Chemical Kinetic PDF
Chemical Kinetic PDF
Chemical Kinetic PDF
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. A substance having initial concentration 'a' mole/L reacts according to zero order reaction. The time taken for
completion of reaction is
2a a a k
(1) (2) (3) (4)
k k 2k a
Sol. Answer (2)
Initial concentration is [A]0 = a M
Reaction follows zero-order kinetics
x = kt
x a
Here, x = a t = =
k k
2. Rate constant of a first order reaction is 6.93 × 10–3 min–1. If we start with 10 mol/L. It is reduced to 1.25 mol/L
in
(1) 100 minute (2) 200 minute (3) 30 minute (4) 300 minute
Sol. Answer (4)
Given, k = 6.93 × 10–3 min–1
[A]0 = 10 M; [A]t = 1.25 M
Hence, for 1st order reaction we can write
1 [A]0 1 ⎛ 10 ⎞
t=
k
ln [A] =
t 6.93 10 –3 ln ⎜ ⎟
⎝ 1.25 ⎠
3. The reaction A + 2B + C 2D + E is found to be 1, 2 and zero order with respect to A, B and C respectively.
What will be the final rate, if concentration of each reactant is doubled?
(1) 2 times (2) 4 times (3) 8 times (4) 16 times
Sol. Answer (3)
The given reaction is
A + 2B + C 2D + E
Order = 1 w.r.t. A; 2 w.r.t. B and zero w.r.t. C
dx
Initially = k [A] [B]2
dt
Now when concentration is doubled
⎛ dx ⎞ 2 2
⎜ dt ⎟ = k(2) [A] (2) [B]
⎝ ⎠
⎛ dx ⎞
⎛ dx ⎞ 2 ⎛⎜ dx ⎞⎟ = 8 ⎜ ⎟
⎜ dt ⎟ = 8k [A] [B] ⎝ dt ⎠
⎝ ⎠ ⎝ dt ⎠
The rate of reaction increases by 8 times.
1
4. For a reaction N2O5 2NO2 O2
2
Given :
d (N2O5 )
k1[N2O5 ]
dt
d (NO2 )
k 2 [N2O5 ]
dt
d (O 2 )
k 3 [N2O5 ]
dt
The relation between k1, k2 and k3 are
(1) 2k1 = k2 = 4k3 (2) k1 = k2 = k3 (3) 2k1 = 4k2 = k3 (4) ½k1 = k2 = ¼k3
Sol. Answer (1)
For the reaction,
1
N2O5 2NO2 O2
2
We can express the rate as,
K2
K1 = = 2K3
2
2K1 = K2 = 4K3.
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 189
5. The concentration of a reactant in a solution falls from 0.2 M to 0.1 M in 2 hours and to 0.05 M in 4 hours.
The order of reaction is
(1) Zero (2) Two (3) One (4) Half
Sol. Answer (3)
Same % decay in same time. So, it indicates that reaction is of first order.
1
For second order reactions t1/2 = K A
0
ln 2
For 1st order, t1/2 = and is independent of concentration.
k
dx
= K (both are same)
dt
7. For a hypothetical reaction x + y = A + B, Rate = k [x]5/2 [y] –1/2 on doubling the concentration of x and y the
rate will become
(1) 2 times (2) 4 times (3) 8 times (4) Remains same
Sol. Answer (2)
Rate given is
Rate = K [x]5/2 [y]–1/2
On doubling the concentration of x and y
5 1
Rate = K(2)5/2 (2)–1/2 [x]5/2 [y]–1/2 = K (2) 2 2
[x]5/2 [y]–1/2 = K.(2)2 [x]5/2 [y]–1/2 = 4 K [x]5/2 [y]–1/2
8. The gaseous reaction A (g) 2B (g) + C (g) obeys first order kinetics. If the initial P = 90 mm and pressure
after 10 minutes = 180 mm. The velocity constant k of the reaction is
(1) 1.15 × 10+3 s–1 (2) 2.30 × 10+3 s–1 (3) 3.45 × 10–3 s–1 (4) 1.15 × 10–3 s–1
Sol. Answer (4)
A(g) 2B(g) + C(g)
t =0 P0 0 0
t = t P0–P 2P P
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190 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
Pt = 0; = P0 ; Pt = P0 – P + P + 2P
Pt = P0 + 2P
After 10 min; Pt = 180 mm Hg
180 = 90 + 2P 90 = 2P
P = 45 mmHg
Applying I-order kinetics:
1 ⎧ 90 ⎫ ln 2
K= ln ⎨ ⎬ =
10 ⎩ 90 – 45 ⎭ 10
0.693 0.693
K= = = 1.15 × 10–3 s–1
60 10 600
9. The half life period of a radioactive substance is 69.3 minutes. In how much time will it be disintegrated 80% of
its original amount?
(1) 80 minutes (2) 100 minutes (3) 140 minutes (4) 161 minutes
Sol. Answer (4)
For radioactive disintegration
20 N0
t1/2 = 69.3 min. Nt = N0 =
100 5
ln 2 0.693
= t = = 0.01 min–1.
1/2 69.3
1 ⎛ 5N0 ⎞ ln 5
t = 0.01 ln ⎜ N ⎟ =
⎝ 0 ⎠ (0.01)
2.303 0.7
Time taken (t) =
(0.01)
t = 161 minutes
10. For a reaction 2N2O5 4NO2 ( g) O2 ( g) , the rate and rate constant are 1.02 × 10–4 mol L–1 s–1 and 3.4×10–5
s–1 respectively. The concentration of N2O5 at this time will be
(1) 1.732 mol/L (2) 3 mol/L (3) 1.02 × 10–4 mol/L (4) 3.2 × 105 mol/L
Sol. Answer (2)
The given reaction is 2N2O5 4NO2 + O2
R = 1.02×10–4 m/s; K = 3.4×10–5s–1.
Reactions follows I-order kinetics as units of K is s–1
Rate = K [N2O5]
1.02 × 10–4 = (3.4 × 10–5) [N2O5]
1.02 10 –4 1.02 10
[N2O5] = 3.4 10 –5 =
3.4
=3M
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 191
11. A gas phase reaction R A + B + C + D is of first order. The initial pressure was x0 where pressure after 10
minutes was y. The correct expression for rate constant k is
⎛ y– x 0 ⎞
3P = (y – x0) P = ⎜ ⎟
⎝ 3 ⎠
1 x0
K= ln x P
10 0
2.303 x0
K= log
10 ⎛ y – x0 ⎞
x0 – ⎜ ⎟
⎝ 3 ⎠
2.303 3 x0
K= log
10 3 x0 y x0
2.303 3 x0
K= log
10 4 x0 y
226
88Ra 86Rn
RaA
RaB RaC
(1) 13th group & 6th period (2) 16th group & 3rd period
(3) 15th group & 7th period (4) 15th group & 6th period
Sol. Answer (4)
226
88 Ra 2He4 + 222
86 Rn
222
86 Rn 218
84 RaA + 2He4
218
84 RaA 218
85 RaB + –1
0
218
85 RaB 2He4 + 214
83 RaC
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192 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
13. One gram atom of 79Au198 (t1/2 = 65 hours) decays by -emission to produce stable nuclide of Hg. How much
Hg will be present after 260 hours?
1 1 15 16
(1) g atom (2) g atom (3) g atom (4) g atom
16 32 16 15
Sol. Answer (3)
No. grams atom, t = 0 of Au is equal to 1
After 260 hours (t1/2 = 65 hours)
ln 2
=
65
ln 2 1 ⎧ 1⎫
= ln ⎨ ⎬
65 260 ⎩ x ⎭
260 ln 2 ⎛ 1⎞
= ln ⎜ ⎟
65 ⎝x⎠
⎛ 1⎞ 1
4 ln2 = ln ⎜ ⎟ ln24 = ln
⎝x⎠ x
1 1 1
= 24 or x = 4 = g atoms
x 2 16
1 15
No. of gram atoms after 260 hrs = 1 – =
16 16
14. For the reaction 2NO Br2 2NOBr , the following mechanism has been given
NO + Br2 NOBr2
Slow
NOBr2 + NO 2NOBr
Hence rate law is
(1) K[NO]2 [Br2] (2) K[NO] [Br2] (3) K[NOBr2] [NO] (4) K[NO] [Br2]2
Sol. Answer (1)
Mechanism given is
Kc
NO Br2
NOBr2
K
NOBr2 NO 2NOBr
slow
dx
From II- reaction, = K [NOBr2] [NO] …(i)
dt
NOBr2
Kc =
[NO][Br2 ]
[NOBr2] = Kc [NO][Br2] …(ii)
Substituting eq. (ii) in eq. (i), we get,
dx dx
= KKc [NO]2 [Br2] or = K’ [NO]2 [Br2]
dt dt
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 193
15. 1.0 g atom of an -emitting isotope (t1/2 = 10 days) is sealed in a container. The volume of gas accumulated in the
container at STP after 10 days would be
(1) 1.0 L (2) 44.8 L (3) 11.2 L (4) 22.4 L
Sol. Answer (3)
[N0] = 1 g atoms
since it is a-emitting
Isotope it produces 2He4 (1/2 mole)
1
Volume of gas liberated at STP = 22.4 × = 11.2 L
2
K = A.e Rt
The rate constant is inversely related to activation energy. It is energy required to make it equal to threshold
level and it can be greater than H for the reaction.
1 3
–
= K (2) 2 2
[A]–1/2 [B]3/2
18. Half life of a chemical reaction at a particular concentration is 50 minutes. When the concentration of the reactant
is doubled, the half life becomes 100 minutes, then the order of reaction is
(1) Zero (2) First (3) Second (4) Third
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194 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
19. There are two radio nuclei A and B. A is -emitter and B is a -emitter, their decay constant are in the ratio
of 1 : 2. What should be the number of atoms of A & B at time t = 0, so that probability of getting and -
particles are same at time t = 0?
(1) 2 : 1 (2) 1 : 2 (3) 1 : 4 (4) 4 : 1
Sol. Answer (1)
Rate1 = 1N1 …(i)
Rate2 = 2N2 …(ii)
According to question,
Rate1 = Rate2
1N1 = 2N2
N1 2 2
N2 = 1 = 1
20. In the first order reaction t99.9% is 60 minute. t50% of the reaction would be nearly
(1) 360 minute (2) 600 minute (3) 6 minute (4) 60 minute
Sol. Answer (3)
Let the initial concentration = a
Reaction follows I-order kinetics
⎧ ⎫
⎪
⎪ a ⎪⎪
1 1 ⎛ 100a ⎞
K= ln ⎨⎪ 99.9 ⎬⎪ = in ⎜ ⎟
(60) a– a (60) ⎝ 100a–99.9a ⎠
⎩⎪ 100 ⎭⎪
1 ⎛ 100a ⎞
= ln ⎜ ⎟
(60) ⎝ 0.1a ⎠
1 ⎧1000a ⎫ ln(1000)
= ln ⎨ ⎬ =
(60) ⎩ a ⎭ 60
For 50% decomposition we can write
ln2 60(ln2)
t= =
K ln(1000)
t = (60) (0.3)
60log 2 60log2
t = log (1000) =
log(103 )
60log2
t= = 20 log2
3
t = 20 × 0.3 = 6 minute
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 195
21. The temperature coefficient of most of the reactions lie between
(1) 2 and 4 (2) 3 and 4 (3) 1 and 2 (4) 2 and 3
Sol. Answer (4)
Temperature coefficient for the reaction is given by
K T 10
Tc = KT = 2 and 3
22. For a first order reaction t0.75 is 138.6 seconds. Its specific rate constant (in s–1) is
(1) 10–2 (2) 10–4 (3) 10–5 (4) 10–6
Sol. Answer (1)
T = 138.6 s
For 75% decomposition we can write
⎧ ⎫
⎪⎪ a ⎪⎪
1 ⎨ ⎬ 1 ⎛ 100a ⎞
K= ln ⎪ 75 a ⎪ = ln ⎜ ⎟
t a– t ⎝ 100a–75a ⎠
⎩⎪ 100 ⎭⎪
1 ⎧100 a ⎫ ⎧ ln 4 ⎫
K= ln ⎨ ⎬ = ⎨ ⎬
t ⎩ 25 a ⎭ ⎩138.6 ⎭
2.303 2 0.3010
K= = 0.01 = 10–2s–1
138.6
23. The activity of a radioactive sample reduced from 20 Ci to 1.25 Ci in 2000 years. The half life of the sample
and its decay constant are respectively
(1) 4000 years and 1.1 × 10–3 y–1 (2) 500 years and 1.1 × 10–2 y–1
(3) 500 years and 1.386 × 10–3 y–1 (4) 1000 years and 1.386 × 10–3 y–1
Sol. Answer (3)
The activity of radioactive sample decreases from 20 to 1.25
t = 2000 yrs.
1 ⎛ 20 ⎞ ln16
= ln ⎜ ⎟ =
2000 ⎝ 1.25 ⎠ 2000
= 1.386 ×10–3 y–1
Half life is
ln 2 ln 2
t1/2 = × 2000 = × 2000 = 500 years.
ln16 4ln 2
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196 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
1
25. The plot of log k versus of a first order is linear with a
T
(1) Positive slope and zero intercept (2) Positive slope and non-zero intercept
(3) Negative slope and non-zero intercept (4) Negative slope and zero intercept
Sol. Answer (3)
According to Arrhenius logarithmic form,
Ea
log K = log A – 2.303 RT
1
Log K versus graph gives straight line having intercept = log A
T
–Ea
And slope (m) =
2.303R
Since Ea > 0; m < 0
Slope is negative having non-zero intercept.
2.303 P 2.303 P0
(1) k log 0 (2) k log
t Pt t P0 2Pt
2.303 P0 2.303 P0
(3) k log (4) k log
t 2P0 Pt t P0 Pt
1 ⎧ P0 ⎫ 1 ⎧ P0 ⎫
K = ln ⎨ P P ⎬ = ln ⎨ P (P –P ) ⎬
t ⎩ 0 ⎭ t ⎩ 0 t 0 ⎭
1 ⎧ P0 ⎫ 2.303 P0
ln ⎨ 2P –P ⎬ = log
t ⎩ 0 t⎭ t 2P0 – Pt
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 197
27. In the first order reaction, x
y; the concentration of ‘x’ changes from 0.1 M to 0.025 M in 40 minutes. The
rate of reaction (mol/L/min) when concentration of x is 0.01 M, would be
(1) 3.47 × 10–5 (2) 3.47 × 10–4 (3) 5.8 × 10–4 (4) 5.8 × 10–6
Sol. Answer (2)
[X]0 = 0.1 M; [X]t = 0.025 M
t = 40 minute.
1 ⎛ 0.1 ⎞ ln 4
K= ln ⎜ ⎟ =
40 ⎝ 0.025 ⎠ 40
Rate of reaction = K[X]
⎧ ln 4 ⎫ 2ln 2
= ⎨ ⎬ × (0.01) ⇒ × (0.01)
⎩ 40 ⎭ 40
2 0.693 0.01
= = 3.47 × 10–4 m/s
40
28. The amount of U-235 required per day to run a power house of capacity 15 MW (efficiency of nuclear reactor
75%. Assume energy liberated by fission of 1 U-235 atom is 200 MeV) is
(1) 15.8 g (2) 28.1 g (3) 21.1 g (4) None of these
Sol. Answer (3)
1 watt = 1 J s–1
Capacity of power house = 15 × 106 J s–1
1 day = 86400 s
For 1 day (86400 sec) energy required
= 86400 × 15 × 106 J
= 1.296 × 1012 J
200 MeV = 200 × 106 × 1.6 × 10–19 = 3.2 × 10–11 J
∵ 3.2 × 10–11 J energy produced by 1 atom of U-235.
1.296 1012 1
1.296 × 1012 J energy will be produced = = 4.05 × 1022 atoms
3.2 10 –11
⎛ 4.05 1022 ⎞
Mass of 4.05 × 1022 atoms = ⎜ 6.023 1023 ⎟ × 235 = 15.80 g
⎝ ⎠
100
Since efficiency is 75% hence actual mass required = 15.8 × = 21.06 g
75
29. The radiation from a naturally occurring radioactive substance as seen after deflection by a magnetic field in
one direction are
(1) rays (2) rays
(3) Both (1) & (2) (4) Either or -rays
Sol. Answer (4)
Since and –rays are +vely and –vely charged particles, hence, they will be deflected by magnetic field in
one direction.
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198 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
30. The rate constant, the activation energy and Arrhenius parameter of a chemical reaction at 25°C are K, Ea
and A respectively. The value of rate constant as T is
(1) Ea (2) Ea × A (3) A – Ea (4) A
Sol. Answer (4)
–Ea
K = A.e RT
A
When T , K = =A
e0
as T; K = A.
31. A reaction : aA product. Follows zero order the concentration of A with respect to time(t) is given as
kt
(1) [A]0 = [A] – kt (2) [A] = [A]0 – kt (3) [A] = [A]0 + kt (4) [A] = [A]0
a
Sol. Answer (2)
aA product
1 d[A]
R
k (zero order)
a dt
32. The half life for decay of a radio active isotope is 14 hrs. Determine the fraction of radio isotope remaining
undecayed after 30 hours
(1) 4.456 (2) 0.227 (3) 0.256 (4) 0.358
Sol. Answer (2)
ln 2 ln 2
t1/2 14
⎛ ln 2 ⎞
Nt ⎜ ⎟ 30
t
e e ⎝ 14 ⎠ 0.227
N0
k
A + B2
2
AB + B (slow)
A+B
AB (fast)
k1 [A]2 k1
⇒ [A] [A 2 ]
k 1 [A 2 ] k 1
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 199
Rate = k2[A] [B] (r.d.s.)
k1
= k 2 k [A 2 ] [B2 ]
1
k1 1/2
= k 2 k [A 2 ] [B2 ]
1
1
Order of reaction = 11.5
2
35. When the activation energies of forward and backward reactions are equal, then
But S 0 R P
G 0 also
23
36. A positron is emitted from 11 Na . The ratio of the atomic mass and atomic number of the resulting nuclide is
[IIT-JEE 2007]
22 22 23 23
(1) (2) (3) (4)
10 11 10 12
Sol. Answer (3)
23
11 Na 10
23
X 01e
37. Consider a reaction aG + bH Products. When concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when concentration of G is doubled keeping the concentration of H fixed,
the rate is doubled. The overall order of the reaction is [IIT-JEE 2007]
(1) 0 (2) 1 (3) 2 (4) 3
Sol. Answer (4)
r = K[G] [H]
8r = K[2G] [2H]
2r = K[2G] [H]
=1=2
order of reaction = 3
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200 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
38. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half in 40
⎛ k1 ⎞
seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio ⎜⎜ k ⎟⎟ of the rate
⎝ 0⎠
constants for first order (k1) and zero order (k0) of the reactions is [IIT-JEE 2008]
(1) 0.5 mol–1 dm3 (2) 1.0 mol dm–3 (3) 1.5 mol dm–3 (4) 2.0 mol–1 dm3
Sol. Answer (1)
0.693
k1 = t1/2
0.693
k1 = (first order kinetics) …(1)
40
1.386
k0 = 2 20 (zero order kinetics) …(2)
k1
3
k 0 = 0.5 mol–1 dm .
39. For a first order reaction A P, the temperature (T) dependent rate constant (k) was found to follow the equation
1
log k = – (2000) + 6.0. The pre-exponential factor A and the activation energy Ea, respectively, are
T
[IIT-JEE 2009]
(1) 1.0 × 106 s–1 and 9.2 kJ mol–1 (2) 6.0 s–1 and 16.6 kJ mol–1
(3) 1.0 × 106 s–1 and 16.6 kJ mol–1 (4) 1.0 × 106 s–1 and 38.3 kJ mol–1
Sol. Answer (4)
1 Ea
log k = – (2000) + 6.0; comparing this equation with log k = log A – 2.303 RT
7
We get log A = 6 A = 106 s–1
Ea 2000
and – 2.303 RT = –
T
Ea = 2000 × 2.303 × 8.314
Ea = 38.3 kJ mol–1
40. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is [IIT-JEE 2010]
k
k
(1) k (2) k (3) (4)
T T
T T
Sol. Answer (1)
Ea
k A e RT
Ea
ln k = ln A –
RT
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 201
41. Bombardment of aluminium by -particle leads to its artificial disintegration in two ways, (i) and (ii) as shown.
Products X, Y and Z respectively are [IIT-JEE 2011]
(ii)
27 30
13Al 15P +Y
(i)
30 30
14 Si +X 14Si +Z
(1) Proton, neutron, positron (2) Neutron, positron, proton
(3) Proton, positron, neutron (4) Positron, proton, neutron
Sol. Answer (1)
He4
27
13 Al
2
30
14 Si 1H1
(X)
He4
27
13 Al
2
30
15 P 10 n
(Y)
30
14 Si 01 e
(Z)
[Q]0
[Q]
Time
(1) 2 (2) 3 (3) 0 (4) 1
Sol. Answer (4)
The order of reaction with respect to P is one since t3/4 is twice of t1/2. From the given graph the order of
reaction with respect to Q is zero. Therefore, overall order of reaction is one.
43. For the elementary reaction M N, the rate of disappearance of M increases by a factor of 8 upon doubling
the concentration of M. The order of the reaction with respect to M is [JEE(Advanced)-2014]
(1) 4 (2) 3 (3) 2 (4) 1
Sol. Answer (2)
r2 ⎛ [M]2 ⎞
⎜ ⎟
r1 ⎝ [M]1 ⎠
8 = (2)
=3
So, order of reaction is 3.
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202 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
SECTION - B
Objective Type Questions (More than one options are correct)
1. The rate law for the reaction, RCl + NaOH
ROH + NaCl is given by Rate = K[RCl]. The rate of the
reaction is
(1) Doubled by doubling the concentration of NaOH
(2) Halved by reducing the concentration of RCl by one half
(3) Increased by increasing the temperature of the reaction
(4) Unaffected by change in temperature
Sol. Answer (2, 3)
The rate law is given by
Rate = K [RCl]
For reaction, RCl + NaOH ROH + NaCl .
The rate [RCl] hence when [RCl] reduces to half, rate also becomes half and is not affected by [NaOH].
The rate always increases with the increase in temperature.
[B] 1 [C]
=
t 2 t
RateTº 10º C
(1) 2 Endothermic reaction
RateT C
RateTº 10º C 1
(2) Exothermic reaction
RateT C 2
RateTº 20º C
(3) 4 Exothermic reaction
RateT C
RateTº 20º C 1
(4) Endothermic reaction
RateT C 4
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 203
Sol. Answer (1, 2)
It is defined as the temperature coefficient of the reaction
k T 10ºC
as = 2 (Endothermic)
kT
k T 20ºC
and k = 4 (Exothermic)
TºC
241
(3) 30
15 P
30
14 Si (4) 95 Am 2He 4 244
97 Bk
⎛ q 13 2 15 0 ⎞
27
Al 24He 30
P 0n1 ⎜ ⎟
13 15
⎝ m 27 4 30 1⎠
⎛ 12 1 13 1⎞
12
C 1H1 0 n1 7N13 ⎜ ⎟
6
⎝6 1 7 0 ⎠
⎛ m 30 30 1⎞
30
P 30
Si e0 0n1 ⎜ ⎟
15 14 1
⎝ q 15 14 1 ⎠
⎛ 241 4 244 1⎞
241
Am 24He 244
Bk 0n1 ⎜ ⎟
95 97
⎝ 95 2 97 ⎠
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204 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
1 ⎛ 1 ⎞
K= ln ⎜ ⎟
t ⎝ 1–x ⎠
–Kt = ln (1–x)
e–Kt = (1 –x) ⇒ x = 1–e–Kt
Degree of dissociation is (1–e–Kt)
–Ea
ln2
(t1/2)I =
K
For 75% completion
⎛ ⎞
⎜ a ⎟
1 ⎜ ⎟ ln 4
t= ln ⎜ 75 a ⎟ =
K ⎜a – ⎟ K
⎝ 100 ⎠
2ln2
t= = 2t1/2
K
1
[A]t versus t graph gives a straight line for II-order and not for I-order.
1
(1) A plot of log kp versus is linear
T
(2) A plot of log [x] versus time is linear for zero order reaction
1
(3) A plot of P versus is linear at constant volume
T
1
(4) A plot of P versus is linear at constant temperature and number of moles
V
Sol. Answer (1, 4)
According to Boyle’s law
1 K
P (at constant T and no. of moles) P =
V V
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 205
⎛ 1⎞
Between P and ⎜ ⎟ the graph will be straight line
⎝V⎠
P versus T graph will be straight line. For zero order x = kt
i.e., x versus t graph gives straight line and not log x versus t.
⎛ K2 ⎞ H ⎛ T2 T1 ⎞
log ⎜ K ⎟ = ⎜ ⎟
⎝ 1⎠ 2.303 K ⎝ T1T2 ⎠
1
Hence the graph between log Kp versus will be linear.
T
Which of the following statements about this decay process is/are correct?
(1) After two hours, less than 10% of the initial X is left
(2) Maximum amount of Y present at any time before 30 minute is less than 50% of the initial amount of X
(3) Atomic number of X and Y are same
(4) Mass number of X and Y are same
Sol. Answer (1, 2)
–decay
(X) (Y)
–2
(Z)
t1/2 = 30 minute t1/2 = 2 days
When above decays take place
–
– 2
A
Z X A–4
Z–2 Y A–4
Z Z
After 2 hrs
4
x
⎛ 1⎞ ⎛ N0 ⎞
Nt = N0 ⎛⎜ 1 ⎞⎟ = N0 ⎜ ⎟ = ⎜ ⎟ < 10%
⎝2⎠ ⎝2⎠ ⎝ 16 ⎠
Hence (Y) amount at any time before 30 minute is less than 50% as (Y) disintegrate to give Z also.
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206 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
M 1
K has units = 2 ⇒
s.M M.s
1 litre
= litre mol–1s–1
moles s
and it depends upon temperature.
11. Two reactions A products and B products have rate constant kA and kB at temperature T and activation
energies EA and EB respectively. If kA > kB and EA < EB and assuming ‘A’ is same for both the reactions, then
(1) At higher temperature kA will be greater than kB
(2) At lower temperature kA and kB will be close to each other in magnitude
(3) As temperature rises, kA and kB will be close to each other in magnitude
(4) At lower temperature kB > kA
Sol. Answer (1, 3)
It can be concluded from the Arrhenius equation.
that KA > KB at higher temperature.
And they will approach each other as we increase the temperature
(i.e. K A K B )
12. In the formation of sulphur trioxide by the contact process, 2SO2 + O2
2SO3, the rate of reaction was
d(SO 2 )
measured as = 6.0 × 10–4 mol L–1s–1. Select correct statements
dt
(1) The rate of reaction expressed in terms of SO3 will be 6.0 × 10–4 mole L–1s–1
(2) The rate of reaction expressed in terms of O2 will be 6.0 × 10–4 mole L–1s–1
(3) The rate of reaction expressed in terms of O2 will be 3.0 × 10–4 mole L–1s–1
(4) The rate of reaction expressed in terms of O2 will be 12 × 10–4 mole L–1s–1
Sol. Answer (3)
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 207
14. In a hypothetical reaction,
A2 + B2
2AB
follows the mechanism as given below
A2 A + A(fast reaction)
A + B2
AB + B (slow reaction)
A+B
AB (fast reaction)
Select the correct statement
3
(1) R = k[A]2 [B2] (2) Order of reaction is
2
A 2 B2
2AB
Mechanism
A A (fast)
A 2
A + B2 AB + B (Slow reaction)
A + B AB (Fast reaction)
Applying the rate equation w.r.t. slow reaction
dx
= k [A] [B2] …(i)
dt
dx
= K {Kc[A2]}1/2[B2]
dt
dx
= K’ [A2]1/2 [B2]
dt
Here K’ = K.Kc1/2
According to above rate law
1
Order = 1 = 3/2
2
And since two reactants are involved hence molecularity is equal to 2.
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208 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
Y
1
(1) 2nd order reaction vs. time (2) 1st order reaction t1/2 vs. concentration
[A]
(3) Zero order reaction t1/2 vs. concentration (4) nth order reaction rate vs. concentration
Sol. Answer (1, 2, 4)
16. A catalyst lowers the activation energy of forward reaction . It also changes the activation energy of backward
reaction by an amount
(1) Equal to that of forward reaction
(2) Twice to that of forward reaction
(3) Determined only by average energy of products
(4) Determined by average energy of products relative that of reactants
Sol. Answer (1)
(E)af
Potential (E)ab Reaction path without catalyst
Energy
R Reaction path with catalyst
Collision number
CH2
(1) O3 O2 + [O] (2) CH3 – CH = CH2
CH2 CH2
2.303 A
t log
m 0.4 102 Α
9
4 Be 1
1H 84Be 12H
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210 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
22. The %yield of ammonia as a function of time in the reaction N 2 g + 3H 2 (g) 2NH3 (g), H < 0 at (P, T1)
is given below
T1
%yield
time
If this reaction is conducted at (P, T2), with T2 > T1, the %yield of ammonia as a function of time is represented
by [JEE(Advanced)-2015]
T2
T2 T1 T1
T1 T1
%yield
%yield
T2
%yield
%yield
T2
(1) (2) (3) (4)
24. A plot of the number of neutrons (N) against the number of protons (P) of stable nuclei exhibits upward deviation
from linearity for atomic number, Z > 20. For an unstable nucleus having N/P ratio less than 1, the possible
mode(s) of decay is/are [JEE(Advanced)-2016]
Capture : 11 H 0
1 e 10 n X-rays
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 211
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
The following data are for the reaction A + B Products
Concentration Concentration Initial rate
[A] (M) [B] (M) (mol L–1s1)
0.1 0.1 4.0 × 10–4
0.2 0.2 1.6 × 10–3
0.5 0.5 1.0 × 10–2
0.5 0.2 1.0 × 10–2
1. What is the order with respect to A and B for the reaction respectively?
(1) 0, 0 (2) 2, 2 (3) 2, 0 (4) 0, 2
Sol. Answer (3)
3. Determine the reaction rate when [A] and [B] are 0.2 M and 0.35 M, respectively.
(1) 1 × 10–2 (2) 1.6 × 10–3 (3) 4 × 10–4 (4) 1 × 10–4
Sol. Answer (2)
Comprehension-II
According to Soddy Fajan Law
“When an -particle is emitted, the daughter element has atomic number 2 units less than that of parent element.
It is consequently displaced two places (groups) to the left in the periodic table. When a -particle is emitted, the
daughter element has an atomic number 1 unit higher than that of parent element. It is consequently displaced one
place (group) to the right in the periodic table”.
222
86 A 2He 4 218
84 B
218
84 B 2He 4 214
82 C
214
82 C 214
83 D 01B
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212 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
2. 90Th
234 disintegrates to give 82Pb206. The number of and -particle emitted in this process will be respectively
(1) 7, 6 (2) 6, 7 (3) 8, 8 (4) 6, 4
Sol. Answer (1)
Th234
90 82
Pb206
Since atomic mass decreases from 234 to 206 the difference is 28 and per -particle emission the mass
decreases by 4 units.
28
Number of -particles emitted = =7
4
Atomic no. decreases by 7 × 2 = 14 or it becomes 76.
In the product no. of protons is 82 hence 6 particles are emitted
No. of -particles emitted = 7
No. of -particles emitted = 6
3. Number of neutrons and group number after emission of an -particle from 92U
238 group III
(1) N =146, group III (2) N = 144, group I
(3) N = 144, group III (4) None of these
Sol. Answer (3)
Comprehension-III
Hydrolysis of sucrose (C12H22O11), a first order reaction gives glucose (C6H12O6) and fructose (C6H12O6).
HO
S
2
G + F
(Dextro) (Dextro) (Laevo)
The rotation of plane polarised light at different angles by S, G and F is directly proportional to their concentration.
Given
Time 0 t
Rotation (S + G + F) r0 rt r
r0
1. If combined rotation of glucose and fructose is equal to the value of initial rotation, then r is equal to
r0 a r10
1
r a(r20 r30 )
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 213
r
2. If amount of rotation of glucose (per mole) is equal to amount of rotation of fructose (per mole), then r is equal
0
to
(1) 0 (2) 1 (3) (4) a
Sol. Answer (1)
r20 r30
r a(r20 r30 )
0.(∵ r 0)
r0 ar10
3. In previous question, after 30 seconds total rotation is equal to half of initial rotation. Then value of rate constant
is (in s–1)
30 ln2
(1) ln2 (2) (3) (4) 10–2
ln2 30
Sol. Answer (3)
1 ⎛ r r0 ⎞
k ln ⎜ ⎟
30 ⎝ r rt ⎠
1 ⎛ r0 ⎞ 1 ⎛ 1 ⎞
ln ⎜ ⎟ ln 2 ⎜∵ rt r0 ⎟
30 ⎝ rt ⎠ 30 ⎝ 2 ⎠
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Rate of Radioactive decay is independent of external factors (like pressure, temperature).
and
STATEMENT-2 : Radioactive decay follows second order kinetics.
Sol. Answer (3)
Radioactivity is a nuclear phenomenon and is independent of external factors like temperature, pressure etc.
Radioactivity follows first order kinetics and number of nuclei at any time ‘t’ is given by
Nt = N0 e–t
Statement (1) is correct but statement (2) is false.
3. STATEMENT-1 : Half life of first order reaction is independent of initial concentration of reactants.
and
STATEMENT-2 : Half life of first order reaction is inversely proportional to the rate constant.
Sol. Answer (2)
Half life for I-order reaction is given as
ln2
t1/2 = (independent of initial concentration & inversely proportional to K)
K
Statement (1) & (2) both are correct but statement (2) is not the correct explanation of statement (1).
4. STATEMENT-1 : Activation energy of forward reaction (Eaf) is greater than activation energy of backward reaction
(Eab) for an endothermic reaction.
and
STATEMENT-2 : Rate constant for a first order reaction is dependent on temperature.
Sol. Answer (2)
H for the reversible reaction is given by
(H) = (Ea)f – (Ea)b
For endothermic reaction H > 0 (Ea)f – (Ea)b > 0 or (Ea)f > (Ea)b
The rate constant for the first order reaction is given by
–E /RT
K = A.e a
Hence, statement (2) is not the correct explanation.
7. STATEMENT-1 : The rate of reaction increases generally by 2 to 3 times for every 10°C rise in temperature.
and
STATEMENT-2 : Increase in temperature increases the collision frequency.
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 215
Sol. Answer (2)
The rate of reaction generally increases the rate by 2 times to 3 times. We also define
K T 10
= TC (Temp. coefficient)
KT
and with the increase in temperature collision frequency increases as more molecules cross the energy barrier
and acquire activation energy.
8. STATEMENT-1 : For a first order reaction, rate of the reaction doubles as concentration of reactant gets doubled.
and
STATEMENT-2 : Rate is directly proportional to concentration of reactant.
Sol. Answer (1)
Rate = k [reactant].
H
9.
STATEMENT-1 : The pseudo order of reaction CH3COOC2H5 + H2O
CH3COOH + C2H5OH is 2.
and
STATEMENT-2 : The molecularity of given reaction is two.
Sol. Answer (4)
Order of reaction is 1 (pseudo-order)
10. STATEMENT-1 : If activation energy is zero, then temperature will have no effect on rate constant.
and
STATEMENT-2 : Lower the activation energy, faster is the reaction.
Sol. Answer (2)
k Ae Ea /RT
For Ea = 0 k = A
11. STATEMENT-1 : The plot of atomic number (y-axis versus number of neutrons (x-axis) for stable nuclei shows
a curvature towards x-axis from the line of 45° slope as the atomic number is increased.
and
STATEMENT-2 : Proton-proton electrostatic repulsions begin to overcome attractive forces involving protons and
neutrons in heavier nuclides. [IIT-JEE 2008]
Sol. Answer (2)
Elements with higher atomic number are more stable if they have slight excess of neutron as this increase
the attractive force and also reduces repulsion between protons.
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216 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
SECTION - E
Matrix-Match Type Questions
1. Match the following :
Column-I Column-II
(D) 20Ca
40 + ........
19K37 + 2He4 (s) 1H
1
⎛ mass 14 4 17 1⎞
(C) 7N14 + 2He4 8O17 + 1H1 ⎜ ⎟
⎝ charge 7 2 8 1 ⎠
⎛ mass 40 1 4 37 ⎞
(D) Ca40 + 1H1 19K37 + 2He4 ⎜ ⎟
20
⎝ charge 20 1 19 2 ⎠
1
(A) Half life of zero order reaction (p) k.a
0.693
(C) Temperature coefficient (r)
k
a
(D) Half life of second order reaction (s)
2k
Sol. Answer A(s), B(r), C(q), D(p)
Half life for the reaction is inversely related to (a)n–1 where ‘n’ is the order of the reaction
ln2 0.693
For I-order; t1/2 = =
k k
a
for zero order; t1/2 =
2k
for II-order reaction
1
t1/2 =
k.a
The temperature coefficient of reaction is the ratio of rate constants differing by a temperature of 10ºC.
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 217
3. Match the following :
Column-I Column-II
Concentration
(A)
(A) (p) 3
Rate
(B) (q) 2
Concentration
1
(C) A (r) 1
t
Rate
(D) (s) 0
(Conc)3
dx
= k (a – x)3
dt
⎛ dx ⎞
The graph will be straight line between ⎜ ⎟ and
⎝ dt ⎠
3
(a – x) passing through the origin.
1 1
[A]t = [A]0 + kt
1
The graph between [A] versus t is a straight line
t
1
1 [A]
having +ve slope and intercept = [A] .
0
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218 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
⎛ dx ⎞
Hence ⎜ ⎟ (a – x)
⎝ dt ⎠
The graph for I-order is
Rate
For zero-order reaction, the concentration decreases
as time progresses at constant rate
Graph will be
(conc.)
4. Match the following :
Column I Column II
K T 10
(A) (p) Arrhenius equation
KT
(B) e Ea /RT (q) Temperature coefficient
[C]
(A) A B C D (p)
[B] [A]
time
[B]
Concentration
[D]
(B) A B D (q)
[A]
C [C]
time
Concentration
[D]
B
(C) A (r) [B]
C D
[C] [A]
time
[D]
Concentration
[C]
B C
(D) A (s)
D [B] [A]
time
Note : Assume that all reactions are moderately fast reactions.
Sol. Answer A(r), B(p), C(q), D(s)
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 219
SECTION - F
Integer Answer Type Questions
1. Two radioactive elements X and Y have half lives of 100 and 50 minutes respectively. Initial sample of both the
elements have same number of atoms. Find the ratio of remaining no. of atoms of X and Y after 200 minutes.
Sol. Answer (4)
After 200 minutes,
a
Remaining about of X
22
a
Remaining about of Y
24
24
Ratio = =4
22
2. H2O and O atom react in upper atmosphere bimolecularly to form two OH radicals. H for the reaction is
72 kJ at 500 K and energy of activation is 77 kJ / mol. Estimate Ea (kJ / mol) for bimolecular recombination
of two OH radicals to form H2O & O atom.
Sol. Answer (5)
Ea
H2 O O 2OH H 72 kJ
Eb
2OH H2 O O H 72 kJ
Also, Ea – Eb = H
Eb = 5 kJ/mol
3. For the reaction given below, the rate expression is given as : RX OH ROH X
5
4.7 10 RX OH
0.24
10
5
RX
rate =
SN 2 SN 1
dC KC
1
dt 1 K 2 C
What will be the order of reaction, when concentration C is very low?
Sol. Answer (1)
∵ C is low, then 1 k 2 C 1
dC
k1C
dt
Hence, reaction is of 1st order.
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220 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
2.303 1 2.303
t 90% log10 1
k 10 k
238 214
6. The total number of and particles emitted in the nuclear reaction 92 U 82 Pb is [IIT-JEE 2009]
Sol. Answer (8)
238 214
92 U
82 Pb X24He y01e
24 = 4x; x = 6
10 = 2x – y
y=2
x+y=8
7. The concentration of R in the reaction R P was measured as a function of time and the following data is
obtained [IIT-JEE 2010]
dx
k
dt
from 1 to 0.75 (M) from 0.75 to 0.40 from 0.40 to 0.10
Fe belongs to group-8.
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 221
1 1
9. An organic compound undergoes first-order decomposition. The time taken for its decomposition to and
8 10
⎡ ⎤
⎢t 1 ⎥
t1 t1 ⎣ 8 ⎦ 10 ?
of its initial concentration are and respectively. What is the value of (take log102 = 0.3)
8 10 ⎡ ⎤
⎢t 1 ⎥
⎣ 10 ⎦ [IIT-JEE 2012]
Sol. Answer (9)
2.303 1
t1/8 log10 …(i)
k 18
2.303 1
t1/10 log10 …(ii)
k 1 10
[t1/8 ] log8
10 10 3 0.3 10 9
[t1/10 ] log10
238
10. A closed vessel with rigid walls contains 1 mol of 92 U and 1 mol of air at 298 K. Considering complete decay
238 206
of 92 U to 82 Pb, the ratio of the final pressure to the initial pressure of the system at 298 K is
[JEE(Advanced)-2015]
Sol. Answer (9)
238 206 4 0
92 U 82 Pb 8 2He 6 –
Now number of moles in gas phase = 1 + 8 = 9 mole
at constant temperature and pressure
PF nF 9
9
Pin nin 1
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Helium present in uranium mineral is formed from -particles.
STATEMENT-2 : If helium and uranium contents of a mineral are known, the age of the mineral can be
estimated.
STATEMENT-3 : Most of the rocks contain lead / uranium ratio much less than unity indicating that the age
238
of rocks may be more than half life period of U92 .
(1) T T F (2) TFT (3) FFT (4) FTF
Sol. Answer (1)
Facts about age of minerals and rocks.
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222 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
SECTION - H
Aakash Challengers Questions
1. From the following data for the reaction between A and B
–1 –1
[A] [B] Initial rate (mole L sec ) at
–1 –1
(mole L ) (mole L ) 300 K 320 K
–4 –5 –4 –3
2.5 10 3.0 10 5.0 10 2.0 10
–4 –5 –3
5.0 10 6.0 10 4.0 10 ________
–3 –5 –2
1.0 10 6.0 10 1.6 10 ________
Calculate:
(i) Order of reaction w.r.t. A and w.r.t. B
(ii) Rate constant at 300 K
(iii) Pre-exponential factor
Sol. (i) Order w.r.t. A = 2
Order w.r.t. B = 1
(ii) K300 = 2.66 × 108 L2 mol–2 s–1.
(iii) A = 1.15 × 1018 L2 mol–2 s–1.
From data at 300 K,
5 × 10–4 = k[2.5 × 10–4]m [3.0 × 10–5]n …(i)
–3 –4 m –2 n
4 × 10 = k[5.0 × 10 ] [1.6 × 10 ] …(ii)
1.6 × 10–2 = k[1.0 × 10–3]m [6.0 × 10–2]n …(iii)
m 2, n 1
5.0 104
K300 =
(2.5 10 4 )2 (3.0 10 5 )
K
300 2.66 108 L2mol2 s1
2.0 10 3
K320 =
[2.5 104 ]2 [3.0 105 ]
K320 = 1.07 × 109 L2 mol–2 s–1
K Ea ⎡ 1 1 ⎤
log10 320
K 300 2.303 8.314 ⎣ 300 320 ⎥⎦
⎢
Ea 55.34103
∵ k Ae RT ⇒ 2.66 10 8
Ae 8.314300
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 223
2. The rate of a first order reaction is 0.04 mole L–1 sec–1 at 10 minutes and 0.03 mole L–1 sec–1 at 20 minutes,
respectively after initiation. Find the half life of the reaction
Sol. Rate at (t = 10 min) = 0.04 mol L–1 sec–1 = kC10 = R10
Rate at (t = 20 min) = 0.03 mol L–1 sec–1 = kC20 = R20
C10 R10 4
So, C
20 R20 3
2.303 C 2.303 4
K log 10 min1 log min1
(20 10) C20 10 3
0.693 0.693 10 3 3
t1/2 min = 24.19 min
K ⎛ 4 ⎞ 4 0.124
2.303 ⎜ log ⎟ log
⎝ 3⎠ 3
(iii) Time taken for 75% completion of reaction (iv) Total pressure when Px = 700 mm of Hg
t=0 800 mm 0 0
t = 100 minute 400 mm 600 mm 400 mm
t = 200 minute 200 mm 900 mm 600 mm
K100 = K200 above reaction is first order
2.303 800
K log10
⇒ k 6.93 103 min1
100 400
2.303 1
t 75% log ⇒ t 75% 200min
6.93 103 0.25
800 – 2x = 700 x = 50 mm Hg
Ptotal = 800 – 2x + 3x + 2x = 800 + 3 × 50
Ptotal = 950 mm Hg
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224 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
4.
The progress of a reaction A
nB with time is presented in the figure determine
0.7
0.6
Concentration (mol/lt)
0.5
0.4
0.3
0.2
0.1
1 2 3 4 5 6 7
Time (hour)
(i) The value of n
Sol. (i) n = 2, (ii) k = 1.2 mol L1, (iii) Rate = 0.1 mol L1 hour 1
0.6 0.5
Loss in [A] in 1 hour = 0.1
1
0.2 0
Gain in [B] in 1 hour = 0.2
1
[B]2
Equilibrium constant, k =
[A]
(0.6)2
k ⇒ k 1.2 mol L–1
(0.3)
– d[A]
Initial rate of conversion of A =
dt
[0.5 0.6]
=
(1 0)
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 225
5. 227Ac has a half life of 22.0 years with respect to radioactive decay. The decay follows two parallel paths, one
leading to 222Th and the other to 223Fr. The percentage yield of 222Th is 2%. What are the decay constant() for
each of the separate paths?
Fr) 0.03087 yr 1
Th) 0.00063 yr –1, 2 (for
Sol. 1(for
0.693 0.693 1
overall decay constant, yr .
t1/2 22
0.693
1 2
22
1
% Yield of 222
Th = 2% = 100
1 2
2
% Yield of 223
Fr = 98% = 100
1 2
6. On analysis, a sample of uranium was found to contain 0.277 gram of 82Pb206 and 1.667 gram of 92U238. The half
life period of 92U238 is 4.51 109 years. If all the lead was assumed to come from decay of 92U238, what is the
age of earth?
Sol. Age = 1.1 × 109 years
Energy
R y
P
z
Reaction path
CO(g) NO2 (g)
CO2 (g) NO(g)
(i) What are the activation energies of forward and backward reactions?
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226 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
Sol. (i) x, x + y
(ii) y I
(iii) x + y + z
(iv) y + z, z (E)af (E)ab
ETh
Energy R
H
HR P
HP
Reaction path
8. Rate constant for the decomposition of ethylene oxide into CH4 and CO may be described by the equation
1.25 104
log10k (sec–1) = 14.34 –
T
(i) What is the energy of activation of this reaction?
E0
log0 k log10 A
2.303 RT
Ea
1.25 104
2.303 R
Ea = 2.303 × 8.314 × 10–3 × 1.25 × 104
Ea = 234.339 kJ/mol
1.25 104
Also, log10 k
14.394
4.3167
670
k = 4.82 × 10–5 s–1
9. The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the energy of activation by
75%. What will be effect on rate of reaction at 20°C (other things being equal) in presence of catalyst?
Sol. Rate increases by 2.34 × 1013 times
k Ae Ea /RT
In absence of catalyst, k1 = Ae–100/RT
In presence of catalyst, k2 = Ae–25/RT
r2 Rate in presence of catalyst k
2
r1 Rate in absence of catalyst k1
k2 k 75
e75/RT ⇒ 2.303log 2
k1 k1 8.314 103 293
k2
2.34 1013
k1
r2
2.34 1013
r1
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 227
10. A radioactive isotope zAm (t1/2 = 10 days) decays to give z – 6Bm–12 stable atom along with -particles If 'm' gram
of A are taken and kept in a sealed tube, how much He will accumulate in 20 days at S.T.P. (in litre)?
zA
m
z 6 Bm12 32 He4
m
Moles of A 1
m
20
Number of half lives = 2
10
2
⎛ 1⎞ 3
Moles of A decayed = 1 ⎜ ⎟
⎝2⎠ 4
3 9
Moles of He formed = 3
4 4
9
Volume of Heat STP = 22.4
4
VHe = 50.4 liters
11. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction, if
the catalyst lowers the activation barrier by 20 kJ/mol.
Sol. According to Arrhenius equation we have
–E /RT
K = A.e a
At T = T1 = 500 K
– (Ea )1
R 500
K1 = A.e
At T = T2 = 400 K
– (Ea )2
R 400
K2 = A.e
According to problem
Reactions are having same rate at 400 K and 500 K
Therefore,
K1 = K2
– (Ea )1 – (Ea )2
R 500 R 400
A.e = A.e
Ea1 E a2 500
= , Ea1 = E
R 500 R 400 400 a2
5
Ea1 = Ea2
4
and Ea1 – Ea2 = 20 kJ/mol
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228 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
12. The mean lives of a radioactive substance are 1620 years and 405 years for -emission and -emission
respectively. Find out the time during which three fourth of a sample will decay if it is decaying both by
-emission and -emission simultaneously.
⎡ 1 1 ⎤
Sol. K = K1 + K2 = ⎢ ⎥ = 3.09 × 10–3
⎣ 1620 405 ⎦
⎛ a ⎞
kt = ln ⎜ ⎟
⎝a/ 4⎠
2 ln 2
t= = 448.7 yrs.
3.09 10 –3
X
Y is 4.5 × 10–3 min–1. If the initial concentration of X is 1 M, calculate rate of reaction after 1 hour.
Sol. X Y K = 4.5 × 10–3 min–1
rate = K [X]
⎛ [X]0 ⎞
Kt = ln ⎜ ⎟
⎝ [X] ⎠
1
4.5 × 10–3 × 60 = ln
[X]
14. A counter rate meter is used to measure the activity of a radioactive sample. At a certain instant, the count rate
was recorded as 475 counters per minute. Five minutes later, the count rate recorded was 270 counts per
minute. Calculate the decay constant and half life period of the sample.
N0
Sol. t = ln
N
⎛ 475 ⎞
× 5 = ln ⎜ ⎟
⎝ 270 ⎠
= 0.113 min–1
0.693
t1/2 = = 6.134 min
15. For the following reaction, the rate law has been determined as
2A + B + C
A2B + C
[A] = 0.1 mol L–1, [B] = 0.2 mol L–1, [C] = 0.8 mol L–1. Determine the rate after 0.04 mol L–1 of A has reacted.
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Solution of Assignment (Set-2) Chemical Kinetics and Nuclear Chemistry 229
Sol. Rate = K [A] [B]2
K = 2×10–6 mol–2 L2s–1
Reaction is 2A + B + C A2 B + C
t=0 0.1 0.2 0.8 0 0
t = t (0.1 – 0.04) (0.2 – 0.02) (0.02) (0.02)
dx dx
= (2×10–6) (0.1 – 0.04) (0.2 – 0.02)2 = 0.00388 × 10–6
dt dt
Hence, rate is 3.89 × 10–9 mol L–1 s–1.
16. If for the first order reaction, rate constant varies with temperature according to the graph given below. At 27°C,
1.5 × 10–4 percent of the reactant molecules are able to crossover the potential barriers. At 52°C, the slope of
this graph is equal to 0.2 K–1 s–1. Calculate the value of rate constant at 52°C, assuming that activation energy
does not change in this temperature range. Rate constant
Temperature (t)
dK Ea
0.2 = = A . e– Ea/RT at T = 325 K …(ii)
dT RT 2
At T = 300 K, e– Ea/RT = 1.5 × 10–4 × 10–2 (Given)
Ea
= 4023 …(iii)
R
Putting (iii) in (ii), we get,
4023
0.2 = K52ºC K52ºC = 5.251 sec–1
3252
17. The reaction given below, involving the gases is observed to be first order with rate constant 7.48 × 10–3 s–1.
Calculate the time required for the total pressure in a system containing A at an initial pressure of 0.1 atm to
rise to 0.145 atm and also find the total pressure after 100 s.
2A(g)
4B(g) + C(g)
Sol. Reaction involves 1st order Kinetics 2 A 4 B + C
K = 7.48 × 10–3 s–1
2A 4B + C
P0 0 0
P0–2P 4P P
Pt = P0 – 2P + P + 4P = P0 + 3P
P0 = 1 atm; Pt = 0.145 atm
0.145 = 0.1 + 3P 3P = 0.145 – 0.1
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230 Chemical Kinetics and Nuclear Chemistry Solution of Assignment (Set-2)
3P = 0.045
P = 0.015 atm
1 0.1
t= –3 ln t = 47.8 s
7.48 10 0.1– (2 0.015)
1 ⎛ 0.1 ⎞
7.48 × 10–3 = ln ⎜ ⎟ P = 0.026 atm
100 ⎝ 0.1 – 2P ⎠
Now, Pt = P0 + 3P = 0.1 + 3 (0.026) = 0.18 atm
18. At 380°C, the half life period for the first order decomposition of H2O2 is 360 minutes. The energy of activation of
the reaction is 200 kJ mol–1. Calculate the time required for 75% decomposition at 450°C.
Sol. 20.39 minutes
0.693
k1 at 380 C
360
⎛k ⎞ Ea ⎡1 1⎤
log10 ⎜ 2 ⎟
⎢ ⎥
k
⎝ 1⎠ 2.303 R T
⎣ 1 T2⎦
2.303 100
t 2
log ⇒ t 20.39 minutes
6.81 10 25
k 35ºC
19. Temperature coefficient µ = k of a reaction is 1.82. Calculate the energy of activation in calories.
25ºC
k Ae Ea /RT
E ⎛ 1 1 ⎞
k 35 C k 308 k a
⎜ ⎟
e R ⎝ 298 308 ⎠
1.82
k 25C k 298 k
Ea 10
3
ln(1.62)
2 10 298 308
Ra = 10.924 kcal/mol
20. The following data were obtained for a given reaction at 300 K
Reaction Energy of activation (kJ/mol)
(1) Uncatalysed 76
(2) Catalysed 57
By what factor the rate of catalysed reaction is increased?
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