ELECTRO CHEMISTRY

Cells are of two types:-

Electrolytic cell Electrochemical cell

Electrical energy is converted into Chemical energy is converted into

chemical energy. electrical energy.

Electrolytic cells works on direct redox Indirect redox reaction principle i.e.
reaction principle i.e. oxidation and oxidation and reduction take place in
reduction takes place inside the same different vessels.
vessel.

Electrolytic cell: Anode sign is (+) and Anode’s sign is (-) ve and cathode sign is
cathode is (-) (+)ve

Sign of G is +ve .In this case, energy is Sign of G is (-) ve chemical energy is
supplied from external sources hence converted into electrical energy hence
chemical potential keeps increasing or the chemical potential keeps decreasing
G will be +ve or G will be (-)ve.

Electrochemical cell.
An electrochemical cell consists of two half cells called as the anode half cell and
cathode half cell.The two are connected with the help of a salt bridge which helps to
maintain electrical neutrality and completes the inner circuit.The external circuit consists
of electrodes connected to a voltmeter.

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Electrochemical cell

Electrode Potential.
When a metal is placed in solution of its own ions there are three possibilities.
1)The metal ions strikes the metal surface and bounces off .
2)Metal could change into a metal ion by loosing electron and go into solution or
3)Metal could get deposited by accepting electrons.
The tendency to loose or gain electrons in solution is expressed in terms of its
potential.oxidation potential measures the tendency to loose electrons in solution and
reduction potential measures the tendency of a substance to gain electrons in solution.

EMF of a cell and cell representation.

When two different metals are placed in their own solutions and if concentration remains
constant, automatically a difference of potential is established since no two species
have the same value of potential.It is this difference of potential which is the driving
force behind the working of a cell and is called as the EMF of a cell .EMF can be
calculated as the difference of either oxidation or reduction potential. However by
convention the standard potential is always taken to be reduction potential and in terms
of reduction potential EMF is potential of cathode(half cell reaction with higher electrode
potential) minus potential of anode(half cell reaction with lower electrode potential).
(both values being in terms of reduction potential).

Ecell=Ec-Ea

E⁰cell=E⁰c-E⁰a
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Net cell reaction is the sum of anode and cathode half reactions.A cell is represented as
Anode // Cathode.The electrode on the left is written in the
order:electrode/ion(e.g.Zn/Zn2+) and on the right is written in the order: ion/electrode
(e.g.Cu2+/Cu).Anode half reaction is always the oxidation reaction and cathode half
reaction is reduction reaction.

Thermodynamic aspects of cell reactions.

Electrical energy of a reversible cell originates from the free energy decrease (-∆G) of
the reaction occurring in the cell.
-∆G=nFE
-∆G⁰=nFE⁰
A cell works if its emf is positive.If emf is negative it either means that the cell does not
work or it is working in the reverse direction.standard conditions refers to temperature
25⁰C and 1 bar pressure. If EMF is positive,∆G will be negative and the reaction will be
spontaneous i.e.the cell will function.

Salt bridge
Salt bridge consists of an inverted U glass tube filled with electrolytes like KNO3 mixed
with agar-agar.It helps to maintain electrical neutrality by facilitating the movement of
ions through it.If salt bridge is removed the cell loses its neutrality and ceases to work.

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Reference electrode -Standard Hydrogen Electrode (SHE or NHE)

SHE or NHE consists of a platinum wire or gauze dipped in 1 M Conc.HCl solution.This

electrode is enclosed in a glass vessel with an opening through which hydrogen gas is
bubbled in at 1 bar pressure.Platinum is inert to hydrogen and facilitates flow of
electrons. By convention the standard potential of SHE is taken as zero.The electrode is
reversible with respect to H+.
H+(aq) + e- 1 H2(g)
2
Arrangement of species in order of their potential is called as electrochemical series.

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Applications of electrochemical series.
1)In determining the electrodes of a cell .For a feasible cell reaction ,the one with
higher oxidation potential should act as anode and the one with higher reduction
potential should act as cathode.
2)It can be used to predict the feasibility of a process.
3)Amongst different species,the one with higher oxidation potential will be the strongest
reducing agent and the one with higher reduction potential will be the strongest
oxidising agent.
4)Elements with negative reduction potential values can displace hydrogen from acids
or alkalis.
5)Elements with higher oxidation potential can displace elements with lower oxidation
potential from solution but not the other way around.Similarity elements with higher
oxidation potential can be stored in vessel of lower oxidation potential.

NERNST EQUATION
Nernst equation gives the variation of emf with concentration and is written in terms of
reduction potential only.

E = E⁰- 2.303 RT log Qc

nF

At 25⁰C (298K),Nernst equation becomes

E = E⁰- 0.0591 log Qc

n
For an electrochemical reaction of the type aA + bB cC + dD

E = E⁰- 0.0591 log [C]c [D]d

n [A] a [B]b
As the concentration at anode increases emf decreases,whereas when the
concentration at cathode increases emf increases.(while writing expressions for Qc all
solids and gases at 1 bar pressure are avoided).

Nernst equation can also be used to calculate emf of a half cell .

For an electrode of metal M,,which shows an equilibrium like

Mn+ + ne M

E = E⁰- 0.0591 log 1

n Mn+
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and for anion like electrode e.g.
Cl + e Cl-

E = E⁰- 0.0591 log [Cl-]

n

Relationship between emf and equilibrium constant (K c).

At equilibrium, ∆G=0,i.e. E = 0 and Qc becomes Kc . substituing in Nernst equation

E = E⁰- 0.0591 log Qc

n
we get,

E⁰ = 0.0591 log Kc
n
Thus equilibrium constant (Kc) is related only to E⁰ and not E.

Similarly maximum work obtainable from a cell is also related only to E⁰ and not E.
maximum work = -∆G⁰ = nFE⁰.

Concentration cells
Concentration cells are those cells which work due to difference in potential across
electrodes arising due to difference in concentrations. They can be made in several
ways.In one type the same metal constitutes the anode and cathode but the cell works
due to different concentrations of the electrolyte at anode and cathode.For such a type
of cell E⁰ will be zero and we get

E= 0.0591 log [cathode]

n [anode]

Thus increase of lonic concentration at cathode increases emf and increase of lonic
concentration at anode decreases emf.

Faraday’s laws of electrolysis.

Faraday’s first law states that the mass of a substance deposited at any electrode is
directly proportional to the quantity of charge that is passed though the electrolyte.
(Faraday is the charge carried by one mole of electrons or can be defined as the
amount of charge that produces one equivalent of chemical change).Its approximate
value is 96500C).
WαQ Q=charge in coulomb.

W= ZQ Z= electrochemical equivalent.

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W= ZIt (Q=It) I= current in amperes,t=time in seconds.
W= EIt Z= E E=equivalent weight,F= Faraday(96500C)

F F
Faraday’s second law states that when current is passed through different electrolytes
connected in series (same current),the weight of metal deposited at each electrode is
directly proportional to the equivalent weights of the different metals.
W1 = E1
W2 E2

Predicting products of electrolysis.

The products of electrolysis depends upon nature of electrode and electrolyte.

Inert electrodes do not react with any of the ions or gases present whereas reactive
electrodes react with one or more ions present in solution. Electrolyte may be in molten
form or in aqueous form.

Keeping electrode inert, in electrolysis of molten electrolytes,the only anion and cation
present move to the anode and cathode respectively.e.g In electrolysis of molten NaCl
sodium goes to cathode and chlorine to anode.

In aqueous solutions,more than one type of cation and anion will be present and there
will be competition between ions.In such cases if concentration of ions are the same,
then the one with higher oxidation potential will be liberated at the anode and the one
with higher reduction potential will be liberated at the cathode.
e.g.In electrolysis of aqueous NaCl with inert electrode like platinum, hydrogen is
liberated at cathode and at the anode chlorine(though oxygen was expected) due to the
phenomenon of overvoltage.The change of water to oxygen is kinetically inert and
higher voltage is required to decompose water as compared to chlorine. Thus with
increasing voltage,chlorine would be liberated first.

If concentrations are not the same, predictions are done with E values obtained from
Nernst equation and not with E⁰ values.e.g.In electrolysis of both dilute and conc H2SO4
with inert electrode like platinum,hydrogen is liberated at cathode as it is the only cation
present. At anode water gives oxygen in case of dilute H2SO4 and S2O82- in the case of
conc H2SO4.

If electrode is reactive, anode gets oxidised and ions from anode move into solution.To
keep the concentration the same, ions from solution move towards the cathode where it
gets reduced and gets deposited. Thus with the passage of time, the anode
disintegrates and the cathode gets bulkier and bulkier.This principle is employed in
electrolytic refining where impure metal is taken as anode and pure metal as cathode
and electrolyte a solution of the same metal.

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Electrolytic or ionic conduction.
Conduction is of two types 1) Electronic or metallic conduction due to movement of
electrons and electrolytic or ionic conduction due to movement of ions.Metallic
conduction decreases with increase of temperature (refer-solid state)whereas
electrolytic conduction increases with increase of temperature (due to greater
dissociation).

Factors affecting electrolytic conduction.

1)Nature of electrolyte-In general for the same concentration a strong electrolyte will
conduct more than a weak electrolyte.
2)Temperature-As temperature increases,conduction increases as more of the
electrolyte undergoes dissociation.
3)Dilution-In general as dilution increases,conduction increases as more of the
electrolyte undergoes dissociation.
4)Solvation effects-Conductance is ultimately dependent on the mobility of ions in
solution.ions which are extensively solvated will have to carry a large sheet of solvent
while moving and hence will conduct less.Thus small ions with high charge to radius
ratio which are extensively solvated will conduct less. e.g.amongst alkali metal cations
the order of conduction is Li+<Na+<K+<Rb+<Cs+.
5)Viscosity of solvent-If viscosity of solvent is high,conduction would be less.

Conductivity.
Resistance(R) of ionic solutions cannot be measured using a Wheatstone bridge as:-
1)passing direct current (DC) changes the composition of the solution.
2)A solution cannot be connected to the bridge unlike a metallic wire or other solid
conductor.
These problems are overcome by using alternate current(AC) and specially designed
cell called as Conductivity cell.
Conductivity cell consists of two platinum electrodes coated with platinum black.The
solution whose resistance is to be measured is confined between these electrodes of
length ‘l’ and area of cross section ‘A’.thus resistance of such a column of solution will
be
Rαl
A

R=ρ l (ρ= resistivity)

A
1 = 1×l
ρ R A

for a particular cell l is a constant called as cell constant represented by G*.

A
1 = conductivity (represented by κ) , 1 = conductance (represented by G).
ρ R
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Hence κ=G×G*.

Hence,specific conductivity(κ) is the conductivity of a solution in which the electrodes

are kept 1 cm apart and area of cross section is 1cm2 or it is the conductivity of 1cc of
solution.It is representative of the total conductance of solution.If its value is high,total
conductance will also be high.

Molar conductivity (λ⁰m).

Molar conductivity is the conductivity of a solution which contains1mole of the
electrolyte in it.

Effect of dilution on conductivity

Specific conductivity decreases with increase of dilution,whereas molar conductivity
increases with increase of dilution..Specific conductivity is the conductivity of a cc of
solution and is a measure of the number of ions present per cc of solution. As dilution
increases more of electrolyte undergoes dissociation leading to higher number of ions
but the specific conductivity decreases due to huge increase in volume associated with
dilution where solvent is added in large excess. Molar conductivity on the other hand
increases due to the large increase in volume of solution which contains one mole of the
electrolyte during dilution,which more than compensates for the expected decrease due
to decrease of specific conductivity.

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Variation of molar conductivity with dilution (strong electrolytes)
For strong electrolytes no increase in molar conductivity was expected as they are
completely ionised and dilution does not increase the number of ions. However,even for
strong electrolytes the molar conductivity increases with increase of dilution. This
increase is not due to the increase in the effective number of ions but rather is due to
decrease in inter-ionic attractions.Strong electrolyte though completely ionised are not
completely dissociated as the electrostatic forces of attraction between oppositely
charged ions hinders their mobility.As dilution increases,the ions are separated and
inter-ionic attractions decrease leading to enhanced conductivity which keeps
increasing till it reaches a maximum or limiting value corresponding to infinite dilution;
called as conductance at infinite dilution represented by λ⁰m.The variation is given by
Debye Huckel Onsager’s equation mathematically as:-
λcm =c- A√c (λcm= molar conductivity at a certain conc ‘c ‘)
(c= concentration in terms of moles/litre.)
(A=constant).
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The plot of λcm against √c will be a straight line with slope equal to –‘A’ and intercept on
y-axis equal to λ⁰m .Thus for strong electrolyte λ⁰m can be obtained directly from graph
by extrapolating it back to zero.
The value of ‘A’ for a given solvent and temperature depends on the type of
electrolyte.Electrolytes are classified as 1-1,e.g(NaCl),2-1e.g(CaCl2),2-2e.g(MgSO4)
electrolyte etc depending upon the charges on the cation and anion produced on
dissociation.All electrolytes of a particular type have the same value of ‘A’.

Variation of molar conductivity with dilution (weak electrolytes)

In the case of weak electrolyte it is not possible to determine their λ⁰m as in their case
conductance keeps on increasing with dilution and towards the end it spurts.Hence for
weak electrolytes λ⁰m is determined indirectly by using Kohlrausch’s law.(also called as
Kohlrausch’s law of independent migration of ions).
Kohlrausch’s law states that molar conductance at infinite dilution of any electrolyte is
equal to the sum of conductance of all the individual ions .(conductance of the individual
ions multiplied by the time they appear in one mole).i.e. each ion contributes
independently to total conductance.e.g.
λ⁰NaCl = λ⁰Na+ + λ⁰Cl-

λ⁰CaCl2 = λ⁰Ca2+ + 2λ⁰Cl-

λ⁰AlCl3 = λ⁰Al3+ + 3 λ⁰Cl-

Applications of Kohlrausch’s law

1) In determining ionic product of water
2)In determination of λ⁰m for weak electrolytes from knowledge of λ⁰m for strong
electrolytes.
λ⁰m CH3COOH=λ⁰m CH3COO- +λ⁰m H+
λ⁰m CH3COOH= λ⁰m CH3COONa +λ⁰m HCl -λ⁰m NaCl
3)To determine the degree of dissociation and dissociation constants of acids and
bases etc.

degree of dissociation α= no of moles dissociated

total no of moles

degree of dissociation α= λcm

λ⁰m

BATTERIES
A battery is galvanic cell which converts chemical energy into electrical energy-Batteries
are to two types primary and secondary.primary battery can be used only once and
cannot be recharged whereas secondary batteries can be used time and again after
recharging.
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PRIMARY BATTERIES
Leclanche cell Consists of Zinc container that also acts as anode and the cathode is a
graphite rod surrounded by powdered manganese dioxide and carbon.The space
between electrodes is filled by a moist paste of ammonium chloride (NH4Cl)and Zinc
chloride(ZnCl2).
Anode:Zn(s) Zn2+ +2e-
+
Cathode:MnO2 + NH4 + e- MnO(OH) +NH3
At the cathode manganese is reduced from +4 to +3 oxidation state and ammonia
produced in the reaction forms a complex with Zn2+ [Zn(NH3)4]2+.The cell has a potential
of nearly 1.5 V.

Mercury cell Is used for low current devices and consists of Zn-Hg amalgam as anode
and a paste of HgO and carbon as the Cathode, The electrolyte is a paste of KOH and
ZnO. The cell has an approximate Voltage of 1.35Vand remains Constant throughout its
life as the overall reaction does not involve any change of Concentration of ions in
solution
Anode:Zn(Hg) + 2OH- ZnO + H2O +2e-
-
HgO + H2O +2e Hg(l) + 2OH-

SECONDARY BATTERIES
Lead storage battery Consist of lead anode and a grid of lead packed with lead
dioxide as cathode. A 38% solution of sulphuric acid is used as an electrolyte.
cell reaction when is use (discharging) is.
Anode:Pb(s) +SO42- PbSO4 + 2e-

Cathode:PbO2 + SO42- + 4H+ +2e- PbSO4 + 2H2O

Overall reaction;
Pb(s) + PbO2 + 2H2SO4 2PbSO4 +2H2O
On charging the battery the reaction is reversed and PbSO4 on anode and cathode is
converted into Pb and PbO2 respectively.
Nickel Cadmium cell-It has longer life than the lead storage cell but is more expensive
to manufacture.Cadmium is oxidised,hence it acts as the anode and nickel is reduced
hence it acts as the Cathode
Cd(s) + 2Ni(OH)3 CdO(s) + 2Ni(OH)2(s) + H2O(l)

Fuel cells are galvanic cells designed to convert the energy of combustion of fuels like
H2, CH4, methanol etc directly into electrical energy.

Hydrogen oxygen fuel cell

In this cell hydrogen and oxygen are bubbled through porous Carbon electrodes Into
conc aqueous sodium hydroxide solution. catalysts Iike. finely divided platinum or
palladiut metal are incorporated into the electrodes for increasing the rate of electrode
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reactions.
Anode:2H2(g) +4OH-(aq) 4H2O(l) + 4e-
-
Cathode:O2(g) + 2H2O(l)+4e 4OH-(aq)
Overall equation is 2H2(g) + O2(g) 2H2O(l)
These cells runs continuously as long as the reactants are supplied and have a high
efficency of around 70% as compared to 40% efficency of thermal plants.Moreover they
are environment friendly as the only byproduct is water.

CORROSION
Corrosion is the degradation of properties of a metal due to the action of
air,moisture,acids etc, Corrosion of iron is called as rusting and occurs in presence of
water and air.Corrosion is an electro-chemical process.At a particular spot of an object
made of iron,oxidation takes place and that spot acts as anode.
Anode: 2Fe(s) 2Fe2+ +4e- E⁰(Fe2+/Fe) = -0.44V

Electrons released at the anode move though the metal and reduce oxygen in presence
of H+ions (coming from dissolution of oxides like CO2 SO2 etc in water).This spot
behaves as cathode.The ferrous ions are further oxidised by atmospheric oxygen to
ferric ions which come out as rust in the form of hydrated ferric oxide-with further
production of H+ ions.

Cathode:O2(g) + 4H+(aq)+4e- 2H2O(l) E⁰(H+/O2/H2O) = 1.23V

Overall reaction is

2Fe(s) + O2(g) + 4H+(aq) 2Fe2+ + 2H2O(l) E⁰(cell) =1.67V.

Prevention of corrosion can be done by covering surface with paint or chemicals like
bis-phenol or metals Iike.Sn,Zn that are inert or react to save the object.
Electrochemical method provides an electrode of another reactive metal like Mg,Zn etc
which acts as a sacrificial electrode.by corroding itself but saves the object.

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 EXERCISES
1. Can you store copper sulphate solution in a zinc pot? (NCERT)
2. Can a solution of 1M copper sulphate be stored in a vessel made of nickel metal ?
Given that E°Ni, Ni 2+ = +0-25 volt, E0Cu, Cu2+ = – 0.34 volt.
3. Can chlorine gas he stored in a copper cylinder ?Given E°Cu2+ , Cu = 0.34 V and

= 1.36 V.
4. Predict whether zinc and silver react with 1M sulphuric acid to give out hydrogen gas
or not. Given that the standard reduction potentials of zinc and silver are – 0.76 volt and
0.80 volt respectively.
5.

6. Arrange the following metals in the order in which they displace each other from the
solution of their salts .Al, Cu, Fe, Mg and Zn. (NCERT)
7. Consult the table of standard electrode potentials and suggest three substances that
can oxidize ferrous ions under suitable conditions. (NCERT)
8. Given the standard electrode potentials, K+/K = –2.93V, Ag+/Ag = 0.80V,Hg 2+/Hg =
0.79V,Mg 2+/Mg = –2.37 V, Cr 3+/Cr = – 0.74V.Arrange these metals in their increasing
order of reducing power. (NCERT)
9. Depict the galvanic cell in which the reaction Zn(s)+2Ag+(aq) →Zn2+(aq)+2Ag(s) takes
place. Further show :(i) Which of the electrode is negatively charged? (ii)The carriers of
the current in the cell.(iii) Individual reaction at each electrode. (NCERT)
10. A cell is prepared by dipping a copper rod in 1M CuSO4 solution and a nickel rod in
1 M NiSO4 solution. The standard reduction potentials of copper electrode and nickel
electrode are 0.34 volt and – 0.25 volt respectively. What will be the cell reaction?
What will be the standard EMF of the cell? Which electrode will be positive? How will
the cell be represented?
10. How would you determine the standard electrode potential of the system Mg 2+|Mg?
(NCERT)
11. Calculate the standard cell potentials of galvanic cell in which the following reactions
take place:(i) 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd
(ii)Fe 2+(aq) + Ag+ (aq) → Fe 3+(aq) + Ag(s).Calculate the ∆rG and equilibrium constant of
the reactions. (NCERT)
12.

(NCERT)

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13. Calculate the electrode potential of a copper wire dipped in 0.1 M CuSO4 solution at
25°C. The standard electrode potential of copper is 0.34 volt.
14. Calculate at 25°C the electrode potential of Mg2+ / Mg electrode in which
concentration of Mg2+ ions is 0 .1 M. (E°Mg2+/ Mg = – 2.36V, R = 8.3143 K–1 mol–1, F =
96500 coulombs mol–1)
15. Calculate the potential of a zinc-zinc ion electrode in which the zinc ion actvity is
0.001 M
(E°Zn2+ / Zn = – 0.76 V, R = 8.314 J K–1 mol–1 , F = 96,500 C mol–1 )
16. A zinc rod is dipped in 0 1 M solution of ZnSO4. The salt is 95% dissociated at this
dilution at 298K. Calculate the electrode potential ( )
17. Calculate the potential of hydrogen electrode in contact with a solution whose p H is
10. (NCERT)
18. At what pH of HCl solution will hydrogen gas electrode show electrode potential of
– 0.118 V? H2 gas is bubbled at 298 K and 1 atm pressure.
19. If E° for copper electrode is + 0 34V, how will you calculate its emf value when the
solution in contact with it is 0.1 M in copper ions? How does the emf for copper
electrode change when concentration of Cu2+ ions in the solution is decreased ?
20.Write the Nernst equation and calculate emf of the following cells at 298 K:
(i) Mg(s)|Mg 2+(0.001M)||Cu 2+(0.0001 M)|Cu(s)
(ii)Fe(s)|Fe 2+(0.001M)||H+ (1M)|H2 (g)(1bar)| Pt(s)
(iii) Sn(s)|Sn 2+(0.050 M)||H+(0.020 M)|H2 (g) (1 bar)|Pt(s)
(iv) Pt(s)|Br2(l)|Br–(0.010 M)||H+(0.030 M)| H2(g) (1 bar)|Pt(s). (NCERT)
21.Represent the cell in which the following reaction takes place
Mg(s) + 2Ag+(0.0001M) → Mg2+(0.130M) + 2Ag(s).Calculate its Ecell if E°cell = 3.17 V.
22. Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+ (0.002 M) → Ni 2+(0.160 M) + 2Ag(s).Given that E°cell= 1.05 V.
23.Represent schematically the cell made up of the following cell reactions :
Mg Mg2+ (0.01 M) + 2e—, E° = + 2.34 volt
2+ –
Sn (0 .1M) + 2e Sn, E° = – 0.136 volt
Calculate the emf of the above cell at 25°C.
24. Calculate the emf of the following cell at 25°C.
Cd | Cd2+ (0.001M) || Fe2+ (0.6M) | Fe. The standard reduction potential of Cd / Cd2+ and
Fe / Fe2+ electrodes are –0.403 and –.0 .441 volt respectively.
25. Calculate the e.m.f. of the cell Cr | Cr3+ (0.1 M) || Fe2+ (0.01 M) | Fe
Given: E° Cr3+ / Cr = – 0. 75V: E° Fe2+/ Fe = – 0.45 V.
26. The standard electrode potentials are given as :E°Cu2+ / Cu = 0.34 V and E° Ag+ / Ag =
0.80 V. Calculate the cell potential (E) for the cell containing 0.100 M Ag+ and 4.00 M
Cu2+ at 25°C.
27. Calculate the potential (emf) of the cell
Cd | Cd2+ (0.10 M) || H+ (0.201M) | Pt , H2 (0.5 atm).(Given E° for Cd2+ / Cd = –0 . 403
V, R =8.314 J K–1 mol –1, F = 96, 500 C mol–1)
28.Calculate the EMF of the following concentration cell at 298 K
Zn | ZnSO4 (0.05 M) || ZnSO4 (0.5 M) | Zn

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29.A cell consists of two hydrogen electrodes. The negative electrode is in contact with
a solution having 10–6 M H+ ion concentration. Calculate the concentration of H+ ions at
the positive electrode,if the emf of the cell is found to be 0.118 V at 298 K.
30. The EMF of the following cell is found to be 0.20 V at 298 K.
Cd | Cd2+ (?) || Ni2+ (2.0 M)| Ni.
What is the molar concentration of Cd2+ ions in the solution ?
(E°Cd2+ / Cd = – 0.40 V, )
31. Calculate the electrode potential of silver (electrode dipped in 0.1 M solution of silver
nitrate of 298 K assuming AgNO3 to be completely dissociated. The standard electrode
potential of Ag+ | Ag is 0.80 V at 298 K. (b) At what concentration of Ag+ ions will this
electrode have a potential of 0.0 volt ?
32. For what concentration of Ag+ (aq) will the e.m.f. of the given cell be zero at 25°C, if
the concentration of Cu2+ (aq) is 0.1 M ? Cu(s) | Cu2+ (0.1 M) || Ag+ (aq) | Ag(s)
[Given E°Ag + / Ag = + 0.80 V, E°cu2+/Cu = + 0 .34 V]
33. A galvanic cell is constructed with Ag / Ag+ as one electrode and Fe2+ / Fe3+ as the
second electrode. Calculate the concentration of Ag+ ions at which the E.M.F of the cell
will be zero at equimolar concentrations of Fe2+ and Fe3+ ions. Given E° Ag+ |Ag = 0.80 V,
E°Fe3+ | Fe2+ = 0.77 V).
34. Cu2+ + 2 e– Cu, E° = + 0.34 V
+ – o
Ag + 1 e Ag, E = + 0 .80 V
(i) Construct a galvanic cell using the above data.
(ii) For what concentration of Ag+ ions will the emf of the cell be zero at 25°C, if the
concentration of Cu2+ is 0.01 M? (Log 3.919 = 0.593)
35. The standard electrode potential for Daniel cell is 1.1V. Calculate the standard
Gibbs energy for the reaction: Zn(s) + Cu 2+(aq) → Zn 2+(aq) + Cu(s) (NCERT)
36. Calculate the standard free energy for the following reaction at 25°C.
Au (s) + Ca2+(aq, 1 M) Au3+(aq, 1 M) + Ca (s),
=+ 1 .50 V , = – 2.87 V.Predict whether the reaction will be spontaneous
or not at 25°C. Which of the above two half cells will act as an oxidizing agent and
which one will be a reducing agent?
37. Estimate the minimum potential difference needed to reduce Al2O3 at 500°C. The
free energy change for the decomposition reaction

Al2O3 Al + O 2 is G = + 960 kJ ( F = 96500 C mol –1 ).

38. Calculate the equilibrium constant of the reaction:
Cu (s) + 2Ag+(aq) → Cu 2+(aq) + 2Ag(s).E° cell= 0.46 V(NCERT)
39. The cell in which the following reaction occurs :) 3 2 2Fe 2I 2Fe I aq 2 s→ + has
E°cell = 0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium
constant of the cell reaction. (NCERT)
40. Calculate the equilibrium constant for the reaction at 298 K.
4 Br – + O2 + 4 H + 2 Br2 + 2 H2O.Given that = 0.16 V
41. Calculate the equilibrium constant for the reaction at 298 K :
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2 Fe3+ + 2I– 2 Fe2+ + I2 if = 0.235 V.
42. Calculate at 25°C the equilibrium constant for the reaction
2 Fe3+ + Sn2+ 2 Fe2+ + Sn4+.
Given that [E°Sn /Sn ] Pt = 0.150 V. [Eo Fe3+/ Fe2+] Pt =0.771 V
4+ 2 +

43. Calculate the equilibrium constant for the following reaction at 298 K
Cu (s) + Cl2 (g) CuCl2 (aq)

(R = 8.314 JK–1 mol–1,Eo Cu2 +/ Cu = 0.34 V, = 1.36 V,F = 96500 C mol–1)

44. For the reaction N2 (g) + 3H2(g) →2NH3(g) at 298 K, enthalpy and entropy changes
are –92.4 kJ and –198.2 JK–1 respectively. Calculate the equilibrium constant of the
reaction (R = 8.314 JK–1 mo1–1).
45. For the equilibrium, 2 H2 (g) +O2 (g) → 2H2O (l) at 25°C, G° is –474.78 kJ mol–1.
Calculate log K for it (R = 8.314 JK–1 mol–1).
46. Calculate the standard free energy change and maximum work obtainable for the
reaction occurring in the cell : (Daniel cell) .
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
[Given Eo Zn2+ / Zn = – 0.76 V, E° Cu2+ / Cu = + 0.34 V, F = 96500 C mol–1]
Also calculate the equilibrium constant for the reaction ?
47. Calculate the maximum work that can be obtained from the cell
Zn|Zn2+ (1M) || Cu2+ (1M) |Cu. Given and are – 0.76 and + 0.34 V
respectively.
48. Calculate the cell e.m.f. at 25°C for the following cell :
Mg (s) | Mg2+ (0.01 M) || Sn2+ (0.1 M) | Sn (s)
Given E°Mg2+/Mg = – 2.34 V, = – 0.136 V, 1 F = 96,500 C mol–1
Calculate the maximum work that can be accomplished by the operation of this cell.
49. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many
electrons would flow through the wire? (NCERT)
50. How much charge is required for the following reductions: (i)1 mol of Al3+ to Al?(ii)1
mol of Cu2+ to Cu?(iii)1 mol of MnO4–to Mn2+?(NCERT)
51. How much electricity in terms of Faraday is required to produce (i) 20.0 g of Ca from
molten CaCl2? (ii) 40.0 g of Al from molten Al2O3? (NCERT)
52. How much electricity is required in coulomb for the oxidation of (i) 1 mol of H 2O to
O2(ii)1 mol of FeO to Fe2O3? (NCERT)
53. Consider the reaction: Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O.What is the quantity of
electricity in coulombs needed to reduce 1 mol of Cr2O72–? (NCERT)
54. How many coulombs are required for the following oxidation? i)1 mol of H2O to
O2.ii)1 mol of FeO to Fe2O3.
55. How many coulombs of electricity at required for i) Complete oxidation of 90 g of
H2O.ii) Complete reduction of 100 mL of 0.1 M KMnO4 solution.
56. Find the charge in coulombs on 1 g-ion of N3–.
57. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of
5 amperes for 20 minutes. What mass of Ni is deposited at the cathode? (NCERT)

17
58. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes.
What is the mass of copper deposited at the cathode? (NCERT)
59. How much copper will be deposited on the cathode of an electrolytic cell containing
copper sulphate solution by the passage of a current of 2 amperes for 30 minutes ? (At.
mass of Cu = 63.5)
60. How many grams of chlorine can be produced by the electrolysis of molten NaCI
with a current of 1.00A for 15 min ?
61. How many hours does it take to reduce 3 mol of Fe3+ to Fe2+ with 2.00 A current ? (1
Faraday = 96,500 C mol–1, R = 8.314 JK–1 mol–1)
62. When a current of 0.75 A is passed through CuSO4 solution for 25 min, 0.369 g of
copper is deposited at the cathode. Calculate the atomic mass of copper.
63. In the electrolysis of acidulated water, it is desired to obtain hydrogen at the rate of 1
cc per second at NTP condition. What should be the current passed?
64. Silver is electrodeposited on a metallic vessel of total surface area 900 cm2 by using
a current of 0.5 amp for two hours. Calculate the thickness of silver deposited. Density
of silver = 10.5gcm–3 (Atomic mass of silver = 180 amu, F = 96500C mol–1)
65. Silver is electro-deposited on a metallic vessel of surface area 800 cm2 by passing a
current 0.2 ampere for 3 hours. Calculate the thickness of silver deposited. Given the
density of silver as 10.47 g/cc (Atomic mass of Ag = 107.92 amu)
66. Two electrolytic cells containing silver nitrate solution and copper sulphate solution
are connected in series. A steady current of 2.5 ampere was passed through them till
1.078 g of Ag was deposited. How long did the current flow? What weight of copper will
be deposited? (At mass of Ag = 107.8, Cu = 63. 5) (NCERT)
67. Three electrolytic cells A, B,C containing solutions of ZnSO4, AgNO3 and
CuSO4,respectively are connected in series. A steady current of 1.5 amperes was
passed through them until 1.45 g of silver deposited at the cathode of cell B. How long
did the current flow? What mass of copper and zinc were deposited?
68. Predict the products of electrolysis in each of the following:(i) An aqueous solution of
AgNO3 with silver electrodes.(ii) An aqueous solution of AgNO3 with platinum
electrodes.(iii) A dilute solution of H2SO4 with platinum electrodes.(iv) An aqueous
solution of CuCl2 with platinum electrodes. (NCERT)
69. Suggest a list of metals that are extracted electrolytically. (NCERT)
70. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss
their variation with concentration. (NCERT)
71. Why does the conductivity of a solution decrease with dilution? (NCERT)
72. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is
1500 Ω. What is the cell constant if conductivity of 0.001M KCl solution at 298 K is
0.146 × 10–3 S cm–1. (NCERT)
73. The conductivity of an aqueous solution of sodium chloride in a cell is 92 × 10 –4
ohm–1 cm–1. The resistance offered by this cell is 247.8 ohm. Calculate the cell constant
for this cell.
74. The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1
cm and length 50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar
conductivity. (NCERT)

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75. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm –1. Calculate its
molar conductivity. (NCERT)
76. The resistance of a decimolar solution of an electrolyte in a conductivity cell was
found to be 245 ohms. Calculate the molar conductivity of the solution if the electrodes
in the cell were 2 cm apart and each has an area of 3.5 sq. cm.
77. A potential difference of 20 volts applied to the ends of a column of M/10 AgNO 3
solution, 4 cm in diameter and 12 cm in length gave a current of 0.20 ampere. Calculate
the specific and molar conductivities of the solution.
78. The conductivity of a solution containing 1 gram of anhydrous BaCl2 in 200 cm3 of
water has been found to be 0.0058S cm–1. What are the molar conductivity and
equivalent conductivity of the solution? (At. wt. of Ba = 137 and Cl = 35.5).
79. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 Ω. If the
resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 Ω, calculate
the conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of
0.1 mol L–1 KCl solution is 1.29 S/m. (NCERT)
80. The resistance of a conductivity cell with 0.1 M KCI solution is found to be 200 at
298 K.When the same cell is filled with 0.02 M NaCI solution, the resistance at the same
temperature is found to be 1100 . Calculate i)the cell constant of the cell in m–1ii)the
molar conductivity of 0.02 M NaCI solution in S m2 mol–1.Given that the conductivity of
0.1M KCl solution at 298 K is 1.29 S m–1.
81. A cell with N/50 KCl solution showed a resistance of 550 ohms at 25°C. The specific
conductivity of N/50 KCl at 25° C is 0 .002768 ohm –1 cm–1.The cell filled with N/10
ZnSO4 solution at 25°C shows a resistance of 72.18 ohms. Find the cell constant and
molar conductivity of ZnSO4 solution.
82. Calculate ^°m for CaCl2 and MgSO4 from the data given in Table 3.4. (NCERT)
83. Suggest a way to determine the Λ °mvalue of water. (NCERT)
84.

(NCERT)
85.From the following molar conductivities at infinite dilution,
–1
for Ba (OH)2 = 457.6 cm2 mol–1 for BaCl2 = 240.6 –1
cm2 mol–1
for NH4Cl = 129.8 –1cm2 mo1–1,calculate for NH4OH.
86.The molar conductivity of NH4Cl at infinite dilution is 149.7 S cm2 and the ionic
conductivities of OH— and Cl– ions are 198 and 76.3 S cm2 respectively. Calculate the
molar conductivity of NH4OH at this dilution.
87. The molar conductances of NaOH, NaCI and BaCl2 at infinite dilution are 2.481 ×
10–2, 1.265 ×10–2 and 2.800 ×10–2 S m2 mol–1 respectively. Calculate for Ba (OH)2.
88.The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 S cm–1.Calculate its
dissociation constant if Λ °m for acetic acid is 390.5 S cm2 mol–1. (NCERT)
89. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar
conductivity. If Λ0m for acetic acid is 390.5 S cm2mol–1, what is its dissociation constant?
(NCERT)

19
90. The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2mol–1.Calculate
its degree of dissociation and dissociation constant. Given λ0 (H+) = 349.6 S cm2 mol–1
and λ0 (HCOO–) = 54.6 S cm2mol–1(NCERT).
91. The conductivity of 0.001 M acetic acid is 4.95 x 10–5 S cm–1. Calculate its
dissociation constant. Given for acetic acid, is 390.5 S cm2 mol–1.
92. The molar conductivity of acetic acid at infinite dilution is 387 –1 cm2 mol–1. At the
same temperature,but at a concentration of 1 mole in 1000 litres, it is 55 –1 cm2 mol–1.
What is the % age dissoication of 0.001 M acetic acid ?
93. The molar conductivities at infinite dilution of potassium chloride, hydrochloric acid
and potassium acetate are 130.1, 379.4 and 95.6 –1 cm2 mol–1 respectively. Calculate
the value of molar conductivity at infinite dilution for acetic acid. If the molar conductivity
of a given acetic acid solution is 48.5 –1 cm2 mol–1 at 25°C, calculate the degree of
dissociation of acetic acid at this temperature.
94.

(NCERT)
95.

(NCERT)
96. Write the chemistry of recharging the lead storage battery, highlighting all the
materials that are involved during recharging. (NCERT)
97. Explain how rusting of iron is envisaged as setting up of an electrochemical cell.
(NCERT)
98. Suggest two materials other than hydrogen that can be used as fuels in fuel cells.
(NCERT)

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