1 Electrochemistry

1. (b) Lesser the E ° value of redox couple, higher is the ° 0.059 0.059
Ecell = log KC = log KC
reducing power. n 2
Cu 2+ + 2e - ¾® Cu; E ° = 0.34 V = 0.04
2H+ + 2e - ¾® H 2 ; E ° = 0.00 V 2 ´ 0.04
or log KC = = 1.356
0.059
Since, 2H+ / H 2 has lower standard reduction
potential than Cu 2+ / Cu redox couple. KC = antilog 1.356 = 22.70
Therefore, 9. We know that,
(i) Cu 2+ / Cu redox couple is a stronger oxidising º 2 .303 RT
Ecell = Ecell - log Q
agent than H + / H 2 . nF
At equilibrium,
(ii) Cu cannot displace H 2 from acids.
Thus, option (b) is correct. Q = Keq and Ecell = 0

2. (c) Using, DG3 = DG1 + DG2 º 2 .303RT

\ Ecell = log Keq …(i)
nF
\ - 2 FE ° = - 1 F ´ 0.15 + (- 1F ´ 0.50)
º
Given, Ecell = 0.59 V
- 2FE ° = - 0.15 F - 0.50 F
0.65 2.303RT
E° = - = 0.325 V = 0.059 V
2 F
3. (d) Cell constant is defined as the ratio of distance T = 298 K, n = 1
between the electrodes and their area of On substituting the given values in Eq. (i),
cross-section.
0.059
l we get 0.59 = log Keq
G* = 1
A
0.59
Since, land A remain constant for any particular cell, \ log Keq = = 10
0.059
hence value of cell constant always remains
constant for a cell. Þ Keq = 1010 = 1.0 ´ 1010
4. (d) Given, L°(Ca 2 + ) = 119 S cm 2 mol - 1 10. According to Nernst equation,
2 -1
L°(Cl - ) = 71S cm mol 2.303 RT
Ecell = E °cell - log Q
nF
As we know that,
2.303 RT
L°(CaCl 2 ) = L°Ca 2+ + 2 ´ L°Cl - Given, = 0.059 V
F
L°(CaCl 2 ) = 119 + 2 ´ 71 0.059
\ Ecell = E °cell - log Q
n
\ L°(CaCl 2 ) = 261S cm 2 mol - 1
At equilibrium, Ecell = 0
5. (c) A is true, but R is false. 0.059
In the reaction of copper with nitric acid, it is nitrate E °cell = log KC
n
ion which is responsible for the oxidation of Cu to
Cu 2+ ion. For the given reaction, n = 2
6. (b) Both A and R are true but R is not the correct Also, KC = 10 ´ 1015 [given]
explanation of A. 0.059
\ E°cell = log (10 ´ 1015 )
Conductivity always decreases with decrease in 2
concentration because the number of ions (current = 0.472 ~
- 0.473 V
carrying species) per unit volume decreases on
dilution. However, molar conductivity increases on 11. As we know that,
dilution because total volume of solution containing 1 1
Conductance = = S
one mole of electrolyte also increases. Resistance 50
7. (a) Both A and R are true and R is the correct Specific conductance = conductance ´ cell constant
explanation of A. 1
\ 1.3 Sm -1 = S ´ cell constant
°
8. Ecell °
= Ecathode °
- Eanode 50
Þ Cell constant = 1.3 ´ 50 m -1 = 65 m -1
= - 0.40 - (- 0.44) = - 0.40 + 0.44 = 0.04 V
= (65 / 100) cm -1
 Molar conductivity Ecell ° 3+
° = E 1/° 2 Br / Br - - E Fe
2 / Fe 2 +
1000 ´ conductance ´cell constant = 1.09 - 0.77 = 0.32 V (feasible)
=
molarity
13. (i) Given, L°H+ = 349.6 S cm 2 mol -1
1000 1 65
= ´ ´ L°CH3COO -
= 40.9 S cm 2 mol -1
0.4 260 100
= 6.25 S cm 2mol -1 Molarity = 0.0024M
k (conductivity) = 8 ´ 10 –5 S cm 2 mol –1
= 6.25 ´ 10 -4 S m 2 mol -1
According to Kohlraush’s law,
12. The reaction will be feasible, if emf of the cell
reaction is positive. L°CH3COOH = L°H+ + L°CH COO –
3

3+ - 1 2+ = 349.6 + 40.9 = 390.5 cm 2 mol -1

(i) Fe (aq ) + I (aq ) ¾® Fe (aq ) + I2
2 k ´ 100
As we know, Lc =
Ecell
° = EFe
° 3 + / Fe 2 + - E °1/ 2 I – m C
2 /I

= 0.77 - 0.54 8 ´ 10 -5 S cm -1 ´ 1000 cm 3 L-1

\ Lm =
= 0.23 V (feasible) 0.0024 mol L–1

(ii) 2Ag+ (aq ) + Cu(s) ¾® 2Ag(s) + Cu 2 + (aq ) = 33.33 S cm 2mol –1

Ecell
° = E Ag ° + / Ag - E °Cu 2 + / Cu L
Degree of dissociation, a = °m
= 0.80 - 0.34 = 0.46 V (feasible) Lm
1 33.33 S cm 2 mol -1
(iii) Fe (aq ) + Br - (aq ) ¾® Fe 2 + (aq ) + Br2
3+
\ a=
2 390.5 S cm 2 mol -1
Ecell
° = EFe ° 3 + / Fe 2 + - E °1/ 2 Br 2 / Br -
= 0.085
= 0.77 - 1.09 (ii) Electrolyte B is a strong electrolyte. This can be
explained as follows
= - 0.32 V (not feasible)
Limiting molar conductivity increases only to a
(iv) Ag (s) + Fe 3 + (aq ) ¾® Ag + ( aq ) + Fe 2 + (aq ) smaller extent for a strong electrolyte, as on
dilution the interionic interactions are overcome.
° = E° 3 +
E cell 2+ - E °Ag + / Ag
Fe / Fe Limiting molar conductivity increases to a larger
= 0.77 - 0.80 = - 0.03 V (not feasible) extent for a weak electrolyte, as on dilution, the
degree of dissociation increases, therefore the
1
(v) Br2 (aq ) + Fe 2 + (aq ) ¾® Br - + Fe 3 + number of ions in total volume of solution
2 increases.