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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 , Fe2
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 105 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 SO42 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
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
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 24
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
Anode(-) cathode(+)
Porous
draphragm
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 (104 M ) 2e 2 Ag ( s )
has Ecell
0
0.236 V at 298K. Calculate the
Mg ( s ) 2 Ag (104 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
It is costlier.
Overall reaction : 2 H 2 g O2 g 2 H 2Ol 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
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
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
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 xAn yBn
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 103 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 ECSRP E ASRP
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 mol1 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 102
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.
log 101
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 72 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 61.92104Smol1m2 at 250C the
91.0 1cm 2 eq 1 . Its conductivity would be
ionic mobility of Ag will be
1) 1.45 103 1cm 1 2) 2.17 103 1cm 1
1) 6.4 108 2) 6.192
3) 2.90 103 1cm 2 4) 2.9 103 1cm 1
3) 6.192 104 4) 3.2 104
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.litre1 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) 1.64 105 2) 3 104 3) 3 105 4) 3 106 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
Ohm1 . If the conductance of 0.1M are –2.37v, –0.44v and –0.76v respectively.
NaOH filled in the same cell is Z Ohm1 , 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
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
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) 402 104 4) 262 104
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
24. eq CH COOH eqCH 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 CSRP 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. (EFe3
/ Fe2
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) 105 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) 1.1102 g 1 2) 1.9 103 gL1 electrode
3) Zn Cu 4) Zn Cu
2 2 2 2
3) 1.3 10 5 gL1 4) 2.1106 gL1
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 1010 mole L1 2) 1.0 109 mole L1
propanoic acid solution is
1) 7 2) 3.3 3) 1.3 4) 6.8 3) 1.0 104 mole L1 4) 1.0 105 mole L1
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 1010 M 2 2) 2.5 1011 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
1.4 105 , 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
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
2
o n i n d i c a t e s t h a t 2 m o l o f H
2
22. Given 0eq 386.6 ohm1 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
ceq K sp
33. Cu
2
or ceq 0eq 2
0eq OH
0.0167 386.6 6.46 ohm1 cm2 eq1
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 105 W = zit
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 Zn2 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 Zn2 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 Gf pr oducts
H electrolyte is complete. each ion makes a definite
contribution towards the molar conductance of
– Gf 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 yB0x
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,