Chapter–4

Chemical
Kinetics

1. Chemical Kinetics: It is the branch of physical chemistry which deals with the study of the rate of chemical
reaction and the mechanism by which the reaction occurs.
2. Rate of Reaction: It may be defined as the change in concentration of a reactant or product in unit time.
For a general reaction, interval of R P, the rate of reaction may be expressed as
Decrease in concentration of R
Rate of reaction =
Time taken
Increase in concentration of P
=
Time taken
– D [R] D [P]
= Rate of reaction =
Dt Dt
The negative sign in the rate expression indicates the decrease in the concentration of the reactant and gives
a positive value of the rate.
Units of rate are mol L–1 s–1 or atm s–1 (in gaseous reactions).
The above expression of rate gives us the average rate of reaction.
3. Instantaneous Rate of Reaction: It is the rate of reaction at a particular moment of time and measured as
a very small concentration change over a very small interval of time.
Mathematically, Instantaneous rate = (Average rate) Dt → 0
For a general reaction, R P
[R]0

(P)
Concentration of products
Concentration of reactants

[R] – (c2 – c1) d[R] d[P]

c1 rinst = = slope
rav = = dt dt
t (t2 – t1) c2
[R]
c2 –d[R] [P]
rinst = = – slope
dt
d[R] c1 [P] (c2 – c1)
t rav = =
dt t (t2 – t1)

t1 t2 t Time t1 t2 t Time
(a) (b)
Fig. 4.1: Instantaneous and average rate of reaction
d [R] d [P]
Instantaneous rate = – =
dt dt

Chemical Kinetics 145

 Instantaneous rate can be determined graphically by drawing a tangent at time t on either side of the curve
for concentration of A or B vs time and calculating its slope.
– d [R]
Thus, rinst = = – slope (for R)
dt
+ d [P]
rinst = = slope (for P)
dt
4. General Expression for Rate of Reaction: For a general reaction,
aA + bB cC + dD
–1 D [ A] –1 D [B] 1 D [C ] 1 D [D]
rav = a = =c =
Dt b Dt Dt d Dt
–1 d [A] –1 d [B] 1 d [C ] 1 d [D]
rinst = a = =c =
dt b dt dt d dt

5. Factors Affecting the Rate of a Chemical Reaction:
Rate of a reaction is influenced by following factors:
(a) Nature of reactants: It has been observed that ionic substances react more rapidly than the substances
with covalent bond. This is because ions are immediately available in aqueous solution on dissociation
hence, react rapidly but covalent molecules consume part of energy in breaking of bonds.
(b) Concentration of reactants: Rate of a reaction is directly proportional to the concentration of
reactants.
(c) Temperature: Rate of a reaction increases with the increase in temperature.
(d) Presence of catalyst: In presence of catalyst, the rate of reaction generally increases and the
equilibrium state is attained quickly in reversible reactions.
(e) Surface area of the reactants: The smaller the particle size, greater the surface area and faster is the
reaction.
(f) Radiations: There are many reactions which either do not take place at all or are quite slow in the dark
but take place at a considerable speed when exposed to sunlight or ultraviolet radiations, such reactions
are called photochemical reactions. Examples are photosynthesis of carbohydrates, photography, etc.
6. Rate Law: It is an experimentally determined expression which relates the rate of reaction with concentration
of reactants.
For a hypothetical reaction,
A + B Products
Rate ∝ [A] [B]n
m

or Rate = k[A]m [B]n

where k is a constant called specific rate of reaction or rate constant.
If [A] = [B] = 1 mol L–1 then
Rate = k
Thus, rate constant may be defined as the rate of reaction when the concentration of each reactant in the
reaction is unity.
7. Order of Reaction: It may be defined as the sum of powers of the concentration of the reactants in the rate
law expression.
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
For a hypothetical reaction,
aA + bB + cC Products
m n p
Let rate = k[A] [B] [C]
where, m = order of reaction with respect to A
n = order of reaction with respect to B
p = order of reaction with respect to C
Overall order of reaction = m + n + p

146 Xam idea Chemistry–XII

 Units of rate constant:
For an nth order reaction, A Product
Rate = k[A]n
Rate concentration 1
or k= = #
[A] n time (concentration) n
= (concentration)1 – n time–1
On considering S.I. unit of concentration as mol L–1 and time as seconds, the unit of k = (mol L–1) 1–n s–1
(a) Examples of zero order reactions
(i) Some enzyme catalysed reactions and reactions which occur on metal surfaces.
(ii) Decomposition of gaseous ammonia on a hot platinum surface.
1130K
2NH3 (g) Pt Catalyst
N 2 (g) + 3H 2 (g)
h
(iii) H 2 ( g)  Cl2 ( g)   2 HCl (g)
gold
(iv) 2 HI( g)   H 2 ( g)  I 2 ( g)
Unit of k = mol L–1s–1
(b) Examples of 1st order reactions
(i) All radioactive disintegrations are of the first order.
(ii) Decomposition of sulphuryl chloride.
SO2Cl2 SO2 + Cl2
–1
Unit of k = s . Therefore, change in unit concentration does not alter the value of k.
(c) Examples of 2nd order reactions
(i) CH3COOC2H5 + NaOH CH3COONa + C2H5OH
(ii) NO(g) + O3(g) NO2(g) + O2(g)
Unit of k = litre mol second–1
–1

(d) Examples of 3rd order reactions

(i) 2NO(g) + O2(g) 2NO2(g)
(ii) 2NO(g) + Br2(g) 2NOBr(g)
Unit of k = litre2 mol–2 second–1
8. (a) Elementary reaction: A reaction which take place in one step is called an elementary reaction.
When a sequence of elementary reactions gives the products, the reaction is called complex reaction.

(b) Molecularity: The number of reacting species (molecules, atoms, ions) taking part in an elementary
reaction which must collide simultaneously in order to bring about a chemical reaction.
Reactions are classified as unimolecular, bimolecular and trimolecular for molecularity 1, 2 and 3
respectively.
Examples:
NH4NO2 N2 + 2H2O (Unimolecular reaction)
2HI(g) H2(g) + I2(g) (Bimolecular reaction)
2NO(g) + O2(g) 2NO2(g) (Trimolecular reaction)
The probability of more than three molecules colliding simultaneously is rare. Therefore, molecularity
of a reaction does not extend beyond three. Molecularity can be defined only for an elementary reaction
and has no meaning for a complex reaction.
(c) Intermediates: The species which are produced in one step and consumed in another are called
intermediates.

Chemical Kinetics 147

 (d) Mechanism of reaction: A series of elementary reactions proposed to account for the overall reaction
is called mechanism of reaction. The overall rate of the reaction is controlled by the slowest step in a
reaction and is called the rate determining step.
I–
Consider the reaction, 2H2O2 Alkaline medium
2H2O + O2

The rate equation for this reaction is found to be

1 d
Rate = – [H O ] = k[H2O2] [I –]
2 dt 2 2
Evidences suggest that this reaction takes place in two steps as follows:
Slow
Step I.
H2O2 + I – H2O + IO– (Intermediate)
Step II. H2O2 + IO– Fast
H2O + I – + O2
The first step, being slow, is the rate determining step. Thus, the rate of formation of intermediate,
IO– will determine the rate of reaction.
9. Pseudo First Order Reaction: A reaction which is not truly of first order but under certain conditions
becomes reaction of the first order is called a pseudo first order reaction. For example, the inversion of cane
sugar is a bimolecular reaction but it is a first order reaction as concentration of H2O is quite large and does
not change appreciably.
H+
C12H22O11 + H2O C6H12O6 + C6H12O6
Rate = k [C12H22O11]
10. Zero Order Reactions: In such reactions, the rate remains constant throughout the course of reaction, i.e.,
the rate does not change with the change in concentration of reactants.
Rate = k [Reactant]0 or Rate = k
Zero order reactions generally occur in a heterogeneous system, wherein the reactant is absorbed on the
surface of a solid catalyst (here it is converted into product). The fraction of the surface of the catalyst
covered by the reactant is proportional to its concentration at low values and the rate of reaction is of the
first order. However, after certain concentration limit of the reactant, the surface of the catalyst is fully
covered. As the concentration of the reactant further increases, no change in it takes place. Thus, rate
becomes independent of concentration and the order of reaction becomes zero.
Integrated rate law for zero order reaction:
Consider a general zero order reaction
R P
As it is a reaction of zero order
– d [R]
\
= k[R]0 = k ⇒ – d[R] = kdt
dt
– ∫ dt[R] = k ∫ dt
– [R] = kt + C …(i) [R]0
where C is constant of integration.
Concentration

When t = 0, [R] = [R]0 k = – slope of

C = – [R]0 straight line
Substituting the value of C in equation (i), we get
– [R] = kt – [R]0
A
kt = [R]0 – [R] O
Time
1
t= {[R] 0 – [R]} …(ii) Fig. 4.2: Variation of
k concentration with time for a
1 zero order reaction
or k = t {[R] 0 – [R]}

148 Xam idea Chemistry–XII

 Half-life of a reaction: It is the time in which the concentration of a reactant
is reduced to half of its original value.
Half-life period of a zero order reaction:
[R] 0 1
Slope =
2k

t1/2
When [R] = , t = t1/2
2
Substituting these values in equation (ii), we get
[R] 0
t1/2 = ( [R] 0 – 2
1
\ Initial conc. [R]0
k 2
Fig. 4.3: Plot of t1/2 versus
[R] 0 initial concentration [R]0
t1/2 = for a zero order reaction
2k
t1/2 ∝ [R]0
11. First Order Reactions: In this class of reactions, the rate of reaction is directly proportional to the first
power of the concentration of reacting substance.
Rate = k[Reactant]1
Integrated rate law for 1st order reaction: log [R] 0
Consider the general first order reaction
R P k
Slope = –
As the reaction follows first order kinetics, 2.303

log [R]
– d [R]
\ ∝ [R]
dt
– d [R] – d [R]
= k[R]  ⇒ = k[dt]
dt [R] O Time, t
Integrating both sides, we get Fig. 4.4: Plot of log [R] versus t
– ln [R] = kt + C ...(i)
where C is constant of integration
When t = 0, [R] = [R]0
– ln [R]0 = 0 + C
Substituting the value of C in (i), we get [R]0 k
log Slope =
– ln [R] = kt – ln [R]0 [R] 2.303

ln [R] = – kt + ln [R]0
[R] 0 [R] 0
kt = ln = 2.303 log O Time
[R] [R]
Fig. 4.5: Plot of log [R]0/[R]
[R] 0 kt versus time (t)
log =
[R] 2.303
2.303 [R] 0
t= log
k [R]
where [R]0 is initial concentration and [R] is the final concentration.
Half-life period for a first order reaction
[R] 0
When   t = t1/2, [R] =
2
2.303 [R] 0 2.303
t1/2 = log = log 2
k [R] 0 /2 k
2.303 0.693
t1/2 = # 0.3010 or t1/2 =
k k
Since no concentration term is involved, therefore, t1/2 for a first order reaction is independent of initial
concentration.

Chemical Kinetics 149

 12. Integrated Rate Equation for a Gaseous System: Consider a typical first order gas phase reaction.
A(g) B(g) + C(g)
Let Pi be the initial pressure of A and Pt the total pressure at time ‘t’ and PA, PB and PC be the partial
pressures of A, B and C respectively at time t.
Total pressure, Pt = PA + PB + PC (pressure units)
If x atm be the decrease in pressure of A at time t and one mole each of B and C is being formed, the increase
in pressure of B and C will also be x atm each.
A(g) B(g)    +    C(g)
At t = 0 Pi atm 0 atm 0 atm
At time = t (Pi – x) atm x atm x atm
Pt = (Pi – x) x x Pi x or x = Pt – Pi
+ + = +
PA = Pi – x = Pi – (Pt – Pi) = 2Pi – Pt
2.303 Pi 2.303 Pi
k= t log PA = t log (2Pi – Pt)
13. Determination of Order of Reaction:
There are many methods available for the determination of order of reaction.
(a) Graphical method   (b) Initial rate method (c) Integrated rate law method
(a) Graphical method: This method is applicable to those reactions wherein only one reactant is involved.
Zero order First order Second order Third order
Rate

Rate

Rate

Concentration Concentration (Concentration)2 Rate (Concentration)3

Fig. 4.6
(b) Initial rate method: This method is used to determine the order of reaction in such cases where more
than one reactant is involved. It involves determination of order of reaction with respect to each reactant
separately. For this, order of a particular reactant is determined. A series of experiment are carried out
in which the concentration of that particular reactant is changed whereas the concentration of other
reactants are kept constant. In each experiment, the rate is determined from the plot of concentration
vs time. Similarly, concentration of another reactant is varied keeping the concentration of rest of the
reactant constant and initial rate is determined. The data obtained are then compared to see how the
initial rate depends on the initial concentration of each reactant. Thus, on the basis of the results the
form of rate law is determined.
(c) Integrated rate law method: There are integrated rate law equations which are very convenient to
understand the variation in concentration with time, for different order of reactions. After studying the
concentrations at various intervals of time, the data are put in all the integrated rate law equations one by
one. The expression which gives a constant value of the rate constant decides the order of the reaction.
[R] 0 – [R]
Zero order equation; k = t ,

2.303 [R] 0
First order equation; k = log
t [R]
14. Temperature Dependence of Rate of a Reaction:
(a) Temperature coefficient: It is defined as the ratio of rate constants of the reaction at two temperatures
differing by 10°.
Rate constant at (T  10)
Temperature coefficient =
Rate constant at T 
For most of the reactions, temperature coefficient lies between 2 and 3.

150 Xam idea Chemistry–XII

 (b) Collision frequency (z): It is defined as total number of collisions per unit volume per unit time.
(c) Effective collisions: Collisions which lead to the formation of product molecules are called effective
collisions.
Rate of reaction = f × z, where z is the collision frequency and f is the fraction of collisions, which are
effective.
(d) Threshold energy: The minimum energy that the reacting molecules must possess in order to undergo
effective collisions to form the product is called threshold energy.
(e) Activated complex: The arrangement of atoms corresponding the energy maxima (threshold energy)
during the course of a reaction is called activated complex or transition state. The activated complex
has partial reactant character and partial product character.
H H H H H H
+ +
I I I I I I
Reactant molecules Activated complex Product molecules

Fig. 4.7: Formation of activated complex from H2 and I2 during HI formation

Characteristics of an activated complex
(i) The potential energy of the activated complex is maximum.
(ii) The activated complex has a transient existence and breaks up at a definite rate to form the
products.
Exothermic Reaction Endothermic Reaction
Activated Activated
complex complex

Ea
Ea Products
Potential energy

Potential energy

∆H

Reactants Reactants
∆H

Products

Progress of the reaction Progress of the reaction

Fig. 4.8: Concept of Activation Energy

(f) Activation energy: The energy required to form activated complex is called activation energy. It is the
difference between the threshold energy and the average energy possessed by the reacting molecules.
Activation energy (Ea) = Threshold energy – Average energy possessed by reacting molecules
Activation energy Energy
Reactants Activated complex Products
For fast reactions, activation energies are low whereas for slow reactions activation energies are high.
(g) Arrhenius equation: It relates rate constant with temperature in the following way:
k = Ae –Ea /RT
where A is constant called frequency factor, Ea is the energy of activation.
Ea
ln k = ln A –
RT
Ea
log k = log A –
2.303 RT
Ea
A plot of log k vs. 1/T is a straight line whose slope is – and intercept is log A.
2.303 R

Chemical Kinetics 151

 If k1 and k2 are the rate constants at two temperatures T1 and T2, then
Ea
log k1 = log A – ...(i)
2.303 RT1 log A
– Ea
Ea Slope =
log k2 = log A – ...(ii) 2.303 R
2.303 RT2
Subtracting (i) from (ii), we get,

log k
Ea
<T – T F
1 1
log k2 – log k1 =
2.303 R 1 2
k2 Ea T2 – T1
or log = = G 1/T
k1 2.303 R T1 T2
(h) Effect of temperature on rate of reaction: Fig. 4.9: log k vs 1/T

Increasing the temperature of a reaction

mixture increases the fraction of
molecules, which collide with energies

Fraction of molecules
greater than Ea. It is clear from the t
Energy of This area shows
diagram alongside that with 10° rise in t +10 activation fraction of additional
temperature, the area showing the fraction molecules which
react at (t + 10)
of molecules having energy equal to or This area shows
greater than activation energy gets almost fraction of molecules
reacting at t
double leading to almost doubling of the
Kinetic energy
rate of reaction.
Fig. 4.10: Distribution curve showing temperature
15. Catalyst: A catalyst is a substance which alters dependence of rate of a reaction
the rate of reaction without itself undergoing
any chemical change at the end of the reaction.
For example, catalyst MnO2 increases the rate of decomposition of potassium chlorate to a great extent.
MnO 2
2KClO3 2KCl + 3O2
Heat
According to intermediate complex theory, a catalyst participates in a chemical reaction by forming
temporary bonds with the reactants resulting in an intermediate complex. This has a transitory existence
and decomposes to yield products and the catalyst.
A+B + X A B A B + X
Reactants Catalyst Products Catalyst
X (Regenerated)
Intermediate
complex

It is believed that the catalyst provides an alternate pathway by reducing the activation energy between
reactants and products hence lowering the potential energy barrier as shown in Fig. 4.11.
Reaction path without catalyst

Ea without catalyst
Reaction path
with catalyst
Potential energy

Ea with
catalyst

Products

Progress of reaction
Fig. 4.11: Effect of catalyst on activation energy

152 Xam idea Chemistry–XII

 It is clear from the Arrhenius equation (k = Ae –Ea /RT ) that lower the value of activation energy faster will
be the rate of reaction.
For example, SO2 is oxidised to SO3 in the presence of nitric oxide as catalyst.
NO (g)
2SO2(g) + O2(g) 2SO3
O2(g) + 2NO(g) 2NO2(g)
Reactant Catalyst Intermediate
NO2(g) + SO2(g) SO3(g) + NO(g)
    Intermediate Reactant Product Catalyst
Characteristics of a catalyst
(i) It can only catalyse the spontaneous reaction but not the non-spontaneous reaction.
(ii) It does not change the equilibrium constant, but only helps in attaining equilibrium faster.
(iii) It can catalyse both forward and backward reactions to the same extent to maintain the equilibrium
state in case of reversible reaction.
(iv) It does not alter the free energy change (DG) of a reaction.
(v) A small amount of the catalyst can catalyse a large amount of reactions.
16. Collision Theory of Chemical Reactions:
(i) Only effective collisions bring about a chemical reaction. The collisions in which molecules collide
with sufficient kinetic energy (threshold energy) and proper orientation, so as to facilitate breaking of
bonds between reacting species and formation of new bonds to form products are called as effective
collisions.
(ii) In collision theory, activation energy and proper orientation of the molecules together determine the
criteria of an effective collision and hence the rate of chemical reaction.
Rate = PZ AB e –Ea /RT
Where, ZAB = The collision frequency of reactants A and B
P = Probability factor or steric factor
 (It take into accounts the fact that in a collision, molecules must be
properly oriented)
–Ea/RT
e = Fraction of molecules with energies equal to or greater than Ea.
Important Formulae
1. Integrated Rate Equations
(i) For a zero order reaction:
[R] 0 – [R] [R] 0
t= and t1/2 =
k 2k
(ii) For a first order reaction:
2.303 [R] 0 0.693
t= log and t1/2 =
k [R] k [R] 0
Amount of the substance left after n half lives of Ist order reaction = .
2n
2. Arrhenius Equation
(i) k = A e –Ea /RT
where k = Rate constant, A = Arrhenius factor or frequency factor, Ea = Activation energy,
R = Gas constant, T = Temperature in Kelvin
k2 Ea T2 – T1
(ii) log = =G
k1 2.303 R T1 T2
where k1 = Rate constant at T1 and k2 = Rate constant at T2
(iii) Ea = – 2.303 × R × slope ain a plot of log k vs k
1
T

Chemical Kinetics 153

NCERT Textbook Questions

NCERT Intext Questions

Q. 1. For the reaction R → P the concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes.
Calculate the average rate of reaction using units of time both in minutes and seconds.
D [R] [R2] – [R1]
Ans. The average rate = – =– t –t
Dt 2 1

0.02 M – 0.030 M – 0.01 M

   = – =– = 4 × 10–4 M min–1
25 min 25 min
0.01 M
or     = = 6.66 × 10–6 M s–1.
25 # 60 s
Q. 2. In a reaction 2A → Products, concentration of A decreases from 0.5 mol L–1 to 0.4 mol L–1 in
10 minutes. Calculate the rate during this interval.
Ans. Rate of reaction = Rate of disappearance of A

1 D [A]
–1
1 (0.4 – 0.5) mol L
     = – =– = 0.005 mol L–1 min–1
2 Dt 2 10 min
Q. 3. For a reaction, A + B → Product, the rate law is given by r = k [A] 1 2 [B] 2 . What is the order of the
reaction?
1 5
Ans. Order of reaction = + 2 = .
2 2
Q. 4. The conversion of molecule X to Y follows second order kinetics. If concentration of X is increased to
three times, how will it affect the rate of formation of Y ?
Ans. Rate = k [X]2
r1 = k [X]2 ...(i)
r2 = k [3X]2 ...(ii)
r2 9k [X] 2
Dividing (ii) by (i), r1 =
k [X] 2
r2 = 9r1
Thus, rate of formation of Y will increase by nine times.
Q. 5. A first order reaction has a rate constant 1.15 × 10–3 s–1. How long will 5 g of this reactant take to
reduce to 3 g?
Ans. Given [R] 0 = 5 g, [R] = 3g, k = 1.15×10 –3 s –1 . As the reaction is of first order,

2.303 [R] 0 2.303 5g

` t= log = log = 2.00 ×103 (log 1.667) s
k [R] –
1.15×10 s 3 – 1 3g

= 2.0 × 103 × 0.2219 s = 443.8 s = 444 s

Q. 6. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decomposition
is a first order reaction, calculate the rate constant of the reaction.
0.693 0.693
Ans. For a first order reaction, k = t1/2
= = 1.155 × 10–2 min–1
60 min
Q. 7. What will be the effect of temperature on rate constant?
Ans. The rate constant of a reaction is nearly doubled with rise in temperature by 10°. The exact dependence of
the rate constant on temperature is given by Arrhenius equation, k = Ae –Ea RT where A is called frequency
factor and Ea is the activation energy of the reaction.

154 Xam idea Chemistry–XII

 Q. 8. The rate of the chemical reaction doubles for an increase of 10 K in absolute temperature from 298 K.
Calculate Ea.
k2 Ea T2 – T1
Ans.      log = = G
k1 2.303 R T2 T1
k2 T1 T2
Ea = 2.303 R log = G
k1 T2 – T1

= (2.303) (8.314 J K–1 mol–1) c log m#c m

2 298 K # 308 K
1 308 K – 298 K
= 52898 J mol–1 = 52.9 kJ mol–1
Q. 9. The activation energy for reaction, 2HI(g) H2(g) + I2(g), is 209.5 kJ mol–1 at 581 K. Calculate
the fraction of molecules of reactants having energy equal to or greater than activation energy.
Ans. Fraction of molecules having energy equal to or greater than activation energy,
n
x= = e –Ea /RT
N
Ea Ea
\ ln x = – or log x = –
RT 2.303 RT
209.5 # 103 J mol –1
or log x = – = – 18.8323
2.303 # 8.314 J K –1 mol –1 # 581 K
x = Antilog (– 18.8323)
= Antilog (19.1677) = 1.471 × 10–19

NCERT Textbook Exercises

Q. 1. From the rate expression for the following reactions, determine their order of reaction and the
dimensions of the rate constants:
(a) 3NO (g) N 2 O (g) + NO 2 (g)    rate = k [NO] 2
(b) H 2 O 2 (aq) + 3I – (aq) + 2H + 2H 2 O (l) + I 3– (aq) rate = k [H 2 O 2][I –]
(c) CH 3 CHO (g) CH 4 (g) + CO (g) rate = k [CH 3 CHO] 3 2

(d) C 2 H5 CI (g) C 2 H 4 (g) + HCl (g) rate = k [C 2 H5 Cl ]

Ans. (a) Rate = k [NO] , Order of reaction w.r.t. reactant NO = 2, Order of reaction = 2
2

Rate mol L–1 s –1

Unit of k: k = = = L mol –1 s –1
[NO] 2 (mol L–1) 2
(b) Rate = k [H 2 O 2] [I –], Order of reaction w.r.t. reactant H2O2 = 1, Order of reaction w.r.t. reactant
I – = 1,
Order of reaction = 1 + 1 = 2.
Rate mol L–1 s –1
Unit of k: k = – = = L mol –1 s –1
[H 2 O 2] [I ] (mol L–1) (mol L–1)
3 3
(c) Rate = k [CH3 CHO] 3/2 , Order of reaction w.r.t. reactant CH3 CHO = , Order of reaction =
2 2
Rate mol L–1 s –1
Unit of k: k = 3/2
= –1 3/2
= mol –1/2 L1/2 s –1
[CH3 CHO] (mol L )
(d) Rate = k [C 2 H5 Cl] , Order of reaction w.r.t. reactant C 2 H5 Cl = 1 , Order of reaction = 1.
Rate mol L–1 s –1
Unit of k:
k= = –1
= s –1
[C 2 H5 Cl] mol L

Chemical Kinetics 155

 Q. 2. For the reaction 2A + B → A2B, the rate = k [A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the
initial rate of the reaction when [A] = 0.1 mol L–1 and [B] = 0.2 mol L–1. Calculate the rate of reaction
after [A] is reduced to 0.06 mol L–1.
Ans. Initial rate = k [A][B]2 = (2.0 × 10–6 mol–2 L2 s–1) (0.1 mol L–1) (0.2 mol L–1)2
= 8 × 10–9 mol L–1 s–1
When [A] is reduced from 0.10 mol L–1 to 0.06 mol L–1, i.e., 0.04 mol L–1 of A has reacted,
1
B reacted = × 0.04 mol L–1 = 0.02 mol L–1
2
Now [B] = 0.2 – 0.02 = 0.18 mol L–1
Rate = (2.0 × 10–6 mol–2 L2 s–1) (0.06 mol L–1) (0.18 mol L–1)2
= 3.89 × 10–9 mol L–1 s–1
Q. 3. The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of production
of N2 and H2 if k = 2.5 × 10–4 mol L–1 s–1?
Ans. 2NH3 N 2 + 3H 2
1 d [NH3] d [N 2] 1 d [H 2]
Rate = – = =
2 dt dt 3 dt
For zero order reaction, rate = k
1 d [NH3] d [ N 2 ] 1 d [ H 2]
\ – = =
2 dt dt 3 dt

= 2.5 × 10–4 mol L–1 s–1

d [N2]
Rate of production of N2 = = 2.5 × 10–4 mol L–1 s–1
dt
d [H2]
Rate of production of H2 =
dt
= 3 × (2.5 × 10–4 mol L–1s–1) = 7.5 × 10–4 mol L–1 s–1
Q. 4. The decomposition of dimethyl ether leads to the formation of CH4, H2 and CO and the reaction rate
is given by
Rate = k [CH3OCH3]3/2.
The rate of reaction is followed by increase in pressure in a closed vessel, so the rate can also be
expressed in terms of the partial pressure of dimethyl ether, i.e.,
Rate = k[PCH3OCH3]3/2

If the pressure is measured in bar and time in minutes, then what are the units of rate and rate
constant?
Ans. In terms of pressure, unit of rate = bar min–1
Rate bar min –1
Unit of k = = = bar–1/2 min–1
[PCH ] 3/2 (bar) 3/2
3 OCH3

Q. 5. Mention the factors that affects the rate of a chemical reaction.

Ans. Refer to Basic Concepts Point 5.
Q. 6. A reaction is second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is (i) doubled (ii) reduced to half?
Ans. Rate = k [A]2 = ka2
If [A] = 2a, Rate = k [2a]2 = 4ka2 = 4 times of the initial rate

Rate = k a k = ka 2 = times of the initial rate

1 a 2 1 1
If [A] = a,
2 2 4 4

156 Xam idea Chemistry–XII

 Q. 7. What is the effect of temperature on the rate constant of a reaction? How can this effect of temperature
on rate constant be represented quantitatively?
Ans. The rate constant of a reaction increases with increase in temperature and becomes nearly double for every
10°C rise of temperature. The effect can be represented quantitatively by Arrhenius equation,
k = A e –Ea /RT
where Ea is the activation energy of the reaction and A is the frequency factor.
Q. 8. In a pseudo first order hydrolysis of an ester in water, the following results were obtained:
t/s 0 30 60 90
–1
[A]/mol L 0.55 0.31 0.17 0.085

Calculate the average rate of reaction between the time interval 30 to 60 seconds.
Ans. Average rate of reaction between the interval 30–60 s.
C2 – C1
= – t – t
2 1

(0.17 – 0.31) 0.14

= – = mol L–1 s–1
60 – 30 30
= 4.67 × 10–3 mol L–1 s–1
Q. 9. A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when concentration of both A and B are doubled?
– d [R]
  Ans. (i) Rate = = k [A] [B] 2
dt
(ii) If the concentration of B is tripled, then
Rate = k [A] [3B] 2 = 9k [A] [B] 2, i.e., the rate of reaction becomes 9 times.
(iii) If the concentration of both A and B are doubled, then
Rate = k [2A] [2B] 2 = 8k [A] [B] 2, i.e., the rate of reaction becomes 8 times.
Q. 10. In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial
concentrations of A and B as given below:
A/mol L–1 0.20 0.20 0.40

B/mol L–1 0.30 0.10 0.05

–1 –1 –5 –5
r0/mol L s 5.07 × 10 5.07 × 10 1.43 × 10–4

What is the order of reaction with respect to A and B?

Ans. Let the rate law be r0 = k[A]m [B]n
(r0)1 = 5.07 × 10–5= k (0.20)m (0.30)n ...(i)
(r0)2 = 5.07 × 10–5= k (0.20)m (0.10)n ...(ii)
–4 m n
(r0)3 = 1.43 × 10 = k (0.40) (0.05) ...(iii)
(r0)1 5.07×10 –5 k (0.20) m (0.30) n
Dividing (i) by (ii), = =
(r0) 2 5.07×10 –5 k (0.20) m (0.10) n

1 = 3n or 30 = 3n ⇒ n=0
(r0) 3 m
1.43 # 10 –4 k (0.40) (0.05)
n
Dividing (iii) by (ii), = = m n
(r0) 2 5.07 # 10 –5 k (0.20) (0.10)

Chemical Kinetics 157

 2.821 = 2m × (1/2)0
⇒ log 2.821 = m log 2
log 2.821
⇒
m= = 1.496 = 1.5
log 2
Thus, order of reaction w.r.t. A = 1.5 and order of reaction w.r.t. B = 0.
Q. 11. The following results have been obtained during the kinetic studies of the reaction:
2A + B C+D
Initial rate of formation
Experiment [A]/mol L–1 [B]/mol L–1
of D/mol L–1 min–1
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–2
III 0.3 0.4 2.88 × 10–1
IV 0.4 0.1 2.40 × 10–2

Determine the rate law and the rate constant for the reaction.
Ans. Suppose order of reaction w.r.t. reactant A is m and with respect to B is n. Then the rate law will be
Rate = k [A]m [B]n
Substituting the values of experiments I to IV, we have
(Rate)expt I = 6.0 × 10–3 = k (0.1)m (0.1)n ...(i)
–2 m n
(Rate)expt II = 7.2 × 10 = k (0.3) (0.2) ...(ii)
(Rate)expt III = 2.88 × 10–1 = k (0.3)m (0.4)n ...(iii)
–2 m n
(Rate)expt IV = 2.4 × 10 = k (0.4) (0.1) ...(iv)
m n
(Rate) exp t I 6.0 # 10 –3 k (0.1) (0.1)
\
= = m n
(Rate) exp t IV 2.4 # 10 –2 k (0.4) (0.1)
(0.1) m 1 m
m = c m , m =1
1
or =
4 (0.4) 4
(Rate) exp t II 7.2 # 10 –2 k (0.3) m (0.2) n
= = m n
(Rate) exp t III 2.88 # 10 –1 k (0.3) (0.4)
(0.2) n 1 n
c m
1
or = =
4 (0.4) n 2

1 n
c m = c m   or
1 2
or n=2
2 2
\ Rate law expression is given by
Rate = k [A] [B]2
Order of reaction w.r.t. A = 1;
Order of reaction w.r.t. B = 2.
Overall order of reaction = 1 + 2 = 3
Rate 6.0 # 10 –3 mol L–1 min –1
k= =
[A] [B] 2 (0.1 mol L–1) (0.1 mol L–1) 2

= 6.0 mol–2 L2 min–1

158 Xam idea Chemistry–XII

Q. 12. The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in
the blanks in the following table:
Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/ mol L–1 min–1
I 0.1 0.1 2.0 × 10–2
II — 0.2 4.0 × 10–2
III 0.4 0.4 —
IV — 0.2 2.0 × 10–2

[CBSE 2019 (56/5/2)]

Ans. The rate expression for the reaction is given as
Rate = k [A]1 [B]0 = k[A]
For experiment I, Rate = 2.0 × 10–2 mol L–1 min–1 = k (0.1 M) or k = 0.2 min–1
For experiment II, Rate = 4.0 × 10–2 mol L–1 min–1 = (0.2 min–1) [A] or [A] = 0.2 mol L–1
For experiment III, Rate = (0.2 min–1) (0.4 mol L–1) = 0.08 mol L–1 min–1
For experiment IV, Rate = 2.0 × 10–2 mol L–1 min–1 = 0.2 min–1 [A] or [A] = 0.1 mol L–1
Q. 13. Calculate the half-life of a first order reaction from their rate constants given below:
(i) 200 s–1 (ii) 2 min–1
–1
(iii) 4 years
0.693
Ans. Half-life period of a first order reaction, t1/2 =
k
0.693 –3
(i) t1/2 = = 0.346 × 10 s = 3.46 × 10 s
–2
200 s –1
0.693
(ii) t1/2 = = 0.346 min = 3.46 × 10 –1 min
2 min –1
0.693
(iii) t1/2 = = 0.173 year = 1.73 × 10 –1 year
4 year –1
Q. 14. The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood
had only 80% of the 14C found in a living tree. Estimate the age of the sample.
Ans. Radioactive decay follows first order kinetics.
0.693 0.693 –1 –4 –1
k= t1/2 = 5730 year = 1.21 × 10 year
2.303 [R] 0 2.303 100
t= log = log
k [R] –4
(1.21 # 10 year )–1 80
2.303
= # 0.09691
1.21 # 10 –4 year –1
= 1845 years (approx.)
Q. 15. The experimental data for the decomposition of N2O5
[2N 2 O5 4NO 2 + O 2]
in gas phase at 318 K are given below:
t (s) 0 400 800 1200 1600 2000 2400 2800 3200
5 –1
10 × [N2O5]/mol L 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log [N2O5] and t.
(iv) What is rate law?

Chemical Kinetics 159

 (v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).
Ans.
t (s) 0 400 800 1200 1600 2000 2400 2800 3200
5 –1
10 × [N2O5]/mol L 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
log [N2O5] – 1.79 – 1.87 – 1.94 – 2.03 – 2.11 – 2.19 – 2.28 – 2.37 – 2.46
(i) Plot of [N2O5] versus time

(ii) Initial concentration of [N2O5] = 1.63 × 102 M
Half of the concentration = 0.815 × 102 M
Time corresponding to this concentration = 1450 s. Hence, t1/2 = 1450 s.
(iii) Plot of log [N2O5] versus time

(iv) As plot of log [N2O5] vs time is a straight line, hence it is a reaction of first order.
` Rate law is,
Rate = k [N2O5]
k
(v) Slope of the line = – ...(i)
2.303
–2.46 – (–1.79) 0.67
Slope = =– ...(ii)
3200 – 0 3200
From equation (i) and (ii), we get
k – 0.67 0.67×2.303
– = or k =
2.303 3200 3200
or k = 4.82 × 10 –4 s –1

160 Xam idea Chemistry–XII

 0.693 0.693
(vi) t1/2 = = = 1438 s
k 4.82 × 10 –4 s –1
The two values are almost same within limits of possible error.
Q. 16. The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
concentration of the reactant to its 1/16th value?
[R] 0 [R] 0
as 6R@ =
2.303
Ans. t= log
k [R] 16
2.303 [R] 0 2.303
t= log = # 4 log 2
k [R] 0 60
16
2.303
= # 4 # 0.3010 = 4.62 × 10–2 s
60
Q. 17. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1 µg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after
10 years and 60 years if it is not lost metabolically?
Ans. As radioactive disintegration follows first order kinetics,
0.693 0.693
\ Decay constant of 90Sr, k = t = = 2.466 × 10–2 y–1
1/2 28.1
To calculate the amount left after 10 years:
[R]0 = 1 µg, t = 10 years, k = 2.466 × 10–2 y–1, [R] = ?
2.303 [R] 0
k= t log
[R]
–2 2.303 1
2.466 × 10 = log
10 [R]
or log [R] = – 0.1071
or [R] = Antilog 1.8929 = 0.7814 µg
To calculate the amount left after 60 years:

2.303 1
2.466 × 10–2 = log
60 [R]
or log [R] = – 0.6425
or [R] = Antilog 1.3575 = 0.2278 µg
Q. 18. For a first order reaction, show that time required for 99% completion is twice the time required for
the completion of 90% of reaction. [CBSE 2019 (56/5/2)]
Ans. For a first order reaction,
2.303 [R] 0
t= log
k [R]
When the reaction is 99% completed, [R] = [R]0 – 0.99 [R]0 = 0.01 [R]0
When the reaction is 90% completed, [R] = [R]0 – 0.9[R]0 = 0.1[R]0
2.303 [R] 0
t99% k
log
0.01 [R] 0 log 10 2 2 log 10
t90% = = = =2
2.303 [R] 0 log 10 log 10
log
k 0.1 [R] 0
Hence, t99% = 2t90%
Q. 19. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Ans. For a first order reaction
2.303 [R] 0
k= t log
[R]

Chemical Kinetics 161

 [R] 0100 10
When t = 40 minutes, = =
[R]
100 – 30 7
2.303 10
k= log
40 7
2.303 2.303
k= log 1.428 = × 00.1547
# .1548
40 40
–3 –1
k = 8.91 × 10 min
0.693 0.693
t1/2 = =
k 8.91 # 10 –3
t1/2 = 77.78 min
Q. 20. For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are
obtained:
t (s) 0 360 720
P (mm of Hg) 35.0 54.0 63.0
Calculate the rate constant.
Ans.     (CH3)2CHN—NCH(CH3)2(g) N2(g) + C6H14(g)
Initial pressure P0 0 0
After time t P0 – p p p
Total pressure after time t (Pt) = (P0 – p) + p + p = P0 + p or p = Pt – P0
a ? P0 and (a – x) ? P0 – p or substituting the value of p,
a – x ? P0 – (Pt – P0), i.e., (a – x) ? 2P0 – Pt
For a first order reaction
2.303 a
k= t log a – x
2.303 P0
= t log
2P0 – Pt
2.303 35.0 2.303 35
When t = 360 s k= log = log
360s 2 # 35.0 – 54.0 360 s 16
2.303
= (0.3400) = 2.175 × 10–3 s–1
360 s
2.303 35.0 2.303
When t = 720 s, k= log = log 5
720 s 2 # 35.0 – 63.0 720 s
2.303
= (0.6990) = 2.235 × 10–3 s–1
720 s
2.175 + 2.235
Average value of k = × 10–3 s–1 = 2.20 × 10–3 s–1
2
Q. 21. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO 2 Cl 2 (g)
SO 2 (g) + Cl 2 (g)
Experiment Time/s Total pressure/atm
1 0 0.5
2 100 0.6

Calculate the rate of reaction when total pressure is 0.65 atm.

Ans. SO 2 Cl 2 (g) SO 2 (g) + Cl 2 (g)
2.303 P0
k= t log 2P0 – Pt

162 Xam idea Chemistry–XII

 2.303 0.5 2.303
When t = 100 s, k= log = log (1.25)
100 s 2 # 0.5 – 0.6 100 s
2.303
= (0.0969) = 2.2316 × 10–3 s–1
100 s
When Pt = 0.65 atm, i.e., P0 + p = 0.65 atm
\ p = 0.65 – P0 = 0.65 – 0.50 = 0.15 atm
Pressure of SO2Cl2 at time t ( pSO2Cl2) = P0 – p = 0.50 – 0.15 atm = 0.35 atm
\ Rate = k × pSO2Cl2 = (2.2316 × 10–3 s–1) (0.35 atm)
= 7.8 × 10–4 atm s–1
Q. 22. The rate constant for the decomposition of N2O5 at various temperatures is given below:
T°C 0 20 40 60 80
105 × k/s–1 0.0787 1.70 25.7 178 2140
Draw a graph between ln k and 1/T and calculate the values of A and Ea. Predict the rate constant at
30°C and 50°C.
1
Ans. To draw the graph of ln k versus T , we can re-write the given data as follows:
T (K) 273 293 313 333 353
1/T (K–1) 0.003663 0.003413 0.00319 0.003003 0.002833
ln k – 14.055 – 10.982 – 8.266 – 6.331 – 3.844

–1
–2
–3
–4 (2.833, –3.844)
–5
–6 (3.003, –6.331)
–7 –14.055 – (–10.982)
–8 (3.195, –8.266) (3.663 – 3.413) × 10–3
–9
–10
–11 (3.413, –10.98)
–12
–13
–14 (3.663, –14.055)
–15
2.8 3.0 3.2 3.4 3.6 3.8
10–3
Graph of ln k vs 1/T
From the graph, we find that
–Ea – (– 3.073)
Slope = =
R 0.25 × 10 –3
3.073
\ Activation energy, Ea =  8.314 = 102195.7 J mol–1 = 102.20 kJ/mol
0.25  10 3
Ea
We know that ln k = ln A –
RT
Ea 1
or ln A = e o + ln k
R T
At T = 273 K, ln k = – 14.055
102.20
\ ln A =  14.055  30.973
8.314  10 3  273
Frequency factor, A = 2.83 × 1013

Chemical Kinetics 163

 The value of rate constant at two different temperatures can be determined as follows:
T 1/T Value of ln k (from graph) Value of k
303 0.003300 – 9.7 6.13 × 10–5 s–1
323 0.003096 – 6.3 1.84 × 10–3 s–1

Q. 23. The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5 s–1 at 546 K. If the energy of
activation is 179.9 kJ/mol, what will be the value of pre-exponential factor?
Ans. Given, k = 2.418 × 10–5 s–1, Ea = 179.9 kJ mol–1, T = 546 K.
Ea
log k = log A –
2.303 RT
Ea
or log A = log k +
2.303 RT
179.9 kJ mol –1
log A = log (2.418 × 10–5 s–1) +
2.303 # 8.314 # 10 –3 kJ K –1 mol –1 # 546 K
= (– 5 + 0.3834) s–1 + 17.2081
= 12.5915 s–1
or A = Antilog (12.5915) s–1
= 3.904 × 1012 s–1
Q. 24. Consider a certain reaction A Products with k = 2.0 × 10–2 s–1. Calculate the concentration of A
remaining after 100 s if the initial concentration of A is 1.0 mol L–1.
2.303 [R] 0
Ans. The units of k show that the reaction is of first order. Hence, k = t log
[R]
–2 –1 2.303 1.0 mol L–1
\ 2.0 × 10 s = log or log [A] = – 0.8684
100 s [A]
\
[A] = Antilog (– 0.8684) = Antilog (1.1316) = 0.1354 mol L–1
Q. 25. Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law
with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours?
Ans. Since sucrose decomposes according to first order rate law,
2.303 [R] 0
k= t log [R]
As t1/2 = 3.0 hours,
0.693 0.693
\ k= t = = 0.231 h–1
1/2 3 h
2.303 [R] 0
0.231 h–1 = log
8h [R]
[R] 0
or log = 0.8024
[R]
[R] 0
or = Antilog (0.8024) = 6.345
[R]
[R] 1
or = = 0.158
[R] 0 6.345
Q. 26. The decomposition of hydrocarbon follows the equation: k = (4.5 × 1011 s–1) e– (28000 K)/T.
Calculate Ea.
Ans. From Arrhenius equation, k = A e –Ea /RT
Ea 28000 K
\ – = –
RT T
or Ea = 28000 K × R = 28000 K × 8.314 J K–1 mol–1
= 232.79 kJ mol–1

164 Xam idea Chemistry–XII

Q. 27. The rate constant for the first order decomposition of H2O2 is given by the following equation:
log k = 14.34 – 1.25 × 104 K/T
Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes.
1.25 # 10 4
Ans. Given, log k = 14.34 –
T
Ea
Comparing with the equation, log k = log A – , we get
2.303 RT
Ea
= 1.25 × 104
2.303 R
or Ea = 1.25 × 104 × 2.303 × 8.314
= 23.934 × 104 J mol–1
Ea = 239.34 kJ mol–1
Given, t1/2 = 256 min = 256 × 60 s
0.693 0.693 –5 –1
k= t1/2 = 256 × 60 = 4.5 × 10 s
Substituting the value of k in given equation, we get
1.25 # 10 4
log (4.51 × 10–5) = 14.34 –
T
1 . 25 # 10 4
log 4.51 + log 10–5 = 14.34 –
T
1.25 # 10 4
or log 4.51 – 5 log 10 = 14.34 –
T
1.25 # 10 4 1.25 # 10 4
0.6542 – 5 = 14.34 – or = 18.6858
T T
1.25 # 10 4
or T= = 669 K (approx.)
18.6858
Q. 28. The decomposition of A into product has value of k as 4.5 × 103 s–1 at 10°C and energy of activation
is 60 kJ mol–1. At what temperature would k be 1.5 × 104 s–1?
Ans. k1 = 4.5 × 103 s–1, T1 = 10 + 273 K = 283 K; k2 = 1.5 × 104 s–1, T2 = ?, Ea = 60 kJ mol–1
From Arrhenius equation,
k2 Ea T2 – T1
log = 2.303 R = T T G
k1 2 1

e o
1.5 # 10 4 60000 J mol –1 T2 – 283
log =
4.5 # 10 3 –1
2.303 # 8.314 JK mol –1 283T2

T2 – 283 T2 – 283
log 3.333 = 3133.63 e o
0.5228
or or =
283T2 3133.63 283T2
or 0.0472 T2 = T2 – 283
or 0.9528 T2 = 283
283
or T2 = = 297 K = 297 – 273°C = 24°C
0.9528
Q. 29. The time required for 10% completion of a first order reaction at 298 K is equal to that required for
its 25% completion at 308 K. If the value of A is 4 × 1010 s–1, calculate k at 318 K and Ea.
2.303 [R] 0 2.303 100
Ans. k1 = t1 log = t log
[R] 0 – 0.10 [R] 0 1 90
2.303 0.1055 0.1055
= t1 (0.0458) = t1 or t1 =
k298K

Chemical Kinetics 165

 2.303 [R] 0 2.303 100
k2 = t2 log = t log
[R] 0 – 0.25 [R] 0 2 75
2.303 0.2879 0.2879
  = t2 (0.125) = t2 or t2 =
k308K
0.1055 0.2879 k2
But t1 = t2. Hence, = or = 2.7289
k1 k2 k1
k2 Ea T2 – T1
Now, from Arrhenius equation, log = = G
k1 2.303 R T2 T1
Ea (308 – 298) K
\ log (2.7289) = #
2.303 # 8.314 J K –1 mol –1 298 K × 308 K
Ea 10
0.4360 = #
#
2.303 8.314 298 × 308

or Ea = 76.623 kJ mol–1
Calculation of k at 318 K:
Ea
log k = log A –
2.303 RT
76.623 kJ mol 1
= log (4  1010 ) 
2.303  8.314  10 3 kJ K 1 mol 1  318 K
= 10.6021 – 12.5843 = – 1.9822
or k = Antilog (– 1.9822) = Antilog (2.0178)
= 1.042 × 10–2 s–1
Q. 30. The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the
energy of activation of the reaction assuming that it does not change with temperature.
[CBSE 2019 (56/4/1)]
k2
Ans.       k2 = 4k1 ⇒ =4
k1
k2 Ea T2 – T1
log = = G
k1 2.303 R T2 T1
Ea
c m
313 – 293
⇒ log 4 =
2.303 # 8.314 293 # 313
Ea
c m
20
2 × log 2 =
19.147 91709
2 # 0.3010 # 19.147 # 91709
Ea = = 52.85 kJ/mol
20

Multiple Choice Questions [1 mark]

Choose and write the correct option(s) in the following questions.
1. In the reaction,
BrO 3– (aq) + 5Br – (aq) + 6H + 3Br2 (l ) + 3H 2 O (l )
The rate of appearance of bromine is related to rate of disappearance of bromide ion as
d [Br2] –5 d [Br –] d [Br2] 5 d [Br –]
(a) = (b) =
dt 3 dt dt 3 dt
d [Br2] 3 d [Br –] d [Br2] –3 d [Br –]
(c) = (d) =
dt 5 dt dt 5 dt

166 Xam idea Chemistry–XII

 2. A graph of volume of hydrogen released vs time for the reaction
between zinc and dil. HCl is given in figure. On the basis of this V5
mark the correct option.      [NCERT Exemplar] V4
V3 – V2
(a) Average rate upto 40 seconds is V3
40
V3 – V2 V2
(b) Average rate upto 40 seconds is
40 – 30 V1
V3
(c) Average rate upto 40 seconds is
40
V3 – V1 O 20 30 40 50
(d) Average rate upto 40 seconds is
40 – 20
3. Consider the graph given in the above question. Which of the following options does not show
instantaneous rate of reaction at 40th second? [NCERT Exemplar]
V5 – V2 V4 – V2 V3 – V2 V3 – V1
(a) (b) (c) (d)
50 – 30 50 – 30 40 – 30 40 – 20
4. The rate constant of reaction is 2.0 × 10–6 mol–2 L2 s–1. The order of the reaction is
(a) 0 (b) 2 (c) 1 (d) 3
5. The rate of a gaseous reaction is given by the expression, rate = k[A] [B]. If the volume of the reaction
vessel is suddenly reduced to 1/4 of the initial volume, the reaction rate related to original rate will be
1
(a) 1/16 (b) (c) 8 (d) 16
8
6. Which of the following is not correct about order of a reaction? [NCERT Exemplar]
(a) The order of a reaction can be a fractional number.
(b) Order of a reaction is experimentally determined quantity.
(c) The order of a reaction is always equal to the sum of the stoichiometric coefficients of reactants in the
balanced chemical equation for a reaction.
(d) The order of a reaction is the sum of the powers of molar concentration of the reactants in the rate law
expression.
7. Which of the following statements are applicable to a balanced chemical equation of an elementary
reaction? [NCERT Exemplar]
(a) Order is same as molecularity. (b) Order is less than the molecularity.
(c) Order is greater than the molecularity. (d) Molecularity can never be zero.
8. For the reaction,
H 2 (g) + Br2 (g) 2HBr (g)
The experimental data suggests,
1
Rate = k [H 2] [Br2] 2
The molecularity and order for the reaction is
1 1 1 1
(a) 2 and 2 (b) 2 and 1 (c) 1 and 2 (d) 1 and 1
2 2 2 2
9. The unit of rate constant of a zero order reaction is
(a) litre second–1 (b) litre mole–1 second–1 (c) mole litre–1 second–1 (d) mole second–1
10. Rate law cannot be determined from balanced chemical equation if _________. [NCERT Exemplar]
(a) reverse reaction is involved (b) it is an elementary reaction
(c) it is a sequence of elementary reactions (d) any of the reactants is in excess
11. In the reaction, A B, the rate of reaction increases two times on increasing the concentration
of A four times, the order of reaction is
1
(a) 2 (b) 0 (c) (d) 3
2

Chemical Kinetics 167

 12. Which of the following is a zero order reaction?
(a) Decomposition of N2O5 (b) Decomposition of NH3
(c) Decomposition of N2O (d) Radioactive decay of unstable nuclei
13. Diazonium salt decomposes as
C6 H5 N2 Cl C6 H5 Cl + N 2
at 0° C. The evolution of N2 becomes two times faster when the initial concentration of the salt is
doubled. Therefore it is
(a) a first order reaction
(b) a second order reaction
(c) independent of the initial concentration of the salt
(d) a zero order reaction
14. In the graph plotted between ln [R] and t for a first order reaction, the intercept on y-axis is
(a) – k (b) [R]0 (c) ln [R]0 (d) k/2.303
15. If 75% of the first-order reaction was completed in 32 minutes, 50% of the same reaction would be
completed in:
(a) 8 min (b) 4 min (c) 16 min (d) 24 min
16. The half life of a first order reaction is 69.35 sec. The value of rate constant of the reaction is
(a) 1.0 s–1 (b) 0.1 s–1 (c) 0.01 s–1 (d) 0.001 s–1
17. Consider a first order gas phase decomposition reaction given below: [NCERT Exemplar]
A ( g) B (g) + C (g)
The initial pressure of the system before decomposition of A was pi. After lapse of time 't', total
pressure of the system increased by x units and became 'pt'. The rate constant k for the reaction is
given as ________________.
2.303 pi 2.303 pi
(a) k = t log p – x (b) k = t log
i 2p – p i t

2.303 pi 2.303 pi
(c) k = t log 2pi + pt (d) k = t log
pi + x
18. The activation energy of a reaction is zero. The rate of the reaction
(a) increases with increase of temperature (b) decreases with decrease of temperature
(c) decreases with increase of temperature (d) is nearly independent of temperature
19. The activation energy of a reaction can be determined from the slope of which of the following graphs?
1 T 1
(a) ln k vs
(b) vs
T ln k T
(c) ln k vs T (d) ln k vs T
T
20. Consider figure and mark the correct option. Activated complex

[NCERT Exemplar]
(a) Activation energy of forward reaction is E1 + E2 and product E1
is less stable than reactant.
(b) Activation energy of forward reaction is E1 + E2 and product Products
Energy

is more stable than reactant.

(c) Activation energy of both forward and backward reaction is
E2
E1 + E2 and reactant is more stable than product.
(d) Activation energy of backward reaction is E1 and product is Reactants
more stable than reactant.
Reaction coordinate

168 Xam idea Chemistry–XII

 21. The role of a catalyst is to change ________________. [NCERT Exemplar]
(a) gibbs energy of reaction (b) enthalpy of reaction
(c) activation energy of reaction (d) equilibrium constant
22. In the presence of a catalyst, the heat evolved or absorbed during the reaction ________________.
[NCERT Exemplar]
(a) increases (b) decreases
(c) remains unchanged (d) may increase or decrease
Answers
1. (d) 2. (c) 3. (b) 4. (d) 5. (d) 6. (c) 7. (a), (d) 8. (b) 9. (c) 10. (a,c,d)
11. (c) 12. (b) 13. (a) 14. (c) 15. (c) 16. (c) 17. (b) 18. (d) 19. (a) 20. (a)
21. (c) 22. (c)

Assertion-Reason Questions
In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement.
1. Assertion (A)
: Instantaneous rate is used to predict the rate of a reaction at a particular moment of time.
Reason (R)
: Average rate is constant for the time interval for which it is calculated.
2. Assertion (A)
: For the reaction, CHCl3 + Cl2 CCl4 + HCl, rate = k[CHCl3] [Cl2]1/2
Reason (R)
: Rate law for any reaction can be predicted with the help of a balanced chemical equation.
3. Assertion (A)
: The rate of the reaction is the rate of change of concentration of a reaction or a product.
Reason (R)
: Rate of reaction remains constant during the course of reaction.
4. Assertion (A)
: Order of the reaction can be zero or fractional.
Reason (R)
: We cannot determine order from balanced chemical equation.
5. Assertion (A)
: Order and molecularity are same.
Reason (R)
: Order is determined experimentally and molecularity is the sum of the stoichiometric
coefficient of rate determining elementary step.
6. Assertion (A) : For the reaction
2N 2 O5 4NO 2 + O 2;
Rate = k [N 2 O5] .
Reason (R) : Rate of decomposition of N2O5 is determined by slow step.
7. Assertion (A) : The inversion of cane sugar,

H
C H O  H 2 O   C6 H12 O6  C6 H12 O6
12 22 11
is a pseudo first order reaction.
Reason (R) : H2O in this reaction is present in very less amount as compared to C12H22O11.
8. Assertion (A) : For each ten degree rise of temperature the specific rate constant is nearly doubled.
Reason (R) : Energy-wise distribution of molecules in a gas is an experimental function of temperature.
9. Assertion (A) : If the activation energy of a reaction is zero, temperature will have no effect on the rate
constant.
Reason (R) : Lower the activation energy, faster is the reaction.

Chemical Kinetics 169

 10. Assertion (A) : R
 ate constants determined from Arrhenius equation are fairly accurate for simple as well
as complex molecules.
Reason (R) : Reactant molecules undergo chemical change irrespective of their orientation during
collision.
11. Assertion (A) : The enthalpy of reaction remains constant in the presence of a catalyst.
Reason (R) : A catalyst participating in the reaction, forms different activated complex and lowers
down the activation energy but the difference in energy of reactant and product remains
the same.
12. Assertion (A) : All collision of reactant molecules lead to product formation.
Reason (R) : Only those collisions in which molecules have correct orientation and sufficient kinetic
energy lead to compound formation.

Answers
1. (b) 2. (c) 3. (c) 4. (b) 5. (d) 6. (b) 7. (c) 8. (b) 9. (c) 10. (c)
11. (a) 12. (d)

Passage-based/Case-based Questions
Read the given passages and answer the questions that follow.

PASSAGE–1
The rate of a chemical reaction is expressed either in terms of decrease in the concentration of a reactant per
unit time or increase in the concentration of a product per unit time. Rate of the reaction depends upon the nature
of reactants, concentration of reactants, temperature, presence of catalyst, surface area of the reactants and presence
of light. Rate of reaction is directly related to the concentration of reactant. Rate law states that the rate of reaction
depends upon the concentration terms on which the rate of reaction actually depends, as observed experimentally.
The sum of powers of the concentration of the reactants in the rate law expression is called order of reaction while
the number of reacting species taking part in an elementary reaction which must collide simultaneously in order to
bring about a chemical reaction is called molecularity of the reaction.
1. Express the rate of the following reaction in terms of different reactants and products.
4NH3(g) + 5O2(g) 4NO2(g) + 6H2O(g)
1 d [ NH3 ]
Ans. Rate of reaction  
4 dt
      1 d [ O 2] 1 d [ NO2 ] 1 d [ H 2 O]
 
5 dt 4 dt 6 dt
2. Why do pieces of wood burn faster than a log of wood of the same mass?
Ans. Pieces of wood have larger surface area than the log of wood of the same mass. Greater the surface area,
faster is the reaction.
3. Why does the rate of any reaction generally decrease during the course of the reaction?
Ans. The rate of reaction depends on the concentration of reactants. As the reaction progresses, reactants
start getting converted to products so the concentration of reactants decreases hence the rate of reaction
decreases.
4. Why is molecularity applicable only for elementary reactions and order is applicable for elementary
as well as complex reactions?
Ans. A complex reaction proceeds through several elementary reactions. Number of molecules involved in
each elementary reaction may be different, i.e., the molecularity of each step may be different. Therefore,
discussion of the molecularity of overall complex reaction is meaningless. On the other hand, order of a
complex reaction is determined by the slowest step in its mechanism and is not meaningless even in the case
of complex reactions.

170 Xam idea Chemistry–XII

 5. The kinetics of the reaction
mA + nB + pC m′X + n′Y + p′Z
obey the rate expression dx/dt = k[A]m[B]n
Calculate total order and molecularity of the reaction.
Ans. The total order of reaction = m + n
The molecularity of the reaction = m + n + p

PASSAGE–2
Temperature has a marked effect on the rate of reaction. For most of the reactions,the rate of reaction becomes
nearly double for every 10 degree rise in temperature. The effect of temperature is usually expressed in terms of
temperature coefficient. The quantitative dependence of reaction rate on temperature was first explained by Swante
Arrhenius. Arrhenius proposed a simple equation known as Arrhenius equation
k = Ae–Ea/RT
This equation provides a relationship between the rate constant (k) of a reaction and the temperature of the
system. A is the Arrhenius factor or pre-exponential factor, Ea is the activation energy and R is the gas constant.

1. Define ‘activation energy’ of a reaction. [CBSE (AI) 2011]

Ans. The energy required to form the intermediate called activated complex is known as activation energy.
Activation energy = Threshold energy – Average energy of the reactants
2. How does a catalyst affect the rate of a reaction? Explain with respect to the Arrhenius equation.
Ans. A catalyst decreases the activation energy. According to Arrhenius equation, lower the activation energy,
greater will be the rate constant and thus the rate of reaction increases.
3. Can a reaction have zero activation energy? Justify.
Ans. No, Ea ≠ 0.
If Ea = 0, then according to Arrhenius equation,
k = Ae–Ea/RT
k = Ae0 = A,
i.e., Rate constant = Collision frequency
This means every collision results into a chemical reaction which cannot be true.
4. The plot of log k vs X is linear with slope = – Ea/2.303R. What is X?
Ans. 1/T
5. What is the fraction of molecules having energy greater than activation energy, Ea?
Ans. e–Ea/RT at temperature T.

Very Short Answer Questions [1 mark]

Q. 1. For the assumed reaction X2 + 3Y2 2XY3 , write the rate of equation in terms of rate of
disappearance of Y2. [HOTS]
d [X2] 1 d [ Y2
] 1 d [ XY 3]
Ans. Rate = – =– =+
dt 3 dt 2 dt
d [Y2] d [ X 2] 3 d [XY3]
Rate of disappearance of Y2 = – =–3 =+
dt dt 2 dt
Q. 2. Why does the rate of a reaction increase with rise in temperature? [NCERT Exemplar]
Ans. At higher temperatures, larger fraction of colliding particles can cross the energy barrier (i.e., the activation
energy), which leads to faster rate.
Q. 3. Define ‘order of a reaction’. [CBSE 2019 (56/2/1)]
Ans. Order of a reaction may be defined as the sum of the powers of the concentration terms of the reactants in
the rate law expression.

Chemical Kinetics 171

 Q. 4. Identify the order of reaction from the following unit for its rate constant:
L mol–1s–1 [CBSE (F) 2010]
Ans. Second order.
Q. 5. For the reaction A B , the rate of reaction becomes three times when the concentration of A is
increased by nine times. What is the order of reaction? [HOTS]
Ans. Let, r = k [A]n …(i)
Given, 3r = k [9A]n …(ii)
Dividing equation (ii) by (i), we get
3r k [9A] n 9 n k [A] n
r = =
k [A] n k [A] n
3 = 9n    or 31 = 32n
1
⇒
2n = 1    or n=
2
\
Rate, r = k[A]1/2
1
Order of reaction =
2
Q. 6. For which type of reactions, order and molecularity have the same value? [NCERT Exemplar]
Ans. If the reaction is an elementary reaction, order is same as molecularity.
Q. 7. Why is the probability of reaction with molecularity higher than three very rare? [NCERT Exemplar]
Ans. The probability of more than three molecules colliding simultaneously is very small. Hence, possibility of
molecularity being three is very low.
Q. 8. For a reaction, A + B Products, the rate law is Rate = k[A][B]3/2. Can the reaction be an
elementary reaction? Explain. [HOTS]
Ans. During an elementary reaction, the number of atoms or ions colliding to react is referred to as molecularity.
Had this been an elementary reaction the order of reaction with respect to B would have been 1, but in the
3
given rate law it is . This indicates that the reaction is not an elementary reaction.
2
Q. 9. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of the
reaction? [HOTS]
Ans. As t75% = 2t50%
Therefore, it is a first order reaction.
Q. 10. What is the effect of adding a catalyst on
(i) Activation energy (Ea), and
(ii) Gibbs energy (DG) of a reaction? [CBSE Delhi 2017; (AI) 2017]
Ans. (i) Decreases
(ii) No effect
Q. 11. Define threshold energy of a reaction.
Ans. Threshold energy is the minimum energy which must be possessed by reacting molecules in order to
undergo effective collision which leads to formation of product molecules.
Q. 12. Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain with
the help of one example. [NCERT Exemplar]
Ans. Thermodynamically the conversion of diamond to graphite is highly feasible but this reaction is very slow
because its activation energy is high.
Q. 13. In some cases, it is found that a large number of colliding molecules have energy more than threshold
value, yet the reaction is slow. Why? [CBSE Delhi 2013]
Ans. This is due to improper orientation of the colliding molecules at the time of collision.

172 Xam idea Chemistry–XII

Short Answer Questions–I [2 marks]
Q. 1. For the reaction 2N 2 O 5 (g) 4NO 2 (g) + O 2 (g) the rate of formation of NO2(g) is 2.8 × 10–3 Ms–1.
Calculate the rate of disappearance of N2O5(g). [CBSE 2018]
–1 3 (N 2 O5) 1 3 (NO 2) 3 ( O 2)
Ans. Rate = =+ =+
2 3t 4 3t 3t
3 (N 2 O5) 1 3 (NO 2)
Rate of disappearance of N2O5 = – =
3t 2 3t
1
         = × 2.8 × 10 Ms = 1.4 × 10 –3 Ms –1 –3 –1
2
Q. 2. The rate law for the reaction: Ester + H+ Acid + Alcohol is:
dx
= k [Ester] [H+]0
dt
What would be the effect on the rate if (i) concentration of the ester is doubled? (ii) concentration of
H+ is doubled?
Ans. (i) The rate of reaction will be doubled. (ii) No effect on rate.
Q. 3. Differentiate between rate of reaction and reaction rate constant.
Ans.
S. No. Rate of Reaction Reaction Rate Constant
(i) Rate of reaction is the change in concentration of a It is the rate of reaction when the molar
reactant or product in a unit interval of time. concentration of each of the reactants is unity.
(ii) The rate of reaction at any instant of time depends upon The rate constant does not depend upon the
the molar concentrations of the reactants at that time. concentrations of the reactants.
(iii) Its units are always mol litre–1 time–1. Its units depend upon the order of reaction.

Q. 4. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if
the concentration of the reactant is reduced to half? What is the unit of rate constant for such a
reaction? [CBSE (AI) 2011]
Ans. Consider the reaction nR Products
As the reaction is of second order
\ Rate, r = k [R]2 ...(i)
If the concentration of the reactant reduced to half, then
R 2
Rate, r′ = k : D ...(ii)
2
Dividing equation (ii) by (i), we get
r′ k [R] 2 1
= =
r 4k [R] 2 4
1 1
r l = r , i.e., rate of reaction becomes th of the initial rate.
4 4
The unit of rate constant is mol–1 L s–1.
Q. 5. What do you understand by the rate law and rate constant of a reaction? Identify the order of a
reaction if the units of its rate constant are: [CBSE (AI) 2011]
(i) L–1 mol s–1 (ii) L mol–1 s–1.
Ans. An experimentally determined expression which relates the rate of reaction with the concentration of
reactants is called rate law while the rate of reaction when concentration of each reactant is unity in a rate
law expression is called rate constant.
(i) Comparing power of mole in L–1 mol s–1 and (mol L–1)1–n s–1,
We get
1 = l – n ⇒ n = 0 i.e., zero order reaction
(ii) Again comparing power of mole in L mol–1s–1 and (mol L–1)1–n s –1, we get
–1 = 1 – n ⇒ n = 2, i.e., second order reaction

Chemical Kinetics 173

Q. 6. Calculate the overall order of a reaction which has the rate expression,
(i) Rate = k[A]1/2 [B]3/2 (ii) Rate = k[A]3/2 [B]–1
1 3
Ans. (i) Order = + = 2, i.e., second order.
2 2
3 1
(ii) Order = + (–1) = , i.e., half order.
2 2
Q. 7. Write two differences between ‘order of reaction’ and ‘molecularity of reaction’. [CBSE Delhi 2014]
Ans. Differences between order and molecularity of reaction:
S.No. Order Molecularity
(i) It is the sum of the powers of the concentration of It is the number of reacting species taking part in an
the reactants in the rate law expression. elementary reaction, which must collide simultaneously
so as to result into a chemical reaction.
(ii) It is determined experimentally. It is a theoretical concept.
(iii) It can be zero or a fraction. It cannot be zero or a fraction.
(iv) Order is applicable to elementary as well as complex Molecularity is applicable only for elementary reactions.
reactions. For complex reactions it has no meaning.
(Any two)
Pt
Q. 8. For a reaction: 2NH3(g) N2(g) + 3H2(g)
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k. [CBSE South 2016]
  Ans. (i) Zero order, bimolecular
(ii) mol L–1 s–1
Q. 9. Why is molecularity applicable only for elementary reactions and order is applicable for elementary
as well as complex reactions? [NCERT Exemplar]
Ans. A complex reaction proceeds through several elementary reactions. Number of molecules involved in
each elementary reaction may be different, i.e., the molecularity of each step may be different. Therefore,
discussion of molecularity of overall complex reaction is meaningless. On the other hand, order of a
complex reaction is determined by the slowest step in its mechanism and is not meaningless even in the
case of complex reactions.
Q. 10. Consider the decomposition of hydrogen peroxide in alkaline medium which is catalysed by iodide ions.
OH –
2H 2 O 2 2H 2 O + O 2
This reaction takes place in two steps as given below:
Step-I H2 O2 + I – H 2 O + IO – (slow)
Step-II H 2 O 2 + IO – H 2 O + I – + O 2 (fast)
(i) Write the rate law expression and determine the order of reaction w.r.t. H2O2.
(ii) What is the molecularity of each individual step?
Ans. (i) Rate = k [H2O2]1 [I–]1

Order of reaction w.r.t H2O2 = 1

(ii) Molecularity of step I = 2 and step II = 2.
Q. 11. For a chemical reaction R → P, the variation in the concentration (R) vs.
time (t) plot is given alongside.
(i) Predict the order of the reaction.
(ii) What is the slope of the curve? [CBSE (AI) 2014]
Ans.
(i) Order of the reaction is zero.
d [R]
(ii) Slope = = –k
dt

174 Xam idea Chemistry–XII

Q. 12. The rate constant for a reaction of zero order in A is 0.0030 mol L–1 s–1. How long will it take for the
initial concentration of A to fall from 0.10 M to 0.075 M?
Ans. k = 0.0030 mol L–1s–1, [R]0 = 0.10 M, [R] = 0.075 M
We know that
[R] = – kt + [R]0
0.075 = – 0.0030t + 0.10
⇒
3t = 100 – 75 ⇒ t = 8.33 seconds
Q. 13. Define the following terms:
(i) Pseudo first order reaction
(ii) Half life period of reaction (t1/2) [CBSE Delhi 2014]
  Ans. (i) A reaction which is not truely of first order but under certain conditions becomes a reaction of first
order is called pseudo first order reaction, e.g., acid hydrolysis of ethyl acetate.
+
CH3COOC2H5 + H2O 
H
 CH3COOH + C2H5OH
Rate ∝ [CH3COOC2H5] as H2O is in excess.
(ii) The half life (t1/2) of a reaction is the time in which the concentration of reactant is reduced to one half
of its initial concentration [R]0.
0.693
For a first order reaction, t1/2 = , i.e., independent of [R]0.
k
[R] 0
For a zero order reaction, t1/2 = , i.e., t1/2 ∝ [R]0.
2k
Q. 14. For a reaction: A + H2O B, Rate ∝ [A].
What is its (i) molecularity (ii) order of reaction?
Ans. (i) Pseudo unimolecular
(ii) Order = 1.
Q. 15. The rate for the reaction R P is rate = k[R]. It has been shown Y
graphically alongside. What is rate constant for the reaction?
s )

3×10–2
–1 –1

Ans. From the graph

Case I: Rate = k[A]
Rate (mol L

2×10–2
1 × 10–2 mol L–1 s–1 = k (0.1 mol L–1)
1×10–2
1 # 10 –2 mol L–1 s –1
\
k= = 0.1 s–1
0.1 mol L–1 O
Case II: 0.1 0.2 0.3 X
[R] (mol L–1)
3 × 10–2 mol L–1s–1 = k (0.3 mol L–1)
3 # 10 –2 mol L–1 s –1
k= = 0.1 s–1
0.3 mol L–1
Hence, k = 0.1 s–1
Q. 16. The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
1
concentration of the reactant to th of its initial value? [CBSE (F) 2013]
10
2.303 [R] 0 [R] 0
Ans. t = log as [R] =
k [R] 10

2.303 [R] 0 2.303 2.303

` t=
log = × log 10 = ×1 = 3.838×10 –2 s
k [R] 0 60 60
10

Chemical Kinetics 175

Q. 17. (i) For a reaction A + B P, the rate law is given by,
1/2 2
    r = k[A] [B] .
What is the order of this reaction?
(ii) A first order reaction is found to have a rate constant k = 5.5 × 10–14 s–1. Find the half life
of the reaction. [CBSE (AI) 2013]
1 5
Ans. (i) Order of reaction = +2=
2 2
(ii) Radioactive decay follows first order kinetics.
0.693 0.693
t1/2 = = s = 1.26 × 1013 s
k 5.5 # 10 –14
Q. 18. 87.5% of the substance disintegrated in 45 minutes (first order reaction). What is its half-life?
1 n 12.5
Ans. c m = because 87.5% has disintegrated, amount left is 12.5%.
2 100
1 n 1 n
c m =c m c m =c m
1 1 3
&
2 8 2 2
Number of half lives = 3
45
t1/2 = = 15 minutes
3
Q. 19. After 24 hrs, only 0.125 gm out of the initial quantity of 1 gm of a radioactive isotope remains behind.
What is its half life period? [CBSE Sample Paper 2017]
Ans. Here, [R]0 = 1 g, [R] = 0.125 g, t = 24 h
2.303 [R] 0
k = t log
[R]
2.303 1 2.303
k= log ⇒ k= log 8
24 0.125 24
2.303
k= ×0.9031 ⇒  k = 0.0866 h –1
24
0.693 0.693
t1 =    ⇒  t1/2 = or t1/2 = 8 h
2 k 0.0866 h –1
Q. 20. Show that in a first order reaction, time required for completion of 99.9% is 10 times that of half-life
(t1/2) of the reaction. [CBSE (F) 2016]
2.303 [R] 0
Ans. t = log
k [R]
2.303 100 100
t99.9% k
log
100 – 99 .9
log
0.1 log 103 3 log 10
t50% = = = =
2.303 100 100 log 2 0.3010
log log
k 100 –50 50
t99.9% 30
t50% = 3.01 - 10

t99.9% = 10t50%

Q. 21. Rate constant k for first order reaction has been found to be 2.54 × 10–3 s–1. Calculate its three-fourth
life. [CBSE Sample Paper 2013]
2.303 [ R] 0
Ans. t = log ...(i)
k [R]
[R] 0
k = 2.54×10 –3 s –1; [R] =
4

176 Xam idea Chemistry–XII

 Substituting these values in equation (i), we get
2.303 [R] 0
t3/4 = log = 0.9066×103 log 4
2.54×10 –3 [R] 0
4
t3/4 = 0.9066 × 103 × 0.6021 s
 = 5.46 × 102 s
Q. 22. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO 2 Cl 2 (g) SO 2 (g) + Cl 2 (g)
Experiment Time/second–1 Total pressure/atm
1 0 0.4
2 100 0.7

Calculate the rate constant.

(Given: log 4 = 0.6021, log 2 = 0.3010) [HOTS]
2.303 P0
Ans. k= t log
2P0 – Pt
Here, P0 = 0.4 atm, t = 100 s, Pt = 0.7 atm
2.303 0.4
\ k= log
100 2 # 0.4 – 0.7

2.303 0.4 2.303

= log = log 4
100 0.1 100
2.303
= # 0.6021
100
k = 1.386 × 10–2 s–1
Q. 23.
(i) Explain why H2 and O2 do not react at room temperature.
(ii) Write the rate equation for the reaction A 2 + 3B 2 2C , if the overall order of the
reaction is zero. [CBSE (AI) 2017]
Ans. (i) Due to high activation energy for the reaction.
(ii) Rate = k[A2]0[B2]0 or Rate = k
C
Q. 24. Answer the following questions on the basis of the given plot 300
of potential energy vs reaction coordinate:
Potential Energy (kJ)

250
(i) What is the threshold energy for the reaction?
200
(ii) What is the activation energy for forward reaction?
150
(iii) What is the activation energy for backward reaction? R
100
(iv) What is enthalpy change for the forward reaction? P
–1 50
Ans. (i) Threshold energy for the reaction = 300 kJ mol
(ii) Activation energy for the forward reaction = 300 – 150 Reaction Coordinate
       = 150 kJ mol–1
(iii) Activation energy for the backward reaction = 300 – 100
= 200 kJ mol–1
(iv) Enthalpy change for the forward reaction DrH = 100 – 150
    = – 50 kJ mol–1

Chemical Kinetics 177

 1
Q. 25. A graph between ln k and for a reaction is given. y
T
Here k is rate constant and T is temperature in kelvin. B
If OA = a and OB = b, answer the following:
(i) What is the activation energy (Ea) of the reaction?
(ii) What is the frequency factor (A) for the reaction? In k

     [HOTS]
Ea
Ans. According to Arrhenius equation, ln k = – + ln A x
RT O 1 A
OB b Ea b T
(i) Slope = – =– a =– or Ea = a R
OA R
(ii) Intercept on y-axis = OB = b = ln A or A = eb

Short Answer Questions–II [3 marks]

Q. 1. A + 2B 3C + 2D. The rate of disappearance of B is 1 × 10–2 mol L–1 s–1. What will be
(i) Rate of the reaction (ii) Rate of change in concentration of A and C?
– d [B]
Ans. (i) As = 1 × 10–2 mol L–1 s–1
dt
1 d [B] 1
\ Rate = – = × 1 × 10–2 = 0.5 × 10–2 mol L–1 s–1
2 dt 2
d [A] 1 d [B] 1 d [C]
(ii) Rate = – =– =+
dt 2 dt 3 dt
Rate of change in concentration of A
d [A] 1 d [B]
= – =–
dt 2 dt
= 0.5 × 10 mol L–1 s–1 –2

Rate of change in concentration of C

d [C] 3 d [B] 3
= + =– = # 1 # 10 –2
dt 2 dt 2
= 1.5 × 10–2 mol L–1 s–1
Q. 2. The rate of reaction, 2NO + Cl 2 2NOCl is doubled when concentration of Cl2 is doubled
and it becomes eight times when concentration of both NO and Cl2 are doubled. Deduce the order of
the reaction. [HOTS]
Ans. Let r = k [NO]x [Cl2]y …(i)
2r = k [NO]x [2Cl2]y …(ii)
x y
8r = k [2NO] [2Cl2] …(iii)
Dividing (iii) by (ii), we get
8r k [2NO] x [2Cl 2] y
=
2r k [NO] x [2Cl 2] y
22 = [2]x
x =2
Putting the value of x in (i) and (ii), we get
r = k [NO]2 [Cl2]y
2r = k [NO]2 [2Cl2]y
2r [2Cl2 ] y
r =
[Cl2 ] y

178 Xam idea Chemistry–XII

 2 = [2]y
y =1
Rate = k [NO]2 [Cl2]1
Overall order of reaction = x + y = 2 + 1 = 3
Q. 3. Following reaction takes place in one step:
2NO (g) + O 2 (g) 2NO 2 (g)
How will the rate of the above reaction change if the volume of the reaction vessel is reduced to one-third of
its original volume? Will there be any change in the order of the reaction with reduced volume? [HOTS]
Ans. Rate = k [NO]2 [O2]
Let initially, moles of NO = a, moles of O2 = b, volume of the vessel = V. Then
a b
[NO] = M, [O2] = M
V V
Rate (r1) = k a k c m = k 3
a 2 b a2 b
\ …(i)
V V V
V
Now, new volume =
3
a 3a
\ New concentrations: [NO] = =
V/3 V
b 3b
[O2] = =
V/3 V
3a 2 3b 27ka 2 b
\ New rate (r2) = k c m c m = …(ii)
V V V3
r2
\ r = 27   or    r2 = 27r1, i.e., rate becomes 27 times.
1
Thus, there is no effect on the order of reaction.
Q. 4. Nitric oxide, NO, reacts with oxygen to produce nitrogen dioxide. [HOTS]
2NO (g) + O 2 (g) 2NO 2 (g)
The rate law for this reaction is:
Rate = k [NO]2 [O2]
Propose a mechanism for the reaction.
Ans. The probable proposed mechanism may be,
NO + O 2 NO3 (fast) Step I
k1
NO3 + NO NO 2 + NO 2 (slow) Step II
Since slowest reaction is the rate determining step, therefore
Rate = k1 [NO3] [NO]
[NO3]
K=
[NO] [O 2]
[NO3] = K [NO] [O2]
Rate = k1K [NO] [O2] [NO] = K′[NO]2 [O2], where K ′ = k1.K
Q. 5. The reaction, N 2 (g) + O 2 (g) 2NO (g) contributes to air pollution whenever a fuel is burnt in
air at a high temperature. At 1500 K, equilibrium constant K for it is 1.0 × 10–5. Suppose in a case
[N2] = 0.80 mol L–1 and [O2] = 0.20 mol L–1 before any reaction occurs. Calculate the equilibrium
concentrations of the reactants and the product after the mixture has been heated to 1500 K.
[CBSE (AI) 2012] [HOTS]
Ans.    N2 + O2    2NO
Initial conc. in mol L–1 0.8 0.2 0
Change in conc. in mol L–1 –x –x +2x
Equilibrium conc. in mol L–1 0.8–x 0.2 – x 2x
[NO] 2 (2x) 2
KC = ` 1 × 10 –5 =
[ N 2] [ O 2 ] (0.8 – x) (0.2 – x)

Chemical Kinetics 179

 As x << 0.2, therefore 0.8 – x . 0.8 and 0.2 – x . 0.2
4x 2
\ 1 × 10–5 = ⇒  4x2 = 16 × 10–7
0.16
x = 6.324 × 10–4 mol L–1
Thus at equilibrium,
[NO] = 2x = 2 × 6.324 × 10–4 = 12.648 × 10–4 mol L–1
[N2] = 0.8 – 6.324 × 10–4 mol L–1 = 0.799 mol L–1
[O2] = 0.2 – 6.324 × 10–4 mol L–1 = 0.199 mol L–1
Q. 6. Define order of reaction. How does order of a reaction differ from molecularity for a complex
reaction? [CBSE 2019 (56/3/2), 2020 (56/5/1)]
Ans. l The sum of powers of the concentration of the reactants in the rate law expression is known as order of
that reaction.
Consider the general reaction,
aA + bB cC + dD
Let
Rate = k[A]x[B]y
where x and y represent the order w.r.t. t. The reactants A and B respectively. Overall order of reaction
= x + y.
l Order is applicable to elementary as well as complex reactions whereas molecularity is applicable only

for elementary reactions.

For a complex reaction molecularity has no meaning and order is given by the slowest step. Molecularity
of the slowest step is same as the order of the overall reaction.
Q. 7. Observe the graph in diagram and answer the following questions.
[R] 0
(i) If slope is equal to –2.0 × 10–6 sec–1, what will be the
value of rate constant?
(ii) How does the half-life of zero order reaction relate to its
log [R]

rate constant?         [CBSE Sample Paper 2017]

k
Ans. (i) Slope = – or k = – 2.303 × Slope
2.303
\   k = –2.303 × (–2.0 × 10–6 s–1)
    k = 4.606 × 10–6 s–1
Time
(ii) For a zero order reaction
[ R]0  [ R]
t
k
[ R]0
At t  t1/2 , [ R] 
              2
[ R]0
[ R ]0 
2 [ R]0
 t1/2  or t1/2 
k 2k
Q. 8. A solution of H2O2 when titrated against KMnO4 solution at different intervals of time gave the
following results:
Time (minutes) 0 10 20
Volume of KMnO4 (mL) 23.8 14.7 9.1
Show that decomposition of H2O2 is first order reaction.
2.303 23.8 2.303
Ans. (i) k = log = # 0.2093 = 0.048 min–1
10 14.7 10
2.303 23.8 2.303
(ii) k = log = # 0.4176 = 0.048 min–1
20 9.1 20
Since the value of k comes out to be constant in both the cases, therefore the reaction is of first order.

180 Xam idea Chemistry–XII

 Q. 9. Define half-life of a reaction. Write the expression of half-life for [CBSE (F) 2014]
(i) zero order reaction and (ii) first order reaction.
Ans. The half life (t1/2) of a reaction is the time in which the concentration of a reactant is reduced to one half of
its initial concentration.
[R] 0
(i) t1/2 for a zero order reaction = where [R]0 = initial concentration, k = rate constant
2k
0.693
(ii) t1/2 for a first order reaction =
k
Q. 10. A first order reaction is 50% complete in 25 minutes. Calculate the time for 80% completion of the
reaction. [CBSE 2019 (56/3/2)]
0.693 0.693
Ans. t1/2 = & k= t   
k 1/2
0.693
k= = 2.772 × 10 –2 min
25 min
80 × [R] 0
[R] = [R]0 – 80% of [R]0 or [R] = [R]0 – or [R] = 0.2[R]0
100
Substituting the value of k and [R] in the expression
2.303 [R] 0
t= log , we get
k [R]
2.303 [R] 0
t= × log
2.772 × 10 –2 0 . 2 [R] 0
2.303
t= log 5
2.772 × 10 –2
2.303 × 0.699
t= or t = 58.07 min
2.772 × 10 –2
Q. 11. Following data are obtained for the reaction:
1
N2 O5 2NO 2 + O 2
2
t/s 0 300 600
–1 –2 –2
[N2O5]/mol L 1.6 × 10 0.8 × 10 0.4 × 10–2
(i) Show that it follows first order reaction.
(ii) Calculate the half-life.
(Given log 2 = 0.3010, log 4 = 0.6021) [CBSE Delhi 2017]
Ans. (i) At 300 s,
2.303 [ R ]0
k log
t [ R]
2.303 1.6  10 2 2.303
 log  log 2
300 0.8  10 2 300
2.303
 0.3010  2.31  10 3 s 1
k
300
At 600 s
2.303 [ R ]0
k log
t [ R]
2.303 1.6  10 2 2.303
 log  log 4
600 0.4  10 2 600
2.303
k  0.6021  2.31  10 3 s 1
600

Chemical Kinetics 181

 k is constant and is equal to 2.31 × 10–3 s–1 when we use first order equation. Hence, it follows first
order reaction.
0.693 0.693
(ii) t1/2 = = = 300 s
k 2.31#10 –3 s – 1
Q. 12. 238 206
92U changes to 92Pb by successive radioactive decay. A sample of uranium ore was analysed and
found to contain 1.0 g of 238U and 0.1 g of 206Pb had accumulated due to decay of 238U, find out the
age of the ore. (Half-life of 238U = 4.5 × 109 years) [HOTS]
Ans. [A]0 = Initial amount of 238U = amount of 238U left at time t + amount of 238U decayed
[A]0 = 1.0 + amount of 238U decayed
0.1 # 238
Now, amount of 238U decayed = g = 0.1155 g
206
\ [A]0 = 1.0 g + 0.1155 g = 1.1155 g
0.693 0.693 –9 –1
Determination of k: k= t1/2 = 4.5 # 109 = 0.154 × 10 year
2.303 [A] 0
Determination of time: t= log
k [A]
Substituting the values of [A]0 = 1.1155 g and k = 0.154 × 10–9 year–1
2.303 1.1155
t= log
0.154 # 10 –9 1
9
= 0.7099 × 10 year
= 7.099 × 108 year
Q. 13. The following data were obtained during the first order thermal decomposition of N2O5(g) at a
constant volume:
2N 2 O5 (g) 2N 2 O 4 (g) + O 2 (g)
S. No. Time/s Total Pressure/atm
1. 0 0.5
2. 100 0.512

Calculate the rate constant. [HOTS]

Ans. Let the pressure of N2O5(g) decrease by 2x atm. As two moles of N2O5 decompose to give two moles of
N2O4(g) and one mole of O2(g), the pressure of N2O4(g) increases by 2x atm and that of O2(g) increases by
x atm.
2N2O5(g) 2N2O4(g) + O2(g)
At t = 0 0.5 atm 0 atm   0 atm
At time t (0.5 – 2x) atm 2x atm   x atm
pt = pN2O5 + pN2O4 + pO2
= (0.5 – 2x) + 2x + x = 0.5 + x
x = pt – 0.5
pN2O5 = 0.5 – 2x = 0.5 – 2 (pt – 0.5) = 1.5 – 2pt
At t = 100 s; pt = 0.512 atm,
pN2O5 = 1.5 – 2 × 0.512 = 0.476 atm
2.303 pi
Thus, k= t log pA
2.303 0.5 atm
log =
100 s 0.476 atm
= 2.303 × 0.02136 = 4.92 × 10–4 s–1
100 s

182 Xam idea Chemistry–XII

Q. 14. The rate constant for the first order decomposition of H2O2 is given by the following equation:
1.0 × 10 4
log k = 14.2 – K
T
Calculate Ea for this reaction and rate constant k if its half-life period be 200 minutes.
(Given: R = 8.314 JK–1 mol–1) [CBSE Delhi 2016]
1.0 # 10 4 Ea
Ans. Comparing the equation, log k = 14.2 – K with the equation, log k = log A – , we get
T 2.303 RT
Ea 1.0×10 K4
= or Ea = 1.0 × 104 K × 2.303 × R
2.303 RT T
Ea = 1.0 × 104 K × 2.303 × 8.314 J K–1 mol–1
= 19.1471 × 104 J mol–1 = 191.47 kJ mol–1
0.693 0.693
For a first order reaction, t1/2 = or k = t
k 1/2
0.693
` k= = 3.465 × 10–3 min–1
200 min
Q. 15. The rate constant of a first order reaction increases from 2 × 10–2 to 4 × 10–2 when the temperature
changes from 300 K to 310 K. Calculate the energy of activation (Ea).
(log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021) [CBSE Patna 2015]
Ans. Substituting k1 = 2×10 –2, k2 = 4×10 –2, T1 = 300 K, T2 = 310 K, R = 8.314 J K –1 mol –1 in the expression
k2 Ea T2 – T1
log = f p , we get
k1 2.303×R T1 T2
Ea
c m
4×10 –2 310 – 300
log =
2×10 –2 2.303 × 8.314 300 × 310
Ea 10
log 2 = ×
19.147 300 × 310
Ea = 0.3010 × 19.147 × 300 × 31 = 53598 J mol–1
Ea = 53.598 kJ mol–1
Q. 16. For a reaction, the energy of activation is zero. What is the value of rate constant at 300 K, if
k = 1.6 × 106 s–1 at 280 K? [R = 8.31 J K–1 mol–1]
Ans. Given T1 = 280 K, k1 = 1.6 × 106 s–1, k2 = ?, Ea = 0, T2 = 300 K.
By Arrhenius equation,
k2 Ea T2 – T1
log = = G
k1 2.303 R T2 T1
As, Ea = 0
k2
\
log =0
k1
k2
or = 1    or k2 = k1
k1
Thus, the rate constant at 300 K is 1.6 × 106 s–1.
Q. 17. A certain reaction is 50% complete in 20 minutes at 300 K and the same reaction is again 50%
complete in 5 minutes at 350 K. Calculate the activation energy if it is a first order reaction.
[R = 8.314 J K–1 mol–1; log 4 = 0.602] [HOTS]

0.693
Ans. For a first order reaction, k= t1/2

0.693

T1 = 300 K, k1 = = 3.456 × 10–2 min–1
20

Chemical Kinetics 183

 0.693

T2 = 350 K, k2 = = 1.386 × 10–1 min–1
5
k2 Ea T2 – T1
log = = G
k1 2.303 R T2 T1
Ea
c m
1.386 # 10 –1 350 – 300
log =
3.465 # 10 –2 2.303 # 8.314 350 # 300
Ea
c m
50
log 4 =
2.303 # 8.314 350 # 300
Ea
c m
50
0.602 =
19.147 350 # 300
0.602 # 19.147 # 350 # 300
Ea =
50
= 24205.63 J mol–1
= 24.206 kJ mol–1
Q. 18. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K. Calculate
the activation energy of the reaction. [CBSE 2018]
(Given: log 2 = 0.3010, log 4 = 0.6021, R = 8.314 J K–1 mol–1)
0.693
Ans. For a first order reaction, k = t
1/2
0.693 0.693
So, k1 = min –1 and k2 = min –1
40 20
k2 0.693 min –1 /20
= =2
k1 0.693 min –1 /40
Here, T1 = 300 K, T2 = 320 K and R = 8.314 J K–1 mol–1
Substituting these values in the expression
k2 Ea T2 – T1
log = f p , we get
k1 2.303 × R T1 T2
Ea
d n
320 K – 300 K
log 2 =
2.303 × 8.314 JK mol –1 –1 300 K × 320 K
Ea × 20
0.3010 =
19.147 J mol –1 × 300 × 320
0.3010 × 19.147 × 300 × 320 J mol –1
or Ea = = 27663.58 J mol –1
20
    Ea = 27.66 kJ mol–1

Long Answer Questions [5 marks]

Q. 1. For the reaction,
2NO (g) + Cl 2 (g) 2NOCl (g),
the following data were collected. All the measurements were taken at 263 K:
Experiment Initial [NO] Initial [Cl2] Initial rate of disappearance of Cl2
(M) (M) (M/min)
1 0.15 0.15 0.60
2 0.15 0.30 1.20
3 0.30 0.15 2.40
4 0.25 0.25 ?

184 Xam idea Chemistry–XII

 (i) Write the expression for rate law.
(ii) Calculate the value of rate constant and specify its units.
(iii) What is the initial rate of disappearance of Cl2 in experiment 4? [CBSE Delhi 2012]
Ans. Suppose order w.r.t. NO is m and order w.r.t. Cl2 is n. Then the rate will be
Rate = k [NO]m [Cl2]n
Substituting the values of experiment 1 to 3 in the rate expression, we get
0.60 = k(0.15)m (0.15)n ...(i)
1.20 = k(0.15)m (0.30)n ...(ii)
2.40 = k(0.30)m (0.15)n ...(iii)
Dividing equation (iii) by (i), we get
2.40 k (0.30) m (0.15) n
=
0.60 k (0.15) m (0.15) n
4 = 2m or 22 = 2m or m = 2
Dividing equation (ii) by (i), we get
1 . 20 k (0.15) m (0.30) n
=
0 . 60 k (0.15) m (0.15) n
2 = 2n or n = 1
(i) Rate law expression is, Rate = k[NO]2 [Cl2]
(ii) 0.60 mol L–1 min–1 = k(0.15 mol L–1)2 (0.15 mol L–1)
     k = 177.78 mol–2 L2 min–1
(iii) Rate = 177.78 mol–2 L2 min–1 × (0.25 mol L–1)2 (0.25 mol L–1)
= 2.778 mol L–1 min–1
k
Q. 2. Consider the reaction R P . The change in concentration of R with time is shown in the following
plot: [CBSE 2019 (56/4/1)]
(i) Predict the order of the reaction.
(ii) Derive the expression for the time required for the y
completion of the reaction.
Concentration

(iii) What does the slope of the above line indicate?

[R]

Ans. (i) The reaction R P is a zero order reaction.

k
(ii) For the reaction R P
– d [R] x
rate = =k Time (t)
dt
d [R] = – k dt
Integrating both sides,
[R] = – kt + C, where C = constant of integration ...(i)
At t = 0, [R] = [R]0
Substituting this in equation (i)
C = [R]0
Substituting the value of C in equation (i)
[R] = – kt + [R]0 ...(ii)
kt = [R]0 – [R]
[R] 0 – [R]
⇒ t =
k
On completion of reactions, [R] = 0
[R] 0

`    t =
k
(iii) From equation (ii), we have slope of curve
d [R]
Slope = =–k
dt

Chemical Kinetics 185

Q. 3. For a certain chemical reaction variation in the concentration
y
ln [R] vs. time plot is given alongside. [HOTS]
For this reaction In[R]
(i) what is the order of the reaction?
(ii) what are the units of rate constant k?
(iii) give the relationship between k and t1/2 (half-life period).
(iv) what is the slope of the curve? t (s)
x
(v) draw the plot log [R]0 /[R] vs time t(s).
Ans.
(i) First order (ii) time–1 (s–1)
0.693
(iii) k = t (iv) slope = – k (rate constant)
1/2
(v) y

[R]0
log
[R]

x
Time (s)
Q. 4. Nitrogen pentoxide decomposes according to equation:
2N2O5(g) 4NO2(g) + O2(g)
This first order reaction was allowed to proceed at 40°C and the data below were collected:
[N2O5] (M) Time (min)
0.400 0.00
0.289 20.0
0.209 40.0
0.151 60.0
0.109 80.0
(i) Calculate the rate constant. Include units with your answer.
(ii) What will be the concentration of N2O5 after 100 minutes?
(iii) Calculate the initial rate of reaction. [CBSE Delhi 2011]
–1
  Ans. (i) When t = 20 min, [R] = 0.289 mol L
Also, [R]0 = 0.400 mol L–1
For a first order reaction
2.303 [R] 0
k= t log
[R]
2.303 0.400 2.303 4.00
\ k= log    ⇒ k = log
20 0.289 20 2.89
2.303 2.303
⇒ k= [log 4.00 – log 2.89] ⇒ k = [0.6021 – 0.4609]
20 20
2.303
⇒ k= × 0.1412    ⇒ k = 2.303 × 0.00706 = 0.016259 min–1
20
⇒ k = 1.6259 × 10–2 min–1
2.303 [R] 0
(ii) t = log
k [R]
Here, [R]0 = 0.400 mol , t = 100 min, k = 1.626 × 10 min–1
–1 –2

2.303 0.400
100 = log
#
1.626 10 –2 [R]

186 Xam idea Chemistry–XII

 100 # 1.626 # 10 –2 0.4 0.4
= log & 0.7060 = log
2.303 [R] [R]
0.4
Antilog (0.7060) =
[R]
0.4 0.4
5.082 = & [R] = = 0.0787 M
[R] 5.082
(iii) Initial rate, i.e., rate of reaction when t = 0
When, t = 0.00 min, [R] = 0.400 mol L–1
Also, k = 1.626 × 10–2 min–1
\ Initial rate = k [R]
= 1.626 × 10–2 min–1 × 0.400 mol L–1
= 6.504 × 10–3 mol L–1 min–1
Q. 5. (i) A first order reaction is 75% completed in 40 minutes. Calculate its t1/2. [CBSE (F) 2017]
(ii) Predict the order of the reaction in the given plots: [CBSE 2019 (56/2/1)]
(a) (b)

t1/2 t1/2

[R]0 [R]0
where [R]0 is the concentration of reactant.
(Given: log 2 = 0.3010, log 4 = 0.6021)
2.303 [R ]0
Ans. (i) For a first order reaction, t = log
k [ R]
2..303 100
log
t3 / 4 k 25  log 4  0.6021
 
t1 / 2 2.303 100 log 2 0.3010
log
k 50
40 min
2 or t1 / 2  20 min.
t1 / 2
(ii) (a) First order (b) Zero order
Q. 6. For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained:
t/s 0 30 60
–1
[CH3COOCH3]/mol L 0.60 0.30 0.15
(i) Show that it follows pseudo first order reaction, as the concentration of water remains
constant.
(ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(Given log 2 = 0.3010, log 4 = 0.6021) [CBSE Delhi 2015]
2.303 [ R] 0
Ans. (i) k = t log [R] …(i)
–1 –1
Substituting [R]0 = 0.60 mol L , [R] = 0.30 mol L and t = 30 s in equation (i), we get
2.303 0.60
k = log
30 0.30
2.303 2.303
k = log 2 = # 0.3010
30 30
–1
k = 0.0231 s

Chemical Kinetics 187

 Again substituting, [R]0 = 0.60 mol L–1, [R] = 0.15 mol L–1 and t = 60 in equation (i), we get
2.303 0.60
k = log
60 0.15
2.303 2.303
k = # log 4 = # 0.6021
60 60
–1
k = 0.0231 s
As the value of k is same in both the cases, therefore, hydrolysis of methylacetate in aqueous solution
follows pseudo first order reaction.
[CH3 COOCH3 ] – [0.15 – 0.30] 0.15
(ii) Average rate =  = =
t 60 – 30 30
Average rate = 0.005 mol L–1 s–1
  Q. 7. (i) Write the rate law for a first order reaction. Justify the statement that half life for a first
order reaction is independent of the initial concentration of the reactant.
(ii) The activation energy of a reaction is 75.2 kJ mol–1 in the absence of a catalyst and it
lowers to 50.14 kJ mol–1 with a catalyst. How many times will the rate of reaction grow in
the presence of a catalyst if the reaction proceeds at 25°C?
  Ans. (i) Consider the first order reaction,
R P
For this reaction, rate law which relates the rate of reaction to the concentration of reactants can be
given as
–d [R]
Rate = = k [R]
dt
For a first order reaction,
2.303 [R] 0
t = log , where [R]0 = initial concentration, [R] = concentration at time t.
k [R]
At t1/2, [R] = [R]0 /2
So, the above equation becomes
2.303 [R] 0
t1/2 = log
k [R] 0 /2
2.303 2.303
t1/2 = log 2 or t1/2 = × 0.3010
k k
0.693
t1/2 =
k
This shows that half life of a first order reaction is independent of the initial concentration of the reactant.
(ii) According to Arrhenius equation,
Ea
log k = log A –
2.303 RT
For uncatalysed reaction, For catalysed reaction,
Ea Ea
log k1 = log A – ...(i)     log k2 = log A –
1 2
...(ii)
2.303 RT 2.303 RT
A is equal for both reactions.
Subtracting equation (i) from equation (ii),
k2 Ea – Ea (75.2 – 50.14) kJ mol –1
1 2
log = = = 4.39
k1 2.303 RT 2.303×8.314 JK –1 mol –1 ×298 K
k2
= antilog (4.39) = 2.45×10 4
k1
Rate of reaction increases by 2.45 × 104 times.

188 Xam idea Chemistry–XII

Self-Assessment Test
Time allowed: 1 hour Max. marks: 30
Choose and write the correct answer for each of the following. (3 × 1 = 3)
1. Rate law for the reaction A + 2B C is found to be
Rate = k[A] [B]
Concentration of reactant ‘B’ is doubled, keeping the concentration of ‘A’ constant, the value of
rate constant will be _________________.
(a) the same (b) doubled
(c) quadrupled (d) halved
2. Which of the following expressions is correct for the rate of reaction given below?
5Br – (aq) + BrO3– (aq) + 6H + (aq) 3Br2 (aq) + 3H2 O (l)
+
D [Br ] –
D [H ] D [Br –] 6 D [H +]
(a) =5 (b) =
Dt Dt Dt 5 Dt
+
–
D [Br ] 5 D [H ] D [Br ]–
D [H+]
(c) = (d) =6
Dt 6 Dt Dt Dt
3. Which of the following statement is not correct for the catalyst?
(a) It catalyses the forward and backward reaction to the same extent.
(b) It alters DG of the reaction.
(c) It is a substance that does not change the equilibrium constant of a reaction.
(d) It provides an alternate mechanism by reducing activation energy between reactants and
products.
In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement. (3 × 1 = 3)
4. Many of photochemical changes have positive sign of DG , yet they are
Assertion (A) : 
spontaneous.
Reason (R) : The activation energy in photochemical reactions is provided by light energy.
5. Assertion (A) : In a reversible endothermic reaction, Eact of the forward reaction is higher
than that of the backward reaction.
Reason The threshold energy of the forward reaction is more than that of the
(R) : 
backward reaction.
6. Assertion (A) : The order of the reaction
2NO (g) + 2H2 (g) 2H2 O (g) + N2 (g) is 3.
Reason (R) : Order of reaction with respect to a given reactant is the power of the
reactant's concentration in the rate equation.

Answer the following questions:

7. State a condition under which a bimolecular reaction is kinetically first order. (1)

Chemical Kinetics 189

 8. Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain
with the help of one example. (1)
9. A first order reaction takes 40 minutes for 30% decomposition. Calculate t1/2. (2)
10. For a zero order reaction will the molecularity be equal to zero? Explain. (2)
11. (i) The conversion of the molecule X to Y follows second order kinetics. If the concentration X
is increased to three times, how will it affect the rate of formation of Y?
(ii) The specific reaction rate of a reaction is 6.2 × 10–3 mol L–1 s–1. What is the order of
reaction? (2)
12. Derive an expression to calculate time required for completion of zero order reaction. (2)
13. The rate constant for the decomposition of ethyl iodide
C2 H5 I (g) C2 H4 (g) + HI (g)
–5 –1
at 600 K is 1.60 × 10 s . Its energy of activation is 209 kJ/mol. Calculate the rate constant of
the reaction at 700 K. (3)
14. For a general reaction A B, plot of concentration of A vs
time is given in figure. Answer the following questions on the A B
basis of this graph.

Conc. of A
(i) What is the order of the reaction?
(ii) What is the slope of the curve?
(iii) What are the units of rate constant? (3)
t
15. The following data were obtained for the reaction:
A + 2B C
Experiment [A]/M [B]/M Initial rate of formation of C/M min–1
1 0.2 0.3 4.2 × 10–2
2 0.1 0.1 6.0 × 10–3
3 0.4 0.3 1.68 × 10–1
4 0.1 0.4 2.40 × 10–2

(i) Find the order of reaction with respect to A and B.

(ii) Write the rate law and overall order of reaction.
(iii) Calculate the rate constant (k). (3)
16. (i) For an elementary reaction
2A + B 3C
the rate of appearance of C at time ‘t’ is 1.3 × 10–4 mol L–1 s–1.
Calculate at this time
(a) rate of the reaction.
(b) rate of disappearance of A.
(ii) The decomposition of N2O5(g) is a first order reaction with a rate constant of 5 × 10–4 s–1
at 45°C, i.e., 2N2 O5 (g) 4NO2 (g) + O2 (g) . If initial concentration of N2O5 is 0.25 M,
calculate its concentration after 2 min. Also, calculate half-life for decomposition of
N2O5(g). (5)
Answers
1. (a) 2. (c) 3. (b) 4. (b) 5. (c) 6. (a) 9. 77.78 min 13. 6.36 × 10–3 s–1
15. (iii) 6.0 L2 mol–1 min–1 –4 –1 –1 –4 –1 –1
16. (i) (a) 0.43 × 10 mol L s , (b) 0.86 × 10 mol L s (ii) 0.235 M, 1386 s
zzz

190 Xam idea Chemistry–XII