CLASS -XII

BOARD COMPANION
CHEMISTRY
 CONTENTS
Chapter Name Page No.
Chemical Kinetics
Theory .................................................................................................................................................................. 1
Exercise-1 .............................................................................................................................................................. 10
Exercise-2 .............................................................................................................................................................. 29
Answerkey ........................................................................................................................................................... 35

SOLUTIONS
EXERCISE-2

Chemical Kinetics .................................................................................................................................. 36

 Chemical Kinetics

1
Chemical Kinetics
INTRODUCTION Using this we can say the following about the reaction
Chemical Kinetics is the branch of chemistry, which 1. Rate of disappearance of A
deals with the study of reaction rates and their Decrease in concentration of A  A
mechanisms. Kinetic studies not only help us to  
Time taken t
determine the speed or rate of a chemical reaction but
2. Rate of appearance of B
also describe the conditions by which the reaction rates
can be altered. The factors such as concentration, Increase in concentration of B   B
 
temperature, pressure and catalyst affect the rate of a Time taken t
reaction. Since, [A] is a negative quantity (as concentration of
reactants is decreasing), it is multiplied with –1 to make
Note : Thermodynamics tells only about the feasibility the rate of the reaction a positive quantity.
of a particular reaction whereas chemical kinetics tells
Units of rate of reaction
about the rate of the reaction.
The unit of rate is concentration time–1. Now if the
concentration is in mol L–1’ and time is in seconds then
RATE OF A CHEMICAL REACTION the unit will be mol L–1 s–1.
The speed of a reaction or the rate of a reaction can be In gaseous reactions, when the concentration of gases
defined as the change in concentration of a reactant or is expressed in terms of their partial pressures, then the
product in unit time. It can be expressed in terms of : unit of the rate equation will be atm s–1
(i) the rate of decrease in concentration of any one of
the reactants, or Instantaneous rate of reaction
(ii) the rate of increase in concentration of any one of Instantaneous rate of reaction is the rate at a particular
moment. It is obtained when we consider the average
the products.
rate at the smallest time interval say dt (i.e. when t
Rate for the Reaction of the form A  B
approaches zero). Hence, mathematically for an
Consider a hypothetical reaction, assuming that the infinitesimally small time dt instantaneous rate is given
volume of the system remains constant. by
AB
  A    B
One mole of the reactant A produces one mole of the rav  
product B. If [A]1 and [B]1 are the concentrations of A
t t
and B respectively at time t1 and [A]2 and [B]2 are their d  A  d  B
concentrations at time t2 then, t = t2– t1 As t  0 or rinst  
dt dt
[A] = [A]2 – [A]1
* Please note that the negative signs have been
[B] = [B]2 – [B]1
incorporated for the reactants as their concentrations
(The square brackets in the above expressions are used are decreasing as the reaction proceeds
to express molar concentration.) Note:
It can be determined graphically by drawing a tangent
Average rate of reaction - The change in concentration at time t on either of the curves for concentration of A
of reactants or products and the time taken for that and B vs time t and calculating its slope (figure).
change to occur

1
Chemical Kinetics

[A]

d[B]
[B] (c -c ) rinst= ––– =slope
C2 rav = ––– = (t–––
2 1
dt
Concentration of reactants t 2-t1) (B)
[A]
d[A] d[B]

Concentration of products
C1
t d[B] c2
rinst= ––– =slope [B]
dt
c1 [B] (c -c )
t rav = ––– = (t–––
2 1

dt t 2-t 1)

t1 t2 t
t1 t2 t
Time Time
(a) (b)

Instantaneous and average rate of a reaction

Reaction of a more general form aA+bB  cC+dD Instantaneous rate of reaction

It is not always that the reactions are such Instantaneous rate of reaction for the above reaction is
straightforward i.e. A B. The reactions can have more given by Instantaneous rate of the reaction

1 d  A 1 d  B 1 d  C  1 d  D 
than one reactant to give more than one product. In the
balanced equation these reactions can also have some    
a dt b dt c dt d dt
stoichiometric coefficients attached to it.
Thus for a general reaction aA+bB  cC+dD where * Please note that the negative signs have been
[a,b] [c,d] are the stoichiometric coefficients of the incorporated for the reactants as their concentrations
are decreasing as the reaction proceeds*.
reactants and products A, B, C and D respectively, in a
RATE LAW
balanced chemical equation.
The mathematical expression that shows how the rate
Average rate of reaction of a reaction depends upon concentration of the
If [A]1. [B]1 ,[C]1 and [D]1,are the concentrations of A, reactants is called the rate law.
B, C and D respectively at time t1 and [A]2, [B]2. [C]2
and [D]2 are their concentrations at time t2then, Dependence of Rate on concentration of reactants
t = t2 – t1, [A] = [A]2-[A]1 It is possible to express differential rate law as the
[B] = [B]2 – [B]1 product of concentration(s) of reactants(s), raised to
[C] = [C]2 – [C]1 some power. For example consider a general reaction
[D] = [D]2 –[D]1 aA + bB  cC + dD the rate law may have the form rate
(The square brackets in the above expressions are of the reaction

used to express molar concentration). 1 d A 1 d  B 1 d  C  1 d  D 

The average rate for such reactions is given by:    
a dt b dt c dt d dt
Average rate of the reaction
 k  A   B
n m

1  A 1   B 1   C  1   D 
   
a t b t c t d t
ORDER OF A REACTION
* Please note that the negative signs have been
The sum of powers of the concentration of the reactants
incorporated for the reactants as their concentrations
in the rate law expression is called the order of that
are decreasing as the reaction proceeds*.
chemical reaction.

2
 Chemical Kinetics

In the rate equation Rate determining step

Rate = k[A]n [B]m The overall rate of the reaction is controlled by the
n and m indicate how sensitive the rate is to the change slowest step in a reaction called the rate determining
in concentration of A and B. Sum of these exponents, step.
i.e., [m + n] in gives the overall order of a reaction Example:
whereas n and m represent the order with respect to Consider the decomposition of hydrogen peroxide
the reactants A and B respectively. which is catalysed by iodide ion in an alkaline medium.
Note: The exponents of the, concentration terms are
not the same as their stoichiometric coefficients. Thus, I
2H 2 O 2 2H 2 O  O 2
we can say that: Rate law for any reaction cannot be Alkaline medium
predicted by merely looking at the balanced chemical The rate equation for this reaction is found to be
equation, i.e., theoretically but must be determined
experimentally. d  H 2 O 2 
Rate   k  H 2O 2   I  
Reaction dt
Experimental rate expression
This reaction is first order with respect to both H2O2
1. CHCl3 + Cl2  CCl4 + HCl
and I– . Evidences suggest that this reaction takes place
Rate = k [CHCl3] [Cl2]1/2
in two steps
2. CH3COOC2H5 + H2O  CH3COOH + C2H5OH
(1) H2O2+ IH2O + IO–
Rate = k [CH3COOC2H5]1[H2O]0
(2) H2O2 + IO–  H2O + I– + O2
Order of a reaction can be 0, 1.2,3 and even a fraction. A
Both the steps are bimolecular elementary reactions.
zero order reaction means that the rate of reaction is
independent of the concentration of reactants. Species IO– is called as an intermediate since it is formed
during the course of the reaction but not in the overall
Bimolecular reactions balanced equation.
Bimolecular reactions involve simultaneous collision The first step, being slow, is the rate determining step.
between two species, for example, dissociation of Thus, the rate of formation of intermediate will determine
hydrogen iodide. the rate of this reaction.
2HI  H2 + I2 Note:
(i) Order of a reaction is an experimental quantity. It
Trimolecular or termolecular reactions can be zero and even a fraction but molecularity
Trimolecular or termolecular reactions involve cannot be zero or a non integer.
simultaneous collision between three reacting species, (ii) Order is applicable to elementary as well as complex
for example, reactions whereas molecularity is applicable only
2NO + O2  2NO2 for elementary reactions. For complex reaction
molecularity has no meaning.
A special note on molecularity (iii) For complex reaction, order is given by the slowest
The probability that more than three molecules can step and generally, molecularity of the slowest step
collide and react simultaneously is very small. Hence, is same as the order of the overall reaction.
the molecularity greater than three is not observed.
It is, therefore; evident that complex reactions involving RATE EQUATION CORRESPONDING TO THE ORDER OF
more than three molecules in the stoichiometric A REACTION
equation must take place in more than one step.
Zero order Reaction
Example:
In some reactions the rate of reaction is independent of
KClO3 + 6FeSO4 + 3H2SO4  KCl + 3Fe2(SO4)3 + 3H2O
the concentration of the reactant and these are termed
This reaction which apparently seems to be of tenth
as zero-order reactions. It may therefore be noted that
order is actually a second order reaction. This shows
for a zero-order reaction the rate of reaction is constant
that this reaction takes place in several steps.
as the reaction progresses.

3
Chemical Kinetics

I Consider the reaction A  B I Consider the reaction A  B

d A d A
Having rate equation, Rate   k A Having rate equation Rate   k  A
dt dt
The integrated rate equation then is [A]t = –kt + [A]0; The integrated rate equation then is given as
where the initial (t = 0) concentration is given by [A]0
and concentration at time t as [A]t.
In
 A   kt; where the initial(t = 0) concentration
Also consider a reaction a A + bB  cC + dD  A 0
If the experimentally determined rate law of this reaction
is given by [A]0 and concentration at time t is given as
is independent of the concentration of the reactants
[A]t.
then the rate can be expressed as:
The first order rate equation can also be written in the
d A form
  k  A   B where k is the constant called
0 0

dt

specific rate constant. 2.303 A 0  A 0 kt

k log OR log 
Let us represent this ‘initial’ concentration by [A]0 and t  A t  A t 2.303
concentration at time t as [A]t.
The equation for concentration at time t is again given If we plot a graph between log [A]0/[A], vs t, (Figure
by [A]t = – kt + [A]0. (b)), the slope = k/2.303

Example:
The decomposition of gaseous ammonia on a hot In[A0]
platinum surface is a zero order reaction at high

log ([A]0/[A]t)
k = –slope
pressure.
In[A0]

Slope = k/2.303
2NH 3  g  
1130K
Pt catalyst
 N 2  g   3H 2  g 

Rate = k [NH3]0 = k 0 t
0 Time
In this reaction, platinum metal acts as a catalyst. At A plot between ln[A] vs t Plot of log [A] 0/[A] t vs time for a first
for a first order reaction order reaction
high pressure, the metal surface gets saturated with- Figure (a) Figure (a)

gas molecules. So. a further change in reaction

conditions is unable to alter the amount of ammonia or.
the surface of the catalyst making rate of the reaction II Consider a reaction aA + bB  cC + dD
independent of its concentration. The thermal If the experimentally determined rate law of this reaction
decomposition of HI on gold surface is another example is directly proportional to the concentration of the
of zero order reaction. reactant A then the rate can be expressed as-
By integration we get

First order reaction lne [A]t –lne[A]0 = –kt or, [A]t = [A]0e–kt
where [A]0 = concentration of the reactant A at time t.
In some reactions the rate of a reaction is proportional
[A]0= (initial) concentration of the reactant A at time t =
to the first power of the concentration of a reactant.
0
Then the reaction is said to be first-order with respect
k = constant of proportionality also called rate constant,
to the reactant or in other words rate of reaction for a
t = time at which we wish to find the concentration.
first order reaction varies linearly with the concentration
Examples:
of a particular reactant. Hydrogenation of ethene is a first order reaction.

4
 Chemical Kinetics

C2H4(g) + H2 (g)  C2H6(g) Consider a reaction aA + bB  cC + dD

Rate = k [C2H4] If the experimentally determined rate law of this reaction
All natural and artificial radioactive decay of unstable is directly proportional to the product of rate of the
nuclei take place by first order kinetics reaction concentration of A as well as B then we have
the rate equation as:
226
88 Ra  24 He  222
86 Rn rate of the reaction
Rate = k [Ra]
1 d A 1 d  B 1 d  C  1 d  D 
• Decomposition of N2O5 and N2O are also first order      k  A  B
a dt b dt c dt d dt
reactions.
*(Note here that the value of constant is adjusted

d A
First Order Reaction for gas phase
Let us consider a typical first order gas phase reaction depending if we express rate as  k '  A  B or
dt
A(g)  B(g) + C(g)

d  B d C
Let pi be the initial pressure ofA and pt the total pressure
at time’t’. Integrated rate equation for such a reaction  k " A  B or  k m  A  B and so on.
dt dt
can be derived as Total pressure pt = pA + PB + pC
(pressure units) This difference in values of constants depends on the
pA, pB and pC are the partial pressures of A, B and C, stoichiometric coefficients. For
respectively. If x atm be the decrease in pressure of A at
k' k"
time t and one mole each of B and C is being formed, e.g.   a,   b and so on).
k k
from one mole of A(g) the increase in pressure of B and
C will also be x atm each. Example 1:
At t = 0 Consider a chemical reaction between two substances
At timet when one reactant is present in large excess. During
the hydrolysis of 0.01 mol of ethyl acetate with 10 mol
A(g)  B(g) + C(g) of water, amounts of the various constituents at the
pi atm 0 atm 0 atm beginning (t = 0) and completion (t) of the reaction are
given as under.
 pi  x  atm x atm x atm

CH3COOC2H5 + H2O 
H
 CH3COOH + C2H5OH
where, pt is the initial pressure at time t = 0. t = 0 0.01 mol 10 mol 0 mol 0 mol
pt = (pi – x) + x + x = pi + x t 0 mol 9.9 mol 0.01 mol 0.01 mol
x = (pt – pi) The concentration of water does not get altered much
where, pA = pi – x = pi-(pt – pi) = 2pi – pt during the course of the reaction. So, in the rate equation
Rate = k’ [CH3COOC2H5] [H2O]
 2.303   pi 
k    log  the term [H2O] can be taken as constant. The equation,
 t  pA 
thus, becomes
Rate = k [CH3COOC2H5] where k = k’ [H2O]
2.303 pi
 log and the reaction behaves as first order reaction.
t  2pi  p t  Such reactions are called pseudo first order reactions.
Example 2:
PSEUDO FIRST ORDER REACTIONS
Inversion of cane sugar is another pseudo first order
Psuedo First-Order Reaction
reaction.
In some reactions the rate of a reaction is proportional 
C12H22O11  H2O 
H
 C6H12O6  C6 H12O6
to the first power of the concentration of two of the
Canesugar Glucose Fructose
reactants, then the reaction is said to be first-order with
Rate = k[C12H22O11]
respect to both the reactants

5
Chemical Kinetics

THEORIES ON CHEMICAL KINETICS

Ea
In this section we will present following theories on ln k1    ln A
chemical reaction RT1
I Temperature dependence of rate constants (iii) At temperature T2, equation (ii) is
II Effect of Catalyst
III Collision Theory of Chemical Reactions Ea
ln k 2    ln A
RT2
I Temperature dependence of rate constants
Arrhenius Equation (iv) (since A is constant for a given reaction)
For most reactions, the rate constant increases as the k 1 and k 2 are the values of rate constants at
temperature increases. These rate constants in most of temperatures T1 and T2 respectively.
the cases vary with temperature according to the Subtracting equation (iii) from (iv), we obtain
Arrehenius equation:
Ea E
ln k 2  ln k1  a
k  Ae  Ea / RT RT1 RT2
(i) The parameters A and Ea for a given reaction are
collectively called Arrhenius parameters. Ea is called
k 2 Ea  1 1 
the activation energy. Value of Ea is determined from ln    
k1 R  T1 T2 
1
the graph for and In k determined
T k2 Ea  1 1 
experimentally. Value of Ain turn is calculated once log    
k1 2.303R  T1 T2 
Ea is known.
 Ea /RT
In the Arrhenius equation (i) the factor e k2 E a  T2  T1 
corresponds to the fraction of molecules that have (v) log   
k1 2.303R  T1T2 
kinetic energy greater than Ea.
Taking natural logarithm of both sides of equation
(i) we get Mechanism based on Intermediate formation
Ea For understanding it let us use the following simple
Ink = In A  reaction
RT
(ii) The plot of In k vs 1/T gives a straight line according H2(g) + I2(g)  2HI(g)
to the equation (ii) as shown in (Figure below).
H I H I H I
+ +
Intercept = ln A H I H I H I

Slope = –Ea/R Formation of HI through the intermediate

In k
For understanding the product formation in the above
reaction we highlight the following points: According
to Arrhenius, this reaction can take place only when a
0 1/T
A plot between ln k vs 1/T molecule of hydrogen and a molecule of iodine collide
to form an unstable intermediate (Figure). It exists for a
Thus, it has been found from Arrhenius equation (i) very short time and then breaks up to form two molecules
that increasing the temperature or decreasing the of hydrogen iodide.
activation energy will result in an increase in the rate of The energy required to form this intermediate, called
the reaction and an exponential increase in the rate activated complex (C), is known as activation energy (Ea).
constant.
Figure is obtained by plotting potential energy v/s
In the plot, slope   E a and intercept = In A. So we reaction coordinate. The reaction coordinate represents
R the profile of energy change when reactants change
can calculate Ea and A using these values. into products.
At temperature T’i, equation (ii) is

6
 Chemical Kinetics

curve at (T + 10), the area showing the fraction of

Activated molecules having energy equal to or greater than
complex
C activation energy gets doubled leading to doubling
the rate of a reaction.
Potential energy Activation
energy

A
H

Fraction of molecules
H2+I2 B t
2HI (t+10) Energy of This area shows
activation fraction of additional
Reaction coordinate
This are molecules which
Diagram showing plot of potential shows fraction react at (t + 10)
energy vs reaction coordinate. of molecules
reacting at r
Kinetic energy
Some energy is released when the complex decomposes
Distribution curve showing temperature
to form products. So, the final heat of the reaction dependence of rate of a reaction
depends upon the nature of reactants and products.
Effect of Catalyst
All the molecules in the reacting species do not have
A catalyst is a substance which alters the rate of a
the same kinetic energy.
reaction without itself undergoing” any permanent
chemical change. For example, MnO2 catalyses the
following reaction so as to increase its rate
considerably.
Fraction of molecules

2KClO3 
MnO 2
 2 KCl  3O 2
Catalytic Mechanism
The action of the catalyst can be explained by
Most probable kinetic energy intermediate complex theory. According to this theory,
Kinetic energy a catalyst participates in a chemical reaction by forming
Distribution curve showing energies temporary bonds with the reactants resulting in an
among gaseous molecules
intermediate complex. This has a transitory existence
Maxwell’s- Boltzmann Distribution Curve and decomposes to yield products and the catalyst.
It is believed that the catalyst provides an alternate
Since it is difficult to predict the behaviour of any one
pathway or reaction mechanism by reducing the
molecule with precision, Ludwig Boltzmann and James
Clark Maxwell used statistics to predict the behaviour activation energy between reactants and products and
hence lowering the potential energy barrier as shown
of large number of molecules. According to them, the
in the figure.
distribution of kinetic energy may be described by
plotting the fraction of molecules (NE/NT) with a given It is clear from Arrhenius equation, k  Ae  Ea /RT ,
kinetic energy (E) vs kinetic energy (Figure). Here, NE
that the lower the value of activation energy faster will
is the number of molecules with energy E and NT is
be the rate of a reaction.
total number of molecules.
Reaction path
The peak of the curve corresponds to the most probable without catalyst
kinetic energy, i.e., kinetic energy of maximum fraction Energy of
Reactionts Energy of activation
of molecules. There are decreasing number of molecules activation without
with energies higher or lower than this value. When Reaction with catalyst
path with catalyst
the temperature is raised, the maximum of the curve catalyst
moves to the higher energy value (Figure) and the curve
Products
broadens out, i.e., spreads to the right such that there
is a greater proportion of molecules with much higher
energies. The area under the curve must be constant Reaction coordinate
since total probability must be one at all times. We can Effect of catalyst on activation energy
mark the position of E a on Maxwell Boltzmann
distribution curve. Note for catalysts
Increasing the temperature of the substance increases A small amount of the catalyst can catalyse a large
the fraction of molecules, which collide with energies amount of reactants.
greater than Ea. It is clear from the diagram that in the
7
Chemical Kinetics

A catalyst does not alter Gibbs energy, G of a reaction. Example : The formation of methanol from bromoethane
It catalyses the spontaneous reactions but does not depends upon the orientation of reactant molecules as
catalyse non-spontaneous reactions. shown in the figure. The proper orientation of reactant
It is also found that a catalyst does not change the molecules lead to bond formation whereas improper
equilibrium constant of a reaction rather, it helps in orientation makes them simply bounce back and no
attaining the equilibrium faster, that is, it catalyses the products are formed.
forward as well as the backward reactions to the same
extent so that the equilibrium state remains same but is H
 – –
reached earlier. Improper No products
H H C– Br + OH
 – – Orientation
H C– Br + OH H
Collision Theory of Chemical Reactions proper H
H Orientation
H
 – – –
Though Arrhenius equation is applicable under a wide H C– Br + OH HO– C–H + Br
range of circumstances, collision theory, which was H
H
developed by Max Trautz and William Lewis in 1916 –
Intermediate
18, provides a greater insight into the energetic and
mechanistic aspects of reactions. It is based on kinetic Steric Factor
theory of gases. To account for effective collisions, another factor P,
Collision Theory called the probability or steric factor is introduced. It
According to this theory, the reactant molecules are takes into account the fact that in a collision, molecules
assumed to be hard spheres and reaction is postulated must be properly oriented i.e.,
to occur when molecules collide with each other.
 E a /RT
Various noteworthy points of collision theory are: Rate  PZ AB e
• Collision Frequency- The number of collisions per Note for collision theory:
second per unit volume of the reaction mixture is known In collision theory activation energy and proper
as collision frequency (Z). orientation of the molecules together determine the
Activation Energy- Another factor which affects the criteria for an effective collision and hence the rate of a
rate of chemical reactions is activation energy (as we chemical reaction.
have already studied). Collision theory also has certain drawbacks as it
considers atoms/ molecules to be hard spheres and
Bimolecular Elementary Reaction- ignores their structural aspect.
For a bimolecular elementary reaction Comparing the equation(vi) with Arrhenius equation,
A + B  Products we can say that A(of Arrhenius Equation) is related to
rate of reaction can be expressed as collision frequency.
 E a / RT
Rate =  Z AB e
DERIVATIONS
(vi) where ZAB represents the collision frequency of
DERIVATION OF RATE EQUATION FOR THE ZERO
reactants, A and B and e  Ea / RT represents the fraction ORDER REACTION REACTION A  B
of molecules with energies equal to or greater than Ea. Zero order Reaction
Consider the reaction: A  B
Threshold Energy and Orientation of colliding
[A0]
molecules-
Concentration of A

The equation (vi) predicts the value of rate constants k = –slope

fairly accurately for the reactions that involve atomic
species or simple molecules but for complex molecules
significant deviations are observed. The reason could
be that all collisions do not lead to the formation of 0 Time
products. The collisions in which molecules collide with Variation in the concentration vs
sufficient kinetic energy (called threshold energy*) and time plot for a zero order reaction
proper orientation, so as to facilitate breaking of bonds
between reacting species and formation of new bonds d A
  k A
0
to form products are called as effective collisions. Rate
dt

8
 Chemical Kinetics

As any quantity raised to power zero is unity (ii) Rearranging this equation

d A  A t
  k  10 ln  kt
 A 0
Rate
dt
d[A] = – kdt
Integrating both sides , 1  A 0
or k  ln
[A]t = – kt +I t  A t
(i) where, I is the constant of integration.
At t = 0, the concentration of the reactant A = [A]0, (iii) At time ti from equation (i)
where [A]0 is initial concentration of the reactant. ln[A]1 = –kt1 + ln[A]0
Substituting in equation (i) (iv) At time t2
[A]0= – k × 0 + I ln[A]2 = – kt2 + ln[A]0
[A]0=I (v) where, [A]1 and [A]2are the concentrations of the
Substituting the value of I in the equation (i) reactants at time t1 and t2 respectively.
[A]t= – kt + [A]0 Subtracting (v) from (iv) we have
(ii) Comparing (ii) with equation of a straight line, y = ln [A]1 – ln[A]2 = – kt1 – (–kt2)
mx + c, if we plot [A] against t, we get a straight line
 A 1
with slope = –k and intercept equal to [A]0 ln  k  t 2  t1 
Further simplifying equation (ii), we get the rate  A 2
constant, k as
 A 1
 A 0   A t k
1
ln
k
t
 t 2  t1   A 2
Derivation of rate equation for the First Order reaction
Reaction A  B  A t
(vi) Equation (ii) can also be written as ln  kt
 A 0
First order reaction
Consider the reaction A  B
Taking antilog of both sides [A]t = [A]0e–kt
d A
 k  A  or     kdt
d A (vii) Comparing equation (ii) with y = mx + c, if we plot
Rate  
dt A In [A] against t we get a straight line with slope = –
k and intercept equal to In [A]0
Integrating this equation, we get The first order rate equation (iii) can also be written
In [A] = –kt + I in the form
(i) Here I is the constant of integration and its value
can be determined easily, i.e. when t = 0, A= [A]0, where 2.303  A 0
k log
[A]0 is the initial concentration of the reactant. t  A t (Taking log to the base 10)
Therefore, equation (i) can be written as
In [A]0 = – k × 0 + I  A 0 kt
Thus log 
In [A]0 = I
 A t 2.303
Substituting the value of I in equation (i)
ln[A] = – kt + ln[A]0

9
Chemical Kinetics

EXERCISE 1
Previous Years Examination Questions Q.6 Why does the rate of a reaction not remain constant
Rate of a chemical reaction and Factors influencing throughout the reaction process? [Delhi 2011]
Rate of a Reaction Sol.  r  [concentration]order
One Mark Questions change in concentration
Q.1 For a reaction R   P, half-life (t1/2) observed to be i.e. =
tim
 [concentration attime 'r']
independent of the initial concentration of reactants.
Hence, as time increases rate decrease.
What is the order of reaction? [Delhi 2017]
Sol. For a reaction R   P, half-life (t1/2) is observed to
Q.7 Define rate of a reaction. [Delhi 2010: All India 2010]
be independent of the initial concentration of reactants.
Sol. Rate of a reaction : Change in concentration of reactants
Thus, it follows first order reaction
or products in unit time is known as rate of a reaction.
Its unit is mol L–1 s–1.
Q.2 For a reaction A + B   P, the rate law is given by,,
1/2 2
r = k[A] [B] . What is the order of this reaction? Q.8 For a reaction : H2 + Cl2 hv
 2HCl
[All India 2013] Rate = k
Sol. For a reaction, A + B  P (i) Write the order and molecularity of this reaction.
Given, rate of a reaction, (ii) Write the unit of k. [All India 2016C]
r = k [A]1/2[B]2 Sol. (i) For a reaction, H2 + Cl2  hv
 2HCl
1 Rate = k, suggests that the reaction is of zero order.
Order wrt A = , Order wrt B = 2 Further, the molecularity of a given reaction is 2 as
2
two molecules are participating in the reaction.
1 5 Hence, order = zero and molecularity = two
 Overall order of a raction = +2= (theoritaly)
2 2
(ii) The unit of k for zero order reaction is equal to the
Q.3 Express the rate of the following in terms of ammonia. rate of a reaction which is mol L–1 s–1, Hence, the
unit of k for the given reaction is mol L–1 s–1.
N2(g) + 3H2(g) 
 2NH3(g)
[Delhi 2013C] [All India 2012] Q.9 For a reaction, 2NH3(g)  Pt
 N2(g) + 3H2)g)
Sol. N2(g) + 3H2(g) 
 2NH3(g) Rate = k
(i) Write the order and molecularity of this reaction.
d[N 2 ] 1d[H 2 ] 1 d[NH 3 ] (ii) Write the unit of k. [Delhi 2016]
Rate =  
dt 3dt 2 2dt Sol. (i) For a reaction,
2NH3( g)  Pt
 N2(g) + 3H2(g)
Q.4 Define order of a reaction. Rate = k, suggests that the reaction is of zero order.
[Foreign 2012. All India 2011. 2010, 2009, 2008; Further, the molecularity of a given reaction is 2 as two
Delhi 2011C. 2010, 2008C] molecules are participating in the reaction. Hence, order
Sol. Order of a reaction The sum of the powers of the = zero and molecularity = two.
concentration of the reactants of a chemical reaction in (ii) The unit of k for zero order reaction is equal to the
the rate law expression is called the order of that rate of a reaction which is mol L–1 s–1. Hence, the unit of
chemical reaction. k for the given reaction is mol L–1 s–1.
a A + b B 
 cC + dD
Q.10 Define rate of reaction. Write two factors that affect the
Rate = k [A]x [B]y rate of reaction. [All India 2015]
Order of reaction = x + y Sol. (i) Refer to solution 7.
(ii) Two factors on which rate of reaction depends are :
Q.5 Identify the reaction order from the following rate
(a) Concentration of reactants: Generally rate increases
constant.
with the increase in concentration.
k = 2.3 × 10–5 L mol–1 s–1 [All India 2011C]
(b) Temperature : Generally rate of reaction increases
Sol. It is the second order reaction because unit of rate
about 2-3 times for every I0°C rise in temperature.
constant for second order reaction is L mol–1s–1.
10
 Chemical Kinetics

Q.11 Write units of rate constants for zero order and for the Sol. Let R be the initial concentration of reactant and r be
second order reactions if the concentration is expressed the initial rate. So, the rate law for the second order
in mol L–1 and time in seconds. [All India 2015C] reaction is,
Sol. Unit of rate constant (k) Rate, r  [R]2
(i) When the concentration of the reactant is doubled,
concentration 1
k=  i.e. R' = 2R
time (concentration) n Then new rate,
Unit of rate constant for zero order r'  [R']2 = [2R]2 = 4[R]2 .......(ii)
From Eqs. (i) and (ii),
molL1 1
=  = mol L–1 s–1 r [R]2 1
s (molL1 )0   or r' = 4r
r ' 4[R]2 4
Unit of rate constant for second order.
Hence, the rate becomes four times of the initial rate on
mol L1 1 doubling the concentration of reactant.
=  = mol–1 L s–1 (ii) When the concentration is reduced to half,
s (mol L1 ) 2
R
R' =
Q.12 Write two differences between ‘order of reaction’ and 2
‘molecularity of reaction’. [All India 2014] 2

New rate, r"  [R "]2     [R]2 .... (iii)

R 1
 
2 4
Sol. S. Molecularity a Order of reaction From eqs. (i) and (iii),
No. reaction
1. The number of reacting The sum of powers of r [R]2 r
species which must the concentrations of   4 or r" =
r" 4 4
collide simultaneously the reactants in the rate [R]
in order to bring about a law expression is called 4
chemical reaction is the order of that Hence, the rate becomes one fourth of the initial rate
called molecularity of a chemical reaction.
reaction. when concentration of the reactant is reduced to half.
2. Molecularity is always Order may have zero,
a whole number value. whole number or Q.15 What do you understand by the rate law and rate
fractional values. constant of a reaction? Identify the order of a reaction,
if the units of its rate constant are
(i) L–1 mol s–1. (ii) Lmol–1 s–1.
Q.13 (i) For a reaction, A + B  Product, [Delhi 2014C, Delhi 2012: All India 2011]
The rate law is given by, OR
Rate = k [A]1 [B]2. What is the order of the reaction? Distinguish between rate expression and rate
(ii) Write the unit of rate constant 'k' for the first order constant of a reaction. [Delhi 2011]
reaction. [Delhi 2014C] OR
Sol. (i) The sum of the powers of the concentrations of the Express clearly, what do you understand by rate
reactants in the rate law expression is called the order expression and rate constant of a reaction?
of that chemical reaction. [Foreign 2011]
Sol. Rate law is the expression in which reaction rate is
Rate = k[A]1[B]2
given in terms of molar concentration of reactants with
Order of reaction = (1 + 2) = 3
each term raised to some power, which may be or may
(ii) Unit of rate constant for first order reaction is s–1 or
not be same as the stoichiometric coefficient of the
min–1 or time–1.
reacting species in a balanced chemical equation, e.g.
for a general reaction,
Q.14 A reaction is of second order with respect to a reactant.
aA + bB  cC + dD
How is its rate affected if the concentration of the Rate = k [A]x[B]y
reactant is Rate constant (k) is equal to the rate of reaction when
(i) doubled? molar concentration of reactants is unity.
(ii) reduced to half? Its unit depends upon the order of reaction.
[Delhi 2014C: All India 2012: Delhi 2009; (i) Zero order
Foreign 2009, 2008] (ii) Second order
11
Chemical Kinetics

Q.16 A reaction is of second order with respect to a reactant. Q.22 Discuss any four factors which affect the rate of a
How is the rate of reaction affected, if the concentration chemical reaction. [Delhi 2010C; All India 2008]
of the reactant is reduced to half? What is the unit of OR
rate constant for such a reaction?
List the factors on which the rate of a chemical reaction
[Delhi 2014C; All India 2011]
depends. [Delhi 2008: All India 2008: Foreign 2008]
Sol. Attempt yourself
The unit of rate constant is L mol–1 s–1 Sol. Factors influencing the rate of a chemical reaction are
(second order reaction) (i) Nature of reactants Different reactants require
different amount of energies for breaking the old
Q.17 Define bonds and for the formation of new bonds. Hence,
(i) Order of reaction the reactivity of a substance is related to the ease
(ii) Elementary step in a reaction. [Foreign 2011] with which the specific bonds are broken or formed,
Sol. (i) Attempt yourself
e.g. 2NO+ O2  2NO2 (fast)
(ii) Each step of a complex reaction is called the
2CO + O2  2CO2 (slow)
elementary step of the reaction.
(ii) Concentration of reactants Rate of reaction is directly
Q.18 List two main differences between order of a reaction proportional to the concentration of the reactants.
and molecularity of a reaction. [Delhi 2011C] (iii) Temperature Rate of reaction increases with increase
OR in temperature.
Distinguish between molecularity and order of a (iv) Catalyst It alters the rate of reaction without being
reaction. [All India 2010; Delhi 2008C] consumed in the reaction. It provides an alternative
Sol. Refer to solution 12 path to the reaction with a low energy barrier.

Q.19 Identify giving reasons, the reaction order from each

Q.23 Explain the difference between the average rate and
of the following rate constants.
(i) k = 2.3 × 10–5 L mol–1 s–1 instantaneous rate of a chemical reaction.
(ii) k = 3.0 × 10–4 s–1 [Delhi 2011C] [All India 2010C]
Sol. (i) Unit of k indicates that the reaction is of second Sol. Average rate of reaction It is defined as the change in
order reaction. the concentration of any one of the reactants or
(ii) Unit of k indicates that it is a first order reaction. products over a long time interval.

Q.20 Explain the following terms. Changein concentration

(i) Rate determining step of a reaction. Average rate of reaction = Time int erval
(ii) Molecularity of a reaction. [All India 2011C, 2010]
Sol. (i) The slowest step in the reaction mchanism is the For a reaction, R 
P
rate determining step of a reaction.
(ii) Molecularity of a reaction refer to solution 12. [R] [R]
rav = –  
t t
Q.21 A reaction is of first order in reactant A and of second
order in reactant B. How is the rate of this reaction Instantaneous rate of reaction At any instant of time is
affected when define as the rate in change in concentration of any
(i) the concentration of B alone is increased to three times? one of the reactants or products at that particular instant
(ii) the concentrations of A as well as B are doubled? of time.
[Delhi 2010] For a reaction, R  P
Sol. Since, the reaction is of first order wrt A and second
order wrt B, then the rate law can be given as, d[R] d[P]
rinst =  [d = very small interval of time.]
(Rate)1 = k [A] [B]2 dt dt
(i) When the concentration of B is increased to three
times (3B), the rate would be
Q.24 Define the following.
(Rate)2 = k [A] [3B]2
(Rate)2 = 9k [A] [B]2 = 9 × (Rate)1 (i) Elementary step in a reaction
Rate is increased by 9 times. (ii) Rate of a reaction [All India 2009; Foreign 2009]
(ii) (Rate)3 = k[2A] [2B]2 Sol. (i) Elementary step in a reaction (Attempt yourself)
(Rate)3 = 2 × 2 × 2 × k [A] [B]2 = 8 × (Rate)1 (ii) Rate of a reaction (Attempt yourself)
 Rate is increased by 8 times.

12
 Chemical Kinetics

Q.25 Explain the term order of reaction. Derive the unit for Q.28 For a chemical reaction, what is the effect of a catalyst
first order rate constant. [Delhi 2009C] on the following?
Sol. Order of a reaction Refer to solution 4. (i) Activation energy of the reaction.
Unit of rate constant for first order, (ii) Rate constant of the reaction. [All India 2008C]
Sol. (i) A catalyst decreases or increases the activation
dx
Rate =  k[A] energy of the reaction. It provides an alternative
dt
path to the reaction.
molL1 (ii) A catalyst increases the rate of a reaction therefore,
  k(molL1 ) rate constant of the reaction increases.
s
k = s–1 Three Marks Questions
Q.29 A reaction is second order wrt A and first order wrt B.
Q.26 What is meant by rate constant, k of a reaction? If the (i) Write the differential rate equation.
concentration be expressed in mol L–1 units and time in (ii) How is the rate affected on increasing the
seconds, what would be the unit of k. concentration of A three times?
(i) for a zero order reaction and (iii) How is the rate affected when the concentrations
(ii) for a first order reaction? [Delhi 2008; Foreign 2008] of both A and B are doubled? [HOTS: Delhi 2013]
Sol. The rate constant, k is equal to the rate of a reaction Sol. A reaction is second order w.r.tA and first order w.r.t. B.
when the concentration of the reactants is unity. Its
unit depends upon the order of reaction. d[R]
(i) Differential rate equation = (Rate)1= = k [A]2 [B]
Unit of k dt
(i) For a zero order reaction, rate= k [R]0 (ii) When the concentration of A is increased three
times, i.e. 3A then
Rate molL1s 1
k=  (Rate)2 = k [3A]2 [B] = 9K[A]2 [B] = 9 (Rate)1
[R]0 [molL1 ]0
This shows that rate will be increased 9 times to the
k = mol L–1 s–1 initial rate.
(ii) For first order reaction, rate = k [R] (iii) when concentrations of both A and B are doubled
then, (Rate)3 = k [2A]2 [2B] = k 8[A]2 [B]
Rate mol L1s 1
k=  = s–1 = 8 K [A]2 [B] = 8 (Rate)1
[R] mol L1
This shows that rate will be increased 8 times to the
initial rate.
Q.27 The decomposition of NH3 on platinum surface is a
zero order reaction. What are the rates of production of
Q.30  2NO (g) contributes
The reaction : N2 (g) + O2 (g) 
N2 and H2 if k = 2.5 × 10–4 mol L–1 s–1?
[Delhi 2008 : All India 2008; Foreign 2008] to air pollution whenever a fuel is burnt in air at a high
temperature. At 1500K, equilibrium constant K for it is
Sol.  N2(g) + 3H2(g)
2NH3(g)  1.0 × 10–5. Suppose in a case [N2] = 0.80 mol L–1 and
[O2] = 0.20 mol L–1 before any reaction occurs. Calculate
1 [NH 3 ]
Rate reaction =  the equilibrium concentrations of the reactants and the
2 t
product after the mixture has been heated in 1500 K.
[N 2 ] 1 [H 2 ] [All India 2012]
= 
t 2 t Sol. N 2 (g)  O2  2NO(g) K  1 10 5

For zero order reaction, rate of reaction = k Initia conc. 0.80 molL1 0.20molL 1
0
At equilibrium 0.80 – x 0.20  x x
= 2.5 × 10–4 mol L–1 s–1
[N 2 ] [NO]2
 2.5  10 4 molL1s 1 K
t [N 2 ][O 2 ]

[H 2 ]
 3  2.5  10 4 (2x) 2
t –5
1 × 10 =
(0.8  x)(0.2  x)
= 7.5 × 10–4 mol L–1 s–1

13
Chemical Kinetics

On solving by neglecting x in the denominator as it is (ii) Rate constant can be calculated by substituting the
very small, we get value of rate, [NO] and [Cl2] for any of the experiments.

4x 2 Rate 0.60
1 × 10–5 = or x = 6.32 × 10–4 k = [NO]2 [Cl ]  (0.15) 2 (0.15)
0.8  0.2 2

 [N2] = 0.7994 mol L–1, [O2 ] = 0.199 mol L–1

0.60
and [NO] = 0.001264 mol L–1 = = 177.61 mol–2 L2 min–1
0.00338
Q.31 For the reaction, (iii) Let initial rate of disappearance of Cl2 in experiment
2NO(g) + Cl2(g)  2NOCl(g) 4 is r4.
The following data were collected. All the  r4 = k [NO]2 [Cl2] = 177.51 × (0.25)2 (0.25)= 2.78 M/min
measurements were taken at 263 K.
Q.32 Consider the reaction,
Exp. Initial Initial Initial rate to 2A + B  C + D
No. [NO] [Cl2](M) disappearance Following results were obtained from experiments
(M) of Cl2(M/min.) designed to study the rate of reactions.
1. 0.15 0.15 0.60
Exp. Initial Initial rate of
2. 0.15 0.30 1.20 No. concentration formation
3. 0.30 0.15 2.40 (mol L–1) [D] (M/min.)
4. 0.25 0.25 ? [A] [B]

1. 0.10 0.10 1.5×10 –3

(i) Write the expression for rate law. 2. 0.20 0.20 3.0×10 –3
(ii) Calculate the value of rate constant and specify its 3. 0.20 0.40 6.0×10 –3
unit.
(iii) What is the initial rate of disappearance of Cl2 in (i) Write the rate law for the reaction.
experiment 4? [Delhi 2012] (ii) Calculate the value of rate constant for the reaction.
Sol. Rate law may be written as (iii) Which of the following possible reaction
Rate = k [NO]p [Cl2]q mechanisms is consistent with the rate law?
The initial rate becomes I. A + B  C+ E (slow)
(Rate)0 = k [NO]p [Cl2]q A + E  D (fast)
Comparing experiments 1 and 2, II. B  C + E (slow)
(Rate)1 = k (0.15)p (0.15)q = 0.60 ......(i) A + E  F (fast)
p q
(Rate)2 = k (0.15) (0.30) = 1.20 ......(ii) A + F  D (fast) [HOTS: Foreign 2012]
Dividing eq. (ii) by eq.(i), Sol. Rate law may be written as
Rate = k[A]p [B]q
(Rate) 2 k(0.15) p (0.30) q 1.20 Comparing experiments (2) and (3), we g et
 
(Rate)1 k(0.15) p (0.15) q 0.60 (Rate)2 = k (0.2)p (0.2)q = 3 × 10–3 ....(i)
(Rate)3 = k (0.2)p (0.4)q = 6 × 10–3 ....(ii)
or 2q = 21  q = 1
Dividing eq. (ii) by eq. (i), we get
 Order with respect to Cl2 = 1
Comparing experiments 1 and 3, (Rate)3 k(0.2) p (0.4) q 6  10 3
 
(Rate)1 = k (0.15)p (0.15)q = 0.60 ........(iii) (Rate) 2 k(0.2) p (0.2) q 3 10 3
(Rate)3 = k (0.30)p (0.15)q = 2.40 ........(iv)
Dividing eq. (iv) by eq.(iii) or 2q = 2, q = 1
Comparing experiments (i) and (ii)
(Rate) 2 k(0.30) p (0.15) p 2.40 (Rate)1 = k (0.1)p(0.1)q = 1.5 × 10–3 .....(iii)
 
(Rate)1 k(0.15) p (0.15) p 0.60 (Rate)2 = k (0.2)p(0.2)q = 3.0 × 10–3 .....(iv)
Dividing eq.(iv) by eq. (iii), we g et
or 2p = 4  2p = 22  p = 2
Thus, order with respect to NO is 2. 3  10 3 k(0.2) p (0.2)q

Rate law = k [NO]2 [Cl2] 1.5 103 k(0.1) p (0.1)q
(i) The rate law for the reaction
Rate = k [NO]2[Cl2] 2 = (2)p (2)q

14
 Chemical Kinetics

p
where, q = 1, 1 = 2 , Q.34 The data given below is for the reaction,
20 = 2p 2N2O5(g)  2NO2(g) + O2(g)
p=0 S. N 2 O5 Rate of
No. (mol L–1) disappearance of
(i) Thus, the rate law is rate = k [A]0 [B] = k [B] N 2 O5
(ii) Rate = k [B] (mol L–1min–1)
1. 1.13 × 10–2 34 × 10–5
Rate 3 10 3 2. 1.84 × 10–2 25 × 10–5
k=   15 10 3 min 1 3. 0.62 × 10–2 18 × 10–5
[B] 0.2
Determine for this reaction,
(iii) B  C + E (slow) is the possible reaction which is (i) order of reaction, (ii) rate law
consistant with the rate law, rate = k [B]. (iii) rate constant [All India 2008C]
Sol. Let the rate law in terms of rate of disappearance of
N2O5 be
Q.33 The following results have been obtained during kinetic
Rate = k [N2O5]a
studies of the reaction:
34 × 10–5 = k (1.13 × 10–2)a ......(i)
2A + B  C + D 25 × 10–5 = k (0.84 × 10–2)a ......(ii)
Divide eq. (i) by eq. (ii), we get
Exp. [A] [B] Initial rate of
34  105 k(1.13  102 ) a
No. formation of [D] 
1. 0.1M 0.1M 6.0×10 –3 M min–1 25  10 5 k(0.84  10 2 ) a
2. 0.3M 0.2M 7.2×10 –3 M min–1
3. 0.3M 0.4M 2.88×10 –2 M min–1
1.36 = (1.35)a
4. 0.4M 0.1M 2.40×10 –2 M min–1 a=1
(i) Order of reaction = 1
(ii) Rate = k [N2O5] (Rate law expression)
Determine rate law and the rate constant for the reaction.
(iii) Rate constant
[Delhi 2010 C]
Sol. Let the rate law in terms of rate of formation of D be Rate 34  10 5
k=  2
 30.09  10 3 min 1
[N 2 O 5 ] 1.13  10
d[D] dx
 = k [A]a [A]b
dt dt
Integrated Rate equation, Pseudo First order Reaction
1. 6.0 × 10–3 = k (0.1)a (0.1)b .....(i) Q.35 A first order reaction is found to have a rate constant,
2. 7.2 × 10–3 = k (0.3)a (0.2)b .....(ii) k= 5.5 ×10–14 s–1. Find the half-life of the reaction.
3. 2.88 × 10–2 = k (0.3)a (0.4)b .....(iii) [All India 2013]
4. 2.40 × 10–2 = k (0.4)a (0.1)b .....(iv) Sol. Given, k = 5.5 × 10–14 s–1
Divide eq. (iv) by eq.(i), we get For first order reaction,
4 = (4)a 0.693 0.693
t1/2 = = = 0.126 × 1014s= 1.26 × 1013s
a=1 k 55  10 14
Divide eq. (iii) by eq.(ii), we get
4 = (2)b Q.36 If half-life period of a first order reaction is X and 3/4th
22 = (2)b life period of the same reaction is y, how are x and y
b=2 related to each other? [Delhi 2013C]
Order with respect to A = 1 Sol. For first order reaction ,
Order with respect to B = 2 0.693 0.693
k= 
t 1/ 2 x
d[D]
Rate law = = k[A] [B]2
dt
3 3
For th life period, x = a
On putting the vale of 'A' and 'B' in any equation say (i) 4 4
6.0 × 10–3 M min–1 = k (0.1 M) (0.1 M)2
3 1
 k = 6 M–2 min–1 a–x=a– a= a
4 4

15
Chemical Kinetics

Sol. (i) The reaction is of zero order.

2.303 a
 k = y log (a  x) (ii) For zero order reaction, [R] = –kt + [R0].Compare
with equation of a straight line (y = mx + c). If we plot
0.693 2.303 a [R] against t, we get a straight line with slope = – k and
 log intercept equal to [R0],
x y a/4

0.693 2.303
 2 log 2 [R0 ]
x y
[R] k = –Slope
0.693 0.693  2

x y

y = 2x Time(t)
Alternate method
 For first order,, Variation in the concentration
t1/2 = x and amount left (a – x) after the period 'y' vs time plot for a zero order reaction.
3 1
a–x=1– 
4 4 Q.39 Hydrogen peroxide, H2O2(aq) decomposes to H2O(l)
and O2(g) in a reaction that is first order in H2O2 and
1
 (where n = number of half-life) has a rate constant k = 1.06 × 10–3 min–1.
2n
(i) How long will it take for 15% of a sample of H202 to
1 1 1 decompose?
On comparing  , ,n  2
4 2n 22 (ii) How long will it take for 85% of the sample to
 y = T = n × t1/2 = 2 × x decompose? [Delhi 2014C, Foreign 2009]
i.e. y = 2x Sol. (i) When 15% of a sample of H2O2 is decomposed
For a first order reaction,
Q.37 Define the following terms.
2.303 [R ]
(i) Half-life of a reaction (t1/2). k= log 0
t [R]
(ii) Rate constant (k) [Delhi 2015C]
Sol. (i) Half-life (t1/2) of a reaction is the time in which the Given, k = 1.06 × 10–3 min–1,
concentration of a reactant is reduced to one half of its [R0] = 100 M
initial concentration. [R] (after time, t) = 100 – 15 = 85 M
(ii) Rate constant (k) is equal to the rate of reaction
when molar concentration of reactants is unity. Its unit 2.303 100
t= log
is depend upon the order of reaction 1.06  10 3 85

2.303
Q.38 For a chemical reaction, R P, the variation in the t= log1.176
1.06  10 3
concentration of R versus time (t) plot is given as

2.303  0.0704
t= = 153.3 ,om
1.06  10 3

[R] (ii) When 85% of a sample of H2O2 is decomposed [R]

= 100 – 85 = 15 M

2.303 100 2.303

t= log = log 6.667
t 1.06  10 3 15 1.06  10 3

(i) Predict the order of the reaction. 2.303  0.8240

t= = 1790.05 min
(ii) What is the slope of the curve? [Delhi 2014] 1.06  10 3
16
 Chemical Kinetics

Q.40 Define half-life of a reaction. Write the expression of  n log 2 = log 1.43
half-life for n × 0.3010 = 0.1553,
(i) zero order reaction 0.1533
(ii) first order reaction [Foreign 2014] i.e. n= = 0.515
0.3010
Sol. Half life(t1/2) of a reaction is the time in which the
  Total time (T) = n × t1/2
concentration of ractant is reduced to one half of its
initial concentration. 40
 t1/2 = = 77.7 min–1
0.515
[R 0 ]
(i) For a zero order reaction, t1/2 =
2k
Q.42 A reactant has a half-life of 10 min.
(i) Calculate the rate constant for the first order reaction.
0.693
(ii) For first order reaction t1/2 = (ii) What fraction of the reactant will be left after an
k
hour of the reaction has occurred? [Delhi 2011C]
0.693 0.693
Q.41 A first order reaction takes 40 min for 30% Sol. (i) k = t   0.0693min 1
decomposition. Calculate t1/2 for this reaction. 1/ 2 10
(Given, log 1.428 = 0.1548) n
1
[Delhi 2013; All India 2008] (ii) N = N0  
Sol. For a reaction 2

Total time 60
A 
 P where, n = = =6
t1/ 2 10
t0 a 0
tt (a  x) x N 1 1
6

  
For 30% decomposition, it takes 40 min which means N0  2  64
after 40 min, reactant left 70% of its initial concentration. [Where, N0 = initial amount of reactant and
N = amount of reactant left after time.
70 7
Thus, (a  x)  a  a
100 10 Q.43 What are pseudo first order reactions? Give one example
of such reactions. [All India 2011]
2.303 a
k=  log Sol. Pseudo first order reactions The reaction which is
t ax bimolecular but has order one, is called pseudo first
order reaction, e.g. acidic hydrolysis of ester.
2.303 a
or k  log
40 (7 /10)a 
CH3COOC2H5 + H2O 
H
 CH3COOH + C2H5OH

2.303 Q.44 In a first order reaction, the concentration of the reactant

 log1.428 is reduced from 0.6 mol L–1 to 0.2 mol L–1 in 5 min.
40
Calculate the rate constant of the reaction.
 k = 0.00891 min–1
[All India 2011C]
 Half - life of the reactant (t1/2) Sol. Rate constant,
0.693 0.693 2.303 [R ]
   77.76 min log 0
k 0.00891 k=
t [R]
Alternate method Given, [R0] = 0.6 mol L–1
[R] = 0.2 mol L–1, t = 5 min
100
 a–x=
2n 2.303 0.6
k= log
5 0.2
100
 70 = 2.303
2n log 3
k= [log 3 = 0.477]
[where a – x = amount left, n = no. of half-life] 5

2.303
100 k=  0.4771 = 0.2197 min–1
2n = 5
70
17
Chemical Kinetics

Q.45 The rate constant for a zero order reaction in Ais 0.0030 where, k = Rate constant
mol L–1s –1. How long will it take for the initial a = initial concentration
concentration of A to fall from 0.10 M to 0.075 M? (a – x) = concentration after time 't'.
[Delhi 2010; Foreign 2010] When a first order reaction is 25% complete in 20 min.
Sol. For zero order raction, a = 100, a – x = 100 – 25 = 75, t = 20 min
[R 0 ]  [R]
Rate constant, k = 2303 a 2303 100
t k= log  log
t ax 20 75
Give, [R0] = 0.10 M
[R] = 0.075 M and k = 0.0030 mol L–1 s–1 2303
= [log 4  log 3]  0.0143min 1
[R 0 ]  [R] t
t=
k For 75% completion of reaction,
a = 100, a – x = 100 – 75 = 25, k = 0.0143 min–1
0.10  0.075
t= = 8.33 s 2303 a 2.303 100
0.0030 log  log
t=
k a  x 0.0143 25
Q.46 Show that for a first order reaction, the time required
2303
for half the change (half-life period) is independent of = log 4  96.961min
0.0143
initial concentration. [Delhi 2009C]
Or
Derive the general form of expression for the nall-liie of Q.48 Following data are obtained for the reaction :
first order reaction. [Delhi 2008; All India 2008]
1
Sol. For a first order reaction, rate costant N2O5  2NO2 + O2
2
2.303 [R ]
k= log 0
t [R] t/s 0 300 600
[N2O5] / 1.6 × 10 –2 0.8 × 10 –2 0.4 × 10–2
 R0  molL–1
when t = t1/2 [R] =  
 2  (a) Show that it follows first order reaction.
(b) Calculate the half-life.
2.303 [R 0 ] (Given: log 2= 0.3010 , log 4= 0.6021) [Delhi 2017]
t1/2 = log
k  R0  Sol. When time and rate of a reaction is given then can use
 2 
  hit and trial method to find out the order of reaction by
substituting the values of defferent integrated
2.303 2.303  0.3010
t1/2 = log 2 = equation.
k k
Using data, to find out the rate constant.
0.693 t/s 0 300 600
t1/2 = [N2O5]/molL–1 1.6×10–2 0.8×10–2 0.4×10–2
k
For a first order reaction, half - life period is constant. It Using hit and trial method,
is independent of initial concentration of the reacting
species. 2303 [R]0
For first order reaction, k = log
t [R]
Three Marks Questions Here, t = 300 s, [R]0 = 1.6 × 10–2 mol L–1
Q.47 A first order reaction takes 20 minutes for 25% and [R] = 0.8 × 10–2 mol L–1
decomposition. Calculate the time when 75% the
reaction will be completed. 2303 (1.6  10 2 )molL1
k= log
[Given : log 2 = 0.3010, log 3 = 0.4771, t (0.8  10 2 )molL1
log 4= 0.6021 [All India 2017]
Sol. For a first order reaction 2303 2.303
= log 2   0.3010
2303 a t 300
K= log
t ax k = 2.31 × 10–3 s–1

18
 Chemical Kinetics

2303 (1.6  10 2 )mol L1 a

Similarly, k = log  Here, a – x =
600 (0.4  10 2 )mol L1 10

k = 2.31 × 10–3 s–1 2.303 a 2.303 a

Thus, it is proved that reaction proceed through first t= log  log
k ax 60 a /10
order kinetics as the rate constant remains same.
2.303
0.693 t= log10 t = 0.0384
(b) Half life (t1/2) = 60
k

0.693
t1/2 = s 1 Q.51 The following data were obtained during the first order
2.31  10 3 thermal decomposition of SO2C12 at a constant volume:
t1/2 = 300 s SO2Cl2 (g)  SO2(g) + Cl2(g)

Q.49 For the first order thermal decomposition reaction, the Experiment Time Total
pressure/atm
following data obtained: 1 0 0.4
C2H5Cl(g)  C2H4(g) + HC1 (g) 2 100 0.7
Time/s Total pressure/atm
0 0.30 Calculate the rate constant.
300 0.50 (Given, log 4 = 0, 6021, log 2 = 0.3010)
Calculate the rate constant. [Delhi 2014, All India 2014, Foreign 2014]
(Given: log 2 = 0.3010, log 3 = 0.4771,
Sol. SO 2 Cl2 (g) 
 SO 2 (g) Cl2 (g)
log 4 = 0.6021) [All India 2016]
Initial pressure pi 0 0
Sol. C2H5Cl(g)  C2H4(g) + HC1 (g)
After time pi  p p p
Initial pressure at t = 0, 0.30 atm
After 300s, Ptotal = 0.30 – p + p + p atm i.e. pt = pi – p + p + p = pi + p
= 0.30 + p atm  p = pt – pi
ptotal(given ) = 0.50 = 0.30 + p Thus, a = pi and a – x = pi – p = pi – (pi – pt)
 p = 0.50 – 0.30 atm = 0.20 atm = pi – pt + pi = 2pi – pt
Pressure of C2H5Cl(g) after 300 sec. Substituting the value of a and (a – x) in equation,
(pC2 H5Cl ) = 0.30 – 0.20 atm = 0.10atm
2.303 a
k= log
t ax
2.303 (PC2 H5 Cl )0
k= log
t (PC2 H5 Cl )300 2.303 pi
k= log
t (2pi  p t )
2.303 0.30 atm
= 300 log 0.10 atm Calculating rate constant (k), when t = 100 s
Given, pi = 0.4 atm adn pt = 0.7 atm
2.303 2.303
= log3   0.4771 = 3.66×10–3 s–1 2.303 pi
300 300 Then, k = 100 log (2p  p )
i t

Q.50 The rate constant for a first order reaction is 60 s–1.

How much time will it take to reduce the initial 2.303 0.4
concentration of the reactant to its l/10th value? = 100 log (2  0.4  0.7)
[All India 2015C]
Sol. For a reaction 2.303 0.4 2.303
= log  log 4
100 0.1 100
A 
 P
t0 a 0 2.303
=  0.6021  0.01387  1.387 10 2 s 1
tt ax x 100

19
Chemical Kinetics

Q.52 A first order reaction takes 100 min for completion of

2303 [R ]
60% of the reaction. Find the time when 90% of the Sol. (i) k = log 0
t [R]
reaction will be completed. [Delhi 2013C]
Sol. For the first order reaction, when t = 100 min [R0] = 0.400 M
When [R] = 0.289 M, t = 20 min
2.303 a
rate constant, k = log 2303 0.400
100 ax k= log
20 0.289
For 60% completion of the reaction,
if a = 100 % 2303
k= log1.384
a – x = 100 – 60 = 40% 20

2.303 100 2303

Then, k = log ......(i) =  0.1411 = 0.01625 min–1
100 40 20
For 90% completion of the reaction, When t = 40 min, [R] = 0.209 M
a = 100 %
2303 0.400
and a – x = 100 – 90 = 10% K= log log1.914
40 0.209
2.303 100
Then, k = log .....(ii) 2303
t 10 =  0.2819 = 0.01623 min–1
40
Substituting the value of k in eq.(ii), we have ,
Similarly, when t = 60 min, [R] = 0.151
2.303 100 2.303
log  [ log10  1] 2303 0.400
100 40 t k= log
60 0.151

1 1 100
or  log 2303
 0.4231 = 0.01623 min–1
t 100 40 k=
60

1 0.3979

100 0.01625  0.0163  0.01623
t= k=
t 100 0.3979 3
t = 251.2 min = 0.016236 min–1

2.303 [R ]
Q.53 Nitrogen pentoxide decomposes according to the (ii) k = log 0
t [R]
equation
2N2O5 (g)  4NO2(g) + O2(g) 2.303 0.4
This first order reaction was allowed to proceed at 40° 1.6236 × 10–2 = log
100 [R]
C and the data below were collected.
0.4 1.6236
log  = 0.705
[N2O5]M Time(min) [R] 2.303
0.400 0.00
0.289 20.0 0.4
0.209 40.0  antilog 0.705
[R]
0.151 60.0
0.109 80.0
0.4
 5.070
[R]
(i) Calculate the rate constant. Include units with your
answer. 0.4
or [R] =  0.07889
(ii) What will be the concentration of N2O5 after 100 5.070
min? (iii) Initial rate = k [N2O5] = 0.016236 × 0.4
(iii) Calculate the initial rate of reaction. [Delhi 2011] = 0.00649 mol L–1 min–1

20
 Chemical Kinetics

Q.54 The thermal decomposition of HCOOH is a first order Q.56 A first order reaction has a rate constant value of 0.00510
reaction with a rate constant of 2.4 × 10–3 s–1 at a certain min–1. If we begin with 0.10 M concentration of the
temperature. How long will it take for three fourth of reactant, how much of the reactant will remain after
initial quantity of HCOOH to decompose? 3.0 h?
(log 0.25 = – 0.6021) [All India 2011] [Foreign 2011. 2009: Delhi 2009; All India 2009]
Sol. Three fourth of initial quantity of HCOOH is
Sol. Given, k = 0.00510 min–1, [R0 ] = 0.10 M and
decomposed means that initial concentration = [R0] and
t = 3 h = 3 × 60 min
concentration after time,
[R 0 ] 2.303 [R ]
t= t= log 0
4 k [R]
k = 2.4 × 10–3 s–1
Thus, for the first order reaction, rate constant 2.303 0.10
3 × 60 = log
0.00510 [R]
2.303 [R ]
k= log 0
r [R] 0.10 180  0.00510
log  = 0.3986
[R] 2.303
2.303 [R 0 ]
2.4 × 10–3 s–1 = log
r [R 0 ] / 4
0.1
 antilog 0.3986
2.303 [R]
t=  log 4
2.4  10 3
0.1
 2.503
2.303 [R]
or t =  0.6021 = 5.77 × 102 s
2.4  103
0.1
[R]   0.0399 M
Q.55 Nitrogen pentoxide decomposes according to equation, 2.503
2N2O5(g)  4NO2(g)+O2(g)
This first order reaction was allowed to proceed at 40° Q.57 The decomposition of phosphine, PH 3 proceeds
C and the data below were collected.
according to the following equation:
[N2O5]M Time(min) 4PH3(g)  P4(g) + 6H2 (g)
0.400 0.00 It is found that the reaction follows the following rate
0.289 20.0 equation
0.209 40.0 Rate = k [PH3]
0.151 60.0 The half-life of PH3 is 37.9 s at 120°C.
0.109 80.0 (i) How much time is required for 3/4th of PH3 to
decompose?
(i) Calculate the rate constant. Include units with your
answer. (ii) What fraction of the original sample of PH3 remains
(ii) Calculate the initial rate of reaction. behind after 1 min? [All India 2010; Foreign 2009]
(ii) After how many minutes will [N2O6] be equal to Sol. Given, t1/2 = 37.9s, initial concentration = [R0]
0.350 M? [Foreign 2011] [R 0 ] 3
Sol. (i) Refer to solution 19 (i). concentration after time, t = (because th of
4 4
(ii) Refer to solution 19 (iii).
PH3 is decomposed).
2.303 [R ]
(iii) k = log 0
t [R] 0.693 0.693 1
(i) k = t  s
1/ 2 37.9
2.303 0.400M
t= 2
log
1.6236  10 0.350M 2.303 [R ] 2.303
t= log 0  log 4
2.303 k [R 0 ] 0.693
t=  log1.143 37.9
1.6236  102

2.303 2.303  37.9  0.6020

t=  0.0581 = 8.24 min or t = = 75.82 s
1.6236  102 0.693

21
Chemical Kinetics

Q.58 The decomposition of a compound is found to follow a

0.693
(ii) t = 1 min = 60s and k = = 0.0183 s–1 first order rate law. If it takes 15 min for 20% of original
37.9
material to react, calculate
2.303 [R ] (i) the rate constant.
t= log 0 (ii) the time at which 10% of the original material remains
k [R]
unreacted. [Delhi 2010 C]
2.303 [R ] Sol. (i) 20% decomposition means [R0] = 100,
60 = log 0 and [R] = 100 – 20 = 80
0.0183 [R]
2.303 [R ]
[R 0 ] 60  0.0183 k= log 0
or log   0.4763 t [R]
[R] 2.303
2.303 100
[R 0 ] log
= anti log 0.4768 15 80
[R]
2.303 2.303
[R 0 ] k= log1.25 =  0.0969 = 0.0148 min–1
= 2.992 15 15
[R] (ii) Time at which 10% of the original material remains
Let the intial amount is 100, unreacted, i.e.
100 [R]0 = 100, [R] = 10
 =[R]  [R] = 33.41 %
2.992 2.303 [R ]
t= log 0
Alternate method k [R]
a 3 1 2.303 100
(i) (a)  a – x (amount left) = n
 1  t= log (log 10 = 1)
2 4 4 0.0148 10
1 1 1 1 2.303  1
  n  2  n
4 2 2 2 t= = 155.6 min
0.0148
On comparing powers Alternate method
n = 2 (no. of half -life's) (i) Given, amount left (a – x)
(b) Total time(t) = n + t1/2(half life) After 15 min = 100 – 20 = 80 %
 T = 2 × 37.9 = 75.8 sec. t (min) = 15 min, n = no. of half - life's
(ii) (a) To find fraction left (a – x) after 1 min (i.e. 60 s)
T = n × t1/2 100 100
n 2 =
n
(a) a – x = = 1.25
2 80
T 60
n = t  37.9  1.583 Taking log both the sides
1/ 2
n log 2 = log 1.25
 n × 0.3010 = 0.0969
1 1
(b) a – x = 1.583  21.583 = (a  x) 0.0969
2 n= = 0.321
Taking log of both the sides
0.3010
(b)  T = n × t1/2 (Half life)
1
1.583 log 2 = log (a  x) 0.693
15 = 0.321 × t1/2 = 0.321 ×
k
1  k = 0.0148 min or t1/2 = 46.8 min
–1

1.58 × 0.3010 = log (a  x)

100
(ii) (a) when, a – x = 0 and a – x =
2n
1
(a  x) = antilog 0.476 100 nd
100
10 = n , i.e. 2 = = 10
2 10
1 Taking log of both the sides
2.992 = (a  x)
1
n log 2 = log 10  n = = 3.32
1 0.3010
a–x= = 0.3342
2.992 (b)  T = n × t1/2  n = 3.32 × 46.8 = 155.4 min
22
 Chemical Kinetics

Q.59 In a pseudo first order hydrolysis of ester in water, the Q.61 A first order reaction is 20% completed in 5 min.
following results are obtained. Calculate the time taken for the reaction to be 60%
t (ins) 0 30 60 90 complete. [All Indio 2009C]
(Ester)M 0.55 0.31 0.17 0.085
Sol. When a first order reaction is 20% completed in 5 min,
(i) Calculate the average rate of reaction between the time [R0] = 100 M, [R] = 100 – 20 = 80 M and t = 5 min.
interval 30 to 60 s.
2.303 [R ]
(ii) Calculate the pseudo first order rate constant for the k= log 0
hydrolysis of ester. [All India 2010C] t [R]
Sol. (i) Average rate of reaction betwen the time interval 30
2.303 100
to 60s is k= log
5 80
(0.17  0.31) (0.14)
rav =  =
60  30 30 k=
2.303
log1.25
5
= 4.67 × 10–3 s–1
2.303
2.303 [R ]
log 0 k=  0.0969 = 0.0446 min–1
(ii) k = 5
t [R]
When the reaction is 60% completed, [R0] = 100 M and
At t = 30s , [R] = 0.31 M, [R0 ] = 0.55 M
[R] = 100 – 60 = 40 M
2.303 0.55 2.303 k = 0.0446 min–1
k= log  log1.774
30 0.31 30 Time taken to complete 60% reaction.
2.303 2.303 [R ]
k=  0.5099 = 1.96 × 10–2 s–1 t= log 0
30 k [R]
Average
2.303 100
log
1.91 102  1.96 102 t=
0.0446 40
k= = 1.93 × 10–2 s–1
3
2.303 2.303  0.3979
= log 2.5  = 20546 min
Q.60 The half-life for a first order reaction is 5 × 104 s. What 0.0446 0.0446
percentage of the initial reactant will react in 2 h? Alternate method
[All Indio 2009C]
t1 log[a / a  x]1
Sol. 4
Give, t1/2 = 5 × 10 s and t = 2h = 2 × 60 × 60 s  
t 2 log[a / a  x]2
0.693 0.693
k= t  [where, a – x = amount, a = initial ammount]
1/2 5  104
Given, t1 = 5 min
2.303 [R ] (a/a – x)1 = 100 / 80 = 1.25
k= log 0 (a/a – x)2 = 100 / 40 = 250
t [R]
5 log1.25 0.09
0.693 2.303 [R ] Thus, t  log 250  0.39
 log 0
5  10 4
2  60  60 [R]
5  0.398
[R ] 0.693  2  60  60  t= = 20.54 min
log 0  = 0.0433 0.0969
[R] 5  104  2.303

[R 0 ] Q.62 The half-life for decay of radioactive 14C is 5730 yr. An

=Antilog (0.0433) archaeological artifact containing wood had only 80%
[R]
of the 14C found in a living tree. Estimate the age of the
[R 0 ] [R] 1100 sample. [Delhi 2008; All India 2008; Foreign 2008]
=1.105  [R ]  1.105 = 90.497%
[R] 0

23
Chemical Kinetics

Sol. Given, t1/2 = 5730 yr, [R0] = 100 and [R] = 80 Q.64 (i) For a reaction, A + B  P, the rate is given by
Decay constant, Rate = k [A] [B]2
0.693 0.693 1 (a) How is the rate of reaction affected if the
k= t  yr concentration of B is doubled?
1/2 5730
(b) What is the overall order of reaction if A is present
0.693 [R ] in large excess?
t= log 0
k [R] (ii)Afirst order reaction takes 30 min for 50% completion.
Calculate the time required for 90% completion of this
2.303  5760 100
t= log reaction.
0.693 80
(log 2 = 0.3010) [All India 2015, Delhi 2015]
2.303  5760 Sol. (i) A + B  P,,
t= log1.25
0.693 Rate = k [A] [B]2 (given)
(a) If concentration of B is doubled, then rate of reaction
2.303  5760
=  0.0969 = 1845.37 yr = k [A] [2B]2 = 4K [A] [B]2
0.693  Rate becomes 4 times the original rate.
(b) If A is present in large excess, then the reaction will
Q.63 For the hydrolysis of methyl acetate in aqueous be independent of the concentration of A and will be
solution, the following results were obtained.
dependent only on the concentration of B. As [B]2 will
t1/2 (ins) 0 10 20
[CH3COOCH3]/molL–1 0.10 0.05 0.025 be the only determining factor in the order of reaction,
the overall order of the reaction will be two.
[All India 2016C]
(ii) For the given first order reaction, the rate constant
(i) Show that it follows pseudo first order reaction, as
for 50% completion is given by
the concentration of water remains constant.
(ii) Calculate the average rate of reaction between the 2.303 [R ]
time interval 10 to 20 s. k= log 0 .....(i)
t [R]
(Given : log 2= 0.3010, log 4= 0.6021)[All India 2015]
Sol. (i) For the hydrolysis of methyl acetate the a pseudo Here, t = time taken for 50% completion = 30 min
first order reaction, the reaction should be first order [R0] = initial concentration of reactant
with respect to ester when [H2O] k is constant. The rate [R] = final concentration of reactant
constant (k) for a first order reaction is given by let [R0] be 100 and due to 50% completion of reaction,
2.303 [R ] [R] will be
k= log 0 100 – 50, i.e. 50
t [R]
Putting values in (i), we get
Where, [R0] = initial concentration of the reactant
[R]= final concentration of the reactant. 2.303 100 2.303
At t1 = 10s k= log = log 2 = 0.023 min–1
30 50 30
2.303 0.10 For same reaction, the time required for 80% completion
k1 = log = 6.93 × 10–2 s–1
10 0.05 or reaction can be computed using the expression,
At t2 = 20s
2.303 [R ]
2.303 0.10 k= log 0
k2 = log = 6.93 × 10–2 × 10–2 s–1 t [R]
20 0.025
Here, [R] = final concentration of reactant
It can be seen that the rate constant (k) for the reaction
= 100 – 90 = 10
has a constant value under any given time interval.
Hence, the given reaction follows the pseudo first order 2.303 100
kinetics. 0.023 = log
t 10
(ii) Average rate of reaction between the time interval
of 10 - 20s is given by 2.303
t= log 10
[Ester] 0.023
Average rate =
t = 100.13 min
Thefefore, the time required for 90% completion of the
 0.025  0.05  0.025
=–   = = 0.0025 mol L–1s–1 given first order reaction is 100.13 min.
 20  10  10

24
 Chemical Kinetics

Q.65 For the hydrolysis of methyl acetate in aqueous

2.303 [R ]
solution, the following results were obtained. k= log 0
t [R]
t/s 0 30 60
[CH3COOCH3]/molL–1 0.60 0.30 0.15 2.303 100
= log
(i) Show that it follows pseudo first order reaction, as t 90 10
the concentration of water remains constant.
(ii) Calculate the average rate of reaction between the 2.303
= log(10) .....(ii)
time interval 30 to 60 s. t 90
(Given : log 2= 0.3010, log 4= 0.6021) [Delhi 2015] Equating eqs. (i) and (ii)
Sol. (i) 2.3 × 10–2 s–1
(find k using two sets which is equal in both sets) 2.303 2.303
log(102 )  log(10)
(ii) 0.005 mol L–1 s–1 Refer to solution 29 (ii), t 99 t 90

Q.66 (i) For a chemical reaction R  P, the variation in the 2


1
 t 99  2t 90
concentration, In [R] vs time(s) plot is given as t 99 t 90
Hence, time required for 99% completion of a reaction
of first order is double the time equired for 90%
completion of the reaction.
ln[R]

Temperature Dependence of the Rate of a reaction,

Collision theory of Chemical Reactions
t(s)

(a) Predict the order of the reaction. Q.67 What is the effect of adding a catalyst on
(b) What is the slope of curve? (a) Activation energy (Ea) and
(c) Write the unit of rate constant for this reaction. (b) Gibbs energy (G) of a reaction?
(ii) Show that the time required for 99% completion is [All India 2017]
double of the time required for the completion of 90% Sol. (a) Catalyst lowers the activation energy and changes
reaction. [Foreign 2015] the path of the reaction.
Sol. (i) The first order rate constant is given by , (b) A catalyst does not alter Gibbs energy (G) of a
reaction.
1 [R 0 ]
k = ln where, [R0] is the initial
t [R] Q.68 In some cases, it is found that a large more than
concentration of reactant and [R] is the concentration threshold energy, yet the reaction is slow. Why?
of reactant at time t. [Delhi 2013C]
 ln [R] = ln [R0] – kt Sol. It is due to improper orientation, or due to another factor
y = c + mx P called steric factor, which refers to the orientation of
(a) The order of the reaction is first order. the colliding molecules. These are the two main factors
(b) slope of the curve = – k which are responsible for a reaction to occur slowly.
(c) Unit of rate constant for first order reaction.
= time–1 or s–1 or min–1. Q.69 Define activation energy.
(ii) Let [R0] = 100 [All India 2012, 2011, 2010, 2009]
For the reaction which is 99% completed [R] = 1% of Sol. Attempt yourself
[R0] = 1, and for the reaction which is 90% completed,[R]
= 10% of [R0] = 10. Q.70 Define the following terms.
(i) Rate constant (k)
2.303 [R ] 2.303 100
k= log 0  log (ii) Activation energy (Ea) [Delhi 2014C]
t [R] t 99 1 Sol. (i) Rate constant is the coefficient of proportionality
related to the rate of reaction at a given temerature to
2.303 the concentrations of reactants.
= log(102 ) .....(i)
t 99 (ii) Refer to solution 3

25
Chemical Kinetics

Q.71 Define each of the following Q.74 The rate of most reactions become double when their
(i) Specific rate of a reaction. temperature is raised from 298 K to 308 K. Calculate
(ii) Energy of activation of a reaction. their activation energy? (Given, R = 8.314 J mol–1 K–1)
[All India 2014C] [Delhi 2011C]
Sol. (i) Attempt yourself Sol. Given, T1 = 298 K, T2 = 308 K and k2 / k1 = 2 and
(ii) Attempt yourself R = 8.314 J mol–1 K–1

k2 E a  T2  T1 
log k  2.303R  T T 
Q.72 How does a change in temperature affect the rate of a
reaction? How can this effect on the rate constant of a 1  1 2 
reaction be represented quantitatively?
[All India 2014C] Ea  308  298 
log 2 
Sol. Rate of reaction increases with temperature. 2.303  8.314  298  308 
Temperature coefficient is the ratio of rate constant at
temperature (T + 10) K to the rate constant at Ea  10 
2.303  8.314  298  308 
0.3010 =
temperature TK.

Rate constant at (T  10)K Ea 10

= 0.3010 = 
Rate constant at TK 2.303  8.314 298  308
It is observed that for a chemical reaction with rise in Ea = 52903.05 J mol–1
temperature by 10°, the rate constant is nearly doubled.
Q.75 The rate of a reaction becomes four times when the
Q.73 With the help of diagram, explain the role of activated temperature changes from 300 K to 320 K. Calculate the
complex in a reaction. [Delhi 2013C] energy of activation of the reaction, assuming that it
Sol. When the colliding molecules possess the kinetic does not change with temperature.
energy less than the threshold energy (Et), they require [R = 8.314 J K–1 mol–1) [All India 2010, Foreign 2008]
the energy to achive Et. This amount of energy (energy Sol. Refer to solution 8. Ans 55327.581 J mol–1
required) is known as activation energy (Ea). After
 k2 
achieving the activated energy (i.e. Ea), they reach to  Hint  4, T1  300K, T2  320K 
an activated state. This stage is different from the  k1 
reactant as wll as the product.
e.g. in the reaction between H2(g) and I2(g) activated Q.76 What is the effect of temperature on the rate constant
complex has configuration in which H–H and I – I bonds of a reaction? How can this temperature effect on rate
are breaking and H– I bonds are forming as shown constant be expressed quantitatively?
below. [Delhi 2010C, All India 2009C]
Sol. Attempt yourself
H I H I H I
+ Three Marks Questions
H I H I H I Q.77 The rate constant for the first order decomposition of
Reactants Activated Products
complex H2O2 is given by the following equation:

Potential energy diagram of this reaction is shown below 1.0  10 4

log k  14.2 – K
T
Calculate Ea for this reaction and rate constant k if its
half-life period be 200 min. (Given: R = 8.314 JK–1mol–1)
[Delhi 2016]
Sol. Calculation of activation energy, Ea
According to Arrhenius equation, k = Ae–Ea/RT
Ea
log k = log A – .....(i)
2.303RT

1.0  10 4
log k = 14.2 – .....(ii)
T
26
 Chemical Kinetics

On comparing eqs. (i) and (ii) Q.80 The decomposition of A into products has a value of
k as 4.5 × 103 s–1 at 10°C and energy of activation
Ea 1.0 104
 K 60 kJ mol–1.At what temperature would k be 1.5 × 104 s–1?
2.303RT T [Delhi 2013C]
Ea = 2.303 R × 1.0 × 104 K Sol. Given, T1 = 10°C + 273 = 283 K
= 2.303 × 1.0 × 104 K × 8.314 JK–1 mol–1
k T1 = 4.5 × 103 s–1
= 1914 × 104 J mol–1
= 191.4 kJ mol–1 Ea = 60 kJ mol–1 = 60 × 103 J mol–1
Calculation of rate constant, k T2 = ?
Given, t1/2 = 200 min = 200 × 60 s k T2 = 1.5 × 104 s–1
0.693 0.693 We know that,
k= t =
200  60
E a  T2  T1 
1/ 2
k T2
k = 5.775 × 10–5 s–1 log k  2.303R  T T 
T1  1 2 
Q.78 The rate constants of a reaction at 500 K and 700 K are On putting values,
0.02 s–1 and 0.07 s–1 respectively. Calculate the value of
1.5  10 4 60  103 Jmol 1  T2  283 
activation energy,Ea.(R = 8.314 J K– 1 mol– 1). log 4.5 103  2.303  8.314  283T 
[Delhi 2015C]  2 

Sol. Given, k1 = 0.02 s–1 , k2 = 0.07 s–1 , T1 = 500 K

, T2 = 700 K , R = 8.314 JK–1 mol–1  T  283 
0.523  3133.63  2 
 283T2 
k2 E a  T2  T1 
log k  2.303R  T  T 
1  1 2 T2  283
–4
283T2 = 1.67 × 10
0.07 Ea  700  500 
log 
0.02 2.303  8.314  500  700 
T2 – 283 = 0.0472T2
0.953 T2 = 283
Ea = 18230.35 J mol–1 T2 = 297 K
T2 = 24 °C
Q.79 For a decomposition reaction, the values of k at two
different temperatures are given below. Q.81 Rate constant 'k' of a reaction varies with temperature
k1 = 2.15 × 10–8 L /(mol.s) at 650 K 'T' according to the equation
k2\ = 2.39 × 10–7 L /(mol.s) at 700 K.
Calculate the value of Ea for the reaction. Ea  1 
log k = log A –  
(Given, log l1.11 = 1.046, R = 8.314 J K–1 mol–1) 2.303R  T 
[All India 2014C, 2009; Foreign 2009] where Ea is the activation energy. When a graph is
Sol. Given, k1 = 2.15 × 10–8 L /mol s–1 at 650 K
1
k2 = 2.39 × 10–7 L /mol s–1 at 700 K plotted for log k vs , a stright lile with a slope of
T
k2 Ea  1 1 
log k  2.303R  T  T 
– 4250 K is obtained. Calculate Ea for the reaction.
1  1 2  (R = 8.314 K–1 mol–1) [Delhi 2013]
Sol. Given, Slope = – 4250 K,
2.39  107 L / mol R = 8.314 JK–1 mol–1
log
2.15  108 L / mol From equation
Ea  1 1  Ea
=    log K = log A –
2.303  8.314  103 kJ / mol  650 700  2.303RT

Ea 700  650 Comparing with straight line equation y = mx + c

log 11.12 = 3

2.303  8.314 10 kJ / mol 4.55  105 Ea
– = – 4250
2.303R
1.046  2.303  8.314  102  4.55
Ea =  Ea = 2.303 × 8.314 × 4250 = 81.37 kJ mol–1
50
Ea = 182.25 kJ

27
Chemical Kinetics

Q.82 The rate of a reaction becomes four times when the Q.84 The decomposition of phosphine,
temperature changes from 293 K to 313 K. Calculate the 4PH3(g)  P4(g) + 6H2(g)
energy of the activation (Ea) of the reaction assuming has the rate law, rate = k [PH3].
that it does not change with temperature. The rate constant is 6.0 × 10–4 s–1 at 300 K and activation
(R = 8.314 JK–1 mol–1, log 4 = 0.6021) [Delhi 2010] energy is 3.05 × 105 J mol–1. Calcualte the value of rate
constant at 310 K.
Sol. Given, T1 = 293 K
[Given, R = 8.314 JK–1 mol–1] [Delhi 2008C]
T2 = 313 K
Sol. Given, T1 = 300 K, T2 = 310 K,
k2 / k1 = 4
Ea = 3.05 × 105 J mol–1
R = 8.314 J K–1 mol–1 k = 6.0 × 10–4 s–1 , k2 = ?
log 4 = 0.6021
k  E a  T2  T1 
log  2    
k E a  T2  T1 
log 2     k1  2.303R  T1 .T2 
k1 2.303R  T1T2 
k  3.05 105  310  300 
log  2    
Ea  313  293   k1  2.303  8.314  300  310 
log 4   
2.303  8.3014  293  313 
k  3.05 105  10
E a  20  log  2  = 1.7128
0.6021 =    k1  2.303  8.314  300  310
19.147  91709 
k2
0.6021  19.147  91709 k1 = antilog (1.7128)
Ea = = 52862.94 J mol–1
20
k2
1
Q.83 The activation energy for the reaction k1 = 5.162 × 10 = 51.62
2HI(g)  H2(g) + I2(g) is 209.5 kJ mol–1 at 581 K.
k2
Calculate the fraction of molecules having energy equal = 51.62 or k2 = 3.0972 × 10–2 s–1
6.0  10 4
to or greater than activation energy.
[All India 2010]
Five Marks Questions
Sol. Given,
Q.85 (i) Define the following terms.
Ea = 209.5 kJ mol–1 = 209500 J mol–1
(a) Activation energy
R = 8.314 JK–1 mol–1
(b) Rate constant
T = 581 K
(ii) A first order reaction takes 10 min for 25%
Fraction of molecules = x decomposition. Calculate t1/2 for the reaction.
E a [Given : log 2 = 0.3010, log 3 = 0.4771, log 4 = 0.6021)
log x = [Foreign 2015]
2.303RT
Sol. (i) (a) Activation energy Refer to solution 4 (ii).
209500 (b) Rate constant Refer to solution 4(i).
log x = (ii) Given, t = 10 min,
2.303  8.314  581
Amount of reactant decomposed in time (t = 10 min) =
log x = – 18.8323 25% if [R0] = 100, then amount of reactant left = 75% of
 [R0 ] = 75.
x = antilog (19.1677)
= 1.471 × 10–19 2.303 [R ] 2.303 100
k= log 0  log
Alternative method t R 10 75
Fraction of molecules = e–Ea/RT = 0.2303 × 0.124
209.51000
k = 0.028 min–1
8.314581
=e = e–43.37 = 1.461 × 10–19 0.693 0.693
t1/2 =  = 24.75 min
k 0.028

28
 Chemical Kinetics

EXERCISE 2
Q.1 (i) For a chemical reaction, 2A + B  A2B the rate is given Q.5 The following results have been obtained during the
by expression = k [A] [B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. kinetic studies of a chemical reaction,
Calculate the initial rate of reaction when 2A+ B  C + D
[A]0 = 0.1 mol L–1, [B]0 = 0.2 mol L–1.
(1) 8 × 10–2 (2) 8 × 10–6
Initial rate of formation of
(3) 8 × 10 –5
(4) 8 × 10–9 Experiment  A mol L1  B mol L1
D / mol L1 min 1
[NCERT EXERCISE] I 0.1 0.1 6.0  10 3
II 0.3 0.2 7.2  10 2
(ii) Calculate the rate of above reaction after [A] is reduced III 0.3 0.4 2.88  101
to 0.06 mol L–1 IV 0.4 0.1 2.40  10 2
(1) 3.89 × 10–9 (2) 3.89 × 10–5
(3) 3.89 × 10–4 (4) 3.89 × 10–7
Determine the rate constant for the reaction.
Q.2 The decomposition of NH3 on platinum surface is a (1) 12 L2 mol–2 min–1 (2) 18 L2 mol–2 min–1
zero order reaction. What is the rate of production of (3) 36 L2 mol–2 min–1 (4) 6 L2 mol–2 min–1
H2 if k = 2.5 × 10–4 mol–1 L s–1 ? [NCERT EXERCISE]
(1) 3.75 × 10–8 (2) 3.75 × 10–4
(2) 3.75 × 10–2 (3) 3.75 × 10–6 Q.6 The reaction between A and B is first order with respect
[NCERT EXERCISE] to A and zero order with respect to B. in the following
table :
Q.3 The decomposition of dimethyl ether leads to the
formation of CH4, H2 and CO and the reaction rate is
given by :
Experiment  A mol L1  B  mol L1 Initial rate mol L1 min 1
I 0.1 0.1 2.0  102
Rate = k [CH3OCH3]3/2.The rate of reaction is followed
II  0.2 4.0  102
by increase in pressure in a closed vessel, so the rate
III 0.4 0.4 
can be expressed in terms of the partial pressure of
IV  0.2 2.0  102

dimethyl ether, i.e., Rate = k   C H 

3/2

3O C H 3
if the
Find k in experiment -1 : with the about table
pressure is measured in bar and time in minutes, then
(1) 0.2 min–1 (2) 0.6 min–1
what are the units of rate constant?
(3) 0.8 min–1 (4) 0.4 min–1
(1) bar–3/2min–1 (2) bar–1/2min–1
–1/2 –1
[NCERT EXERCISE]
(3) bar min (4) bar–1
[NCERT EXERCISE]
Q.7 Calculate the half -life of a first order reaction with
rate constant 200 s–1
Q.4 (i) A reaction is second order with respect to a reactant.
(1) 3.46 × 10–5 sec–1 (2) 3.46 × 10–7 sec–1
How is the rate of reaction affected if the concentration –8 –1
(3) 3.46 × 10 sec (4) 3.46 × 10–3 sec–1
of the reactant is doubled?
[NCERT EXERCISE]
(1) 4 times (2) 6 times (3) 8 times (4) 2 times
[NCERT EXERCISE]
Q.8 The half-life for radioactive decay of 14C is 5730 yr.
An archaeological article containing wood had only
(ii) A reaction is second order with respect to a reactant.
80% of the 14C that is found in a living tree. Estimate
How is the rate of reaction affected if the concentration
the age of the sample.
of the reactant is reduced to half ?
(1) 1845 year (2) 9000 year
(1) 1/2 times (2) 1/8 times
(3) 9220 year (4) 3690 year
(3) 1/16 times (4) 1/4 times
[NCERT EXERCISE]

29
Chemical Kinetics

Q.9 The experimental data for decomposition of N2O5 Q.15 The following data were obtained during the first order
[2 N2O5  4NO2+O2] in gas phase at 318 K are given thermal decomposition of SO2CI2 at a constant volume.
below: SO2CI2(g)  SO2 (g) + CI2 (g)

t (s ) 0 400 800 1200 1600 2000 2400 2800 3200

Experiment Time / s 1 Total pressure / atm
102   N2O5  mol L1 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
1 0 0.5
Calculate the rate constant k for above reaction
2 100 0.6
(1) 4.82 × 10–8 sec–1 (2) 4.82 × 10–16 sec–1
–6 –1
(3) 4.82 × 10 sec (4) 4.82 × 10–4 sec–1 Calculate the rate of the reaction when total pressure is
[NCERT EXERCISE] 0.65 atm.
(1) 7.8 × 10–4 atm sec–1 (2) 15.6 × 10–4 atm sec–1
Q.10 The rate constant for a first order reaction is 60 s-1.
(3) 3.9 × 10–4 atm sec–1 (4) 31.2 × 10–4 atm sec–1
How much time will it take to reduce the initial
[NCERT EXERCISE]
concentration of the reactant to its 1/16th value?
(1) 4.6 × 10–4 sec (2) 2.3 × 10–4 sec
–2 Q.16 The rate constant for the decomposition of
(3) 4.6 × 10 sec (4) 2.3 × 10–1 sec
hydrocarbons is 2.418 × 10-5 s-1 at 546 K. If the energy
[NCERT EXERCISE]
of activation is 179.9 kJ/mol, what will be the value of
Q.11 During nuclear explosion one of the products is 90Sr preexponential factor?
with half-life of 28.1 yr. If 1 µ g of 90Sr was absorbed (1) 3.9 × 1014 sec–1 (2) 3.9 × 1012 s–1
in the bones of a newly born baby instead of calcium, (3) 7.8 × 1012 sec–1 (4) 3.8 × 1020 sec–1
how much of it will remain after 60 yr if is not lost [NCERT EXERCISE]
metabolically?
(1) 0.2280 µ g (2) 0.448 µ g Q.17 Consider a certain reaction; A  products with
(2) 0.160 µ g (3) 0.32 µ g k = 2.0 × 10-2 s-1. Calculate the concentration of A
[NCERT EXERCISE] remaining after 100 s, if the initial concentration of A
is 1.0 mol L-1.
Q.12 For a first order reaction, how many times is the time (1) 0.0135 mol L–1 (2) 0.00135 mol L–1
required for 99% completion than for completion of (3) 0.135 mol L–1 (4) 0.270 mol L–1
90% of reaction. [NCERT EXERCISE]
(1) 4 times (2) 6 times
(3) 8 times (4) 2 times Q.18 Sucrose decomposes in acid solution into glucose and
[NCERT EXERCISE] fructose according to the first order rate law, with
t1/2 = 3.00 h. What fraction of sample of sucrose remains
Q.13 A first order reaction takes 40 min for 30% after 8 h?
decomposition. Calculate t1/2. for the reaction (1) 0.0158 (2) 0.30
(1) 140 min (2) 250 min (3) 0.40 (4) 0.158
(3) 77.78 min (4) 36.9 min
[NCERT EXERCISE]
[NCERT EXERCISE]
Q.19 The decomposition of hydrocarbon follows the
Q.14 For the decomposition of azoisopropane to hexane and
equation k = (4.5 × 1011 s-1 ) e–28000 K/T. Calculate the
nitrogen at 543 K, the following data are obrained.
activation energy Ea.
Calculate the rate constant for the reaction
(1) 23.2796 kJ/mole (2) 0.232796 kJ/mole
(3) 0.0232796 kJ/mole (4) 232.792 kJ/mole
t  s p  mm of Hg 
[NCERT EXERCISE]
0 35.0 Q.20 The rate constant for the first order decomposition of
360 54.0 H 2 O 2 is given by the following equation,
720 63.0 log k = 14.34 – 1.25 × 104 K/T. At what temperature
will its half-life period be 256 minutes?
(1) 4.42 × 10–3 sec–1 (2) 1.11 × 10–5 sec–1 (1) 66.9 K (2) 669 K
(3) 8.84 × 10–3 sec–1 (4) 2.27 × 10–3 sec–1 (3) 0.669 K (4) 6.69 K
[NCERT EXERCISE] [NCERT EXERCISE]

30
 Chemical Kinetics

Q.21 The decomposition of A into product has values of rate Q.27 Consider the figure and mark the correct option.
constant as 4.5 × 10 3 s –1 at 10°C and energy of
Activated complex
activation 60 kJ mol–1. At what temperature would K
be 1.5 ×104 s–1.
E1
(1) 24°C (2) 75°C
Products
(3) 100°C (4) 50°C
E2
[NCERT EXERCISE]
Reactants

Q.22 The time required for 10% completion of a first order

reaction at 298 K is equal to that required for its 25% (1) Activation energy of forward reaction is E1 + E2
completion at 308 K. If the value of A is 4 × 1010 s–1. and product is less stable than reactant.
Calculate Ea. (2) Activation energy of forward reaction is EI+E2 and
product is more stable than reactant.
(1) 0.7664 kJ/mole (2) 766.4 kJ/mole
(3) Activation energy of both forward and backward
(3) 7664 kJ/mole (4) 76.640 kJ/mol
reaction is E1+E2 and reactant is more stable than
[NCERT EXERCISE] product.
(4) [NCERT EXEMPLAR]
Q.23 The rate of a reaction quadrauples when the temperature
changes from 293 K to 313 K. Calculate the energy of Q.28 Consider a first order gas phase decomposition reaction
activation of the reaction assuming that it does not given below:
change with temperature. A (g) 
 B(g)  C(g) The initial pressure of the system
(1) 52.86 kJ mol–1 (2) 104 kJ mol–1 before decomposition of A was pi. After lapse of time
(3) 208 kJ mol–1 (4) 26 kJ mol–1 ‘t’, total pressure of the system increased by x units
[NCERT EXERCISE] and became‘p’,The rate constant k for the reaction is
given as ______
Q.24 The role of a catalyst is to change_______. 2.303 Pi 2.303 Pi
(1) k  log (2) k  t
log
2Pi – Pt
(1) Gibbs energy of reaction t Pi – x
(2) enthalpy of reaction
2.303 Pi 2.303 Pi
(3) activation energy of reaction (3) k  t
log
2Pi – Pt (4)
k
t
log
2pi – x
(4) equilibrium constant
[NCERT EXEMPLAR] [NCERT EXEMPLAR]

Q.29 According to Arrhenius equation rate constant k is equal

Q.25 In the presence of a catalyst, the heat evolved or to A e –Ea/RT. Which of the following options represents
absorbed during the reaction_________
1
(1) increases the graph of In k vs ?
t
(2) decreases
(3) remains unchanged
(4) may increase or decrease
In k
[NCERT EXEMPLAR] (1) In k (2)
1/T
Q.26 Activation energy of a chemical reaction can be 1/T
determined by_________
(1) determining the rate constant at standard
temperature (3) In k (4) In k
(2) determining the rate constants at two temperatures
1/T
(3) determining probability of collision 1/T
(4) using catalyst [NCERT EXEMPLAR]
[NCERT EXEMPLAR]

31
Chemical Kinetics

Q.30 Consider the Arrhenius equation given below and mark Q.33 Consider the graph given in figure of Q.8. which of the
the correct option following options does not show instantaneous rate of
K = Ae –Ea/RT reaction at 40th second ?
(1) Rate constant increases exponentially with V5 – V2 V4 – V2
increasing activation energy and decreasing (1) (2)
50 – 20 50 – 30
temperature.
(2) Rate constant decreases exponentially with V3 – V2 V3 – V1
(3) (4)
increasing activation energy and decreasing 50 – 30 40 – 20
temperature [NCERT EXEMPLAR]
(3) Rate constant increases exponentially with
Q.34 Which of the following statements is correct ?
decreasing activation energy and decreasing
(1) The rate of a reaction decreases with passage of
temperature.
time as the concentration of reactants decreases.
(4) Rate constant increases exponentially with (2) The rate of a reaction is same at any time during the
decreasing activation energy and increasing reaction.
temperature. (3) The rate of a reaction is independent of temperature
[NCERT EXEMPLAR] change
(4) The rate of a reaction decreases with increase in
Q.31 A graph of volume of hydrogen released vs time for concentration of reactants (s).
the reaction between zinc and dil. HCI is given in figure. [NCERT EXEMPLAR]
On the basis of this mark the correct option.
Q.35 Which of the following expressions is correct for the
V5 rate of reaction given below ?
V4 5Br(qq )  BrO 3 –  aa   6H   qq  
 3Br2(qq )  3H 2O ( I )

  Br –   H  
5  
V3
(1)
t t
V2
V1   Br –  6   H 


(2)  
t 5 t
  Br –  5   H 


20 30 40 50 (3)  
t 6 t
v – v2
(1) Average rate upto 40 s is 3   Br –    H  
40 (4) 6 [NCERT EXEMPLAR]
t t
v3 – v 2
(2) Average rate upto 40 seconds is .
40 – 30 Q.36 Which of the following graphs represents exothermic
reaction ?
v3
(3) Average rate upto 40 seconds is . Activated complex Activated complex
40
v3 – v1
Energy

Energy

(4) Average rate upto 40 seconds is

40 – 20. (i) (ii) Products
Reactants
[NCERT EXEMPLAR] Products Reactants
Reaction coordinate Reaction coordinate

Q.32 Which of the following statements is not correct about

Activated complex
order of a reaction ?
(1) The order of a reaction can be a fractional number
(2) Order of a reaction is experimentally determined
Energy

quantity. (iii) Products

Reactants
(3) The order of a reaction is always equal to the sum
of the stoichiometric coefficients of reactants in the Reaction coordinate

balanced chemical equation for a reaction. (1) (i) only (2) (ii) only
(4) The order of a reaction is the sum of the powers of (3) (iii) only (4) (i) and (ii)
molar concentration of the reactants in the rate law
[NCERT EXEMPLAR]
expression .[NCERT EXEMPLAR]
32
 Chemical Kinetics

Q.37 Rate law for the reaction A+2B C is found to be Q.41 Which of the following statements is not correct for
Rate = k [A] [B] the catalyst ?
(1) It catalyses the forward and backward reaction to
concentration of reactant ‘B’ is doubled, keeping the
the same extent.
concentration of ‘A’ constant, the value of rate constant (2) It alters G of the reaction.
will be______ [NCERT EXEMPLAR] (3) It is a substance that does not change the equilibrium
(1) the same (2) doubled constant of a reaction.
(3) quadrupled (4) halved (4) It provides an alternate mechanism by reducing
activation energy between reactants and products.
[NCERT EXEMPLAR]
Q.38 Which of the following statements is incorrect about
the collison theory of chemical reaction ? Q.42 The Value of rate constant of a pseudo first order
(1) It considers reacting molecules or atoms to be hard reaction_______
(1) depends on the concentration of reactants present
spheres and ignores their structural features.
in small amount
(2) Number of effective collisions determined the rate (2) depends on the concentration of reactants present
of reaction. in excess
(3) Collision of atoms or molecule possessing sufficient (3) is independent of the concentration of reactants
threshold energy results into the product formation (4) depends only on temperature
(4) Molecules should collide with sufficient threshold [NCERT EXEMPLAR]
energy and proper orientation for the collision to Q.43 Consider the reaction AB. The concentration of both
be effective. [NCERT EXEMPLAR] the reactants and the products varies exponentially with
time. Which of the following figures correctly describes
the change in concentration of reactants and products
Q.39 A first order reaction is 50% completed in 1.26×1014 s.
with time ?
How much time would it take for 100% completion?
(1) 1.26 × 1015 s (2) 2.52 × 1015s [B]
28
(3) 2.52 × 10 s (4) infinite
[NCERT EXEMPLAR] (1)
[A]
Time
Q.40 Compounds ‘A’and ‘B’ react according to the following
chemical equation.
[B]
Concentration®

A (g)  2B(g) 
 2C(g)
(2)
Concentration of either ‘A’or ‘B’were changed keeping
[A]
the concentrations of one of the reactants constant and
rates were measured as a function of initial Time®
concentration, Following results were obtained. Choose
the correct option for the rate equations for this reaction.

Experiment 1 2 3 (3)
Initial concentration of 0.30 0.30 0.60
[A]/ mol L–1
Initial concentration of 0.30 0.60 0.30
[B] mol L–1
Initial rate of formation of 0.10 0.40 0.20
[C]/ mol L–1 s–1

(4)
(1) Rate = k [A]2 [B] (2) Rate = k [A] [B]2
(3) Rate = k [A] [B] (4) Rate = k [A]2[B]0
[NCERT EXEMPLAR]
[NCERT EXEMPLAR]

33
Chemical Kinetics

Q.44 Rate law cannot be determined from balanced chemical Q.49 During decomposition of an activated complex
equation if __________ (1) energy is always released
(1) reverse reaction is involved_________ (2) energy is always absorbed
(2) it is an elementary reaction (3) energy does not change
(3) it is a sequence of elementary reactions (4) reactants may be formed.
(4) any of the reactants is in excess [NCERT EXEMPLAR]
[NCERT EXEMPLAR]
Q.50 According to Maxwell Boltzmann distribution of
Q.45 Which of the following statements are applicable to a energy__________
balanced chemical equation of an elementary reaction? (1) the fraction of molecules with most probable kinetic
(1) Order is same as molecularity. energy decreases at higher temperatures
(2) Order is less than the molecularity. (2) the fraction of molecules with most probable kinetic
(3) Order is greater than the molecularity. energy increases at higher temperatures
(4) Molecularity can never be zero. (3) most probable kinetic energy increases at higher
[NCERT EXEMPLAR] temperatures
(4) most probable kinetic energy decreases at higher
temperatures
Q.46 In any unimolecular reaction___________
(1) only one reacting species is involved in the rate
determining step Q.51 In the graph showing Maxwell Boltzmann distribution
(2) the order and the molecularity of slowest step are of energy,_______
equal to one (1) area under the curve must not change with increase
(3) the molecularity of the reaction is one and order is zero in temperature
(4) both molecularity and order of the reaction are one (2) area under the curve increases with increase in
[NCERT EXEMPLAR] temperature
(3) area under the curve decreases with increase in
Q.47 For a complex reaction ________ temperature
(1) order of overall reaction is same as molecularity of (4) with increase in temperature curve broadens and
the slowest step shifts to the right hand side
(2) order of overall reaction is less than the molecularity [NCERT EXEMPLAR]
of the slowest step
(3) order of overall reaction is greater than molecularity Q.52 Which of the following statements are in accordance
of the slowest step with the Arrhenius equation ?
(4) molecularity of the slowest step is never zero or (1) Rate of a reaction increases with increase in
non interger [NCERT EXEMPLAR] temperature.
(2) Rate of a reaction increases with decrease in
Q.48 At high pressure the following reaction is zero order. activation energy.
1130K (3) Rate constant decreases exponentially with increase
2NH 3(g) N 2(g )  3H 2(g )
Platinumcatalyst in temperature.
Which of the following option are correct for this (4) Rate of reaction decreases with decrease in
reaction ? activation energy. [NCERT EXEMPLAR]
(1) Rate of reaction = Rate constant
(2) Rate of the reaction depends on concentration of Q.53 Mark the incorrect statements.
ammonia. (1) Catalyst provides an alternative pathway to reaction
(3) Rate of decomposition of ammonia will remain mechanism.
constant until ammonia disappears completely. (2) Catalyst raises the activation energy.
(4) Further increase in pressure will change the rate of (3) Catalyst lowers the activation energy.
reaction. (4) Catalyst alters enthalpy change of the reaction.
[NCERT EXEMPLAR]

34
 Chemical Kinetics

Q.54 Which of the following graphs is correct for a zero order Q.55 Which of the following graphs is correct for a first order
reaction ? reaction ?

Reaction rate
t1
2

(1) (1)

[R]0
Time

t1
Reaction rate

(2) (2)
[R]0
Time
Reaction rate

(3)
(3)
Time

Time

(4)
(4)

[NCERT EXEMPLAR]
[NCERT EXEMPLAR]

ANSWER KEY
EXERCISE 2
Q.1 (i) (4) (ii) (1) Q.2 (2) Q.3 (3) Q.4 (i) (1), (ii) (4) Q.5 (4) Q.6 (1) Q.7 (4) Q.8 (1)
Q.9 (4) Q.10 (3) Q.11 (1) Q.12 (4) Q.13 (3) Q.14 (4) Q.15 (1) Q.16 (2) Q.17 (3) Q.18 (4)
Q.19 (4) Q.20 (2) Q.21 (1) Q.22 (4) Q.23 (1) Q.24 (3) Q.25 (3) Q.26 (2) Q.27 (1) Q.28 (2)
Q.29 (1) Q.30 (4) Q.31 (3) Q.32 (3) Q.33 (2) Q.34 (1) Q.35 (3) Q.36 (1) Q.37 (1) Q.38 (3)
Q.39 (4) Q.40 (2) Q.41 (2) Q.42 (2) Q.43 (2) Q.44 (1,2,3) Q.45 (1,4) Q.46 (1,2) Q.47 (1,4) Q.48 (1,3,4)
Q.49 (1,4) Q.50 (1,3) Q.51 (1,4) Q.52 (1,2) Q.53 (2,4) Q.54 (1,4) Q.55 (1,4)
35
 Chemical Kinetics

SOLUTION
1. Chemical Kinetics Q.3 (3) : Unit of rate = bar min–1

Rate
Q.1 (i) (4) : Case I Rate = k [A] [B]2 Unit of k  3/ 2
 p CH3OCH3 
= ( 2.0 × 10–6 mol–2 L–2s–1) × (0.1 × mol L–1)
× (0.2 mol L–1)2
–9 –1 –1 bar min 1
= 8.0 × 10 mol L s   bar 1/ 2 min 1
 bar  3/ 2
(ii) (1) : CaseII Concentration of A at a particlular time
= 0.06 mol L–1 Q.4 (i) (1): For a reaction, A  Products
Amount of A reacted = (0.1 – 0.06 mol L–1) Rate = k [A]2 = ka2 = R
= 0.04 mol L–1 (i) When concentration of A is doubled
Therefore, concentration B reacted i.e., [A] = 2a
1 –1 –1
Rate = k (2a)2 = 4 ka2 = 4R
  0.04 mol L = 0.02 mol L Rate of reaction would increases by 4 times.
2
Then, Concentration of B at a particular time [B] 1
(ii) (4) : When concentration of A is reduced to
= (0.2 – 0.02) mol L–1 2
= 0.18 mol L–1 1
After [A] is reduced to 0.06 mol L–1, then rate of the i.e., A  2 a
reaction is given by
2
Rate = k [A] [B]2  a 1 2 1
Rate  k    ka = R
= ( 2.0 × 106 mol–2 L2 s–1 ) × (0.06 mol L–1)  2 4 4
× (0.18 mol L–1)2
1 th
= 3.89 × 10–9 mol L–1 s–1 Rate of reaction becomes times i.e., reduced to
4
Q.2 (2) : The decomposition of NH3 on platinum surface is one fourth.
represented by the following equation
2NH3 N2 + 3H2 Q.5 (4) : Rate law may be expressed as
By dividing the equation by 2 Rate = k [A]x[B]y
1 3 (Rate)1 = 6.0 × 10–3 = k (0.1)x (0.1)y .......(i)
NH 3  N2  H2
2 2 (Rate)2 = 7.2 × 10–2 = k (0.3)x (0.2)y .......(ii)
(Rate)3 = 2.88 × 10–1 = k (0.3)x (0.4)y.......(iii)
d  NH 3  2d  N 2  3 d  H 2  (Rate)4 = 2.40 × 10–2 = k (0.4)x (0.1)y.......(iv)
Rate    
dt dt 2 dt
 Rate   6.0 103 k  0.1  0.1
x y
For zero order reaction, rate = k 
 Rate  2.40 102 k  0.4   0.1
x y

 d  NH 3  2d  N 2  3 d  H 2 
So,   =k
dt dt 2 dt
1  0.1
x x
1
= 2.5 × 10 mol L s –4 –1 -1
or   
4  0.4  x  4 
d  H2 
 Rate of production of N 2   x=1
dt

 2.5  10 4
mol L1s 1   1.25  10  Rate 2 7.2 102 k  0.3  0.2 
x y

 4 1 1  
2
mol L s  Rate 3 2.88 101 k  0.3 x  0.4  y

 Rate of production of
1  0.2 
y y
1
d H2  3   
H2 
dt

  2.5  104 mol L1s 1
2
 or 4  0.4  y  2 

= 3.75 × 10–4 mol L–1 s–1  y=2

36
Chemical Kinetics

Rate law expression is given by 0.693

Rate = k [A][B]2 Q.7 (4) : Half-life period for first order reaction t1/ 2 
k

Rate constant k  Rate 0.693

 0.346  10 2 s  3.46  10 3 ssec–1
(i) t1/ 2 
 A B 
2
200 s 1

For experiment I, 0.693

(ii) t1/ 2   0.346 min  3.46 10 1 min
2 min 1
we obtain k  6.0 10 3 mol L1 min 1
0.693
(0.1 mol L1 )  0.1mol L1  (iii) t1/ 2   0.173 yr = 1.73 × 10-1 yr
2

4 yr 1

= 6.0 L2 mol–2 min–1

For experiment II, we obtain 0.693 0.693 1
Q.8 (1) : Decay constant  k   t 
5730
yr
1/ 2
7.2 102 mol L1 min 1
k
 0.3mol L  0.2mol L 
1 1 2 Radioactive decays follow first order kinetics

2.303  A0
= 6.0 mol–2L2 min-1 t log
k  A
for experiment (IV), we obtain
Given, [A] = 80% It means that [A]0 = 100%
2.40 10 2 mol L1 min 1 2.303  5730
k t yr  log
100
(0.4 mol L1 ) (0.1 mol L1 ) 2 0693 80

= 6.0 L2 mol–2 min–1 2.303  5730  0.0969

 = 1845 yr
0.693
Q.6 (1) : The rate expression Hence, the age of the sample is 1845 years.
1 0
Rate = k [A] [B] = k [A]
For Ist experiment, Q.9 (4) : Slope of the line
-1
[A] = 0.1 mol L
k 2.46   1.79  0.67
So, Rate = 2.0 × 10–2 = k [0.1 mol L-1]   
2.303 3200  0 3200

2.0  102 mol L1 min 1 k 0.67

k  0.2 min 1 
0.1 mol L1 2.303 3200

For IInd experiment, 0.67  2.303

k
4.0 ×10-2 mol L–1 min-1 = 0.2 min-1[A] 3200
or k = 4.82 × 10-4s-1
4.0 102 mol L1 min 1
 A   0.2mol 1 L1
0.2 min 1

[A] = 0.2 mol L-1 Q.10 (3) : For Ist order reaction t 
2.303  R 0 ......(i)
log
For IIIrd experiment, Rate = k [A]
k  R
Rate = 0.2 min-1 ×0.4 mon L–1
Rate = 8 ×10-2 mol L-1 min-1 2.303 1 2.303
 1
log  log16
60 s 1 60 s 1
For IVth experiment,
16
Rate
Rate  k  A ;  A 
k 2.303 2.303
 1
 4 log 2   4  0.3010
60 s 60 s 1
2.0 102 mol L1 min 1
 A  = 0.1 mol L–1 = 4.62 ×10-2s
0.2 min 1
Hence, the req. time is 4.6 × 10–2 s
[A] = 0.1 mol L-1

37
 Chemical Kinetics

0.693 0693 1
Q.11 (1) : t1/ 2  28.1 yr ; k   yr Q.13 (3) : t 
2.303
log
[R]0
t1/ 2 28.1 k [R]
Here it is known that
2.303 100 2.303 10
t
2.303 [R]0 k log log
k
log
[R] 40 min 100  30 = 40 min 7

= 8.918 × 10–3 min–1

2.303 1
10  log Therefore, t1/2 of the decomposition reaction is
0.693 [R]
28.1 0.693 0.693
t1/ 2    77.78 min
k 8.91 103 min 1
2.303
10 
0.693
  log[R] t1/2 = 77.78 min
28.1
Q.14 (4) :(CH3)2CHN = NCH (CH3)2 (g)  N2(g) + C6H14(g)
10  0.693
log [R] = 2.303 28.1 Initial pressure pi 0 0
[R] = antilog (– 0.1071) After time t pi  p p p
= antilog (1.8929)
Total pressure after time t, i.e.
= 0.7814 g
(pt) = (pi – p) + p + p = pi + p
Therefore 0.7814 g of 90Sr will remain after 10 year
or p = pt – pi
2.303 [R]0
Again, t  log a = pi; (a – x) = pi – p on substituting the values of p ;
k [R] (a – x) = pi – (pt – pi) i.e., (a – x) = 2pi – pt
2.303 1 The decomposition reaction is of gaseous nature and
60  log the rate constant k can be calculated as:
0.693 / 28.1 [R]
Amount left after 10 yr = 0.7819µg 2.303 a
k log
t ax
60  0.693
log [R]  2.303  28.1 substitution of value of a and (a – x) gives

[R] = Antilog (– 0.6425) 2.303  pi 

= antilog (1.3575) = 0.2278 g k log  
t  2 pi  pt 
There fore, 0.2278 g of 90Sr will remain after 60 year
Amount left after 60 yr = 0.2280 µg Rate constant after 360 s = k1

Q.12 (4) : Case I If a = 100 ; (a – x) = (100 – 99) = 1 k1 

2.303
log
 35 atm 
For 99% completion of the reaction  360s   70  54  atm
2.303 100 2.303 2.303  2
t99%  log  log10 2  2.303 35 2.303
k 1 k k  log  log 2.1875
 360s  16  360s 
4.602
t99%  ....(i) 2.303  0.33995
k   2.17 103 s 1
CaseII If a = 100; (a – x) = (100 – 90) = 10  360s 
For 90% completion of the reaction
2.303 100 2.303 2.303 Q.15 (1) : SO2Cl2(g)  SO2 (g) + Cl2 (g)
t90%  log  log10  ....(ii)
k 10 k k Initially pi 0 0
On dividing Eq. (i) by Eq. (ii), we get After time pi – p p p
t99% 4.602 k Total pressure after time t i.e.,
  2 pt = pi – p + p + p = pi + p
t90% k 2.303
So, a = pi
It means that time required for 99% completion of the
a – x = pi – (pt – pi)
reaction is twice the time required to complete 90% of
the reaction. = pi – pt + pi = 2pi – pt

38
Chemical Kinetics

Substitutions of the value of a and (a – x) gives

 A 0 = Antilog 0.8684 = 7.3858
k
2.303
log
pi  A
t  i  pt 
2 p
 A 0 M 
(a) Calculation of rate constant k  A    0.135 M
7.3858 7.3858
Given pi = 0.5 atm ; pt = 0.6 atm,
[A] = 0.135 mol L–1
2.303 pi 2.303 0.5 atm Hence, the remaining concentration of A is
k log  log
t  2 pi  pt  100s  0.4 atm 0.135 mol L–1

2.303 2.303
 log1.25   0.0969 (4) : For Ist order reactions k 
0.693 0.693

100 s  100s  Q.18
t1/ 2  3.0 h 
= 2.23 × 10–3 s–1
2.303  A 0
(b) Calculation of reaction rate when total pressure is t log
0.65 atm
k  A
pSO2CI2  0.5   0.65  0.50   1  0.65   0.35 atm  A 0 k  t
or log 
k = 2.23 × 10 s –3 –1  A 2.303
Rate = k × pSO2CI 2 = (2.23 × 10–3 s–1) × (0.35 atm)
 A0 0.693  8h 
log    0.8045
Rate = 7.8 × 10 atm s –4 –1
 A  3h 2.303

Q.16 (2) : According to Arrhenius equation,  A 0

= Antilog 0.8024 = 6.345
Ea
 A
log k  log A 
2.303RT
 A 0 1M
[A]0 = 1M ; [A] =   0.1576 m
k = 2.418×10–5 s–1 ; s–1 6.345 6.345
Ea = 179.9 kJ mol–1 or 179900J mol–1 Hence, the fraction of sample of sucrose that remain
R = 8.314 JK–1 mol–1 after 8 hours is 0.158
T = 546 K

Ea Q.19 (4) : According to Arrhenius equation

log A  log k 
2.303RT k  Ae  Ea / RT ......(i)
According to the available data
179900 J mol1
 log  2.418 10 s  
5 1 k = (4.5 × 1011s–1)e–28000 K/T .......(ii)
2.303   8.314 JK 1 mol 1   546 K On comparing both equations ;

= – 4.6184 + 1721 = 12.5916 E a 28000K

 
A = Antilog 12.5916 = 3.9 × 1012 s–1 RT T
A = 3.9 × 1012 s–1 Ea = (28000 K) ×R = (28000 K) × (8.314 k–1 J mol–1)
= 232792 kJ mol–1
Q.17 (3) : For the first order reaction Ea = 232.792 kJ mol–1

2.303  A0  A 0 k  t Q.20 (2) : (a) Calculate of activation energy Ea

t log or log 
k  
A  A  2.303 According to Arrhenius equation; k  Ae  Ea / RT
k = 2.0 × 10-2 s-1 ; t = 100 s; [A]0 = 1.0 mol L-1 = 1.0 M
Ea
log k  log A  ....(i)
 A 0  2.0  102 s 1   100s  2.303RT
log   0.8684
A 2.303 1.25 104 K
log k  14.34  ....(ii)
T
39
 Chemical Kinetics

On comparing both equations. Q.22 (4) : (a) Calculation of activation energy (Ea)
Ea

1.25  104 K
For Ist order reaction : k 
2.303  A 0
log
2.303RT T t A
Ea = 1.25 × 104 K × 2.303 ×8.314 (JK–1 mol–1)
= 23.93 × 104 J mol-1 2.303 100
At 298 K; k1  log ....(i)
= 239.3 KJ mol –1 t 90
(b) Calculation of required temperature 2.303 100
At 308 K; k2  log ....(ii)
If t1/2 = 256 min. t 75
For Ist order reaction ; Dividing eq. (ii) by (i) ;
.693 0.693 0.693
k   –5 –1 100
t1/ 2  256 min  256  60s = 4.51 × 10 s k2
log
75  0.1249  2.73

According to Arrhenius theory, k1 log 100 0.0458
90
1.25 104 K
log k  14.34  According to Arrhenius theory;
T
k2 Ea T T
1.25  104 K log   2 1
log  4.51 10   14.34 
5 k1 2.303R T1T2
T
E a  308  298 
1.25  104 K log 2.73 
– 4.35 = 14.34  2.303R  298  308 
T
0.4361 2.303   8314 J mol1   298  308
1.25 104 Ea 
= 14.34+4.35 = 18.69 10
T
Ea = 76640 J mol = 76.640 kJ mol–1
–1

1.25  104
(b) Calculation of rate constant (k)
T  668.95 K
18.69 Ea
Ea = 239.3 KJ mol–1 log k=log A – log k
2.303RT
T = 669 K
76640 J mol1
log k = log (4 × 1010) – 
2.303   8.314 Jmol 1 K 1    318 K 
Q.21 (1) : According to Arrhenius equation
log k = 10.6021 – 12.5870 = – 1.9849
k Ea T T
log 2   2 1 k = Antilog (– 1.9849)
k1 2.303R T1T2 = Antilog (20.151) = 1.035 × 10–2 s–1
k1 = 4.5 ×103 s–1; k2 = 1.5 ×104 s–1 ; T1 = 10°C = 283 K Ea = 76.640 kJ mol–1
k = 1.035 × 10–2 s–1
1.5 104

 60,000 J mol1   T2  283 
log  
4.5 103 2.303   8.314 J mol1   283T2  Q.23 (1) : According to Arrhenius equation

k2 Ea  1 1 
 T  283  log     ;given
log 3.333  3133.62  2  k1 2.303R  T1 T2 
 283T2 
[ T1= 293 K ; T2 = 313 K ; T2 – T1 = 20 K ]
0.5288 T2  283
 4 Ea 20
log  
1 2.303  8.314 J mol1K 1  293  313
3133.62 283T2

0.5288  283 T2  283

 Ea 20
3133.62 T2 0.6021  
2.303   8.314 J mol1  293  313
283 283 283
1  0.04776 or T2  
T2 1  0.04776 0.95224 0.6021 2.303  8.314  293  313
Ea  J mol 1
20
T2 = 297.19 K
= 52863 J mol–1
=(297.19 273.0 ) = 24.19°C
Ea = 52.863 kJ mol–1
Temperature = 24.19°C ~ 24°C
Hence, the required energy of activation is
Hence, K would be 1.5 × 10–4 s–1 at 24°C
52.86 kJ mol–1.
40
Chemical Kinetics

Q.24 (3) : Activation energy of a reaction is lowered when Q.30 (4) : k = Ae–Ea/RT from the equation it is clear that value
catalyst is used. of rate constant k increases exponentially with decrease
in activation energy Ea and increase in temperature.
Q.25 (3) : There is no effect on the heat evolved or absorbed
during the reaction in the presence of a catalyst since –E a
As Ea decreases, increases and k increases.
it does not participate in the reaction. RT

Ea –E a
As T increases, decreases and increases and
k Ea  1 1  RT RT
Q.26 (2) : log 2   – 
k1 2.303R  T1 T2  k increases.

Q.27 (1) : Ea(forward)= E1+E2 Q.31 (3) : Average rate of reaction upto 40 seconds on the
Since energy of reactants is less than products, product
V3 – 0 V3
is less stable than the reactant. basis of the graph is 
40 – 0 40
Q.28 (2) : Consider a first order gas phase decomposition
reaction: Q.32 (3) : The order of a reaction may or may not be equal
A (g) 
 B(g)  C(g) to the sum of stoichiometric coefficients. It is the sum
of the powers of concentration to which reactants are
The initial pressure of the system before decomposition
raised in a rate equation.
of A was Pi.
After lapse of time (t), total pressure of the system
increased by x units and became ‘P’,. In other words, V4 – V2
the pressure of A(g) decreased by x atm. Q.33 (2) : does not show instantaneous rate if
50 – 30
A (g) 
 B(g )  C(g ) reaction at 40th second.
Initial pressure: Piatm 0 0
Q.34 (1) : The rate of a reaction depends upon the
Pressure after time, t: (Pi–x) atm x atm x atm
concentration of reactants.
Pt   Pi –        Pi   atm

  Pt – Pi Q.35 (3) : 5Br(qq)  BrO3 – (qq)  6H (qq) 

 3Br2(qq)  3H 2 O( I )
Pressure of A after time t,PA=Pi–x
–1   Br    BrO3 –  –1   H  
–
=Pi – Pt + Pi =2Pi – Pt
Rate  –  
5 t t 6 t
2.303  A 0  2.303 log Pi
K log
t A t 2Pi – Pt   Br –  5   H 



t 6 t
1
Q.29 (1) : Fig (1) shows the graph between ln k and .
T Q.36 (1) : For an exothermic reaction,
Arrhenius equation, Ea(products ) > Ea(reactants)
k = Ae – Ea/RT Slope=
–Ea H(products) < (reactants)
R
Ea In K In A
In k = In A –
RT Q.37 (1) : Rate constant of a reaction does not depend upon
This equation is of the form 1 concentrations of the reactants.
T
y = mx+c,i.e., the equation of
a straight line. Q.38 (3) : Collision of atoms or molecules possessing
sufficient threshold energy and proper orientation
1
Thus, a plot of In k Vs is a straight line with results into the product formation.
T

–E a Q.39 (4) : Reaction would be 100% complete only after

slope  and intercept = In A.
R infinite time which cannot be calculated.
41
 Chemical Kinetics

Q.40 (2) : Rate = k [A]x[B]y Q.50 (1.3) According to Maxwell Boltzmann distribution of
When concentration of B is doubled keeping the energy, the fraction of molecules with most probable
concentration of A constant, then the rate of formation kinetic energy decreases with increase in temperature
of C increases by a factor of four.This indicates that and the most probable kinetic energy increases at higher
the rate of reaction depends upon the square of temperatures.
concentration of B. When concentration ofA is doubled
the rate of formation of C also doubles from the initial Q.51 (1,4) : Area under the curve remains same with increase
value. This shows that the rate depends on first power in temperature and with increase in temperature curve
of concentration of A. Hence, Rate = k[A] [B]2 broadens and shifts to the right hand side.

Q.41 (2) : The catalyst does not change G of the reaction.

Q.42 (2) The value of rate constant of a pseudo first order

reaction depends on the concentration of reactants
present in excess.

Q.43 (2) : A 
B

Q.52 (1,2) : Rate of reaction increases with temperature. It

becomes double with every 10º change. It increases
with decrease in activation energy.
The concentration of reactants decreases with time and
concentration of products increases with time. Q.53 (2,4) : Catalyst lowers the activation energy and it does
not change the enthalpy of the reaction.
Q.44 (1,2,3) : In a sequence of reactions, the slowest step is
the rate determining step.
Q.54 (1,4) : If we plot [R] against t we get a straight line
with slope = –k and intercept equal to [R]0 from the
Q.45 (1,4) : For an elementary reaction, the order and
equation
molecularity are same. Molecularity of a reaction can
[R] =–kt +[R]0
never be zero.
For the zero order reaction the rate is proportional to
the zero power of concentration
Q.46 (1,2) : For any unimolecular reaction, only one reactant
is involved in rate determining step and the order and dR 
Rate  –  k R 
0

molecularity of rate determining or slowest step are one. dt

A 
B Rate  k[A]
Q.55 (1,4) : For a first order reaction
Q.47 (1,4) : A complex reaction takes place in many steps. 0.693 d R 
the slowest step. The molecularity of the slowest step t1/ 2  and Rate  –  k R 
k dt
is never zero or fractional.
Q.48 (1,3,4) : For a zero order reaction, the rate of reaction  R 0 kt
or log 
is independent of concentration of ammonia.  R  2.303
Q.49 (1,4) : Activated complex is formed at the highest level If we plot a graph between log [R] 0/[R]us t, the
of energy of the system. It is unstable and decomposes
k
to give products with release of energy. Reactants may slope =
2.303
be formed if the reaction is reversible.

42