Electrochemistry

1. Differentiate between Galvanic cell and electrolytic cell.

Galvanic cell converts chemical energy (Gibbs Free Energy) liberated during redox reaction into
electrical energy.
Eg: Daniel Cell
In an electrolytic cell, an external source of voltage is used to bring a chemical change.

2. How would you determine the standard electrode potential of the system Mg2+|Mg?
A cell is constructed by taking standard hydrogen electrode as (reference half cell) cathode and Mg
wire as anode.
The Mg wire is dipped in 1M MgSO4
The emf of the cell gives reduction potential of the other half cell.
If the concentration of the reduced and oxidized species are unity then cell potential is standard
electrode potential.
E° (cell) = E° (cathode) - E° (anode)
E°(cell) = 0– E° (anode) = - E° (anode) = standard electrode potential of the system Mg2+|Mg.

3. Depict the galvanic cell in which the reaction 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.
Zn (s) | Zn2+ (aq)||Ag+(aq) |Ag(s)
(i) Anode (Zn electrode) will be negatively charged.
(ii) Electrons. Current flows from Ag to Zn.
(iii) Anode: Zn → Zn2+ + 2e-
Cathode: Ag+ + e- → Ag

4. How is electrode potential different from cell potential?

The potential difference between electrode and electrolyte called electrode potential.
The potential difference between 2 electrodes of galvanic cell is called cell potential.

5. Describe the construction and working of standard hydrogen electrode.

 The standard hydrogen electrode has a platinum electrode coated with platinum black.
 It is dipped in acidic solution and pure hydrogen gas is bubbled through it.
 Pressure of hydrogen gas is 1 bar and concentration of H+ in solution is 1 M.
 The standard electrode potential is represented as
Pt(s) | H2 | H+ (aq)
 It has a zero potential according to the reaction
H+ + e- → ½ H2 (g)

6. What is the purpose of salt bridge placed between two half cells of a galvanic
cell?
 To complete circuit and allow flow of ions through it.
 To maintain electrical neutrality.

7. Give the representation of the Daniel cell.

|Zn(s) | Zn 2+|| Cu2+| Cu(s) |
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 Anode – Zn → Zn 2+ (aq) + 2e- = (-.0.76)
Cathode – Cu + 2e- → Cu2+ = ( +0.34)
Emf = E°(cell) = E° (cathode) - E° (anode)
= ( +0.34) - (-.0.76)
= 1.10 V

8. Define resistivity and conductivity.

Electrical resistance is given as

l = length and A = area of cross section

ρ = resistivity or specific resistance

Resistivity is the resistance of a solution placed between two parallel wires with unit area of cross section
and a distance of unit length.
Unit is Ωm.
The inverse of resistance is called conductance G. Its unit is siemens S or Ω-1.

κ = conductivity
Conductivity of solution at any concentration is the conductance of of 1 unit volume of solution kept
between 2 platinum electrodes with unit area of cross section and a distance of unit length.
Unit is Sm -1

9. What is cell constant? How is it determined?

 Cell constant is the ratio of distance between electrodes (l) to area of cross section (A) between electrodes.
 Cell constant is measured using conductivity cell.
 It consists of 2 platinum electrodes coated with platinum black.
 They have an area of cross section A and are separated by distance l which confines the solution.
 Cell constant is determined by measuring resistance of cell containing solution
whose conductivity is known (KCl).
 The set up consists of 2 resistances R3 and R4, a variable resistance R1 and
conductivity cell with unknown resistance R 2.
 Wheatstone bridge is fed by oscillator O (AC power of 500 – 550 cps).
 P is a suitable detector
 Bridge is balanced when no current passes through detector.

 Thus cell constant is given as

10. What are the problems faced in measuring R of ionic solutions and how are they overcome (or)
Why is alternating current used to measure electrolytic conductivity?
Problems in measuring R of ionic solutions
a) Direct current changes composition of ionic solution
b) Ionic solution cannot be connected to bridge
Problems are overcome

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 a) Using AC source of power
b) Using conductivity cell.

11. Differentiate between metallic and electrolytic conduction.

Metallic or electronic conductance through metals is due to movement of electrons
It depends upon
a) Nature and structure of metal
b) No. of valence electrons per atom
c) Temperature ( decreases with increase in temperature).
Electrolytic or ionic conductance is due to movement of ions
It depends upon
a) Nature of electrolyte
b) Size of ion produced and their salvation
c) Nature of solvent and viscosity
d) Concentration of electrolyte
e) Temperature ( increases with increase in temperature)

12. Define the terms conductivity and molar conductivity for solution of an electrolyte. Discuss their variation
with concentration.
Conductivity of solution
Conductivity of solution at any concentration is the conductance of of 1 unit volume of solution kept
between 2 platinum electrodes with unit area of cross section and a distance of unit length.
Conductivity decreases with decrease in concentration for weak and strong electrolytes because the number
of ions per unit volume that carry current in a solution decreases on dilution.
Molar Conductivity of solution
Molar Conductivity of solution at a given concentration is the conductance of the volume V of the solution
containing 1 mole of electrolyte kept between 2 electrodes with area of cross section A and distance of unit
length.
Molar conductivity increases with decrease in concentration. This is because the total volume V of solution
containing 1 mole of electrolyte increases.

13. What is the unit of molar conductivity?

Molar Conductivity

If κ = Sm-1 and c = molm-3

unit of Λm = Sm2mol-1

If κ = Scm-1 and c = molcm-3

unit of Λm = Scm2mol-1

14. What is limiting molar conductivity? (or)

At what concentration the molar conductance of electrolyte approach the maximum limiting value?
When the concentration approaches 0, the molar conductivity is called Limiting Molar Conductivity.

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15. Describe the characteristics of variation of molar conductivity with dilution for a) strong electrolyte b)
weak electrolyte. (or)
With the help of a graph explain why it is not possible to determine the limiting molar conductivity for a
weak electrolyte by extrapolating the concentration-molar conductance curve as for strong electrolytes.
(or)
Express the relationship between degree of dissociation of an electrolyte and its molar conductivities.
Strong Electrolytes
For strong electrolytes, Λm increases slowly with dilution
Λm = Λ0m - Ac1/2
If we plot Λm against C1/2 we get a straight line. Intercept = Λ0m
and slope is = -A
Value of A depend upon type of electrolyte i.e charge on anion and
cation
Weak Electrolytes
Weak electrolytes have lower degree of dissociation at higher
concentration
The change Λm with dilution is due to increase in the degree of
dissociation.
Λ m increases steeply on dilution, especially near lower
concentrations.
Λ0m cannot be determined by extrapolation of Λ m to zero
concentration.
Therefore, Λ0m for weak electrolytes is obtained by using Kohlrausch law of
independent migration of ions

For weak electrolytes

16. How is the molar conductivity of a weak electrolyte at infinite dilution determined? (or)
State and explain Kohlrausch’s Law. Write two applications of Kohlrausch’s Law.
Kohlrausch Law of Independent Migration
Limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions
of the anion and cation of the electrolyte.
Λ0m = v+Λo+ + v-Λo-
Λo+ and Λo+ are the limiting molar conductivities of the cation and anion respectively.
Eg-: Λ0m(NaCl) = ΛoNa+ + ΛoCl-
Applications
 To calculate Λ0mfor any electrolyte from the Λo of individual ions.
 To determine the value of its dissociation constant once we know the Λ0m and Λm at a given
concentration c.

17. How will you determine Λm0 for water?

Λ0m(H2O) = (ΛoNaOH + Λo HCl ) – (ΛoNaCl)
18. State Faraday’s Laws of Electrolysis.
First Law

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  The amount of substance liberated or deposited at the cathode during electrolysis is directly proportional
to quantity of electricity passed.
WαQ
Q = It
W α It
W = Zit
Z = Electrochemical equivalent, W = mass of substance liberated or deposited
Q = quantity of electricity passed in Coulomb I = current in ampere
t = time in seconds
 Quantity of electricity needed to deposit or liberate 1 mole of substance = nF where F is Faraday’s
constant and = 96500 C/mol
Second Law
 The amount of different substances liberated by same quantity of electricity passing through electrolytic
solution are proportional to chemical equivalent weight
19. What is the difference between primary cell and secondary cell?
Primary Battery
 They cannot be recharged.
 Ex- Lechlanche Cell or Dry Cell, Mercury Cell
Secondary Battery
 A secondary battery after use can be recharged by passing current through it in opposite direction.
 Ex- Lead storage Battery, Nickel Cadmium Cell.

20. Describe the Lechlanche cell with reference to electrodes used and reactions occurring at electrodes.
Lechlanche Cell or Dry Cell - Primary Battery
 Has a zinc container as anode and graphite rod as cathode
 Cathode is surrounded by powdered MnO2 and C.
 Space between electrodes is filled with moist paste of NH4Cl and ZnCl2
 Potential is 1.5 V
 Used in transistors and clocks.

21. Describe the composition of anode and cathode in mercury cell. Write the electrode reactions.
Mercury Cell - Primary Battery
 Zinc mercury amalgam is anode and paste of HgO and C is cathode.
 Electrolyte is a paste of KOH and ZnO.
 Used in hearing aid and watches

 The overall reaction is

22. Write the cell reactions which occur in lead storage battery when battery is in use and when it is on
charging
Lead storage Battery - Secondary Battery
 Lead is anode and a grid of lead dioxide is cathode.
 Electrolyte is a 38% solution of H2SO4.
 Used in automobiles and invertors.

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  The overall reaction is

 On charging the battery the reaction is reversed

Anode: PbSO4 → Pb
Cathode: PbSO4 → PbO2

23. What is the reaction taking place in Nickel cadmium cell?

Nickel Cadmium Cell - Secondary Battery
 Is more expensive but has a longer life.
 Cadmium is anode and a metal grid of nickel (v) oxide is cathode immersed in KOH
 The overall reaction is

24. What are fuel cells? Suggest two materials other than hydrogen that can be used as fuels in fuel cell.
Fuel cells produce electrical energy directly from combustion of fuels like H2 CH3OH or CH4.

25. Describe the hydrogen fuel cell.

 In hydrogen cell hydrogen and oxygen are bubbled through conc. aq. NaOH solution.
 Catalysts like Pt or Pd are used to increase rate of electrode reactions.

 The overall reaction is

Advantages
 Efficiency is 70%.
 Pollution free.
 Continuous supply of energy if supply of gases is continuous.

26. Rusting is an electrochemical process. Explain.

 Iron is corroded in presence of O2 and moisture
 The water layer present on surface of iron dissolves oxides of air that dissociate to form H+ ions
 In presence of H+ iron loses electrons at some spots to form ferrous ions. The spot acts as anode
 The electrons move to another spot where H+ ions and dissolved oxygen gain these electrons and
reduction takes place. This spot acts as cathode.

 The overall reaction is

 The ferrous ions are further oxidized by atmospheric oxygen into Fe3+ and come out as hydrated ferric
oxide and H+.

27. How can corrosion be prevented?

 Prevent metal surface from coming in contact with atmosphere by painting or covering with chemicals
like bisphenol.
 Cover surface with other metals (Sn, Zn) that are inert.
 Provide sacrificial electrodes of another metal (Mg, Zn) which corrodes itself. The more rective metal
acts as anode while the metal to be protected acts as cathode – Cathodic Protection.

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28. Account for the following
a) Rusting of iron is quicker in saline water than in ordinary water.
b) Alkaline medium inhibits the rusting of iron.
c) Iron does not rust even if zinc coating is broken in a galvanized iron pipe.
a) In saline water, presence of Na+ and Cl- increases the conductance of solution in contact with the
metal surface. This accelerates formation of Fe2+ ions and hence rusting.
b) Alkaline medium neutralizes the H+ ions and prevents further reactions of rusting from occurring.
c) Zinc is more reactive than Fe and hence gets corroded.

29. 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.
(i) An aqueous solution of AgNO3 with silver electrodes.
AgNO3 → Ag+ + NO3-
H2O → H+ + OH-
Cathode: As Ag+ has lower discharge potential than H+, it is preferentially deposited as Ag on
cathode.
Ag+ + e- → Ag
Anode: As Ag anode is attacked by NO3- ions, Ag of anode will dissolve to form Ag+ ions in
solution
Ag → Ag+ + e-
(ii) An aqueous solution of AgNO3 with platinum electrodes.
AgNO3 → Ag+ + NO3-
H2O → H+ + OH-
Cathode: As Ag+ has lower discharge potential than H+, it is preferentially deposited as Ag on
cathode.
Ag+ + e- → Ag
Anode: OH – has a lower discharge potential than NO3- , it is discharged at anode
OH – → OH + e-
4OH → 2H2O + O2
(iii) A dilute solution of H2SO4 with platinum electrodes
H2SO4 → 2H+ + SO42-
H2O → H+ + OH-
Cathode: 2H+ + 2 e- → H2
Anode: OH – has a lower discharge potential than SO42-, it is discharged at anode
OH – → OH + e-
4OH → 2H2O + O2
(iv) An aqueous solution of CuCl2 with platinum electrodes.
CuCl2 → Cu2+ + 2Cl-
H2O → H+ + OH-
Cathode: As Cu2+ has lower discharge potential than H+, it is preferentially deposited as Cu on
cathode
Cu2+ + 2 e- → Cu
Anode: Cl – has a lower discharge potential than OH-, it is discharged at anode
2Cl- → Cl2 + 2 e-

30. Standard reduction potentials are given below

Half cell E0 value
F2/F -
+2.9V
Ag /Ag
+
- 0.8V
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 Cu+/Cu +0.5V
Fe2+/Fe -0.4V
Na+/Na -2.7V
K+/K -2.9V
a) Arrange oxidizing agents in order of increasing strength
b) Which will oxidize Cu to Cu+ under standard conditions
a) K+/K < Na+/Na < Ag+/Ag < Cu+/Cu < F2/F-
b) F2/F-

31.. Standard reduction potentials are given below

Half cell E0 value
Zn(OH)2/Zn -1.245V
Mg(OH)2/Mg -2.690V
Fe(OH)2/Fe -0.877V
Al(OH)2/Al -2.30V
a) Which is the strongest reducing agent?
b) Which can reduce Zn(OH)2 to Zn?
c) Which can reduce Fe(OH)2 to Fe?
a) Mg(OH)2/Mg
b) Mg(OH)2/Mg , Al(OH)2/Al
c) Mg(OH)2/Mg , Al(OH)2/Al, Zn(OH)2/Zn

32. Suggest a list of metals that are extracted electrolytically.

Na, Mg, Ca, Al.

33. Why is it necessary to platinize the electrodes of a conductivity cell before it is used for conductance
measurement?
To reduce polarization effects.

34. 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.
Mg > Al > Zn > Fe > Cu.

35. Given the standard electrode potentials,

Arrange these metals in their increasing order of reducing power.

Ag < Hg < Cr Mg < K .

36. Can you store copper sulphate solutions in a zinc pot?

No, because zinc is mare reactive than copper and will displace copper from its solution.
Zn + CuSO4 → ZnSO4 + Cu

37. Consult the table of standard electrode potentials and suggest three substances that can oxidise ferrous
ions under suitable conditions.
F2, Cl2, Br2.

Important formulae
 The decrease in Gibbs Free Energy of the cell is given by
∆G° = -nFE°(cell)

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 The Nernst equation for an electrochemical cell is given by

 Relationship between Nernst equation and Equilibrium constant is given by