Chemical Kinetics-1

04
Chemical
Kinetics
Chemical kinetics is that branch of science which deals with the speeds or the IN THIS CHAPTER ....
rate of chemical reactions, the factors affecting the rate of reactions and the Chemical Reactions
mechanism by which reactions proceed.
Rate of a Chemical Reaction
Rate Law and Rate Constant
Chemical Reactions Molecularity of Reaction
When one or more substance(s) undergoes a change which results in the
formation of new product(s) that differ from the original one in composition Order of Reaction
and properties, the change is called as a chemical reaction. Differential and Integral Forms of
Chemical reactions involve breaking and formation of bonds. Therefore, Different Order Reactions
different bonds require different amount of energy for breaking and different Methods of Determination of
amount of energy is evolved during bond formation. Thus, the rates of Order of Reaction
different reactions are different. Effect of Temperature on Rate of
Depending upon their rates or speeds, chemical reactions can be classified as: Reaction
Theories of Rate of Reaction
1. Instantaneous or Fast Reactions
These are infact very fast reactions and it is practically impossible to measure
the speed of such reactions. Typical examples of such reactions include
• ionic reactions
• organic substitution reactions
• explosive reactions of oxygen with hydrogen and hydrocarbons.
2. Extremely Slow Reactions

Such reactions proceed at very slow speed and here the speed is so slow that
again it is not possible to measure the speed of such reactions, e.g. rusting of
iron.
710 JEE Main Chemistry
3. Moderately Slow Reactions Types of Rate of Reactions

Reactions belonging to third category, i.e. with The rate of a reaction can be categorised into two types
moderate speed are utilised for the study of chemical
(i) Average rate of reaction Average rate of a reaction
kinetics as in inversion of cane sugar and hydrolysis of
is defined as the rate of change of concentration per
starch. unit time. It is calculated by dividing the total change
Depending upon number of steps, chemical reactions are in concentration of any one of the reactant or product
classified in the following ways by the total time taken to do so. For the reaction,
PCl5 ¾® Cl2 + PCl3
Elementary Reactions
decrease in conc. of PCl5
A balanced chemical equation never gives us a true Average rate =
time taken
picture of how a reaction takes place. It can be complete
in one step or in many steps. The reactions taking place It can also be expressed in terms of increase in
in one step are called elementary reactions. concentration of PCl3 and Cl2 as,
D[PCl5 ] D [Cl2 ] D[PCl3 ]
Complex Reactions Rate = - =+ =+
Dt Dt Dt
The reactions which do not take place in one step are (ii) Instantaneous rate of reaction The rate of
called complex reactions. These are the reactions in reaction at any particular instant of time is known as
which all the atoms, ions or molecules as represented in instantaneous rate of reaction. It is equal to the
the balanced chemical reaction may not come together to small change in concentration ( dx ) in small interval of
collide simultaneously. e.g. time ( dt ).
+
5Brs ( aq ) + BrOs
3 ( aq ) + 6H ( aq ) ¾® 3Br2( aq ) + 3H 2O ( l ) dx
Rate =
It is impossible for all the 12 ions of the reactant to come dt
together simultaneously to collide. Such reactions take In general, for a reaction,
place in a sequence of a number of steps. Each of these n1 A + n 2B ¾® m1C + m2D
step reaction is an elementary reaction.
1 d [ A] 1 d [B]
Remember Different steps of complex reaction are Instantaneous Rate = - =-
n1 dt n 2 dt
elementary reactions.
+1 d [C ] +1 d [D ]
= =
Rate of a Chemical Reaction m1 dt m2 dt
The rate or speed or velocity of a reaction is the rate of Note In aqueous solution, the rate of reaction is not expressed
change of concentration of reactants or products in in terms of change of concentration of water because there is a
unit time. When a reaction occurs, the concentration of negligible change, e.g. from 55.5 M to 55.49 M.
reactant starts decreasing while the concentration of 3
product starts increasing. Therefore, Example 1. For the reaction 2 A + 3B + C ® 3P, which
statement is correct ? 2 (JEE Main 2020)
Rate of a reaction
decrease in the concentration of reactant dnA 2 dnB 3 dnC dnA 3 dnB 3 dnC
= (a) = = (b) = =
time interval dt 3 dt 4 dt dt 2 dt 4 dt
or Rate of reaction dnA dnB dnC dnA 2 dnB 4 dnC
(c) = = (d) = =
increase in the concentration of product dt dt dt dt 3 dt 3 dt
=
time interval 3
Sol. (d) For a reaction, 2A + 3B + C ¾® 3P
In general for a reaction, n1 A + n 2B ¾® m1C + m2D 2
For a reaction, aA + bB = cC
The rate expression may be expressed as, Rate of reaction,
1 D [ A] 1 D[B ] -1 d [ A] -1 d [B] 1 d [C ]
Rate of reaction = - =- Þ = =
n1 D t n2 D t a dt b dt c dt
\ For given reaction,
1 D[ C ] 1 D[D ]
=+ =+ -1 d [ A] -1 d [B] -2 d [C ] 1 d [P ]
m1 D t m2 D t = = =
2 dt 3 dt 3 dt 3 dt
Remember The negative sign indicates that the
d [ A] 2 d [B] 4 d [C ] -2 d [P ]
concentration of reactant decreases with time whereas the = = =
positive sign indicates that the concentration of product dt 3 dt 3 dt 3 dt
increases with time.
Chemical Kinetics 711
Example 2. NO 2 required for a reaction is produced by Units of Rate of Reaction

the decomposition of N2O 5 in CCl4 as per the equation, Rate of reaction has the units of concentration or molarity
2N2O 5( g ) ® 4NO 2( g ) + O 2( g ) divided by time. Therefore,
Unit of concentration
Unit of rate of reaction =
The initial concentration of N2O 5 is 3.00 mol L-1 and it is Unit of time
2.75 mol L -1 after 30 minutes. The rate of formation of NO 2 is
(JEE Main 2019)
= mol L -1 s -1 or mol L -1 min -1
(a) 4.167 ´ 10 -3 mol L -1 min -1 (b)1667
. ´ 10 -2 mol L -1 min -1 In case of gaseous reactions, the units of rate of reaction
(c) 8.333 ´ 10 -3 mol L -1 min -1 (d)2.083 ´ 10 -3 mol L -1 min -1 becomes atmosphere/sec or atmosphere/min etc.
Sol. (b) The rate of a chemical reaction means the speed with Factors Affecting Rate of Reaction
which the reaction takes place. The factors which affect the rate of reaction are as follows
For R ¾® P
(i) Concentration of reactants An increase in
Decrease in conc. of R D[R ]
Rate of disappearance of R = =- concentration of reactant increase the reaction rate.
Time taken Dt
Increase in conc. of P D[P ]
(ii) Nature of Reactants The nature of bonds in a
Rate of appearance of P = =+ molecule influences the rate of reaction at which it
Time taken Dt
-1
changes into products.
Given, [N2O5 ]initial = 3.00 mol L
(iii) Temperature Reaction rates are normally favoured
After 30 min, [N2O5 ] = 2.75 mol L-1 by increase of temperature. The temperature effect is
2N2O5( g ) ¾® 4NO2( g ) + O2( g ) expressed in terms of temperature coefficient which is
t= 0 3.0 M the ratio of the velocity constant of a reaction at two
t = 30 2.75 M temperature differing by 10°C.
From the equation, it can be concluded that k( t +10) ° C
1 - D[N 2O 5 ] 1 D[NO 2 ] Temperature coefficient =
´ = ´ kt ° C
2 Dt 4 Dt
For most of the reactions, the rate is doubled for every
- D[N 2O 5 ] - (2.75 - 3.00) mol L- 1 0.25
= = Þ 10°C rise in temperature.
Dt 30 30
(iv) Presence of catalyst A catalyst is a substance which
D[NO2] D(N2O5) D[NO2] 0.25 alters the reaction rate but itself remains unchanged in
and = -2 Þ =2 ´
Dt Dt Dt 30 amount and chemical composition at the end of the
= 1.667 ´ 10 - 2 mol L- 1 min - 1 reaction. Actually the reactants in a reaction have to
cross an energy barrier to form the product. The higher
Calculation of Rates by Graphical Method the energy barrier, the slower is the reaction rate.
To calculate rate, a graph is plotted between the A catalyst provides a new reaction path with a lower
concentration and time. energy barrier. So, that more and more reactant
Then, rate is calculated as molecules can form the product.
(v) Surface area of reactants The rate of reaction
increases as the surface area of the reactant
P increases.
(vi) Presence of light Reaction rate normally becomes
C1
faster in the presence of light. Light gives the
A
necessary activation energy for starting the reaction.
Dx
D
Rate Law and Rate Constant
conc.
B
C2
The mathematical relation between the rate of
Dt
reaction and the concentration of the reactants is
O t1 t2 Q termed as the Rate Equation or Rate Law Expression.
Time The rate law for a given reaction has to be established by
Graph of concentration vs time experimental study of the rate over a wide range of
concentration of the reactants. The rate law thus
Dx C2 - C1 OP
Average rate = = ; Instantaneous rate = established is also called differential rate equation or
Dt t2 - t1 OQ rate expression.
If we consider the reaction Now, the unit of different rate constants would be listed in
A + B ¾® products the following table.
Now, if [ A]a and [B]b are the molar concentrations of A Units of Rate Constant
and B respectively, then Units of k

Rate µ [ A]a [B]b Reaction Order Unit of rate constant for gaseous
reactions
or Rate = k[ A]a [B] b
(mol L–1 ) 1 atm s-1
Zero order 0 ´ = mol L-1s -1
here, k = velocity constant or rate constant reaction s (mol L-1 ) 0
Now, if all concentrations are taken as unity, i.e. First 1 (mol L–1 ) 1 s-1
´ = s -1
order (mol L–1 )
[ A] = [B] = 1 mol /L reaction
s
then Rate = k Second 2 (mol L-1 ) 1 atm -1 s -1

´ = mol -1 Ls -1
Thus, rate constant is defined as the rate of the order s (mol L–1 ) 2
reaction when the concentration of each reactant reaction
is taken as unity. It is also known as specific reaction nth order n (mol L-1 ) 1 atm1 - n s -1
´
rate. reaction s (mol L–1 ) n
Different characteristics of rate constant are given = (mol / L)1 - n s -1

below = mol1 - n Ln - 1s -1
• It is the measure of the rate of reaction. Greater is

the value of rate constant, faster is the reaction. Molecularity of Reaction
• Each reaction has a particular value of rate
It can be defined as “The number of atoms or molecules
constant at a particular temperature.
which collide together at the same time for the reaction to
• The value of rate constant for a particular reaction occur”.
changes with temperature. Reactions are classified in terms of molecularity as
• The value of rate constant for a reaction does not unimolecular, bimolecular, termolecular, trimolecular
depend upon the concentration of the reactants. depending upon the number of molecules involved in the
reaction.
Unit of Rate Constant Example of these reactions are as follows
Since the dimensions of rate are concentration/time and Unimolecular reaction,
the SI units for concentration are mol m -3 , mol dm -3 or PCl5 PCl3 + Cl2
mol L -1 and second for time. º
Bimolecular reaction,
For the nth order of a reaction,
nA ¾® Product CH3COOC2H5 + NaOH º CH COONa + C H OH 3 2 5
Rate = k[ A]n . Termolecular reaction,

2FeCl3 + SnCl2 ¾® 2FeCl2 + SnCl4
Rate
\ k= Remember Only a few termolecular reactions are known while
[ A]n no reaction having molecularities more than three is known
Thus, the dimensions of k are equal to because more than three molecules may not mutually collide
Concentration / Time with each other.
= [Concentration]1 - n [Time]-1
[Concentration]n
= (mol)1 - n Ln -1 s-1 Determination of Molecularity
where, n = order of reaction. In case of simple reactions (elementary reactions), the
molecularity is simply the sum of the molecules of different
Units of Rate Constants for reactants as represented by the balanced chemical
Gaseous Reactions equation, e.g.
In case of gaseous reactions, concentrations are O2F2 ¾® O2 + F2 (Unimolecular)
expressed in terms of pressure in the units of 2HI ¾® H 2 + I2 (Bimolecular)
atmosphere. Thus, the rate has the units of atm per
second. 2NO + O2 ¾® 2NO2 (Termolecular)
In case of complex reactions (multistep reactions) the The main differences between molecularity and order of
slowest step is the rate determining step. reaction are tabulated below.
So atoms, molecules or ions participating in this rate Difference between Order and Molecularity
determining step, determine the molecularity of the
reaction. Molecularity Order of reaction
e.g. Consider the reaction, It is the total number of It is the sum of powers of molar
reacting species (molecules, concentrations of the reacting
HBrO3 + 6HI ¾® HBr + 3H 2O + 3I2 atoms or ions) which bring the species in the rate equation of
The reaction takes place through following steps chemical change. the reaction.
It is a theoretical concept. It is experimentally determined.
Slow
HBrO3 + HI ¾¾® HBrO2 + HIO It is always a whole number. It may be a whole number, zero,
fractional, positive or negative.
Fast
HBrO2 + 4HI ¾¾® HBr + 2H 2O + 2I2 It is meaningful only for simple It is meant for the reaction and
reactions or individual steps of not for its individual steps.
Fast a complex reaction.
HIO + HI ¾¾® H 2O + I2
Here, 2 molecules participate in the slowest step, thus
reaction is of bimolecular type. Differential and Integral Forms
Characteristics of Molecularity of Different Order Reactions
• Molecularity of a reaction is always a whole number. For a general reaction,
It can never be fractional or zero. aA + bB ¾® cC + dD
• It does not provide any idea about the rate or -d [R ]
mechanism of the reaction. Rate = = k[ A]a [B ]b
dt
• Molecularity is defined just for elementary reactions
not for complex reactions. This form of the equation is called differential rate
equation. It relates the rate of change of concentration
with time or instantaneous rate. It is measured by the
Order of Reaction determination of the slope of the tangent at point t in the
In chemical kinetics the reactions are generally classified concentration versus time curve. This makes it difficult
in terms of their order. The order of a reaction is defined as to determine the rate law and hence, the determination
“The sum of the concentration terms on which the rate of a of the order of the reaction.
reaction actually depends as observed experimentally”. In order to avoid this difficulty, we can integrate the rate
Or equation and obtain integrated rate equation that gives a
relation between directly measured experimental
“The order of reaction is given as the sum of the
quantities, i.e. concentrations at different times. The
exponents (powers) to which the concentration terms in
integrated rate equations are different for reactions of
the rate law equation are raised to express the observed
different orders.
rate of the reaction.” In the reaction rate expression,
Rate = k[ A]a [B]b Zero Order Reactions
the sum a + b = order of reaction Reactions in which the concentration of reactants do not
Order of reaction is purely experimental quantity. It may change with time and the rates remain constant
be whole number, zero or in fractions. Depending upon throughout are said to be zero order reactions.
whether a + b is equal to zero, 1, 2 or 3, the reactions are For the reaction,
said to be of zero order, first order, second order or third k
order respectively. A ¾® products
Remember [ A]t = [ A]0 - kt …(i)
• Order of a reaction can change with change in 1
conditions such as temperature, pressure etc. or, k = {[ A]0 - [ A]t }
t
• When one of the reactants is present in large excess,
the second order rate expression becomes a first order where, [ A]t = concentration of ‘A ’ at any time ‘t ’
rate expression because the value of change in [ A]0 = initial concentration of ‘A ’
concentration for other reactant is taken as negligible. k = rate constant of zeroth order reaction
2.303 a0
Characteristics of Zero Order Reactions or k= log
• Any reaction of zero order must obey Eq. (i)
t a0 - x
[ A ] = [ A ]0 - kt where, [ A]0 = a0 = initial concentration
This shows that the plot of concentration of reactants [ A]t = a0 - x = concentration of ‘A ’ at any time ‘t ’
against time will be a straight line. k = rate constant for 1st order reaction
• Also, as the rate is independent of concentration, the x = amount of ‘A ’ reacted at time ‘t ’
plot of rate versus concentration will be a straight line
parallel to the concentration axis. Characteristics of First Order Reactions
• The units of rate constant for zero order reaction is • Any reaction of the first order must obey above
mol L -1 time -1. equation which can also be written as,
• The time required to reduce the initial concentration -kt
log [ A] = + log [ A]0
of the reactant to half of its initial value is called 2.303
half-life time or half-life period and is denoted by This is the equation of a straight line ( y = mx + c)
t1/ 2. When [ A] = [ A]0 / 2, t = t1/ 2 , substituting these
values in Eq. (i), we get Thus, if log [ A] or log ( a - x ) values are plotted
[ A]0 against time t, the graph obtained should be a
t1/ 2 = straight line.
2k
The intercept on y-axis would be log [ A]0 and the slope
or t1/ 2 µ [ A]0.
æ -k ö -k
Thus, the half-life period of zero order reaction is
of the line would be equal to ç ÷ ,i.e. slope =
è 2.303 ø 2.303
directly proportional to initial concentration, i.e.,
t1/ 2 µ [ A]0. –k
slope =
Remember 2.303
log [A]
• In zero order reaction, it is the amount of reactant that
changes and not the reaction rate.
• The rate of reaction remains constant throughout the course
of the reaction.
t
Plot of log [ A ] vs time ( t )
[ A]0
Thus, if we plot log versus t, a staight line graph
Rate
[ A]
k
will be obtained with slope = as shown belown,
Concentration 2.303
Plot of rate versus concentrations for the
reaction of zero order
Some Examples of Zero Order Reactions log

[A]0 k
Slope =
[A] 2.303
• Photochemical synthesis of HCl, i.e.
hn
H 2( g) + Cl2( g) ¾® 2HCl
• Decomposition of ammonia in the presence of a t
catalyst, i.e. Plot of log ([ A 0 ]/[ A ]) vs time (t )
Mo or W
2NH3 ¾¾¾¾® N 2 + 3H 2 • The time taken for the completion of same fraction of
change, i.e. half-life is independent of initial
First Order Reactions concentration. e.g. For half change,
The first order reaction is defined as “The reaction in x = 0.5a and t = t1/ 2
which the reaction rate is determined by the change of 2.303 a 2.303 0.693
one concentration term of the reactant only”. so, k= log = log 2 =
t1/ 2 0.5a t1/ 2 t1/ 2
For the reaction,
k 0.693
A ¾® products or t1/ 2 =
k
[ A]t = [ A]0 e-kt …(i)
Thus, t1/ 2 is independent of initial concentration a.
2.303 [ A]0
or k= log • Since, the rate is dependent of concentration, the unit
t [ A]t
of k will be time-1 , i.e. s-1 or h-1.
1 t 0.693
• Average life ( l) = = 1/ 2 = 1.443 t1/ 2 Also, we know l = (decay constant) =
k 0.693 t1/ 2
• Relation between t1/ 2 and tx % (amount decomposed) where, t1/ 2 = 6.93 yr (given)
2.3 æ 100 ö Also, we know 90% nuclei are decayed
tx % decomposes = log çç ÷÷ N0 100
k è 100 - x ø \ = = 10
Nt 10
Divide Eq. (vi) by (viii),
N
Put the values of l and 0 in Eq. (i), we get
t1/ 2 0.3 Nt
=
tx % æ 100 ö 6.93
log çç ÷÷ \ t= ´ 2.303 ´ log 10 = 23.03 (yr)
è 100 - x ø 0.693
Example 4. The reaction, 2 X ® B is a zeroth order
Examples of First Order Reactions reaction. If the initial concentration of X is 0.2 M, the half-life
• Decomposition of H 2O2 , is 6 h. When the initial concentration of X is 0.5 M, the time
1 required to reach its final concentration of 0.2 M will be
H 2O2 ¾® H 2O + O2 (JEE Main 2019)
2
• Dissociation of N 2O5 , (a) 7.2 h (b) 18.0 h (c) 12.0 h (d) 9.0 h
2N 2O5 ¾® 4NO2 + O2 Sol. (b) For zero order reaction, [ A0 ] - [ At ] = kt ...(i)
• Hydrolysis of methyl acetate, where, [ A0 ] = initial concentration
CH3COOCH3 + H 2O º CH3COOH + CH3OH [ At ] = final concentration at time ‘t’
• Inversion of cane sugar, k = rate constant
[A ]
Also, for zero order reaction, t1/ 2 = 0
H O/H+ 2k
C12H 22O11 ¾¾¾¾®
2
C6H12O6 +C6H12O6
Sucrose Glucose Fructose Given, t1/ 2 = 6 h and [ A0 ] = 0.2 M
All natural and artificial radioactive decay of unstable 0.2 0.2 1
\ 6= or k = =
nuclei take place by first order kinetics. 2k 2 ´ 6 60
226
¾® 4
+ 222 Now, from Eq. (i)
88 Ra 2 He 86 Rn
[ A0 ] - [ At ] = kt
Rate = k (Ra) Given, [ A0 ] = 0.5 M, [ At ] = 0.2 M
If, N 0= atoms of the radioactive element present initially 1 é 1ù
\ 0.5 - 0.2 = ´t êëQk = 60 úû
N = atoms of the radioactive element present after 60
time t
1
2.303 N 0.3 = ´t
then, K = log o 60
t N
Þ t = 0.3 ´ 60 = 18 h
where, K = disintegration or decay constant
0.693 Example 5. Decomposition of H2O 2 follows a first order
and half-life (t1/ 2) =
K reaction. In 50 min, the concentration of H2O 2 decreases
Thus, half-life period of a radioactive element is from 0.5 to 0.125 M in one such decomposition. When the
independent of the initial amount of the element. concentration of H2O 2 reaches 0.05 M, the rate of formation
of O 2 will be (JEE Main 2016)
Example 3. During the nuclear explosion, one of the (a) 6.93 ´ 10 -4 mol min -1 (b) 2.66 L min -1 at STP
products is 90 Sr with half-life of 6.93 years. If 1 mg of 90 Sr was
absorbed in the bones of a newly born baby in place of Ca, . ´ 10 -2 mol min -1
(c) 134 (d) 6.93 ´ 10 -2 mol min -1
how much time, in years is required to reduce it by 90% if it 2.303 a
is not lost metabolically ……… . Sol. (a) For first order reaction, k = log
(JEE Main 2020) t a-x
Given, t = 50 min, a = 0.5 M, a - x = 0.125 M
Sol. (23.03) Radioactive decay follows first order kinetics.
2.303 0. 5
\Time taken for decay from N0 to Nt is \ k= log = 0.0277 min -1
50 0.125
(N = number of nuclei)
1 N Now, as per reaction
t = ln 0 2H2O2 ¾® 2H2O + O2
l Nt
1 N 1 d[H2O2] 1 d[H2O] d[O2]
t = ´ 2.303 log 0 …(i) - = =
l Nt 2 dt 2 dt dt
d [H2O2] Sol. (d) Let the pressure of N2O5( g ) decreases by 2x atm. As

Rate of reaction, - = k [H2O2]
dt 2 moles of N2O5 decompose to give 2 moles of N2O4( g ) and
d [O2] 1 d [H2O2] 1 1 mole of O2( g ), the pressure of N2O4( g ) increases by 2x atm and
\ =- = k [H2O2] …(i)
dt 2 dt 2 that of O2( g ) increases by x atm.
When the concentration of [H2O2] reaches 0.05 M, 2N2O5( g ) ¾® 2N2O4( g ) + O2( g )
d[O2] 1 When, t = 0 0.5 atm 0 atm 0 atm
= ´ 0.0277 ´ 0.05 [from Eq. (i)]
dt 2 At time t ( 0.5 - 2x) atm 2x atm x atm
d[O2] Total pressure ( pt ) = p(N2O5 ) + p(N2O4 ) + p(O2 )
or = 6.93 ´ 10 -4 mol min -1
dt = (0.5 - 2x) + 2x + x
= 0.5 + x
Alternative Method
\ x = pt - 0.5
In fifty minutes, the concentration of H 2O2 decreases from pN2O5 = 0.5 - 2x
0.5 to 0.125 M or in one half-life, concentration of H 2O2
= 0.5 - 2( pt - 0.5)
decreases from 0.5 to 0.25 M. In two half-lives,
= 1.5 - 2pt
concentration of H 2O2 decreases from 0.5 to 0.125 M or
At t = 100 s; pt = 0.512 atm
2 t1/ 2 = 50 min
æ 0.693 ö -1 p(N2O5 ) = 1.5 - 2 ´ 0.512 = 0.476 atm
t1/ 2 = 25 min Þ k = ç ÷ min
è 25 ø 2.303 æ p0 (N2O5) ö
\ k= log çç ÷÷
d [O2 ] 1 d [H 2O2 ] k [H 2O2 ] t è pA (N2O5) ø
or =- =
dt 2 dt 2 æ 0.5 atm ö
2.303
= 6.93 ´ 10 mol min-1
-4 = log çç ÷÷
100 s è 0.476 atmø
Typical First Order Gas Phase Reactions 2.303
= ´ 0.02136
Consider a typical first order gas phase reaction 100 s
A( g) ¾® B( g) + C( g) = 4.92 ´ 10 -4 s-1
Let p0 be the initial pressure of A at time t = 0 and pt is the
Direct or Indirect Estimation of Reactants
total pressure at time t. Total pressure ( pt ) = pA + pB + pC
(pressure units), where pA , pB , and pC are the partial Sometimes volumes of reagents are given in volumetric
pressures of A, B and C, respectively. analysis (when one of the reactant is estimated directly
or indirectly, i.e. when V ¥ is not given).
If x atmosphere be the decrease in the pressure of A at time
t and one mole each of B and C is being formed, then 2.303 V
k= log 0
increase in the pressure of B and C will also be x atm each. t Vt
A( g) ¾® B( g) + C( g) where, V 0 = volume of the reagent used at time t = 0
At t = 0 p0 atm 0 atm 0 atm V t = volume of the reagent used at time t
At time t ( p0 - x ) atm x atm x atm V ¥ = volume of reagent used at infinite time or
when the reaction ends
pt = p0 + x
For example, 2H 2O2 ¾® 2 H 2O( l ) + O2( g)
and x = ( pt - p0 )
where, and pA = 2 p0 - pt The rate of this first order reaction is measured by
æ 2.303 ö æç p ö titrating a fixed volume of H 2O2 against a standard
k=ç ÷ çlog 0 ÷÷ solution of KMnO4
è t øè pA ø
2.303 p0 Example 7 In the dehydration of oxalic acid by conc. H2SO 4
or = log …(i)
t (2p0 - pt )
(COOH) 2 ¾® CO+ CO2 + H2O
Example 6 The following data were obtained during the first 2 mL of the solution was withdrawn at different times and titrated
order thermal decomposition of N2O 5( g ) at constant volume. against 0.1 N KMnO 4 solution. Find the order of reaction.
2N2O 5( g ) ¾® 2N2O 4 ( g ) + O 2( g )
Time (mins) 0 300 450 600
Time(s) Total pressure (atm) Vol of KMnO4 used (mL) 22.0 17.0 15.0 13.4
0 0.5
(a) 0 (b) 1 (c) 2 (d) 3
100 0.512
Calculate the rate constant. (NCERT Exemplar)

Sol. (b) Here, KMnO4 act as oxidising agent and (COOH) 2 act as
reducing agent. The volumes of KMnO4 used for (COOH) 2 after
(a) 3.39 ´ 10 -4 s-1 (b) 1.39 ´ 10 -5 s-1
regular internals of time are given in question.
(c) 5.45 ´ 10 -4 s-1 (d) 4.98 ´ 10 -4 s-1
Volume of KMnO4 at t = 0 corresponds to volume of (COOH) 2 Inversion of Sugar Cane

initially present C 0 µ V0
2.303 r -r
Volume of KMnO4 used at time t1, t 2, t3, ......... corresponds to k= log o ¥
t rt - r¥
volume of (COOH) 2 remaining after t1, t 2, t3, .........
where, ro = initial optical rotation of sugar cane
C t ´ Vt
rt = optical rotation after time t
2.303 V r¥ = optical rotation at infinite time (at the end of
\ k= log 0
t Vt reaction)
Now, using the above expression if we calculate the values of k
for different intervals t1, t 2, ......... (for given data), the values of k Example 8 Methyl acetate is hydrolysed with 0.1 N HCl at
should be same if the reaction follow first order kinetics. 25°C. 5 mL of the reacting mixture is withdrawn at various
(COOH) 2 ¾® CO+ CO2 + H2O time intervals and is quickly titrated with 1.0 N NaOH.
2.303 V The volumes of NaOH consumed are as follows
k= log 0
t Vt Time (s) 339 1242 2745 4546 ¥
2.303 22 2.303 ´ 0.119 Volume of NaOH (mL) 26.34 27.80 29.70 31.81 39.81
(i) k = log = = 0.00085 min -1
300 17 300
2.303 22 Find the average rate constant (k).
(ii) k = log = 0.00085 min -1 (a) 4.29 ´ 10 -4 s-1 (b) 3.29 ´ 10 -4 s-1
450 15
-4 -1
2.303 22 (c) 8.68 ´ 10 s (d) 1.23 ´ 10 -4 s-1
(iii) k = log = 0.00085 min -1
600 13.4
Sol. (d) CH3COOR¢ (Ester) + H2O + HCl(HÅ ) ¾®
The value of k is constant. Hence, the reaction is of first order.
CH3 COOH + R ¢ OH
Direct or Indirect Estimation of Products The reaction rate is measured by titrating the acid (CH3COOH)
Consider a condition when one of the product is estimated produced against a standard alkali solution.
directly or indirectly, i.e. when V 0 is not given. Note that when a test sample is prepared from the reacting
For general equation, A ¾® B+ C mixture, there are two acids : one is mineral acid HÅ (HCl or any
At time, t =0, volume of reactant = 0 other) and second is CH3 COOH produced. So, the volume of
time t = ¥ means end of a reaction. alkali used gives the titration value for both acids.
When V0 is given,
At time t = ¥, V = V ¥ , this corresponds to initial volume of
reactant At t = 0 ,V0 is the volume NaOH used to neutralise the mineral
Here x = V t (product formed) acid present (HÅ ) being used as catalyst
(At t = 0 , no CH3 COOH is yet produced)
C 0 - x=V ¥ - V t
2.303 V¥ At t = ¥ (i.e. at the end of hydrolysis), V¥ is the volume of NaOH
\ Hence, from first order kinetics, k= log used to neutralise whole of CH3 COOH plus the volume of HCl
t V¥ - Vt
present. At t = ¥ , the volume of CH3 COOH corresponds to the
For example, in the decomposition of NH 4NO2, the volume volume of ester taken initially.
of N 2 is directly measured at different intervals of time Þ c0 µ V¥ - V0 (as V0 º volume of HCl)
Hydrolysis of Ester (CH 3COOR ¢ ) in Acidic At t = t1, t 2, t3 , ... , V1, V2, V3 , K correspond to the volume of HCl
Medium plus the volume of CH3 COOH being produced.
Þ x µ Vt - V0
When V 0 is not given
Þ c0 - x µ (V¥ - V0) - (Vt - V0)
Let [V ¥ - V 0 = C0 and V ¥ - V t = Ct ] Þ c0 - x µ V¥ - Vt
When t = t1 , then Hence, from the first order kinetics, it follows
2.303 C
k= log 0 …(i) 2.303 V - V0
t1 Ct1 k= log ¥
t V¥ - Vt
Similarly, when t = t2 For ester hydrolysis, equation
2.303 C V - V0
k= log 0 …(ii) k=
2.303
log ¥
t2 Ct2 t V¥ - Vt
Operating Eq. (i) – Eq. (ii), we get Since, V0 is not given
Ct 2.303 ct
2.303 or k= log 2
or k= log 2 …(iii) (t1 - t 2) ct1
( t1 - t2 ) Ct1
Now, find ct . Some examples of second order reactions are

t 339 s 1242 s 2745 s 4546 s (i) Dissociation of HI,
2HI ¾® H 2 + I2
ct = V¥ - Vt 39.81 - 26.34 39.81 - 27.80 39.81 - 29.70 39.81 - 31.81
= 13.47 mL » 12.0 mL = 10.11 mL = 8.0 mL (ii) Saponification of ethyl acetate,
CH3COOC2H5 + NaOH ¾® CH3COO– Na + + C2H5 OH
and t1 - t 2 = 339 - 1242 = - 903 s
t1 - t3 = 339 - 2745 = - 2406 s (iii) Reaction between NO and O3 ,
t1 - t 4 = 339 - 4546 = - 4207 s NO + O3 ¾® NO2 + O2
Using relation given in Eq. (iii) , (iv) Reaction between potassium persulphate and potassium
2.303 12.0 iodide,
\ k1 = log = - 0.0025 ´ log (0.89)
-903 13.47 K 2S2O8 + 2KI ¾® 2K 2SO4 + I2
= - 0.0025 ´ - 0.0506 = 1.27 ´ 10 -4 s-1
2.303 10.11
Third Order Reactions
k2 = log = - 0.0095 ´ log (0.75) A reaction is said to be of third order if its rate is
-2406 13.47
determined by the variation of three concentration terms.
= - 0.00095 ´ - 0.1249 = 1.19 ´ 10 -4 s-1
The units of rate constant for third order reaction are
k3 =
2.303
log
8.0
= - 0.00054 ´ log (0.59) L2 mol-2 time-1.
-4207 13.47
Reactions of third and higher orders are rare, but some
= - 0.00054 ´ - 0.2291 = 1.23 ´ 10 -4 s-1 examples of 3rd order reactions are definitely seen. This is
kaverage = 1.23 ´ 10 -4 s-1 due to the fact that the probability of trimolecular collisions
is much less as compared to unimolecular or bimolecular
collisions.
Second Order Reactions
Examples of third order reactions are
The reaction is said to be of second order, if its reaction (i) 2NO + O2 ¾® 2NO2
rate is determined by the variation of two
(ii) 2NO + X 2 ¾® 2NOX (where, X = Halogen)
concentration terms of reactants.
(iii) 2CH3COOAg + HCOONa ¾® 2Ag + CO2
For the reaction,
+ CH3COOH + CH3COO – Na +
2A ¾® product
or A + B ¾® product Reactions Involving Order in Fraction
If the initial concentrations of both ‘A ’ and ‘B ’ are There are some reactions, rate of which is expressed by
equal, the rate constant ‘k ’ is given by fractions of concentration terms. e.g.
1 x (i) CO + Cl2 ¾® COCl2
k= ´
t a0 ( a0 - x ) Rate = k [CO]2 [Cl2 ]1/ 2
In case, the concentrations are not equal, Order = 2.5
2.303 b (a - x) (ii) COCl2 ¾® Cl2 + CO
k= log 0 0
t( a - b) a0( b0 - x ) Rate = k [COCl2 ]3/ 2
where, a0 = initial concentration of ‘A ’ Order = 1.5
b0 = initial concentration of ‘B’ (iii) Reaction between H2 and D2
x = amount of ‘A ’ or ‘B ’ reacted Rate = kpH2 ( pD2 )1/ 2
The units of k are given as L mol -1 time -1. The conversion of parahydrogen to orthohydrogen at high
The time required to complete a certain fraction of the temperature; Rate = k( pH2 )1.5 . The non-integer values are
reaction is inversely proportional to the initial generally due to complex nature of reaction which involves
concentration of reactants in the case of second order more than one elementary step. The overall rate law is
reactions. obtained by combining rates of individual elementary steps.
Differential Equations, Corresponding Integral Rate Equation,

t1/ 2 , Unit of k and Nature of Plot of Various Reactions
Differential t1/2
Reaction Order Integral equation Units of k Nature of plot
equation
log (a – x)
k dx x a mol dm -3s -1 Slope = k or Intercept = a
A ¾® product =k k=
x
0
(a) dt t 2k
Time Time
log (a – x)
2.303 a 0.693
k dx
k= ´ log Slope = k/2.303, Intercept = log a
A ¾® product 1 = k (a - x ) k s -1
(a) dt t (a - x )
Time
1/(a – x)
1 æ a 1ö 1
A + B ¾®
k dx
= k (a - x ) 2 k= ´ç - ÷
1 mol -1 dm 3s -1 Slope = k , Intercept =
2 a
(a ) ( a ) product
dt t èa - x aø ka
Time
log b(a – x)/

a(b–x)
dx 2.303 b( a - x )
A + B ¾®
k
= k ( a - x )( b + x ) k = ´ log mol -1 dm 3s -1 Passing through
(a ) (b ) 2 dt t ( a - b) a (b - x ) – the origin
product k (a – b )
Slope =
2.303
Time
Negative Order Reactions • Decomposition of ethylene oxide

k1 k2
Sometimes the rate of reaction decreases as the (CH 2 )O ¾® CH3CHO ¾® CO + CH 4
concentration of one of the constituent is increased, e.g.
• Pyrolysis of acetone
transformation of ozone into oxygen, i.e. 2O3 ¾® 3O2. k1 k2
(CH3 )CO ¾® CH 4 + CH 2 ==C==O ¾® C2H 4 + CO
Consecutive or Sequential Reactions
A reactant ( A) decomposes to ( B), which in turn decomposes Side or Parallel or Concurrent
to (C), i.e. Elementary Reactions
k1 k2 A single reactant gives two products B and C
A ¾¾¾® B ¾¾¾® C
Step1 Step 2 simultaneously with different decay constants.
For first order reaction,
For the above sequential reaction we have
k1
[ A] = [ A]0 e- kt …(i) ¾® B (90%) (Main reaction)
[B] = [ A]0
k1 –k t
( e 1 - e– k2t ) …(ii) A ¾¾
k2
k2 - k1 ¾® C (10%) (Side reaction)
æ 1 + k1e- k2t - k2e- k1 t ö If after a time interval say x M of B and y M of C are
[C ] = [ A]0ç ÷ …(iii)
ç k2 - k1 ÷ formed, then if reaction is carried out with A, when
è ø t = 0, [B] = [C ] = 0.
(where, [ A]0 = initial concentration of ( A)
k1 = (% yield of B) ´ kav
d [B] k k1
[B] is maximum, when =0 Þ % yield of B = 1 =
dt kav k1 + k2
On differentiation Eq. (iii), we get
k2 = (% yield of C ) ´ kav
2.303 ék ù
tmax = log ê 2 ú Þ
k
% yield of C = 2 =
k2
k2 - k1 ë k1 û kav k1 + k2
Some examples Example 9. For an elementary chemical reaction,

(i) Phenol ¾¾¾¾® o -nitrophenol + p -nitrophenol k1
(ii)
Nitration A2 º 2 A , the expression for ddt[A] is
k- 1 [JEE Main 2019)
¾® H 2C==CH 2 + KBr + H 2O
C2H5 Br + KOH ¾¾ (a) 2k1[ A2] - k-1[ A]2
(b) k1[ A2] - k-1 [ A]2
¾® C2H5OH + KBr 2
(c) 2k1[ A2] - 2k-1 [ A] (d) k1[ A2] + k-1[ A]2
Opposed or Reversible Sol. (c) The elementary reaction, A2

k1
Elementary Reactions º 2A
k -1
The elementary reaction given below follows opposing or follows opposing or reversible kinetics,
reversible kinetics. (i) Rate of the reaction,
Case I First order-opposed by first order r = rforward - rbackward
When concentration of B = 0 at time t = 0 = k1[ A2] - k- 1[ A]2 … (i)
k1 (ii) Again, rate of the reaction can be expressed as,

A º B d[ A2] 1 d[ A]
k2 r=- =+
dt 2 dt
Case II First order-opposed by first order
So, the rate of appearance of A,
When concentration of B is not zero at t = 0 d[ A]
i.e. = 2r = 2k1[ A2] - 2 k- 1 [ A]2 [From Eq. (i)]
Let concentration of B at time zero be b dt
Formula for both the cases is k1 k2
X eq Example 10 For a reaction scheme, A ¾® B ¾® C , if the
2.303
t= log rate of formation of B is set to be zero then the concentration
( k1 + k2 ) X eq - x of B is given by (JEE Main 2019)
( X eq = [B] formed a equilibrium) æk ö
(a) k1k2[ A] (b) çç 1 ÷÷[ A]
Some examples è k2 ø
k1 (c) (k1 - k2)[ A] (d) (k1 + k2)[ A]
(i) H 2 + I2 º 2HI
k2 Sol. (b) k1 k2
A ¾® B ¾® C
1 d[HI]
Rate = = k1 [H2 ][I2 ] - k2 [HI]2 Rate of formation of B is
2 dt
d[B]
k1 = k1[ A] - k2[B]
(ii) 2NO2 º N O - d [NO
k2
2 4
dt
]
= 2k [NO ] - k [N O ]
2
1 2
2
2 2 4
Þ
dt
0 = k1[ A] - k2[B]
é d[B] ù
êëQ Given, dt = 0 úû
Pseudomolecular Reactions Þ k2[B] = k1[ A]
There are several reactions which are considered as k
Þ Concentration of B, [B] = 1 [ A]
unimolecular, although in reality they are bi-or k2
tri-molecular, e.g. consider the hydrolysis of methyl
acetate in the presence of acid
Methods of Determination of
Acid
CH3COOCH3 + H 2O ¾¾® CH3COOH + CH3OH Order of Reaction
According to the law of mass action, this reaction seems Several methods are used to determine order of a
to follow bimolecular process with the rate dependent on reaction, like initial rate method, integration method,
concentration of both ester and water. However, it is half-life method, Ostwald isolation method, etc.
found that the rate is independent of water, it depends
only on concentration of ester. 1. Integration Method or Hit and
This can be explained on the basis of the fact that here Trial Method
water is present in such excess that its concentration
In this method a, x and t are determined and substituted
remains practically constant during the course of
in kinetic equations of various orders. The equation
reaction. Hence, reactions showing such a behaviour are
which gives the most constant value of rate constant for a
called pseudounimolecular reactions or pseudo first
series of time intervals is the one to which the order of
order reactions.
reaction corresponds.
In this method the kinetic equation used for same molar Zero order
concentration are
2.303 a 1st order
k= log10 for first order reactions t1/2
t a-x
1é 1 1ù
k= ê - ú for second order reactions 2nd order
t ëa - x a û
Concentration
In general for the reactions of n order, given as below,
Plots between half-life period and concentration
nA ¾® products
the rate equation of the form given below is obtained.
1 é 1 1 ù
3. Ostwald Isolation Method
kn = -
t ( n - 1) êë( a - x )n -1 a n -1 úû
This method is employed in determining the order of
complicated reactions by isolating one of the
This equation is applicable for all orders except first order. reactants. Suppose the reaction under consideration is
n1 A + n 2B + n3C ¾® products
2. Half-life Method or Fractional In this reaction for the determination of any of the
Change Method reactants say A, rest of the reactants, i.e. B and C are
The half-life period (time required to reduce the initial taken in large excess, so that there is no change
concentration to half of its value) depends differently on the practically in their concentrations.
initial concentrations of reactants for different orders of The order of the reaction for A is then determined by
reactions, i.e. using any of the methods written before. The procedure
For zero order reaction, is likewise for B and C also. e.g.
t1/ 2 µ [ A]i It is observed as follows
For first order reaction, t1/2 is independent of initial • Keeping the concentrations of B and C constant, if
concentration of A is doubled, the rate of reaction
concentration actually it depends upon the rate constant
becomes 4 times. This means that
as,
Rate µ [ A]2
0.693
t1/ 2 = i.e. order of reaction with respect to A is 2.
k
• Keeping the concentrations of A and C constant, if
and t3/ 4 = 2 t1/ 2 concentration of B is doubled, the rate of reaction
and similarly t94. 9% = 10 t1/ 2 becomes 2 times. This means that
For n order reaction Rate µ [B ]
1 i.e. order of reaction with respect to B is 1.
t1/ 2 µ
[ A]ni - 1 • Keeping the concentrations of A and B constant, if
Starting with two independent reactions having initial the concentration of C is doubled, the rate of the
concentrations a1 and a2 at corresponding half-lives ( t1/ 2 )1 reaction remains unaffected. This means that rate
and ( t1/ 2 )2 we have is independent of concentration of C, i.e. order of
n -1 reaction with respect to C is zero.
( t1/ 2 )1 æ a2 ö
or =ç ÷ Hence, the overall rate law expression will be
( t1/ 2 )2 çè a1 ÷ø
Rate = k [ A]2 [B] [C ]0
By taking log on both the sides and rearranging the
equation, we obtain Thus, order of reaction = 2 + 1 + 0 = 3
log [(t1/ 2 )1 /(t1/ 2 )2 ] 4. Initial Rate Method
n = 1+
log (a2 /a1 )
In this method, the order of a reaction is determined by
• From this equation, n, the order of reaction is calculated. varying the concentration of one of the reactants while
• For gaseous equations, the initial pressure ( p) is taken
others are kept constant The initial rate, r1 is
instead of initial concentration a, thus, for them the determined either numerically or from the slope of the
above formula is changed to curve of concentration versus time.
Thus, for the reaction
log [(t1/ 2 )1 / (t1/ 2 )2 ] aA + bB + cC ¾® product
n = 1+
log ( p2 / p1 ) ri = k [ Ai ]a [Bi ]b [Ci ]c
Now, if [B] and [C ] remain constant, Þ So, r µ [ A]1[B]0 Þ r µ [ A]

ri = ki [ Ai ]a where, ki = k[Bi ]b [Ci ]c Order of the reaction (n) = 1
Here the value of a can be determined by inspecting the Þ Now, let for the 1st experiment,
rate at different values of [ A] as, it we know the initial r1 = k × [ A]
rates at different concentration of A we have r 6.93 ´ 10 - 3
Þ k= 1 =
[ri ]1 = ki [ Ai ]1a , [ri ]2 = ki [ Ai ]a2 [ A] 0.1
where, [ri ]1 and [ri ] 2 are the initial rates of reaction and = 6.93 ´ 10 - 2 s- 1
[ Ai ]1 , and [ Ai ] 2 are initial concentrations of A. On 0.693
Þ t50 =
dividing both the equations, we get k
a 0.693
[ri ]1 é [ Ai ]1 ù = = 10 s
=ê ú 6.93 ´ 10 - 2
[ri ] 2 êë [ Ai ] 2 úû
Taking log on both the sides, we obtain 5. Graphical Method
[r ] [A ] In this method, the values of Dx/ Dt at different intervals
log i 1 = a log i 1 ,
[ri ] 2 [ Ai ] 2 of time is determined by plotting a curve between x
(the amount of substance decomposed) and time t.
log [(ri )1 /(ri )2 ]
a= The value of Dx/ Dt at a particular time corresponding to a
log [( Ai )1 /( Ai )2 ]
particular value of ( a - x ) is given by the slope of the
In this way, the order of reaction with respect to a is curve at that curve. Linear Plots for Different Order
determined. Similarly, it can also be determined for other Reactions are as
reactants also, The overall order of reaction is the sum of
all such orders, i.e. n = a + b + c ¼ Plot of Differential Equations to
Example 11. The following results were obtained during
Corresponding Rate Equation
kinetic studies of the reaction
2A + B ¾® products
log
[A ] x
Experiment [A] [B] Initial rate of reaction (a-x)
Conc.
(in mol L-1) (in mol L-1) (in mol L-1 min -1)
I. 0.10 6.93 ´10 -3

0.20
t t
II. 0.10 6.93 ´10 -3
0.25
For zero order For first order
III. 0.20 1.386 ´10 -2
0.30
The time (in minutes) required to consume half of A is
(JEE Main 2019)
(a) 5 (b) 10 (c) 100 (d) 1 x 1
a-x (a-x) 2
Sol. (b) Let, the rate expression is
r µ [ A]a [B] b . t t
From experiment I, For second order For third order
a b
r2 æ 0.1ö æ 0.25 ö
= ç ÷ ´ç ÷
r1 è 0.1ø è 0.20 ø
6.93 ´ 10 - 3
b dx dx
æ5ö
Þ = 1´ ç ÷ dt dt
6.93 ´ 10 - 3 è 4ø
b
æ5ö
Þ 1= ç ÷ (a-x) (a-x)
è 4ø
0 b For zero order For first order
æ5ö æ5ö
Þ ç ÷ =ç ÷ Þ b =0
è ø
4 è 4ø
a b
r3 æ 0.2 ö æ 0.30 ö
From experiment II, =ç ÷ ´ç ÷ dx dx
r1 è 0.1ø è 0.20 ø dt dt
1.386 ´ 10 - 2
Þ = (2) a ´ (1.5) 0
0.693 ´ 10 - 2 (a-x) 2 (a-x) 3
Þ 2 = 2 a ´ 1 Þ 21 = 2 a Þ a =1
For second order For third order
æ dx ö The concept of activation energy as applied to chemical

If graphs are plotted between log ç ÷ and log ( a - x ), the
è dt ø reaction can be explained by plotting energy against the
slope of the line gives the order of reaction. progress of reaction as shown in the figure below.
Threshold energy B
Eth
Activation
dx Ea1 energy for
log q
forward reaction
Energy
dt
Heat of
log (a – x) reaction
Activation A
æ dx ö Reactants DE
Plot of log ç ÷ vs log (a - x) energy for C Products
è dt ø reverse reaction
dx (Ea1+DE) = Ea2
Q = k ( a - x )n Progress of reaction
dt
Ea = Eth - ER
æ dx ö
\ log ç ÷ = log k + n log( a - x ) where, Eth = threshold energy (the minimum energy
è dt ø required over and above the energy possessed by the
Thus, slope n = tan q
reactants in order to cross the energy barrier).
ER = energy possessed by the reactant.
Effect of Temperature on All the molecules in the reacting species do not have the
Rate of Reaction same kinetic energy and it is not easy to predict the
Rate constants and, therefore rate of a chemical reaction behavior of any one molecule.
depends strongly on temperature. Typically rates of all Ludwig Boltzmann and James Clark Maxwell used
reactions increase with increase in temperature. statistics to predict the behaviour of large number of
A rough rule, valid for many reactions in solution, is that molecules and give Maxwell and Boltzmann distribution
near room temperature, rate constant ( k) doubles or curve.
Fraction of molecule
triples for each 10°C rise in temperature.
Arrhenius Equation
In year 1889, Arrhenius noted that k(T ) data for many Most probable
velocity
reactions fit the equation.
k = Ae- E a / RT
Here, A = a constant called frequency factor (because it Kinetic energy
Maxwell and Boltzmann distribution curve
gives the frequency of binary collisions of the
NE
reacting molecules per second per litre). It is Fraction of molecules =
also called collision number or NT
pre-exponential factor NE = number of molecules with energy E
R = gas constant, T = absolute temperature NT = total number of molecules.
Ea = energy of activation ● Peak of the curve corresponds to the most probable
The factor e- E a / RT is referred as Boltzmann factor and kinetic energy. There is decrease in number of
gives the fraction of molecules having energy equal to or molecules with higher energies or lower energies than
greater than activation energy. this peak value.
● When the temperature is raised the curve is broaden
Activation Energy out and peak of the curve moves to the higher energy
The activation energy can also be defined as, “The energy value. But area under the curve is constant since total
that activates passive or non-active molecules after its probability must be one at all times.
adsorption or minimum energy in excess to normal
Ea(t1) T1 > T2
Fraction of molecule
energy of molecules, which molecules must possess in T1

order to form product on collision. T2
The concept of activation energy gives us an idea whether
a given reaction is slow or fast at a given temperature. A Ea(t1)
reaction which has lower activation energy proceed at a
faster rate at a given temperature or vice-versa.
The differences in activation energy are mainly
responsible for observed difference in rates of reactions.
Kinetic energy
● By increasing the temperature of the substance Remember

increases the fraction of molecules which collide with Different reactions have different rates because their
energies greater than Ea . activation energies are different. Lesser the activation
energy, faster is the reaction rate.
Calculation of Activation Energy Activation energy can never be zero. If E a = 0, then
Activation energy can be calculated by knowing the rate according to Arrhenius equation, k = A , i.e. every
collision between molecules leads to a chemical reaction.
constants at two different temperatures, assuming that
This can never be true.
Ea and A remains constant.
Taking log of both the sides in Arrhenius equation, we get Example 12. The rate constant (k) of a reaction is measured
at different temperature (T ), and the data are plotted in the given
E
ln k = ln A - a …(i) figure. The activation energy of the reaction in kJ mol -1 is (R is
RT gas constant) (JEE Main 2020)
Now, if the values of rate constant at temperatures T1 10
and T2 are k1 and k2 respectively then
E In k
ln k1 = ln A - a …(ii) 5
RT1
Ea
ln k2 = ln A - …(iii) 0
RT2 1 2 3 4 5
Subtracting the Eq. (ii) from (iii), we get 103/T
2 1
(a) (b) (c) R (d) 2R
k E éT - T1 ù R R
In 2 = a ê 2
k1 R ë T1T2 úû -E
k = Ae a /
RT
Sol. (d) \
k2 Ea æ T2 - T1 ö Taking natural logarithm on both sides, the Arrhenius
or log = ç ÷ [Here, T2 > T1] …(iv)
k1 2.303R çè T1T2 ÷ø equation becomes.
æE ö 1 æ E a ö 10 3
This relation is used when rate constants at two different Þ ln k = ln A - ç a ÷ = ln A - çç ÷´
3÷
temperatures are given.
èRøT è R ´ 10 ø T
-E a -10
d log k E Slope of a graph = =
Equation (i) is also written as, = a2 R ´ 10 3 5
dT RT
E a = 2R ´ 10 3 J mol -1 Þ E a = 2R kJ mol-1
Graphical Representation Example 13 How faster would a reaction proceed at 25°C
of Arrhenius Equation than at 0°C if the activation energy is 65 kJ?
Arrhenius equation is purely an empirical equation that (a) 11 times (b) 9 times (c) 6 times (d) 2 times
gives a reasonably good representation of temperature
dependence of the rate constant. k2 E a é T2 - T1 ù
Sol. (a) 2.303 log =
When log k is plotted against 1/ T , we get a straight line k1 R êë T1T2 úû
which is represented by Arrhenius equation as, k2 65 ´10 3 é 25 ù
- E a / RT \ 2.303 log = Þ k2 / k1 = 11.05
k = Ae k1 8.314 ë 298 ´ 273 úû
ê
or ln k = ln A - Ea/ RT Example 14 Milk turns sour at 40°C three times faster as
Ea at 0°C. The energy of activation for souring of milk is
or log k = log A -
2.303 RT (a) 5.683 kcal (b) 2.532 kcal (c) 4.693 kcal (d) 4.246 kcal
The intercept of this line is equal to log A and slope is k E [T - T ]
Ea Sol. (c) 2.303 log 2 = a 2 1
equal to - . Therefore, Ea = -2.303 R ´ slope k1 R T1T2
2.303 R
E a [313 - 273]
–5.0 \ 2.303 log 3 = Þ E a = 4.693 kcal
2 313 ´ 273
–6.0 –Ea
–7.0 Slope =
In k –8.0
2.303 R
Theories of Rate of Reaction
–9.0 Ea = – 2.303 ´ R ´ slope Following theories are given to explain the rate of a
–10.0 reaction.
–11.0
–12.0 Collision Theory of Bimolecular Reactions
–13.0 The collision theory states that
1.3 1.4 1.5 1.6
●If two molecules are to react together, they must collide
(1/T) with each other.
● The collision between all molecules do not lead to Remember This theory explains the results of a number of
chemical reaction. reactions but it does not give satisfactory explanation in some
● The collisions in which the molecules acquire energy cases as it consider atoms/molecules to be hard sphere and
greater than the activation energy, results in chemical ignores their structural aspect.
reaction.
Transition State Theory
N Effective N
Cl Cl + This theory is also known as absolute reaction rate
collisions
theory or activated complex theory. This theory is
Properly oriented collisions to form products based on the idea that bond breaking and bond making
involved in a chemical reaction must occur continuously
or simultaneously. According to this theory
● The reactant molecules must come together to form an
C N
activated complex, whose energy is higher than the
OR reactant molecules.
C Effective ● The activated complex is supposed to be in equilibrium
Required products
collisions are not formed with the reactant molecules and has all the attributes
N of normal molecule except that one of the vibrational
degree of freedom is converted into translational degree
of freedom.
Collisions are not properly oriented ● This complex though unstable, has a transient
Orientation of reactants existence and its potential energy is maximum. Finally

● The colloiding molecules must posses certain minimum it decomposes into products.
energy (threshold energy) to make the collision ● The energy of activation according to this theory is the
effective. additional energy which the reacting molecules must

● The additional energy required by the molecule to acquire to form the activated complex.
attain threshold energy is called activation energy.
Transition state
During the collisions, this energy is acquired by the
or activated complex
molecules as a result of interchange of energies. Thus,
Activation energy = threshold energy – energy of E1
E1 = activation
colliding molecules energy of reactant
Energy
E2
● If we assume that the rate of reaction is equal to the E2 = activation
rate of collisions per unit volume per unit time energy of products
multiplied by the fraction of collisions (that have
sufficient relative kinetic energy to overcome the
energy barrier E * ) then the rate constant is given by
Reaction path
the expression *
k = Z AB × e- E / KT Energy profile diagram of an exothermic reaction
Here, Z AB = collision frequency factor, i.e. the

number of collisions between reactant molecules A and B Action of Catalyst
per unit volume per unit time divided by N A and N B , the A catalyst can increase the rate of a chemical reaction by
number of molecules per unit volume of A and B lowering the activation energy as shown below :
respectively.
B Activated complex without catalyst
For a successful collision, however it is also important Activated complex with catalyst
that the molecules must be oriented properly in space
(placing in correct)
Lower energy of activation

alongwith their energy requirements. Thus, if P is the Ea provided by the catalyst
orientation factor (also called steric factor) then above through new reaction
Energy
rate equation can be changed as. ER pathway

K = PZ AB e- E a / RT Reactants
EP
Now, if we compare above equation, with Arrhenius
Products
equation we get
Progress of reaction
A = PZ AB
where, A = Arrhenius collision factor Energy profile diagram in the absence and presence of catalyst
Practice Exercise
ROUND I Topically Divided Problems
Rate of Reaction and Factors 5. The rate equation for the reaction 2 A + B ® C is
Affecting It found to be rate = k [ A ] [ B ]
1. Consider the reaction, 2 A + B ¾® products. When The correct statement in relation to this reaction is
concentration of B alone was doubled, the half-life that the (AIEEE 2004)
did not change. When the concentration of A alone (a) unit of k must be s -1
was doubled, the rate increased by two times. The (b) t1/ 2 is a constant
unit of rate constant for this reaction is (AIEEE 2007) (c) rate of formation of C is twice the rate of
disappearance of A
(a) L mol-1 s -1 (b) no unit
(d) value of k is independent of the initial
(c) mol L-1 s -1 (d) s -1 concentrations of A and B
1
2. For a reaction A ¾® 2 B, rate of disappearance 6. Which of the following expression is correct for the
2
rate of reaction given below? (NCERT Exemplar)
of ‘A’ is related to the rate of appearance of ‘B’ by
-
the expression (AIEEE 2008) 5Br ( aq) + BrO 3- ( aq) +
+ 6H ( aq) ¾® 3Br2 ( aq)
+ 3H 2O ( l)
d [ A ] 1 d [B] d [ A ] 1 d [B]
(a) - = (b) - =
dt 2 dt dt 4 dt D [Br - ] D [H+ ] D [Br - ] 6 D [H+ ]
(a) =5 (b) =
d [ A ] d [B] d [ A] d [B] Dt Dt Dt 5 Dt
(c) - = (d) - =4
dt dt dt dt D [Br - ] 5 D [H+ ] -
D [Br ] D [H+ ]
(c) = (d) =6
Dt 6 Dt Dt Dt
3. For the reaction : H 2 + I 2 ¾® 2HI, the
differential rate law is (AIEEE 2002) 7. A graph of volume of hydrogen released vs time for
d [H2] d [I2] d [HI] the reaction between zinc and dil.HCl is given in
(a) - =- =2
dt dt dt figure. On the basis of this mark the correct option.
d [H2] d [I2] d [HI]
(b) - 2 = -2 =
dt dt dt V5
V4
d [H2] d [I2] d [HI]
(c) - =- =
dt dt dt V3
d [H2] d [I2] d [HI]
(d) - =- = V2
2dt 2dt dt V1
4. The rate of a reaction is expressed in different ways
as follows
1 d [C ] 1 d [D ] 1 d [A ] d [B ] O 20 30 40 50
+ =- =+ =-
2 dt 5 dt 3 dt dt V3 - V 2
(a) Average rate upto 40 seconds is
The reaction is 40
V3 - V 2
(a) 4 A + B ¾® 2 C + 3 D (b) Average rate upto 40 seconds is
40 - 30
(b) B + 5 D ¾® 3 A + 2 C
V3
(c) 4 A + 2 B ¾® 2 C + 3 D (c) Average rate upto 40 seconds is
1 40
(d) B + D ¾® 4 A + 2 C V - V1
2 (d) Average rate upto 40 seconds is 3
40 - 20
8. Which of the following statements is correct ? 16. The conversion of molecules x to y follows second
(NCERT Exemplar) order kinetics. If concentration of x is increased to
(a) The rate of a reaction decreases with passage of three times, the rate of formation of y will (NCERT)
time as the concentration of reactants decreases
(a) increase by three times
(b) The rate of a reaction is same at any time during
the reaction (b) decrease by three times
(c) The rate of a reaction is independent of (c) increase by nine times
temperature change (d) decrease by nine times
(d) The rate of a reaction decreases with increase in 17. The rate of a gaseous reaction is equal to k[ A ][ B ].
concentration of reactant(s) The volume of the reaction vessel containing these
9. Consider the graph given in Q. 7. Which of the gases is reduced by one-fourth of the initial volume.
following options does not show instantaneous rate The rate of the reaction would be
of reaction at 40th second? (NCERT Exemplar) 1 16 1 8
(a) (b) (c) (d)
V - V2 V - V2 16 1 8 1
(a) 5 (b) 4
50 - 30 50 - 30 18. For a first order reaction, the graph log [ A ] vs t is
V3 - V 2 V3 - V1 given below.
(c) (d)
40 - 30 40 - 20
10. The rate constant for the reaction,
log [A]
Slope = x
2N 2O 5 ¾® 4NO 2 + O 2 is 3.0 ´ 10–5 s -1. If the rate is
2.40 ´ 10-5 then the concentration of N 2O 5 (in mol/L) is
(a) 1.4 (b) 1.2 (c) 0.04 (d) 0.8
11. For a chemical reaction 2 X + Y ¾® Z , the rate of Time
appearance of Z is 0.05 mol L-1 min -1. The rate of x is equal to
disappearance of X will be 0.693 k
(a) (b)
(a) 0.05 mol L-1 h -1 (b) 0.05 mol L-1 min -1 k 2.303
(c) 0.1 mol L-1 min -1 (d) 0.25 mol L-1 min -1 k
(c) - (d) log [ A ]0
2.303
Molecularity and Rate Law Expression
19. The hydrolysis of ethyl acetate was carried out
12. Units of rate constant of first and zero order separately with 0.05 M HCl and 0.05 M H 2SO 4 .
reactions in terms of molarity M unit are
respectively The rate constants were found to be ( k1) and ( k2 )
(a) s -1 , M s -1 (b) s -1 , M (c) M s -1 , s -1 (d) M, s -1 respectively then
(a) k1 < k2 (b) k1 > k2 (c) k1 = k2 (d) k2 = 2k1
13. For which type of reaction order and molecularity
have the same value? (NCERT Exemplar) 20. In the sequence of reaction,
(a) First order reaction (b) Bimolecular reaction 1 2 k 3 k k
A ¾® B ¾® C ¾® D
(c) Termolecular reaction (d) Elementary reaction
k3 > k2 > k1 then the rate determining step of the
14. The rate of the reaction,
reaction is
CCl 3CHO + NO ¾® CHCl 3 + NO + CO (a) A ¾® B (b) B ¾® C
is equal to rate k[CCl 3CHO][NO]. If concentration (c) C ¾® D (d) A ¾® D
is expressed in mol/L, the unit of k is 21. Given the hypothetical reaction mechanism
(a) L mol–1 s –1 (b) mol L–1 s –1 I
II III IV
(c) L2 mol–2 s –1 (d) s -1 A ¾® B ¾® C ¾® D ¾® E
and the data as,
15. Rate law for the reaction A + 2 B ¾® C is found to be
Rate = k[ A ][ B ] Species formed Rate of its formation
Concentration of reactant ‘ B ’ is doubled, keeping B 0.002 mol/h, per mole of A
the concentration of ‘ A ’ constant, the value of rate C 0.030 mol/h, per mole of B
constant will be (NCERT Exemplar) D 0.011 mol/h, per mole of C
(a) the same (b) doubled E 0.042 mol/h, per mole of D
(c) quadrupled (d) halved
The rate determining step is Order of Reaction

(a) step I (b) step II (c) step III (d) step IV
27. In the reaction A + B ¾® products, if B is taken
22. A reaction involving two different reactants can
in excess, then it is an example of
never be (AIEEE 2005)
(a) second order reaction
(a) bimolecular reaction (b) second order reaction (b) zero order reaction
(c) first order reaction (d) unimolecular reaction (c) pseudounimolecular reaction
23. Consider the reaction, (d) first order reaction
Cl 2 ( aq) + H 2S ( aq) ¾® S ( s) + 2H + ( aq) + 2Cl - ( aq) 28. Half-life of a reaction is found to be inversely
The rate equation for this reaction is, proportional to the cube of initial concentration.
rate = k[Cl 2 ] [H 2S] The order of reaction is
Which of these mechanisms is/are consistent with (a) 4 (b) 3 (c) 5 (d) 2
this rate equation? (AIEEE 2010) 29. For a general reaction, A ¾® B, plot of
(A) Cl2 + H 2S ¾® H + + Cl+ + Cl+ + HS (slow)
concentration of A vs time is given in figure.
Cl+ + HS - ¾® H + + Cl- + S (fast)
What are the units of rate constant?
(B) H 2S s H + + HS (fast equilibrium) (NCERT Exemplar)
- +
Cl2 + HS ¾® 2Cl + H + S (slow)
(a) (B) only (b) Both (A) and (B) A B
Conc. of A
(c) Neither (A) or (B) (d) (A) only
24. For the reaction system,
2NO ( g) + O 2 ( g) ¾® 2NO 2 ( g) t
volume is suddenly reduced to half its value by (a) mol L-1 s -1 (b) mol-1 L s -1
increasing the pressure on it. If the reaction is of (c) s -1 (d) mol-2 L2 s -1
first order with respect to O 2 and second order with 30. It is true that (JEE Main 2020)
respect to NO; the rate of reaction will (AIEEE 2003) (a) a second order reaction is always a multistep
(a) diminish to one-fourth of its initial value reaction
(b) diminish to one-eight of its initial value (b) a zero order reaction is a multistep reaction
(c) increase to eight times of its initial value (c) a first order reaction is always a single step
(d) increase to four times of its initial value reaction
(d) a zero order reaction is a single step reaction
25. For the reaction,
2H 2 ( g) + 2NO( g) ¾® N 2 ( g) + 2H 2O( g) 31. Higher order (>3) reactions are rare due to
(JEE Main 2015)
the observed rate expression is, rate = kf [NO]2 [H 2 ].
(a) low probability of simultaneous collision of all the
The rate expression for the reverse reaction is reacting species
(JEE Main 2020)
(a) kb [N2][H2O]2 / [H2] (b) kb [N2][H2O] (b) increase in entropy and activation energy as more
molecules are involved
(c) kb [N2][H2O]2 / [NO] (d) kb [N2][H2O]2
(c) shifting of equilibrium towards reactants due to
26. For the reaction, 2 A + B ¾® C, the values of elastic collisions
initial rate at different reactant concentrations are (d) loss of active species on collision
given in the table below. 32. Which of the following statements is not correct
The rate law for the reaction is (JEE Main 2019) about order of a reaction? (NCERT Exemplar)
(a) The order of a reaction can be a fractional number.
[A] [B] Initial rate (b) Order of a reaction is experimentally determined
(mol L-1 ) (mol L-1 ) (mol L-1s -1 )
quantity.
0.05 0.05 0.045 (c) The order of a reaction is always equal to the sum
0.10 0.05 0.090 of the stoichiometric coefficients of reactants in
the balanced chemical equation for a reaction.
0.20 0.10 0.72
(d) The order of a reaction is the sum of the powers of
2
(a) rate = k [ A ][B] (b) rate = k [ A ] [B]2
2
molar concentration of the reactants in the rate
(c) rate = k [ A ][B] (d) rate = k [ A ]2[B] law expression.
33. Radioactive decay is a 40. In a second order reaction when the concentrations
(a) first order reaction (b) zero order reaction of both the reactants are equal, the reaction is
(c) second order reaction (d) third order reaction completed 20% in 500 s. How long will it take for
34. The rate law for the reaction, the reaction to go to 60% completion?
RCl + NaOH ¾® ROH + NaCl is given by (a) 1000 s (b) 300 s
(c) 3000 s (d) 2000 s
Rate = k [ RCl]. The rate of this reaction
(a) is doubled by doubling the concentration of NaOH 41. 1 g of 79 Au198 ( t1/ 2 = 65 h) gives stable mercury by
(b) is halved by reducing the concentration of RCl by b-emission. What amount of mercury will left after
one half 260 h?
(c) is increased by increasing the temperature of the (a) 0.9375 g (b) 0.3758 g
reaction (c) 0.7586 g (d) 0.9000 g
(d) in unaffected by change in temperature
42. A first order reaction is 50% completed in
35. The reaction L ¾® M is started with 10.0 g of L. 1.26 ´ 1014 s. How much time would it take for
After 30 and 90 min, 5.0 g and 1.25 g of L 100% completion? (NCERT Exemplar)
respectively are left. The order of the reaction is (a) 1.26 ´ 1015 s (b) 2.52 ´ 1014 s
(a) 0 (b) 1 (c) 2 (d) 3 (c) 2.52 ´ 1028 s (d) Infinite
36. The rate constant of a zero order reaction is 43. The rate of a first order reaction is
0.2 mol dm –3 h -1. If the concentration of the 1.5 ´ 10 –2 mol L–1 min –1 at 0.5 M concentration of
reactant after 30 min is 0.05 mol dm -3, then its the reactant. The half-life of the reaction is
initial concentration would be (a) 13.6 min (b) 42.5 min (c) 23.1 min (d) 32.5 min
(a) 0.01 mol dm-3 (b) 0.15 mol dm-3
(c) 0.25 mol dm-3 (d) 4.00 mol dm-3 44. The time for half-life period of a certain reaction,
A ® products is 1 h. When the initial concentration
37. What is the two third life of a first order reaction of the reactant ‘ A ’ is 2.0 mol L-1, how much time
having k = 5.48 ´ 10 -14 s-1 ? does it take for its concentration to come from 0.50
(a) 2.01 ´ 1013 s (b) 2.01 ´ 1012 s
to 0.25 mol L-1, if it is a zero order reaction?
(c) 4.02 ´ 1013 s (d) 4.02 ´ 1026 s (AIEEE 2010)
38. Sucrose decomposes in acid solution into glucose (a) 4 h (b) 0.5 h
and fructose according to the first order rate law, (c) 0.25 h (d) 1 h
with t1/ 2 = 3.00 h. What fraction of sample of 45. Rate constant, k of the first order reaction when
sucrose remains after 8 h? (NCERT) initial concentration (C0 ) and concentration at time
(a) 1.023 M (b) 0.8725 M t, (Ct ) is given by the equation
(c) 0.023 M (d) 0.1576 M kt = log C0 - log Ct
39. Consider the following reactions Graph is a straight line if we plot (AIEEE 2002)
A ® P1; B ® P2; C ®P3; D ® P4, (a) t vs log C 0
The order of the above reactions are a, b, c and d, (b) t vs log C t
respectively. The following graph is obtained when (c) t -1 vs log C t
log[rate] vs log[conc.] are plotted: (d) log C 0 vs log C t
[D]
[B] 46. The rate constant for a first order reaction is 60 s-1.
[A ] How much time will it take to reduce the initial
log [rate]
[C] concentration of the reactant to its 1/16th value?

(NCERT)
(a) 0.046 s (b) 0.025 s
(c) 0.098 s (d) 0.060 s
log [conc.]
47. A flask contains a mixture of compounds A and B.
Among the following, the correct sequence for the Both compounds decompose by first-order kinetics.
order of the reactions is (JEE Main 2020) The half-life for A and B are 300 s and 180 s,
(a) D > A > B > C (b) A > B > C > D respectively. If the concentrations of A and B are
(c) C > A > B > D (d) D > B > A > C equal initially, the time required for the
concentration of A to be four times that of B (in s) is Initial rate

Initial Initial
(Use ln 2 = 0.693) (JEE Main 2020) of formation
Experiment concentration concentration
of [C]/mol L -1
(a) 120 (b) 180 (c) 300 (d) 900 of [A]/mol L -1 of [B]/mol L -1
s -1
48. The given plots represent the variation of the 1. 0.30 0.30 0.10
concentration of a reaction R with time for two 2. 0.30 0.60 0.40
different reactions (i) and (ii). The respective orders 3. 0.60 0.30 0.20
of the reactions are (JEE Main 2019)
Choose the correct option for the rate equations for
(i) (ii) this reaction. (NCERT Exemplar)
In [R] [R] (a) Rate = k[ A ]2[B] (b) Rate = k[ A ][B]2

(c) Rate = k[ A ][B] (d) Rate = k[ A ]2[B]0
53. A bacterial infection in an internal wound grows as
time time
N ¢ ( t) = N0 exp ( t), where the time t is in hours. A
(a) 1, 1 (b) 0, 2 (c) 0, 1 (d) 1, 0
dose of antibiotic, taken orally, needs 1 hour to
49. For the reaction, 2 A + B ¾® products reach the wound. Once it reaches there, the
When concentration of both (A and B) becomes dN
bacterial population goes down as = - 5 N 2.
double, then rate of reaction increases from 0.3 mol dt
N
L -1 s -1 to 2.4 mol L -1 s -1. What will be the plot of 0 vs t after 1 hour ?
N (JEE Main 2019)
When concentration of only A is doubled, the rate of
reaction increases from N0
N0
0.3 mol L -1 s -1 to 0.6 mol L -1 s -1 (a)
N
(b)
N
Which of the following is true? (JEE Main 2019)
t(h) t(h)
(a) The whole reaction is of 4th order
(b) The order of reaction w.r.t B is one
(c) The order of reaction w.r.t B is 2 N0 N0
(c) (d)
(d) The order of reaction w.r.t A is 2 N N
50. For a first order reaction given is, ( A) ¾® products t(h) t(h)
. The concentration of A changes from 0.1 M to
0.025 M in 40 min. The rate of reaction when the Effect of Temperature on
concentration of A is 0.01 M is (AIEEE 2012) Rate of Reaction
(a) 1.73 ´ 10-5 M / min (b) 3.47 ´ 10-4 M / min 54. Arrhenius equation may not be represented as
(c) 3.47 ´ 10-5 M / min (d) 1.73 ´ 10-4 M / min A Ea
(a) ln =
51. At 518°C, the rate of decomposition of a sample of k RT
gaseous acetaldehyde, (initially at a pressure of d ln k E
(b) =
363 torr), was 1.00 torr s-1 when 5% had reacted dT RT 2
Ea
and 0.5 torr s-1 when 33% had reacted. The order of (c) log A = log k +
2.303 RT
the reaction is (JEE Main 2018)
é E ù k
(a) 2 (b) 3 (c) 1 (d) 0 (d) log ê - a ú =
ë RT û A
52. Compounds ‘A’ and ‘B’ react according to the
55. When a graph is plotted between ln k and 1/T for a
following chemical equation.
first order reaction, a straight line is obtained. The
A ( g) + 2 B ( g) ¾® 2C ( g) slope of the line is equal to
Concentration of either ‘A’ or ‘B’ were changed (a) -
Ea
(b) -
Ea
keeping the concentrations of one of the reactants 2.303 2.303R
constant and rates were measured as a function of 2.303 E
(c) - (d) - a
initial concentration. Following results were E aR R
obtained.
56. According to Arrhenius equation rate constant k is (c) Rate constant increases exponentially with
- Ea / RT decreasing activation energy and decreasing
equal to Ae . Which of the following options
1 temperature
represents the graph of ln k vs ? (d) Rate constant increases exponentially with
T (NCERT Exemplar)
decreasing activation energy and increasing
temperature
60. In Arrhenius equation, k = Ae- Ea / RT ; A may be
called the rate constant at
(a) ln k (b) ln k
(a) very low temperature
(b) zero activation energy
(c) the boiling temperature of reaction mixture
1/T ® 1/T ®
(d) All of the above
61. Rate of a reaction can be expressed by Arrhenius
equation as
(c) ln k (d) ln k
k = Ae- E / RT
In this equation, E represents [AIEEE 2006]
1/T ® (a) the energy above which all the colliding molecules
1/T ® will react
(b) the energy below which colliding molecules will
57. Which of the following graphs represents
not react
exothermic reaction? (c) the total energy of the reacting molecules at a
Activated complex Activated complex temperature, T
(d) the fraction of molecules with energy greater than
the activation energy of the reaction
Energy
Energy
(i) (ii)
Reactants Products 62. Consider figure and mark the correct option.
Products Reactants
Activated complex
Reaction coordinate Reaction coordinate
Activated complex E1
Energy
Products
Energy
(iii) E2
Reactants Products Reactants
Reaction coordinate
Reaction coordinate
(a) (i) only (b) (ii) only (c) (iii) only (d) (i) and (ii)
(a) Activation energy of forward reaction is E1 + E 2
58. The rate constant ( k¢ ) of one of the reaction is and product is less stable than reactant.
found to be double that of the rate constant ( k¢ ¢ ) of (b) Activation energy of forward reaction is E1 + E 2
another reaction. Then the relationship between and product is more stable than reactant
the corresponding activation energies of the two (c) Activation energy of both forward and backward
reactions (Ea ¢ and Ea ¢ ¢ ) can be represented as reaction is E1 + E 2 and reactant is more stable
(a) E a ¢ > E a ¢ ¢ (b) E a ¢ = 4E ¢ ¢ than product.
(c) E1 ¢ = E a ¢ ¢ (d) E a ¢ < E a ¢ ¢ (d) Activation energy of backward reaction is E1 and
product is more stable than reactant
59. Consider the Arrhenius equation given below and
mark the correct option. (NCERT Exemplar)
63. An endothermic reaction A ¾® B has an
activation energy of 15 kcal/mol and the energy of
k = Ae- Ea / RT reaction is 5 kcal/mol. The activation energy for the
(a) Rate constant increases exponentially with reaction B ¾® A is
increasing activation energy and decreasing (a) 20 kcal/mol
temperature (b) 15 kcal/mol
(b) Rate constant decreases exponentially with (c) 10 kcal/mol
increasing activation energy and decreasing (d) zero
temperature
64. If the reaction rate at a given temperature becomes 68. If a reaction follows the Arrhenius equation, the plot
slower then lnk vs 1/(RT) gives straight line with a gradient (- y)
(a) the free energy of activation is higher unit. The energy required to activate the reactant is
(b) the free energy of activation is lower (JEE Main 2019)
y
(c) the entropy changes (a) unit (b) - y unit (c) yR unit (d) y unit
R
(d) the initial concentration of the reactants remains
constant 69. Consider the following plots of rate constant versus
65. Which of the following statements is incorrect about 1
for four different reactions. Which of the
T
the collision theory of chemical reaction?
(NCERT Exemplar) following orders is correct for the activation
(a) It considers reacting molecules or atoms to be hard energies of these reactions? (JEE Main 2020)
spheres and ignores their structural features
(b) Number of effective collisions determines the rate of
reaction
log k a
(c) Collision of atoms or molecules possessing d c
sufficient threshold energy results into the product
formation b
(d) Molecules should collide with sufficient threshold
energy and proper orientation for the collision to be
1/T
effective
66. Consider the given plot of enthalpy of the following (a) Eb > E a > E d > E c
reaction between A and B. (b) E a > E c > E d > Eb
A + B ¾® C + D (c) Eb > E d > E c > E a
Identify the incorrect statement. (JEE Main 2019) (d) E c > E a > E d > Eb
20 70. The energies of activation for forward and reverse

reactions for A2 + B2 2 AB are 180 kJ mol -1
r
Enthalpy 15 -1
and 200 kJ mol respectively. The presence of a
(kJ mol–1)10
D catalyst lowers the activation energy of both
5 (forward and reverse) reactions by 100 kJ mol -1.
A+B
C The enthalpy change of the reaction
Reaction ( A2 + B2 ® 2 AB) in the presence of catalyst will
coordinate
be (in kJ mol -1) (AIEEE 2007)
(a) D is kinetically stable product. (a) 300 (b) 120
(b) Formation of A and B from C has highest enthalpy (c) 280 (d) 20
of activation.
(c) C is the thermodynamically stable product. 71. A reactant (A) forms two products
(d) Activation enthalpy to form C is 5 kJ mol -1 1 k
A ¾® B, Activation energy Ea1
less than that to form D.
2 k
67. Consider the given plots for a reaction obeying A ¾® C, Activation energy Ea 2
Arrhenius equation (0°C < T < 300°C) : ( k and E a If Ea 2 = 2 Ea 1 , then k1 and k2 are related as (AIEEE 2011)
are rate constant and activation energy, respectively)
Ea 2 /RT Ea1 /RT
(a) k1 = 2k2e (b) k1 = k2e
Ea 2 /RT Ea1 /RT
(c) k2 = k1e (d) k1 = A k2e
k k
72. Consider an endothermic reaction X ® Y with the
activation energies Eb and E f for the backward
Ea T(°C) and forward reactions respectively. In general
I II (AIEEE 2005)
Choose the correct option. (JEE Main 2019) (a) there is no definite relation between Eb and E f
(a) Both I and II are wrong (b) Eb = E f
(b) Both I and II are correct (c) Eb > E f
(c) I is wrong but II is right
(d) Eb < E f
(d) I is right but II is wrong
73. For the reaction of H 2 with I2 , the rate constant is reaction at 400 K is 10 - 5 s- 1, then the rate
2.5 ´ 10 - 4 dm3 mol - 1s - 1 at 327°C and constant at 500 K is (JEE Main 2019)
1.0 dm3 mol -1 s -1 at 527°C. The activation energy for

the reaction, in kJ mol - 1 is (R = 8.314 JK -1
mol -2019)
(JEE Main
1
) Slope = –4606
ln k
(a) 59 (b) 72
(c) 150 (d) 166
1/ T
74. For a reaction, consider the plot of ln k versus 1 / T
(a) 4 ´ 10- 4 s - 1 (b) 10- 6 s - 1
given in the figure. If the rate constant of this (c) 10- 4 s - 1 (d) 2 ´ 10- 4 s - 1
ROUND II Mixed Bag

1. The chemical reaction 2O 3 ¾® 3O 2 proceeds as Select the correct answer by using the codes given
follows below.
(a) 1 and 3 (b) 1, 2 and 3
O3 º O 2 + O (fast) (c) 2 and 3 (d) 1 and 2
O + O 3 ¾® 2O 2 (slow) 5. An exothermic chemical reaction occurs in two
The rate law expression should be steps as follows
(a) r = k [O3 ]2 (b) r = k [O3 ]2[O2]-1 (i) A + B ¾® X (fast) (ii) X ¾® AB (slow)
(c) r = k [O3 ][O2] (d) unpredictable The progress of the reaction can be best
2. Two first order reactions have half-lives in the ratio represented by
8 : 1. Calculate the ratio of time intervals t1 : t2 . The X
time t1 and t2 are the time period for (1 / 4) th and X
(3/4)th completion.
(a) 1 : 0.602 (b) 2 : 301 (a) (b)
A+B A+B
AB AB
(c) 0.256 : 0.603 (d) 0.2 : 0.301
3. The rate constant of a reaction is given by
k = 2.1 ´ 1010 exp ( - 2700 RT). X
It means that (c) (d) All are correct

A+B
(a) log k vs 1/T will be a curved line with slope AB
2700
=-
2.303 R
6. The decomposition of hydrocarbon follows the
(b) log k vs 1/T will be a straight line with intercept
on log k axis = log 2.1 ´ 1010 equation k = ( 4.5 ´ 1011 s-1) e-28000 K/T. Calculate
(c) the number of effective collisions are the activation energy Ea . (NCERT)
2.1 ´ 1010 cm–3 s –1 (a) 232.79 kJ mol-1 (b) 425.25 kJ mol-1
(d) half-life of the reaction increases with increase of (c) 300 kJ mol-1 (d) 885.2 kJ mol–1
temperature
7. The rate law for a reaction between the substances A
4. Which of the following statements are correct? and B is given by rate = k [ A ]a [B]b. On doubling the
concentration of A and halving the concentration of B,
1. Order of a reaction can be known from the ratio of the new rate to the earlier rate of the
experimental result and not from the reaction will be as
stoichiometry of reaction. 1
(a) 2 a+ b (b) a + b (c) a - b (d) 2( a-b)
2. Overall molecularity of a reaction may be
determined in a manner similar to overall order 8. For a chemical reaction, A ® B, the rate of reaction
of reaction. increases by a factor of 1.837 when the
concentration of A is increased by 1.5 times. The
3. Overall order of reaction,
order of reaction with respect to A is
A m + B n ¾® ABx is ( m + n) (a) 0 (b) 1 (c) 1.5 (d) 2
9. The rate constant k, for the reaction 15. For following reactions
1 700 K
N 2O 5 ( g) ¾® 2NO 2 ( g) + O 2 ( g) is 2.3 ´ 10 – 2 s-1. A ¾¾¾® Product;
2 500 K
Which equation given below describe the change of A ¾¾¾® Product
Catalyst
[N 2O 5 ] with time? [N 2O 5 ]0 and [N 2O 5 ]t correspond It was found that the Ea is decreased by 30 kJ/mol
to concentration of N 2O 5 initially and at time t. in the presence of catalyst. If the rate remains
(a) [N2O5 ]t = [N2O5 ]0 + kt unchanged, the activation energy for catalysed
(b) [N2O5 ]t = [N2O5 ]0 ekt reaction is (Assume pre exponential factor is same):
[N O ] (JEE Main 2020)
(c) ln 2 5 0 = kt
[N2O5 ] t (a) 198 kJ/mol (b) 105 kJ/mol
(d) log10 [N2O5 ]t = log10 [N2O5 ]0 - kt (c) 75 kJ/mol (d) 135 kJ/mol
10. A substance undergoes first order decomposition. 16. The results given in the below table were obtained
The decomposition follows the parallel first order during kinetic studies of the following reaction :
2A + B ® C + D
reactions as
k1 B –4 –1 Initial rate/mol L-1
k1 = 1.26 × 10 s Experiment [A]/mol L-1 [B]/mol L-1
A min -1
–5 –1
k2 C k2 = 3.8 × 10 s I 0.1 0.1 6.00 ´ 10-3
The percentage distribution of B and C are II 0.1 0.2 2.40 ´ 10-2
III 0.2 0.1 1.20 ´ 10-2
(a) 76.83, 23.17 (b) 24.9, 75.1
IV X 0.2 7.20 ´ 10-2
(c) 60, 40 (d) 50, 50
V 0.3 Y 2.88 ´ 10-1
11. For a reaction A + B ¾® C + D, if the X and Y in the given table are respectively
concentration of A is doubled without altering the (JEE Main 2020)
concentration of B, the rate gets doubled. If the (a) 0.4, 0.4 (b) 0.4, 0.3 (c) 0.3, 0.4 (d) 0.3, 0.3
concentration of B is increased by nine times 17. The time required for 10% completion of a first
without altering the concentration of A, the rate order reaction at 298 K is equal to that required for
gets tripled. The order of the reaction is its 25% completion at 308 K. If the value of A is
(a) 1 (b) 1.5 (c) 2 (d) –1 4 ´ 1010 s-1. Calculate k at 318 K. (NCERT)
12. The half-time of a first order decomposition of (a) 2.89 ´ 10-2 s -1 (b) 3.26 ´ 10-2 s -1
nitramide is 2.1 h at 15°C. (c) 1.03 ´ 10-2 s -1 (d) 0.03 ´ 10-2 s -1
NH 2 NO 2 ( aq) ¾® N 2O ( g) + H 2O ( l) 18. The following data were obtained during the first
order thermal decomposition of SO 2Cl 2 at a
If 6.2 g of nitramide is allowed to decompose then
constant volume.
time taken for it to decompose 99% will be
SO 2Cl 2 ( g ) ¾® SO 2 ( g ) + Cl 2 ( g )
(a) 2.1 h (b) 12 h
(c) 13.96 h (d) 33 h Total
Experiment Time/s-1
pressure/atm
13. The activation energy for the given reaction
1 0 0.5
2HI ( g) ¾® H 2 ( g) + I 2 ( g) is 209.5 kJ mol -1 at
2 100 0.6
581 K. Calculate the fraction of molecules of
Calculate the rate of the reaction when total
reactants having energy equal to or greater than
pressure is 0.65 atm. (NCERT Exemplar)
activation energy. (NCERT)
(a) 2.84 ´ 10-7 atm s -1 (b) 7.80 ´ 10-4 atm s -1
(a) 1.82 ´ 10-18 (b) 1.47 ´ 10-19 (c) 4.42 ´ 10-7 atm s -1 (d) 5.62 ´ 10-4 atm s -1
(c) 2.67 ´ 10-16 (d) 3.89 ´ 10-19
19. For the decomposition of azoisopropane to hexane
14. In the following reaction; xA ® yB and nitrogen at 543 K, the following data are
é d[ A ] ù é d[ B ] ù obtained. Calculate the rate constant. (NCERT)
log10 ê - = log10 ê + 0.3010
ë dt úû ë dt úû t (s) p (mm of Hg)
A and B respectively can be (JEE Main 2019)
0 35.0
(a) n-butane and isobutane (b) C2H2 and C6H6
360 54.0
(c) C2H4 and C4H8 (d) N2O4 and NO2
720 63.0
(a) 2.21 ´ 10-3 s -1 (b) 3.48 ´ 10-3 s -1 26. The decomposition of formic acid on gold surface
(c) 1.26 ´ 10-3 s -1 (d) 8.46 ´ 10-3 s -1 follows first order kinetics. If the rate constant at
20. The rate of a certain biochemical reaction at 300 K is 1.0 ´ 10 -3 s-1 and the activation energy
physiological temperature (T) occurs 10 6 times Ea = 11. 488 kJ mol -1, the rate constant at 200 K is
faster with enzyme than without. The change in ……´ 10 -5 s-1. (Given : R = 8.314 J mol -1 K -1)
the activation energy upon adding enzyme is : (JEE Main 2021)
(JEE Main 2020)
27. The rate of a chemical reaction doubles for every
(a) + 6 RT (b) - 6(2.303) RT
10°C rise of temperature. If the temperature is
(c) + 6 (2.303) RT (d) - 6 RT
raised by 50°C, the rate of the reaction increases by
21. For the non-stoichiometric reaction, about ........ (times). (AIEEE 2011)
2 A + B ¾® C + D, the following kinetic data
28. In a first order reaction the concentration of the
were obtained in three separate experiments, all
reactant, decreases from 0.8 M to 0.4 M in 15 min.
at 298 K.
(JEE Main 2014) The time taken for the concentration to change from
0.1 M to 0.025 M is ........ (min).
Initial Initial Initial rate of
concentration concentration formation of C 29. The rate of a reaction decreased by 3.555 times when
(A) (B) (mol L -1 s -1) the temperature was changed from 40° C to 30° C.
0.1 M 0.1 M 1. 2 ´ 10-3 The activation energy (in kJ mol -1) of the reaction is
0.1 M 0.2 M 1. 2 ´ 10-3 ……… .
0.2 M 0.1 M 2. 4 ´ 10-3 (Take; R = 8.314 J mol -1K -1, ln 3.555 = 1.268)
The rate law for the formation of Cis (JEE Main 2020)
(a)
dc
= k [ A ] [B] (b)
dc
= k [ A ]2 [B] 30. The half-life for radioactive decay of 14 C is 5730 yr.
dt dt An archaeological artifact containing wood had only
dc dc
(c) = k [ A ] [B]2 (d) = k [ A] 80% of the 14 C found in a living tree. The age of the
dt dt
sample is ......... yr. (NCERT)
22. A first order reaction is 50% completed in 30 min
31. If 75% of a first order reaction was completed in 90
at 27°C and in 10 min at 47°C. Calculate the
minutes, 60% of the same reaction would be
activation energy of the reaction.
completed in approximately (in minutes) ........... .
(a) 43.8 kJ mol–1
(b) 4.38 kJ mol–1 (Take : log 2 = 0.30; log 2.5 = 0.40) (JEE Main 2020)
(c) 0.438 kJ mol–1 32. The number of molecules with energy greater than
(d) 438 kJ mol–1 the threshold energy for a reaction increases five fold
23. The rate constant, the activation energy and the by a rise of temperature from 27 °C to 42 °C. Its
Arrhenius parameter of a chemical reaction at energy of activation in J/mol is ……… .
25°C are 3.0 ´ 10 –4 s-1, 104.4 kJ mol –1 and (Take ln 5 = 1.6094; R = 8.314 J mol -1 K -1)
(JEE Main 2020)
6.0 ´ 1014 s-1 respectively. The value of the rate
constant at T ® ¥ is 33. A sample of milk splits after 60 min. at 300 K and
(a) 2.0 ´ 1018s -1 (b) 6.0 ´ 1014s -1 after 40 min at 400 K when the population of
(c) 3.6 ´ 1030s -1 (d) infinity lactobacillus acidophilus in it doubles. The activation
energy (in kJ/mol) for this process is closest to
Numeric Value Questions 2
(Given, R = 8.3 J mol -1K -1 ln æç ö÷ = 0.4, e-3 = 4.0)
24. The half-life of two samples are 0.1 and 0.8 sec. è3ø
(JEE Main 2020)
Their respective concentration are 400 and 50
respectively. The order of the reaction is ......... . 34. The decomposition of A into product has values of k
as 4.5 ´ 10 3 s-1 at 10°C and energy of activation
25. A and B decompose via first order kinetics with
60 kJ mol -1. The temperature at which k would be
half-lives 54.0 min and 18.0 min respectively.
1.5 ´ 10 4 sec -1 is ......... .
Starting from an equimolar non-reactive mixture
of A and B, the time taken for the concentration 35. The rate constant of the chemical reaction doubled
of A to become 16 times that of B is …… min. for an increase of 10 K in absolute temperature from
(JEE Main 2021) 295 K. The value of Ea will be ......... kJ mol -1.
Answers
Round I
1. (a) 2. (b) 3. (b) 4. (b) 5. (d) 6. (c) 7. (c) 8. (a) 9. (b) 10. (d)
11. (c) 12. (a) 13. (d) 14. (a) 15. (a) 16. (c) 17. (b) 18. (c) 19. (a) 20. (a)
21. (a) 22. (d) 23. (d) 24. (c) 25. (a) 26. (a) 27. (c) 28. (a) 29. (a) 30. (b)
31. (a) 32. (c) 33. (a) 34. (b) 35. (b) 36. (b) 37. (a) 38. (d) 39. (d) 40. (c)
41. (a) 42. (d) 43. (c) 44. (c) 45. (b) 46. (a) 47. (d) 48. (d) 49. (c) 50. (b)
51. (a) 52. (b) 53. (a) 54. (d) 55. (d) 56. (a) 57. (a) 58. (d) 59. (d) 60. (b)
61. (b) 62. (a) 63. (c) 64. (a) 65. (c) 66. (d) 67. (b) 68. (d) 69. (d) 70. (d)
71. (b) 72. (d) 73. (d) 74. (c)
Round II
1. (b) 2. (a) 3. (b) 4. (d) 5. (c) 6. (a) 7. (d) 8. (c) 9. (c) 10. (a)
11. (b) 12. (c) 13. (b) 14. (c) 15. (c) 16. (c) 17. (c) 18. (b) 19. (a) 20. (b)
21. (d) 22. (a) 23. (b) 24. (2) 25. (108) 26. (10) 27. (32) 28. (30) 29. (100) 30. (1845)
31. (60) 32. (84297.5) 33. (3.98) 34. (24.02) 35. (51.8)
Solutions
Round I 5. 2 A + B ¾® C
1. 2 A + B ¾® products
Rate = k [ A ] [B]
[B] is doubled, half-life didn’t change, i.e. half-life is It represents second order reaction.
independent of change in conc. of reactant, i.e. first
order. First order wrt to B. Thus, unit of k is M -1 s -1.
When [ A ] is doubled, rate increased by two times t1/ 2 is dependent of concentration but not constant.
Þ First order wrt A 1 d [ A ] d [C ]
and - =
Hence, net order of reaction = 1 + 1 = 2 2 dt dt
Unit for the rate constant = conc.(1- n) t -1 1 D [Br - ] 1 D [H+ ]

6. Rate = - =-
5 Dt 6 Dt
= (mol L-1 )-1 × s -1 = L × mol-1 s -1
1 D [Br - ] 5 D [H+ ]
2. A ¾® 2B or =+
2 Dt 6 Dt
For the given reaction DR V3
7. Average rate = =
2d [ A ] 1 d [B] Dt 40
- = = Rate of reaction - D [R]
dt 2 dt 8. Rate of reaction =
Dt
Where negative sign shows that rate of reaction
Rate of disappearance of A
decreases as concentration of reactants decreases.
d [ A] 1 d [B] 1 d [B]
=- = = x2 - x1
dt 2 ´ 2 dt 4 dt 9. Instantaneous speed =
t2 - t1
3. H2 + I2 ¾® 2HI
V5 - V 2
- d [H2] - d [I2] 1 d [HI] \ Instantaneous speed =
Rate of reaction = = = 50 - 30
dt dt 2 dt
V3 - V 2
- 2d [H2] - 2d [I2] d [HI] =
or = = 40 - 30
dt dt dt
V3 - V1
4. B + 5D ¾® 3 A + 2C =
40 - 20
- d [5] - 1 d [D] + 1 d [A] + 1 d [C]
= = = V4 - V2
at 5 at 3 dt 2 dt =
45 - 30
10. For a first order reaction, 18. For first order reaction,
rate = k [reactant] - kt
log[ A ] = + log[ A ]0
rate 2.303
[reactant] =
k
2.40 ´ 10–5
conc. of N2O53 = = 0.8 Slope = – k
3.0 ´ 10-5 log A 2.303

2X + Y ¾® Z t
1 d [X ] d [Z ] 19. In the presence of acid, hydrolysis of ethyl acetate is a
Rate = - =
2 dt dt pseudo-unimolecular reaction but the actual value of k
= 0.05 mol L -1
min -1 depends upon the concentration of H+ ion. As H2SO4 is
stronger acid than HCl and moreover H+ ions produced
1 d [X ]
- = 0.05 from 0.05 M H2SO4 is double than 0.05 M HCl therefore,
2 dt k1 < k2.
d [X ]
- = 2 ´ 0.05 1 k k k
dt 20. A ¾® B ¾®
2
C ¾®
3
D
= 0.1 mol L-1 min -1 Q k3 > k2 > k1
12. For nth order reaction, As k1 is smallest hence reaction is slowest therefore
k = (mol L–1 )1- n s -1 A ¾® B is the rate determining step of the reaction.
13. If the reaction is an elementary reaction, 21. The slowest step is the rate determining step. Formation
order = molecularity. of B (i.e. step I) is the slowest step, therefore, step I is
dx the rate determining step.
14. Rate = = k [CCl3CHO][NO]
dt 22. There are two different reactants (say A and B ).
dx A + B ¾® product
k=
dt ´ [CCl3CHO][NO] Thus, it is a bimolecular reaction.
mol / L dx
= If = k [ A ] [B]
s ´ mol / L ´ mol / L dt
k = L mol-1 s -1 it is second order reaction
æ dx ö
15. Value of rate constant remains unaffected from change If ç ÷ = k [ A ] or = k [B]
è dt ø
in concentration.
it is first order reaction.
16. For second order kinetics, rate = k [reactant] 2, So
make two equation first by taking initial rate and Molecularity is independent of rate, but is the sum of
concentration, second by taking tripled concentration the reacting substances, thus it cannot be unimolecular
and unknown rate (r¢ ). Compare them to find a reaction.
relation between r and r¢. 23. Slowest step is the rate determining step. Thus, in case
For the reaction, x ¾® y (A), rate law is given as rate = k [Cl2][H2S] While for the
Reaction rate (r ) = k [x]2 …(i) reaction given in case (B), rate law is given as,
If the concentration of x is increased three times, then rate = k [H2S][Cl2][H+ ]–1.
Reaction rate (r ¢ ) = k [3x]2 = k ´ [9x2] …(ii) Hence, only mechanism (A) is consistent with the given
rate law.
Dividing Eq. (ii) by Eq. (i);
r ¢ k ´ [9x2] æ dx ö 2
= =9 24. ç ÷ = k [NO] [O2]
è dt ø
r k ´ [x2]
2
It means that the rate of formation of y will increase by æ n ö æ nO ö
= k ç NO ÷ ç 2 ÷
nine times. è V ø è V ø
17. Rate (r ) = k [ A ][B] = kab æ dx ö k 2

ç ÷ = 3 (nNO ) (nO2 )
è dt ø V
When volume is reduced by one fourth then
2
concentration becomes 4 times. æ dx ö k (nNO ) (nO2 ) æ dx ö
ç ÷= =8 ç ÷
Hence, r ¢ = k(4a )(4b) = 16kab è dt ø æ ö
V
3 è dt ø
\ r ¢ = 16r ç ÷
è2ø
25. 2H2( g ) + 2NO( g ) = N ( g) + 2H O ( g)

2 2
It means, the rate of reaction is halved by reducing the
concentration of RCl by one half.
Rate law for forward reaction is given as:
Rate = kf [NO]2 [H2] 36. For zero order reaction,
x = kt
Rate of forward reaction is equal to rate of reverse 30
reaction at equilibrium and also, = 0.2 mol dm–3 h –1 ´ h
60
k = 0.1 mol dm–3
at equilibrium (K ) = f
kb Now, concentration = 0.05 mol dm–3
where, K (equilibrium constant) Hence, initial concentration = 0.1 + 0.05
[N2] [H2O]2 k [N ] [H O]2 = 0.15 mol dm-3
= 2 2
Þ f = 22 2 2
[H2] [NO] kb [H2] [NO]
37. For 2/3 of a reaction,
Rearranging : 2 a
kf [H2] [NO]2 = kb [N2] [H2O]2 / [H2] [ A ]0 = a , [ A ] = a - a=
3 3
\ Rate of reverse reaction = kb [N2] [H2O]2 / [H2] Q t 2/3 =
2.303
log
[ A ]0
26. Let the rate equation be k [ A ]x [B]y k [ A]
2.303 a
From Ist values, = log
x y 5.48 ´ 10–14 a /3
0.045 = k[0.05] [0.05] …(i)
From 2nd values, 2.303
= log 3
0.090 = k [0.10] [0.05] x y
…(ii) 5.48 ´ 10–14
From 3rd values, t2/3 = 2.01 ´ 1013 s
x y
0.72 = k[0.20] [0.10] …(iii)
38. For first order reactions,
On dividing equations (i) by (ii), we get 0.693 0.693
x 1 x k= =
0.045 é 0.05 ù é 0.05 ù é 0.05 ù t1/2 (3.0 h)
= Þ ê =ê
0.09 êë 0.10 úû ë 0.10 úû ë 0.10 úû 2.303 [ A ]0
t= log
\ x=1 k [ A]
Similarly on dividing Eq. (ii) by (iii) we get [ A ]0 k ´ t
or log =
x y y [ A ] 2.303
0.09 é 0.1 ù é 0.05 ù 0.01 0.1 é 0.05 ù
= Þ = [ A ]0 0.693 (8 h)
0.72 êë 0.2 úû êë 0.10 úû 0.08 0.2 êë 0.1 úû log = ´ = 0.8024
y [ A] 3h 2.303
é 0.05 ù
0.25 = ê Þ 0.25 = [0.5]y [ A ]0
ë 0.10 úû [ A]
= Antilog 0.8024 = 6.345
[0.5]2 = [0.5]y Þ y=2 [ A ]0 1M
[ A ]0 = 1 M ; [ A ] = =
Hence, the rate law for the reaction 6.345 6.345
Rate = k [ A ] [B]2 39. We know that,
28. t1/ 2 µ
1 Rate = k (concentration) n
n-1
a log (Rate) = log k + n log [concentration]
1 Slope of graph is the order of reaction. Greater the
When, t1/ 2 µ 3
a slope, greater is the order of reaction.
n – 1 = 3 Þ n = 3 +1 = 4 \Correct sequence for the order of reaction is
Hence, order of reaction = 4 D > B > A > C.
29. From the graph it is clear that the reaction is of zero Hence, the correct option is (d).
order and hence, the units of rate constant = mol L-1 s -1 1 é x ù
40. k= ê ú
32. Order of reaction may or may not equal to the sum of t ë a (a - x) û
stoichiometric coefficient of reactants in a balanced 1 é 0.2 a ù 1
k= =
500 êë a (a - 0.2 a ) úû 2000a
chemical equation.
34. RCl + NaOH ¾® ROH + NaCl
1 1é 0.6a ù
Rate = k [RCl] = ê ú
2000a t ë a (a - 0.6 a ) û
For this reaction, rate of reaction depends upon the
t = 3000 s
concentration of RCl.
-b 2.303 a ´ 16 2.303 2.303

41. 79 Au
198
¾® 80 Hg
198 t= log = log 16 = log24
60 s -1 a 60 s -1 60 s -1
0.693 0.693
k= = 2.303 2.303
t1/2 65 = ´ 4 log 2 = ´ 4 ´ 0.3010
60 s -1 60 s -1
After 260 hr,
2.303 a = 4.62 ´ 10-2 s
k= log
260 a-x Time = 4.62 ´ 10-2 s
0.693 2.303 a
= log 47. We know that, N = N 0e- Kt
65 260 a-x
a 1 K can be calculated as
= 16 Þ = 16
a-x 1-x K =
ln 2
(Here, t1/ 2 = half-life)
15 t1/ 2
x= g = 0.9375 g
16
Q The time required for the concentration of A to be
42. Since, the reaction is 50% completed in 1.26 ´ 1014 s. four times that of B. Hence,
\ t1/ 2 = 1.26 ´ 1014 s A = 4B
0.693 0.693
k= = - ln 2t - ln 2t
t12 1.26 ´ 1014 ln 2 t ln 2 t
N 0e 300 = 4 × N 0e 180 Þ - = ln 4 -
300 180
For 100% completion,
é 1 1 ù
2.303 a Þ ln 2 t ê - = 2 ln 2;
t= log ë 180 300 úû
k a-x
2 ´ 180 ´ 300
Þ t= = 900 s
2.303 ´ 1.26 ´ 1014 100 120
t= log =¥
0.693 0
48. In first order reaction, the rate expression depends on
43. For a first order reaction, the concentration of one species only having power
Rate = k (concentration) equal to unity.
Rate 1.5 ´ 10–2 mol L–1 min -1 nr ¾® products
\ k= =
concentration 0.5 mol L–1 - d [r ]
= k [r ]
dt
= 3 ´ 10-2 min -1
0.693 0.693 On integration, - ln [r ] = kt - ln[r0 ]
t1/ 2 = = min
k 3 ´ 10-2 or ln(r ) = ln(r0 ) - kt Þ y = c + mx
69.3 m = slope = -k (negative); c = intercept = ln (r0 )
= min or 23.1 min
3 The graph for first order reactions is
[ A ]0
44. For a zero order reaction, k0 =
2 t1/ 2
Since, [ A ]0 = 2 M, t1/ 2 = 1 h
ln (r)
So, k0 = 1
Dx
and k0 =
t t
0.50 - 0.25 In zero order reaction,

or t= = 0.25 h
1 [r ] ¾® product
45. kt = - log e C t + log e C 0 - d [r ] t
\ = k or - d [r ] t = kdt
1 dt
t = - log e C t + log e C 0
k
On integrating, - [r ] t = kt + c
y = mx + c, straight line, negative slope.
If t = 0, [r ] t = [r ]0
46. For first order reaction,
2.303 a \ - [r ] t = kt - [r ]0
t= log …(i)
k (a - x) Þ [r ] t = [r ]0 - kt
a Thus, the graph plotted between [r ] t and t gives a
Given, (a - x) = ; k = 60 s -1
16 straight line with negative slope (-k) and intercept
Placing the given values in Eq. (i) equal to [r ]0.
The graph for zero order reaction is Þ 2 = (1.41)m or m = 2

52. Let the order of reaction with respect to A is x and B is y.
\ rate law, r = k [ A ]x [B]y …(iv)
[r] On putting values, we get
0.10 = k [0.30]x [0.30]y …(i)
x y
0.40 = k [0.30] [0.60] …(ii)
t x
0.20 = k [0.60] [0.30] y
…(iii)
49. For the reaction, 2 A + B ¾® products. From Eq. (i) and (ii) we get
x y
Let, the rate expression is r µ [ A ]a [B]b 0.1 æ 0.30 ö æ 0.30 ö
=ç ÷ ç ÷
a
r2 æ 2 A ö æ 2B ö
b 0.4 è 0.30 ø è 0.60 ø
Expt. 1 =ç ÷ ç ÷
r1 è A ø è B ø 1 æ1ö
y
=ç ÷
2.4 4 è2ø
Þ = 2a ´ 2b Þ 23 = 2a + `b
0.3
or 4 = 2y
Þ 3=a+ b … (i)
a b (2)2 = 2y or y=2
r2 æ 2 A ö æ B ö
Expt. 2 =ç ÷ ç ÷ From Eq. (ii) and (iii), we get
r1 è A ø è B ø
x y
0.6 0.40 æ 0.30 ö æ 0.60 ö
Þ = 2a ´ 1 Þ 21 = 2a Þ a = 1 …(ii) =ç ÷ ç ÷
0.3 0.20 è 0.60 ø è 0.30 ø
\ From Eq. (i), 1 + b = 3 Þ b = 2 æ1ö
x
2 = ç ÷ (2)y
Þ Order of the reaction (n ) = a + b = 1 + 2 = 3 è2ø
Þ Order of the reaction wrt. A = 1
On putting the values of y, we get
Þ Order of the reaction wrt. B = 2 x
æ1ö
50. Rate constant for the first order reaction is given by, 2 = ç ÷ (2)2
è2ø
2.303 æ a ö
k= log ç ÷ 2 æ1ö
x
æ1ö æ1ö
1 x
t è a - xø =ç ÷ Þ ç ÷ =ç ÷
4 è2ø è2ø è2ø
a = 0.1 M
(a - x) = 0.025 M Þ t = 40 min or x=1
2.303 0.1 On putting the values of x and y in Eq. (iv), we get
\ k= log = 0.0347 min -1
40 0.025 M r = k [ A ]1 [B]2 = k [ A ][B]2
æ dx ö 53. The expression for bacterial growth is
Rate = ç ÷ = k[ A ]1 = 0.0347 ´ 0.1
è dt ø
N0
= 3.47 ´ 10–4 M min –1 N = N 0et Þ = e- t
N
From 0 to 1 hour N ¢ (t ) = N 0et
Decomposes
CH3CHO( g ) ¾¾¾¾® CH4 + CO dN
From 1 hour onwards, = -5N 2
dt
Let order of reaction with respect to CH3CHO is m.
Its given, r1 = 1 torr/sec when CH3CHO is 5% reacted i.e. On differentiating the above equation from N ¢ to N
95% unreacted. Similarly, r2 = 0.5 torr/sec when CH3CHO we get.
is 33% reacted, i.e. 67% unreacted. N t
-2
Use the formula, r µ (a - x)m òN dN = -5ò dt [Q At 1 hour, N ¢ = eN 0]
eN0 1
where (a - x) = amount unreacted
m
r1 (a - x1 )m r1 é a - x1 ù é1 1 ù
so, = or = ê - ú = 5(t - 1)
r2 (a - x2)m r2 êë a - x2 úû ë N eN 0û
Now, putting the given values Multiply both sides by N 0 , we get

m N0 1 N 1
1 æ 0.95 ö - = 5N 0 (t - 1) or, 0 = 5N 0 (t - 1) +
=ç ÷
0.5 è 0.67 ø N e N e
N0 é1 ù 62. Activation energy of backward reaction = E1

= 5N 0t + ê - 5N 0 ú
N ëe û \ Activation energy of forward reaction = E1 + E 2
On comparing the above equation with equation of Since the energy of product > energy of reactants
straight line, y = mx + c 1
and energy µ
1 stability
we get, m = 5N 0 c= - 5N 0
e \ Products are less stable than reactants.
N0 63. For endothermic reaction, A ¾® B
\ Plot of vs t is shown in graph (a).
N Activation energy = 15 kcal/mol
55. Arrhenius equation is Energy of reaction = 5 kcal/mol
Hence, activation energy for the reaction B ¾® A is
k = Ae-Ea /RT
15 - 5 = 10 kcal/mol
E
ln k = ln A - a
RT
E
ln k = ln A - a 15 – 5 = 10
RT
Energy
15 B
E
Slope = - a
R
5
A
ln k
Ea Progress of reaction
Slope = –
R
66. Only statement (d) is incorrect. Corrected statement is;
‘‘Activation enthalpy to form C is 15 kg mol -1 more than
5 kg mol -1 that is required to form A + B.’’ It can be easily
1/T
explained by following graph.
-Ea /RT
56. k = Ae
On taking log, we get
Ea 20
log k = log A -
2.203RT 15
Ea Enthalpy Activation
or ln k = ln A - (kJ mol–1) 10 D
enthalpy
RT
5
\ A graph between ln k vs 1 /T is a straight line A+B
(according to equation of straight line viz. y = mx + c) Reaction C
E coordinate
with - a slope (negative slope) and ln A intercept.
k Activation enthalpy (or energy) is the extra energy
\ Correct graph is graph (a). required by the reactant molecules that result into
In all other graphs slope is positive. effective collision between them to form the products.
57. For exothermic reaction, 67. The Arrhenius equation is, k = A. e-Ea /RT
Energy of reactants > energy of product, which is the From the equation, it is clear that k decreases
case given in (i). exponentially with E a . So, the plot-I is correct.
58. Q Rate constant (k¢ ) > rate constant (k¢ ¢ ) In the plot-II, k is plotted with temperature (in °C but
Greater the rate constant lesser will be the activation not in K). So, at 0°C, k ¹ 0 and k will increase
energy. exponentially with temperature upto 300°C. Therefore,
\ Ea ¢ < Ea ¢ ¢ the plot-II is also correct.
59. The given equation clearly has shown that the rate 68. The temperature dependence of rate of a chemical
constant k increases exponentially with decreasing reaction is expressed by Arrhenius equation as,
activation energy and increasing temperature. k = Ae-Ea /RT …(i)
- E/RT where, A = Arrhenius factor or frequency factor or
61. k = Ae
pre-exponential factor
E is activation energy. It is that energy, which
molecule must have to give the product. R = Gas constant, E a = Activation energy
Taking log on both sides of the Eq. (i), the equation T1 = (273 + 327) K = 600 K
becomes k2 = 1 dm3 mol -1 s -1 at T2 = (273 + 527) K = 800 K
E
ln k = ln A - a The Arrhenius equation for rate constants
RT at two different temperatures is
On comparing with equation of straight line
1 k E a æ T2 - T1 ö
(y = mx + c), the nature of the plot of lnk vs will be log 2 = ç ÷
RT k1 2.303R è T1T2 ø
(i) Intercept = C = ln A 1 Ea æ 800 - 600 ö
Þ log = ç ÷
(ii) Slope/gradient = m = - E a = - y Þ E a = y 2.5 ´ 10-4 2.303 ´ 8.314 ´ 10-3 è 600 ´ 800 ø
So, the energy required to activate the reactant, (10 ´ 103 ) Ea 200
(activation energy of the reaction, E a is = y ) Þ log = ´
2.5 0.019 48 ´ 104
69. According to Arrhenius equation, ~ E a ´ 0.022
Þ log 4 + 3 log 10 -
k = Ae -Ea /RT
Þ log k = log A -
E act 2 ´ log 2 + 3 3.6 ~
Þ Ea = = – 163.6 kJ mol -1
2.303RT 0.022 0.022
E act = activation energy
1 -E act 74. The temperature dependence of a chemical reaction is
Slope of the graph of ‘log k’ vs is expressed by Arrhenius equation,
T 2.303R
Greater the value of E act , more will be the negative k = Ae- Ea$ /RT …(i)
slope. Taking natural logarithm on both sides, the Arrhenius
E
From the graph, equation becomes, ln k = ln A - a
RT
most -ve slope = c, followed by a , d and b.
E
\ Order of activation energies must be where, - a is the slope of the plot and ln A gives the
R
E c > E a > E d > Eb intercept.
k1
k2
71. A ¾¾® B, A ¾ ¾ ® C, Eq. (i) at two different temperatures for a reaction
-Ea1 /RT becomes,
By Arrhenius equation, k1 = A ¢ e
k2 E a æ 1 1ö
and k2 = A ¢ e-Ea 2/RT . ln = ç - ÷ …(ii)
k1 R è T1 T2 ø
(A' is Arrhenius constant.)
Þ In the given problem,
(Since, E a2 = 2E a1 )
T1 = 400 K, T2 = 500 K, k1 = 10- 5 s -1, k2 = ?
\ k2 = A ' e-2Ea /RT E
-E /RT - a (Slope) = - 4606
k1 A ' e a1 E /RT R
= = e a1
k2 A ' e-2Ea1 /RT On substituting all the given values in Eq. (ii), we get
\ k1 = k2e
Ea /RT k æ 1 1 ö
1
ln -2 5 = 4606 ç - ÷
10 è 400 500 ø
72. X ® Y is an endothermic reaction, DH = + ve k
ln -2 5 = 2.303
10
k2
Eb = 10 Þ k2 = 10- 4 s -1
Energy
u
Ef 10-5
Therefore, rate constant for the reaction at
DH 500 K is 10- 4s - 1.
Round II
Eb = energy of activation of backward reaction 1. Rate depends upon the slowest step.
Hence, from equation
E f = energy of activation of forward reaction
O + O3 ¾® 2O2
DH = heat of reaction
r = k [O3 ][O]
Thus, E f = Eb + DH
Thus, E f > Eb and from equation O3 º O +O 2
[O ][O]
73. For the reaction, H2 + I2 ¾® 2HI K eq = 2
[O3 ]
-4 3 -1 -1
Given k1 = 2.5 ´ 10 dm mol s
K eq [O3 ] The unit of rate constant (i.e. s -1), shows that reaction
[O] =
[O2] is of first order.
K eq [O3 ] For first order reaction,
\ r = k [O3 ] = k¢ [O3 ]2[O2]-1 1 a 1 [N O ]
[O2] k = ln Þ k = ln 2 5 0
t a-x t [N2O5 ]t
2.303 (t1/2)1 æ 1 ö
2. t1 = log ç ÷ [N2O5 ]0
= kt
0.693 è 1 - (1 /4) ø or ln
[N2O5 ] t
2.303 (t1/2)2 æ 1 ö
and t2 = log ç ÷ k1
0.693 è 1 - (3 /4) ø 10. % distribution of B = ´ 100
k1 + k2
t1 8 log (4 / 3)
= ´ 1.26 ´ 10–4
t2 1 log 4 = ´ 100
1.26 ´ 10–4 + 3.8 ´ 10–5
8 ´ 0.125
= = 1 :0.602 = 76.83%
0.602 k2
and, % distribution of C = ´ 100
3. k = 2.1 ´ 1010 exp (-2700 /RT ) k1 + k2
i.e. log k vs 1 /T will be straight line 3.8 ´ 10–5
= ´ 100
intercept of log k axis = log 2.1 ´ 1010 1.26 ´ 10–4 + 3.8 ´ 10–5
= 23.17%
4. Am + Bn ¾® ABx
In this case, 11. For reaction, A + B ¾® C + D
overall order of reaction may or may not be = m + n r1 = k [ A ]a [B]b …(i)
Hence, code 3 is wrong. r2 = 2r1 = k [2 A ]a [B]b …(ii)
5. The reaction occurring in two steps has two activation and r3 = 3r1 = k[ A ]a [9B]b …(iii)
energy peaks. The first step, being fast needs less From (i) and (ii) a = 1
activation energy. The second step being slow, needs 1
more activation energy. Therefore, second peak will be Form (i) and (iii), b =
2
higher than the first. 1 3
\ Order = a + b = 1 + = = 1.5
6. According to Arrhenius equation, 2 2
k = Ae-Ea /RT …(i)
12. For first order reaction,
0.693 0.693
According to the available data k= = = 0.33 h –1
t1/2 2.1
k = (4.5 ´ 1011s -1 ) e-28000 K / T …(ii)
2.303 a
On comparing both equations; and k= log10
t (a - x)
E - 28000 K
- a = 2.303 100
RT T or t= log10
k (100 - 99)
E a = (28000 K) ´ R = (28000 K) ´ (8.314 K -1J mol-1 )
2.303 2.303
= 232792 kJ mol-1 = ´ log10100 = ´ 2 = 13.96 h
0.33 0.33
E a = 232.792 kJ mol-1
13. Fraction of molecules (x) having energy equal to or more
7. r1 = k [ A ]a [B]b
than activation energy may be calculated as follows
b
é Bù x = n / N = e-Ea /RT
r2 = k [2 A ] ê ú = k [ A ]a [B]b 2( a-b)
a
ë2û -E a Ea
r2 ( a-b )
ln x = or log x = -
\ =2 RT 2.303 RT
r1
209.5 ´ 103 J mol-1
8. r1 = k [ A ]n or log x = -
2.303 ´ (8.314 JK -1 mol-1 ) ´ 581 K
r2 = 1.837 r1 = k [1.5 A]n = - 18.8323
r2
\ = 1.837 = (1.5)n x = Antilog (- 18.8324) = Antilog 19.1677
r1
= 1.471 ´ 10-19
3
Þn = = 1.5 (On solving by logarithmic method) Fraction of molecules = 1.471 ´ 10-19
2
1 14. In the given reaction; x A ¾¾® y B
9. N2O5 ( g ) ¾® 2NO2( g ) + O2( g )
2 é -d [ A ] ù é d [B] ù
log10 ê = log10 ê + 0.3010
Rate constant = 2.3 ´ 10-2 s -1 ë dt úû ë dt úû
Value of log 2 = 0.3010 2.303 100

At 308 K, k2 = log …(ii)
Substituting 0.3010 by log 2 t 75
é d[ A] ù é d [B] ù Dividing eq. (ii) by (i);
log10 ê - = log10 ê + log 2
ë dt úû ë dt úû log
100
k2 75 = 0.1249 = 2.73
Using logarithm rules, =
k1 log 100 0.0458
é -d [ A ] ù é d [B] ù 1 é d [ A ] ù é d [B] ù 90
êë dt úû = 2 ´ êë dt úû Þ - 2 êë dt úû = êë dt úû …(i)
According to Arrhenius theory,
Using the rate equation (i) to determine the reaction k Ea T - T1
log 2 = ´ 2
involved is k1 2.303 R T1 T2
2 A ¾¾® B
Ea é 308 - 298 ù
Option that fits correct in the above reaction is (c). log 2.73 = ê ú
2.303 R ë 298 ´ 308 û
2C2H4 ¾¾® C4H8
0.4361 ´ 2.303 ´ (8.314 J mol-1 ) ´ 298 ´ 308
15. For catalysed reaction, let E a be x. Ea =
10
Then, for uncatalysed reaction, E a = 76640 Jmol-1 = 76.640 kJ mol-1
E a = x + 30 (given in question) Now, according to Arrhenius equation
Also, rate of reaction at 700 K (without catalyst) = rate Ea
of reaction at 500 K (with catalyst). log k = log A -
2.303 RT
\k at 700 K without catalyst = k at 500 K with
log k = log (4 ´ 1010 )
catalyst.
76640 J mol-1
Using relation, -
k = Ae-Ea /RT 2.303 ´ (8.314 J mol-1K -1 ) ´ (318 K)
E a = Activation energy. log k = 10.6021 - 12.5870 = - 1.9849
\ Ae-( x + 30)/ 700R = Ae- x/500R k = Antilog (- 1.9849)
x + 30 x = Antilog (2.0151) = 1.035 ´ 10-2 s -1
\ = Þ 7x = 5x + 150
700 500 18. SO2Cl2( g ) ¾® SO2 ( g ) + Cl2 ( g )
2x = 150 Þ x = 75 kJ mol -1 Initially pi 0 0
pi - p p p
16. Let, the rate law is : r µ [ A ]a [B]b After time t
\ a and b are the order of reaction w.r.t A and B Total pressure after time t, i.e.
respectively. pt = pi - p + p + p = pi + p
Þ Comparing first three (I, II, III) experiments : So, a = pi
2.4 ´ 10-2
a b
rII æ 0.1 ö æ 0.2 ö a - x = pi - ( pt - pi )
=ç ÷ ´ç ÷ Þ = 1 ´ 2b
rI è 0.1 ø è 0.1 ø 6 ´ 10-3 = pi - pt + pi = 2 pi - pt
b
Þ 2 =4Þb =2 Substitutions of the value of a and (a - x) gives,
rIII æ 0.2 ö
a 2
1.2 ´ 10-2 2.303 pi
æ 0.1 ö k= log
=ç ÷ ´ç ÷ Þ = 2a ´ 1 t ( 2 pi - pt )
rI è 0.1 ø è 0.1 ø 6 ´ 10-3
(a) Calculation of rate constant k
Þ 2a ´ 2 Þ a = 1
Given, pi = 0.5 atm ; pt = 0.6atm
Þ rI = k ´ (0.1)1 (0.1)2 Þ 6 ´ 10-3 = k ´ 10-3
2.303 pi 2.303 0.5 atm
Þ k = 6 L 2 mol -2 min -1 k= log = log
t (2 pi - pt ) (100 s) 0.4 atm
Þ Expt. IV : rII = 6 ´ (X )1 ´ (0.2)2 2.303 2.303
= log 1.25 = ´ 0.0969
Þ 7.2 ´ 10-2 = 6 ´ (X ) ´ (4 ´ 10-2) (100 s) (100 s)
-3 -1
Þ X = 0.3 mol L -1 = 2.23 ´ 10 s
Þ Expt. V : rv = 6 ´ (0.3)1 ´ (Y )2 (b) Calculation of reaction rate when total pressure is
-1 2 0.65 atm
Þ 2.88 ´ 10 = 6 ´ 0.3 ´ (Y )
pSO2Cl 2 = 0.5 - (0.65 - 0.50)
Þ Y = 0.4 mol L -1
2.303 [ A ]0 = (1 - 0.65) = 0.35 atm
17. For first order reaction : k = log k = 2.23 ´ 10-3 s -1
t [ A]
2.303 100 Rate = k ´ pSO2Cl 2 = (2.23 ´ 10-3 s -1 ) ´ (0.35 atm)
At 298 K, k1 = log …(i)
t 90 Rate = 7.8 ´ 10-4 atm s -1
19. (CH3 )2CHN == NCH(CH3 )2( g ) ¾® N2( g ) + C6H14 ( g ) E a*

\ log k = log A - -6 ...(ii)
Initial pressure pi 0 0 RT (2.303)
After time t pi - p p p Comparing Eqs. (i) and (ii)
Total pressure after time t, Ea E a*
= +6
i.e. ( pt ) = ( pi - p) + p + p = pi + p RT (2.303) RT (2.303)
or p = pt - pi
\ E a* - E a = - 6 (2.303)RT
a = pi ; (a - x) = pi - p on substituting the values of p ;
dc
(a - x) = pi - ( pt - pi ), i.e. (a - x) = 2 pi - pt 21. Rate law equation is given by, = k [ A ] x [B] y
dt
The decomposition reaction is of gaseous nature and dc
the rate constant k can be calculated as, \ for C at various concentrations are
dt
2.303 a
k= log 1 . 2 ´ 10-3 = k(0 . 1)x (0 . 1) y …(i)
t a-x
-3 x y
1 . 2 ´ 10 = k(0 . 1) (0 . 2) …(ii)
Substitution of value of a and (a - x) gives
-3 x y
æ 2 . 4 ´ 10 = k(0 . 2) (0 . 1) …(iii)
2.303 pi ö
k= log ç ÷
t è 2 pi - pt ø Solving for x [divide Eq. (iii) by Eq. (i)]
(i) Rate constant after 360 s = k1 2 . 4 ´ 10-3 k (0 . 2)x (0 . 1) y

=
2.303 (35 atm) 1 . 2 ´ 10-3 k (0 . 1)x (0 . 1) y
k1 = log
(360 s) (70 - 54) atm 2 = (2)x Þ x = 1
2.303 35 2.303 Solving for y [divide Eq. (iii) by Eq. (i)]
= log = log 2.1875 y
(360 s) 16 (360 s) 2 . 4 ´ 10-3 k (0 . 2) x (0 . 1) y æ 0. 1 ö
= Þ 2 = (2)x ç ÷
2.303 ´ 0.33995 1 . 2 ´ 10-3 k (0 . 1) x (0 . 2) y è 0. 2 ø
= = 2.17 ´ 10-3 s -1
(360 s) Put x = 1 in above Eq., we get
y
(ii) Rate constant after 720 s = k2 æ 0. 1 ö
2 = (2)¢ ç ÷ Þ 1 = (0. 5) y
2.303 (35 atm) è 0. 2 ø
k2 = log
(720 s) (70 - 63) atm (1 )0 = (0. 5) y Þ y = 0
2.303 2.303 ´ 0.6990 dc dc
= log 5 = Thus, = k [ A ]1 [B] 0 Þ = k [ A ]1
(720 s) (720 s) dt dt
= 2.24 ´ 10-3 s -1 22. At 27°C, t1/ 2 = 30 min

0.693
(2.17 + 2.24) ´ 10-3 s -1 k1 = = 0.0231
Average rate constant k = 30
2
and at 47°C, t1/ 2 = 10 min
k = 2.21 ´ 10-3 s -1 0.693
k2 = = 0.0693
20. Let the activation energy with and without enzyme be 10
E a* and E a. k Ea é 1 1ù
From, log 2 = ê - ú
Rate constant of reaction without catalyst is given by k1 2.303 R ë T1 T2 û
Arrhenius equation. 0.0693 Ea é 1 1 ù
Þ log = -
k = Ae -Ea /RT
0.0231 2.303 ´ 8.314 ë 300 320 úû
ê
Taking log on both sides, we get Ea é 20 ù

or log3 =
Ea 2.303 ´ 8.314 êë 300 ´ 320 úû
log k = log A - ...(i)
RT (2.303) E a ´ 20
or 0.4771 =
6
2.303 ´ 8.314 ´ 300 ´ 320
With catalyst, rate constant is 10 times more
or E a = 43848 J mol–1 = 43.8 kJ mol–1
-Ea
\ 106 k = Ae RT 23. Given, T1 = 25° C = 298 K, T2 = T (say)
E a* E a = 104.4 kJ mol–1 = 104.4 ´ 103 J mol–1
log k + log 106 = log A -
RT (2.303) k1 = 3 ´ 10-4 s -1 , k2 = ?
k2 Ea é1 1ù 27. For every 10°C rise of temperature, rate is doubled.

From, log = ê - ú
k1 2.303 R T
ë 1 T2û Thus, temperature coefficient of the reaction = 2
3
k2 104.4 ´ 10 é 1 1ù When temperature is increased by 50°, rate becomes
log = -
3 ´ 10-4 2.303 ´ 8.314 êë 298 T úû = 2(50 10) = 25 times = 32 times
3
k2 104.4 ´ 10 1 é 1 ù 28. Order = 1
or log -4
= ´ ê as T ® ¥ , ® 0ú
3 ´ 10 2.303 ´ 8.314 298 ë T û Concentration changes from 0.8 M to 0.4 M in (50%) 15
k2 min, thus half-life = 15 min = T50
or log = 18.297
3 ´ 10-4
A change from 0.1 M to 0.025 M is 75% and for first
k2
or = 1.98 ´ 1018 order reaction
3 ´ 10-4
T75 = 2 ´ T50 = 2 ´ 15 = 30 min
or k2 = 1.98 ´ 1018 ´ 3 ´ 10-4
or T50 = 15 min
= 5.94 ´ 1014 » 6 ´ 1014s -1
2.303 log 2 2.303 log 2
24. We know that, k= =
T50 15
n-1
(t1/2)1 é a 2 ù
= a = 0.1 M
(t1/2)2 êë a1 úû
(a - x) = 0.025 M
where, n = order of the reation For first order :
Given (t1/2) = 0.1 sec, a1 = 400 2.303 æ a ö
k= log ç ÷
25. Given, t(1/ 2)A = 54 min t(1/ 2)B = 18 min t è a - xø
2.303 log 2 2.303 0.1
A B = log
15 t 0.025
t = 0 ‘x’ M t = 0 ‘x’ M 2.303
= log 4
Þ To calculate : [ At ] = 16 ´ [Bt ] …(1) time = ? t
2.303 log 2 2 ´ 2.303 log 2
A0 \ =
Þ For I order kinetic : [ At ] = 15 t
(2)n
\ t = 30 min
n ® no. of half lives
29. The Arrhenius eqaution is
Þ Now, from the relation (1)
æ KT2 ö E a é 1 1ù
[ At ] = 16 ´ [Bt ] ln ç ÷= ê - ú
è KT1 ø R ë T1 T2 û
x x KT2
Þ = ´ 16 Þ (2)n2 = (2)n1 ´ (2)4 Given, = 3.555
(2)n1 (2)n2 KT1
Þ n2 = n1 + 4 Þ
t
=
t
+4 R = 8.314 JK - 1 mol- 1
(t1/ 2)2 (t1/ 2)1 T1 = 30 + 273 = 303 K; T2 = 40 + 273 = 313 K
æ1 1ö 4 ´ 18 ´ 54 Substituting the given values in the Arrhenius
Þ tç - ÷ =4 Þ t=
è 18 54 ø 36 equation,
Ea é 1 1 ù
Þ t = 108 min ln (3.555) = - (ln3.555 = 1.268)
8.314 êë 303 313 úû
26. K 300 = 10-4 K 200 = ? é 313 - 303 ù

Ea
1 .268 = ê ú
ë 303 ´ 313 û
8.314
E a = 11.488 kJ/mol R = 8.314 J/mol-K
1.268 ´ 8.314 ´ 303 ´ 313
æK ö E Ea =
æ 1 1 ö 10
So, ln ç 300 ÷ = a ç - ÷
è K 200 ø R è 200 300 ø
= 99980.7 = 99.98 kJ /mol
æ K ö 11.488 ´ 1000 ´ 100 0.693 0.693 -1
ln ç 300 ÷ = = 2.303 = ln 10
30. Decay constant (k) = = yr
è K 200 ø 8.314 ´ 200 ´ 300 t1/2 5730
All radioactive decay follow first order kinetics
K 300
So, = 10 2.303 [ A ]0
K 200 t= log
k [ A]
1
K 200 = ´ K 300 = 10-4 = 10 ´ 10-5 sec-1 Given, [ A ] = 80% It means that [ A ]0 = 100%
10
2.303 ´ 5730 100 Ea 15

t= yr ´ log 1.6094 = ´
0.693 80 8.314 300 ´ 315
2.303 ´ 5730 ´ 0.0969 1.6094 ´ 8.314 ´ 300 ´ 315
= = 1845 yr Ea =
0.693 15
Estimated age = 1845 yr E a = 84297.47 50 Joules /mol
31. Given, first order reaction, 1
33. Time taken for milk to split µ
t75 = 90 minute Þ t60 = ? k
Consider the following reaction, where, k = rate constant of the process
A ¾® B and, k at 2 different temperatures and activation
(Reactant) (Product) energy are related.
Time, t = 0 100
k -E a æ 1 1ö t
t15% = 90 min (100 - 75) = 25 ln 2 = ç - ÷ = ln 1
k1 R è T1 T2 ø t2
t60% = ? (100 - 60) = 40
æ 60 ö -E a æ 1 1 ö
For first order reaction, \ ln ç ÷ = ç - ÷
è 40 ø 8.3 è 400 300 ø
2 .303 æ a 0 ö é a 0 = Initial concentration ù
t= log ç ÷ ê ú E a = 0.4 ´ 8.3 ´ 1200
k è a ø ë a = Concentration û
= 3984 J mol-1 = 3.984 kJ mol-1
For 75%, 2 3
é Initial conc. = 100 ù Given, ln = 0.4 Þ ln = - 0.4
2 .303 æ 100 ö 3 2
t75% = log ç ÷ …(i) ê ú
k è 25 ø ë Conc. = 100 - 75 = 25 û 2 3
(These are wrong values, because ln is –ve and ln
For 60%, 3 2
é Initial conc. = 100 ù is +ve, but assume them to be correct).
2 .303 æ 100 ö
t60% = log ç ÷ …(ii) êConc. = 100 - 60 = 40ú
k è 40 ø ë û 34. It is given that the decomposition of ‘A’ into product has
value of K = 4.5 ´ 103 s -1 at 10°C.
On equating Eqs. (i) and (ii),
2 .303 æ 100 ö æ K ¢ö E a æ T ¢-T ö
log ç ÷ log ç ÷ = ç ÷
t60% è 40 ø è K ø 2.303R è TT ¢ ø
k
=
t75% 2 .303 æ 100 ö æ 1.5 ´ 104 ö 60 ´ 103 æ T ¢-283 ö
log ç ÷ Þ log ç =
k è 25 ø ÷ ç ÷
è 4.5 ´ 103 ø 2.303 ´ 8.314 è 283 T ¢ ø
æ 0.3979 ö 0.3979
t60% = t75% ´ ç ÷ Þ t60% = 90 ´ é T ¢-283 ù
è 0.602 ø 0.602 Þ 0.5228 = 3132.62 ê ú
t60% = 59.48 minute » 60 min ë 283 T ¢ û
32. Given, temperature rise 27°C to 42°C Þ T ¢-283 = 0.0472 T ¢
Hence, T1 = 273 + 27 = 300 K Þ T ¢ = 297.02 K
T2 = 273 + 42 = 315 K
Þ T ¢ = 297.02 K - 273K = 24.02° C
{ln 5 = 1.6094 R = 8.314 J mol-1K -1}
According to question kT2 = 5kT1 as molecules activated 35. According to Arrhenius equation,
are increased five times so k will increases 5 times. æK ö Ea é 1 1ù
Now, k = Ae-Ea /RT (Arrhenius equation) log ç 2 ÷ = ê - ú
è K 1 ø 2.303 R ë T1 T2 û
On apply log both sides, K2
Þ =2 ;
æ kT ö E æ 1 1ö K1
ln çç 2 ÷÷ = a ç - ÷
è kT1 ø è
R T1 T2 ø T1 = 295 K, T2 = 305 K
kT2 R = 8.314 J K -1mol-1
Here, =5
kT1 Ea é 1 1 ù
\ log (2) = ´ -
Ea æ 1 1 ö 2.303 ´ (8.314) êë 295 305 úû
ln 5 = ç - ÷ Ea 10
R è 300 315 ø or, 0301 = ´
-1 -1
8.314 JK mol 295 ´ 305
E a æ 315 - 300 ö
ln 5 = ç ÷ 0.301 ´ 2.303 ´ 8.314 ´ 295 ´ 305
8.314 è 300 ´ 315 ø or, Ea =
10
Ea 15
ln 5 = ´ = 51860 J mol-1
8.314 300 ´ 315 = 51.86 mol-1

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04

2. Extremely Slow Reactions

3. Moderately Slow Reactions Types of Rate of Reactions

Example 2. NO 2 required for a reaction is produced by Units of Rate of Reaction

and B respectively, then Units of k

then Rate = k Second 2 (mol L-1 ) 1 atm -1 s -1

Different characteristics of rate constant are given = (mol / L)1 - n s -1

• It is the measure of the rate of reaction. Greater is

Rate = k[ A]n . Termolecular reaction,

Some Examples of Zero Order Reactions log

d [H2O2] Sol. (d) Let the pressure of N2O5( g ) decreases by 2x atm. As

Calculate the rate constant. (NCERT Exemplar)

Volume of KMnO4 at t = 0 corresponds to volume of (COOH) 2 Inversion of Sugar Cane

Now, find ct . Some examples of second order reactions are

Differential Equations, Corresponding Integral Rate Equation,

log b(a – x)/

Negative Order Reactions • Decomposition of ethylene oxide

Some examples Example 9. For an elementary chemical reaction,

Opposed or Reversible Sol. (c) The elementary reaction, A2

k1 (ii) Again, rate of the reaction can be expressed as,

Now, if [B] and [C ] remain constant, Þ So, r µ [ A]1[B]0 Þ r µ [ A]

I. 0.10 6.93 ´10 -3

æ dx ö The concept of activation energy as applied to chemical

triples for each 10°C rise in temperature.

energy of molecules, which molecules must possess in T1

● By increasing the temperature of the substance Remember

Orientation of reactants existence and its potential energy is maximum. Finally

effective. additional energy which the reacting molecules must

Here, Z AB = collision frequency factor, i.e. the

Lower energy of activation

rate equation can be changed as. ER pathway

10. The rate constant for the reaction,

The rate determining step is Order of Reaction

[C] concentration of the reactant to its 1/16th value?

concentration of A to be four times that of B (in s) is Initial rate

In [R] [R] (a) Rate = k[ A ]2[B] (b) Rate = k[ A ][B]2

20 70. The energies of activation for forward and reverse

1.0 dm3 mol -1 s -1 at 527°C. The activation energy for

ROUND II Mixed Bag

It means that (c) (d) All are correct

Unit for the rate constant = conc.(1- n) t -1 1 D [Br - ] 1 D [H+ ]

11. For the reaction,

17. Rate (r ) = k [ A ][B] = kab æ dx ö k 2

25. 2H2( g ) + 2NO( g ) = N ( g) + 2H O ( g)

-b 2.303 a ´ 16 2.303 2.303

0.50 - 0.25 In zero order reaction,

The graph for zero order reaction is Þ 2 = (1.41)m or m = 2

Now, putting the given values Multiply both sides by N 0 , we get

N0 é1 ù 62. Activation energy of backward reaction = E1

Value of log 2 = 0.3010 2.303 100

19. (CH3 )2CHN == NCH(CH3 )2( g ) ¾® N2( g ) + C6H14 ( g ) E a*

(i) Rate constant after 360 s = k1 2 . 4 ´ 10-3 k (0 . 2)x (0 . 1) y

= 2.24 ´ 10-3 s -1 22. At 27°C, t1/ 2 = 30 min

Taking log on both sides, we get Ea é 20 ù

k2 Ea é1 1ù 27. For every 10°C rise of temperature, rate is doubled.

26. K 300 = 10-4 K 200 = ? é 313 - 303 ù

2.303 ´ 5730 100 Ea 15

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