Solution

WORKSHEET - CHEMICAL KINETICS

Class 12 - Chemistry
Section A
1. Read the text carefully and answer the questions:
The order of the reaction is the sum of the powers of the concentration of the reactants in the rate law. It can either be a whole
number or a fraction the order of the reaction is determined by the experimental methods based on this value, reactions may be
classified as first-order, second-order, third-order, etc. A reaction whose order is different from the actual due to large excess
concentration of one of the reactants is called pseudo order reaction. Another property of a reaction called molecularity helps in
understanding its mechanism. The number of reacting species (atoms, ions, or molecules) taking part in an elementary reaction,
which must collide simultaneously in order to bring about a chemical reaction is called the molecularity of a reaction. The reaction
can be unimolecular when one reacting species is involved, bimolecular reactions involve a simultaneous collision between two
species & trimolecular or termolecular reactions involve a simultaneous collision between three reacting species.
(i) When volume is reduced to rd, then, the concentration will increase three times
1

r1 = k[A][B] ...(i) 2

r = k[3A][3B ]
2 ...(ii) 2

From equations (i) and (ii)

r1 1
=
r2 27

r2 = 27r1
Therefore, the rate will increase 27 times.
(ii) The H+ acts as a catalyst only whereas alkali acts as one of the reactants.
(iii)The order of the reaction is zero order.
(iv)If the reaction is an elementary reaction, the order is the same as molecularity.
2. Read the text carefully and answer the questions:
Chemical kinetics deals with rate of chemical reactions, how fast reactants get used up or how fast products are formed in the
reaction. Different chemical reactions have different speed. Rate of reaction depends upon concentration of reactants, temperature,
pressure especially in gaseous reactions and presence of catalyst. Chemical reaction takes place as a results of collision between
reacting molecules. The rate of reaction does not depend upon total number of collisions rather it depends upon number of
effective collisions. In a redox reaction, if E is + ve, ΔGo will be -ve and ‘K’ equilibrium constant will be high i.e. products
o

cell

formed will be more than the reactants.

(i) The extra energy which must be supplied to reactants in order to undergo effective collision to form products.
(ii) It represents fraction of molecules possessing activation energy (Ea) or more than Ea.
o

(iii)log K = nE

0.0591
=2× 0.24

0.0591V
= 8.122
The value indicates that products are formed 108, times than reactants.
(iv)Those molecules which possess activation energy and collide in proper orientation undergo effective collisions.
3. Read the text carefully and answer the questions:
A reaction is said to be of the first order if the rate of the reaction depends upon one concentration term only. For a first order
reaction of the type A → Products, the rate of the reaction is given as : rate = k[A], The differential rate law is given as : =- dA

dt

[A]
k[A]. The integrated rate law is : In = -kt, where [A] is the concentration of reactant left at time t and [A]0 is the initial
[A]
0

concentration of the reactant, k is the rate constant.

(i) (c) s-1
Explanation: Unit of rate constant for a reaction of nth order = (cone.)1-n time -1
For a first order reaction, n = 1
Unit of rate constant = (mol L-1)1-1s-1 = s-1
(ii) (b) 0.0693 × 3 M min-1
t t
1/2 1/2

Explanation: 12M ⟶ 6M ⟶ 3M
Initial conc

t1/2 = 10 min

1 / 12
 k= 0.693

10
= 0.0693 min-1
As t1/2 is 10 min, after 20 minutes the concentration will be 3 M.

Hence, Rate = 0.0693 × 3 M min-1

(iii) (d) 76.4 minutes
Explanation: t1/2 = 23 minute

min-1
0.693 0.693 0.693
t1/2 = k
⇒ k= t
⇒ k= 23
1/2

For 90% completion,

t= 2.303
log(
k
)
a

a−x

2.303×23 100
t= 0.693
log(
100−90
)

t = 76.4 minutes
(iv) (b) 3.47 × 10-4 M/min
Explanation: For the first order reaction,
k= 2.303
log
t
a

a−x

a = 0.1 M, a - x = 0.025 M, t = 40 min

k= 2.303

40
log
0.1

0.025
= 2.303

40
log 4 = 0.0347 min-1
[A] → product
Thus, rate = k[A]
rate = 0.0347 × 0.01 M min-1 = 3.47 × 10-4 M min-1
(v) (b) 6.25%
Explanation: t1/2 = 0.693

k
⇒
0.693

t
=k⇒ 0.693

60
=k
1/2

k = 0.01155 min-1
k= 2.303
log(
t
)
a−x
a

Let the initial amount (a) be 100.

0.01155 min-1 = 2.303

240 min
log(
100

a−x
)

−1
0.01155 min

2.303
×240 min
=log( 100

a−x
)

1.204 = log 100 - log (a - x)

1.204 = 2 - log (a - x)0
log (a - x) = 2 - 1.204 = 0.796
(a - x) = 6.25%
4. Read the text carefully and answer the questions:
Δ

The following reaction, A (g) ⟶ P(g) + Q(g) + R(g) , follows first order kinetics. The half-life period of this reaction is 69.3 s at
500°C. The gas A is enclosed in a container at 500°C and at a pressure of 0.4 atm.
(i) (a) 0.01 s-1
Explanation: t1/2 = 69.3 s
For first order reaction,
k= 0.693

t1/2
= 0.693

69.3
= 0.01 s-1

(ii) (b) 0.04 atm

Explanation: k = 2.303

t
log
a

a−x
= 2.303

230
log
0.4

0.4−x

0.01 = 2.303

230
log
0.4

0.4−x
= 0.01 log 0.4

0.4−x
0.01 0.4 0.4

0.01
= log 0.4−x
⇒ 1 = log 0.4−x

antilog of 1 = 0.4

0.4−x
⇒ 10 = 0.4

0.4−x
⇒ x = 0.36
∴ a - x = 0.4 - 0.36 = 0.04 atm
(iii) (d) 1.12 atm
Explanation: For the given reaction,

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 Total pressure = (0.4 - 0.36) + (3 × 0.36) = 1.12 atm
(iv) (a) linear with intercept = In [A]0
Explanation: Expression that relates concentration of reactant and time for first order reaction is
ln[A] = -kt + ln[A]0
So, the plot of In [A] vs t will be linear with slope = -k and intercept = In [A]0
Pt
(v) (c) 2NH −→N2(g) + 3H2(g)
3(g)

Explanation: Decomposition of ammonia on a hot platinum surface at high pressure is a zero order reaction.
5. Read the text carefully and answer the questions:
For the reaction : 2NO(g) + Cl2(g) → 2NOCl(g), the following data were collected. All the measurements were taken at 263 K.

Experiment No. Initial [NO] (M) Initial [Cl2] (M) Initial rate of disapp. of Cl2 (M/min)

1. 0.15 0.15 0.60

2. 0.15 0.30 1.20

3. 0.30 0.15 2.40

4. 0.25 0.25 ?

(i) (b) 3
Explanation: 2NO(g) + Cl2(g) → 2NOCl(g)
Molecularity = 3
(ii) (a) r = k[NO]2[Cl2]

Explanation: Let rate of this reaction, r = K[NO]m[Cl2]n

m n
r1 k(0.15) (0.15)
then r2
=
0.60

1.20
= m n
k(0.15) (0.30)

1 1 n
or, 2
=( 2
) ⇒ n=1
m n
r2 1.20 k(0.15) (0.30)
Again from r3
=
2.40
= m n
k(0.30) (0.15)
m m
or 1

2
=( 1

2
) . 2

1
or 1

4
=( 1

2
) ⇒ m=2
Hence, expression rate law is
r = k[NO]2 [Cl2]1

(iii) (a) 3
Explanation: As the order w.r.t. NO is 2 and order w.r.t. Cl2 is 1, hence the overall order is 3.

(iv) (d) 177.77 M-2 min-1

Explanation: Substituting the values of experiment 1 in rate law expression
0.60 M min-1 = k(0.15 M)2 (0.15 M)1
−1

= 177.77M-2 min-1
0.60Mmin

or k = 0.0225×0.15M
3

(v) (c) 2.77 M min-1

Explanation: r = 177.7 M-2 min-1 × (0.25 M)2 (0.25 M) = 2.77 M min-1
6. Read the text carefully and answer the questions:

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 The progress of the reaction, A ⇌ nB with time is represented in the following figure:

(i) (c) 2
Explanation: According to the figure, in the given time of 4 hours (1 to 5 ) concentration of A falls from 0.5 to 0.3
M, while in the same time concentration of B increases from 0.2 to 0.6 M
Decrease in concentration of A in 4 hours
= 0.5 - 0.3 = 0.2 M
Increase in concentration of B = in 4 hours
= 0.6 - 0.2 = 0.4 M
Thus, increase in concentration of B in a given time is twice the decrease in concentration of A. Thus, n = 2.
(ii) (d) 1.2 M
2 2
[B] (0.6)
Explanation: K = = 0.3
= 1.2 M
[A]

(iii) (a) 0.1 mol L-1 hr-1

Explanation: From t = 0 to t = 1 hr,
For A, dx = 0.6 - 0.5 = 0.1 mol L-1
dx
∴ Initial rate of conversion of A = dt

= 0.1 mol L-1 hr-1

−1
0.1 mol
= 1hr

(iv) (a) 10-4

Explanation: A ⇌ 2B
2 × 10-4 = 10-4
d[A] d[B]
−
dt
=+ 1

2 dt
= 1

2
×

(v) (a) Molecularity

Explanation: The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction is
called molecularity and it has no influence on the rate of reaction.
7. Read the text carefully and answer the questions:
In a reaction, the rates of disappearance of different reactants or rates of formation of different products may not be equal but rate
of reaction at any instant of time has the same value expressed in terms of any reactant or product. Further, the rate of reaction
may not depend upon the stoichiometric coefficients of the balanced chemical equation. The exact powers of molar concentrations
of reactants on which rate depends are found experimentally and expressed in terms of ‘order of reaction.’ Each reaction has a
characteristic rate constant depends upon temperature. The units of the rate constant depend upon the order of reaction.
(i) (a) 3
Explanation: Unit of k for nth order = (mol L-1)1 - n sec -1...(i)
Here, k = 3 × 10-3 mol-2 L2 sec-1
Unit of k = mol-2 L2 sec-1 ⇒ (mol L-1)-2 sec-1 ...(ii)
Comparing (i) and (ii) we get, 1 - n = -2 ⇒ n = 3
(ii) (c) twice the rate of consumption of A
d[A] d[B] d[C]
Explanation: Rate = =− 1

3
= 1

2
dt dt dt

(iii) (c) 18 times

Explanation: Given, R1 - k[A]2[B]

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 According to question, R2 = k[3A]2[2B]

= k × 9[A]2 × 2[B] = 18 × k[A]2[B] = 18 R1

(iv) (d) 1
Explanation: Rate (r) = k[H+]n
When pH = 3; [H+] = 10-3
and when pH = 1; [H+] = 10-1
−3 n
k(10 ) −3 n
r1
∴
r2
= −1 n
⇒
1

100
=( 10

−1
) (∵ r2 = 100r1 )
k(10 ) 10

⇒ (10-2)1 = (10-2)n ⇒ n = 1
(v) (d) 2
Explanation: Let the order of reaction w.r.t. A is x and w.r.t. B is y.
r1 = k[A]x [B]y ...(i)

r2 = k[2A]x [B]y ...(ii)

r3 = k[A]x [2B]y ...(iii)

x y
r1 k[A] [B]

r2
= x y
k[2A] [B]

x 2 x
⇒
1

4
=( 1

2
) ⇒(
1

2
) =( 1

2
) ⇒ x=2
x y
r1 k[A] [B]
Similarly, r3
= x y
k[A] [2B]

y 0 y
⇒ 1=( 1

2
) ⇒ (
1

2
) =( 1

2
) ⇒ y=0
Hence the rate law equation is
Rate = A[A]2[B]0 ⇒ Order of reaction = 2
8. Read the text carefully and answer the questions:
The half-life of a reaction is the time required for the concentration of reactant to decrease by half, i.e.,

[A]t = 1

2
[A]

For first-order reaction,

0.693
t1/2 = k

this means t1/2 is independent of initial concentration. Figure shows that typical variation of concentration of reactant exhibiting
first order kinetics. It may be noted that though the major portion of the first order kinetics may be over in a finite time, but the
reaction will never cease as the concentration of reactant will be zero only at infinite time.
(i) (d) 230.3 s
Explanation: For a first order reaction :
= 3.01 × 10-3 s-1
0.693
t1/2 = k
,k

0.693
∴ t1/2 = −3
= 230.3 s
3.01×10

(ii) (b) 990 s

Explanation: Half life (t1/2) of a first order reaction is given as:
t1/2 = 0.693

k
= 0.693

−4
= 990 s
7.0×10

(iii) (c) It is independent of temperature

0.693
Explanation: For a first order reaction t1/2 = k

5 / 12
 therefore t1/2 depends upon k and hence depends on temperature because rate constant k is a function of temperature.

(iv) (d) 24.086 min

Explanation: Let the concentrations of the reactant after 10 min and 20 min be C1 and C2 respectively.
∴ Rate after 10 min = k.C1

= 0.04 × 60 mol L-1 min-1

and rate after 20 min = k.C2

= 0.03 × 60 mol L-1 min-1

C1 4
∴ =
C2 3

Let the reaction starts after 10 minutes.

2.303 C1 2.303 4
k= 10
log
C2
= 10
log
3
= 0.02878
0.6932 0.6932
∴ t1/2 = k
= 0.02878
= 24.086 min

(v)

(d)

Explanation: For a first order reactions, t1/2 = k[A] = k. 0

0

Thus t1/2 is independent of initial concentration.

Hence plot of t1/2 vs [A]0 will be a horizontal line.
Section B
9.
(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.
10.
(c) A is true but R is false.
Explanation: According to the Arrhenius equation (k = Ae-Ea/RT); it is found almost accurate for single as well as complex
reactions.
However, orientation is essential for the reactant molecules participating in the reaction.
11.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: The formation of an activated complex takes place when the vibration degree of freedom converts into a
translational degree of freedom. This statement is given by transition state theory. Also, the energy of the activated complex is
higher than the energy of the reactant molecule, which is true but it is not the correct explanation of the assertion.
12.
(d) A is false but R is true.
Explanation: Every collision among reactant molecules does not lead to the formation of the product. Only effective collision
brings out the formation of the product.
13. (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.
14. (a) Both A and R are true and R is the correct explanation of A.
Explanation: The molecularity of the reaction H2 ​+ Br2​ → 2HBr is 2 because two molecules of the reactants are involved in
the given elementary reactions.
2
The order of the reaction is 3
and it is determined experimentally.
15. (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.

6 / 12
16. (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.
17.
(d) A is false but R is true.
Explanation: A is false but R is true.
18.
(c) A is true but R is false.
Explanation: A is true but R is false.
19.
(c) A is true but R is false.
Explanation: A is true but R is false.
20. (a) Both A and R are true and R is the correct explanation of A.
Explanation: The reaction that is the hydrolysis of ester happens to be a pseudo-first-order reaction and not an absolute one
just because the concentration of water which is present as the solvent liquid does not change considerably throughout the
course of the reaction and hence it can be said that this hydrolysis reaction is a first-order reaction.
21.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Both A and R are true but R is not the correct explanation of A.
22.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Molecularity of reaction is the number of molecules acting in the rate-determining step while the order of the
reaction is the sum total of all powers to which concentration is raised in the rate law expression. So both may or may not be
the same.
23.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Order of a reaction may be zero or fractional. Order can be determined by rate law expression.
Section C
24. Zero order reaction.
25. Let us consider a biomolecular reaction:
A + B → Product
Rate = k[A][B] ...(i)
When the concentration of [B] is taken in large excess that its concentration hardly change, rate law will become Rate =k'[A]
where, k' = k[B]
The order of reaction will be equal to one.
26. Molecularity of a reaction can never be equal to zero as it shows the number of reactants taking part in a reaction, which can never
be zero.
27. Rate = k [NO]x [O2]y
order of a reaction = x + y
3
So order = + = 2, i.e., second order of reaction.
1

2 2

28. Given,
T1 = 300K, T2 = 310K,

Ea = 3.05 × 105 J mol-1

k1 = 6.0 × 10-4 s-1, k2 = ?

Using Arrhenius equation,
k2 Ea T2 − T1
log( ) = ( )
k1 2.303R T1 T2

k2 5
3.05×10 310−300
log( ) = ( )
k1 2.303×8314 300×310

k2 5
3.05× 10 ×10
log( ) = = 1.7128
k1 2.303×8.314×300×310

k2

k1
= antilog (1.7128)

7 / 12
 k2 1
= 5.162 × 10 = 51.62
k1

or k2 = 3.0972 × 10-2 s-1

k2
= 51.62
−4
6.0×10

29. For the reaction, A → Product

2
Rate = k[A] . . . . . . . . (i)

Let the concentration of the reactant be [A] = a

Rate of reaction,Rate = k[A] = ka ⟹ R = ka 2 2 2

i. If the concentration of the reactant is doubled, i.e. [A] = 2a, then the rate of the reaction (i) would be
′ 2 2 2
R = k(2a) = 4ka = 4R [∵ R = ka ]

Therefore, the rate of the reaction would become 4 times the original rate.
ii. If the concentration of the reactant is reduced to half, i.e. [A] = a, then the rate of the reaction would be1

2
1 2 1 2 1
R "= a = Ka = R
2 4 4

Therefore, the rate of the reaction would be reduced to ¼th the original rate of reaction.
30. The order of a reaction is equal to the sum of the powers (exponents) to which the various concentrations terms are raised in the
rate law expression of the reaction. For example, if the the rate law is
Rate = k [A]x [B]y, the order of reaction is x+y. Order of reaction can be zero, fraction or an integer.
31. i. As the rate is first order in A and second order in B, so the differential rate equation is given as
dx 2
Rate = = k [A] [B]
dt

where k=rate constant

ii. If concentration of B is increased three times
′ dx 2 2
Rate = = k [A] [3B] = 9k[A][B] = 9Rate
dt

So the rate will increase to 9 times the original rate.

iii. When concentration of both A and B are doubled,
′′ dx 2 2
Rate = = k [2A] [2B] = 8k[A][B] = 8Rate
dt

So the rate will increase to 8 times the original rate.

32. It is given that T = 298 K 1

∴ T = (298 + 10) K = 308 K

2

We also know that the rate of the reaction doubles when temperature is increased by 10°.
Therefore, let us take the value of k = k and that of k = 2k 1 2

Also, R = 8.314J K mol −1 −1

Now, substituting these values in the equation:

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

We get:
2k E 10
log = [ ]
k 2.303×8.314 298×308

Ea 10
⇒ log 2 = [ ]
2.303×8.314 298×308

2.303×8.314×298×308×log 2
⇒ Ea
10

= 52897.78 J mol −1

Ea = 52.9 kJ mol −1

33. a. From the figure-

Energy of reactants Er = 100 kJ/mol
Energy of products, Ep = 25 kJ/mol
Energy of reaction=Change in energy=ΔE = E P − ER

= 25 - 100 = -75 kJ/mol

Threshold energy, Et = 350 kJ/mol
Activation energy= Ea = Et - Er
= 350 - 100
= 250 kJ/mol.
b. The curve B is for catalysed reaction because it represents the lower energy path for the reaction.
c. In the presence of catalyst, Threshold energy E = 200 kJ /mol t

Activation energy= Ea = 200 - 100

8 / 12
 = 100 kJ/mol
34. The rate law can be determined by measuring the rate of this reaction as a function of initial concentration by keeping the
concentration of one of the reactants constant and changing the concentration of other reactants or by changing the concentration
of both the reactants. From the concentration dependence of rate, rate law can be determined. The rate law for any reaction cannot
be predicted by merely looking at balanced chemical equation.
35. Effective collision takes place only if molecules have energy more than activation energy, moreover they collide in proper
orientation. In some cases reaction is slow because molecules overcome energy barrier but are not in correct orientations.
36. Given, t1/2 = 37.9s, initial concentration= [R]0

of PH3 is decomposed).
[R]
concentration after time, t = 4
0
(because 3

4
th

0.693 0.693
i. k = t
=
37.9
s
−1

1/2

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

4
2.303
= log 4
0.693

37.9

2.303×37.9×0.6020
or t = = 75.82s
0.693
0.693
ii. t = 1 min = 60s and k = 37.9
= 0.0183s
−1

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

[R]
2.303 0
60 = log
0.0183 [R]

[R]
or log 0
=
60×0.0183

2.303
= 0.4763
[R]

[R]
0
= antilog 0.4763
[R]

[R]
0
= 2.994
[R]

Let the initial amount is 100

100
∴ = [R]
2.994

⇒ [R] = 33.40%

37. a.

b.

38. Let the order of the reaction with respect to A be x and with respect to B be y.
Therefore, rate of the reaction is given by,
x y
Rate = k[A] [B]

According to the question,

6.0 × 10
−3
= k[0.1] [0.1]
x y
...... (i)
7.2 × 10
−2
= k[0.3] [0.2]
x y
..... (ii)
2.88 × 10
−1
..... (iii)
= k[0.3] [0.4]
x y

2.40 × 10
−2
= k[0.4] [0.1] ..... (iv) x y

Dividing equation (iv) by (i), we obtain

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 −2 x y
2.40×10 k[0.4] [0.1]
= x y
−3 k[0.1] [0.1]
6.0×10
x
[0.4]
4 = x
[0.1]
x
0.4
4 = ( )
0.1

1 x
(4) = 4

x=1
Dividing equation (iii) by (ii), we obtain
x y
−1 k[0.3] [0.4]
2.88×10
= x y
−2
7.2×10 k[0.3] [0.2]
y
0.4
4 = ( )
0.2

y
4 = 2
2 y
2 = 2

y=2
Therefore, the rate law is
2
Rate = k[A][B]
Rate
k =
2
[A][B]

From experiment I, we obtain

−3 −1 −1
6.0× 10 mol L min
k =
−1 −1 2
(0.1 mol L )(0.1 mol L )

2 −2 −1
= 6.0 L mo l min

From experiment II, we obtain,

−2 −1 −1
7.2× 10 mol L min
k =
−1 −1 2
(0.3 mol L )(0.2 mol L )

2 −2 −1
= 6.0 L mo l min

From experiment III, we obtain

−1 −1 −1
2.88× 10 mol L min 2 −2 −1
k = = 6.0 L mo l min
−1 −1 2
(0.3mol L )(0.4mol L )

From experiment IV, we obtain

−2 −1 −1
2.40× 10 mol L min 2 −2 −1
k = = 6.0 L mo l min
−1 −1 2
(0.4mol L )(0.1mol L )

Therefore, rate constant, k= 6.0 L 2

mo l
−2
min
−1

39. 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
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

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40. i. The chemical reaction which look like higher order reaction but in real they follow lower order kinetics.
For example,
+
H

CH3 COOC2 H5 + H2 O ⟶ CH5 COOH + C2 H5 OH

Rate = K[CH3COOC2H5]
Order = 1
Ea
ii. Slope =
2.303R
= −4250K

So, Ea = -2.303 × R × Slope

= -2.303 × 8.314 J K-1 mol-1 × 4250

= 81375.3 J mol-1
= 81.375 KJ mol-1
0.17−0.31
41. i. Average rate during 30-60 sec. = 60−30
−3
= 4.67 × 10
−1
molL sec
−1

2.303 [A]0 2.303 0.55

ii. K 30 =
t
log
[A]
=
30
log
0.31

2.303 0.55
K60 = log
60 0.17
2.303 0.55
K90 = log
90 0.085

Average K = 1.98 × 10 −2
sec
−1

42. Here K 1
= 2.15 × 10
−8
L mo l
−1
s
−1

−7 −1 −1
K2 = 2.39 × 10 L mo l s

T1 = 650 K , T2 = 700K and

−1 −1
R = 8.314 J K mo l

Using the formula

K2 Ea T2 − T1
log = ( )
K1 2.303R T1 T2

−7 Ea
2.39×10 700−650
log = = ( )
−8 2.303×8.314 650×700
2.15×10

Ea 50
log 1.11 × 10 = ×
19.147 455000
Ea 1
1.0457 = ×
19.147 9100

Ea = 182200.365 J mol-1
43. For the reaction 2N O (g) → 4N O 2 5 2 (g) + O2 (g)

Assume rate law expression as

Rate = k[N O ] 2 5
x

According to question
34 × 10
−5
= k[1.13 × 10
−2 x
] ... (i)
25 × 10
−5
= k[0.84 × 10
−2 x
] ...(ii)
18 × 10
−5
= k[0.62 × 10
−2 x
] ...(iii)
From eq.(i) and eq.(ii)
−5 −2 x
34×10 k[1.13× 10 ]
=
−5 −2 x
25×10 k[0.84 × 10 ]

x
[1.36] = [1.36]

x=1
i. Order of reaction=1
ii. Rate law expression
Rate = k[N O ] 2 5

iii. Rate constant

[Rate] −5
34×10
k = =
[ N2 O5 ] −2
1.13×10

−3
k = 30.09 × 10

−2 −1
k = 3.0 × 10 min

44. SO 2 C l2 (g) → SO2 (g) + C l2 (g)

2.303 P1
k = log
t 2P1 − Pt

Where P is the initial pressure at time t = 0

1

P = total pressure
t

When t = 100 s, for first-order reaction we have

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 2.303 0.5
k = log
100 Sec 2×0.5−0.6
2.303
= log(1.25)
100 s
2.303
= (0.0969)
100 s

−3 −1
= 2.2316 × 10 s

When P t = 0.65atm

P1 + P = 0.65

P = 0.65 − P1

= 0.65 − 0.50 = 0.15 atm

Pressure of SO 2 C l2 at time t
(PS O ) = P1 − P
2 C l2

= 0.5 - 0.15
= 0.35 atm
Rate at that time = k × P S O 2 C l2

) (0.35 atm)
−3 −1
= (2.2316 × 10 s

−5 −1
= 7.8 × 10 atm s

45. The rate constant is nearly doubled with a rise in temperature by 10 0C for a chemical reaction.The temperature effect on the rate
constant can be represented quantitatively by Arrhenius equation,
k = Ae where, k is the rate constant, A is the Arrhenius factor or the frequency factor, R is the gas constant, T is the
− Ea /RT

temperature, and is the energy of activation for the reaction.

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