Solution

PRACTICE PAPER ELECTROCHEMISTRY AND CHEMICAL KINETICS

Class 12 - Chemistry

1.
(d) Y
Explanation: Y
2.
(b) 0.03V, -2.895 kJ/mol, 3.22
0 0 3+
E Ag
Explanation: E 0

cell
= E
0

cathode
− E
o

anode
= −
E Fe

2+
= +0.8 − (−0.78) = +0.03V
Ag Fe

Δr G
0
= −nF E
0
cell = −1 × 96500 × 0.03 = -2895J/mol = -2.895kJ/mol
0 0.0591
E = log Kc
cell n
0
n×E
cell 1×0.03
log Kc = = = 0.508
0.0591 0.0591

kc = 3.22

3.
(c) -88.78 kJ
Explanation: Δ rG
∘
= −nF E
0

(cell)

Where, G = standard Gibbs Energy

= - 2× 96500 × 0.46 = -88.78KJ
4.
(b) 3F
Explanation: Al 2 O3 → 2Al
3+
+ 3O
2−

3−
Al + 3e
−
→ Al (For 1 mole)
3F charge is required to obtain 1 mole Al from Al2O3. Hence to neutralize Al​3+ ion 3F is required.

5. (a) Cr3+
Explanation: E o

Cr
3+
/Cr
has the most negative value equal to -0.74 among given four choices. So, Cr3+ is the most stable
oxidized species.
6.
(c) 16 min
Explanation: 75% completion means 2 half lifes so 50% completion means only one half life.
2.303 a
k = log
t a−x

2.303 100
k = log( ). . . (1)
32 100−75

2.303 100
k = log( ). . . (2)
t 100−50

from (1) and (2), we get

t = 16 mins
7.
(b) eight times
Explanation: eight times
8.
(b) mol L-1 s-1
Explanation: mol L-1 s-1
9. (a) 40.0 minutes
Explanation: For second-order reaction:
t1 [R]
/
2k 2
t1 = ⇒ k =
/2 [R] 2

Applying this equation,

1 / 10
 ′ ′
t1 [R] t 1 [R ]
/ /
2 2
=
2 2
′
t 1 ×0.10
/
8.0×0.50 2
=
2 2

′ 8×0.50
t 1/ = = 40
2 0.10

10. (a) k[A][D]

2

Explanation: Rate of reaction is first-order w.r.t A reactant and 2nd-order w.r.t D reactant, therefore:
2
rate = k[A][D]

11.
(d) A is false but R is true.
Explanation: Since conductivity depends upon the number of ions per unit volume. Therefore the conductivity of all
electrolysis decreases on dilution due to a decrease in the number of ions per unit volume.
12.
(b) Both (A) and (R) are true, but (R) is not the correct explanation of (A).
Explanation: Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution
containing one mole of electrolyte also increases
13. (a) Both A and R are true and R is the correct explanation of A.
Explanation: The formation of oxygen has a lower value of Eo than the formation of chlorine at anode even then it is not
formed because it requires overvoltage.
14.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Faraday's second law of electrolysis states that, when the same quantity of electricity is passed through several
electrolytes, the mass of the substances deposited are proportional to their respective chemical equivalent or equivalent weight.
n=1 for Ag and hence it's equivalent weight is Eq. wt. of Ag=108
n=2 for Cu and hence it's equivalent weight is Eq. wt. of Cu=63.5​/2=31.75
So here equivalent weight of silver and copper are different and hence Assertion is correct.
Reason is also correct as the molecular weights of Ag and Cu are different.
But the correct reason is because of there different equivalent weights but not molecular weights.
15.
(b) Both (A) and (R) are true, but (R) is not the correct explanation of (A).
Explanation: Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution
containing one mole of electrolyte also increases
16.
(d) A is false but R is true.
Explanation: Molecularity and order of reaction are identical if the reaction is elementary. They may become different when
the reaction is complex and has a mechanism.
17. (a) Both A and R are true and R is the correct explanation of A.
Explanation: Both A and R are true and R is the correct explanation of A.
18.
(d) Assertion (A) is false, but Reason (R) is true.
Explanation: Order and molecularity may or may not be same as order of reaction is sum of power of reactant which can be
determined experimentally. But molecularity is sum of stoichiometric coefficient of rate determining elementary step.
19. (a) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A).
Explanation: Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A).
20. (a) Both A and R are true and R is the correct explanation of A.
Explanation: Both assertion and reason are true and reason is the correct explanation of assertion. Rate expression
dX m n
= k[A] [B]
dt

shows that the total order of reactions is m + n + 0 = m + n as the rate of reaction is independent of concentration of C, i.e.,
the order with respect to C is zero. This is the reason that C does not figure in the rate expression.

2 / 10
21. We know from Kohlrausch law that molar conductivity of CaCl​2​and MgSO​4

Λ
∘
m( CaCl 2 )
=λ ∘
2+
+ 2λ
∘

Cl
−
= 119.0 S cm2 mol-1 + 2(76.3) S cm2 mol-1
Ca

= (119.0 + 152.6) S cm2 mol-1

= 271.6 S cm2 mol-1
Λ
o
=λ
m(MgS O4 )
∘
2+
+ λ
∘
2−
Mg SO
4

= 106.0 S cm2 mol-1 + 160.0 S cm2 mol-1

= 266 S cm2 mol-1
22. i. Limiting molar conductivity is equal to the sum of individual contributions of the anion and cation of the electrolyte.
∧m
ii. α = ∧m∘

= 400
48
= 0.12
23. For the reaction.
Mg(s) +Cu2+ (aq) → Mg2+ (aq) +Cu(s)
n=2
E
∘
cell
= +2.71 V, IF= 96500 C mol-1 (given)
ΔG
∘
= -nF E ∘
cell

= −2 × 96500 × 2.71 = -523030J mol-1

= - 523.030 kJ mol-1.
24. Given, m = 1.27g. I = 2A
Molarmass of Cu= 63.5g mol-1,
Equivalent weight
Z= F

F = 96500 C mol-1
m=Z×I×t
m 1.27×2×96500
t= Z ×I
=
63.5×2

t = 1930 s
= 32.1 min
25. The two advantages of H2 - O2 fuel cell over ordinary cells are-
i. It is highly efficient
ii. It is pollution free.
26. For the button cell, chemical reactions are:
At anode:
2+ −
Zn(s) → Zn (aq) + 2e

At Cathode:
− −
Ag2 O(s) + H2 O(l) + 2e → 2Ag(s) + 2O H (aq)

Complete reaction is:

Zn (s) + Ag2 O (s) + H2 O (l) → Zn
2+
(aq) + 2Ag (s) + 20H
−
(aq) , for this reaction, n=2 moles of electrons.
Now,
Θ Θ Θ
E = E − E
cell Ag + /Ag Zn
2+
/Z n

= 0.80 - (-0.76) = 1.56V

We know that
Θ Θ
Δr G = −nF E
cell

Here, n = 2
F = 96500 C mol-1
Θ −1
ΔG = −2 × 1.56 V × 96000 C mo l

= -301080 J mol-1
= -301.08 kJ mol-1
Θ −1
∴ ΔG = −308.08 kJ mo l

27. i. Standard Gibbs Free energy is given by

ΔG = −nF E
∘
... (i) ∘
cell

3 / 10
 where, n = number of moles of electrons transferred, F = Faraday's constant = 96500 C mol-1
Eocell = Cell potential
Two half-reactions for the given redox reaction can be written as
3+ − 2+
2Fe (aq) + 2e ⟶ 2Fe (aq)
− −
2I (aq) ⟶ I2 (s) + 2e

2 moles of electrons are involved in the reaction, hence n = 2

Therefore, by substituting all the values in Eq. we get (i)
∘ −1
∴ Δr G = −(2mol) × (9%500Cmol ) × (0.236V)

= -45548 J
∘
Δr G = −4555kJ

ii. Given, current (I) = 0.5A, time (t) = 2h Quantity of charge (Q) passed= Current (I) × time (t) = (0.5A) × (2 × 60 × 60s) =
3600C
Again, Q = ne-
where, n = number of electrons
e- = charge on electron
Q
n= −
=
3600C

−19
= 2250 × 10
19

e 1.6× 10 C

Thus, number of electrons= 2.250 × 1022.

28. Cell B contains AgNO3 and reaction may be represented as:
+ −
AgN O3 ⇌ Ag + NO
3

+ −
Ag + e ⇌ Ag (At cathode)

According to the equation,

1 mol or 108 g of silver is deposited by 96500 C
1.45 g silver is deposited by = 96500×1.45

108

= 1295.6 C
Now, Q = I × t

1295.6 = 1.5 × t
1295.6
∴ t = = 863 s
1.5

The weights of copper and zinc can be calculated by using Faraday's second law of electrolysis.
In cell A, the electrode reaction is
2+ −
Zn + 2e → Zn

2 mol of electrons or 2 × 96500 C of current produce 1 mol or 65.3 g of Zn so that

2 × 96500 C of electricity deposit Zn = 65.3 g

1295.6 C of electricity deposit Zn = = 0.438 g

65.3×1295.6

2×96500

In cell C, The electrode reaction is

2+ −
Cu + 2e → Cu

2 mol of electrons or 2 × 96500 C of current produce 1 mol or 63.5 g of Cu so that

2 × 96500 C of current deposit Cu = 63.5 g
63.5×1295.6
1295.6 C of current deposit Cu = 2×96500
= 0.426 g

29. We know that

[Cu = 63.5g mol-1, 1F = 96500C mol-1]
2+ −
Cu (aq) + 2e → C u(s)

m = Z × I × t
63.5
= × 5amp × 45 × 60
2×96500
857250
= = 4.44g
193000

30. Concentration of methanoid acid = 2 × 10-3 M

The conductivity of methanoic acid = 8 × 10-5 S cm–1
1000× Conductivity (k)
(λm ) =
Concentration (c)

So,
= 40 S cm2 mol-1
−5
1000×8×10
(λm ) = −3
2×10

4 / 10
 ∧m 40
α = o
∧m
= 404

= 0.099
31. a. Primary Batteries: In the primary batteries, the reaction occurs only once and after use over a period of time battery becomes
dead and cannot be reused again.
Example: Dry cell (Leclanche cell).
b. Given parameters are:
κ = 7.896 × 10 Ʌ = 39.5 S cm −5
S cm
−1
m
2 −1
mo l Molarity = 0.00241 M=0.00241 mol L-1
As we know, Molar conductivity (Λ ) is m

κ×1000
Λm =
C
−5 −1 3 −1
7.896× 10 S cm ×1000cm L
=
−1
0.00241 mol L

2 −1
Λm = 32.76 S cm mo l

Degree of dissociation (α)

Λm 32.76 −2
α = = = 8.38 × 10
0 390.5
Λ
m

Dissociation constant of acetic acid,

2
Cα
Ka =
1−α

−2 2
0.00241(8.38× 10 )
Ka =
(1−0.0838)

−5
Ka = 1.8 × 10

32. a. Molar conductivity of methanoic acid ∧ m =

k

c
× 1000 S cm2 mol-1
1000 S cm2 mol-1
−5
8×10
= ×
−3
2×10

= 40 S cm2 mol-1
∧m
α =
∧m∘

40
=
404

= 0.099
b. Δ G = −nFE
r
∘ ∘
cell

= -2 × 96500 C mol-1 × (0.80 + 0.25) V

= -2 × 96500 × 1.05 J mol-1
= -202,650 J mol-1 or -202.65 kJ mol-1
∘
nE
log Kc = 0.059
c e ll

=
2×1.05

0.059
= 35.6
33. i. Faraday's first law of electrolysis - states that the mass of a substance deposited /liberated at the electrodes is directly
proportional to the charge/quantity of electricity passed through the electrolyte.
2F charge is required.
2+
[Mg ]

ii. E cell = Ecell −

∘ 0.0591

2
log
2+
[ Cu ]

0.0591 0⋅1
= 2.71 V - 2
log 0.01
0.0591
= 2.71 V - 2
log 10
= 2.71 V - 0.0295
= 2.68 V
34. The molar conductivity of methanoic acid
c 2 −1
λm = 46.1 S cm mo l

c 0 + 0 −
λm = (HC OOH) = λ (H )+ λ (HC O O )

= 349.6 + 54.6S cm2 mol-1

= 404.2 S cm2 mol-1
c
λm
α =
0
λm
46.1
= = 0.114
404.2

− +
HC OOH ⇌ HC O O + H
−1
n mol L 0
Initial conc.
n(1 − α) nα

5 / 10
 2
xα
∴ Ka =
1−α
2
0.025×(0.114)
=
1−0.114

−4
= 3.67 × 10

−5 −1 3
κ 4.95×10 Scm 1000cm
35. a. A m =
c
=
0.001
×
L
2
= 49.5Scm mol
−1

2 −1
Am 49.5Scm mol
α = o
= = 0.126
−1
Λm 390.5Scm 2 mol
−1 2
2 0.001molL ×(0.126)
cα 5 −1
K = = = 1.8 × 10 molL
(1−α) 1−0.126

((If K = cα , then K= 1.6 × 10−5 mol L-1

2

3+ 2
⌊Al J

b. E ( cell )
= E
⊖

( cell )
−
0.059

6
log
3
2+
[cu ]

c. Batteries which are rechargeable

Example- Lead storage, Ni-Cd batteries
36. k = 0.00510 min −1
, [R]0 = 0.10 M and

t = 3h = 3 × 60 min.
[R]
2.303 0
t = log
k [R]

2.303 [0.10]
3 × 60 = log
0.00510 [R]

[0.10]
180×0.00510
log = = 0.3986
[R] 2.303

[0.1]
= Antilog(0.3986)
[R]

0
0.1/[R] = 2.503 × 10
0.1
⇒ [R] = = 0.04 M .
2.503

37. R → P
d[R]
Rate = − dt
= k[R]

d[R]
or = −kdt
[R]

Integrating this equation, we get

ln [R] = -kt + I ...(i)
When t = 0, R = [R]0.
where, [R]0 is the initial concentration of the reactant.
Therefore, equation (i) can be written as
ln [R]0 = -k × 0 + 1
ln [R]0 = 1
Substituting the value of I in equation (i)
ln [R] = -kt + ln [R]0
Rearranging this equation
[R]
ln = −kt
[R]
0

[R]
1 0
k = ln
t [R]

[R]
2.303 0
k = log
t [R]

38. Calculation of activation energy, Ea:

According to Arrhenius equation,
k = Ae-Ea/RT
Ea
log k = log A −
2.303RT
...(i)
4
1.0×10
log k = 14.2 −
T
...(ii)
On comparing Eqs. (i) and (ii)
Ea 4
1.0×10
=
2.303RT T

Ea = 2.303R × 1.0 × 104

= 2.303 × 1.0× 104 × 8.314

= 19.14 × 104 J mol-1

6 / 10
 = 191.4 kJ mol-1
Calculation of rate constant, k:
Given, t1/2 = 200 min = 200× 60 sec
0.693 0.693
k = =
t 200×60
1/2

k = 5.775 × 10-5 s-1

Average rate (Rav) Instantaneous rate(Rav)
39.
i. Average rate of reaction is the change in the concentration i. Instantaneous rate of reaction is the change of concentration of
of reactant or product in a specified time interval. reactant or product at particular moment of time.

ii. It is concerned with the whole reaction process. ii. It is concerned with the particular moment of reaction.
Δ[R] Δ[P] d[R] d[P]
iii. Average rat = − Δt
= +
Δt
iii. Instantaneous rate = − dt
= +
dt

40. Rate of disappearing of I- = = 2 × 10-3 M min-1

−d[ I ] −(0.28−0.30) 0.02

dt
= 10−0
= 10
−

2 × 10-3 = 10-3 M min-1

d[I2] −d[ I ]
Rate of production of I2 = dt
= dt
= 1

2
×

41.

When the temperature has raised the maximum of the curve moves to the higher energy value and the curve broadens out i.e
spread to the right so that there is a greater proportion of the molecules with much higher energies area under the curve must
constant. Most probable kinetic energy increases with an increase in temperature. As the temperature increases, activation energy
Ea decreases which will result in an increase in the rate of reaction.
42. T 1 = 295K , T2 = 305K

T2 T1 k2
Ea = 2.303R [ ] [log ] , wherek2 = 2k1
T2 − T1 k1

305×295 2k1
Ea = 2.303 × 8.314 × [ ] log
305−295 k1

= 2.303 × 8.314 × 8997.5 log2 = 51855.2J /mol

43. For the reaction 2A + B → C + D

Let rate law expression as
Rate = k[A] [B] a b

According to question
−3 a b
6.0 × 10 = k(0.1) (0.1) . . . . (i)

−3 a b
7.2 × 10 = k(0.3) (0.2) . . . . (ii)

−2 a b
2.88 × 10 = k(0.3) (0.4) . . . . (iii)

−2 a b
2.40 × 10 = k(0.4) (0.1) . . . . (iv)

Divide eq. (iv) by (i)

a
(4) = (4)

∴ a= 1

Divide eq. (iii) by (ii)

b
4 = (2)

2 b
2 = (2) ⇒ b = 2

Order with respect to A=1

Order with respect to B=2

7 / 10
 d[D]
2
Rate law = = k[A][B]
dt

On putting the value of 'a' and 'b' into any equation say (i)
6.0 × 10-3 M min-1 = k [0.1M] [0.1M]2
6.0 × 10-3 M min-1 = k [0.1 M]3
k= 6.0 M-2 min-1
44. 2N H 3 → N2 + 3H2
d[N H3 ] d[ N2 ]
Rate = − 1

2 dt
= +
dt
d[ H2 ]
1
= +
3 dt

For zero order reaction rate = k

d[N H3 ] d[ N2 ] d[ H2 ]
1 1
∴ − = =
2 dt dt 3 dt

−4 −1 −1
= 2.5 × 10 mol L s

d[ N2 ]
Rate of production of N 2 =
dt

−4 −1 −1
= 2.5 × 10 mol L s

Rate of production of H 2

1 d[ H2 ]
= k
3 dt
d[ H2 ]
= 3k
dt
−4 −1 −1
= 3 × 2.5 × 10 mol L s
−4 −1 −1
= 7.5 × 10 mol L s

d[Ester]
45. i. Average rate of reaction between the time interval, 30 to 60 seconds,= dt
0.31−0.17 0.14 −3 −1 −1
= = = 4.67 × 10 mol L s
60−30 30

ii. For a pseudo first order reaction,

[R]
2.303 0
k = log
t [R]

For t= 30s,k 1 =
2.303

30
log
0.55

0.31
= 1.911 × 10
−2 −1
s

For t= 60s, k 2 =
2.303

60
log
0.55

0.17
= 1.957 × 10
−2
s
−1

For t= 90s,
2.303 0.55 −2 −1
k3 = log = 2.075 × 10 s
90 0.085

= 1.981 X 10-2 s-1

k1 + k2 + k3
Then, average rate constant,k = 3

46. a. Given half life t1/2 for decomposition of nitramide=2.1 h

0.693 0.693
i. k = t
=
2.1h
1/2

−1
= 0.33 h
2.303 100
t99% = log
k 100−99
2.303 100
= log
K 100−99

2.303 2.303 2.303

= (log 100 − log1) = log 100 = × 2
k k k
4.606
= = 13.96 h
−1
0.33h

ii. Amount decomposed = 99% of 6.2 g

= = 6.138 g
6.2×99

100

1 mole of N H N O (62 g) produces 22.4 L at STP

2 2

6.138 g will produce= × 6.138

22.4

61

= 2.217 L at STP
b. X → Y
Rate = k[X] 2

Rate = k[3X]
′ 2
when concentration of X is increased to 3 times the original concentration
2
= 9k[X] = 9 × Rate

The rate of formation of 'Y' will increase to 9 times the original rate because reaction is second order and concentration is
increased 3 times.
47. i. For a first order reaction
[R]
2.303 o
k = log
t [R]

8 / 10
 where [R]o = initial concentration, [R] = conc. after time t
[R]o
When half of the reaction is completed, [R] = 2
.
Representing, the time taken for half of the reaction to be completed, by t , equation becomes: 1

[R]
2.303 o
k = log
t 1 [R]
o

2 2

2.303
⇒ t 1 = log 2
k
2
2.303
⇒ t 1 = × 0.3010
k
2

0.693
⇒ t 1 =
k
2

The above equation shows that half-life of first order reaction is independent of the initial concentration of the reactant.
ii. For a first order reaction
2.303 a
t = log
k a−x
2.303 100
t99% = log
k 1
2.303
= log 100
k
2.303×2
=
k
4.606
=
k

and t 90%
=
2.303

k
log
100

10
2.303 2.303
= log 10 =
k k
t99%
= 2
t
90%

t99% = 2 × t90%

48. k1 = 4.5 × 10 s
3 −1

0
T1 = 10 C

T1 = 10 + 273K = 283K

k2 = 1.5 × 10 s
4 −1
;T 2 =?

−1
Ea = 60K J mo l

Applying arrhenius equation

k2 Ea T2 − T1
log = [ ]
k1 2.303R T1 T2

4 −1 T2 −283
1.5×10 60000Jmol
log = × [ ]
3 −1 −1 283T2
4.5×10 2.303×8.314JK mo l

T2 −283
or log 3.333 = 3133.63 [ 283T2
]

T2 −283
or 0.5228

3133.63
=
283T2

or 0.0472T 2 = T2 − 283

or 0.9528 T 2 = 283

T2 =
283

0.9528
= 297 K
0 0
= 297 − 273 C = 24 C

[A]
2.303
49. i. k =
0
log
t [A]

2.303 100
= log
40 25
2.303
= × 0.6021
40

k = 0.03466 min-1
0.693
t 1 =
k
2

0.693
t 1 =
0.03466
2

= 19.994 min ≈ 20 mins

ii. a. First order reaction.
b. Zero order reaction.
50. a. i. The order of reaction iis Zero order.
ii. -k
k2 Ea T2 − T1
b. log k1
=
2.303R
[
T1 T2
]

Ea 313−293
log4 = ( −1 −1
)[
313×293
]
2.303×8.314JK mol

9 / 10
0.602 = Ea × 20/19.147 × 91709

Ea = 52862 j mol-1 = 52.862 kJ mol-1

10 / 10