CLS Aipmt 17 18 XII Che Study Package 5 SET 1 Chapter 4
CLS Aipmt 17 18 XII Che Study Package 5 SET 1 Chapter 4
CLS Aipmt 17 18 XII Che Study Package 5 SET 1 Chapter 4
Chemical Kinetics
Solutions
SECTION - A
School/Board Exam. Type Questions
1. The reaction, X + Y ⎯⎯
→ Z has zero order. What is the rate equation?
dx
Sol. Rate = = k[X]0 [Y]0 = k
dt
2. What is the rate-determining step of a reaction?
Sol. The slowest step is the rate determining step.
3. State any one condition under which a bimolecular reaction may be kinetically of first order.
Sol. A bimolecular reaction may become kinetically of first order if one of the reactants is present in excess.
4. Radioactive disintegration is which type of reaction.
Sol. The rate of disintegration of a radioactive substance is directly proportional to the amount of the substance
present. Hence, it is a reaction of first order.
5. Define specific reaction rate.
Sol. Specific reaction rate is the rate of reaction when the molar concentration of each of the reactants is unity.
6. How does the value of rate constant vary with concentration of reactant?
Sol. For a particular reaction at a particular temperature, rate constant is constant and does not depend upon the
concentrations of the reactants.
7. Burning of carbon is highly exothermic process, yet it does not start on its own. Explain.
Sol. Energy is required to cross the energy barrier.
8. The rate of reaction in the remaining mixture is not affected when a portion is removed for analysis.
Sol. Because rate of reaction is affected by change in concentration not amount.
9. Which is greater in magnitudethreshold energy or activation energy?
Sol. Threshold energy.
10. Whether the value of activation energy is higher in exothermic reactions or endothermic reactions and why?
Sol. Cannot be predicted without mentioning the nature of reaction.
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38 Chemical Kinetics Solution of Assignment (Set-1)
11. For a reaction, the rate law is : Rate = [A] [B]1/2. Can this reaction be an elementary reaction?
Sol. For an elementary reaction, order of reaction should be equal to molecularity and further molecularity should
3
be integral. For the given reaction, order of reaction = . Since, molecularity cannot be fractional, therefore,
2
for the given reaction, order is not equal to molecularity. Hence, given reaction cannot be an elementary
reaction.
⎛ 3⎞ 3
Sol. Order = 1 ⎜⎝ ⎟⎠ 1
2 2
3
1
⎛ L ⎞2
of k ⎜ L1/ 2 mol1/ 2 s1
⎝ mol ⎟⎠ s1
Hence, unit
H+
13. For the reaction, C12H22 O11 + H2 O ⎯⎯⎯
→ C6H 12 O6 + C6H12 O6 , write
1
the rate of reaction change if the volume of reaction vessel is reduced to th of its original value?
4
V
If volume of vessel is reduced to , then for same mole of NO and O2.
4
2 2
⎛a⎞ ⎛b⎞ ⎡a⎤ ⎡b⎤
r2 k
⎜ V ⎟ ⎜ V ⎟ 64k ⎢⎣ V ⎥⎦ ⎢⎣ V ⎥⎦
⎜ ⎟ ⎜ ⎟
⎝4⎠ ⎝4⎠
r2 = 64 r1
i.e., rate will increase by 64 times.
16. Why the rate of a chemical reaction does not remain uniform throughout the reaction? Is it possible to have
reaction with a uniform rate?
Sol. It is because rate of reaction depends on concentration which changes with passing of time.
A reaction of zero order proceeds at a uniform rate.
17. For a reaction, the energy of activation is zero. What is the value of rate constant at 300 K, if k = 1.6 × 106
s–1 at 280 K (R = 8.31 J K–1 mol–1)?
k Ea ⎛ T2 T1 ⎞
Sol. log 2
0
k1 2.303R ⎜⎝ T1 T2 ⎟⎠
k2
=1
k1
0.693
Sol. For a first order reaction, t1/2 =
k
k = 10–2 s–1
0.693
t1/2 = = 69.3 s
10 −2
19. The t1/2 of a first order reaction is 60 minutes. What percentage will be left after 240 minutes?
2.303 [A ]
Sol. k = log 0
t [A t ]
0.693 2.303 100
= log
60 240 [A t ]
At = 6.25 %
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40 Chemical Kinetics Solution of Assignment (Set-1)
20. The rate constant for a first order reaction involving compound A was found to be 0.082 min–1. When the initial
concentration of A is 0.15 mol/L, how long will it take for the concentration of A to drop to 0.03 mole/L.
Sol. k = 0.082 min–1
2.303 a
k log
t ax
2.303
= 0.694
0.082
= 19.6 min.
21. The dependence of rate constant on temperature for two reactions is shown in the diagram.
ln k
1
2
–1
T
Which reaction has the higher activation energy?
Sol. The temperature dependence of rate constant is expressed by Arrhenius equation as
Ea
ln k ln A
RT
Ea
Slope =
R
Since reaction 2 has greater negative slope, it has higher activation energy.
22. If rate of a reaction gets doubled as temperature is increased from 27°C to 37°C, what is the activation energy
of the reaction?
Sol. Arrhenius equation of two different temperatures is given as
k2 Ea ⎡ T2 T1 ⎤
log
k1 2.303R ⎢⎣ T1 T2 ⎥⎦
Ea ⎛ 10 ⎞
log2 ⎜ ⎟
2.303 8.31⎝ 300 310 ⎠
Ea = 53.6 kJ
23. What happens exactly at molecular level that leads to increase in rate of reaction as temperature is raised?
Sol. According to collision theory, reaction may take place only when the molecules collide with a kinetic energy
at least equal to activation energy, otherwise, they simply bounce back. As temperature is increased, average
kinetic energy increases and fraction of colliding molecules having energy greater than activation energy
increases.
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Solution of Assignment (Set-1) Chemical Kinetics 41
24. What is known as activation energy? How is the activation energy affected by
Sol. Activation energy is the extra energy which must be supplied to the reactants so that they can change into
products.
becomes eight times when concentration of both NO and Cl2 are doubled. Deduce the order of reaction.
Sol. The order is 1 w.r.t. Cl2 because rate of reaction becomes double when concentration of Cl2 is doubled. When
concentration of both NO and Cl2 is double, rate becomes eight times. It means that it becomes double due
to [Cl2] and 4 times due to [NO].
Order w.r.t. NO is 2
26. Calculate the rate of reaction from the following rate law :
−d[A]
= k[A]1 [B]2
dt
When the concentrations of A and B are 0.01 M and 0.02 M respectively and k = 5.1 × 10–3 L2 mol–2 s–1.
d[A]
Sol. k[A]1 [B]2
dt
= 20.4 × 10–9
Rate = k[NO2]2
Sol. As the rate is dependent on [NO2]2, there are two [NO] terms in the slow step of the reaction.
Rate = k[NO2]2
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42 Chemical Kinetics Solution of Assignment (Set-1)
28. What is meant by rate of reaction? Write the differential rate expressions for the following chemical reactions:
4NH3 (g) + 5O2 (g) ⎯⎯
→ 4NO(g) + 6H2 O(g)
Sol. Relative rates of reaction are defined as change in concentration of reactant or product per unit time w.r.t. each
reactant or product.
30. The rate constant for a first order reaction is 0.0005 min–1. Calculate its half life.
0.693
Sol. t1/2 =
k
0.693
t1/2 =
0.0005
693 10000
t1/2 =
1000 5
6930
=
5
= 1386 min
Long Answer Type Questions :
dx
r= = k[A][B]2 [C]0
dt
(ii) On increasing the concentration of A, B and C, 2 times, then
dx
r= = k[2A] [2B]2 [2C]0
dt
= 2 × 4k[A] [B]2
r = 8k[A] [B]2
i.e., the rate increases 8 times.
(b) Order or reaction is one.
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Solution of Assignment (Set-1) Chemical Kinetics 43
(c) For a particular reaction, the rate of reaction does not change with time. What conclusion can you draw
from this observation?
1
(b) Order =
3
(c) Predict the value of rate constant (K) if temperature approaches infinite. Is the value physically reasonable?
Sol. (a) In the Arrhenius equation rate constant, k = A e −Ea /RT , where Ea is the activation energy. R is gas
constant, T is temperature on kelvin scale and A is the frequency factor. When Ea is zero then every
collision between the reactant molecules lead to the formation of product. This is not possible. Therefore,
activation energy Ea, cannot be equal to zero.
(b) Sometimes, the catalyst may appear in the rate law expression. This is due to the reason that the
catalyst may be reactant in the slow step and may be released in the subsequent steps. For example,
for the acidic hydrolysis of methyl acetate,
H
CH3COOCH3 H2O CH3 COOH CH3 OH
If T then k = A
34. (a) Express the relationship between the rate of production of iodine and hydrogen in the reaction
2HI ⎯⎯
→ H2 + I2
2NO + H2 ⎯⎯
→ N2 + H2O2 (Slow)
H2O2 + H2 ⎯⎯
→ 2H2O (Fast)
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44 Chemical Kinetics Solution of Assignment (Set-1)
d[I2 ] d[H2 ]
Sol. (a) + =+
dt dt
r = k[NO]2[H2]
Order of reaction = 3
(c) Rate constant does not depend upon the concentration of reactants.
constant is 7.8 mol–1 L s–1. What is the value of rate constant at 430°C?
(b) The activation energy for the decomposition of hydrogen iodide at 581 K is 209 kJ mol–1. Calculate the
fraction of molecules having energy equal to or greater than activation energy.
k2 Ea ⎛ T2 T1 ⎞
log
k1 2.303R ⎜⎝ T1 T2 ⎟⎠
k2
log = 0.3643
7.8
k2
= 2.31
7.8
k2 = 2.31 × 7.8
(b) Fraction of the molecules having energy equal to or greater than activation energy.
k
e Ea /RT
A
k Ea
log = 2.303RT
A
209500
=
2.303 8.314 581
= –18.8323
k
1.471 10 19
A
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Solution of Assignment (Set-1) Chemical Kinetics 45
36. The rate law for the reaction,
2Cl2O ⎯⎯
→ 2Cl2 + O2
(b) How many times the [Cl2O] be changed in order to double the rate?
2
⎡ Cl2O ⎤ 1 1
r k
⎢⎣ 3 ⎥⎦ k[Cl2O]2 r
9 9
(b) In order to have the rate = 2r, let the concentration of Cl2O be x.
So, 2r = kx2 ...(i)
2r kx 2
=
r k[Cl2O]2
x2
2=
[Cl2O]2
x2 = 2[Cl2O]2
37. A first order reaction is 20% complete in 10 minutes. Calculate the time taken for the reaction to go to 80%
completion.
Sol. Applying first order equation
2.303 ⎛ 100 ⎞
k log ⎜ ⎟
t ⎝ 100 20 ⎠
2.303 100
k= log = 0.0223 min−1
10 80
2.303 ⎛ 100 ⎞
t log ⎜ ⎟
k ⎝ 100 80 ⎠
2.303 100
t= log
0.0223 20
t = 72.18 min
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46 Chemical Kinetics Solution of Assignment (Set-1)
–1 –1 –1 –1
[A] (mol L ) [B] (mol L ) Initial rate (mol L min )
0.01 0.01 0.005
0.02 0.01 0.010
0.01 0.02 0.005
Determine the order of the reaction with respect to A and with respect to B.
From the data given, it is clear that by doubling the concentration of A, the rate also becomes double when
B is kept constant. Thus, the rate is directly proportional to concentration of A.
When the concentration of A is kept constant and the concentration of B is doubled, the rate does not change,
i.e., y = 0 or the order of reaction w.r.t. B is zero.
dx
k[A]
dt
d[C]
Given, 0.1 mol L1 s 1
dt
1 d[C] 1
Rate of reaction = = 1.0 = 0.5 mol L–1 s–1
2 dt 2
d[D] 3 d[C] 3
= = × 1.0 = 1.5 mol L–1 s–1
dt 2 dt 2
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Solution of Assignment (Set-1) Chemical Kinetics 47
dx
+
40. The rate law for the following reaction : Ester + H ⎯⎯
→ Acid + Alcohol, is = k [ester][H3 O+ ]0 .
dt
r1 = k[a]1 [b]0
If concentration of ester is doubled i.e., [Ester] = 2a, by keeping [H3O+] constant, then suppose rate
becomes r2
r2 = k[2a]1 [b]0
r1 1
=
r2 2 or r2 = 2r1
If concentration of H3O+ (i.e., b) is doubled, i.e., [H3O+] = 2b, by keeping [ester] = a then suppose rate
becomes r3,
r3 = [a]1 [2b]0
r1
= 1 or r = r
r3 1 3
(iii) On increasing the concentration of A two times, of B three times and of C four times, what is the effect
on the rate of reaction?
Order = 2 + 1 + 0 = 3
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48 Chemical Kinetics Solution of Assignment (Set-1)
r1 = 12 r
42. In a first order reaction time taken for initial concentration of a substance to become half, is 100 seconds,
then
(b) Calculate the time required to reduce the concentration of reaction to 0.0125 M from 0.05 M.
0.693 0.693
k 6.93 10 3 s1
t1/2 100
2.303 a
(b) k log
t ax
2.303 0.05
t 3
log
6.93 10 0.0125
t = 2000 s
43. In a reaction with initially 0.12 M, the concentration of reactant is reduced to 0.06 M in 10 hour and to
0.03 M in 20 hour.
2.303 a
k log
t ax
2.303 0.12
For case I: k log 0.069 hr 1
10 0.06
2.303 0.12
For case II : k log 0.069 hr 1
20 0.03
44. Write the rate law expression and find the rate constant for
–1 –1
[A]0 [B]0 Initial rate (mol L s )
0.1 0.2 0.05
0.2 0.2 0.10
0.1 0.1 0.05
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Solution of Assignment (Set-1) Chemical Kinetics 49
Sol. Let the rate law for the reaction is
m = 1, n = 0
0.05 = k[0.1]1
k = 0.5 s–1
45. Four experiments were conducted to discover how the initial rate of consumption of BrO3− ion in the
reaction :
Initial concentration –1 –1
Exp. No. – – + Initial rate (mol L s )
[BrO ]3 [Br ] [H ]
–3
1. 0.10 0.10 0.10 1.2 × 10
–3
2. 0.20 0.10 0.10 2.4 × 10
–3
3. 0.10 0.30 0.10 3.6 × 10
–3
4. 0.20 0.10 0.15 5.4 × 10
Find (a) rate law (b) rate constant (c) rate when each of BrO3 , Br and H+ is 0.2 M.
Rate 1.2 10 3
(b) k =
[BrO3 ] [Br ] [H ]2 (0.1)4
= 12 L3 mol–3 s–1
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50 Chemical Kinetics Solution of Assignment (Set-1)
SECTION - B
Model Test Paper
Very Short Answer Type Questions :
1. Express the rate of the following reaction in terms of disappearance of hydrogen in the reaction.
1 d[H2 ]
Sol.
3 dt
2. In some cases, it is found that a large number of colloiding molecules have energy more than threshold value,
yet the reaction is slow. Why?
1
Sol. Order of the reaction =
3
d[H2 ]
4. For the reaction, 3H2 (g) + N2 (g) ⎯⎯
→ 2NH3 (g), how is the rate of reaction expressions − and
dt
d[NH3 ]
interrelated?
dt
1 d[H2 ] 1 d[NH3 ]
Sol.
3 dt 2 dt
A + H2O ⎯⎯
→ B
Rate [A]
2N2O5 (g) ⎯⎯
→ 4NO2 (g) + O2 (g)
1 [N2O5 ]
Rate = − = k[N2O5 ]
2 t
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Solution of Assignment (Set-1) Chemical Kinetics 51
7. What is the difference between average rate and instantaneous rate of a chemical reaction?
Sol. When change in concentration is measured over long period of time, we get average rate of reaction.
When change in concentration is measured over a very small period of time, or at a particular instant, it is
instantaneous rate.
8. What is meant by rate constant k of a reaction? If the concentration is expressed in mol L–1 units and time
in seconds, what would be the units for k
Sol. Rate constant is the rate of reaction when the concentration of reactants are unity.
(ii) NO3 + CO ⎯⎯
→ CO2 + NO2 (Fast)
dx
Sol. Rate law : = k[NO2 ]2
dt
10. A first order decomposition reaction takes 40 minutes for 30% decomposition. Calculate t1/2 value.
2.303 a
k log
t ax
2.303 a 2.303
k log log 1.4286
40 0.7 a = 40
2.303
k 0.1551 = 0.00893 min–1
40
0.693 0.693
t1/2 = = = 77.6 minutes
k 0.00893
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52 Chemical Kinetics Solution of Assignment (Set-1)
11. For the reaction, 2N2O5 (g)
4NO2 (g) + O2 (g) .
If the concentration of NO2 increases by 3.0 × 10–3 mol/L in six seconds then what is the rate of reaction?
1 [NO 2 ]
Sol. Rate of reaction =
4 t
1 3 10 3
=
4 6
Cl2 + 2I− ⎯⎯
→ 2Cl− + I2
The initial concentration of I– was 0.5 mol/L and concentrations after 10 minutes was 0.46 mol/L. Calculate
the rate of disappearance of I– and rate of appearance of iodine.
[I ]
Rate of disappearance of I– =
t
( 0.04)
=
10
= 0.004 mol/L/min
1
Rate of appearance of I2 = (Rate of disappearance of I− )
2
1
= × 0.004
2
= 0.002 mol/L/min
13. The rate of formation of a dimer in a second order dimerisation reaction is 9.5 × 10–5 mol L–1 s–1 at 0.01
mol/L monomer concentration. Calculate the rate constant.
Sol. 2A A2
Rate = k[A]2
9.5 10 5
k=
10 4
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Solution of Assignment (Set-1) Chemical Kinetics 53
14. The half life period of a reaction of first order is 100 s. Calculate its rate constant.
0.693
t1/2 =
k
0.693
k=
t1/2
0.693
k=
100
15. Why the rate of a chemical reaction does not remain uniform throughout the reaction? Is it possible to have
reactions with a uniform rate?
Sol. It is because rate of reaction depends on concentration which changes with passage of time.
16. The rate constant of a zero order reaction is 1 × 10–3 mol L–1 s–1. Starting with 50 moles, calculate the time
in minutes in which the concentration decreases to 10 moles.
A0 A t
t=
k
50 10
=
10 3
= 40 × 103 s
40 10 3
t=
60
= 667 min
17. Rate constant k of a reaction varies with temperature, according to the equation :
Ea ⎛ 1 ⎞
logk = constant − ⎜ ⎟ (where Ea is the energy of activation for the reaction.)
2.303R ⎝ T ⎠
1
When a graph is plotted for log k vs , a straight line with a slope –6670 K is obtained. Calculate energy
T
of activation for this reaction.
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54 Chemical Kinetics Solution of Assignment (Set-1)
Ea
Slope = 2.303R
Ea = – Slope × 2.303 × R
= – (– 6670) × 2.303 × 8.314
= 127711.44 J/mol
= 127.71144 kJ/mol
3
18. Prove that the time required for the completion of th of reaction of first order is twice the time required for
4
the completion of half of the reaction.
2.303 [A 0 ]
Sol. t 3/4 = log
k 1
[A ]
4 0
2.303
t3/4 = log 4
k
2.303 0.6021
=
k
1.386
=
k
2 0.693
=
k
= 2t1/2
19. The rate of a first order reaction is 0.04 mol L–1 s–1 at 10 minute and 0.03 mol L–1 s–1 at 20 minute after
initiation. Find half life of the reaction.
Sol. Rate = k[A]
0.04 = k[A]10 and 0.03 = k[A]20
[A]10 0.04 4
[A]20 0.03 3
2.303 [A]
Also, t k
log 10
[A]20
2.303 4
10 log
k 3
2.303 4
k= log
10 3
= 0.0288 min–1
0.693 0.693
t1/2 = =
k 0.0288
= 24.06 min
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Solution of Assignment (Set-1) Chemical Kinetics 55
Long Answer Type Questions :
r1 = 1.6 × 10–4
r2 = 3.2 × 10–4
r3 = 3.2 × 10–4
r2 k (0.50)x (1.00)y
=
r1 k (0.50)x (0.50)y
3.2 10 4
1.6 10 4
y
⎛ 1.00 ⎞
⎜ ⎟ 2
⎝ 0.50 ⎠
2y = 2
y=1
r3 k (1.00)x (1.00)y
=
r2 k (0.50)x (0.50)y
3.2 10 4
3.2 10 4
(1.00)x
=1
(0.50)x
2x = 1
2x = 20
x=0
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56 Chemical Kinetics Solution of Assignment (Set-1)
21. The rate constant for an isomerisation reaction A B is 4.5 × 10–3 min–1. If the initial concentration of A is
1 M, calculate the rate of reaction after 1 hour.
Sol. A B
[A]0 = 1 M
2.303 a
k log10
t ax
2.303 1
4.5 10 3 log10
60 ax
(a – x) = 0.7634
= k (a – x)
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