Chemistry - Electrochemistry

[Time : 90 Mins] SOLUTION OF ASSIGNMENT [Max. Marks : 35]

Note : 1. Electrochemistry chapter Weightage total 5 marks. 2. All questions are compulsory. 3. Draw neat and labelled diagram wherever necessary. 4. Figure to the right indicates full marks. 5. Answer to every new question must begin on a new page.

1. Solution :

What is meant by cell constant? Cell constants the ratio of distance between electrodes and area of cross section. If is denoted by l/a. Its unit is cm-1. [1 Mark]

2. Solution :

What does the negative value of E0Cell indicate? E0Cell is ve means G will be +ve, and the cell will not work. [1 Mark]

3. Solution :

What are secondary cells? Secondary cells are those cells which are rechargeable i.e., the products can be charged back to reactants. [1 Mark]

4. Solution :

How does cathodic protection of iron operate? More reactive metal coated on iron acts as anode, ie., loses electrons whereas iron acts as cathode. If any Fe2+ ions are formed will gain electron to form iron. [1 Mark]

5.

Electrolysis of KBr(aq) gives Br2 at anode but of KF(aq) does not give F2. Give reason for disparity in behaviour.

Solution :

Eo F

2 /F

has highest reduction potential, therefore, it reacts with water to liberate O2 and not F2. [1 Mark]

6. Solution :

Can you store copper sulphate solutions in a zinc pot? E0Zn2+ = - 0.76 V, E0 Cu2+/Cu = 0.34V. www.21stideal.com 1

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We have to check whether the following reaction takes place or not. Zn(s) + CuSO4 (aq) ZnSO4 (aq) + Cu (s) E0 Cell = E0 Cu2+/Cu -EZn2+, Zn = 0.34 V (-0.76 V) =1.1 V Since E0 Cell is positive. The reaction takes place and we cannot store. [1 Mark] [1 Mark]

7.

With the help of ionic equations describe what happen : When (i) (ii) pH of a solution of dichromate ions is raised. Potassium mangnate is electro-chemically oxidized. 2CrO42(yellow)

Solution :

(i) Cr2O72+ + 2OH(orange) higher pH

where pH is increased, i.e., solution is more basic, orange coloured dichromate ion change to yellow coloured chromate ion. (ii) At anode
electrolysis MnO42- MnO4-+ e-

[1 Mark]

purple When potassium manganate is electro-chemically oxidised i.e.,undergoes electrolytic oxidation, it forms purple colour KMnO4. [1 Mark]

8. Solution :

How does molar conductance of a strong electrolyte vary with its concentration in solution? The molar conductivity of a strong electrolyte like KCl decreases slightly as the concentration is increased. This is because greater inter ionic attractions retard the motion of the ions and therefore molar conductivity decreases. [1 Mark]

At low concentrations, the molar conductance of strong electrolyte can be expressed by the relationship. m = m - k Where m = molar conductance at concentration C. m = molar conductance at infinite dilution. K = Constant, C = Concentration of solution on molar scale. [1 Mark]

9.

Define molar conductivity of an electrolytic solution. Mention the effect of temperature on molar conductivity?

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Solution :

Molar conductivity is defined as the electrolytic conductivity power of all the ions furnished by 1 mole of the electrolyte at a given concentration in solution. It is gives as m =

k Cm

where m = molar conductivity , k = Specific conductivity, conductivity, Cm = Concentration in molar per litre. [1 Mark] Effect of temperature on molar conductivity conducti : The speed of movement of ions increases with an increase in temperature. Therefore, molar conductivity increases with temperature. [1 Mark]

10. Solution :

Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10. For hydrogen electrode. H+ + e- H2 From Nernst equation,
EH+ / H2 = E 0 H+ / H2 0.0591 1 log + n [H ]

[1 Mark]

=0

0.0591 1 log 10 = 0.0591 10 = 0.591V 1 10

[1 Mark]

11.

Explain Kohlrausch's law of independent migration of ions. Mention one application ap of Kohlrausch's law?

Solution :

Kohlrausch's law of independent migration of ions: The molar conductivity of an electrolyte at infinite solution is the sum of the individual contributions of the anion and cation of the electrolyte.

where 0+ and 0- are the limiting molar conductivities of the cation and anion respectively and v+ and v- are the number of cations and anions formed from a formula unit of the electrolyte. For example, one formula unit of A12(SO4)3 gives two Al + ions and three sulphate ions. Therefore, [1 Mark] Determination of molar conductivity of weak electrolytes at infinity solution: Consider acetic acid CH3COOH as the example of electrolyte. (CH3COOH) = (CH3COO-) + (H+) (HCl) = (H+)+ (Cl-) 0(NaCl) = 0(Na+) + (Cl-) ...(1) ...(2) ...(3)

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[2 Marks]

12.

The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length 50 cm is 5 55 x 103 ohm. Calculate its resistivity, conductivity and molar conductivity.

Solution :

a = r2 =3.14 (0.5 cm)2 = 0.785 cm2 or

= 87.135 cm Conductivity,

[1 Mark]

Molar conductivity, = 0.01148 S cm-1

[1 Mark]

[1 Mark]

13.

Calculate the potential (emf) of the cell Cd | Cd2+ (0.10M) || H+(0.20M)|Pt, H2 (0.5 atm) (Given E for Cd2+ /Cd = - 0.403 V, R = 8.314 JKT-1 mol-1, F = 96,00 C mol-1).

Ans.:

The cell reaction is Cd + 2H+ (0.20M) Cd2+ (0.10M) + H2 (0.5 atm) Ecell = E0H+/1/2H2 - E0Cd2+/Cd = 0 - (-0.403) = 0.403 V Applying Nernst equation to the cell reaction, [1 Mark]

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= 0.403

0.0591 0.1 0.5 log = 0.403 0.02955 0.09691 = 0.403 0.002863 = 0.4001V 2 (0.2)2
[2 Mark]

14.

From the following molar conductivities at infinite dilution. m for Ba(OH)2 = 257.6 mol-1 cm2 mol-1 m for BaCl2 = 240 6 mol-1 cm2 mol-1 m for NH4C; = 129.8 mol-1 cm2 mol-l Calculate m for NH4OH.

Solution :

[2 Marks]
(ii)

= 238.3 mol-1 cm2 mol-1

[1 Mark]

15.

Show that the electrical work obtainable from a galvanic cell is given by the expression. G0 = -nFE0cell.

Ans.:

The cell potential is simply related to the free energy change for the reaction. In an electro-chemical electro cell the system does work by transferring the electric charge through an external circuit. The free energy change G is equal to electrical work done. G = Welectrical [1 Mark]

For a reaction occurring in a electro-chemical electro chemical cell whose electrodes differ in potential by Ecell, the work done when amount of charge nF is transferred is given by Welect = -nFEcell ... G = -nFEcell Under standard state conditions

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G0 = -nFE0cell.

[2 Marks]

16. Solution :

What happens during corrosion of a metal? State the electro-chemical basis of corrosion of iron. Metal reacts with gases present in atmosphere to form surface compounds in corrosion. The electrochemical basis of corrosion of iron is as follows: H2O + CO2 H2CO3; H2CO3 2H+ + CO32- ; H2O 2H+ + OHIron is contact with the dissolved CO2 and O2 undergoes oxidation as follows: Fe Fe2+ + 2eEooxidation = + 0.44 V

The electrons lost by iron are taken up by the H+ ions present on the surface of the metal which were produced by the dissociation of H2CO3 and H2O. H+ + e- H 2H2 + O2 2H2O O2 + 4H+ + 4e- 2H2O O2 + 2H2O + 4e- 4OH2Fe + O2 + 4H+ 2Fe2+(aq) + 2H2O(l) E0cell = 1.67 V 2Fe2+ + O2 + 4H2O 2Fe2O3 + 8H+(aq) Fe2O3 + XH2O Fe2O3 .X H2O (Rust) [1.5 Mark] [Eored = 1.23V] [1.5 Mark] [2 Mark]

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