Chemical Kinetics

2019
(1) The slope obtained by plotting the values of rate of reaction against the concentration of
reactant helps to determine the value of rate constant (k)
(2) The relationship between the rate constant and temperature of a reaction is given by
Arrhenius equation
(3) The order of a given reaction: A + B → product is a second order. Show that the unit of
rate constant is mol−1 litre time−1.
For a second order reaction, the rate of reaction is given as:
r = k [A][B], unit of ‘r’- mol L−1 time−1, unit of concentration - mol L−1
r
k = [A][B]
mol L−1time−1
k = mol L−1 × mol L−1 = mol−1 L time−1
(4) The rate law equation for a reaction A + B → product is rate = k [A]1 [B]0. Complete the
following table.
Experiment [A] mol/L [B] mol/L Initial rate: mol L−1 min−1.
I 0.1 0.1 2.0 × 10−2
II x 0.2 4.0 × 10−2
III 0.4 0.4 y
(i) Calculation of rate constant of experiment I
r 2 ×10−2
k = [A] = = 0.2 min‒1
0.1
(ii) Calculation of value of ‘x’ from experiment II
r = k[A]
4.0 × 10−2 = 0.2 × ‘x’
4.0 ×10−2
‘x’ = 0.2 = 0.2 mol L−1
(iii) Calculation of value of ‘y’ from experiment III
r = k[A]
r (‘y”) = 0.2 × 0.2 = 0.08 mol L−1 min−1.
(5) In a first order reaction, ten percent of the reactant is consumed in 25 minutes.
(a) What is the rate constant of the reaction?
2.303 [A]0
k= × log t = 25 minutes, [A]0 =100, [A] = 90, k =?
t [A]
2.303 100
k= × log = 4.215 ×10−3 min.−1
25 90

(b)Find the time taken for 19 percent and 75 percent of the reaction to take place.
(i) (a) time taken for 19% the reaction to take place
k = 4.215 ×10−3 min.−1, [A]0 =100, [A] = 81 [100-19]. t =?
2.303 [A]0
t= × log
k [A]
2.303 100
t= × log = 50.0021 minutes
4.215 × 10−3 81

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 2.303 100
(ii) × log = 329 .34 minutes
4.215 × 10−3 25
(6) NH4NO2 decomposes as: NH4NO2 ⎯⎯→ N2 + 2H2O
When the initial concentration of the salt is doubled, the evolution of N2 becomes two
times faster. This is an example of a
A zero-order reaction.
B first order reaction.
C second order reaction.
D third order reaction.

2018
(1) The experimentally determined rate law and the rate expression obtained from a balanced
chemical equation is the same for the following reaction: CH3COOC2H5 + NaOH ⎯⎯→
CH3COONa + C2H5OH
The unit for rate constant (K) for the reaction given above is
A mol-1 t-1.
B mol-1 L 1 t-1. [r = k [CH3COOC2H5]1[ NaOH]1, unit of ‘r’- mol L−1 time−1, unit of
concentration - mol L−1
r
k = [CH COOC H ][NaOH]
3 2 5
mol L−1time−1
k = mol L−1 × mol L−1 = mol−1 L time−1 ]

C mol-2 L2 t-2.
D t-1.
(2) For a first order reaction, the half-life of a reactant is 5 minutes. The percentage of the
reactant after 20 minutes will be ……………………

(3) (a)Alkaline hydrolysis of ester ⎯⎯→ second order reaction. [r = k [CH3COOC2H5]1[

NaOH]1, order = 1+ 1 + 2]
(b) Half-life depends upon initial concentration of the reactant → second order reaction
(4) The collisions between the reacting molecules are effective only when they acquire
activation energy.
(5) The rate constant for a reaction is 1.6 x 10-5 s -1 and 6.36 x 10-3 s -1 at 600K and 700K
respectively. Calculate the activation energy for the reactions.
𝑘2 6.36 × 10−3
Given: T1 = 600K T2 =700K =
𝑘1 1.6 × 10−5
log k2 Ea T2 − T1
=
log k1 2.303 R T1 × T2

6.36 × 10−3 Ea 700 − 600

log −5 =
1.6 × 10 2.303 ×8.314 600 × 700

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 Ea 100
log 397.5 =
2.303 ×8.314 290 × 300

2.303 × 8.314 ×600 × 700 × 2.595

Ea = = 208684.7007 J = 208.6847kJ
100

(6) Give TWO differences between rate of reaction and rate constant of a chemical reaction in
the table given below.
Rate of reaction Rate constant

Reaction rate (Rate of reaction) Specific reaction rate (Rate constant)

1. It is rate of change of concentration of a 1. It is a constant of proportionality and is
reactant or a product with respect to time. equal to the rate of reaction when the molar
concentration of each reactant is unity.
2. The reaction rate at a particular instant 2. The specific reaction rate remains constant
depends upon the concentration of reactants for a particular reaction at a particular
at that instant. temperature and does not depends upon the
initial concentration of the reactants.
3. The units are fixed and are mol L−1s−1 3. The units depend upon the order of reaction.
For a reaction of order n, the units of
specific reaction rate is mol1−n Ln – 1 s−1
(7) Plot a graph which can be used to calculate the activation energy of a reaction. What will be
the relation between the slope of the graph and the Ea of the reaction?

Ea = −Slope × 2.303 R

2017
(1) Arrhenius equation is used to calculate activation energy of a reaction. Which of the
following graphs is used to calculate activation energy of a reaction?

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 A B

log K log K

1 1
T T

C D

log K log K

T T

(2) The rate of zero order reaction remain constant with time.
(3) First order reaction ⎯⎯→ Sec-1
(4) The graph for the rate of a reaction against molar concentration of reactant ‘A’ for a reaction
A → B, is shown below:

Rate

[A]
1. What is the order of the reaction?
Zero order reaction
2. Write the relationship between rate constant ‘K’ and half-life period (t ½) for the above
reaction.
[A0 ]
t½ =
2k
(5) Consider the reaction, A + B C + D. → The initial rates for the different concentrations of
the reactants are given below:
Experiment No Initial concentration (mol L-1) Rate (mol L-1s−1)
A B
1 0.38 0.38 5 × 10-3
2 0.76 0.76 4 × 10-2
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 3 0.38 0.76 1 × 10−2
(1) Write the rate law.
r =k [A]x [B]y
5 × 10-3 = k [0.38]x [0.38] y ------------ (i)
4 × 10-2 = k [0.76]x [0.76] y ------------ (ii)
1 × 10−2 = k [0.38]x [0.76] y ------------(iii)
Equations (iii) divide by (i)
1 × 10−2 = k [0.38]x [0.76] y
5 × 10-3 = k [0.38]x [0.38] y
2 = 2y, y =1
Equations (ii) divide by (iii)
4 × 10-2 = k [0.76]x [0.76] y
1 × 10−2 = k [0.38]x [0.76] y
4 = 2x
22 = 2x
x=2
Rate law equation: r = k [A]2[B]1
(2) Calculate the rate constant.
5 × 10-3 = k [0.38]2 [0.38] 1
5 ×10−3
k = 0.38 ×0.38 ×0.38 = 0.09 mol‒2 L2 s‒1
(vi) For both first and second order reactions, the rate increases with increase in concentration,
yet both have different units of rate constant. Why?
In first order reaction, the rate of reaction is directly proportional to the one molar concentration
of reactant. In second order reaction, the rate of reaction is directly proportional to the two-molar
concentration of reactants.
(vii) Define molecularity of a reaction.
The total number of molecules taking part in the rate determining step as represented by the
simple chemical equation is known as the molecularity of the reaction.
2016
(i) The minimum amount of energy which reacting molecules must possess to produce effective
collision is threshold energy
(ii) A plot of log [A] against time for a reaction is shown below:

log [A]

time
(a) What is the order of reaction?
First order reaction
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 1
(b) The slope of the plot of log K versus T for a reaction is −750 K. Find the activation energy of
the reaction.
E
Slope = − a
2.303 R
Ea = − 2.303 × R × Slope
Ea = − 2.303 × 8.314 2.303 × (−750)
Ea = 14360.35 J mol‒1
(iii) Draw an energy diagram for uncatalysed and catalysed reactions.

2015
(i) The rate constant of a reaction is dependent on concentration. (correct the statement)
temperature
(ii) State the law of mass action.
At a constant temperature, rate of chemical reaction is directly proportional to the product of
active masses of reacting substances, with each active mass term raised on the power equals to
the stoichiometric coefficient of that reactant in the chemical equation.
(iii) For the reaction, A+ B ⎯⎯→ Product, the following data were obtained.
Experiment No [A] (mol lit-1) [B] (mol lit-1) Rate (mol L-1 min-1)
1 0.01 0.01 5× 10-3
2 0.02 0.01 1 × 10−2
3 0.01 0.02 5 × 10−3
(a) What is the order of the above reaction?
r =k [A]x [B]y
5 × 10-3 = k [0.01]x [0.01] y ------------ (i)
1 × 10-2 = k [0.02]x [0.01] y ------------ (ii)
5 × 10−3 = k [0.01]x [0.02] y ------------(iii)
Equations (ii) divide by (i)

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 1 × 10-2 = k [0.02]x [0.01] y
5 × 10-3 = k [0.01]x [0.01] y
2 = 2x , x = 1
Equations (iii) divide by (i)
5 × 10−3 = k [0.01]x [0.02] y
5 × 10-3 = k [0.01]x [0.01] y
1 = 2y
20 = 2y
y=0
The order of reaction = 1 + 0 = 1
(b) Write the rate law expression.
r =k [A]1[B]0
(c) Calculate the rate constant.
5 × 10-3 = k [0.01]1 [0.01]0
5 ×10−3
k = 0.01 = 0.5 min‒1
(d) Calculate the half-life period.
0.6931
t½ =
k
0.6931
t½ = = 1.386 min.
0.5
(iv)Write one difference for the following in the table given below:
(a) Order of reaction and molecularity
Order of reaction Molecularity

Order of reaction Molecularity of reaction

1. Order is the sum of exponents in the rate 1. Molecularity is the total number of
law equation. molecules of reactants taking part in a
particular step of reaction.
2. Order of reaction may have fractional 2. There is always a whole number. other than
values Zero.
or it may be zero.
3. For complex reaction the overall rate of 3. There is no significance of overall
reaction depends on the slowest step of the molecularity.
overall order is also determined by the
slowest step.
4. Order of reaction determined 4. Molecularity is determined by theoretically.
experimentally.

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