CHEMISTRY-XII

NOTRE DAME

Chemical Kinetics
Definitions and laws:
1.
2.
3.
4.
5.
6.
7.
8.
9.

Rate of reaction and its units, average rate and instantaneous rate
Rate law or Rate expression
Rate constant definition and its units
Order of the reaction and molecularity of reaction
Half life
Elementary step in reaction and RDS step
Pseudo first order reaction
Activation energy
Factors effecting rate of reaction

10. Temprature coefficient

Formulae:
i)

Rate expression in terms of decreasing concentration of reactants and increasing

concentration of products
ii) Rate law
iii) Order
iv) Rate constant for zero order reaction, Half life and relation between x and t.
v) Rate constant for first order reaction
vi) First order Half life, t75% and and time t
vii) Pseudo first order reaction
viii) Arrhenius equation, relation between k1 and k2 and Graph log k vs 1/T

Concept wise questions

1. Rate expression in terms of decreasing concentration of reactants and increasing
concentration of products
i)

Express the rate of the following reaction in terms of disappearance of hydrogen in the
reaction. 3H2(g)+N2(g)2NH3(g)

ii) The decomposition of NH3 on platinum surface is a zero order reaction. What are the rates of
production of N2 and H2 if k=2.510-4 mol L-1 s-1?
2. Rate law
i)

For the reaction, AB, the rate of reaction becomes twenty seven times when the
concentration of A is increased three times. What is the order of the reaction?

ii)

A reaction is of second order with respect to a reactant. Now is its rate affected if the
concentration of the reactant is (i) doubled (ii) reduced to half?

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iii)

A reaction is of first order in reactant A and of second order in reactant B. How is the rate of this
reaction affected when (i) the concentration of B as alone is increased to three times (ii) the
concentrations of A as well as B are doubled?

iv) A reaction is second order in A and first order in B.

(a) Write the differential rate equation.
(b) How is the rate affected on increasing the concentration of A three times?
(c) How is the rate affected when the concentrations of both A and B are doubled?
v) For the reaction, 2NO (g)+Cl2(g)2NOCl(g). The following data were collected. All the
measurements were taken at 263 K.
Exp. No.
1.
2.
3.
4.

(i)
(ii)
(iii)

Initial [NO]
(M)
0.15
0.15
0.30
0.25

Initial [Cl2]
(m)
0.15
0.30
0.15
0.25

Initial rate of disappearance of Cl2

(M/min)
0.60
1.20
2.40
?

Write the expression for rate law.

Calculate the value of rate constant and specify its units.
What is the initial rate of disappearance of Cl2 in experiment 4?

vi) Consider the reaction, 2A+B C+D. Following result were obtained in experiments designed
to study the rate of reaction.
Exp. No.

1.
2.
3.

Initial concentration
(mol L-1)

Initial rate of formation

[D] (M/min)

0.10
0.20
0.40

0.10
0.20
0.40

1.510-3
3.010-3
6.010-3

(i)
(ii)
(iii)

Write the rate law for the reaction.

Calculate the value of rate constant for the reaction.
Which of the following possible reaction mechanisms is consistent with the rate law
found in
I.
A+BC+E
(slow)
A+ED (fast)
II.
BC+E (slow)
A+EF (fast)
A+FD (fast)
vii) The following results have been obtained during kinetic studies of the reaction.

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2A+BC+D
Exp.No
[A]
[B]
Initial rate of formation of D
1.
0.1 M
0.1 M
6.010-3M min-1
2.
0.3 M
0.2 M
7.210-3M min-1
3.
0.3 M
0.4 M
2.8810-2M min-1
4.
0.4 M
0.1 M
2.4010-2M min-1
Determine rate law and the rate constant for the reaction.
viii) The data given below is for the reaction,
S.No
N2O5(mol L-1)
1.
1.1310-2
2.
0.8410-2
3.
0.6210-2
Determine for this reaction,
(i)
Order of reaction
(ii)
Rate law
(iii)
Rate constant

2N2O5(g)4NO2(g)+O2(g)
Rate of disappearance of N2O5 (mol L-1 min-1)
3410-5
2510-5
1810-5

3. Order

i)

The reaction, A+3BC obeys the rate equation, rate=k*A+1/2[B]3/2. What is the order of reaction?

ii) For a reaction A+B P, the rate law is given by, r=k[A]1/2[B]2. What is the order of this reaction?
iii) Identify the reaction order from the following rate constant, k=2.310-5 L mol-1s-1.
iv) Identify giving reasons, the reaction order from each of the following rate constants:
(i)

k=2.310-5 L mol-1s-1

ii) k=3.010-4 s-1

4. Rate constant for zero order reaction, Half life and relation between x and t.
i)

The rate constant for a zero order reaction in A is 0.0030 mol L-1 s-1. How long will it take for the
initial concentration of A to fall from 0.10 M to 0.075 M?

5. Rate constant for first order reaction

i)

A reactant has a half life of 10 min.

(i) Calculate the rate constant for the first order reaction.
(ii) What fraction of the reactant will be left after an hour of the reaction has occurred?
ii) In a first order reaction, the concentration of the reactant is reduced from 0.6 mol L-1 to 0.2 mol
L-1 in 5 min. Calculate the rate constant of the reaction.

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iii) The decomposition of a compound is found to follow a first order rate law. If it takes 15 min for
20% of original material to react, calculate
(i) Rate constant
(ii) The time at which 10% of the original material remains unreacted.
iv) Nitrogen pentoxide decomposes according to the equation. 2N2O5 (g) 4NO2 (g) +O2 (g). This
first order reaction was allowed to proceed at 400C and the data below were collected.
v) [N2O5] [M]
vi) Time(min)
vii) 0.400

viii) 0.00

ix) 0.289

x) 20.0

xi) 0.209

xii) 40.0

xiii) 0.151

xiv) 60.0

xv) 0.109

xvi) 80.0

i ) Calculate the rate constant. Include units with your answer.

ii) What will be the concentration of N2O5 after 100 min?
iii) Calculate the initial rate of reaction.
v) Nitrogen pentoxide decomposes according to equation:
2N2O5 (g) 4NO2 (g) +O2 (g)
This first order reaction was allowed to proceed at 400C and the data below were collected.
[N2O5] [M]
Time(min)
0.400
0.00
0.289
20.0
0.209
40.0
0.151
60.0
0.109
80.0
(i) Calculate the rate constant. Include units with your answer.
(ii) Calculate the initial rate of reaction.
(iii)
After how many minutes will [N2O5] be equal to 0.350 M?
vi)

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6. First order Half life, t75% and and time t

i)

A first order decomposition reaction takes 40 min for 30% decomposition. Calculate its t1/2 value
-1
ii) Calculate the half life of a first order reaction whose rate constant is 200 s
4
iii) The half life for a first order reaction is 510 s. What percentage of the initial reactant will
react in 2 hours? Calculate.
iv) The half life for decay of radioactive 14C is 5730 yr. An archaeological artifact containing wood
had only 80% of the 14C found in a living tree. Estimate the age of the sample.
v)

Prove that the time required for the completion of of the first order is twice the time required
for the completion of half of the reaction
vi) The decomposition of phosphine, PH3 proceeds according to the following equation.
4PH3(g)P4(g)+6H2(g).
It is found that the reaction follows the following rate equation.
Rate=k[PH3]
The half life of PH3 is 37.9 s at 1200C.
(i) How much time is required for th of PH3 to decompose?
(ii) What fraction of the original sample of PH3 remains behind after 1 min?
vii) A first order reaction is 20% complete in 5 min. Calculate the time taken for the reaction to be
60% complete.
-1
viii) The rate constant for a first order reaction is 60 s . How much time it will take to reduce the
concentration of the reactant to 1/10th of its initial value?
ix) Hydrogen peroxide, H2O2(aq) decomposes to H2O(l) and O2(g) in a reaction that is of first order
in H2O2 and has a rate constant, k=1.0610-3 min-1.
(i)

How long will it take 15% of a sample of H2O2 to decompose?

(ii)

How long will it take 85% of a sample of H2O2 to decompose?

7. Pseudo first order reaction

i)

In a pseudo first order hydrolysis of ester in water, the following results are obtained:
T(in seconds) 0
30
60
90
[Ester] M

0.55

0.31

0.17

0.85

(i) Calculate the average rate of reaction between the time interval 30 to 60 s.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
8. Arrhenius equation, relation between k1 and k2 and Graph log k vs 1/T

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i)

The first order rate constant for the decomposition of ethyl iodide by the reaction,
C2H5I(g)C2H4(g)+HI(g) at 600 K is 1.6010-5 s-1. Its energy of activation is 209 kJ/mol. Calculate
the rate constant of the reaction at 700 K.
ii) The rate of reaction becomes four times when the temperature changes from 300 K to 320 K.
Calculate the energy of activation of the reaction, assuming that it does not change with
temperature. (Given, R=8.314 J mol-1 K-1)
iii) For a decompositon reaction the value of rate constant k at two different temperatures are
given below:
k1=2.1510-8 L mol-1 s-1 at 650 K
k2=2.3910-7 L mol-1 s-1 at 700 K
Calculate the value of activation eneryg for this reaction. [R=8.314 J mol -1 K-1]
0
0
iv) The rate of a particualr reaction triples when temperature change from 50 C to 100 C. Calculate
the activation energy of the reaction. (Given, log 3=0.4771; R=8.314 J K-1 mol-1)
v) Rate constant k of a reaction varies with temperature T according to the equation.

log k log A

Ea 1

2.303R T

Where Ea is the activation energy, when a graph is plotted for log k Vs

1
, a straight line with a
T

slope of 4250 K is obtained. Calculate Ea for a reaction (R=8.314 J K-1 mol-1).

vi)

vii)

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