38 | Chemistry-XII

UNIT 3

CHEMICAL KINETICS

CONCEPT

60
Chemical Kinetics : The branch of physical chemistry which deals with the study
of rate of reaction and factors affecting rate.

E3
Rate of chemical reaction : The change in concentration of any reactant or
product per unit time is called rate of reaction.
Types of Rate of Reaction :
1. Average rate of reaction : The rate of reaction measured over the long time

2.
ID
interval is called average rate of reaction.

Avg rate=
D
∆x
∆t
−∆[R] ∆[P]
=
∆t ∆t
Instantaneous rate of reaction : The rate of reaction measured at a particular
U
time is called instantaneous rate of reaction.
(Rate)i = (Instantaeous rate) dx/dt = –d[R]/dt=+d[P]/dt
YG

Factors affecting Rate of Reaction

1. Concentration of reactant
2. Surface area
3. Temperature
D

4. Nature of reactant
5. Presence of catalyst
U

6. Radiation in photochemical reaction

Rate constant (k) : It is equal to the rate of reaction when molar concentration of
ST

reactant is at unity.
Rate law : The rate of reaction is directly proportional to the product of
concentration of reactant and each concentration is raised to the equal to no of moles
actually participating in the reaction.
For a reaction, aA + bB → cC + dD
 Chemical Kinetics | 39
Rate law = k[A]p[B]q
where powers p and q are determined experimentally.
Molecularity : The total number of reactants taking part in elementary chemical
reaction is called molecularity.
Order of reaction : The sum of powers to which the concentration terms are
raised in a rate law expression is called order of reaction.

60
For above case, Order = P + Q
Orders of reaction is determined experimentally.
Half-life period : The time during which the concentration of the reactant is

E3
reduced to half of its initial concentration is called half-life period.
Activation energy : The minimum extra amount of energy absorbed by reactant
molecules so that their energy becomes equal to the threshold energy is called activation
energy.

ID
Activation energy = Threshold energy – Kinetic energy
Temperature coefficient : The ratio of rate constant at two temperatures having
difference of 10ºC is called temperature coefficient.
U
Temperature coefficient = Rate constant at T + 10ºC/Rate constant at TºC
Arhenius Equation :
YG

K = Ae−Ea/RT
where, K = Rate constant
A = Arrhenius energy (Frequency factor or pre-exponential factor)
Ea = Activation energy
D

R = Rate constant
T = Temperature
U

Ea
= Fraction of molecules having energy equal to or more than activation
RT
energy
ST

Ea
log K = log A –
2.303RT

K2 Ea  1 1 
log =  − 
K1 2.303R  T1 T2 
 40 | Chemistry-XII

K2 Ea  T2 − T1 
log =  
K1 2.303 × 8.314  T2 − T1 
Where R = 8.314 JM–1 mol–1
K E a  T2 − T1   T2 − T1 
=log 2 =   0.0522E a  
K1 19.147  T2 − T1   T2 − T1 
1. Integrated rate law equation for zero order reaction is given as below :

60
[R]0 − [R]t
(a) k =
t
Where k is rate constant and [R]0 is initial molar concentration.
[R]o

E3
(b) t1/2 = , t1/2 is half-life period of zero order reaction.
2k
2. Integrated rate law equation for first order reaction :
2.303 [R]0
(a) k = log
t [R]t

concentration at time 't'. ID

where k is rate constant, [R]0 is initial molar concentration and [R], is final

(b) Half-life period (t1/2) for first order reaction :

U
0.693
t½ =
k
Pseudo chemical reaction : The chemical reaction which looks like higher order
YG

reaction but in real it follows lower order reaction.

CH3COOC2H5 + H2O → CH3COOH + C2H5OH
Rate = k[CH3COOC2H5]1
Order = 1
D

MULTIPLE CHOICE QUESTIONS (1 Mark)

U

1. The half life period of a first order reaction is 100° seconds. Its rate constant is:
(a) 0.693 sec–1 (b) 6.93 × 10–3 sec–1
(c) 6.93 × 10–2 sec–1 (d) None of these
ST

2. In Arrehenius equation if a graph is plotted between 10 gK and 1/T, the slope

of the curve will be:
− Ea − Ea
(a) (b) 2.303R
R
Ea Ea
(c) (d)
R 2.303R
 Chemical Kinetics | 41
3. The rate low for a reaction 2C + D → A + E is
− d [D]
= K[C]2[D]
dt
if C is present in large excess, the order of the reaction will be:
(a) zero (b) first
(c) second (d) third

60
4. What is the activation energy for the reverse of this reaction?
N2O4(g) → 2NO2(g)
Data for the given reaction is ∆H = 54 KJ/mol and εa = 57.2 KJ.
(a) – 54 KJ (b) 3.2 KJ

E3
(c) 60.2 KJ (d) 111.2 KJ
5. The rate constant of a reaction becomes equal to the pre exponential factor
when:
(a) the absolute temperature is zero

ID
(b) the activation energy is infinity
(c) the absolute temperature is infinity
(d) the activation energy is zero
6. The following graph show that the reaction is:
U
(a) zero order [A]
(b) first order
YG

(c) second order

(d) fractional order Time

7. A second order reaction between A and B is elementary reaction:

A + B → Product
rate law expression of this reaction will be:
D

(a) Rate = K[A][B] (b) Rate = K[A]0[B]2

(c) Rate = K[A]2[B]0 (d) Rate = K[A]3/2[B]1/2
U

hν
8. The order and molecularity of the chain reaction, H2(g) + Cl2(g) → HCl
(a) 2, 0 (b) 0, 2
ST

(c) 1, 1 (d) 3, 0
9. Which of the following is pseudo first order reaction?
(a) 2H2O2 → 2H2O + O2
(b) 2O3 → 3O2
(c) CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
(d) CH3COOC2H5 + H2O →
H+
CH3COOH + C2H5OH
 42 | Chemistry-XII
10. A large increase in the rate of reaction for rise in temperature is due to:
(a) Increase in the number of collisions
(b) Increase in the number of activated molecules
(c) Lowering of activation energy
(d) Shortening of the mean free path.
11. For a creactionj, the following data were obtained:

60
Concentration (mol/L) 0.1 0.05 0.025 0.0125
Half life in (sec) 30 29.9 30.1 30
the order of reaction is:
(a) 2 (b) 1

E3
(c) 0 (d) fractional
12. For the formation of SO3 in the following reaction, it is given that
2SO2 + O2 → 2SO3 Ea = Activation energy
SO2 + 1/2 O2 → SO3 E′a = Activation energy
(a) Ea > E1a
(c) Ea1 = Ea1/2 ID (b) Ea < Ea1
(d) Ea = Ea1
13. A first order reaction is 20% complete in one hour. At the end of 3 hrs the
extent of the reaction is:
U
(a) 60% (b) 52.2%
(c) 48.8% (d) 44.4%
YG

14. Radioactive decay is an example of:

(a) first order (b) second order
(c) zero order (d) 0.5 order
15. At 227°C, the presence of catalyst causes the activation energy of a reaction
to decrease by 4.606 KCal, the rate of the reaction will be increased by:
D

(a) 2 times (b) 10 times

(c) 100 times (d) 1000 times
U

16. The decomposition of N2O5 occurs as, 2N2O5 → 4NO2 + O2 and follows first
order kinetics, hence:
(a) the reaction is bimolecular (b) the reaction is unimolecular
ST

mol
(c) tyz ∝ a° (d) unit of K = sec −1
L
17. Rate of which reactions increases with temperature:
(a) of any reactionj (b) of exothermic reaction
(c) of endothermic reaction (d) of none
 Chemical Kinetics | 43
18. For the reaction, N2O5 → 2NO2 + O2; Given
−d
[N 2O5 ] = K [N O ]
dt 1 2 5

d
[NO 2 ] = K2[N2O5]
dt
d
[O 2 ] = K3[N2O5], the relation in between of K1 K2 K3 is

60
dt
(a) 2K1 = K2 = 4 K3 (b) K1 = K2 = K3
(c) 2K1 = 4K2 = K3 (d) 2K1 = 2K2 = 3K3
19. Which of the following statement is/are correct about order of reaction:

E3
(a) order of reaction is determined experimentally
(b) order of reaction can not have fractional value
(c) it does not necessarily depend on stoichiometric coefficients.
(d) it is the sum of power of concentration terms in rate low expression

t
(a) 75% = 1.5
t50%
ID
20. Which one is correct for first order reaction.
t
(b) 75% = 3
t50%
U
t99.9% t87.5%
(c) = 10 (d) =3
t50% 50%

21. Match the column and found out correct option.

YG

L
(A) zero order reaction P. unit of K is .sec −1
mol
mol
(B) first order reaction Q. unit of K is .sec −1
L
(C) second order reaction R. unit of K is sec–1
D

(a) A–R, B–Q, C–P (b) A–P, B–Q, C–R

(c) A–Q, B–R, C–P (d) A–R, B–P, C–Q
U

Assertion and Reasoning:

22. (a) Statement 1: is true, Statement 2 is true, and Statement 2 is a correct explanation
ST

of statement 1
(b) Both statement are true but statement 2 is not a correct explanation for
statement 1
(c) Statement 1 is true and statement 2 is false
(d) Statement 1 is false and Statement 2 is true
(e) Statement 1 the rate of reaction is accelerated by the presence of catalyst.
(f) Statement 2 The presence of catalyst makes the value of ∆G° more negative.
 44 | Chemistry-XII

23. Statement 1: Lower the activation energy, faster is the reaction.

Statement 2 : Catalyst does not affect activation energy of the reaction.
24. Integer type Question:
t
For first order reaction: 99.9 = x , Here x is
t50
(a) 3 (b) 5
(c) 7 (d) 10

60
Fill in the blanks type Questions
25. The reactions taking place in one step is called ............... reactions.
26. The order of reaction is ............... determined.

E3
Answers
1. (b) 2. (b) 3. (b) 4. (b) 5. (c) 6. (a) 7. (a) 8. (b) 9. (d) 10. (b)
11. (b) 12. (d) 13. (c) 14. (a) 15. (c) 16. (c) 17. (a) 18. (a)
19. (a, c, d)
25. elementary
20. (c, d)
26. experimentally

VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)

ID
21. (c) 22. (c) 23. (c) 24. (d)
U
Q. 1. The rate law for a reaction is
Rate = K [A] [B]3/2
YG

Can the reaction be an elementary process ? Explain.

Ans. No, an elementary process would have a rate law with orders equal to its
molecularities and therefore must be in integral form.
Q. 2. For the reaction 3H2 + N2 → 2NH3, how are the rate of reaction expressions
d [H2 ] d [ NH 3 ]
D

− and inter-related ?
dt dt

1 d [H2 ] 1 d [ NH 3 ]
U

Ans. − =
3 dt 2 dt
Q. 3. Identify the order of a reaction from the following rate constant :
ST

k = 2.3 × 10−5 L mol-1 s-1

Ans. Second order
Q. 4. After five half-life periods for a first order reaction, what fraction of reactant
remains ?
1
Ans.
32
 Chemical Kinetics | 45
Q. 5. What is the effect of adding catalyst on the free energy of a reaction ?
Ans. No change in ∆G.
Q.6. What value of k is predicted for the rate constant by Arrhenius equation is T
→ ∞ ? Is this value physically reasonable ?
Ans. From the equation k = Ae − Ea /RT if T → ∞ k → A so that Ea = 0. This is not
feasible.

60
Q.7. Determine the order of reaction :
Step 1. 2NO + H2 → N2 + H2O2 Slow
Step 2. H2O2 + H2 → 2H2O Fast

E3
Ans. Rate = k [NO]2 [H2]
Order = 2 + 1
=3

rate of reaction ?
Ans. Zero order
ID
Q.8. What is the order of reaction whose rate constant has the same units as the

Q.9. Why are reactions of higher order less in number ?

U
Ans. A reaction takes place due to collide of molecules. The chances for a large number
of molecules or ions to collide simultaneously are less. Hence, the reactions of
YG

higher order are less.

Q.10. What will be the effect of temperature on rate constant ?
Ans. Rate constant of a reaction is nearly doubled with rise in temperature by 10º.
Q.11. State a condition under which a bimolecular reaction is kinetically first order
reaction.
D

Ans. A bimolecular reaction becomes first order reaction when one of the reactants is
in excess.
U

Q.12. Why can’t molecularity of any reaction be equal to zero ?

Ans. Molecularity of a reaction means the number of molecules of the reactants taking
place in an elementary reaction. Since at least one molecule must be present, so
ST

that molecularity will be atleast one.

Q.13. The rate constant of a reaction is 3 × 102 min-1. What is its order of reaction ?
(On the basis of units of rate constant)
Ans. First order reaction.
 46 | Chemistry-XII

Q.14. Three-fourth of a reaction is completed in 32 minutes. What is the half life

period of this reaction ?
Ans. 16 minutes.
Q.15. What is meant by an elementary reaction ?
Ans. A reaction which takes place in one step is called an elementary reaction. For

60
example : H2 + I2 → 2HI.
Q.16. Give one example of a reaction where order and molecularity are equal ?
Ans. 2HI → H2 + I2 (Order = Molecularity = 2)
Q.17. For a reaction R → P, the rate becomes 2 times when the concentration of the

E3
reactant A is increased 4 times. What is the order of reaction ?
Ans. r = k(a)n ⇒ 2r = k(4a)n ⇒ 2 = 4n ⇒ n = 0.5
Q.18. The rate constant of a zero order reaction in A is 0.003 mol L-1 sec-1. How long
will it take for the initial concentration of A to fall from 0.10M to 0.075 M ?

Ans. t
=
[ A ]0 − [ A ]
=
k
0.10 − 0.075
= 8.3 sec
0.003
ID
Q.19. In a reaction 2A → Products, the concentration of A decreases from 0.5 mol
U
L-1 in 10 minutes. Calculate the rate during this interval.
−∆ [ A ] 1  0.4 − 0.5 
Ans. Average rate = =
−  =5 × 10−3 M min −1
YG

2∆t 2  10 
Q.20. In some cases large number of colliding reactant molecules have energy more
than threshold energy even then the reaction is slow. Why ?
Ans. Because resultant molecules do not collide in proper orientation.
Q.21. Give an example of a reaction having fractional order.
D

Ans. Decomposition of acetaldehyde (order = 1.5).

CH CHO 
723K
→ CH 4 + CO
U

3
Q.22. Decomposition reaction of ammonia on Pt surface has rate constant = 2.5 ×
10-1 mol L-1 sec-1. What is order of reaction ?
ST

Ans. Unit of k explain that it is zero order reaction.

Q.23. What is order of radioactive decay ?
Ans. First order
Q.24. For a reaction A + B → Product, the rate law is given by r = k[A]½ [B]2. What
is the order of the reaction ?
Ans. Order of reaction = ½ + 2 = 2.5
 Chemical Kinetics | 47

SHORT ANSWER-I TYPE QUESTIONS (2 Marks)

Q. 1. The rate of a particular reaction quadruples when the temperature changes
from 293 K to 313 K. Calculate activation energy.
Ans. K2/K1 = 4
T1 = 293 K, T2 = 313 K
K Ea  1 1

60
log 2 =
−  − 
K1 2.303R  T1 T2 

Thus, on calculating and substituting values, we get :
Ea = 52.86 KJ mol-1

E3
Q. 2. If the decomposition of nitrogen oxide as
2N2O5 → 4NO2 + O2
follows a first order kinetics.

Ans. Rate = K[N2O5]

ID
(a) Calculate the rate constant for a 0.05M solution if the instantaneous rate
is 1.5 × 10−6 mol/l/s ?
U
Rate
K =
[ N 2 O5 ]
YG

1.5 × 10−6
=
0.05
K = 3.0 × 10−5
D

(b) What concentration of N2O5 would give a rate of 2.45 × 10−5 mol L-1 s-1 ?

Ans. Rate = 2.45 × 10−5 mol L-1 s-1

U

Rate 2.45 × 10−5

[N2O5] = =
ST

K 3.0 × 10−5

= 0.82 M
 48 | Chemistry-XII
Q. 3. Write the difference between order and molecularity of reaction.
Ans.
Order Molecularity
1. It is the sum of the powers of concentration It is the number of reacting species
terms in the rate law expression. undergoing simultaneously collision in
a reaction.
2. It is determined experimentally. 2. It is a theoretical concept.

60
3. Order of reaction need not to be a whole num 3. It is whole number only.
ber.

4. Order of reaction can be zero. 4. It can’t be zero or fractional.

E3
Q. 4. Consider the decomposition reaction :

− −
2H 2O 2 →
OH /I
2H 2O + O 2

Step 1.
Step 2.
ID
This reaction takes place in two steps as given below :
H2O2 + I− → H2O + IO− (slow)
H2O2 + IO− → H2O + I− + O2 (fast)
U
(a) Determine rate law expression.
(b) Determine the order of reaction.
YG

Ans. (a) Rate = K[H2O2][I-] because second step is rate determining step.
(b) Order = 1 + 1 = 2
Q. 5. The decomposition of hydrocarbon follows the equation K = (4.5 × 1011 s-1)
e-28000k/T. Calculate Ea.
Ans. K = (4.5 × 1011 s-1) e-28000k/T
D

Comparing the equation with Arrhenius equation,
K = Ae−Ea/RT
U

E
− a = −28000 K
R
ST

Ea = 28000 × 8.314
= 232192 J mol-1
Q. 6. A reaction is of second order with respect to a reactant. How is the rate of
reaction affected if the conc. of the reactant is reduced to half. What is the
unit of rate constant for such a reaction ?
 Chemical Kinetics | 49

Ans. Rate = k[A]2

mol L−1

Unit of k = = k(mol-1)2
S
k = mol-1 L S-1
Q.7. For a first order reaction time taken for half of the reaction to complete is t1
and ¾ of the reaction to complete is t2. How are t1 and t2 related ?

60
Ans. t2 = 2t1 because for 3/4th of the reaction to complete time required is equal to two
half lives.

Q. 8.

E3

(a) What is the order of the reaction ?

(b) What is the slope of the curve ?
ID
U
Ans. (a) Zero order reaction.
(b) [R] = [R0] – kt ∴ Slope = – k
YG

Q.9. Derive an expression to calculate time required for completion of zero order
reaction.
Ans. For a zero order reaction,
R = [R]0 – kt
For completion of the reaction [R] =0
D

∴ kt = [R]
0

[ R ]0
U

Or t=
k
ST

Q.10. For the reaction N2 (g) + 3H2 (g) → 2NH3 (g)

How is the rate of formation of ammonia related to the rate of disappearance
of H2 ?

1 ∆ [H2 ] 1 ∆ [ NH 3 ] ∆ [ NH 3 ] 2 ∆ [H2 ]
Ans. Rate of reaction = − = Or = −
3 ∆t 2 ∆t ∆t 3 ∆t
 50 | Chemistry-XII
Q.11. The rate of a gaseous reaction becomes half when volume of the vessel is
doubled. What is the order of reaction ?
Ans. Suppose, order of reaction is n and the reaction is A (g) → Products
Rate = k[A]n ...(i)
When volume is doubled, molar conc. becomes half and rate of reaction gets
halved.

60
n

Rate  A  ...(ii)
= k 
2 2
Dividing equation (i) by equation (ii),
(2)1 = (2)n

E3
Or n=1
Q.12. A reaction which is first order with respect to A has rate constant 6 min-1. If
we start with [A] = 0.5 mol L-1, when would [A] reach the value of 0.05 ML-1 ?
[ A ]0
Ans. k=
2.303
t
log
[A]
k = 6 min-1, [A]0 = 0.5, [A] = 0.05, t = ?
ID
U
2.303 0.5 2.303
= t = log = log10 0.3838 min
6 0.05 6
YG

Q.13. The conversion of the molecules X to Y follows second order kinetics. If the
concentration of X is increased to three times, how will it affect the rate of
formation of Y ?
Ans. 9 times
Q.14. A first order reaction has a rate constant 1.15 × 10-3 s-1. How long will 5 gram
D

of this reactant take to reduce to 3 grams ?

Ans. t = 444 seconds
U

Q.17. 4NH3 + 5O2 → 4NO + 6H2O. If rate of formation of NO is 6 × 10−4 atm min-1,
calculate the rate of formation of H2O.
ST

Ans. 9.0 × 10−4 atm min-1

Q.18. Consider a certain reaction A → Product with K = 2.0 × 10-2 s-1. Calculate the
concentration of A remaining after 100 s, if the initial concentration of A is
1.0 mol L-1.
Ans. [A] = 0.135 M
 Chemical Kinetics | 51
Q.19. Explain with an example, what is a pseudo first order raction ? The graphs (A
and B) given below are plots of rate of reaction Vs concentration of the reactant.
Predict the order from the graphs.

60
Q.20. Differentiate between :

E3
(a) Average rate and instantaneous rate of a chemical reaction.
(b) Molecularity and order of reaction.
Q.21. Show that in case of first order reaction, the time required for 99.9% of the reaction

ID
to take place is about ten times than that required for half the reaction.
Q.22. For the reaction NO2 + CO → CO2 + NO, the experimentally determined rate
expression below 400 K is rate = k[NO2]2. What mechanism can be proposed for
this reaction ?
U
Q.23. The half life period of a first order reaction is 60 min. What % will be left
after 240 mins. ?
Ans. 6.25%
YG

Q.24. Time for half change for a first order reaction is 25 min. What time will be
required for 99% reaction ?
Ans. 166.16 mins.

SHORT ANSWER TYPE-II QUESTIONS

D

Q. 1. The rate constant for first order reaction is 60/s. How much time will it take
to reduce the concentration of the reaction to 1/10 of its initial value ?
U

[R 0 ] 2.303
Ans. t = log
K [R ]
ST

t=
2.303
log
[R 0 ]

1 [R ]
10
2.303
t= log10
60
 52 | Chemistry-XII
2.303
t=
60
= 3.38 × 10-2 s-1

Q. 2. The rate of most of reaction double when their temperature is raised from
298 K to 308 K. Calculate the activation energy of such a reaction.

K Ea  1 1 

60
Ans. =
log 2  − 
K1 2.303R  T1 T2 

2.303 × 8.314 × 298 × 308 × 0.3010

Ea =
1000

E3
Ea = 52.89 KJ/mol
Q. 3. A first order reaction takes 69.3 min for 50% completion. Set up on equa-
tion for determining the time needed for 80% completion.
0.693
Ans. K =
t1/2
= 10-2 min-1
=
0.693
69.3
min
ID [R 0 ]
U
2.303
T= log

K [R ]
YG

2.303
= log 5
10−2
= 160.9 min
Q. 4. The activation energy of a reaction is 94.14 KJ/mol and the value of rate
constant at 40º C is 1.8 × 10-1 sec-1. Calculate the frequency factor A.
D

Ans. Given, Ea = 94.14 × 103 J mol-1, T = 40 + 273 = 313 K, K = 1.8 × 10-1 sec-1
Ea
By using, − E a /RT ⇒ ln=
K ln A −
U

K = Ae
RT
Ea
Or =
log K log A −
ST

2.303RT
94.19 × 103
Or (
log 1.8 × 10−1 + ) 2.303 × 8.314 × 313
=
log A

Or A = antilog (10.9635) = 9.194 × 1010 sec-1

 Chemical Kinetics | 53

Q. 5. The rate constant of a reaction at 500 K and 700 K are 0.02 s-1 and 0.07 s-1
respectively. Calculate the value of Ea and A.
Ans. 18.23 KJ mol-1, 1.603
Q. 6. The rate constant of a reaction at 700 K and 760 K are 0.011 M-1 s-1 and
0.105 M-1 s-1 respectively. Calculate the value of Arrhenius parameters.
Ans. 2.824 × 1010

60
Q. 7. The initial concentration of N2O5 in the first order reaction N2O5 → 2NO2
+ ½O2 was 1.24 × 10-2 mol L-1 at 318 K. The concentration of N2O5 after 60
minutes was 0.20 × 10-2 mol L-1. Calculate the rate constant of the reaction
at 318 K.

E3
2.303 [ A ]0 2.303 [ N 2O5 ]0 2.303 1.24 × 10−2
=
Ans. K = log =log log
t [A] t [ N 2O5 ]t 60 0.2 × 10−2
2.303 2.303
= =
log 6.2 × 0.7924 min −1




60
= 0.0304 min -1
60
ID
Q. 8. The following data were obtained during the first order thermal decompo-
sition of N2O5 at constant volume :
U
2N2O5 → 2N2O4 + O2

S. No. Time per second Total pressure (atm)
YG

1 0 0.5
2 100 0.512
Calculate rate constant.
Ans. 4.98 × 10−4 sec-1
D

Q. 9. A first order reaction is 20% complete in 20 minutes. Calculate the time

taken for the reaction to go to 80% completion.
Ans. 144.3 minutes
U

Q. 10. For a first order reaction, calculate the ratio between the time taken to com-
plete ¾ of the reaction and the time taken to complete half of the reaction.
Ans. Two
ST

Q. 11. The following results have been obtained during the kinetics studies of the
reaction :
2A + B → C + D
 54 | Chemistry-XII

Experiment [A] mol L-1 [B] mol L-1 Initial rate of formation
of D mol L-1 min-1

I 0.1 0.1 6.0 × 10-3

II 0.3 0.2 7.2 × 10-2

III 0.3 0.4 2.88 × 10-1

60

IV 0.4 0.1 2.40 × 10-1

Determine the rate law and the rate constant for the reaction.
Ans. Rate = K[A][B]2

E3
Q. 12. The rate of reaction triples when the temperature changes from 293 K to
313 K. Calculate the energy of activation of the reaction assuming that it
does not change with temperature.
Q. 13. The decomposition of A into product has value of K as 4.5 × 103 sec-1 at 10º
C and energy of activation 60 kJ/mol. At what temperature would K be
1.5 × 104 sec-1.
Ans. 24º C ID
Q. 14. (a) Write rate law and order of the following reaction :
U
AB + C2 → AB2C + C (slow)
AB2 + C → AB2C (fast)
(b) Define energy of activation of a reaction.
YG

(c) What is the relationship between rate constant and activation energy of
a reaction ?
Ans. (a) Rate = K[AB][C2], Order = 1 + 1 = 2
− E a /RT
(c) K = Ae
D

Q. 15. For a chemical reaction R → P, the variation in the concentration (R) vs time (t)
plot is given :
U
ST

(a) Predict the order of reaction.

(b) Write down its rate law.
(c) What is the slope of the curve ?
 Chemical Kinetics | 55

Q. 17. What do you understand by a first order reaction ? Show that for a first
order reaction time required to complete a definite fraction of the reaction
is independent of initial concentration.
Q. 18. In a pseudo first order reaction of hydrolysis of an ester in H2O, the follow-
ing results were obtained :

t/s 0 30 60 90

60
Ester (M/L) 0.55 0.31 0.17 0.085

(a) Calculate the average rate of reaction between the time interval 30 to
60 sec.

E3
(b) Calculate the pseudo first order rate constant for the hydrolysis of
ester.

0.17 − 0.31
Ans. (a) Average rate during 30-60 sec.
= = 4.67 × 10−3 mol L−1 sec −1
60 − 30

(b)
= K 30
2.303
=
t
log
ID
[ A ]0 2.303 0.55
[ A ] 30
log
0.31
U
2.303 0.55
K 60 = log
60 0.17
YG

2.303 0.55
K 90 = log
90 0.085

Average K = 1.98 × 10-2 sec-1

Q. 19. The decomposition of NH3 on platinum surface is a zero order reaction.

What are the rate of production of N2 and H2 ? [K = 2.5 × 10−4]
D

Ans. 2NH3 → N2 + 3H2

1 d [ NH 3 ] d [ NH 2 ] 1 d [ H 2 ]
U

− = +
2 dt dt 3 dt

d [ NH 3 ]
= rate= k × [ NH 3 ]
ST

dt
= 2.5 × 10−4 mol L-1 sec-1
d [ N2 ] 1 d [ NH 3 ]
= −
dt 2 dt
 56 | Chemistry-XII

1
= × 2.5 × 10−4 mol L−1 sec −1
2

3 d [ NH 3 ] 3
d [H2 ] =
− = × 2.5 × 10−4
2 dt 2

= 3.75 × 10−44 mol L-1 sec-1

60
d [ NH 3 ]
k × [ NH 3 ]
0
Rate =
− =
dt

E3
= 2.5 × 10−4 mol L-1 sec-1

Rate of production of N2 = 2.5 × 10−4 mol L-1 sec-1

LONG ANSWER TYPE QUESTIONS

Q. 1. (a) Define order of reaction.
ID
(b) Rates of reaction double with every 10º rise in temperature. If this
generalization holds for a reaction in the temperature ranges 298 K to
308 K, what would be the value of activation energy for their reaction ?
U
R = 8.314 J K-1 mol-1.
Ans. (a) Order of Reaction : It is the sum of powers to which the conc. terms are
YG

raised in rate law expression.

K Ea  1 1
(b) =
log 2  − 
K1 2.303R  T1 T2 
Here, T1 = 298 K, T2 = 308 K, R = K-1 mol-1
K2
=2
D

K1

Ea  1 1 
= −
U

log 2
2.303 × 8.314  298 308 

Ea  10 
0.3010 =
2.303 × 8.314  298 × 308 
ST

0.3010 × 2.303 × 8.314 × 298 × 308
Ea =
10

= 52898 J mol-1
= 52.898 KJ mol-1
 Chemical Kinetics | 57
Q. 2. (a) What are pseudo order reaction ? Give example.
(b) Rate constant K of a reaction varies with temperature ‘T’ according to
the equation :
Ea 1
=
log K log A −  
2.303R  T 

where Ea is the activation energy. When a graph is plotted for log K vs 1/T,

60
a straight line with a slope of − 4250 K is obtained. Calculate Ea for the
reaction.
Ans. (a) The chemical reaction which look like higher order reaction but in real they
follow lower order kinetics.

E3
For example,
+
CH3COOC2H5 + H2O → CH5COOH + C2H5OH
H

excess
Rate = K[CH3COOC2H5]

(b)
Order = 1

Slope =
Ea
2.303R
ID
= − 4250 K
U
So, Ea = − 2.303 × R × Slope
= − 2.303 × 8.314 J K-1 mol-1 × 4250
YG

= 81375.3 J mol-1

= 81.375 KJ mol-1
Q. 3. (a) Determine the units of rate constant for first and zero order reaction.
(b) Show that time required for the completion of 99% of the first order
D

reaction is twice the 90% of completion of the reaction.

Ans. (a) K = (mol)1 – n Ln – 1 S–1
For zero order, n = 0
U

So, K = (mol)1 – 0 L0 – 1 S–1 = S–1 mol L–1

For first order, n = 1
ST

K = (mol)1 – n Ln – 1 S–1
So, K = (mol)1 – 1 L1 – 1 S–1
= S–1
 58 | Chemistry-XII
(b) For a first order reaction,

2.303 [ A ]0
t= log

K [A]
a × 99
[A]0 = a, [ A ]= a − = 0.01 a
100

60
2.303 a
t ( 99% ) = log
K 0.01a

2.303
= log100
K

E3
2.303
= ×2
K ...(i)
For 90% completion of reaction,

[A] =
a−

t ( 90% ) =
2.303
100ID
a × 99

log
=
0.1a

a
U
K 0.1a

2.303
= ×1
YG

K ...(ii)
Dividing equation (i) by equation (ii), we get
t(99%) = 2 × t(90%)
Q. 4. (a) Define rate constant of reaction.
D

(b) A first order reaction takes 40 mins for 30% decomposition. Calculate
t½.
U

Ans. (a) Rate constant : It is the rate of chemical reaction when the concentration of
reactant taken as unity at a given temperature.
(b) Let initial conc. = a
ST

a × 30
Conc. after 40 mins. = a −
100
= 0.70 a

2.303 [ A ]0
K= log

t [A]
 Chemical Kinetics | 59

2.303 a
= log
40 0.70a

2.303 1
= log
40 0.70
2.303
= × 0.1549

60
40
= 8.92 × 10–3 min–1

0.693
t1/2 =
K

E3

0.693
=

8.92 × 10−3 = 77.7 min

ID
Q. 5. (a) Determine the order of reaction and also determine the units of rate
constant.
U
YG

(b) The following data were given for thermal decomposition of SO2Cl2 at
a constant volume :
SO2Cl2 (g) → SO2 (g) + Cl2 (g)

Exp. Time/s Total p/atm

D

1 0 0.5
2 100 0.6
U

Calculate the rate of the reaction when total pressure is 0.65 atm.
Ans. (a) First order reaction
ST

K = mol1 – n Ln – 1 S–1
n = 1
K = (mol)1 – 1 L1 – 1 S–1
= S–1
 60 | Chemistry-XII

2.303 Pi
(b) k= log
t (2Pi − Pt )
2.303 0.5
= log

100 ( 2 × 0.5 − 0.6 )
2.303 0.5

60
= log
100 0..4

2.303
= × 0.969 =2.23 × 10−3 s −1
100

E3
Now, Rate = PSO Cl
2 2
Pressure of SO2Cl2 when total pressure = 0.65 atm
PSO Cl = 2Pi – Pt
2 2

= 2 × 0.5 – 0.65


= 0.35 atm ID
Rate = 2.23 × 10–3 × 0.35
= 7.8 × 10–4 atm S–1
U
Q. 6. (a) The activation energy of a reaction is 100 kJ/mol. In the presence of
catalyst the activation energy is decreased by 75%. What is the effect on
YG

rate constant of the reaction at 20º C ?

(b) A + 2B → 3C + 2D
The rate of disappearance of B is 1 × 10–2 mol L–1 sec–1. What will be
(i) rate of reaction (ii) rate of change in the concentration of A and C ?
Ans. (a) 2.35 × 1013 times
D

K2 Ea − E p K 75 × 103
[Hint : log = ⇒ log 2 = ]
K1 2.303RT K1 2.303 × 8.314 × 293
U

(b) (5 × 10–3, 5 × 10–3, 15 × 10–3) M L–1 sec–1

ST