environment is achieved by  At particular stage anode stops dissolving due
different ways. They are to formation of invisible metal oxide film. This
(a) Painting phenomenon is called electro - chemical
(b) Alloying (galvanisation) passivity.
(c) To prevent as far as possible the contact of
the metal surface with good electrical C.U.Q
conducting media
(d) Covering by some chemicals like bisphenol.
(e) Cover the surface by other metals (Sn, Zn ELECTROLYTIC CONDUCTANCE
etc) that are inert (or) react to save the object. 1. The best conductor of electricity is a 1M
(f) sacrificial electrode of another metal (like solution of
Mg, Zn, etc) which corrodes itself but saves the 1) Boric acid 2) Acetic acid
object. 3) H2SO4 4) Phosphoric acid
2. Which of the following aqueous solutions will 14. Which of the following is correct for the
conduct an electric current quite well? solution of C2 H 5COOH upon dilution
1) Sugar 2) Glycerol
regarding current carrying species?
3) Pure water 4) HCl
1) The number in 1 cm as well as in total volume
3
3. Pure water does not conduct electricity
because it is increases
1) Neutral 2) Readily decomposed 2) The number in 1 cm 3 decreases whereas that
3) Almost unionised 4) Completely ionised in the total volume remains constant
4. In aqueous solution, strong electrolytes ionize
and yield 3) The number in 1 cm 3 decreases but that in
the total volume increases
1) Ions 2) Electrons 3) Acids 4) Oxides
5. Which of the following is a poor conductor 4) The number in 1 cm 3 as well as in total
of electricity volume decreases.
1) CH3COONa 2) C2H5OH 15. If x is the specific resistance of the solution
3) NaCl 4) KOH and N is the normality of the solution. Then
6. Arrhenius theory is applicable only to equivalent conductivity of the solution is
1) weak electrolyte 2) Strong electrolyte given by
3) both 1 & 2 4) non electrolyte 1000x 1000
7. Which of the following does not conduct 1) 2)
N Nx
current in aqueous solution
1) KNO3 2) CH3COOH 1000N Nx
3) 4)
3) CH3OH 4) NaOH x 1000
8. Which of the following solid is an electronic 16. Which of the following solutions has the
conductor highest equivalent conductance?
1) NaCl 2) Diamond 3) CuS 4) KCl 1) 0.5 M NaCl 2) 0.05 M NaCl
9. The units of conductivity of solution are 3) 0.005 M NaCl 4) 0.02 M NaCl
1) ohm 1 2) ohms 17. Debye-Huckel-Onsager equation is
3) ohm 1cm 1 4) ohm 1eq 1 represented as c  0  b c . ‘b’ is
10. The unit of cell constant is
82.4 8.20 105 82.4 8.20 105
1) ohm 1 2) ohm - cm 1) (DT)1/2   (DT)3/2 ^0 2) (DT)1/2   (DT)1/2 ^0
3) cm 1 4) ohm 1cm 2 eq 1
82.4 8.20 105 8.24 8.20 105
11. The cell constant is the product of resistance 
3) (DT)1/2  (DT)1/2 
4) (DT)1/2 (DT)1/2  ^0
and
1) conductance 2) molar conductance 18. What happens at infinite dilution in a given
3) specific conductance 4) specific resistance solution ?
12. If the specific conductance and conductance 1) The degree of dissociation is unity for weak
of a solution are same, then its cell constant electrolytes
is equal to: 2) The electrolyte is 100% ionised
1) 1 2) 0 3) 10 4) 100 3) All inter ionic attractions disappear
13. A solution of concentration ‘C’ g equiv/litre 4) All the three
has a specific resistance R. The equivalent
conductance of the solution is 19. The relationship m   0 m  B C will not
1000 C R 1000R hold good for the electrolyte?
1) 2) 3) 4)
RC R C C 1) HCl 2) KCl 3) BaCl2 4) HCN
KOHLRAUSCH’S LAW AND 29. The cathode of an electrolysis and a reducing
APPLICATIONS agent are similar because both
20. The Kohlrausch law is related to 1) are metals 2) supply electrons
1) Conductance of ions at infinite dilution 3) remove electrons 4) absorb electrons
2) Independent migration of ions 30. The cathode reaction in electrolysis of dilute
3) Both 1 and 2 4) Neither 1 and 2 sulphuric acid with Platinum electrode is
21. The expression showing the relationship 1) Oxidation 2) Reduction
between equivalent conductance and molar 3) Both oxidation and reduction
conductance is (z = Total positive (or)
4) Neutralization
negative charge per formula unit of
electrolyte) 31. Schematic diagram of an electrolytic-cell is:
1) m  Z   eq 2)  eq  Z  m
 eq 2
3) m  4) m   eq
Z
22. The equation representing Kohlrausch law
from the following is ( V+ = No. of cations, V– 1) 2)
= No. of anions
100K
1) m  C  V  V  2) m0  v  0  v  .0
 

1000K
3) eq  C V 
 V  4) m0  c  a
eq

23. In the plot of  and C , the slope is


2.303 3)
1)  o 2) -b 3) 4) 
R
PHENOMENON OF ELECTROLYSIS
24. Electrolysis of salt solution is due to the 4) None is correct presentation
formation of 32. The following are some statements about
1) Electron 2) Ions 3) Oxides 4) Acids electrolytic cell
25. The reactions taking place at anode and
A) In this, chemical energy converted into
cathode of a cell respectively are
electrical energy
1) Reduction, oxidation
2) Oxidation, reduction B) In this cell, electrons flow from cathode to
3) Hydrolysis, oxidation anode
4) Reduction, hydrolysis C) In this cell reduction reduction takes place
26. Electrode at which electrons flow into the at cathode
electrolyte is D) In this, cathode is a +ve electrode
1) Anode 2) Cathode The correct combination is
3) Both anode & cathode 4) +ve electrode 1) only B 2) only C
27. In an electrolytic cell current flows from 3) only C,D 4) only B,C
1) Cathode to anode in outer circuit
33. In the electrolytic cell, flow of electrons is
2) Anode to cathode outside the cell
from
3) Cathode to anode inside the cell
4) Current does not flow 1) anode to cathode in the solution
28. During electrolysis electrons flow from 2) cathode to anode through external circuit
1) cations to cathode 2) anode to anions 3) anode to cathode through external circuit
3) cathode to anode 4) anions to anode 4) all of these
34. In electrolysis of NaCl when Pt electrode is 41. The number of faradays required to liberate
taken then H2 is liberated at cathode while 1 mole of any element indicates
with Hg cathode, it forms sodium amalgam. 1) weight of the element.
This is because 2) conductance of the electrolyte
1) Hg is more inert than Pt 3) charge on the ion of the element
+
2) More voltage is required to reduce H at Hg 4) isotopic number
than at Pt 42. 6.24 x 1019 electrons are equal approximately
3) Na is dissolved in Hg while it does not to
dissolve in Pt 1) 10 coulombs 2) 96500 coulombs
+
4) Conc. of H ions is larger when Pt electrode 3) one electron volt 4) 0.1F
is taken ELECTROCHEMICAL SERIES & EMF
FARADAY’S LAWS AND APPLICATIONS 43. The metal which cannot liberate H2 gas from
35. Faraday’s laws of electrolysis are related to hydrochloric acid
the 1) Zn 2) Cu 3) Mg 4) Al
1) Molecular mass of the electrolyte 44. For which of the following SOP and SRP are
2) Equivalent weight of the cation /anion equal
3) Atomic weight of the electrolyte 1. SHE 2. Mg electrode
3. Ni electrode 4. Copper electrode
4) Atomic number of the cation/anion
45. The electrode potential measures the
36. The unit of electrochemical equivalent is
1) tendency of the electrode to gain or lose
1) Gram 2) Gram / Ampere
electrons
3) Gram / Coulomb 4) Coulomb / Gram 2) electron affinity of elements
37. When 1 amp of current is passed through an 3) difference in the ionization potential of
electrolyte for one second, the mass deposited electrode and metal ion
is equal to 4) heat of combustion
1) 1 mole of hydrogen 46. The potential across the metal and the
2) 1 gram equivalent of hydrogen aqueous solution of its ions of unit activity at
3) 1 electro–chemical equivalent 298K is known as
4) 1 gram of any substance 1) Electrode potential
38. On electrolysis 1 mole Al atoms will be 2) Standard electrode potential
deposited by 3) Formal electrode potential
1) 1 mole of electrons 2) 2 moles of electrons 4) Oxidation potential
3) 3 moles of electrons 4) 6 moles of electrons 47. Which one of the following metal will not
39. When the same quantity of electricity is reduce H2O?
passed through the solution of different 1) Ca 2) Fe 3) Cu 4) Li
electrolytes in series, the amount of product 48. Arrange the following in the order of their
obtained is proportional to their decreasing electrode potentials: Mg, K, Ba,Ca
1) Atomic weights 1) K,Ba,Ca,Mg 2) Ba,Ca,K,Mg
2) Chemical Equivalent 3) Ca,Mg,K,Ba 4) Mg,Ca,Ba,K
3) Gram molecular mass 49. For the cell reaction to be spontaneous the
4) Gram atomic ions EMF of the cell should be
40. The electric charge for electrode deposition 1) negative 2) positive 3) zero
of 1gm, equivalent of a substance is 4) some times positive and some times –ve
1) 96,500 coulombs 50. The EMF of a galvanic cell is determined by
2) One ampere per sec using a
3) One ampere for one hour 1) Voltmeter 2) Spectrometer
4) Charge in faradays 3) Coulometer 4) Ammeter
51. Cathodic standard reduction potential minus 56. The relationship between free energy and
anodic standard reduction potential is equal electrode potential is
to 1) G  nFE 2) G  nFE
1) Faraday 2) Coulomb nFE H
3) Cell potential 4) Ampere 3) G  4) G 
R nFE
52. Consider following sets
ELECTROCHEMICAL CELLS
57. Which of the following energy changes occur
in galvanic cell?
1) Electrical energy  Chemical Energy
2) Chemical Energy  Electrical Energy
3) Chemical Energy  Internal Energy
4) Internal Energy  Electrical Energy
58. In a galvanic cell electron flow will be from
1) Negative electrode to positive electrode
2) Positive electrode to negative electrode
3) There will be no flow of electrons
Blue colour solution changes to colourless (or 4) Cathode to anode in the external circuit
fades) in: 59. In a galvanic cell, the reactions taking place
1) I, II, III 2) I, II 3) II, III 4) I, III in the anodic half cell and the cathodic half
NERNST EQUATION cell will be
53. The Nernst equation giving dependence of 1) Reduction 2) Oxidation
electrode reduction potential on 3) Oxidation and reduction
concentration is 4) Reduction and oxidation
60. Which of the following is not true for a
0 2.303 RT  M galvanic cell represented in IUPAC system
1) E  E  nF
log
Mn   1) Right hand electrode is a +ve terminal
2) Right hand electrode acts as cathode
2.303 RT  M  n
0
2) E  E  log  3) Electrons are given out in the external circuit
nF M from the anode
4) Electrons are given out in the external circuit
2.303 RT  M  n
0 from the cathode.
3) E  E  nF log M
  61. In a galvanic cell, the positive ions of salt
2.303 RT
bridge migrate towards
4) E  E0  log  M n   1) –ve electrode 2) +ve electrode
nF
54. The potential of a single electrode depends 3) Either anode or cathode
upon 4) Neither anode nor cathode
1) the nature of the electrode 62. A half cell reaction is one that
2) temperature 1) Involves only half a mole of electrolyte
3) concentration of the ion with respect to which 2) Goes only half way to completion
it is reversible 3) Takes place at one electrode
4) all the above 4) Consumes half a unit of electricity
55. The relationship between standard reduction 63. The purpose of the salt bridge in a galvanic
potential of a cell and equilibrium constant cell is to
is shown by 1) Prevent accumulation of charges around the
electrodes
0 n 0.059
1) Ecell  logK c 2) E0cell  logK c 2) Facilitate continuity of the cell reaction
0.059 n
3) To produce current at a constant strength
logK c 4) All the above
3) E0cell  0.059nlogK c 4) E0cell 
n
64. Agar–Agar is used in salt bridge since it is 75. W.r.t. H 2  O2 fuel cell the correct statement
1) Electrolyte 2) Non–electrolyte
is
3) Inert electrolyte 4) A solid
65. The chemical used in salt bridge in a galvanic 1) electrolyte used is pure H 2O
cell is 2) heat of combustion is directly converted to
1) Agar–agar 2) Gum Arabic electrical energy
3) Gel 4) Potassium nitrate
66. The thermodynamic efficiency of cell is given 3) O2 gas gets oxidised to O3 in the cell
by 4) overall reaction in the cell is
1) H / G 2) – nFE / G
H   OH   H 2O
3) – nFE / H 4) – nFE
76. Which of the following statements is true for
BATTERIES fuel cells ?
67. Lithium is generally used as an electrode in 1) They are more efficient
high energy density batteries. This is because 2) They are free from pollution
1) Lithium is the lightest element
3) They run till reactants are active
2) Lithium has quite high negative reduction
potential 4) All of the above
3) Lithium is quite reactive CORROSION
4) Lithium does not corrode easily
77. Corrosion is
68. When a lead storage battery is discharged
1) Physical change 2) Neutralisation
1) SO2 is evolved
3) Electrochemical change 4) None is true
2) lead sulphate is consumed
78. Prevention of corrosion of iron by Zn coating
3) sulphuric acid is consumed
is called
4) lead is formed
1) Galvanization 2)Cathodic protection
69. W.r.t. Ni - Cd storage cell, the incorrect
statement is 3) Electrolysis 4) Photoelectrolysis
1) anode is cadmium metal 79. In which of the following the corrosion of iron
2) it is a primary cell will be most rapid
3) cell potential is 1.4V 1) In pure water 2) In pure oxygen
4) electrolyte used is Cd  OH 2 3) In air and moisture
4) In air and saline water
70. In dry cell cathode is
1) Zn 2) Carbon rod 80. Corrosion can be prevented by
1) Painting the metal surface
3) Zn  NH 4Cl 4) C  MnO2
2) Alloying the metal with more anodic
71. Cathode is made of ........in mercury battery
metal
1) Zn 2) ZnO
3) Carbon in contact with HgO 3)To prevent the contact of the metal surface
4) Zn in contact with HgO with good electrical conducting media
72. In Leclanche cell, Zinc rod is placed in 4) All
1) 10% NH 4Cl 2) 20% NH 4Cl 81. Rusting of iron is catalysed by which of the
following
3) 30% NH 4Cl 4) 40% NH 4Cl 1) Fe 2) Zn 3) O2 4) H+
73. In fuel cell oxidants used are 82. Chemical passivity is possible with
1) O2 2) H2O2 3) HNO3 4) All
74. Theoretical efficiency of fuel cell is 1) Conc HNO3 2) Air
1) Nearly 60% 2) 50% 3) Both 1 and 2 4) Metal oxides
3) 33% 4) Nearly 100%
83. Match the Column -I with Column- II C.U.Q - HINTS
Column-I Column-II 1. Strong acids are strong electrolytes
a) Conductance p) ohm 1.cm 1.mole 1 2. HCl is a strong acid
b) Specific Conductance q) ohm 1 4. In aqueous solutions strong electrolytes will
undergo complete dissociation into ions.
c) Resistance r) ohm 1.cm 1 5. Covalent compound.
d) Molar Conductance s) ohm 6. Arrhenious theory is applicable to weak
1)  a  q  b  r  c  s  d  p  electrolytes only.
7. CH3 OH is a covalent compound.
2)  a  r  b  q  c  p  d  s 
8. Salts like CuS and CdS act as electronic
3)  a  r  b  q  c  s  d  p  conductors due to crystal defects.
9. units of conductivity of solution is
4)  a  q  b  r  c  s  d  p 
 ohm 1cm 1 l cm
84. Match the Column -I with Column- II k  c  ohm 1  2
Column-I a cm
a) Specific Conductance,K l cm
10. Cell constant =  2  cm 1
b) Molar Conductance,  m a cm
c) Resistance of electrolyte solution, R 11. Cell constant = resistance X specific
d) Degree of ionization of electrolyte,  conductance.
Column-II 12. K  conductance X cell constant Here K =
C, then cell constant = 1
p)  c m /  0 m
13. Specific conductance is inversly proportional
q) Decreases with dilution specific resistance.
r) Increases with dilution 16. Equivalent conductance Increases with Increase
s) Increases with increase in the distance in dilution
between parallel plates.
 0.005M Nacl solution has highest equivalent
1)  a  r  b  q  c  q, r  d  p, s  conductance
2)  a  q  b  r  c  q, s  d  p, r  82.4 8.20  105
17. b  
3)  a  r  b  q  c  q, s  d  p, r   DT 1 2  DT 3/ 2
19. Not applicable for weak electrolytel
4)  a  r  b  q  c  p, s  d  s, r 
M  Normality
C.U.Q - KEY 21.   Molarity
eq

1)3 2)4 3)3 4)1 5)2 6)1 7)3


23.  c   0  b c
8)3 9)3 10)3 11)3 12)1 13)1 14)3
15)2 16)3 17)1 18)4 19)4 20)3 21)1 26. Electrons flow into the electrolyte from cathode.
27. In electrolylic cell current flows from cathode
22)2 23) 2 24)2 25)2 26)2 27)1 28)4
to anode because flow of currrent is just opposite
29)2 30)2 31)2 32) 2 33) 3 34) 2 35)2 to flow of electrons.
36)3 37)3 38)3 39)2 40)1 41)3 42)1 2H   2e  H 2   cathode 
43)2 44)1 45)1 46)2 47)3 48)4 49)2
40. 1 Faraday deposits 1 gm equivalent of a
50)1 51)3 52)4 53)2 54)4 55)2 56)1 substance.
57)2 58)1 59)3 60)4 61)2 62)3 63)4 42. 6 .
23 –
0 e s = 96,500 coulombs
2 3 x 1 0

64)2 65)4 66)3 67)2 68)1 69)2 70)2 44. For hydrogen SOP = SRP = O
71)3 72)2 73)4 74)4 75)2 76)4 77)3 47. Copper has higher SRP then Hydrogen
78)1 79)3 80)4 81)4 82)3 83)1 84)2 electrode. So it can not reduce water.
48. Mg > Ca > Ba > K This is the order of SRP. FARADAY’S LAWS AND APPLICATIONS
49. For a cell to be spontaneous, EMF should be 5. When one faraday of current is passed, which
positive. of the following would deposit one gram
50. Voltmeter is used to determine EMF. atomic weight of the metal
51. E  Ecathode  E anode  EMF is in SRP  1) BaCl2 2) NaCl 3) AlCl3 4) CuCl2
54. Electrode potential depends on 6. Number of electrons required to deposit one
1. Temperature mole of Mg2+ ions is
2. Concentration of ion 1) 6.023 x 1023 2) 12.046 x 1023
3. Nature of electrodes used. 3) 18.069 x 1023 4) 3.012 x 1023
58. e flow from anode to cathode. 7. The electrochemical equivalent of an element
59. at anode oxidation takes place while at cathode is 0.001118 gm/coulomb. Its equivalent
reduction takes place. weight is
60. At cathode reduction takes place 1) 10.7 2) 53.5 3) 1007 4) 107
nFE 8. The number of electrons needed to reduce
66. Thermodynamic efficiency of cell = –
H 3gm of Mg2+ to Mg are
67. Lithium has lowest SRP value so it acts as strong N N N
reducing agent. 1) N 2) 2
3) 4)
4 8
70. Carbon rod 9. Three Faradays of electricity was passed
through an aqueous solution of Magnesium
bromide. The weight of Magnesium metal
LEVEL-I (C.W) deposited at the cathode in grams is
1) 56 2) 84 3) 36 4) 168
ELECTROLYSIS 10. List-I
I. In the Electrolysis of fused NaCl the product
A) Electrolysis of aq. Na2 SO4 using Pt
formed at cathode When Pt electrodes are
used is electrodes
1) Cl2 2)Na 3) H 2 4) O2 B) The charge carried by 6.023  10 23
2. If mercury is used as cathode in the electrons is
electrolysis of NaCl solution, the ions C) The amount of electricity required to
discharged at cathode are deposit 27 grams of Aluminium at cathode
1) H+ 2) Na+ 3) OH– 4) Cl– from molten Al2O3 is
D) A gas in contact with an inert electrode.
3. Dilute nitric acid on electrolysis using
List -II
platinum electrodes yields
1) both oxygen & hydrogen at cathode 1) 1 Faraday
2) both oxygen & hydrogen at anode 2) 3 Faradays
3) H2 at cathode and O2 at anode 3) H 2 g  / pt
4) Oxygen at cathode and ‘H2’ at anode
4. Which of the following occurs at cathode 4) O2 at anode H 2 at cathode
 1  A B C D A B C D
1) 2OH  H 2O  O2  2e
2 1) 2 3 4 1 2) 4 1 2 3
2) Ag  Ag   e  3) 3 2 4 1 4) 4 3 2 1
11. During the electorlysis of cryolite, aluminium
3) Fe 2  Fe 3  e  and fluorine are formed in ..... molar ratio
4) Cu 2  2e   Cu 1) 1: 2 2) 2 : 3 3) 1 : 1 4) 1 : 3
12. The electrochemical equivalent of a metal is vessel, then the unit of constant of
“x” g coulomb . The equivalent weight of
–1 proportionality is
metal is 1) S m mol 1 2) S m 2 mol 1
1) x 2) x × 96500
3) x/96500 4) 1.6 × 10–19 × x 3) S 2 m 2 mol 4) S 2 m 2 mol 2
13. The electro chemical equivalent of an element 22. The equivalent conductance at infinite
is 0.0006735 g/C. Its equivalent weight is dilution of a weak acid such as HF
1) 65 2) 67.35 3) 130 4) 32.5 1) Can be determined by extrapolation of
14.Two electrolytic cells, one containing acidified measurements on dilute solutions of HCl, HBr
ferrous sulphate and another acidified ferric and HI
chloride, are in series. The ratio of masses of 2) Can be determined by measurement on very
Iron deposited at the cathode in the two cells dilute HF solutions
will be 3) Can be best determined from measurements
1) 3 : 1 2) 2 : 1 3) 1 : 1 4) 3 : 2 on dilute solutions of NaF, NaCl and HCl
15 1 coulomb of electricity produces m kg of a 4) is an undefined quantity
substance ‘X’. The electrochemical 23. Molar conductance of KCl increases slowly
equivalent of ‘X’ is with decrease in concentration because of
1) m 2) m × 10 3 3) m × 10 4) 0.1 m
-3
1) increase in degree of ionisation
2) increase in total number of current carrying
ELECTROLYTIC CONDUCTANCE
species
16. Water is a non–electrolyte but conducts
3) weakning of interionic attractions and
electricity on dissolving a small amount of
increase in ionic mobilities
1) NaCl 2) Sugar 3)Acetone 4)Oxygen
4) increase in hydration of ions.
17. During electric conduction, the composition
24. The correct order of equivalent conductance
of which of the following is changed ?
at infinite dilution of LiCl, NaCl and KCl is
1) Graphite 2) Zinc wire
1) LiCl>NaCl>KCl 2) KCl>NaCl>LiCl
3) Copper wire 4) H2SO4 3) NaCl>KCl>LiCl 4) LiCl>KCl>NaCl
18. List I List II 25. Which of the following solution of KCl has
A) Electronic conductors 1) Acetic acid the lowest value of specific conductance(
B) Electrolytic conductors 2) Solid salts with same molar
C) Non-electrolyte 3) Sucrose conductance)
D) Weak electrolyte 4)Molten salts 1) 1 M 2) 0.1M
The correct match is 3) 0.01M 4) 0.001M
A B C D A B C D
26. The variation of m of acetic acid with
1) 2 1 3 4 2) 2 4 3 1
3) 1 4 3 2 4) 4 3 2 1 concentration is correctly represented by
19. An aqueous solution of which of the following
concentration of CH 3COOH is the best
conductor.
1) 101M 2) 10–3M 3) 10–1 M 4) 102 M 1) 2)
20. The degree of dissociation of an electrolyte
does not depend on
1) Nature of electrolyte 2) Catalytic action
3) Dilution 4) Temperature
21. Conductance unit Siemen’s (S) is directly
3) 4)
proportional to area of the vessel and the
concentration of the solution in it and is
inversely proportional to the length of the
27. The molar conductance of acetic acid at 32. The standard reduction potentials of Cu+2,
infinite dilution is  . If the conductivity of Ag+, Hg+2 and Mg+2 are 0.34v, +0.80v, +0.79V
0.1M acetic acid is S, the apparent degree of and –2.37V respectively. With increasing
voltage, the sequence of deposition of metals
ionisation is
on the cathode from a molten mixture
10000S 10S containing all those ions is
1)  2)  1) Ag, Hg, Mg, Cu 2) Cu, Hg, Ag, Mg
3) Ag, Hg, Cu, Mg 4) Cu, Hg, Mg, Ag
 100000 33. Which metal pairs when coupled will get
3) 4)  S
100S  maximum emf for a voltaic cell
1) Fe and Cu 2) Pb and Cu
KOHLRAUSCH’S LAW AND 3) Cu and Au 4) Ca and Cu
APPLICATIONS 34. At 298 K, the standard reduction potentials
28. According to Kohlrausch law, the limiting for the following half reactions are given.
value of molar conductance of an electrolyte Which acts as anode with others in
A2 B is electrochemical cell
Zn+2(aq) + 2e–  Zn(s), –0.762
1)   A    B 2)   A    B Cr+3(aq) + 3e–  Cr(s), –0.740
 1  2H+(aq) + 2e–  H2(g), –0.000
3)  A    B  
4) 2 A   B 
Fe+3(aq) + e–  Fe2+(aq), +0.762
2
29. Equivalent conductance at infinite dilution 1) Zn(s) 2) H2(g) 3) Cr(s) 4) Fe2+(aq)
35. Cu – 2e–  Cu2+ , E0 = –0.347V
of BaCl2 , H 2 SO4 and HCl aqueous Sn – 2e–  Sn2+, E0 = +0.143 V
solutions are x1 , x2 and x3 respectively.. The standard EMF of the cell constructed
with these electrodes is
Equivalent conuctance of BaSO4 solution is
1) +0.066V 2) –0.066V
1) x1  x2  x3 2) x1  x2  x3 3) +0.490V 4) –0.82V
36. The voltage of a cell whose half–cells are
3) x1  x2  2 x3 4) x1  2 x2  x3
given below is
ELECTROCHEMICAL SERIES & EMF Mg2+ + 2e–  Mg(s) ; E0=–2.37V
30. The SRP values of Ag +/Ag and Zn 2+/Zn Cu2+ + 2e–  Cu(s) ; E0 = +0.34V
electrodes are 0.80v and –0.76v. In the cell standard EMF of the cell is
built with these two electrodes 1) –2.03V 2) 1.36V 3) 2.7 v 4) 2.03V
1) Ag electrode acts as anode and Zn electrode 37. The standard reduction potentials of Ag,
acts as cathode Cu,Co and Zn are 0.799,0.337,-0.277, –
2) Ag electrode acts as cathode and Zn electrode 0.762V respectively. Which of the following
acts as anode cells will have maximum cell e.m.f ?
3) both the electrodes act as cathode 1) Zn | Zn 2 1M  || Cu 2 1M  | Cu
4) the cell can’t be built with these two
electrodes 2) Zn | Zn 2 1M  || Ag  1M  | Ag
31. Which of the following is most powerful
oxidizing agent? 3) Cu | Cu 2 1M  || Ag  1M  | Ag
1) Cl2 + 2e–  2Cl– ; E0=1.36V 4) Zn | Zn 2 1M  || Co 2 1M  Co
+ –
2) Na + e  Na; E =–2.71V
0

3)MnO4–+2H2O+2e-  MnO2+4OH–, E0=0.6v 38. When Zn metal is added to CuSO4 solution


4) H2O2 + 2H+ + 2e–  2H2O; E0=1.78V Cu is precipitated. It is due to
1) Oxidation of Cu2+ 2) Reduction of Cu2+
3) Hydrolysis of CuSO4 4) Ionization of CuSO4
46. KCl solution such
NERNST EQUATION I r o n r o d i s i m m e r s e d i n

that half its length is exposed to air and the


39. Consider the following four electrodes:
other half immersed in KCl solution. The part
A  Cu2  0.0001 M / Cu s corroded is
1) Part of the rod exposed to air
B  Cu2   0.1 M  / Cu s 
2) Part of the rod immerced in KCl solution
C  Cu2  0.01 M / Cu s 3) Both 1 & 2
4) None of the above
D  Cu2  0.001 M / Cu s 47. The factors that promote electrochemical
If the standard reduction potential of Cu+2/ corrosion are
Cu is +0.34V, the reduction potentials (in 1) The nature of the impurity metal with which
volts) of the above electrodes follow the order the metal under consideration is associated
1) A > D > C > B 2) B > C > D > A 2) The concentration of O2 in contact with the
3) C > D > B > A 4) A > B > C > D surface of the metal
40. Which of the following is always true 3) Highly conducting solutions
regarding the spontaneity of reaction 4) All
occuring in a galvanic cell?
1) E 0 cell  0, G 0  0 and Q  K c LEVEL-I (C.W) - KEY
1)2 2)2 3)3 4)4 5) 2 6)2 7)4
2) E 0 cell  0, G 0  0 and Q  K c
8)3 9)3 10)2 11)2 12)2 13) 1 14)4
3) E 0 cell  0, G 0  0 and Q  K c 15)2 16)1 17)4 18)2 19)2 20)2 21)2
4) E 0 cell  0, G  0 and Q  K c 22)3 23)3 24)2 25)4 26)3 27)1 28)4
41. The potential of hydrogen electrode is -118 29)1 30) 2 31)4 32)3 33)4 34) 1 35)3
mV. The H+ concentration of the solution is 36)3 37)2 38)2 39)2 40) 4 41)1 42)1
1) 0.01M 2) 2M 3) 10–4 M 4) 1M 43)1 44)1 45)2 46)2 47) 4
42. E for F2 + 2e  2F is 2.8 V
0 – –

E0 for 1/2 F2 + e–  F– is
1) 2.8 V 2) 1.4 V 3) –2.8 V 4) –1.4 V LEVEL-I (C.W) - HINTS
1. Fused NaCl undergoes electrolysis to deposit
BATTERIES Na at cathod.
43. On electrolysing K 2SO4 solution using inertt 5. For monovalent ion, 1F will deposit 1g atwt.
electrodes, 1.68L(STP) of gases was obtained. 6. No. of moles of electrons (or) No. of faraday
How many moles of MnO 4 could be reduced required to deposit 1 Mole of an element is equal
to Mn 2  by the same quantity of electricity ? to its charge.
1) 0.02 2) 0.15 3) 0.20 4) 0.10 E
7. e=
F
 E = eF
44. In which of the following cells reactants are
not contained within the cell but are N –
continuously supplied from external source? 8. For 12gm – 1F = Ne–s, 3gm – ¼ F = es
4
1) Fuel cell 2) Dry cell 9. 1F  1g.eq.wt
3) Lithium battery 4) Lead storage battery
3 

CORROSION & PASSIVITY 11. Al  33eF  1 Al


mole

45. Zinc corrodes in 2 F   F2  2e 


1) 2 M alkaline solution 1 mole 2F

2) 2 M acid solution
E
3) 2 M Neutral salt solution 12. e 
4) All of the above 96500
13. E  e  96500 28. Ax By  xAn  yBn
2  3 
14. Fe  22eF  Fe Fe  3e  Fe
56 g 3F 56 g
29.  BaSO4   BaCl2   H2SO4  2  HCl
15. Mass of substance produced when 1 columb
 x1  x 2  x 3
of electricity is passed is equal to
electrochemical equivalent there fore m kg or 30. Electrode with more negative SRP (or) least
positive SRP in comparision acts as oxidation
m 103 g
half cell.
16. Because NaCl when dissolved in water produces 31. Easiest to reduce for element with low SRP.
Ions.
32. Cu cannot displace MgCl2 due to high SRP..
17. Graphite, Zinc wire and Copper wire are
electronic conductors, so composition does not 33. Maximum EMF is produced between electrodes
change by passing current through them. into low SRP and high SRP.
19. Conductance increases with increase in dilution. 34. Lowest SRP act as anode.
20. The Degree of dissociation does not depend on 35. SOP = –SRP, then E  ECSRP  E ASRP
catalyst. 38. Higher SRP will undergo reduction (ion)
39. For Metal electrode
area  conc area  conc
21. C  c  K  const  . 0.059
 length E  E  2
log Cu 
2
n
m mol
S  K  const    3 3  40. EMF should be positive
m 10 m
G should be negative
m2
k  s  sm 2 mol1 K c greater than reaction quotient
m 4 mol
22. The equivalent conductance of weak electrolyte 41. 118mv  0.118v
can be determined indirectly with the help of 0.059
E log  H  
kohlrausch’s law n
 HF   NaF   HCl   NaCl 0.059
0.118  log  H  
1 1
24. Extent of hydration  Size of ion smaller the
log  H    2
size of ion, greater is the hydration ability, lesser
will be the ionic mobility, and hence lesser will  H    102
be the conductance. 46. Zinc reacts with acids easily and liberates
25. k  concentration of electrolyte hydrogen gas.
47. Iron undergoes oxidation after some time it
becomes passive.

26. LEVEL-I (H.W)


ELECTROLYSIS
1. The passage of current through a solution of
v K  1000 certain electrolyte results in the evolution of
27.    ; we know that v  H 2 at cathode and Cl 2 at anode. The
 M
electrolytic solution is
104  S 1) Water 2) H2SO4
  3) Aqueous NaCl 4) Aqueous CuCl2

2. The reaction taking place at the anode when
3) Na+, Cl– ions do not move freely in the fused
a dilute aqueous solution of CuSO 4 is
salt
electrolysed using inert Pt electrodes.
4) Fused NaCl has no ions
1) 2SO 24  S2O 24 + 2e– 10. The extent of ionization of weak electrolyte
2) Cu2+ + 2e–  Cu increases
+ –
3) 2H2O  O2 + 4H + 4e 1) With increase in concentration of the solute
+ –
4) 2H + 2e  H2 2) On addition of excess of water
3. In the electrolysis of NiSO4 using Nickel 3) On decreasing the temperature
4) On stirring the solution vigorously
electrodes the reaction that takes place at
11. The equivalent conductance of a 1 N solution
anode is
of an electrolyte is nearly:
 
 
1) Ni  2e  Ni
2 2) 2 H  2e  H 2 1) 103 times its specific conductance
3) Ni 2  Ni   e  4) Ni  Ni 2 2e  2) 103 times its specific conductance
FARADAY’S LAWS AND APPLICATIONS 3) 100 times its specific conductance
4. The amount of electricity that can deposit 4) The same as its specific conductance
12. Which of the following statements is correct
108gm of silver from AgNO3 solution is
for an electrolytic solution upon dilution
1) Faraday 2) 1 Ampere 1) conductivity increases
3) 1 Coulomb 4) None 2) conductivity decreases
5 The charge required to reduce 1 more Cr2O72 3) molar conductance decreases but equivalent
to Cr 3 ions is conductance increases
4) molar conductance increases while equivalent
1) 3F 2) 3 coulomb
conductance decreases.
3) 6F 4) 2  6.023  1023 e  13. The reason for increase in electrical
6. One ampere of current is passed for 9650 conduction of a weak electrolyte with increase
seconds through molten AlCl3 . What is the in temperature
1) increase in the number of ions
weight in grams of Al deposited at cathode?
2) increase in the speed of ions
(Atomic weight of Al  27 ). 3) increase in the degree of dissociation of
1) 0.9 2) 9.0 3) 0.09 4) 90.0 electrolytes 4) all the three
7. On passing a current through molten 14. The specific conductances of four electrolytes
KCl 19.5g of K is deposited. The amount of in ohm 1cm 1 are given below. Which one
Al deposited by the same quantity of offers higher resistance to passage of electric
electricity if passed through molten AlCl3 is current?
1) 4.5g 2) 9.0g 3) 13.5g 4) 27g 1) 7.0 105 2) 9.2 109
ELECTROLYTIC CONDUCTANCE 3) 6.0 107 4) 4.0 108
8. With increase in temperature the electrical 15. The variation of equivalent conductance of
conduction of metallic conductor a weak electrolyte with (concentration ) 1/ 2 is
1) increases 2) decreases represented as
3) remains the same 4) changes irregularly
9. Fused NaCl has less electrical conductance
than NaCl in the aqueous solution. This is 1)  2) 
due to c c
1) fused NaCl has less number of ions
2) incomplete ionization occurs in the fused state
3)  4) 
c c
16. The variation of equivalent conductance of ELECTROCHEMICAL SERIES & EMF
strong electrolyte with (concentration) 1/ 2 is 21. If a salt bridge is not used between two half
represented by cells, voltage
1) Drops to zero 2) Does not change
3) Increases gradually 4) Increases rapidly
22. The electro chemical cell stops working after
1)  2)  some time because
c c 1) Electrode potentials of both electrodes
become zero
2) Electrode potentials of both electrodes
become equal
3)  4) 
3) Temperature of the cell increases
c c
4) The reaction starts proceeding in opposite
17. Equivalent conductance of 1M direction
CH 3COOH is 10 ohm cm equiv and that
1 2 1 23. Consider a voltaic cell based on these half-
cell reactions
at infinite dilution is 200ohm 1cm 2 equiv 1 .
Ag   aq   e  Ag  s  ; E 0  0.80V
Hence the % ionization of CH 3COOH is
1). 5% 2) 2% 3) 4% 4) 1% Cd 2  aq   2e  Cd  s  ; E 0  0.40V
KOHLRAUSCH’S LAW AND identify the anode and give the voltage of this
APPLICATIONS cell under standard conditions.
1) Ag ; E cell
0
 0 .40 V 2) Ag ; E cell
0
 2 .00 V
18. If  c of NH 4OH is 115 1cm 2 mol 1 , its
degree of dissociation would be 3) Cd ; E cell
0
 1 .20 V 4) Cd ; E cell
0
 2 .00 V
 1 1 24. The reaction ½ H2(g) + AgCl(s)  H+ (aq) +
(Given. NH 4  73.4 cm mol and
2

Ag(s) can be represented in the galvanic cell


 1 1
OH   197.6 cm mol )
2 as
1) Ag/AgCl(s) | KCl(sol) || AgNO3 (sol) | Ag
1) 0.157 2) 0.058 3) 0.0424 4) 0.0848
2) Pt, H2(g) | HCl(sol) || AgNO3 (sol) | Ag
19. The values eq for NH 4Cl , NaOH and 3) Pt, H2(g) | HCl(sol) || AgCl(s) | Ag
NaCl respectively 149.74, 248.1 and 4) H2(g) | HCl(sol) || AgCl(s) | Ag
25. A reversible galvanic cell is connected to an
126.4 ohm 1cm 2 equi 1 . external battery . If theEMF of the battery

The value of eq of NH 4OH is less than EMF of the galvanic cell, current
1) Will not pass through the circuit
1) 371.44 2) 271.44 3) 71.44
2) Flows from the battery into the galvanic cell
4) It cannot be calculated from the data given
3) Flows from the galvanic cell into the battery
20. The molar conductances of HCl , NaCl and 4) All the three may take place
CH 3COONa are 426, 126 and 91  1cm 2 mol 1
NERNST EQUATION
respectively. The molar conductance for 26. The EMF of the cell Ni | Ni2+ (0.01M)
CH 3COOH is Cl–(0.01M)Cl2 , pt is —— V if the SRP of
nickel and chlorine electrodes are –0.25V and
1) 561  1cm 2 mol 1 2) 391  1cm 2 mol 1
+1.36V respectively
3) 261  1cm 2 mol 1 4) 612 1cm2 mol 1 1) +1.61 2) –1.61 3) +1.79 4) –1.79
27. The potential of hydrogen electrode at
pH = 10 and 25oC is
1) 0.59 V 2) zero volts
3) –0.59 V 4) None 3) Fe, Mn and Pb exhibit mechanical passivity
28. The oxidation potential of 0.05 MH2SO4 is 4) All the above
1) –2 × 0.0591 2) –0.01 × 0.0591 34. The Zn acts as sacrificial or cathodic
3) –2.321 × 0.00591 4) + 1 × 0.0591 protection to prevent rusting of iron because
BATTERIES 1) EOP
0
of Zn  EOP
0
of Fe
29. Number of Faradays involved in the net 2) EOP
0
of Zn  EOP
0
of Fe
reaction of Lead accumulator is
1) 1 2) 0.5 3) 2 4)Cannot be predicted 3) EOP
0
of Zn  EOP
0
of Fe
30. Following are some of the facts about dry 4) Zn is cheaper than iron
cell
i) It is also called Leclanche cell
ii) It is also called Daniel cell
LEVEL-I (H.W) - KEY
iii) Electrolyte is a moist paste of NH4Cl and
ZnCl2 in starch 1)3 2)3 3)4 4)1 5) 3 6)1 7)1
iv) Cathodic reaction is 8)2 9)3 10)2 11)1 12)2 13) 4 14)2
MnO2 (s) + NH4+ (aq) + e– 15)1 16)1 17)1 18)3 19)2 20)2 21)1
 MnO(OH)+NH3 22)1 23)1 24)3 25)3 26)3 27)3 28)4
Select correct facts:
1) i, ii, iii 2) i, iii, iv 3) ii, iii, iv 4) i, iv 29)3 30) 2 31)3 32)4 33)4 34)2

CORROSION & PASSIVITY LEVEL-I (H.W) - HINTS


1.
Aqueous NaCl undergoes electrolysis and
31. Iron rod is dipped in concentrated HNO3 .
liberates H 2 at cathode and chlorine at anode.
After some time the iron rod dipped in
9. Ionic mobility is fast in aqueous solution of the
AgNO3 solution. Ag is not displace by Iron. salts.
This is because 10. Degree of Ionization increases with increase in
1) SRP of silver is less than iron dilution (addition of water)
2) Iron and silver have same lattice structure specific conductance (k) 1000
3) Iron becomes passive 11.  eq 
Normality
4) All the above
32. In corrosion of iron : 1000  k
1) An electrochemical reaction (galvanic cell)  eq 
1
is formed in which Fe acts as anode and cathode 13. Increase in temperature Increase the degree of
is where O2 is reduced dissociation. So more no. of ions are formed.
2) Electrons flow from anode to cathode through l 1 
the metal while ions flow through the water 14. S  C  a  S  R  a lower the specific
droplets conductance, more will the resistance.
3) Dissolved O2 oxidises Fe 2 to Fe3 before 15. The equivalent conductance of weak electrolytes
increase with dilution
it is deposited as rust  Fe2O3 .H 2O 
16. The equivalent conductance of strong electrolyte
4) All of the above take place increases with dilution.
33. Which of the following is correct regarding
mechanical passivity 17. eq  200 ohm1cm2eq1 eqv  10 ohm1cm2 eq1
1) Visible metal oxide film is formed  veq 10
2) Visible metal oxide film prevents dissociation degree of Ionisation   =    200  0.05
eq
of metal
 % of ionization = 0.05  100 = 5%.
21. Due to accumulation of charges.
21. EMF becomes zero.
23. SRP of Zn is less than SRP of Hydrogen. Hence
Zn acts as cathode.
24. A cell notation LHS anode RHS cathode.
25. If EMF of the battery less than EMF of electro
chemical cell then current flows from
electrochemical cell to battery .
0.059 2
26. Ecell = E0cell  log  Ni 2  Cl  
2
27. Ecell = - 0.059 x PH
28. N  M  Basicity
 0.05  2  0.1

log 101 
0.059
E  0
1
= - 0.059
Oxidation potential = + 0.059v.
32. Apply electrochemical process of corrosion of
iron to form hydrated ferric oxide
 Fe2O3 .xH 2O 
33. In mechanical passivity coloured oxide film is
formed.
3. ELECTROCHEMISTRY
7. The ratio of mass of hydrogen and
LEVEL-II (C.W) magnesium deposited by the same amount of
electricity from H 2 SO 4 and MgSO 4 is
[CPMJ]
ELECTROLYSIS
1) 1:8 2) 1:12 3) 1:16 4) 1:32
1. In the process of electrolysis using active
metal electrodes the weight of cathode and 8. In a hydrogen - oxygen fuel cell, 67.2 litre of
anode. H 2 at S.T.P is used in 5 min. What is the
1) Increases, decreases 2) Decreases, decreases average current produced?
3) Increases, increases 4) Decreases, increases. 1) 549.4 amp 2) 643.33 amp
2. The passage of current through a solution of 3) 965 amp 4) 1930 amp
certain electrolyte results in the formation of 9. An electric current is passed through a
hydrogen at anode the solution is
copper voltameter and a water voltameter
1) Aqueous HCl 2) Fused CaH2
connected in series. If the copper of the
3) sulphuric acid in water 4) Aqueous K2SO4
copper voltameter now weights 16mg less,
3. During the electrolysis of aqueous solution
hydrogen liberated at the cathode of the
of sodium chloride,pH of the electrolyte
water voltameter measures at STP about
1) Remains constant 2) Gradually increases
3) Gradually decreases 1) 4.0ml 2) 5.6ml 3) 6.4ml 4) 8.4ml
4) Decreases first and then increases. 10. A quantity of electrcity required to reduce
4. Which of the following statements are 12.3 g of nitrobenzene to aniline arising 50%
correct? current efficiency is
a) The electrolysis of aqueous NaCl produces 1) 115800C 2) 579000C
hydrogen gas at cathode and chlorine gas at 3) 231600C 4) 289500C
anode, 11. 9.65 amp of current was passed for one hour
b) The electrolysis of a CuSO4 solution using through Daniel cell. The loss of mass of zinc
anode is
Pt electrodes causes the liberation of O2 at 1) 11.76g 2) 1.176g 3) 5.88g 4) 2.94g
the anode and the deposition of copper at the 12. The electrochemical equivalent of two
cathode. substances are E1 and E2. The current that
c) Oxygen and hydrogen are produced at the flows to deposit their equal amount at the
anode and cathode during the electrolysis of cathodes in the same time must be in the ratio
dilute aqueous solution of H 2 SO4 of
d) All electrolytic reactions are redox 1) E1 :E2 2) E2 :E1
reactions 3) E1 :E2–E1 4) E1XE2:E1+E2
1) Only a is correct 2) a,b are correct 13. How long will a current of 1 ampere take for
3) a,d are correct 4)a,b,c and d are correct complete deposition of copper from 1 litre of
FARADAY’S LAWS AND APPLICATIONS 1NCuSO4. 5H2O solution ?
5. A copper voltameter, a silver voltameter and 1) 96500 sec 2) 2x96500sec
a water voltameter are connected in series  96500   96500 
and current is passed for some time. The 3)  2  sec 4)  4  sec
ratio of the number of moles of copper, silver 14. One faraday of electricity is passed separately
and hydrogen formed at the cathode is through one litre of one molar aqueous
1) 2:1:1 2) 1:1:1 3) 1:2:1 4) 1:2:2 solution of I) AgNO3, ii) SnCl4 and iii) CuSO4.
6. The charge required to reduce 1mole Cr2O 72 The number of moles of Ag, Sn and Cu
+3
to Cr ions is deposited at cathode are respectively
1) 3F 2) 3 coulomb 1) 1.0, 0.25, 0.5 2) 1.0, 0.5, 0.25
3) 6F 4) 2x6.023x1023e– 3) 0.5, 1.0, 0.25 4) 0.25, 0.5, 1.0
15. 0.05M aqueous solution of NaCl is 23. Equivalent conductance  vs concentration
electrolysed. If a current of strength 0.5amp
 
is used for 193sec. The final concentration graphs are given for some electrolytes X, Y
+
of Na ions in the electrolyte will be(volume and Z. Here X, Y and Z are
of solution will be constant)
1) 0.05M 2) 0.049M 3) 0.051M 4) 0.04M
16. Which one of the following could not be X
liberated from a suitable electrolyte by the
passage of 0.25 faraday of electricity through Y
that electrolyte Z
1) 0.25 mole of Ag 2) 16gm of Cu
3) 2gm of O2 (g) 4) 2.8ltrs of H2at STP
17. What is the time (in sec) required for C
deposition of all the silver present in 125ml
of 1M AgNO3 solution by passing a current 1) NiSO4 , KCl , CH 3COOH
of 241.25 amperes? 2) KCl , NiSO4 , CH 3COOH
1) 10 2) 50 3) 1000 4) 100
18. The charge required for the oxidation of one 3) KCl , CH 3COOH , NiSO4
mole of Mn3O4 to MnO42 in alkaliine medium is 4) CH 3COOH , NiSO4 , KCl
(assume 100% current efficiency): 24. The resistance of 0.5 N solution of an
1) 10/3F 2) 6F 3) 10F 4) 4F electrolyte in a conductivity cell was found
19. The density of copper is 8 gm/cc. Number of to be 45 ohms. If the electrodes in the cell
coulombs required to plate an area of 10 cm are 2.2 cm apart and have an area of 3.8cm 2
x 10 cm on both sides to a thickness of 10-2cm then the equivalent conductance
using CuSO4 solution as electrolyte is  in Scm2 eq 1  of a solution is
1) 48,250 2) 24,125 3) 96,500 4) 10,000 1) 25.73 2) 15.75 3) 30.75 4) 35.75
20. The same quantity of electricity is passed
through 0.1 M H 2 SO4 and 0.1 M HCl. The
KOHLRAUSCH’S LAW AND
APPLICATIONS
amounts of H 2 obtained at the cathodes aree 25. The ionic mobilities of the cation and the
in the ratio anion of a salt A2 B are 140 and 80
1) 1 : 1 2) 2 : 1 3) 1 : 2 4) 3 : 1
ohm 1cm 2 eq 1 respectively. The equivalent
ELECTROLYTIC CONDUCTANCE conductivity of salt at infinite dilution is (in
21. A conductivity cell was filled with a
0.02M KCl solution which has a specific ohm 1cm 2 eq 1 ):
conductance of 2.768  10 3 ohm 1cm 1 . If its 1) 160 2) 220 3) 60 4) 360
26. The mathematical expression for law of
resistance is 82.4 ohm at 250 C , the cell independent migration of ions is given by
constant is
 
1)    0m  BC 1/ 2 2) o  F U U 
1) 0.2182 cm 1 2) 0.2281 cm 1

 1  c
3) 0.2821 cm 1 4) 0.2381 cm 1 0
  m
3) 0m  v+λ+ +v-λ- 4)  m  0m K   0 2
22. The equivalent conductivity of a solution a m

containing 2.54g of CuSO4 per litre is 27. The molar ionic conductance at infinite
dilution of Ag is 61.92104Smol1m2 at 250C the
91.0  1cm 2 eq 1 . Its conductivity would be
ionic mobility of Ag  will be
1) 1.45 103  1cm 1 2) 2.17 103  1cm 1
1) 6.4 108 2) 6.192
3) 2.90 103  1cm 2 4) 2.9 103  1cm 1
3) 6.192 104 4) 3.2 104
28. The specific conductance of saturated 33. The standard reducution potentials of


solution of silver chloride is k ohm cm .
1

1 Zn2 | Zn, Cu2 | Cu and Ag  | Ag are respectively -0.76,
0.34 and 0.8V. The following cells were
The limiting ionic conductance of Ag and  constructed.
a) Zn | Zn 2 || Cu 2 | Cu
Cl  ions are x and y respectively. The
b) Zn | Zn 2 || Ag  | Ag
solubility of AgCl in gram.litre1 is : ( Molar mass
c) Cu | Cu 2 || Ag  | Ag
of AgCl  143.5 g mol 1 )
What is the correct order E 0 cell of these cells?
1000 k 1) b  c  a 2) b  a  c
1) k  2) 143.5
x y x y 3) a  b  c 4) c  a  b
k 1000  143.5 x  y 1000 34. Zn gives H 2 gas with H 2 SO4 and HCl but
3) 4) 
x y k 143.5 not with HNO3 because
29. At 250 C, the ionic mobility of CH3COO-, H+ 1) Zn acts as oxidizing agent when reacts with
are respectively 4.1  10 , 3.63  10 cm /sec.
-4 -3
HNO3
The conductivity of 0.001M CH3 COOH is
5  10 -5 S.cm -1 . Dissociation constant of 2) HNO3 is weaker acid than H2SO4 and HCI
CH3COOH is 3) In eletrochemical series Zn is above hydrogen
1) 1.64  105 2) 3  104 3) 3  105 4) 3  106 4) NO3 is reduced in preference to hydronium
ion
ELECTRO CHEMICAL SERIES & EMF 35. For the Daniel Cell involving the cell
30. The hydrogen electrode potential depends on reaction 
 Zn 2 ( aq )  Cu
Zn s   Cu 2 ( aq ) 
 s
1) Nature of metal used as anode the standard free energies of formation of
2) The P H of the solution Zn s  , Cu s  , Cu 2( aq ) and Zn 2 ( aq ) are 0, 0,
3) Both nature of the metal used as anode and 64.4 KJ/Mole and -154.0 KJ/Mole,
the P H of the solution respectively. Calculate the standard EMF of
4) Nature of the metal used as cathode and the the cell
1) 2.13 Volts 2) 1.13 Volts
P H of the solution 3) 2.26 Volts 4) 3.42 Volts
31. The following reaction is non–spontaneous 36. The position of some metals in the electro
1) Zn+2H+  Zn+2+H2 chemical series in decreasing electro positive
2) Cu+2H+  Cu+2+H2 character is given Mg>Al>Zn>Cu>Ag. What
will happen if a copper spoon is used to stir a
3) Zn+Cu2+  Zn2+ + Cu solution of aluminium nitrate?
+ 2+
4) Cu+2Ag  Cu +2Ag 1) The spoon will get coated with aluminium
32. For a cell the cell reaction is 2) An alloy of copper and aluminium is formed
3) The solution becomes blue
Mg(s) + Cu2+ (aq)  Cu(s) + Mg2+(aq). 4) There is no reaction
If the S.R.P. values of Mg and Cu are –2.37v 37. In the Daniel cell which change increases the
and +0.34v respectively, the e.m.f. of the cell cell EMF
is 1) Increase in the concentration of ZnSO4
1) +2.03V 2) –2.03V 2) Increase in the dilution of ZnSO4
3) +2.71V 4) –2.71V 3) Decreasing the concentration of CuSO4
4) Increasing the dilution of CuSO4
38. The chemical reaction 43. The e.m.f. of the following Daniell cell at 298
2 AgCl( s )  H 2( g )  2 HCl( aq )  2 Ag ( s ) E1 Zn/ZnSO4(0.01M)//CuSO4(1.0M)/Cu
K i s

taking place in a galvanic cell is represented When the concentration of ZnSO4 is 1.0 M
by the notation and that of CuSO 4 is 0.01 M, the e.m.f.
changed to E 2. What is the relationship
1) Pt( s ) H 2( g ) .1bar 1MKCl( aq ) | AgCl( s ) | Ag ( s ) between E1 and E2 ?
2) Pt( s ) H 2( g ) .1bar 1M HCl( aq ) |1M Ag  (aq ) | Ag ( s ) 1) E1  E2 2) E1  E2 3) E1  E2 4) E2  0  E1

3) Pt( s ) H 2( g ) .1bar 1M HCl( aq ) | AgCl( s ) | Ag ( s ) 44. Given that EH 2O H 2 pt  0 at 298 K . The


pressure of H 2 gas would be
4) Pt( s ) H 2( g ) .1bar 1M HCl( aq ) | Ag ( s ) | AgCl( s )
39. The following are some statements about 1) 107 atm 2) 1014 atm
normal hydrogen electrode
3) 1010 atm 4) 1012 atm
a) when a Zn electrode is in combination of
NHE, Zn electrode acts as cathode 45. Which graph correctly corelates Ecell as
b) when a Cu electrode is in combination with function for the cell
NHE, Cu electrode is the anode
c) When a “Ag” electrode is in combination Zn Zn2aq  Cu2aq  Cu ,
with NHE, Ag electrode is the anode
d) When a chlorine electrode is in
combination with NHE, chlorine electrode is 0
EZn 2
/ Zn
 0.76V , ECu
0
2
/ Cu
 0.34V
the anode
1) only a is correct 2) all are correct Y  axis  Ecell ,
3) all are incorrect 4) both b and c correct
X  axis  log  Zn 2  Cu 2 
NERNST EQUATION
40. If the solution of the CuSO4 in which copper
rod is immersed is diluted to 10 times, the
electrode potential
1) Increases by 0.295V
2) Decreases by 0.0295V 1) 2)
3) Increases by 0.059V
4) Decreases by 0.059V
41. The standard reduction potentials of
Zn 2 | Zn and Cu 2 | Cu are -0.76V and +0.34
V respectively. What is the cell e.m.f (inV) of
the following cell? 3) 4)
 RT 
  0.059 
 F  46. In the electrochemical cell
Zn / Zn 2 (0.05M)/Cu (0.005M)/Cu
2+ H2(g), 1 atm|H+(1M) || Cu2+(1M) | Cu(s), which
1) 1.1295 2) 1.0705 3) 1.1 4) 1.041 one of the following statements is true?
1) H2 is cathode, Cu is anode
42. E0 Zn 2 / Zn = –0.76V The EMF of the cell Zn/
2) Oxidation occurs at Cu electrode
Zn (21M) || HCl(pH=2) | H2(1atm), Pt is 3) Reduction occurs at H2 electrode
1) 0.878V 2) 0.642V 3) –0.878V 4) 0.701V 4) H2 is anode, Cu is Cathode
47. The potential of the cell containing two 55. Zinc is used to protect corrosion of iron
hydrogen electrodes as represented below Pt, because
H2(g) | H+(10-6M)||H+(10-4M)|H2(g),Pt at 298 K
1) Eoxi of Zn < Eoxi of iron
is
1) –0.118 V 2) –0.0591 V 2) Ered of Zn < Ered of iron
3) 0.118 V 4) 0V.0591 3) Zn is cheaper than iron
48. The e.m.f. of the cell, Zn / Zn 2+(0.01M) //
4) Zn is abundantly available
Fe2+(0.001M) / Fe at 298 K is 0.2957 then the
value of equilibrium constant for the cell 56. In corrosion of iron
reaction is (I.I.T.) 1) electrons flow from anode to cathode through
the metal while ions flow through the water
0.32 0.32 0.26 0.26
1) 0.0295 2) 0.0295 3) 4) 0.0591 droplets
e 10 100.0295 10 2) an electrochemical cell (galvanic cell) is
49. For a cell reaction formed in which Fe acts as anode and cathode
2 2
Cu (C1 , aq)  Zn( s )  Zn (C2 , aq)  Cu( s ) where O2 is reduced
of an electro chemical cell, the change in 3) dissolved O2 oxidises Fe2 to Fe3+ before it is
standared free energy G 0 at a given deposited as rust (Fe2O3.xH2O)
temperature is 4) all of the above takes place
57. In a hydrogen - oxygen fuel cell, combustion
0.591 C2 of hydrogen occurs to
1) ln C1 2) 2 log C
1 1) generate heat
3) ln C2 4) ln(C1  C2 ) 2) remove absorbed oxygen from electrode
surfaces
BATTERIES 3) produce high purity water
50. Which of the following reaction occurs at the 4) create potential difference between the two
cathode during the charging of lead storage electrodes
battery ?
1) Pb 2   2e   Pb ASSERTION & REASON QUESTIONS
2) Pb 2  SO42  PbSO4 1)A and R are correct R is the correct
explanation of A
3) Pb  Pb 2   2e  2) A and R are correct R is not the correct
 2  explanation of A
4) PbSO4(s)  2H2O  PbO2(s)  4H  SO4  2e
51. As lead storage battery is charged 3) A is correct, but R is wrong
1) lead dioxide dissolves 4) A is wrong, but R is correct
2) sulphuric acid is regenerated 58. Assertion(A): The absolute value of the
3) lead electrode becomes coated with lead electrode potential cannot be determined
sulphate experimentally
4) the concentration of sulphuric acid decreases Reason (R): The electrode potentials are
52. Alkali storage cell is commonly called generally determined with respect to
1) lead accumulator 2) Edison battery standard hydrogen electrodes.
3) fuel cell 4) Leclanche cell 59. Assertion A: The molar conductance of weak
CORROSION AND PASSIVITY electrolytes is low as compared to that of
53. Galvanized lron sheets are coated with strong electrolytes at moderate
1) Zn 2) Cr 3) Cu 4) Ni concentrations.
54. Which of the following metals acts as a Reason R: Weak electrolytes at moderate
sacrificial anode for iron articles? concentrations dissociate to a much greater
1) Cu 2) Zn 3) Ag 4) Sn extent as compared to strong electrolytes.
60. Assertion (A): During electrolysis 6. Cr2O7–2  2Cr3+
48250coulombs of electricity will deposit 0.5 Change in O.S. = 6
gramequivalent of silver metal from Ag  ions  Charge required = 6F
Reason (R): One Faraday of electricity will m1 E1
be required to deposit 0.5gram - equivalent 7. 
m2 E2
of any substance
61. Assertion(A): A current of 96.5 amperes is 8. Use Faraday’s first law
passed into aquesous AgNO 3 solution for W1 E1
9. 
100seconds. The weight of silver deposited is W2 E 2
10.8g (At.wt. of Ag=108).
 65.4 / 2 
Reason (R): The mass of a substance 11. m   9.65  1 60  60
deposited during the electrolysis of an 96500
electrolyte is inversely propotional to the 12. E1Q1 = E2Q2
quantity of elctricity passing through the 13. Q= Ct
electrolyte.  4 2 1 1 1
62. Assertion A : Increase in the concentration 14. Ag : Sn : Cu  : :
1 4 2
of copper half cell in Daniel cell increases the
emf of the cell. 15. Aqueous solution of NaCl does not produce ‘Na’
Reason R: According to Nernst equation. cathode. Hence Na+ concentration remains same
16. 0.25F will deposit 0.25 equivalents.
Cu  
Ecell  E
0

0.059
log 125  1 108 /1 108 /1
17.   241.25  t
 Zn  
cell
2 1000 96500
18. Change in O.N per mole of Mn3O4  10
LEVEL-II (C.W) - KEY
1)1 2)2 3)2 4)4 5)3 6)3 7)2 1 mole of Mn3O4  10 equiv  10 F
8)4 9)2 10)1 11)1 12)2 13)1 14)1 19. V = area  thickness = 1cc
Total volume 2cc
15)1 16)2 17)2 18)3 19)1 20)1 21)2
1cc volume = 1 gms of copper
22)4 23)2 24)1 25)2 26)3 27)1 28)3 wt of copper for 2cc = 16 gms
29)1 30)4 31)2 32)3 33)2 34)4 35)2 96500C = 32 gms of copper
36)4 37)2 38)3 39)3 40)2 41)2 42)2 32 gms of copper = 96500C
43)1 44)2 45)2 46)4 47)3 48)2 49)2 16gms = ?
50)1 51)2 52)2 53)1 54)4 55)2 56)4 20. W E
57)4 58)1 59)3 60)3 61)3 62)1 l
21 . Cell constant =
a
LEVEL-II (C.W) - HINTS
2.54 K  1000
1. Cathode concentration increases and anode 22. N  
concentration decreases. 254 N
2.. In a CaH2, Hydrogen has the Oxidation state of 23. KCl – strong electrolyte
-1. Hence hydrogen gas is liberated at anode. CH3 COOH – weak electrolyte
 
4. 2H  2e  H 2  , no. of H  ions decreases, so k  1000 1 l
24. eq  k 
basic nature increases. N R a
5. Acc. Faraday’s second law,
26.   A    B
1  1
1F  Cu  mole   Ag 1mole    H 2  27. At infinite dilution each ion makes definite
2  2
contribution towards molar conductance which
1 1
 :1:  2  1: 2 :1 is given by
2 2
 2. Which of the following on electrolysis would,
28.   not evolve oxygen at the anode?
96,500
1) Dilute H2SO4 with Pt electrodes
33. Electrode with low SRP is always taken as anode
(LHS). 2)Aqueous silver nitrate using Pt electrodes
35. G  nFE 3) Aqueous Na2SO4 with Pt electrodes
36. Copper can’t displace Al from Al  NO3 3
4) 50% H2SO4 with Pt electrodes
3. In which of the following electrolysis, the
because of low SRP value
composition of electrolyte is expected to
37. Cell EMF can be increased by decreasing the
remain constant under optimum conditions
concentration of cathode electrode dipped
electrolyte. 1) Aq. AgNO3 solution between Ag electrodes
0.059
2) Aq. CuSO4 solution between Pt electrodes
40. Decreases by V = 0.0295V 3) Fused NaCl between Pt electrodes
2
4) Aqueous AgNO 3 solution between Pt
 Zn 2 
41. Ecell   Ecathode  E Anode   log  2 
0.059
0 0
electrodes
n Cu 
4. In the electrolysis of Na2 SO4 solution using
 PH 2 
1/ 2
 RT inert electrodes
44. E  F ln  H   when E =0, then a) the anodic reaction is
2 H 2 0  O2 g   4e   4 H 
P 
1/ 2
H2  H   107

PH2 = 10-14 atm. b) H 2 g  and O2 g  is produced in a molar ratio


of 2:1
0.059  Pr oduct 
47. Ecell  E cell  n log Re ac tan t
0
c) 23 grams of sodium is produced at the
  cathode
0.059 d) The cathode reaction is Na   e   Na
48. E cell 
0
log Kc
n 1) a and b are correct 2) c,d are correct
50. Regeneration of H 2 SO4 takes place 3) Only c is correct 4) All are correct
51. When lead accumulator is charging it acts as
electrolytic cell during discharging it acts as FARADAY’S LAWS AND APPLICATIONS
electrochemical cell.
5. How many coulombs of electricity are
53. Fe,Cr,Mo,W,V,Co, Ni etc shows passivity
consumed when a 100mA current is passed
through a solution of AgNO3 for 30 minutes
LEVEL-II (H.W) during electrolysis?
1) 108 2) 180 3) 18000 4) 3000
ELECTROLYSIS 6. A certain quantity of electricity is passed
1. Two platinum electrodes were immersed in through an aqueous solution of AgNO3 and
a solution of CuSO4 and electric current was cupric salt solution connected in series. The
passed through the solution. After sometime amount of silver deposited is 1.08g. The
it was found that colour of CuSO 4 amount of copper deposited is (at.wt. of
disappeared with the evolution of gas at the Cu=63.54; Ag=108)
electrode. The colourless solution contains 1) 0.6454g 2) 6.354g
1) Platinum sulphate 2) Copper sulphate 3) 0.3177g 4) 3.177g
3)Copper hydroxide 4)Sulphuric acid
7. Aluminium oxide may be electrolysed at 13. On passing a current through a molten
aluminium chloride for some time, produced
10000 C to furnish aluminium metal
11.2lit of Cl2 at NTP at anode, the quantity of
(Atomic mass = 27 amu, 1 Faraday = 96,500
aluminium deposited at cathode is
Coulombs). The cathode reaction is
1) 27grams 2) 18gram 3) 9gram 4) 36 gram
Al 3  3e   Al 0 To prepare 5.12 kg of 14. A current of 2A passing for 5 hours deposits
aluminium metal by this method would 22.2g of tin(at.wt. = 119), the oxidation state
require of tin is
1) 5.49×101Cof electricity 1) zero 2) three 3) two 4) four
15. 1 ampere current is passed for 60 seconds into
2) 5.49×104Cof electricity an electrolytic cell. Number of electrons that,
pass through the solution is.
3) 1.83×10 7 C of electricity
1) 6.0x1023 2) 1.2 x 1024
19
7
4) 5.49×10 C of electricity 3) 37.5 x 10 4) 7.48x1021
8. In an electrolytic cell one litre of 1M aqueous 16. The number of electrons passing per second
solution of MnO4– is reduced to MnO4–2 at through a cross–section of copper wire
carrying 10–6 ampere current per one second
cathode. How many faradays would be
is found to be
required so that the solution becomes 0.899M
1) 1.6x10–19 2) 6x10–35 3) 6x10–6 4) 6.24x1012
MnO4– 17. Zinc reacts with CuSO 4 according to the
1) 10 Faradays 2) 0.1 Faradays
equation Zn+CuSO4  ZnSO4 +Cu. If excess
3) 1.0 x 10–4 Faraday 4) 1x10–2 Faraday of zinc is added to 100.0 ml of 0.05M CuSO4,
9. If 90g of water is electrolysed completely with the amount of copper formed in moles will be
50% current efficiency 1) 0.05 2)0.5 3) 0.005 4) 50
a) 10 Faraday of electricity will be consumed 18. Total volume of gases evolved at STP when
b) 20 faraday of electricity will be consumed
36g of H 2O are completely electrolysed
c) 168L (STP) of gases will be produced
d) 84L (STP) of gases will be produced. between platinum electrodes
1) 22.4 lit 2) 44.8 lit 3) 33.6 lit 4) 67.2 lit
Correct statements are
19. What is the approximate quantity of
1) b,c 2) a,b,c 3) a,c,d 4) All electricity in coulombs required to deposit all
10. On electrolysis of a sample of acidified water,
22.4ml of hydrogen was obtained. The the silver from 250 ml 1M AgNO3 aqueous
volume of oxygen in ml obtained is solution (At. wt. of Ag = 108)?
1) 22.4 2) 44.8 3) 11.20 4) 2.24 1) 96500 2) 24125 3) 48250 4) 12062.5
11. Three faradays of electricity are passed ELECTROLYTIC CONDUCTANCE
through molten Al2O3,aqueous solution of 20. The specific conductance of a solution is
CuSO 4 and molten NaCl taken in three 0.3568 ohm-1cm-1. When placed in a cell the
different electrolytic cells. The amount of Al, conductance is 0.0268 ohm-1. The cell constant
Cu and Na deposited at the cathodes will be is
in the ratio of 1) 1.331 cm-1 2) 13.31cm-1
-1
1) 1 mole :2 mole :3 mole 3) 0665cm 4) 6.65cm-1
2) 1 mole:1.5 mole :3 mole 21. The value of molar conductance of HCl is
3) 3 mole :2 mole :1 mole greater than that of NaCl at a given
4) 1 mole :1.5 mole :2 mole temperature and concentration because
12. Number of coulombs of current required to 1) Ionic mobility of H  is greater than that of Na 

convert completely 1 mole of MnO 4 ions in 2) the dipolie moment of NaCl is greater than
2+
acid medium to one mole of Mn ions that of HCl
electrolytically is 3) NaCl is more ionic than HCl
1) 96500 2) 5x96500 4) HCl is Bronsted acid and NaCl is a salt of a
3) 96500x2 4) 96500x6 strong acid and strong base
22. Conductance of 0.1 M KCl (conductivity = ELECTRO CHEMICAL SERIES & EMF
1
X Ohm cm ) filled in a conductivity cell is Y 27. SRP Values of Mg2+ | Mg, Fe2+ | Fe and Zn2+|Zn
1

Ohm1 . If the conductance of 0.1M are –2.37v, –0.44v and –0.76v respectively.
NaOH filled in the same cell is Z Ohm1 , the The correct statement is
molar conductance of NaOH will be 1) Mg oxidizes Fe 2) Zn oxidizes Fe
2+
XZ XZ XZ XZ 3) Zn reduces Mg 4)Zn reduces Fe2+
1) 103 2) 104 3) 10 4) 0.1
Y Y Y Y 28. The EMF of the Daniel cell is 1.1V . The
KOHILRAUSCH’S LAW ANDPPLICATIONS external EMF to be applied for the following
23. Which of the following represents increasing reaction to take place in it.
order of ionic conductance at infinite 2 2
dilution? Cu(s) +Zn (aq)  Cu (aq) + Zn(s)
1) F   CI   Br   I  2) I   Br   F   Cl  1) 0 1.0V 2) 1.1V 3) 1.2V 4) 0.55V
    
3) F  CI  I  Br 4) F  I  CI  Br   2 
29. Given: Fe s  Fe  2e ; E  0.44V
0

24. The equivalent conductances of two strong


electrolytes at infinite dilution at 25 0 C aree Pb s  Pb2  2e ; E 0  0.13V
given below :
 0 CH COONa  91.0 S cm 2 / equiv
3
Ag   e  Ag; E0  0.8V
 HCl  426.2 S cm 2 / equiv
0
Cu 2  2e  Cu; E0  0.34V
What additional information / quantity one Which of the following metal ion will oxidise
needs to calculate  0 of an aqueous solution iron?
of acetic acid ? 1) Ag+ only 2) Cu2+ only
1)  0 of chloroacetic acid (ClCH 2COOH) 3) Pb+2 only 4) All
2)  of NaCl
0
3)  of CH 3COOK 30. If a spoon of copper metal is placed in a
0

4) The limiting equivalent conductance of solution of ferrous sulphate


H  ( 0 H  ) 1) Copper will precipitate out
25. The value of  m for KCl and KNO3 aree 2) Iron will precipitate
3) Cu and Fe will precipitate
149.86 and 154.96  1cm 2 mol 1.
4) No reaction takes place
Also Cl  is 71.44ohm 1cm 2 mol 1. 31. A student made the following observations

The value of NO3 is in the laboratory,
A) Clean copper metal did not react with
1) 76.54 ohm 1cm 2 mol 1
1molar Pb  NO3 2 solution
2) 133.08 ohm 1cm 2 mol 1
B) Clean lead metal dissolved in a 1 molar
3) 37.7 ohm 1cm 2 mol 1 4) Unpredictable.
AgNO3 solution and crystals of Ag metal
26. Specific conductance of 0.1 M CH 3COOH at
appeared
25°C is 3.9  10 4 ohm 1cm 1 C) Clean silver metal did not react with
if   H 3O  and   CH 3COO  at 25°C 1molar Cu  NO3  solution.
   
2
 1
are 349.0 and 41.0 ohm cm mol respectively
2 The order of decreasing reducing character
degree of ionisation of CH 3COOH at the of the three metals is
1) Cu, Pb, Ag 2) Cu, Ag, Pb
given concentration is
1) 1.0% 2) 4.0% 3) 5.0% 4) 2.0% 3) Pb, Cu, Ag 4) Pb, Ag, Cu
39. I 2  s  | I   0.1M  half cell is connected to a
32. Standard reduction potential values for the
electrodes are given below.
Mg2+ + 2e–  Mg is –2.37V H   aq  | H 2 1 bar  | Pt half cell and e.m.f. is
Zn2+ + 2e–  Zn is –0.76V
found to be 0.7714V . If EI 2 |I   0.535V , find
0
Fe2+ + 2e–  Fe is –0.44 V
Which of the following statement is correct
1) Zinc will reduce Fe2+ the pH of H  | H 2 half-cell
2) Zinc will reduce Mg2+ 1) 1 2) 3 3) 5 4) 7
3) Mg oxidises Fe 40. Which of the following will increase the
4) Zinc oxidises Fe voltage of the cell Sn(s)+2Ag+(aq)  2Ag(s) +
33. The life span of a Daniel cell may increased Sn2+
by 1) Increase in the concentration of Sn2+ ions
1) Large Cu electrode 2) increase in the concentration of Ag+ ions
2) Lowering of CuSO4 concentration 3) increase in the size of silver rod
3) Lowering of ZnSO4 concentration 4) removal of salt bridge
4) Large zinc electrode 41. The standard EMF of the cell reaction
34. To the Daniel cell ZnSO4 is added to the left Zn+Cu2+  Cu+Zn2+ is 1.10V at 250C. The
hand side electrode. Then cell emf
EMF for the cell reaction when 0.1M Cu2+
1) Increases 2) Decreases
and 0.1M Zn2+ solutions are used at 250C, is
3) Doest not change
4) First increases & then decreses 1) 1.10V 2) 0.110V 3) –1.10V 4) –0.110V
35. The reaction 42. The E 0 at 250 C for the following reaction at
1 the indicated concentrations is 1.50 V.
H 2( g )  AgCl( s )  H (aq )  Cl(aq )  Ag ( s ) Calculate the G in kJ at 250 C :
2
occurs in the galvanic cell Cr  s   3 Ag   aq, 0.1M 
1) Ag | AgCl( s ) | KCl( So1n ) | AgNO3( so1n ) | Ag
 Ag  s   Cr 3  aq, 0.1 M 
2) Pt , H 2( s ) | HClSo1n ) | AgNO3( so1n ) | Ag
1) 140.94 2) 295 3) 212 4) 422.83
3) Pt , H 2( g ) | HCl( So1n ) | AgCl( s ) | Ag 43. The cell, Zn / Zn (1M)//Cu2+(1M) / Cu
2+

(Ecell0 = 1.10 V), was allowed to be completely


4) Pt , H 2( g ) | KCl( So1n ) | AgCl( s ) | Ag
discharged at 298 K. The relative
NERNST EQUATION concentration of Zn2+ to Cu2+ is
36. The e.m.f of the cell 1) 37.3 2) 1037.3
Ni / Ni 2 1M  // Cl  1M  Cl2 , Pt is
3) 9.65 × 104 4) antilog (24.04)
44. Deduce from the following E° values of half
 E Ni / Ni  0.25eV : 
0 2 cells, what combination of two half cells
  would result in a cell with the largest
 E 0 1 Cl / Cl   1.36eV 
 2
2
 potential?
1) -1.11V 2) 1.11V 3) -1.61V 4) 1.61V I) A  A+ + e ; E° = –0.24V
II) B –
 B+e; E° = –2.1V
37. The reduction potential of a hydrogen
electrode containing a solution of pH=4 is III) C  C2+ + 2e ; E° = –0.38V
IV) D  D + e ;
2– – E° = –0.59V
1) 0.236V 2) 4.059V 3) –0.236V 4) 3.941V
1) I and IV 2) II and III
38. The oxidation potential of a hydrogen
3) III and IV 4) I and II
electrode is related to the pH of the solution
0
by the equation at 25 C BATTERIES
1) –0.059 x pH 2) 0.059 x pH 45. When lead accumulator is charged, it is
0.059 1) An electrolytic cell 2) A galvanic cell
3) pH 4) 0.059 + pH 3) A Daniel cell 4) None of the above
46. During the discharge of a lead storage 54. Assertion A: Copper does not liberate
battery, density of H 2 SO4 fall from 1.3 to hydrogen from the solution of dilute
hydrochloric acid.
1.14 g/mL. Sulphuric acid of density 1.3g/ml
Reason R : Hydrogen is below copper in the
is 40W % and that of 1.14 g/mL is 20W%. electrochemical series.
The battery holds two litre of the acid and
55. Assertion (A) : E 0 value of single electrode
volume remains practically constant during
is determined experimentally by combining
discharging. The number of ampere-sec used
the electrode with SHE
from the battery is.
Reason (R): SHE is taken as a reference
1) 3 x 96,500 2) 6 x 96,500
electrode
3) 9 x 96,500 4) 12 x 96,500
47. Relative efficiency of the following cell is 56. Assertion (A): Equivalent weights of NaCl ,
84% NaOH , KCl , KBr , etc. are equal to their
A S   B2aq   A2aq   B S  H  285kJ
  molecular weights
 ,
Reason (R): Only one electron take part in
then the standard electrode potential of the electrode reaction.
cell will be
1) 1.20V 2) 2.40V 3) 1.10V 4) 1.24V PREVIOUS EAMCET QUESTIONS
57. At 298K the molar conductivities at infinite
CORROSION AND PASSIVITY
48. Zinc is used to protect corrosion of iron  
dilution  0 m of NH 4Cl , KOH and KCl
because
are 152.8,272.6 and 149.8 Scm2 mol 1
1) Eoxi of Zn< Eoxi of iron
respectively. The  m of NH 4OH in
0

2) Ered of Zn < Ered of iron


Scm2 mol 1 and % dissociation of 0.01
3) Zn is cheaper than iron
4) Zn is abundantly available M NH 4OH with  m =25.1 Scm2 mol 1 at the
49. The corrosion of iron object is favoured by same temperature are [2014]
1) presence of H  ion 1) 269.6,9.6 2) 30, 84
2) Presence of moisture in air 3) 275.6,0.91 4) 275.6,9.1
3) Presence of impurities in iron object 58. The no.of moles of Electrons required to
4) All of the above deposit 36g of Al from an aqueous solution
50. The composition of rust is of Al  NO3 3 is [2013]
1) Fe2O3. xH2O 2) Fe2O3 . 2H2O
1)4 2)2 3)3 4)1
3) Fe2O3.6H2O 4) Fe2O3
59. The emf (in V) of a Daniel cell containing
51. Assertion (A): In electrolytic conductors the
flow of current is due to the movement of ions 0.1M ZnSO4 and 0.01 M CuSO4 solutions at
towards oppositely charged electrodes their respective electrodes is [2012]
Reason (R): Electrolytes are only salts 1)1.10 2)1.16 3)1.13 4)1.07
52. Assertion (A): The extent of dissociation is 60. At a certain temperature and at infinite
different for different electrolytes dilution,the equivalent conductances of
Reason (R): The extent of dissociation is sodium benzoate, hydrochloric acid and
dependent on nature of electrolyte and sodium chloride are 240,349 and 229
independent of the concentration of ohm 1 cm 2 equiv 1 respectively. The equivalent
electrolyte. conductance of benzoic acid in
53. Assertion (A): ‘Li’ electrode always
acts as anode in voltaic cell ohm 1 cm 2 equiv 1 at the same conduition is:
Reason (R): ‘Li’ electrode has lowest SRP [2011]
among all the electrodes 1)80 2)328 3)360 4)408
61. A solution of concentration ‘C’ g equiv/litre 3. At Anode : Ag  Ag   e 
has a specific resistance R.The equivalent
The composition of Ag in AgNO3 solution
conductance of the solution is: [2010]
1)R/C 2)C/R 3)1000/RC 4)1000R/C between Ag electrodes, the composition of
62. For the following cell reaction electrolyte reamins constant.
5. Q = Ct
Ag Ag  AgCl Cl  Cl2 , Pt
m1 E1
6. 
G 0f  AgCl   109 KJ / mol m2 E2

G 0f  Cl    129kJ / mol
7. 9 g  96500c 5.12 103 g  ?
8. No. of moles of MnO 4 changed to
G 0
f  Ag   78kJ / mol

MnO 42 = 1–0.899 = 0.101


0
E of the cell is:
For 1 mole = 1F
1) -0.60 V 2) 0.60 V 3) 6.0 V 4) -6.0 V
63. At 250 C the molar conductances at infinite For 0.101 mole = 0.1 F
dilution for the strong electrolytes NaOH, 10. 2.8 lit O2 =4 gm at STP
W E
NaCl and BaCl2 are 248 104 ,126 104 and use W  E
1 1

2 2
280  10 4 s.m .mol respectively
2 -
11. Three faradays will deposit three equivalents of
 Ba  OH 2 in s.m .mol
0
m
2 
each electrolyte
1) 52.4  10 4 2) 524  10 4 MnO 4 Mn 2 
12. 7  2
3) 402  104 4) 262 104
Change in O.S. = 5
Current required = 5F
LEVEL-II (H.W) - KEY 13. 11.2 lit Cl2 at STP = 35.5 gm = 1 GEW
1)4 2)4 3)1 4)1 5)2 6)3 7)4  1 GEW of ‘Al’ will be deposited which is
8)2 9)1 10)3 11)2 12)2 13)3 14)3 ‘9’gm
15)3 16)4 17)3 18)4 19)2 20)2 21)1 Mct
14. m= find ‘Z’
22)2 23)1 24)2 25)1 26)1 27)4 28)3 ZF
29)3 30)4 31)3 32)1 33)4 34)2 35)3 15. 96,500C = 6.023 x 1023 e–s
36)2 37)3 38)2 39)2 40)2 41)1 42)4 60C = ?
43)2 44)4 45)1 46)2 47)4 48)2 49)4 100
17. n   0 .0 5
1000
50)1 51)3 52)3 53)1 54)3 55)1 56)1
57)4 58)1 59)4 60)3 61)3 62) 2 63) 2
18. 2 H 2O  2 H 2  O2

LEVEL-II (H.W) - HINTS 250


19. Weight of silver =  1 108
1. 2Cu 2 
4e 
 2Cu (cathode)
1000
108gms of silver = 96500C
 O2  4H  anode 

4e
2H2 O  27gms = ?
2H  SO42  H2SO4 l
2. On electrolysis of 50% H 2SO4 20. c  k
a
H 2SO 4  H   HSO 4 21. The greater the ionic mobility, the greater the
2H   2e  H 2   cathode  molar conductance. The ionic mobility of H 
2HSO 4  H 2S2 O8  2e  (anode) is greater than that of Na 
22. Conductivity (x)=conductance (c) x cell constant 40. Increase in conc. of cathode in increases the
x voltage.
Cell constant = 42. G  G 0  RT In Q
y
x 
  z   1000
Cr 3 

k  1000  y
    nFE  2.303RT log
0
3
M 0.1  Ag 3 
xz
= y  10
4
G  3  96500 1.50  8.314298
23. Depends on hydration  2.303log
 0.1
 0.1
3

  
24.  eq CH COOH    eqCH COONa    eq  HCl    eq NaCl 
3 3
 422838.3 J or  422.83kJ

25. From  
calculate  
and then  by
Cl  K NO3
0.059  Zn 2 
43. Ecell  E cell  2 log  2 
0
  
using  KNO3   K    NO3
Cu 
k  1000 / conc.
   46. M1  M2  10 1.3  40  1.14  20 
26. CH COO 
 H O  98
3 3

27. Low SRP metal reduces metal with high SRP. = 3Mole / Litre= 6 Moles Per 2 Litres.
28. For the given reaction to take place, G
47. e  
external EMF > EMF of the cell H
29. Fe 2  2e   Fe ; E 0  0.44 V G  nFE
2 
pb  2e  pb ; E  0.13V 0

LEVEL-III
Ag   e   Ag ; E 0  0.8V
Cu 2  2e   Cu ; E 0  0.34 V ELECTROLYSIS AND FARADAY’S LAWS
SRP values of pb, Ag, Cu are higher than Fe. 1. The time required (approx) to remove
So, pb, Ag, Cu oxidises Fe electrolytically one half from 0.2 litres of 1M
30. Copper electrode lies below the iron electrode AgNO3 solution by a current of 1 amp is
in electro chemical series. It can not displaces 1) 320min 2) 80min 3) 160min 4) 40min
the ion from FeSO4 2. The pH of 0.5L of 1.0M NaCl after the
32. Low SRP will reduce high SRP ion . electrolysis for 965 s using 5.0A current
33. Life span can be increased by increasing the size (100% efficiency)is:
of anode electrode. 1) 1.00 2) 13.00 3) 12.70 4) 1.30
34. In Daniel cell ZnSO4 is added to LHE, EMF 3. 0.2 faraday charge is passed in 1 litre solution
decreases. containing 0.1 molar Fe+3 ions. How many
36. E  E CSRP   E A SRP  moles of iron get deposited at cathode
assuming only iron is reduced in electrolytic
37. R.P. of hydrogen electrode = –0.059 x PH
38. O.P of hydrogen electrode = 0.059 x PH
0
process. (EFe3
/ Fe2
 0.77V EFe
0
2
/ Fe
 0.44V )
39. The cell reaction is 1) 0.05 moles 2) 0.033 moles
H 2  g   I 2  s   2H 
 aq   2 I  aq 
 3) 0.67 moles 4) 0.1 moles
4. Using electrolytic method, if cost of
2 2
H   I   production of 10L of oxygen at STP is Rs. x,
log    
0.0591
0.7714  0.535 
2 PH 2 the cost of production of same volume of
hydrogen at STP will be:
pH  3 1) 2x 2) x/16 3) x/32 4) x/2
5. For the electrolytic production of NaClO4 12. During the electrolysis of acidulated water,
the mass of hydrogen obtained is x times that
from NaClO3 according to the equation
of O2 and the volume of H 2 is y times that of
NaClO3  H 2O  NaClO4  H 2 , the number
O2 . The ratio of y and x is
of faradays of electricity required to produce
1) 0.25 2) 8 3) 0.125 4) 16
0.5 mole of NaCIO4 is
13. A 1M solution of H 2 SO4 is electrolyzed.
1) 1 2) 2 3) 3 4) 1.5
Select right statement with respect to
6. When 6  1022 electrons are used in the concentration of electrolyte and products at
electrolysis of a metalic salt, 1.9 gm of the anode and cathode respectively. Given:
metal is deposited at the cahode. The atomic
2SO42  S2O82  2e ; E 0  2.01 V
weight of that metal is 57. So oxidation state
of the metal in the salt is 1
H 2O l   2 H aq   O2 g   2e  ; E 0  1.23V
1)+2 2) +3 3) +1 4) +4 2
7. A copper plate of 10cmx10cm and 0.1cm 1) concentration of H 2 SO4 remain constant ;
thickness is to be plated with silver. If the H 2 , O2
density of Ag is 10.8g/cc, the number of
electrons required for this process is 2) concentration of H 2 SO4 increases ; O2 ,H 2
1) 1 mole 2) 2 moles 3) 0.5moles 4) 2.5 3) concentration of H 2 SO4 decreases ; O2 ,H 2
moles
4) concentration of H 2 SO4 remains constant ;
8. A lead storage battery containing 5.0 L of
1N H 2 SO4 solution is operated for 9.65  105 s S2O82 ,H 2
with a steady current of 100 mA. Assuming 14. The standard oxidation Potential of Ni/
+2
volume of the solution remaining constant, Ni electrode is 0.236V. If this is combined
normality of H 2 SO4 will with a hydrogen electrode in acid solution at
what pHof the solution will measured E.M.F.
1) Remain unchanged 2) Increases by 0.20
will be zero at 250C (  Ni   1M )
2
3) Increase by unity 4) Decrease by 0.40
1) 4 2) 1 3) 2 4) 3
9. On electrolysing K 2 SO4 solution using inertt
15. On electrolysing K 2SO4 solution using inertt
electrodes, 1.68L(STP) of gases were
electrodes, 1.68L(STP) of gases was

obtained. How many moles of M nO 4 could obtained. How many moles of MnO 4 could
be reduced to Mn 2 by the same quantity of be reduced to Mn 2  by the same quantity of
electricity ? electricity ?
1) 0.10 2) 0.20 3) 0.15 4) 0.02 1) 0.02 2) 0.15 3) 0.20 4) 0.10
16. Given the following molar conductivities at
10. In electrolytic reduction of a nitroarene with
50% current efficiency, 20.50g of the 250 C ; HCl ; 426  1 cm 2 mol 1 ; NaCl ,
compound is reduced by 2  96500 C of 126  1cm 2 mol 1 ; NaC (sodium crotonate),
electric charge. The molar mass of the
83 1cm 2 mol 1 . What is the ionization
compound is:
constant of crotonic acid? If the conductivity
1) 20.50g 2) 10.25g 3) 123.00g 4) 61.50g of a 0.001 M crotonic acid solution is
11. The quantity of electricity in faradays
3.83  10 5  1cm 1 ?
required to reduce 1.23 gm of nitro benzene
to aniline is 1) 105 2) 1.11 10 5
1) 0.12 2) 0.03 3) 0.06 4) 0.6 3) 1.11 10 4 4) 0.01
ELECTROLYTIC CONDUCTANCE ELECTRO CHEMICAL CELLS & EMF
17. The specific conductance at 298 K of AgCl is 23. A Daniel cell constructed in the laboratory.
The voltage observed was 0.9V instead of
1.826×10-6 ohm 1cm 1 . The ionic conductances
1.10V of the standard cell. A possible
of Ag + and Cl  are 61.92 and 76.34 explanation is
respectivley. What is the solubility of AgCl 1) Molar ratio of Zn+2: Cu2+ is 2 : 1
in water? 2) The Zn electrode has thrice the surface of Cu
1) 1.1102 g 1 2) 1.9 103 gL1 electrode
3)  Zn   Cu  4)  Zn   Cu 
2 2 2 2
3) 1.3  10 5 gL1 4) 2.1106 gL1
18. The conductivity of 0.1 N NaOH solution is 24. The standard reduction potentials of Cu2+/
0.022 S cm 1 . When equal volume of 0.1 N Cu and Cu 2+/Cu + are 0.337 and 0.153V
HCl solution is added, the conductivity of respectively. The standard electrode
resultant solution is decreases to potential of Cu+/Cu half cell will be
1) 0.184V 2) 0.827V 3)0.521 V 4) 0.490 V
0.0055 S cm 1 . The equivalent conductivity in 25. Given the cell reactions
S cm 2 equivalent 1 of NaCl solution is MX  s   e   M  S   X   aq  ; E 0  0.207 V
1) 0.0055 2) 0.11 3) 110 4) 55
19. Equivalent conductance of 1 M propanoic and M   aq   e   M  s  ; E 0  0.799 V
acid is 10 ohm 1 cm 2 eq 1 and that at infinite The solubility of MX  s  at 298 K is:
dilution 200 ohm 1 cm 2 eq 1 . pH of the 1) 1.0  1010 mole L1 2) 1.0 109 mole L1
propanoic acid solution is
1) 7 2) 3.3 3) 1.3 4) 6.8 3) 1.0 104 mole L1 4) 1.0 105 mole L1
20. Resistance of a conductivity cell filled with 26. EMF of an H 2  O2 fuel cell
a solution of an electrolyte of concentration
0.1 M is 100  . The conductivity of this 1) Is independent of partial pressures of H 2
solution is 1.29 S m 1 . Resistance of the same and O2
cell when filled with 0.2 M of the same 2) Decreases on increasing PH 2 and PO2
solution is 520  . The molar conductivity of 3) Increases on increasing PH 2 and PO2
0.02 M solution of electrolyte will be
4) Varies with the concentration of OH  ions in
1) 1.24  10 4 S m 2 mol 1 2) 12.4  10 4 S m 2 mol 1
the cathodic and anodic compartments.
3) 124  10 4 S m 2 mol 1 4) 1240  10 4 S m 2 mol 1 27. The EMF of the cell
21. The specific conductance and equivalent
conductance of a saturated solution of Pt , Cl2 g   Patm
1  Cl   aq  1M  Cl2 g   P2 atm  ,
5
BaSO4 are 8  10 ohm cm and
1 1 Pt will be positive when:
8000 ohm 1cm 2 equi 1 respectively. Hence K sp 1) P1  P2 2) P1  P2 3) P1  P2
4) Cannot be predicted
of BaSO4 is 28. Standard electrode potential for Fe electrode
1) 2.5  1010 M 2 2) 2.5  1011 M 2 are given as
 
3) 2.5  10 M 20 2 4) 2.5  10 M 23 2
Fe   2e   Fe E 0  0.44 V
22. At 250 C the equivalent conductance of Fe3  e   Fe  E 0  0.77V
butanoic acid at infinite dilution is 386.6 Fe  , Fe  and Fe block are kept together
1 2 1
ohm cm eq . If the ionization constant is then
1.4 105 , calculate equivalent conductance 1)  Fe  decreases 2)  Fe  increases
of 0.05 N butanoic acid solution at
1 2 1
3)  Fe .Fe  remains unchanged
250 C (ohm cm eq ) ?
1) 3.87 2) 6.46 3) 6.94 4) 4.38 4)  Fe  decreases
29. At any instant during the reaction 33. The standard reduction potential for
Zn  Cu   Zn   Cu occurring in an open Cu2 / Cu is 0.34V . Calculate the reduction
beaker at temperatue T potential at pH=14 for the above couple,
 Zn   .Cu  K sp of Cu  OH 2 is 1.0  10 19 .
1) G   RT ln
0
1) –0.2205 V 2) +0.2205V
 Zn . Cu   3) –0.11 V 4) +0.11 V
2) G  work available from the reaction 34. During discharging of lead-storage acid
3) G  0 4) G  0 battery following reaction takes place:
2 2 Pb  S   PbO2  S   2 H 2 SO4
30. Zn  Cu  aq   Cu  Zn  aq  R e a c t i o n
 2 PbSO4  S   2 H 2O
 Zn 2  If 2.5 amp of current is drawn for 965
quotient, Q   2  Variation of Ecell with
Cu  minutes, H 2 SO4 consumed is:
1) 0.75 mol 2) 3.00 mol
log Q is of the type with OA  1.10 V , Ecell will
3) 1.50 mol 4) 4.50 mol
be 1.1591 V When
35. Zn / Zn  C1  / / Zn  C2  / Zn, for this cell
2 2

G is negative if :
1) C1  C2 2) C1  C2
3) C2  C1 4) Both 1 & are correct
36. The oxidation potential of hydrogen
electrode H 2 / H 3O  (aq) will be greater than
zero if,
1) Cu   /  Zn    0.1 2) Cu   /  Zn    0.01 1) Concentration of H 3O  ions is 1M

 Zn   / Cu    0.1 2) Concentration of H 3O  ions is 2M


3)  Zn   / Cu    0.01 4)
31. For the half cell 3) Partial pressure of H 2 gas is 2 atm
4) E(oxidation) can never be +ve
37. The reduction potential of hydrogen
electrode will be positive if
1) p  H 2   1atm,  H   1M

E 0  1.30 V

2) p  H 2   1atm,  H   2 M


At pH  3 electrode potential is 3) p  H 2   2atm,  H    2 M
1) 1.30 V 2) 1.20 V 3) 1.10 V 4) 1.48 V 4) p  H 2   2.5atm,  H   1.5M

32. Find the equilibrium constant for the reaction


38. A galvanic cell is made up to S.H.E and
In 2  Cu 2  In3  Cu  at 298 K another hydrogen electrode. The other
Given, E Cu 2 / Cu   0.15V , E In / In  0.42V
0 0
3
hydrogen should be immersed in which of

the following solutions to get maximum value


E 0 In2 / In  0.40V of e.m.f. :
1) 1010 2) 1011 3) 1012 4) 1014 1) 0.1M HCl 2) 0.1M CH 3 COOH
3) 0.1M H 2 SO4 4) 0.1M H 3 PO4
39. The following facts have been observed: 45. In a fuel cell methanol is used as fuel and

2X  Y2  2Y  X2  oxygen gas is used as an oxidizer. The reaction
is at 298k standard Gibb’s energies of
2W   Y2  No reaction 2Z   X 2  2 X   Z2 formation of CH3 OH l  , H2O l  and CO2 g  aree
Which of the following sequence is true?
–166.2, –237.2 and –394.4 KJ/Mole
1) E0 w  / w 2  E0 Y / Y2  E0 X / X2  E0 Z / z 2 respectively. If standard enthalpy of
2) E0 w  / w 2  E0 Y / Y2  E0 X / X2  E0 Z / z 2 combustion of Methanol is –726 KJ. Mole-1,
3) E0 w  / w 2  E0 Y / Y2  E0 X / X2  E0 Z / z2 efficiency of the fuel cell will be (AIE-2009)
1) 80% 2) 87% 3) 97% 4) 90%
4) E0 w  / w 2  E0 Y / Y2  E0 X / X2  E0 Z / z 2 46. The Gibbs energy for the decomposition of
40. Two weak acid solutions HA1 and HA2 each Al2O3 at 500C is as follows.
with same concentration and having pka
2 4
values 3 and 5 respectively are placed in Al2 O3  Al  O2 , G  966KJ Mole1
3 3
contact with hydrogen electrode (1 atm at
250C) and are interconnected through a salt The potential difference needed for
bridge. Find the emf of the cell? electrolytic reduction of Al2O3 at 500C is at
Pt,H2(1 atm) / HA2//HA1 / H2(1atm), Pt least (AIEEE – 2010)
1) 0.079 2) 0.059 3) 0.118 4) 0.029 1) 4.5 V 2) 3.0 V 3) 2.5 V 4) 5.0 V
41. The standard reduction potentials for 47.
The following are some statements about
Voltaic cell
Zn/Zn+2 Ni 2 / Ni, and Fe2 / Fe are -
I) Chemical energy converted into electrical
0.76,0.23and -0.44 V respectively. energy
2 
The reaction X  Y  X  Y will be 2  II)Electrons flows from anode to cathode
spontaneous when. III) Oxidation occurs at anode
1) X  Ni, Y  Fe 2) X  Ni, Y  Zn IV) Anode is negative and cathode is positive
The correct answer is
3) X  Fe, Y  Zn 4) X  Zn, Y  Ni 1) Only I & III are correct 2) Only I, II & III are
42. What will be the emf for the given cell correct
Pt H2 P1  H  aq  H2 P2  Pt
 3) Only I, III & IV are correct 4) All are correct
48. In an electro chemical process, a salt bridge
RT P1 RT P1 is used
1) F log P 2) 2 F log P a) to maintain electrical neutrality in each
2 2
solution.
RT P2 b) to complete the circuit so that current can
3) F log P 4) none of these flow
1

43. The negative Zn pole of Daniell cell, sending c) as an oxidising agent


a constant current through a circuit, d) as a colour indicator
decreases in mass by 0.13 g in 30 minutes. If 1) only a is correct 2) a and b are correct
the chemical equivalent of Zn and Cu are 32.5 3) a, b and c are correct 4) all are incorrect
and 31.5 respectively, the increase in the mass 49. During the working of a galvanic cell and
of the positive Cu pole in this time is with the passage of time:
1) 0.180 g 2) 0.141g 3) 0.126 g 4) 0.242 g a) spontaneity of the cell reaction decreases,
44. Given the data at 250 C Ecell decreases

Ag  I    AgI  e E 0  0.152V b) reaction quotient Q decreases, Ecell decreases


Ag  Ag   e  E 0  0.800V c) Reaction quotient Q increases, Ecell decreases
What is the value of log K sp for AgI? d) At equilibrium, Q  K e , Ecell  0
Correct statements are
1) -37.83 2) - 16.13 3) - 8. 12 4) + 8. 612
1) b,c,d 2) a,d 3) a,c,d 4) All
50. Following are some of the facts about a dry 55. Resistance of 0.2M solution of an electrolyte
cell is 50 .The specific conductance of the
I : It is also called Leclanche cell solution is 1.4 Sm1 .The resistance of 0.5 M
II : It is also called Daniel cell
solution of same electrolyte is 280 .The
III : Electrolyte is a moist paste of NH 4Cl molar conductivity of 0.5 M solution of the
and ZnCl2 in starch electrolyte in S m 2 mol 1 is: [2014]
IV : Cathodic reaction is 1) 5 103 2) 5 102 3) 5 104 4) 5 103
2 MnO2  s   2 NH 4  aq   2e  56. Given: [2013]
 Mn2O3  s   2 NH 3  g   H 2O  l   1.51V
0
E0 Cr3+  0.74V ; E MnO4-
Cr Mn 2+
Select correct facts :
1) I, II, III 2) I, IV 3) I, III, IV 4) II, III, IV E0 Cr2O72- = 1.33 V ; E0 Cl = 1.36 V
Cr 3+ Cl 3
51. The following are some statements about
Based on the data given above,strongest
electrolysis
oxidising agent will be:
I) Involves flow of electrons from anode to
cathode 1) Cl  2) Cr 3 3) Mn 2 4) MnO4
II) Involves no chemical reaction at electrodes 57. The standard reduction potentials for
III) Oxidation occurs at anode and reduction at Zn 2 / Zn, Ni 2 / Ni , and Fe 2  / Fe aree
cathode –0.76, –0.23 and –0.44 V respectively.
IV) Anions migrate towards cathode The reaction X  Y 2  X 2  Y will
The correct combination is
be spontaneous when : [2012]
1) Only I and III are correct
2) Only I and II are correct (1) X = Ni, Y = Fe (2) X = Ni, Y = Zn
3) Only I, II and III are correct (3) X = Fe, Y = Zn (4) X = Zn, Y = Ni
4) All are correct 58) The reduction potential of hydrogen half cell will
52. For the following cell reaction be negative if : [2011]
Ag | Ag  | AgCl | Cl  | Cl2 , Pt (1) p  H 2  = 1 atm and  H  =1.0 M

G 0f  AgCl   109kJ / mol , (2) p  H 2  =2 atm and  H  =1.0 M


G 0f  Cl    129 KJ / mol and (3) p  H 2  = 2 atm and  H  = 2.0 M


G 0 f  Ag    78 KJ / mol . E 0 of the cell is (4) p  H 2  =1 atm and  H  = 2.0 M


1) - 0.60V 2) 0.60V 3) 6.0V 4) None


53. The half cell reactions for the corrosion are, LEVEL-III - KEY
1 1)3 2)3 3)1 4)4 5)1 6)2 7)1
2 H   O2  2e   H 2O; E 0  1.23V
2 8)4 9)4 10)3 11)3 12)4 13)2 14)1
Fe2  2e  Fe( s ) ; E 0  0.44V . Find the 15)1 16)2 17)2 18)3 19)3 20)1 21)2
22)2 23)4 24)3 25)4 26)3 27)3 28)1
G 0 (in KJ) for the overall reaction 29)2 30)3 31)4 32)1 33)1 34)3 35)3
1) -76 2) -322 3) -161 4) -152
36)3 37)2 38)2 39)2 40)2 41)4 42)4
54. The metal that cannot be obtained by
electrolysis of an aqueous solution of its salts 43)3 44)2 45)3 46)3 47)4 48)2 49)3
is: [2014] 50)3 51)1 52)2 53)2 54)4 55)3
1)Cu 2)Cr 3)Ag 4)Ca 56)4 57)4 58)2
LEVEL-III - HINTS 14. E 0 Ni 2 / Ni  0.236V
1. Find the amount of ‘Ag’ in the solution. 0
Ecell  0.236
Then use the formula m = ect and find ‘t’
0.06 [ Ni 2 ]
1 5  965 0  0.236  log  2
2. Mole of OH  formed =  0.05 2 [H ]
96500
15. The molar conductivity of the dissociated form
3. 0
EFe 3
/ Fe
 0.037V as the reduction potential of of crotonic acid is
Fe 3 / Fe 2 is higher inititaly all Fe converts  m  HCl    m  HCl    m  NaC 
+3

into Fe+2, which further gets reduced to metallic


iron.  m  NaCl 
4. Volume of H 2  2 volume of O2   426  83  126   1cm 2 mol 1
5. 1 mole of NaClO4 requires 2F  383 1cm 2 mol 1
6. 1.9g of metal - 6  1022 e  ? The molar conductivity of HC ,
K
- 6  10 23 e   m  HCl  
C
7. w  vd
8. SO4 3.83 105  1cm 1
T h e r e a c t i

2
o n i n d i c a t e s t h a t 2 m o l o f H

  1000  38.3 1cm 2 mol 1


corresponds to 2 x 96500 C and 2 mol H2SO4  0.001
4 equiv. of H2SO4. 2 x 96500 C consumed 4 The degree of dissociation,
equiv. of H2SO4 and
 m  HC   38.3 cm mol 
1 2 1

100 x 10–3 x 9.65 x 105 C consumed    0.1


 m  HC   383 1cm 2 mol 1 
4  100  103  9.65 105
 2 equiv. H 2SO 4
C 2 10   0.1
 3 2
2  96500
Ka    1.11 105
2 1 1  01
 Decrease in normality =  0.40
5 K 1000
16. Solubility  S  
9. Volume of hydrogen  STP   V ml 
  61.92  76.34  138.26
V
Volume of O2  STP   ml during the 17. Normality of resultant solution
2
0.1 V
electrolysis of K 2 SO4 (aq)   0.05 N
V V
V
V   1.68 0.0055
2 Aeq  1  110 S cm 2 eq 1
0.05
M 50
10. 20.50   2  96500   c eq 10
96500 100 18.     0.05
 0 eq 200
11. Ar  NO2  6 H   6e   Ar  NH 2  2 H 2O
 H    C  1 0.05  0.05
12. M H2  xO2  x  1/8
pH   log  H     log  5  102 
VH 2  yO2  y  2
 2 log 10  log 5  2  0.6990  1.3
l l  Fe  Fe 2  2e   Anode 
19. x  ; cell constt.  a   1.29  100  129
 
R.a
Again conducting of 0.02 M solution and
 Fe 3
 e   Fe 2   2  Cathode 
Fe  2 Fe3  3Fe 2
1
x  129 Thus if Fe 2 , Fe3 and Fe block are kept
520
together Fe3 get reduced to Fe  ie.,
x  1000 129 1000
m     1.24  10 4 Sm 2 mol 1 concentration of Fe3 decreases.
M 520 0.02

k  1000 N  k 1000 0.0591  Zn 2 


20.  eq = ,  eq 30. Ecell  E 0
 log
Cu 2 
cell
N 2
Normality
Solubility = Molarity = charge of ion 0.0591 Zn 2
1.1591  1.10  log 2
2 Cu
Ba SO4  Ba+2 + SO4-2
Ksp = xx . yy . (s)x+y = 11 . 11 (s)1+1 = s2 31. In this equation E  E 0  0.0591 log  H  
2

2
22. Given 0eq  386.6 ohm1 cm2 eq 1
 E 0  0.0591 log  H    E 0  0.0591 pH
C 2 Ka  1.30  0.0591 3  1.48 V
K  1.4  10 As K  5 ; or  
1 C

1.4 105 0.059


  0.0167 32. 0.59  log K C
0.05 1

ceq K sp
33. Cu  
2
 or ceq   0eq 2
0eq OH  
 0.0167  386.6  6.46 ohm1 cm2 eq1
0.059
E RP  E 0RP  log10 Cu 2 
0.059  Zn 2  2
23. Ecell  E 
0
log 34. Oxidation :
Cu 2 
cell
n
Pb  s   SO24  aq   PbSO4  s   2e
Ecell decrease indicates  Zn   Cu 
2 2
Reduction :
24. G03  G10  G02 PbO 2  s   4H   aq   SO 42  aq   2e 
 
25. MX  S   M  aq   X  aq   PbSO 4  s   2H 2 O  l 
0
ECell  0.207  0.799  0.592V During discharging H 2SO 4 consumed
log ksp  10  S  105 W = zit

0.059 Mass of H 2SO 4  2mol  2  98g


26. ECell  Ecell 
0
log pH 2 . pO1/22
2 mass of H 2SO 4
z
0.059 p electrons  96500
27. Ecel  2
log 2 Ecell  ve p2  p1
p1 2  98  2.5  965  60
w
28. Fe 2 / Fe acts as anode; Fe  / Fe acts as 2  96500
cathode.  147 g  1.5 mol
0.059 C 52. Ag  Ag   1e 
35. E cell  0  log 1
2 C2 1 / 2Cl2  1e   Cl 
To obtain E cell +Ve for the sportaneous reaction G 0  GPr0 oduct  GRe
0
ac tan t

C2  C1 G 0   nFE 0
G 0
 PH 2  E0 
1/ 2
0.059
37. EH  / H 2 , Pt  n
log
 H  
nF
53. E 0 cell  1.67v
0.059 C G 0  2  96.5  1.67
38. Eo = log 1
n C2
LEVEL-IV
39.
0.059 ka Passages Type Question
40. Ecell  0  2
log 2
ka1 Passage 1:
An acidic solution of cu 2 salt containing 0.4 g
41. Zn  Fe2  Zn2  Fe of copper is electrolysed until all the copper is
deposited. The electrolysis is continued for
Fe  Ni  Fe2  Ni
seven more minutes using 1.2 amp current.
Zn  Ni 2  Zn2  Ni 1. Which gas is evolved at anode when copper
is deposited at chathode?
All these are spontaneous
1) H 2 2) O2 3) So2
44.  i  Ag  Ag   e E 0  0.800V
4) Both So2 and O2
 ii  Ag  I 
 AgI  e 
E  0.152V
0
2. During another seven minutes of electrolysis.
the substances evolved at cathode and anode
(I) - (II) we have AgI  Ag   I  respectively are:
E 0  0.952V 1) H 2 , So2 2) H 2 , O2 3) Cu, O2 4) H 2 , Cu
3. The time required for deposition of 0.4g
0.952  0.059 log  Ag    I   copper at cathode is:
1) 1013 sec 2) 2013 sec
0.952
  log K sp 16.13  log K sp 3) 3013 sec 4) 4013 sec
0.059
Passage 2:
G At infinite dilution, when the dissociation of
45.   , G  Gf  pr oducts 
H electrolyte is complete. each ion makes a definite
contribution towards the molar conductance of
– Gf  reactants  = –394.4 – 2(237.2) + 166
electrolyte, irrespective of the nature of the ion
= –702 KJ/Mole with which it is associated.
the molar conductance of an electrolyte at
702.6
  100  97% infinite dilution can be expressed as the sum of
726
the contributions from its individual ions.
 G 966  10 3 Ax By  xA y   yB x 
46.  G   nFE , E     2.5V
nF 4  96500
 0m  Ax By   x A0 y  yB0x
where, x and y are the number of cations and STATEMENT-II : Zn is deposited at anode and
anions respectively. Cu is dissolved at cathode.
The degree of ionisation ' ' of weak electrolyte 8. STATEMENT-I : Molar conductivity of a weak
can be calculated as: electrolyte at infinite dilution cannot be
determined experimentally.
m
 STATEMENT-II : Kohlrausch law helps to find
 0m the molar conductivity of a weak electrolyte at
infinite dilution.
4. The ionic conductance of Al 3 and SO42 ions
at infinite dilution are x and y ohm  cm 2 mol  9. STATEMENT-I : H 2 O2 fuel cell gives a
respectively. If Kohlrausch’s law is valid, then constant voltage throughout its life.
molar conductance of aluminium sulphate at STATEMENT-II : In this fuel cell, H2 reacts
infinite dilution will be: with OH  ions yet the overall concentration of
1) 3 x  2 y 2) 3y + 2x 3) 2x + 2y 4) 3x + 3y 
ions does not change.
OH
5. The molar condutance of 0.001M acetic acid 10. STATEMENT-I : The conductivity of solutions
is 50 ohm  cm 2 mol  The maximum value of of different electrolytes in the same solvent and
molar condutance of acetic acid is at a given temperature is same.
250 ohm  cm 2 mol  . What is the degree of STATEMENT-II : The conductivity depends
dissociation (  ) of acetic acid? on the charge and size of the ions in which they
dissociate, the concentration of ions or ease with
1) 0.5 2) 0.2 3) 0.3 4) 0.4 which the ions move under potential gradient.
6. The unit of molar condutance of an 11. STATEMENT-I : In a dry cell zinc acts as
electrolyte solution will be: cathode and carbon rod as anode.
  2 
1) ohm cm mol2 2) mho cm mol STATEMENT-II : A dry cell has a potential of
nearly 1.5V
3) S cm 2 mol  4) mho 1 cm 1 mol 1
LEVEL-IV - KEY
STATEMENTS
1)2 2) 2 3) 1 4)2 5)2 6) 2 7) 2
1) Both STATEMENT-I and STATEMENT-II
are true and STATEMENT-II is the correct 8) 2 9) 1 10) 4 11) 4
explanation of STATEMENT-I.
2) Both STATEMENT-I and STATEMENT-II
are true and STATEMENT-II is not the correct
explanation of STATEMENT-I.
3) STATEMENT-I is true and
STATEMENT-II is false
4) STATEMENT-I is false but
STATEMENT-II is true
7. STATEMENT-I : For the Danniel cell,

Zn Zn 2 Cu 2 Cu with Ecell  1.1V


application of opposite potential greater than
1.1V result into flow of electron from cathode
to anode.

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