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Sol. Rate =
2.
dx
= k[X]0 [Y]0 = k
dt
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.
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.
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.
The rate of reaction in the remaining mixture is not affected when a portion is removed for analysis.
38
3
3
Sol. Order = 1 1
2
2
3
L 2
L1/ 2 mol1/ 2 s1
Hence, unit of k
mol s1
13. For the reaction,
H+
C12H22O11 + H2O
C6H 12O6 + C6H12 O6 , write
(i)
Rate of reaction
(ii)
(iii) Molecularity
(iv)
Sol. (i)
Order of reaction
Rate of reaction =
d[C6H12O6 (glucose)]
d[C12H22O11 ]
= +
dt
dt
= +
(ii)
d[C6H12O6 (fructose)]
dt
Rate = k[C12H22O11]
(iii) Molecularity is 2.
(iv)
Order is 1.
...(i)
2 rate = k[4A]m
...(ii)
1 1
2 4
m=
1
2
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1
th of its original value?
4
a b
r1 k
V V
V
, then for same mole of NO and O2.
4
a
r2 k
V
b
a b
V 64k V V
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 s1
at 280 K (R = 8.31 J K1 mol1)?
Sol. log
Ea T2 T1
k2
0
k1 2.303R T1 T2
k2
=1
k1
k2 = k1 = 1.6 106 s1
18. A first order reaction has rate constant of 102 s1. Calculate the half life period of this reaction.
Sol. For a first order reaction, t1/2 =
0.693
k
k = 102 s1
t1/2 =
0.693
10 2
= 69.3 s
19. The t1/2 of a first order reaction is 60 minutes. What percentage will be left after 240 minutes?
Sol. k =
[A ]
2.303
log 0
t
[A t ]
0.693 2.303
100
=
log
60
240
[A t ]
At = 6.25 %
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20. The rate constant for a first order reaction involving compound A was found to be 0.082 min1. 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 min1
k
2.303
a
log
t
ax
t=
2.303
0.15
2.303
log
log 5
=
0.082
0.03
0.082
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
Slope =
Ea
RT
Ea
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 27C to 37C, what is the activation energy
of the reaction?
Sol. Arrhenius equation of two different temperatures is given as
log
Ea T2 T1
k2
k1 2.303R T1 T2
log2
Ea
10
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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24. What is known as activation energy? How is the activation energy affected by
(i)
(ii)
A rise in temperature.
Sol. Activation energy is the extra energy which must be supplied to the reactants so that they can change into
products.
(i)
(ii)
Order w.r.t. NO is 2
When the concentrations of A and B are 0.01 M and 0.02 M respectively and k = 5.1 103 L2 mol2 s1.
Sol.
d[A]
k[A]1 [B]2
dt
CO2 (g) + NO(g), the experimentally determined rate expression below 400 K is
NO2 (g) + CO(g)
Rate = k[NO2]2
What mechanism can be suggested for above reaction?
Sol. As the rate is dependent on [NO2]2, there are two [NO] terms in the slow step of the reaction.
4NO(g) + 6H2O(g)
4NH3 (g) + 5O2 (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.
1 d[NH3 ]
1 d[O 2 ]
1 d[NO]
1 d[H2 O]
4 dt
5 dt
4 dt
6 dt
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Reaction rate
1.
1.
2.
2.
30. The rate constant for a first order reaction is 0.0005 min1. Calculate its half life.
Sol. t1/2 =
0.693
k
t1/2 =
0.693
0.0005
t1/2 =
693 10000
1000
5
6930
5
= 1386 min
Long Answer Type Questions :
31. (a)
(ii) What is the effect on the rate when concentration of A, B and C, each is increased two times?
(b)
Sol. (a)
dx
= k[A][B]2 [C]0
dt
dx
= 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)
32. (a)
(b)
Product.
Write rate expression for the reaction, A
A 2 the rate of reaction becomes three times when the concentration of A
For a reaction, 2A
is increased 27 times. What is the order of reaction?
(c)
For a particular reaction, the rate of reaction does not change with time. What conclusion can you draw
from this observation?
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Sol. (a)
43
1
3
(b)
Order =
(c)
33. (a)
(b)
(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,
CH3COOCH3
H
H2O
CH3 COOH CH3 OH
k A e Ea /RT
If T then k = A
Which is not reasonable.
34. (a)
Express the relationship between the rate of production of iodine and hydrogen in the reaction
H2 + I2
2HI
(b)
N2 + H2O2 (Slow)
2NO + H2
2H2O (Fast)
H2O2 + H2
(c)
Sol. (a)
(b)
d[I2 ]
d[H2 ]
=+
dt
dt
(c)
35. (a)
(b)
The activation energy for the decomposition of hydrogen iodide at 581 K is 209 kJ mol1. Calculate the
fraction of molecules having energy equal to or greater than activation energy.
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Sol. (a)
We know,
log
Ea T2 T1
k2
k1 2.303R T1 T2
log
k2
110000 703 673
log
k2
= 0.3643
7.8
k2
= 2.31
7.8
k2 = 2.31 7.8
= 18.0 mol1 L s1
(b)
Fraction of the molecules having energy equal to or greater than activation energy.
k
e Ea /RT
A
log
Ea
k
= 2.303RT
A
209500
2.303 8.314 581
= 18.8323
k
1.471 10 19
A
2Cl2 + O2
2Cl2O
at 200C is found to be : Rate = k[Cl2O]2
(a)
How would the rate change if [Cl2O] is reduced to one third of its original value?
(b)
How many times the [Cl2O] be changed in order to double the rate?
Sol. (a)
r = k[Cl2O]2
Let the new rate = r, so
2
1
1
Cl O
r k 2 k[Cl2O]2 r
9
9
3
(b)
...(i)
2
...(ii)
2=
x2
[Cl2O]2
x2 = 2[Cl2O]2
x = 2 [Cl2O]
hence
2 times
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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
log
t
100 20
k=
2.303
100
log
= 0.0223 min1
10
80
2.303 100
log
k
100 80
t=
2.303
100
log
0.0223
20
t = 72.18 min
[A] (mol L )
[B] (mol L )
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.
Sol. Let the rate of reaction be
Rate = k[A]x [B]y
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.
Rate [A], i.e., x = 1
Or the order of reaction w.r.t. A is 1.
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.
Thus, reaction rate,
dx
k[A]
dt
Given,
1 d[A ]
d[B]
1 d[C]
1 d[D]
=
=
=
2 dt
dt
2 dt
3 dt
d[C]
0.1 mol L1 s 1
dt
Rate of reaction =
1 d[C]
1
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d[A] d[C]
d[A]
1.0 mol L1 s 1
1.0 mol L1 s1
dt
dt
dt
d[B]
d[B] 1 d[C]
1
0.5 mol L1 s1
=
= 1.0 = 0.5 mol L1 s1
dt
dt
2 dt
2
d[D] 3 d[C]
3
=
= 1.0 = 1.5 mol L1 s1
dt
2 dt
2
+
Acid + Alcohol, is
40. The rate law for the following reaction : Ester + H
dx
= k [ester][H3 O+ ]0 .
dt
(b)
r1 = k[ester]1 [H3O+]0
r1 = k[a]1 [b]0
Where a and b are initial concentrations of ester and H3O+.
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
(b)
r1 = k[a]1 [b] 0
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
1
3
r3
Product,
excess
(i)
(ii)
(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?
Sol. (i)
Order = 2 + 1 + 0 = 3
(ii)
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(b)
Calculate the time required to reduce the concentration of reaction to 0.0125 M from 0.05 M.
Sol. (a)
(b)
0.693 0.693
6.93 10 3 s 1
t1/2
100
2.303
a
log
t
ax
2.303
6.93 10
log
0.05
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.
(i)
(ii)
2.303
a
log
t
ax
For case I :
2.303
0.12
0.069 hr 1
log
10
0.06
For case II :
2.303
0.12
0.069 hr 1
log
20
0.03
44. Write the rate law expression and find the rate constant for
1
[A]0
[B]0
0.1
0.2
0.05
0.2
0.2
0.10
0.1
0.1
0.05
...(i)
...(ii)
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...(iii)
Initial concentration
Exp. No.
[BrO ]
[Br ]
[H ]
1.
0.10
0.10
0.10
1.2 10
2.
0.20
0.10
0.10
2.4 10
3.
0.10
0.30
0.10
3.6 10
4.
0.20
0.10
0.15
5.4 10
3
3
3
3
Find (a) rate law (b) rate constant (c) rate when each of BrO3 , Br and H+ is 0.2 M.
Sol. (a)
Rate
[BrO3 ]
[Br ] [H ]
1.2 10 3
(0.1)4
= 12 L3 mol3 s1
(c)
Rate = 12(0.2)4
= 19.2 103 mol L1 s1
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.
N2 (g) 3H2 (g) 2NH3 (g)
Sol.
2.
1 d[H2 ]
3 dt
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?
3.
49
1
3
d[H2 ]
and
dt
d[NH3 ]
interrelated?
dt
Sol.
5.
1 d[H2 ]
1 d[NH3 ]
3 dt
2 dt
B
A + H2O
Rate [A]
What is its (i) molecularity (ii) order of the reaction?
Sol. Molecularity = 2, order of reaction = 1
6.
1 [N2O5 ]
= k[N2O5 ]
2
t
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.
Short Answer Type Questions :
8.
What is meant by rate constant k of a reaction? If the concentration is expressed in mol L1 units and time
in seconds, what would be the units for k
(i)
(ii)
Sol. Rate constant is the rate of reaction when the concentration of reactants are unity.
Unit of k for zero order reaction : mol L1 s1
Unit of k for first order reaction : s1
9.
NO + NO3 (Slow)
NO2 + NO2
(ii)
50
dx
= k[NO2 ]2
dt
2.303
a
log
t
ax
2.303
a
2.303
log
log 1.4286
40
0.7 a = 40
2.303
0.1551 = 0.00893 min1
40
t1/2 =
0.693
0.693
=
= 77.6 minutes
0.00893
k
1 [NO 2 ]
4
t
1 3 10 3
4
6
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.
Sol. [I] = 0.46 0.50 = 0.04 mol L1
t = 10.0 0.0 = 10 min
Rate of disappearance of I =
[I ]
t
( 0.04)
10
= 0.004 mol/L/min
Rate of appearance of I2 =
=
1
(Rate of disappearance of I )
2
1
0.004
2
= 0.002 mol/L/min
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13. The rate of formation of a dimer in a second order dimerisation reaction is 9.5 105 mol L1 s1 at 0.01
mol/L monomer concentration. Calculate the rate constant.
A2
Sol. 2A
Since, it is a second order reaction.
Rate = k[A]2
9.5 105 = k[0.01]2
k=
9.5 10 5
10 4
= 0.95 L mol1 s1
14. The half life period of a reaction of first order is 100 s. Calculate its rate constant.
Sol. For a first order reaction,
t1/2 =
0.693
k
k=
0.693
t1/2
k=
0.693
100
= 6.93 103 s1
Short Answer Type Questions :
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.
A reaction of zero order proceeds at a uniform rate.
16. The rate constant of a zero order reaction is 1 103 mol L1 s1. Starting with 50 moles, calculate the time
in minutes in which the concentration decreases to 10 moles.
Sol. For a zero order reaction, A0 At = kt
t=
A0 A t
k
50 10
10 3
= 40 103 s
t=
40 10 3
60
= 667 min
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17. Rate constant k of a reaction varies with temperature, according to the equation :
logk = constant
Ea 1
2.303R T
1
, a straight line with a slope 6670 K is obtained. Calculate energy
T
R = 8.314 J K1 mol1
Ea
Slope = 2.303R
Ea = Slope 2.303 R
= ( 6670) 2.303 8.314
= 127711.44 J/mol
= 127.71144 kJ/mol
18. Prove that the time required for the completion of
the completion of half of the reaction.
Sol. t 3/4 =
t3/4 =
3
th of reaction of first order is twice the time required for
4
[A 0 ]
2.303
log
1
k
[A ]
4 0
2.303
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 L1 s1 at 10 minute and 0.03 mol L1 s1 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
Also, t
[A]
2.303
log 10
k
[A]20
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10
k=
53
2.303
4
log
k
3
2.303
4
log
10
3
= 0.0288 min1
t1/2 =
0.693
0.693
=
k
0.0288
= 24.06 min
Experiment
[A]
[B2]
Initial rate
0.50
0.50
1.6 10
0.50
1.00
3.2 10
1.00
1.00
3.2 10
4
4
4
...(i)
r2 = 3.2 104
= k[0.50]x [1.00]y
...(ii)
r3 = 3.2 104
= k[1.00]x [1.00]y
...(iii)
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
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3.2 10 4
3.2 10 4
(1.00)x
(0.50)x
=1
2x = 1
2x = 20
x=0
21. The rate constant for an isomerisation reaction A B is 4.5 103 min1. If the initial concentration of A is
1 M, calculate the rate of reaction after 1 hour.
Sol. A B
k = 4.5 103 min1
[A]0 = 1 M
For 1st order reaction,
2.303
a
log10
t
ax
2.303
1
log10
60
ax
4.5 10 3
(a x) = 0.7634
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