CHAPTER

10 Chemical Kinetics

Chapter Highlights
Rate of reaction, Factors affecting rate of reaction, Collision theory and activation energy, Molecularity,
Elementary and complex reactions, Order of reactions, Photochemical reactions, Photosensitizer and various
levels of multiple-choice questions.

KINETICS OF CHEMICAL REACTIONS

• Chemical kinetics, or simply kinetics, is the study Here rate of reaction is measured by the decrease in
of rate of reactions and factors affecting it, like concentration of F2.
temperature, pressure, catalyst, radiations. • Units of the rate of reaction are mol L–1 time–1 or atm
• On the basis of rate of reaction, reactions can be of time–1 (gaseous substance).
slow, moderate and very fast types.
• Very fast reactions take 10–14 to 10–16 seconds for Instantaneous Rate of Reactions
their completion, for example, ionic reactions, such
as one shown below Instantaneous rate of reaction is equal to the small change
in concentration (dx) during a small interval of time (dt).
NaCl + AgNO3 AgCl + NaNO3 dx
It is given as __
dt .
• Fast reactions are not studied under kinetics. These are
studied by flash-photolysis and spectrographic methods.
•
Concentration

Very slow reactions like rusting of iron, blackening

Concentration

of white lead, formation of water at room temperature Product

and burning of coal are not studied under kinetics. dx
( mol/L)

( mol/L)

• Reactions with moderate speed, like molecular reac- Reactant

θ
tions, are studied under kinetics. For e.g., Hydrolysis Time dt
Time
of Sugar or Ester
Figure 10.1 Plots for Instantaneous Rate of Reaction

RATE OF REACTION •
dx
__
dt = tan θ = –slope
Rate of reaction is defined as the rate of change of concen • It can be written for any of the reactant or the product
tration of a reactant or a product per unit time. in terms of stoichiometric coefficients (VJ as follows:
C1 – C 2 d(J)
Rate of reaction = ______ dx __
__ 1 ___
T –T2 1 dt = Vj dt
• Rate of reaction decreases with time as concentration Taking N2 + 3H2 2NH3 as an example, the
of the reactant decreases. This can be observed in the instantaneous rate of reaction is calculated as follows:
following reaction. dx –dN
For N2 __ ____2
dt = dt
2NO2 + F2 2NO2F
10.2 Chapter 10

–dx –dH The value of temperature coefficient lies in between 2 and 3.

For H2 ___ ____2
dt = dt
dNH3 (a) A negative temperature coefficient is observed only
dx
For NH3 __ ____
dt = dt in the case of 2NO + O2 2NO2
• For reactants, negative sign indicates decrease in
concentration. negative temperature
• For a reversible reaction at dynamic equilibrium, net coefficient
reaction rate is always zero.

R ate
Features of Rate of Reaction
• Rate of reaction is always a positive quantity. temperature
Figure 10.2 Negative Temperature Coefficient
• It is proportional to the active masses of the
reactant.
1. Concentration: Rate of reaction (dx/dt) α Concentration.
• It is measured by measuring active mass or molar 2. Pressure: For gaseous reactants
concentration of a reactant or a product as a function dx
__
of time. dt ∝ Pressure (as P α C)
• It varies greatly with time so it is better to use average 3. Surface area: In case of heterogenous reactions,
reaction rate. greater the surface area, faster is the rate of reaction
due to more number of active sites.
Specific Reaction Rate or Velocity Constant dx
__
dt ∝ Surface area
Consider n A Product
dx
– __
dt ∝ [A]
n e.g., coal dust burns faster than coal pieces
dx 4. Nature of reactant and product: For ionic reactants,
or – __
dt = k[A]
n
reaction rate is fast, as activation energy is zero for
Rate law equation these. Molecules have slower reaction rate as they
require higher activation energy.
If [A]n = 1 then
5. Radiation: For a photochemical reaction
dx
– __
dt = k (At a particular temperature) dx
__
k = Rate constant or specific reaction rate dt ∝ Intensity of radiation

• It means at unity concentration rate of a reaction is
equal to rate constant.
• k ∝ Temperature (rate constant increases with increase
of temperature)
• Rate constant does not depend upon the presence of
a catalyst or on the nature of the reactant.
• Rate constant does not depend upon concentration,
pressure or volume.
• Unit of rate constant is (mole/litre)1–n time–1 (Here n =
Order of reaction).
Rate of photochemical reactions depends upon the
intensity of light radiations.
6. Positive catalyst: It increases the rate of a reaction by
providing an alternative path which requires a lesser
activation energy
(a) A negative catalyst acts in just the opposite way.
(b) Catalysts are more effective in ‘solid powdered
form’, which provides a greater surface area, that
is, more number of active sites.
Transition State

Factors Affecting Rate of Reaction

+ve Catalyst ↓ Ea by
Physical state of reactants shortening reation path
Ea
Gaseous state > liquid state > solid state
Energy

Decreasing order of rate of reaction R –ve catalyst ↑ Ea by en/

argening path of Reaction
1. Temperature: For every 10°C rise in temperature,
P
dx/dt or rate increases by two to three times.
k at t °C + 10°C Reaction co-ordination
Temperature coefficient =
k at t °C
 Chemical Kinetics 10.3

COLLISION THEORY It is denoted by Ea.

Ea = Threshold energy – Potential energy of reactants
• A reaction takes place as the reacting molecules
undergo collisions with one another. In other words, a Rate of Reaction α __1
E or Average kinetic energy.
a
chemical reaction is the result of effective collisions. Hence, lower the activation energy, faster will be the rate
• For effective collisions of reaction.
(a) Colliding molecules must have sufficient kinetic Activated complex
energy. or
T.H.E
(b) Collision should be properly oriented. Transition state

Activated complex Products Ea Activation

formation energy

Potential Energy
HR and ER

Reactant

ΔH
Effective collision EP or HP

Product
Reaction Co-ordination or
Progress of Reaction
Ineffective collision
Figure 10.4 Activation Energy

Arrehenius Equation
Figure 10.3 Collision in Molecules
Arrehenius equation is used to evaluate energy of activa-
tion and to show the effect of temperature on rate constant
• The minimum energy needed to convert a reactant into
as follows:
product is called threshold energy. It is the minimum
amount of energy possessed by reacting molecules, in k = Ae–Ea/RT
order to have effective collisions for the formation of or alternatively,
Ea
product. log10 k = log10 A – _______
2.303 RT
• Rate of reaction according to this theory is given as
Here A is the Arrhenius or pre-exponential factor
Rate = fPZ Here e–Ea/RT is known as Boltzmann factor.
Here, f = Fraction of molecules with potential • When Ea is zero or temperature is infinite
energy greater than threshhold energy. k = Aeº = A
P = Orientation factor • At two different temperatures T1 and T2
2.303 R T1 T2 k2
f = e–Ea/RT Ea = __________
T2 – T1 log10 __
k1
Z = Collision frequency
k2 Ea (T – T1)
• Transition state or activated state theory or absolute log10 __ ______ _______
2
k1 = 2.303 R (T1 T2)
rate theory was developed by Henry Erying.
A + B C ABC AB + C
Activated Product Graph between log10 k and 1/T
complex
When a graph is plotted between log10 k and 1/T, a straight
Activation Energy line with a negative slope is obtained. Here, slope is equal
to –Ea/2.303R, that is, Εa = –2.303 R slope.
Activation energy is the minimum amount of additional
external energy needed to convert a reactant into product,
or to make potential energy of the reactant equal to the
threshold energy.
10.4 Chapter 10
— Ea
Slope = tan θ =
2.303 R
log10k
θ
1 in a number of steps), the slowest step is called the
T rate determining step or rate limiting step.
Here Intercept = log10 A
Figure 10.5 Graph Between Log k and 1/T
In Exothermic Reactions
Potential energy of reactant > potential energy of product
Ea of backward reaction > Ea of forward reaction
In Endothermlc Reactions
Potential energy of reactant < potential energy of product
Ea of backward reaction < Ea of forward reaction
ELEMENTARY AND COMPLEX REACTIONS
It is interesting to know that a balance chemical equa-
tion never shows us a true picture of how the reaction is
taking place as very rarely a reaction gets completed in
only one step.
• The reaction which occurs in one step is known as
an elementary reaction and when a sequence of such
reactions (mechanism) provide us with the desired
products then these reactions are termed as complex
reactions.
• Such reactions may be consecutive, reverse or side re
actions. For example, in the complete combustion of
an alkane the final products are always carbon dioxide
and water. However during this reaction a series of
elementary reactions take place during which alcohol,
aldehyde and acid are formed.
MOLECULARITY
• Molecularity is the number of atoms, ions or mol-
ecules that must collide with one another simultane-
ously, so as to result in a chemical reaction.
• It is a theoretical value.
• It is always a whole number.
• It does not determine the rate of reaction.
• It does not depend upon external factors like
temperature and pressure.
• Molecularity cannot be more than three as there is
nearly no chance for more than three molecules to
undergo an effective collision at a time.
• In a multistep reaction, molecularity is determined
separately in each step.
• In case of complex reactions, (reactions taking place
• The overall molecularity of a complex reaction is
equal to the molecularity of the slowest step.
• If molecularity of a reaction is 1 the reaction is called
unimolecular as in the following reaction
PCl5 PCl3 + Cl2
• If molecularity is 2, the reaction is called bimolecular.
C12H22O11 + H2O C6H12O6 + C6H12O6
Glucose Fructose
• If molecularity is 3, the reaction is called termolecular.
2FeCl3 + SnCl2 2FeCl2 + SnCl4
ORDER OF REACTION
Order of reaction is defined as number of reactants which
determine rate of reaction, or alternatively, it is the number
of reactants, whose molar concentration changes during
the chemical reaction. It can also be defined as the sum of
exponents, raised on active masses of reactants in a rate law
equation. Look at the example below,
mA + nB Products
For this, the rate law equation is
Rate k = [A]m [B]n
Hence, order = m + n
• It is an experimental value.
• It may be zero, negative or a fraction.
• It determines the rate of reaction.
• Order of reaction depends upon temperature,
pressure and concentration. (external factors)
• Anything present in excess, is not counted in order
of reaction, for example, in hydrolysis of ester and
sugar, water is in excess, so it is neglected for order.
• Order of reaction is determined by the slowest step of
the reaction.
• High order reactions are rare due to less chance of
effective collisions between molecules.
 Chemical Kinetics 10.5

• Rate = k (at all concentrations)

FA C T S TO R E M E M B E R • t1/2 α a (initial concentration)
Rate constant and order for various reactants is an exper- • Here rate and concentration of reactants do not vary
imental finding and can not be directly predicted from the with time.
stoichiometry of the balanced reaction.
eq 2O3 3O2
First-order Reaction
1
mech O3 O2 + O [Fast] (i) Here the reaction rate is determined by one concentration
2 2
O3 + (O) 2O2 [Slow] (ii)
variable term only.
Rate = K [O3] [O] A Products
dx
As [O] = K C ⋅
[O ]
3
from eq (i)
– __
dt ∝ [A]
1

[O ]
2 dx
__
dt = k[A]
So
N = N0 e–kt
Rate = K1[O3]2 [O2]–1
Hence Ist order or
A = A0 e–kt
Zero-order Reaction or
2.303 a N0
In zero-order reactions, rate of reaction is independent of t = _____ ____ __
k log10 a – x or N
the concentration of the reactants. Here t = Time period
dx
__
– dt ∝ [Concentration]0 k = Rate constant
dx
__ A0 or a or N0 = Initial amount
dt = k A or a – x or N = Amount left after time t
On integration we get
It a ∝ P0
x = k.t + c
If t = 0, c = 0 then (a – x) ∝ 2P0 – Pt
x = k.t 2.303 P0
K= log10
k = __xt t 2P0 − Pt
• Unit of is mol L–1 time–1
Examples of a zero-order reaction Examples of a first-order reaction
• Photochemical reactions H2O2 H2O + ½ O2
H2 + Cl2 2HCl NH4NO2 N2 + 2H2O
(studied over water surface) 2N2O5 4NO2 + O2
(Mo) SO2Cl2 SO2 + Cl2
N2O N2 + ½ O2
(studied over platinum surface) C6H5N = NCl + H.OH C6H5OH + N2 + HCl
2NH3 N2 + 3H2 H2C2O4 CO + CO2 + H2O
CH3COCH3 + I2 CH3COCH2 I + HI
2HI H2 + I2 Features of a first-order reaction
(studied over gold surface)
• Unit of k is time–1
• Iodination of acetone.
• K does not depend upon concentration units or change
• Enzyme catalyzed reactions.
in concentration.
Features of a zero-order reaction • t½ does not depend upon initial concentration (a). It
• The concentration of the reactant decreases linearly depends only upon rate constant.
0.693
with time t½ = _____
k
[A]t = [A]0 – kt
10.6 Chapter 10

• The change in the unit of concentration changes the

value of A here.
Slope =
—k • Unit of k is L2 mol–2 time–1
log10 [A] 2.303
Pseudo First-order Reactions
Pseudo first-order reactions are the reactions which are not
truly of the first order but under certain conditions become
reactions of the first order.
Time Here molecularity is more than 1, but order of reaction
Figure 10.6 Graph of First-order reaction is always one. Few examples of pseudo first-order reactions
are as follows:
Second-order Reaction
Hydrolysis of ethyl acetate
dx
– __
dt ∝ [A] or [A] [B]
2 1 1
CH3COOC2H5 + H2O CH3COOH + C2H5OH
Examples of a second-order reaction Rate constant is given as
2O3 3O2
2.303 V − V0
CH3COOC2H5 + NaOH CH3COONa k= log10 ∞
t V∞ − Vt
+ C2H5OH
2Cl2O 2Cl2 + O2 Here V∝ = Volume at infinite
2NO2 2NO + O2 V0 = Initial volume
Vt = Volume at time t
Features of a second-order reaction
• Unit of k is L mol–1 time–1 Hydrolysis of sugar
t1/2 ∝ __1a C12H22O11 + H2O C6H12O6 + C6H12O6
• When concentrations are same Glucose Fructose

k = __1t ______
x Rate constant in this case is given as
a(a – x)
• When concentrations are different 2.303 r −r
k= log10 0 ∞
2.303 b(a – x) t rt − r∞
k = ______ ______
t(a – b) log10 a(b – x)
Here r0 = Initial optical rotation
• The change in the unit of concentration, changes the
value of here. r∞ = Rotation at infinite dilution
rt = Rotation at t time
Third-order Reaction
dx
– __
dt ∝ [A] or [A] [B] [C]
3 1 1 1
SOLVED EXAMPLES
Examples of a third-order reaction Rate of Reaction, Rate Constant
2NO + O2 2NO2 1. The reaction 2A + B + C D + Ε is found to
2NO + Cl2 2NOCl be of first-order in A, second-order in and zero-order
2FeCl3 + SnCl2 SnCl4 + 2FeCl2 in C
2NO2 + 2H2 N2 + 2H2O (i) Give the rate law for the reaction in the form of
O3 + 3NO 3NO2 differential equation.
(ii) What is the effect in rate of increasing concentra-
Features of a third-order reaction tion of and two times?
(2a – x)
1 _______
k = __
T 2a2(a – x)2
Solution
(i) The rate law for the reaction is given by
1
t1/2 α __
a2 dx
__ 2 0
dt = k[A][B] [C]
 Chemical Kinetics 10.7

2.303 a
dx = k[A][B]2
___ k = _____ ____
t log10 a – x
dt
2.303 100
(ii) On increasing the concentration of A, B and two 0.01 = _____ ___
t log10 10
times then,
2.303
dx
__ 2 0
t = _____
0.01 = 230.3 minute
dt = k[2A][2B] [2C]
dx
__ 5. In a first-order reaction A P, value of (a/a–x)
dt
= k[2A][2B]2
was found to be 8 after 60 minutes. Calculate the rate
Therefore, the rate increases by 8 times. of reaction in moles of A reacted per minute, if its con-
centration is 0.1 mole litre–1.
2. Dinitropentoxide decomposes as follows:
N2O5 (g) 2NO2 (g) + ½ O2 (g) Solution
2.303 a mole litre–1
Given k = _____ ____________
t(min) log10 (a – x) mole litre
d[N2O5]/dt = k1 [N2O5]
given that after 60 minutes, a/(a – x) = 8
d[NO2]/dt = k2 [N2O5] 2.303
k = _____
60 log10 8 = 3.466 × 10 minute
–2 –1
d[O2]/dt = k3 [N2O5]
What is the relation between k1, k2 and k3? Rate of reaction = dx/dt = k [A]
= 3.466 × 10–2 × 0.1
Solution
= 3.466 × 10–3 mol litre–1 minute–1
N2O5 (g) 2NO2 (g) + ½ O2 (g)
Rate with respect to N2O5 or NO2 or O2 may be expressed 6. The rate constant for a first-order reaction is 2.2 × 10–5
as follows in the form of relation s–1 at 320°C. Calculate the time in which the reaction
d[N2O5] d[NO ] 2d[O ] is 15% complete.
– ______
dt = + __21 ______
2 _____
dt = + dt
2

Solution
On substituting the given values in the question
For a first order reaction
k1[Ν2Ο5] = k2/2[N2O5] = 2k3[N2O5] 2.303 a
2k1 = k2 = 4k3 t = _____ ____
k log10 a – x
If the initial concentration is 100 mole litre–1, the
3. Write the expression for the rate of following gaseous
amount decomposed is 15 mole litre–1
reaction
2.303 100
2N2O5 (g) 4NO2 (g) + O2 (g) t = _______
2.2 × 10–5
log10 _______
100 – 15
2.303 100
which takes place in a closed vessel. If the concen- = _______
2.2 × 10–5
log10 ___
85
tration of NO2 increases by 1.6 × 10–4 mol L–1’ in 4
2.303
second, find the rate of reaction and rate of change of = _______
2.2 × 10–5
× 0.0706
concentration of N2O5. = 7391 sec.
Solution
7. A reaction obeying second-order in A is 50% complete
2N2O5 (g) 4NO2 (g) + O2 (g) after 450 minute. If [A]o = 1.35 M. Calculate the value
Rate of reaction (r) of rate constant.
d[N2O5] 2d[NO ] d[O ]
–__21 ______
dt = + __14 ______
dt
2
= ____
dt
2
Solution
1.6 × 10–4
Rate of reaction = __14 × _______
4
t = 450 minute
a = 1.35 M
= 1.0 × 10–3 mol L–1 s–1
1.6 × 10–3 x = 0.675 M
Change in concentration of N2O5 = __21 × _______
4 __ x
1 ______
= 2.0 × 10–3 k = t . a(a – x)
0.675
4. A first-order reaction completes 50% in 69.3 minute.
1
k = ___ _________
450 × 1.35(0.675)
How much time will it take for 90% completion?
= 1.646 × 10–3 mol–1 litre min–1.
Solution
0.693 0.693
k = _____
t = _____
69.3 = 0.01
1/2
10.8 Chapter 10

Activation Energy 11. For first-order gaseous reaction, log k, when plotted
against 1/T, gives a straight line with a slope of –8000.
8. At 380°C, the half-life period for the first-order de- Calculate the activation energy of the reaction.
composition of H2O2 is 360 minute. The energy of
activation of the reaction is 200 kJ mole–1. Calculate Solution
the time required for 75% decomposition at 450°C. k = Ae–Ea/RT
Ea
log k = log A – ______ 1
__
2.303R × T
Solution
0.693 0.693 When a curve is plotted between log and 1/T. A straight
k1 = _____
t = _____
360 line is obtained and the slope of this curve
1/2

k Ea (T – T ) Ea
log10 __
2 ______ _______
2 1
k = 2.303 R (T T ) = – ______
2.303 R
1 1 2

k Ea
______
log10 _________
2
2.303 R = 8000
1.925 × 10
–3

200 × 103 _________

[723 – 653]
Εa = 8000 × 2.303 × 1.987 = 36608 calories
= __________
2.303 × 8.314 [653 × 723]
= 36.6 kcal.
k2 = 0.068 min–1
2.303 a Determination of Order of Reaction
t = _____ ____
k log10 a – x
2
12. For the chemical reaction
2.303 100
= _____ ___
0.068 log10 25 = 20.39 minute X +Y + Z A
9. Find the activation energy of a reaction whose rate it was found that the rate of the reaction doubled
constant is tripled by a 10°C rise in temperature, in the when the concentration of Y was doubled, that the
activity of 27°C. rate doubled when the concentration of both X and
Y were doubled and quadrupled when the concentra-
Solution tions of both Y and Ζ were doubled. What is the rate
k2/k1 = 3, expression, the order of each component, and the
T1 = 273 + 37 = 310 K order of the reaction?
k2
__ Ea ________
(T2 – T1)
_______ Solution
log10 k = 2.303 R (T T )
1 1 2 For the above reaction
Ea (310 – 300) Rate = k [X]nX[Y]nY[Z]nZ
log103 = __________ _________
2.303 × 8.314 (300 × 310)
For the conditions given we can write the following
Ea = 84.97 kJ mol–1. expressions.
nX Y nZ
k[X] (2) [Z]
2 ____________
__
10. Given that the temperature coefficient k35/k25 for the
1 = k[X]nX (1)nY [Z]nZ
saponification of ethyl acetate by sodium hydroxide is
1.75. Calculate the activation energy in calories. 2 = (2)ny
nY = l
Solution nX Y nZ
k[2] (2) [Z]
2 ____________
__
Let the rate constants at 35°C and 25°C by k35 and k25 1 = k[1]nX (1)nY [Z]nZ
Since k = Ae–∆E/RT 2 = (2)nx (2)
k35
__ Ae– ∆E\308 ×1.987
_________ 1 = (2)nx
k25 = 1.75 = Ae– ∆E\298 ×1.987
nX = 0
Taking logarithms nX Y nZ
k[xX] (2) [2]
4 ____________
__
∆E
log10 1.75 = __________
(308 – 298)
_________ 1 = k[X]nX (1)nY [1]nZ
2.303 × 1.987 (308 × 298)
298 × 308 4 = (2) (2)nZ
∆E = 2.30 × 1.987 × ________
10 × 0.2430
nZ = 1
= 10210 cal mole–1 = 10.21 kcal mole–1 Rate = k [Y][Z]
Reaction order = 0 + 1 + 1 = 2.
 Chemical Kinetics 10.9

13. Rate of a reaction Solution

A+B C is given below as a function of differ- t1/2 ∝ (a)1–n
ential concentrations of A and B. 425 ∝ (350)1–n (i)
Table 10.1 275 ∝ (540)1–n (ii)
Exp. [A] [B] Rate 941 ∝ (158)1–n (iii)
mol L–1 mol L–1 mol L–1 time–1 Dividing equation (i) by (ii)
1. 0.01 0.01 0.005 425
___
2. 0.02 0.01 0.010 275 = (350/540)1–n
3. 0.01 0.02 0.005 n = 2.
15. For the reaction X Y + Z the following, were
Determine the order of reaction with respect to A and
obtained
and also calculate the half-life of A in the reaction.
Time 0 900 1800
Solution
Conc. of X 50.7 19.6 7.61
Rate = [A]x [B]y
0.005 = k[0.01]x [0.01]y (i) Find the order of the reaction.
0.010 = k[0.02] x [0.01]y (ii) Solution
0.005 = [0.01]x [0.02]y (iii) For t = 900, a = 50.8
Solving for value of x, a – x = 19.7
Divide eq. (ii) by (i)
2.303 50.8
k1 = _____ ____
900 log10 19.7
(2) = (2)x
x=1 k1 = 1.05 × 10–3 s–1
For value of y, divide eq. (3) by (1) For t = 1800, a = 50.8
y=0 a – x = 7.62
2.303 50.8
Rate = k [A]1 [B]0 k1 = _____ ____
1800 log10 7.63
0.005 = k[0.01]1 [0.01]0
0.005 k1 = 1.05 × 10–3 S–1
k = _____
0.01 = 0.5
The constant values of show that the reaction is of first
0.693 0.693
t1/2 = _____ _____
k = 0.5 = 1.386 order.

14. Determine the order of reaction from the following

data of half-life period and initial concentration for a
reaction.
Initial concentration 350 540 158
t1/2 425 275 941
10.10 Chapter 10

CONCEPTS AT A GLANCE
Methods for Determining Order of Reaction Fluorescence
Order of a reaction is determined mainly by: Here emission of light stops instantaneously when radiation
being projected on a fluorescent substance, is cut off, for
1. Initial concentration method example CaF2.
2. Integration method
3. Graphical method: When a graph is plotted between Phosphorescence
l/(a – x)n–t and time t, a straight line is formed. Here emission of light occurs for some time even after light
4. Half-life method radiation being projected on a phosphorescence substance,
is cut off. For example, ZnS.
(t )
1/2 1 a 
n −1

=  2
(t )
1/2 2  a1  Quantum efficiency

or Number of molecules reacting in a given time

φ=
log(t )1 – log(t )2
1 1
Number of quanta absorbed at the same time
2 2
n = 1+
log a 2 – log a1  For HCl, φ is high (as both steps are exothermic).
Here n is the order of reaction.  For HBr, φ is low (as second step is endothermic).

5. Van’t Hoff differential method Rate Law Equation for Reactions Involving Parallel
log( – dC1 / dt) – log( – dC 2 / dt) and Side Reactions
n=
log C1 – log C2 Here reactant reacts/decompases in more than one way

Photochemical Reactions B
K1
Those reactions which take place only in the presence of light
are called photochemical reactions, for example, photosynthe- A
sis and formation of HCl. K2
 For such reactions ∆G0 (standard Gibbs free energy
change) can be positive. For example, synthesis of car-
bohydrate and HCl formation.
 Red light has lowest energy. Some photochemical C
reactions can be initiated by red light. Figure 10.7 Parallel and Side Reactions

 Such reactions are not affected by temperature,

however, they are affected by intensity of light radiations. Rate = (k1 + k2) [A]
 The retina in the eye undergoes geometrical isomerization  Fraction yield of A = k1/k1 + k2
by absorbing photons of light to enable sight.  Fraction yield of B = k2/k1 + k2
 Successive reaction
Photosensitizer k1 k2
It is a substance which when added to a reaction mixture, A B C
helps to start the photochemical reaction, but itself does not Here, rate of disappearance of A = k1 + k2 [A]
undergo any chemical change, for example, chlorophyll in [A]t= [A]0e–k1T
photosynthesis and Hg vapours in dissociation of H2.
k1[A]0
_____
By photosensitizer [B]t= k – k [A]0e–k1T – e–k2T
Non-photoactive Photoactive 2 1

Luminiscence Modified Arrhenius Equation

It is the emission of light unaccompanied by heat. d_____
ln k E
___
dT
= RT2
Chemiluminiscence  The exponential form of the expression for a first order
It is the conversion of chemical energy in to cold-light energy, reaction is given by wilhelmy equation as follows
for example, in fire flies the light emitted is due to oxidation of [A] = [A]0e–kT
luciferin protein by the enzyme luciferase (bioluminiscence).
 Chemical Kinetics 10.11

SOME IMPORTANT GRAPHS

Rate vs Concentration 1
Half-lives vs Concentration t 1/ 2 Vs
a n −1

Zero-order
Rate First-order
Rate Zero-order First-order
t1/2
t1/2

(Conc.)0 (Conc.)1
a a

Second-order
Third-order
Second-order Third-order
Rate t1/2 t1/2
Rate

(Conc.)2 (Conc.)3 1 1
a a2
Figure 10.8 Plots of Rate vs Concentration
Figure 10.10 Plots of Half-lives vs Concertration

Integrated Rate Equation

log10 [A]

First-order
Zero-order
A

Time Time

Third-order
Second-order
a3 or A3
a2 or A2

1
1

Time Time
Figure 10.9 Plots of Integrated Rate Equation
10.12 Chapter 10

TOOL BOX AND SUMMARY OF IMPORTANT RELATIONS

C1 − C2
 Rate of Reaction = Second-order Reaction
t2 − t1
When concentrations are different
 Instantaneous reaction rate is given as
dx 1 d(J) 2.303 b (a − x)
= k= log10
dt Vj dt t ( a − b) a (b − x )
aA + bB cC + dD
Rate of reaction
Half-life Method
1 d[A] 1 d[B] 1 d[C] 1 d[D]
(t )
=− =− = = = 1/2 n −1
a dt b dt c dt d dt a 
1
=  2
 Activation Energy (t )
1/2
2
 a1 
Ea = Threshold energy – Potential energy of reactants log ( t1/2 )1 − log ( t1/2 )2
n = 1+
 Arrehenlus Equation log a2 − log a1
k = Ae –Ea/RT Here n is the order of reaction.
or
Ea Van’t Hoff Differential Method
log10 k = log10 A –
2.303 RT
 At two different temperatures T1 and T2 log ( − dC1/dt ) − log ( − dC2 / dt )
2.303 R T1 T2 k n=
Ea = log10 2 log C1 − log C2
T2 − T1 k1

log10
k2
=
Ea ( T2 − T1 ) Pseudo-Unimolecular Reactions
k1 2.303 R ( T1 T2 )
2.303 v − v∞
Order of Reaction k= log o
 t vt − v∞
Rate = k [A]m [B]n
Here V∞ = Volume at infinity
Order = m + n
V0 = Initial volume
First-order Reaction Vt = Volume at t time
dx Modified Arrhenius Equation
− ∝ [A]1 
dt
d In k E
2.303 a N = 2
t= log10 or 0 dT RT
k a−x N
2.303 a − x1
k= log10  Quantum Efficiency
t2 − t1 a − x2
2.303 r −r Number of molecules reacting in a given time
t= log10 0 ∞ ϕ=
k rt − r∞ Number of quanta absorbed at the same time
 Chemical Kinetics 10.13

EXERCISES

Single Option Correct Type

1. The unit of specific reaction rate constant for a first- (a) [N 2 O4] (b) [N2 O4]
order (if the concentration is expressed in molarity)
would be
(a) s–1 (b) mole s–1 Time Time
(c) [N 2 O4] (d) [N2 O4]
(c) mole L–1 s–1 (d) mole L–1
2. The temperature coefficient of most of the reactions
lies between Time Time
(a) 1 and 3 (b) 2 and 3
8. Activation energy of a chemical reaction can be
(c) 1 and 2 (d) 2 and 4
determined by
3. The activation energy for a simple chemical reaction (a) evaluating rate constant at standard temperature
A B is Ea in forward direction. The activation (b) evaluating velocities of reaction at two different
energy for reverse reaction temperatures
(a) can be less than or more than Ea (c) evaluating rate constants at two different tempera
(b) is always double of Ea tures
(c) is negative of Ea (d) changing concentration of reactants
(d) is always less than Ea
9. The first-order rate constant for the decomposition
4. 3A B+C of N2O5 is 6.2 × 10–4 s–1. The half-life for this
It would be a zero order reaction when decomposition is
(a) the rate of reaction is proportional to square of (a) 1177.7 s (b) 1117.7
concentration of A (c) 6.077 s (d) 110.77
(b) the rate of reaction remains same at any concentra-
10. The given reaction
tion of A
(c) the rate remains unchanged at any concentration 2FeCl3 + SnCl2 2FeCl2 + SnCl4
of B and C is an example of
(d) the rate of reaction doubles if concentration of is (a) first-order reaction
increased to double (b) second-order reaction
5. The rate of reaction depends upon (c) third-order reaction
(d) none of these
(a) molar concentration (b) atomic mass
(c) equivalent mass (d) none of these 11. If the rate of the reaction is equal to the rate constant,
the order of the reaction is
6. For a first-order reaction, the half-life period is inde-
pendent of (a) 3 (b) 0
(c) 1 (d) 2
(a) initial concentration
(b) cube root of initial concentration 12. Which of the following best explains the effects of a
(c) first power of final concentration catalyst on the rate of a reversible reaction?
(d) square root of final concentration (a) It decreases the rate of the reverse reaction
7. Which of these graphs best describes the rate at (b) It increases the kinetic energy of the reacting
which N2O4 decomposes to NO2 if the reaction is of molecules
first-order? (c) It moves the equilibrium position to the right
(d) It provides a new reaction path with a lower
activation energy
10.14 Chapter 10

13. The temperature dependence of rate constant (k) of 20. For the reaction, A + B C + D. The variation
a chemical reaction is written in terms of Arrhenius of the concentration of the products is given by the
equation, k = Ae–Ea/RT. Activation energy Ea of the reac- curve
tion can be calculated by plotting
(a) log vs 1/log T (b) k vs T y
z
(c) k vs 1/logT (d) log k vs 1/T

Conc.
14. For a chemical reaction A B, the rate of reac- w
x
tion doubles when the concentration of A is in creased Time
four times. The order of reaction for A is
(a) zero (b) one (a) w (b) x
(c) two (d) half (c) y (d) z
15. The unit of second-order reaction rate constant is 21. Which of the following is incorrect about order of
(a) L–1. mol–1ds–1 (b) L2 mol–2 s–1 reaction?
–1 –1
(c) L.mol s (d) s–1 (a) it is calculated experimentally
(b) it is sum of powers of concentration in rate law
16. What is the time required for a first-order reaction to expression
be 99% complete, compared to the time taken for the (c) the order of reaction cannot be fractional
reaction to be 90% complete? (d) there is not necessarily a connection between
(a) there is no change order and stoichiometry of a reaction.
(b) time taken is double
(c) time taken is triple 22. Which curve corresponds to the temperature depen-
(d) the reaction is instantaneous dence of the rate R of a simple one-step reaction?
17. The accompanying figure depicts the change in (a) (b)
concentrations of species X and Y for the reaction
X Y, as a function of time. The point of in R R
tersection of the two curves represents
T T

x (c) (d)
Conc.

y
R R
Time
T T
(a) t½ (b) t3/4
(c) t½ (d) unpredictable
23. If Τ is the intensity of absorbed light and ‘C is the
18. Among which of the following factor the specific concentration of AB for the photochemical process
reaction rate of a first-order reaction depends on AB + hv AB•, the rate of formation of AB’ is
(a) temperature directly proportional to
(b) concentration of reactant (a) C (b) I
(c) pressure (c) I2 (d) C.I
(d) volume
24. For a first-order reaction,
19. The molecularity of a reaction is (a) The degree of dissociation is equal to (1 - e–kt)
(a) always two (b) The pre-exponential factor in the Arrhenius
(b) same as its order equation has the dimensions of time t–1.
(c) different than the other (c) The time taken for the completion of 75 % reaction
(d) may be same or different as compared to order is thrice the t 1/2 of the reaction.
(d) both (a) and (b)
 Chemical Kinetics 10.15

25. The rate law for the reaction 32. The function of catalyst in chemical reaction is to
RCl + NaOH (aq) ROH + NaCl (a) increase the product
(b) decrease the product
is given by
(c) accelerate the rate of reaction
Rate = k[RCl]. The rate of the reaction will be
(d) increase the reactants
(a) doubled on doubling the concentration of sodium
hydroxide 33. For a particular gaseous reaction, a graph was plotted
(b) halved on reducing the concentration of alkyl as shown below. It shows that the reaction of A is
halide to one half
(c) decreased on increasing the temperature of
reaction [A]
(d) unaffected by increasing the temperature of the
t
reaction.
26. The equation for the rate constant is k = Ae–Ea/RT. A (a) zero-order w.r.t. A
chemical reaction will proceed more rapidly if there is (b) first-order w.r.t. A
a decrease in (c) second-order w.r.t. A
(a) k (b) A (d) a non-integer order w.r.t. A
(c) Ε (d) Τ 34. According to the collision theory of reaction rates, an
27. The rate law has the form; rate = k[A][B]3/2, can the increase of the temperature at which the reaction oc
reaction be an elementary process? curs will inturn increase the rate of the reaction. This
(a) yes (b) no caused due to
(c) may be yes or no (d) cannot be predicted (a) greater number of molecules are having the activa-
tion energy (threshold energy)
28. For a second-order reaction, 2A Product, a (b) greater velocity of reaction molecules
straight line is obtained if we plot (c) greater number of collisions
(a) concentration vs time (d) none of these
(b) log (conc.) vs time
(c) log (conc.) vs time1 35. For a chemical reaction which can never be a
(d) (concc’)vs time”1 fractional number.
(a) order (b) half-life
29. For an endothermic reaction, where ΔΗ represents (c) molecularity (d) rate constant
the enthalpy of the reaction in kJ/mole, the minimum
value for the energy of activation will be 36. Which of the following is correct for a first order
(a) less than ΔΗ reaction? (k = rate constant t1/2 = half-life)
(b) zero (a) t1/2 = 0.693 x k (b) k. t1/2 = 1/0.693
(c) more than ΔΗ (c) k.t1/2 = 0.693 (d) 6.93 x k x t1/2 = 1
(d) equal to ΔΗ 37. Which of the following relation is correct for a first
30. The rate constant k, of a second-order reaction, A order reaction?
Products, is given by (k = rate constant; r = rate of reaction; C= conc, of
k = l/t{x/a(a – x)} reactant)
the ratio t3/4 /t1/2 is equal to (a) k = r × C2 (b) k = r x
(a) 1/3 (b) 6/1 (c) k = C/r (d) k = r/C
(c) 3/1 (d) 4/3 38. If the rate law of a reaction nA B is expressed
31. The rate constant of a reaction depends on as
d[A] d[B]
Rate = – __1 ____ ____ x
(a) extent of reaction n dt = + dt = k[A]
(b) time of reaction The unit of the rate constant will be
(c) temperature (a) molx /Lx/s (b) Lx/molx/s
(1–x) (x–1) –1
(d) initial concentration of the reactants (c) mol /L .S (d) mol(x–1)/L(1–x).S–1
10.16 Chapter 10

39. For an endothermic reaction 47. The rate constant is given by the equation
(a) Ea>E’ K = P.Ze–E/RT. Which factor should register a decrease
(b) Ea = E’aa for the reaction to proceed more rapidly
(c) there is no relation between Εa and E’a (a) Τ (b) Ζ
(d) Ea<E’a (c) Ε (d) Ρ
40. Rate constant of a reaction (k) is 175 L2 mol–2 sec–1. 48. What is the order of reaction and rate constant for a
What is the order of reaction? chemical change having log t 1 vs log (a) curve as
2
(a) first (b) second given below?
(c) third (d) zero
41. A catalyst is a substance which

ORJWò
(a) supplies energy to the reaction
(b) increases the equilibrium concentration of the
product ƒ
(c) changes the equilibrium constant of the reaction
(d) shortens the time to each equilibrium ORJD
(a) 1, 1 (b) 1, 0
42. The rate of reaction was found to be equal to its rate
(c) 2, 1 (d) 0, 1
constant at any concentration of the reactant. The order
of the reaction is 49. 2O3 3O2. The mechanism is O3 O2 + O;
(a) zero-order (b) first-order O3 + O 2O2. The rate law is
(c) second-order (d) third-order (a) r = k [O3]2 [O2]–1 (b) r = k [O3]2 [O2]
(c) r = k [O3] [O2] (d) r = k [O3]2
43. For the reaction
sunlight 50. Which of the following statement is correct?
H2 + Cl2 2HCl
taking place on water, the order of reaction is (a) A plot of log kp vs 1/t is linear
(b) A plot of log [X] vs time is linear for a first-order
(a) 0 (b) 1
reaction, X Ρ
(c) 2 (d) 3
(c) A plot of log Ρ vs 1/t is linear at constant volume
44. Tav (average life), T50 and T75 in the increasing order are (d) A plot of Ρ vs 1/V is linear at constant pressure
(a) T50<Tav<T75 (b) T50<T75<Tav 51. For a zero-order reaction, the plot of concentration vs
(c) Τgv = T50 < T75 (d) Τav = T50 < T75 time is linear with
45. A catalyst increases rate of reaction by (a) +ve slope and zero intercept
(a) decreasing enthalpy (b) –ve slope and zero intercept
(b) decreasing activation energy (c) +ve slope and non-zero intercept
(c) decreasing internal energy (d) –ve slope and non-zero intercept
(d) increasing activation energy 52. Which curve represents zero-order reaction?
46. For an exothermic chemical process occurring in two (a) (b)
steps as
(i) A + B X(slow) A A
(ii) X AB (fast)
t t
The progress of the reaction can be best described by:
(a) (b) (c) (d)

A+B A+B A
AB
AB
t
(c) (d) all are correct

A+B AB
 Chemical Kinetics 10.17

53. Graph between log10 K and (1/t) is linear with slope S. Now the relation in between k1 k2 and k3 is
Hence Ea is (a) k1 = k2 = k3 (b) 3k1 = k2 = 2k3
(a) R × S (b) S/R (c) 2k1 = 4k2 = k3 (d) 2k1 = k2 = 4k3
(c) R/S (d) 2.303 RS
58. k for a zero-order reaction is 2 × 10–2 mol L–1 s–1. If the
54. A reaction rate is given by concentration of the reactant after 25 s is 0.5 M, the
k = 1.5 × 1015 exp (–25000/RT) s–1 initial concentration must have been
it means that (a) 0.5 Μ (b) 1.25 Μ
(a) half-life period of the reaction will be smaller at (c) 12.5 Μ (d) 1.0 Μ
high temperature 59. 75% of a first-order reaction was completed in 32
(b) log vs Τ will give a straight line min. When was 50% of the reaction completed?
(c) half-life of the reaction will be smaller at lower
(a) 24 min (b) 16 min
temperature
(c) 8 min (d) 64 min
(d) log vs 1/T will give a straight line having a slope
of – 25000 60. For a first-order reaction, t0.75 is 138.6 seconds. Its
specific reaction rate constant (in sec–1) is
55. With respect to the figure given below which of the
following statement is correct? (a) 10–2 (b) 10–4
–5
(c) 10 (d) 10–6
61. The rate of a first-order reaction is 1.5 × 102 mol L–1
min–1 at 0.5 Μ concentration of the reactant. The half-
life of the reaction is
(a) 0.383 hour (b) 23.1 min
(c) 8.73 min (d) 7.53 min
62. For the first-order reaction half-life is 14 s. The time
(a) ∆Ε for the forward reaction is C – B
required for the initial concentration to reduce to 1/8th
(b) ΔΕ for the forward reaction is B – A
of its value is
(c) Ε (for reverse reaction ) = C – A
(d) E(Forward) > E(Backward) (a) 21s (b) 32 s
(c) 42 s (d) 142 s
56. A substance undergoes first-order decomposition, it
follows two parallel reactions 63. The potential energy diagram for a reaction R
Ρ is given below
k1 Y
X
k2 Z
k1 = 1.26 × 10–4 s–1
and k2 = 3.8 × 10–5 s–1 R
The percentage distribution of Y and Ζ are ΔΗ° οf the reaction corresponds to the energy
(a) 80% Y and 20% Ζ
(a) x (b) y
(b) 72.83% Y and 32.71% Ζ
(c) z (d) (x + y)
(c) 76.83% Y and 23.17% Ζ
(d) 62.4 % Υ and 90.5% Ζ 64. For the reaction
57. For the reaction, 2N2O5 (g) 4NO2 (g) + O2 (g)
N2O5 2NO2 + ½O2. Given values are which of the following graph will yield a straight line?
(a) log PN2 O5 vs time with a +ve slope
d [N2O5]
– _______
dt = k1 [N2O5] (b) log PN2 O5 vs time with a –ve slope
d [NO2] (c) (PN2O5)–1 vs time
______
dt = k2 [N2O5] (d) log PN2O5 vs time
d [O2]
_____
dt = k3 [N2O5]
10.18 Chapter 10

65. Under the same reactions conditions, initial concen- (a) 2.226 × 10–3 mol litre–1 min–1
tration of 1.386 mol dm–3 of a substance becomes half (b) 3.466 × 10–3 mol litre–1 min–1
in 40 sec and 20 sec through 1st order and zero order (c) 4.455 × 10–3 mol litre–1 min–1
K  (d) 5.532 × 10–3 mol litre–1 min–1
kinetics respectively. Ratio  1  of the rate constants
 K0  72. For the reaction 2N2O5 4NO2 + O2, rate and
for first order (k1) and zero order (k0) of the reactions is rate constant are 1.02 × 10–4 and 3.4 × 10–5 sec1 respec-
(a) 0.5 mol–1 dm–3 (b) 1 mol dm–3 tively, then concentration of N2O5 at that time will be
(c) 1.5 mol dm –3
(d) 2 mol–1 dm3 (a) 1.732 (b) 3
(c) 3.4 × l0 5
(d) 1.02 × 10–4
66. The half-life of a substance in a first-order reaction is
15 minutes. The rate constant is 73. In the following reaction, how is the rate of appear
(a) 2.46 × 102 min–1 (b) 4.62 × 10–2 min–1 ance of the underlined product related to the rate of
(c) 3 × 10–5 min–1 (d) 3 × 10–9 min–1 disappearance of the underlined reactant?
BrO3– (aq) + 5Br– (aq) + 6H+ (aq) 3Br2 (l)
67. In a second-order reaction, if first-order is observed
+ 3H2O(l)
for both the reactants A and B, then which one of the
d[Br2] d [Br–]
5 ______
__
following reactant mixtures will provide the highest (a) ______ = – 3 dt
initial rate? dt
d[Br2] d [Br–]
(a) 0.1 mol of A and 0.1 mol of in 0.2 litre solvent (b) _____ _____
dt = – dt
(b) 1.0 mol of A and 1.0 mol of in one litre solvent
d[Br2] _____
d [Br–]
(c) 0.2 mol of A and 0.2 mol of in 0.1 litre solvent (c) _____
dt = dt
(d) 0.1 mol of A and 0.1 mol of in 0.1 litre solvent
d[Br2] d [Br–]
3 _____
(d) _____ __
dt = – 5 dt
68. The activation energy of a reaction is 9 kcal/mole. The
increase in the rate constant when its temperature is
74. The experimental data for the reaction
raised from 295 to 300 is
2A + B2 2AB is
(a) 14.9% (b) 28.9%
(c) 78.9 % (d) 82.9 % Table 10.2
69. The rate constant of first-order reaction is 3 × 10–6 per Exp. [A] [B2] Rate (Ms–1)
second. The initial concentration is 0.10 M. The initial 1. 0.50 Μ 0.50 Μ 1.6 x 10–4
rate is 2. 0.50 Μ 1.00 Μ 3.2 x 10–4
(a) 3 × 10 Ms
–7 –1
(b) 3 × 10 Ms
–4 –1
3. 1.00 Μ 1.00 Μ 3.2 x 10–4
(c) 3 × 10 Ms
–5 –1
(d) 3 × 10 Ms
–6 –1
the rate equation for the above data is
70. Consider the following statements: (a) rate = k [B2] (b) rate = k[B2]2
(1) rate of a process is directly proportional to its free (c) rate = k[A] [B] (d) rate = k[A]2 [B]
2 2

energy change
75. The reaction A B follows first order kinet-
(2) the order of an elementary reaction step can be
ics. The time taken for 0.8 mole of A to produce
determined by examining the stoichiometry
0.6 mole of is 1 hour. What is the time taken for
(3) the first-order reaction describe exponential time
conversion of 0.9 mole of A to produce 0.675 mole
course.
of B?
Of the statements
(a) 1 and 2 are correct (a) 2 hour (b) 1 hour
(b) 1 and 3 are correct (c) 0.5 hour (d) 0.25 hour
(c) 2 and 3 are correct 76. Which of the following are the examples of
(d) 1, 2 and 3 are correct pseudo-unimolecular reactions?
71. In a first-order reaction A P, the ratio of (1) acid catalyzed hydrolysis of an ester
a/(a – x) was found to be 8 after 60 minutes. If the (2) inversion of cane sugar
concentration is 0.1 Μ then the rate of reaction in (3) decomposition of ozone
moles of A reacted per minutes is (4) decomposition of N2O5
 Chemical Kinetics 10.19

Select the correct answers using the codes given 84. The rate constant of a first-order reaction is 6 × 10–3
below: s–1. If the initial concentration is 0.10 M, the initial
(a) 1 and 2 (b) 1 and 3 rate of reaction is
(c) 2, 3 and 4 (d) 1, 2 and 4 (a) 6 × 10–3 Ms–1 (b) 6 × 10–1 Ms–1
77. For the reaction (c) 6 × 10–6 Ms–1 (d) 6 × 10–8 Ms–1
2A + B 3C + D 85. A graph plotted between concentration of reactant,
which of the following does not express the reaction consumed at any time (x) and time ‘t’ is found to be a
rate? straight line passing through the origin. The reaction is of
d[D] d[A]
(a) ____
dt (b) – ____
2 dt
(a) first-order (b) zero-order
(c) third-order (d) second-order
d[C] d[B]
(c) ____
3 dt (d) – ____
dt 86. From the following data for the reaction between A and B
78. For a first reaction A B, reactant concentration Table 10.3
of 0.01 Μ is found to be 2.0 × 10–5 mol L–1 s–1. The
[A] [B] Initial rate (mol L–1s–1)
half-life period of the reaction is
molL–1 molL–1 300 K 320 K
(a) 220 s (b) 30 s
(c) 300 s (d) 347 s 2.5 × 10 –4
3.0 × 10–5 5.0 × 10–4 2.0 × 10–3
5.0 × 10–4 6.0 × 10–5 4.0 × 10–3 –

79. A substance reacts according to first-order

1.0 × 10–3 6.0 × 10–5 1.6 × 10–2 –
kinetics. The rate constant for the reaction is 1 ×
10–2 sec1. Its initial concentration is IM. Its initial Calculate the rate equation
rate is (a) r = k[B]1 (b) r = k[A]2
(a) 2 × 102 Ms–1 (b) l × 102 Ms–1 (c) r = k[A]2[B]1 (d) r = A [A] [B]
(c) 1 × 10–2 Ms–1 (d) 2 × l0–2 Ms–1 87. The rate constant, the activation energy and the
Arrhenius parameter of a chemical reaction at 25°C
80. What will be the initial rate of a reaction if its con are 3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6 × 1014 s–1
stant is 10–3 min–1 and the concentration of reactant is respectively.
0.2 mol dm3?
The value of the rate constant as Τ ∞ is
(a) 0.02 mol dm–3 min–1
(b) 0.002 mol dm–3 min–1 (a) 2.0 × 1018s–1 (b) 6.0 × 1014 s–1
(c) 0.0002 mol dm–3 min–1 (c) infinity (d) 3.6 × 1030 s–1
(d) 2 mol dm–3 min–1
88. The experimental rate law for a reaction
81. The rate of a certain hypothetical reaction 2A + 3B Product, is V α CA CB–2. If the
A+B+C Products concentration of both A and are doubled the rate
is given by of reaction
__
increases by a factor of
d[A] (a) √2 __ (b) 2
r = – ____ 1/2 1/3
dt = k [A] [B] [C]
1/4
(c) 2.√2 (d) 4
The order of the reaction is
89. The rate equation for a chemical reaction is
(a) 13/12 (b) 13/14 Rate of reaction = [Χ] [Υ]
(c) 12/13 (d) 13/11
Consider the following statements in this regard
82. The decay constant of 6C14 is 2.31 × 10–4 year–1. Its (1) The order of reaction is one
half life is (2) The molecularity of reaction is two
(a) 2 × l03 yrs (b) 2.5 × 103 yrs (3) The rate constant depends upon temperature
Of these statements
(c) 3 × l03yrs (d) 3.5 × 103 yrs
(a) 1 and 3 are correct
83. A first-order reaction is 50% completed in 30 minutes (b) 1 and 2 are correct
at 27°C. Its rate constant is (c) 2 and 3 are correct
(a) 2.31 × 10–2min–1 (b) 3.21 × 10–2 min–1 (d) 1, 2 and 3 are correct
(c) 4.75 × 10–2 min1 (d) 1.33 × 10–3 min–1
10.20 Chapter 10

90. In a zero-order reaction, 47.5% of the reactant (4) overall order of a reaction Am + Bn ABx is
remains at the end of 2.5 hours. The amount of reac- m + n.
tant consumed in one hour is Select the correct answer using the following codes:
(a) 11.0% (b) 33.0% (a) 2 and 3 (b) 1, 3 and 4
(c) 42.0% (d) 21.0% (c) 2, 3 and 4 (d) 1, 2 and 3
91. During the decomposition of H2O2 to give oxygen, 97. The half-life of a chemical reaction at a particular
48g O2 is formed per minute at a certain point of time. concentration is 50 min, when the concentration of
The rate of formation of water at this point is reactants is doubled, the half-life becomes 100 min.
(a) 0.75 mol min1 (b) 1.5 mol min–1 Find the order.
–1
(c) 2.25 mol min (d) 3.0 mol min–1 (a) zero (b) first
92. The rate constant of a first-order reaction, (c) second (d) third
A products, is 60 × 10–4 s–1. Its rate at [A] = 98. The rate constant of first-order reaction is 10–2 min–1.
–1
0.01 mol L would be The half-life period of reaction is
(a) 60 × 10–6 mol L–1 min–1 (a) 693 min (b) 69.3 min
(b) 36 × 10–4 mol L–1 min–1 (c) 6.93 min (d) 0.693 min
(c) 60 × 10–2 mol L–1 min–1
99. When the reactants are and at one mole per
(d) 36 × 10–1 mol L–1 min–1
litre each the rate equation is, rate = [A]x [B]1/Y
93. In a first-order reaction the concentration of reactant [C]X/Y. The order of the reaction is
decreases from 800 mol/dm3 to 50 mol/dm3 in 2 × 104 (1 + X)
sec. The rate constant of reaction in sec–1 is (a) X + ______
Y
X
(b) X – Y + __
Y
(a) 2 × 104 (b) 3.45 × 10–5 X
(c) X + Y + __ (d) 2(X + Y)
Y
(c) 1.386 × 10 –4
(d) 2 × 10 –4
100. If the half life period of a radioactive isotope is 10s,
94. The activation energies of two reactions with rate then its average life will be
constants k, and k2, are Ea1 and Ea2 respectively. If Ea1 (a) 14.4 s (b) 1.44 s
< Ea2, when the temperature is increased from T, to (c) 0.144 s (d) 2.44 s
T2 the rate constants are k’1 and k’2. Which one of the
following statements is correct? 101. In the first-order reaction, half of the reaction is com
k1 __
´
k2 ´ pleted in 100 seconds. The time for 99% reaction to
(a) k´1 = k´2 (b) __
k´1 < k´2 occur will be
k1´
k2 ´
k1 k__2
´ ´ (a) 664.64 s (b) 646.6 s
(c) __ __
k´1 > k´2 (d) __
k´1 = k´2 (c) 660.9 s (d) 654.5 s
95. In a chemical reaction two reactants take part. The rate 102. For a certain reaction, the activation energy is zero.
of reaction is directly proportional to the concentration What is the value of rate constant at 300 K, if K = 1.6
of one of them and inversely proportional to the con- × 106s–1 at 280K?
centration of the other. The order of reaction is (a) 1.6 × 106 s–1 (b) zero
(a) 0 (b) 1
(c) 4.8 × 108 s–1 (d) 3.2 × 1012 s–1
(c) 2 (d) 4
103. When the temperature of a reaction increases from
96. Which of the following statements is correct?
27°C to 37°C, the rate increases by 2.5 times, the
(1) order of a reaction can be known from experi- activation energy in the temperature range is
mental results and not from the stoichiometry of a
(a) 70.8 kJ (b) 7.08 kJ
reaction.
(c) 35.8 kJ (d) 14.85 kJ
(2) molecularity a reaction refers to (i) each of the
elementary steps in (an overall mechanism of) a 104. The rate of the reaction for A Products is
complex reaction or (ii) a single step reaction. 10 mol L–1 min–1 at time t1 = 2 minutes. What will be
(3) overall molecularity of a reaction may be deter- the rate (in mol L–1 min–1) at time t2 = 12 minutes?
mined in a manner similar to overall order of (a) more than 10 (b) less than 10
reaction. (c) 10 (d) 20
 Chemical Kinetics 10.21

105. Consider the following reaction, 111. The time taken for the completion of 90% of a
A products first-order reaction is ‘t’ min. What is the time
This reaction is completed in 100 minutes. The rate (in seconds) taken for the completion of 99% of the
constant of this reaction at t1 = 10 min is 10–2 min–1. reaction?
What is the rate constant (in min–1) at t2 = 20 min? (a) 2 t (b) t/30
(a) 2 × 10–2 (b)10–2 (c) 120 t (d) 60 t
(c) 5 × 10 –3
(d) 0.1 112. Observe the following reaction
106. Consider the chemical reaction, 2A + B C
N2(g) + 3H2(g) 2NH3 (g) the rate of formation of is 2.2 × 10–3 mol. L–1. What
The rate of this reaction can be expressed in terms of is the value of –d[A]/dt (in mol L–1 min–1)?
time derivatives of concentration of N2 (g), H2 (g) or (a) 2.2 × l0–3 (b) 1.1 × 10–3
NH3 (g). Identify the correct relationship amongst the (c) 4.4 × 10 –3
(d) 5.5 × 10–3
rate expressions. d[B]
(a) rate = –d[N2]/dt = – l/3d[H2]/dt = d[NH3]/dt 113. 3A 2B, rate of reaction + ____ is equal to
dt
(b) rate = –d[N2]/dt = – 3 d[H2]/dt = 2 d[NH3]/dt 3 d[A] d[A]
(c) rate = –d [N2]/dt = – 1/3 d[H2]/dt = 2 d[NH3]/dt (a) –__2 ____
dt (b) –__32 ____
dt
(d) rate = –d [N2]/dt = – d[H2]/dt = d[NH3]/dt d[A] d[A]
(c) –__13 ____
dt (d) +2 ____
dt
107. The rate constant for the reaction, 114. For a reaction A + B C + D if the concentra-
2N2O5 4NO2 + O2 tion of A is doubled without altering the concentration
is 3.0 × 10 s . If the rate is 2.40 × 10–5 mol L–1 s1,
–5 1 of B, the rate gets doubled. If the concentration of is
then the concentration of N2O5 (in mol L4) is increased by nine times without altering the concentra-
(a) 1.4 (b) 1.2 tion of A, the rate gets tripled. The order of the reaction
(c) 0.04 (d) 0.8 is
(a) 2 (b) 1
108. Consider the following reaction
(c) 3/2 (d) 4/3
N2 (g) + 3H2 (g) 2NH3 (g)
115. For the reaction A Products, it is found
The rate of this reaction in terms of N2 at Τ is –d[N2]/ that the rate of reaction increases by a factor of
dt = 0.02 mol L–1 s–1. 6.25, when the concentration of A is increased by
What is the value of –d[H2]/dt (in units of mol L–1s–1) at a factor of 2.5. The order of reaction with respect
the same temperature? to A is
(a) 0.02 (b) 50 (a) 0.5 (b) 1
(c) 0.06 (d) 0.04 (c) 2 (d) 3
109. The rate constant of a reaction at temperature 200 is 116. For a gaseous reaction
10 times less than the rate constant at 400 K. What is the 2A + B 2AB,
activation energy (Ea) of the reaction? (R = gas constant) this following rate data were obtained at 300K.
(a) 1842.4 R (b) 921.2 R
(c) 460.0 R (d) 230.3 R Table 10.4
110. Which one of the following equations is correct for Expt Concentration Rate of disappearance
the reaction [A] [B2] of B2 (mol L min–1)
N2 (g) + 3H2 (g) 2NH3 (g)? 1. 0.015 0.15 1.8 × 10–3

d [NH ] d[H ]
2. 0.09 0.15 1.08 × 10–2
(a) 3 ______
dt
3
= 2 _____
dt
2
3. 0.015 0.45 5.4 × 10–3
d [NH ] d[H ]
(b) 2 ______
dt
3
= –3 _____
dt
2
What is the rate law?
d [NH3] _____
d[H ] (a) r = k[A][B2] (b) r = [A]2 [B2]1
(c) 2 ______
dt = dt 2
(c) r = k[A][B2]2 (d) r = k[B2]
d [NH3] d[H2]
(d) 3 ______
dt = –2 _____
dt
10.22 Chapter 10

117. The basic theory of Arrhenius equation is that 123. The following data pertains to the reaction between A
(1) activation energy and pre-exponential factors are and B
always temperature independent
(2) the number of effective collisions is proportional Table 10.5
to the number of molecule above a certain thresh S. No. [A] mol L –1
[B] mol L–1 Rate mol
old energy. L–1S–1
(3) as the temperature increases, the number of mol- 1. 1 × 10–2 2 × 10–2 2 × 10–4
ecules with energies exceeding the threshold 2. 2 × 10–2 2 × 10–2 4 × 10–4
energy increases. 3. 2 × 10–2
4 × 10–2
8 × 10–8
(4) the rate constant in a function of temperature
(a) 2, 3 and 4 (b) 1, 2 and 3 Which of the following inferences are drawn from the
(c) 2 and 3 (d) 1 and 3 above data?
118. The slope of the line for the graph of log k vs 1/T for (1) rate constant of the reaction is 10–4
the reaction, (2) rate law of the reaction is [A][B]
(3) rate of reaction increases four times by doubling
N2O5 2NO2 + ½ O2
the concentration of each reactant.
is –5000. Calculate the energy of activation of the Select the correct answer the codes given below:
reaction. (a) 1 and 3 (b) 2 and 3
(a) 95.7 kJ mol–1 (b) 9.57 kJ mol–1 (c) land 2 (d) 1, 2 and 3
–1
(c) 957 kJ mol (d) 0.957 kJ mol–1 K–1
124. The rate constant for an isomerization reaction
119. For a 1st order reaction A P, the temperature (T) A B, is 4.5 × 10–3 min–1. If the initial concentra-
dependent rate constant (K) was found to follow the tion of A is 1 M, calculate the rate of reaction after 1 hour.
1 (a) 0.34354 Μ min–1
equation log k = – (2000) + 6 The pre-exponential
T (b) 0.034354 Μ min–1
factor A and activation energy Ea are respectively? (c) 0.0034354 Μ min–1
(a) 1 × 106 S–1 and 9.2 kJ/M (d) 0.0003454 Μ min–1
(b) 1 × 106 S–1 and 38.3 kJ/M
125. Log 1.5 ×107 = log A – 
(c) 1 × 106 S–1 and 16.6 kJ/M 2 
In the above equa-
(d) 6S–1 and 16.6 kJ/M  2.303 R 
tion, what is the value of Arrhenius factor?
120. If for a certain first-order reaction, the initial rate is
0.65% min-1, the half-life in one hour is (a) 3 × 106 (b) 6.3 × 109
(c) 5.42 × 10 13
(d) 5.42 × 1010
(a) 17.76 (b) 27.14
(c) 1.776 (d) 11.66 126. The rate constant of a reaction is 1.5 × 107 s–1 at 50°C
and 4.5 × 107 s–1 at 100°C. What is the value of
121. The reaction X Product follows first-order
activation energy?
kinetics, in 40 minutes, the concentration of X changes
from 0.1 Μ to 0.025 M, then the rate of reaction when (a) 2.2 × 103 J mol–1 (b) 2300 J mol–1
concentration of X is 0.01 Μ is? (c) 2.2 × 104 J mol–4 (d) 220 J mol–1
(a) 3.47 × 10–5 M/min 127. The activation energies of two reactions are 18 kJ
(b) 1.73 × 10–4 M/min mol–1 and 4.0 kJ mol–4 respectively. Assuming the
(c) 1.73 × 10–5 M/min pre-exponential factor to be the same for both reac-
(d) 3.47 × 10–4 M/min tions, the ratio of their rate constants at 27°C is
122. The following data are obtained from the decomposi- (a) 3.656 × 10–3 (b) 3.624 × 10–6
tion of a gaseous compound (c) 36.52 × 10 –8
(d) 4.656 × 10–4
Initial pressure in arm 1.6 0.8 0.4 128. The rate constant of a reaction is given in k (sec–1)
Time for 50% reaction in min 80 113 160 = 14.34 – 0.25 × 104)/T
The order of the reaction is What will be the energy of activation?
(a) 0.5 (b) 1.0 (a) 24.83 kcal mol1 (b) 49.66 kcal mol1
(c) 1.5 (d) 2.0 (c) 12.42 kcal/mol (d) none of these
 Chemical Kinetics 10.23

129. At 380°C, half-life period for the first-order decom- (4) it is proportional to initial concentration for
position of H2O2 is 360 min. The energy of activa- zeroth-order
tion of the reaction is 200 kJ mol1. Calculate the time (a) 1, 2 and 3 (b) 2, 3 and 4
required for 75% decomposition at 450°C if half-life (c) 2 and 3 (d) 3 and 4
for decomposition of H2O2 is 10.17 min at 450°C.
135. When concentrations of the reactants is increased six-
(a) 20.4 min (b) 408 min
teen times, the rate becomes two times. The reaction is
(c) 10.2 min (d) none of these
of
130. A gaseous compound decomposes on heating as per (a) 1/4 order (b) fourth-order
the following equation: (c) third-order (d) 1/8 order
A(g) B (g) + 2C (g). After 5 minutes and 20
136. For the first order reaction, 3X Y concentra-
seconds, the pressure increases by 96 mm Hg. If the rate
tion varies with time as shown in the following graph.
constant for this first order reaction is 5.2 × 10–4 s–1, the
The half-life of the reaction would be
initial pressure of A is

Concentration
(a) 226 mm Hg (b) 37.6 mm Hg
(c) 616 mm Hg (d) 313 mm Hg [Y]
131. The data given below is for the reaction of NO and Cl2 [X]
to form NOCl at 295
2 4 6 8
Table 10.6 Time
[Cl2] [NO] Initial rate (molL–1 s–1)
(a) 4 minutes (b) 2 minutes
0.05 0.05 1 × 10–3 (c) 12 minutes (d) 6 minutes
0.15 0.05 3 × 10–3
137. For the reaction a A xP when [A] = 2.2 mM
0.05 0.15 9 × 10–3 the rate was found to be 2.4 m Μ s–1 On reducing con-
What is the rate law? centration of A to half, the rate changes to 0.6 m Μ s–1.
(a) r = k [NO] [Cl2] (b) r = k [Cl2]1[NO]2 The order of reaction with respect to A is
(c) r = k [Cl2]2 [NO] (d) r = k [Cl2]1 (a) 1.5 (b) 2.0
(c) 2.5 (d) 3.0
132. For the reaction, C2H4 + H2 C2H6, ΔΕ0 = –30
kcal. If the reaction is reversible and if the activation 138. If the initial concentration of reactant in certain
energy for the forward reaction is 28.0 kcal and its reaction is doubled, the half life period of the reaction
drops to 10.5 kcal in the presence of a catalyst, the is also doubled. The order of reaction is
activation energies for the uncatalyzed and catalysed (a) zero (b) first
reverse reaction are respectively (in kcal) (c) second (d) 1.5
(a) 58, 40.5 (b) –58, –40.5 139. For a zero order reaction, the plot of concentration
(c) 40.5, 58 (d) 58.0, –58.0 versus time is linear with
133. For the thermal rearrangement of vinyl allyl ether (g) (a) positive slope with zero intercept
to allyl acetaldehyde (g) at 175°C, = 5 × 1011 exp (b) positive slope with non-zero intercept
(–128000/RT), where is in s–1 and activation energy (c) negative slope with non-zero intercept
in J mol–1. The enthalpy of activation in kJ mol–1 is (d) parallel to time axis.
(a) 224.3 (b) 142.3 140. A certain reaction proceeds in a sequence of three ele-
(c) 12.43 (d) 124.3 mentary steps with the rate constants k1, k2 and k3. If
134. Which of the following statements are correct about the observed rate constant of the expressed as k (obs)
half-life period? 1/ 2
 k1 
(1) time required for 99.9% completion of a reaction = k (obs) =   ´ k 3 , the observed energy of activa-
is 100 times the half-life period  k2 
(2) time required for 75% completion of a first-order tion of the reaction is
reaction is double the half-life of the reaction
(3) average life = 1.44 times the half-life for first- E 3 +E1 1  E1 
(a) (b)   +E 3
order reaction 2 2  E2 
10.24 Chapter 10

1/2 145. The rate low for the hydrolysis of thioacetamide,

1  E1 
(c) E3 + [E1 – E2] (d) E3   CH3CSNH2,
2  E2  S O
|| ||
141. Decomposition of H2O2 is a first order reaction. Rate
CH3 − C − NH2 + H2O → CH3 − C − NH2
constant for decomposition of H2O2 is 0.022 hr. A
solution of H2O2 labelled as ‘x’ volume was left open. + H2S
+
Due to this some H2O2 decomposed. To determine new Is rate = k[H ] [TA], where TA is thioacetamide.
volume strength after 6 hr, 10 ml of this solution was In which of the following solutions, will the rate of
diluted to 100 ml. 10 ml of this diluted solution was hydrolysis of thioacetamide (TA) is least at 25oC?
titrated against 25 ml of 0.025M KMnO4 acidified (a) 0.1 M in TA and 0.20 M in CH3CO2H
solution. The value of ‘x’ is (b) 0.1 M in TA and 0.20 M in HNO3
(a) 20 volume (b) 10 volume (c) 0.1 M in TA and 0.20 M in HCO2H
(c) 15 volume (d) none of these (d) 0.15 M in TA and 0.15 M in HCl
142. Reaction A2 + B2 → 2AB is completed according to 146. A follows parallel path Ist order reactions giving B and
the following mechanism. C as shown:
A2 ⇌ 2A
A + B2 → AB + B (slow step)
A + B → AB
The order of reaction is
(a) 1 (b) 3/2
(c) 1/2 (d) 2 If initial concentration of A is 0.25 M, calculate the
143. For the following reaction concentration of C after 5 hour of reaction.

A (g) → B (g) + C (g) Given, λ1 = 1.5 × 10–5 s–1, λ2 = 5 × 10–6 s–1

(a) 7.55 × 10–3 M
The initial pressure was P0 while pressure after time ‘t’ (b) 1.89 × 10–2 M
was Pt. The rate constant k will be (c) 5.53 × 10–3 M
2.303 P0 (d) 3.51 × 10–3 M
(a) k = t
log10
P0 - Pt 147. Two substance ‘A’ and ‘B’ are present such that [A0] =
4[B0], and half–life of ‘A’ is 5 minutes and that of ‘B’
2.303 P0 is 15 minute. If they start decaying at the same time
(b) k = log10 following first order, how much time later will the con-
t 2P0 - Pt
centration of both of them would be same.
2.303 P (a) 10 min (b) 12 min
(c) k = log10 0 (c) 5 min (d) 15 min
t Pt
148. For a reaction, A → B + C, it was found that at the
2.303 P0 end of 10 min from the start the total optical, rota-
(d) k = t log10 P - 2P tion of the system was 50oC and when the reaction is
0 t
complete it was 100o. Assuming that only B and C are
144. A first order reaction is carried out with an initial con- optically active and dextro rotator, the rate constant of
centration of 10 mol per litre and 80% of the reactant this first order reaction would be
changes into the product in 10 sec. Now if the same
(a) 6.9 min–1 (b) 0.069 min–1
reaction is carried out with an initial concentration of –2 –1
(c) 6.9 × 10 min (d) 0.69 min–1
5 mol per litre the percentage of the reactant changing
to the produce in 10 sec is 149. Two reactants (A) and (B) separately show two chemi-
(a) 160 (b) 80 cal reactions. Both reactions are carried out with same
(c) 50 (d) 40 initial concentration of each reactant. Reactant (A) fol-
lows first order kinetics whereas reactant (b) follows
second order kinetics. If both have same life period.
 Chemical Kinetics 10.25

The ratio of their at the start of reaction is 154. The rate constant, the activation energy and Arrhenius
(a) 2.303 log 2 (b) Log 2 parameter of a chemical reaction at 300 K are K, Ea
and A respectively. The value of rate constant at T →
2.303 ∞ is
(c) (d) log2
log2 2.303 (a) A (b) Ea
(c) Ea x A (d) A – Ea
150. The following data pertains to the reaction between A
and B : 155. An aqueous solution of sugar undergoes acid catalysed
S. No. [A]/mol L –1
[B]/mol L –1
Rate/mol L t –1 –1 hydrolysis. 50 g sugar in 125 mL water rotates the
plane of plane polarized light by +13.1o at t = 0. After
I 1 × 10–2 2 × 10–2 2 × 10–4 complete hydrolysis, it shows a rotation of −3.75o. The
–2 –2
II 2 × 10 2 × 10 4 × 10–4 percentage hydrolysis of sugar at time ‘t’ in the same
III 2 × 10–2 4 × 10–2 8 × 10–4 solution having a rotation of 5o is
Which of the following inferences are drawn from the (a) 42 % (b) 58 %
above data? (c) 48 % (d) 55 %
1. Rate law of the reaction is k [A] [B]. 156. Nitrous oxide decomposes into N2 and O2 where reac-
2. Rate constant of the reaction is 10–4. tants and products are in gas phase. If the reaction is
3. Rate of reaction increases four times by doubling first order then the rate constants for this reaction in
the concentration of each reactant. terms of pressure, i.e., Pi = initial pressure Pf = final
Select the correct answer from the codes given below : pressure of reaction mixture may be denoted as:
(a) 1 and 2 (b) 1 and 3 1 Pi
(c) 1, 2 and 3 (d) 3 alone (a) k= ln
t Pi -Pf
151. For a first order reaction A(g) → B(g) + C(g), the total
pressure of A + B + C at time ‘t’ and ∞ are P2 and P3 1 Pi
(b) k= ln
respectively. The constant k of the reaction is t Pf

1 P3 1 2P3 1 Pi
(a) ln (b) ln (c) k= ln
t 2(P3 - P2 ) t P3 - P2 t 3Pi -2Pf

1 P 1 P3 1 Pi
(c) ln 3 (d) ln (d) k= ln
t P3 - P2 t 2P3 - P2 t 2Pf -3Pi

157. Hydrogenation of vegetable ghee at 27oC reduces the

152. The energy of activation and specific rate constant for pressure of H2 from 3 atm to 2.18 atm in 40 minutes.
a first order reaction at 25°C are 100 kJ/mol and 3.46 The rate of reaction in terms of molarity per second is
× 10–5 sec–1 respectively. Determine the temperature at (R = 0.082 L atm mol–1 K–1)
which half life of reaction is 2 hour. (a) 1.357 × 10–6 (b) 1.537 × 10–5
2N2O5 → 2N2O4 + O2 (c) 1.375 × 10 –5
(d) 6.250 × 10–4
(in CCl4) (in CCl4) 158. In a certain reaction 8% of the reactant decomposes in
(a) 300 K (b) 302 K 30 minutes, 24% in 90 minutes and 48% in 180 min-
(c) 304 K (d) 306 K utes. What are the dimensions of the rate constant?
153. A redox reaction is carried out at 127oC. If the same (a) Mol lit–1 sec–1 (b) Mol sec–1
–1 –1
reaction is carried out in presence of a catalyst at the (c) Lit mol sec (d) Hour–1
same temperature, the rate of reaction is doubled. To 159. The half life (t1) of the first order reaction and half
what extent is the energy barrier lowered by the cata- life (t2) of the second order reaction are in the ratio
lyst? [Use R = 2 cal mol−1 K−1 and log 2 = 0.301] 2:1. Hence the ratio of the rates of the above first and
(a) 455 cal (b) 231 cal second order reactions at the start is
(c) 693 cal (d) 554 cal (a) 1 : 0.4365 (b) 0.3465 : 1
(c) 2 : 1 (d) 1 : 2
10.26 Chapter 10

160. For the reaction, 2NO + Cl2 2NOCl 165. The hypothetical reaction, A2 + B2 → 2AB follows the
The following mechanism has been proposed following mechanism:
NO + Cl NOCl2 (fast) A2 ⇌ A + A (fast)
NOCl2 + NO 2NOCl (slow) A + B2 AB + B (slow)
(a) Rate = k[NO] [Cl2]2 A+B AB (fast)
(b) Rate = k[NO]2 [Cl2] The order of the overall reaction is:
(c) Rate = k[NOCl]2
(a) 1 (b) 2
(d) Rate = k[NOCl2] [NO]
(c) 3/2 (d) 0
161. Consider two first order reactions (1) and (2). The graph
166. Initial concentration of reactant for nth order reaction
of log [A]t vs t for the two reactions is shown in figure.
is ‘a’. Which of the following is correct for t1/2 of the
Choose the correct relation between half life of the first
reaction?
reaction, (t1/2)1 and that of the second reaction, (t1/2)2.
(a) ln t1/2 = n ln a
(b) ln t1/2 = ln n + ln k – ln a
(c) t1/2 = ln n – ln k + ln a
(d) ln t1/2 = ln k – (n – 1)ln a
167. 3A → 2B. Point ‘x’ in the given figure represents

(a) (t1/2)1 < (t1/2)2

(b) (t1/2)1 > (t1/2)2
(c) (t1/2)1 = (t1/2)2
(d) None of these
162. For a zero order reaction, the concentration of reactant
after 10s is 0.2 mol/l. If k0 is 2 × 10– 2 mol l–1 s–1, the (a) half life time.
initial concentration of reactant is (b) average life time.
(c) time when 60% of A is reacted.
(a) 0.6 mol/l (b) 0.4 mol/l
(d) time when 40% of A is reacted.
(c) 0.8 mol/l (d) 1 mol/l
168. The chemical kinetics of the reaction aA + bB →
163. In general the rate of a chemical reaction is doubled
C at 298 K were followed. The initial rates were
with every 10o rise in temperature. If the reaction
recorded rates were recorded under different initial
is carried out in the vicinity at 27oC, the activation
conditions and are summarized as follows.
energy of the reaction is
(a) 51.85 kJ (b) 58.15 kJ Initial conc. Initial conc. Initial rate
[A]0 (mol/L) [B]0 (mol/L) (mol /L s)
(c) 5.81 kJ (d) 8.51 kJ
0.1 0.1 2.4 × 10–3
164. Consider the following statements
0.2 0.1 4.8 × 10–3
(a) The rate of a process is always proportional to its
0.4 0.1 9.7 × 10–3
free energy change.
0.1 0.2 9.6 × 10–3
(b) The molecularity of an elementary chemical
reaction step can be determined by examining its 0.1 0.4 3.8 × 10–2
stoichiometry.
Which of the following statements is incorrect?
(c) The first order reactions follow an exponential
time course. (a) The rate constant k is governed by the activation
(d) Energy of activation is inversely proportional to energy of the reaction
temperature. (b) Reaction rate = k[A] [B]2
(c) In the chemical equation of aA + bB → C, a is 0
The correct statement (s) is/are and b is 3.
(a) 1, 2, 3 (b) 1, 2, 3, 4 (d) The overall order of reaction is third order.
(c) 2 and 3 (d) 1 and 3
 Chemical Kinetics 10.27

169 If a is the initial concentration of reactant and (a – x) (b) x = a(1 – e–k1t)

is the remaining concentration after time ‘t’ in a first 1.414
order reaction of rate constant k1, then which of the (c) t 1/ 2 =
k1
following relations is /are correct?
1
2.303  a  (d) t av =
(a) k1 = log 
 a − x 
k1
t

More than One Option Correct Type

170. The experimental data for the reaction 2A + B2 (d) For the reaction N2O4(g) ⇌ 2NO2 (g), if degrees
2AB is as follows of dissociation of N2O4 are 25%, 50% and 75%,
then gradation of observed molar masses is M1 >
[A] (moL [B] (mol Initial rate M2 > M3 (M1, M2 and M3 are molar masses corre-
Expt. No
L−1) L−1) (mol L−1 s−1)
sponding to vapour densities are 25%, 50% and
1. 0.50 0.500 1.6 × 10−4 75% dissociation respectively)
2. 0.50 1.00 3.2 × 10−4
173. Which of the following is/are correctly matched?
3. 1.00 1.00 3.2 × 10−4
k 20 + T°C 1
(a) = ; Endothermic reaction
Which of the following graph are correct w.r.t. A? kT°C 4
(a) (b) k 20 + T°C
(b) = 4 ; Exothermic reaction
kT°C

k10 + T°C
(c) = 2 ; Endothermic reaction
kT°C

(c) (d) k10 + T°C 1

(d) = ; Exothermic reaction
kT°C 2
174. A radioactive element, X, decays by the sequence and
with half lives, given below:
λ1
X(t1/2 = 30 min) Y+α
171. Identify the correct statements: λ2
Y(t1/2 = 2 days) Z + 2β
(a) The order of an elementary reaction is equal to its
molecularity Which of the following statement(s) is/are incorrect?
(b) The order of a reaction can be zero (a) Atomic numbers of X and Z are same
(c) For second order reaction, order of reaction = 2 × (b) Disintegration constant λ2 > λ1
molecularity. (c) The mass number of Y is greater than that of X.
(d) The order of inversion of cane sugar is 2. (d) Y and Z are isotopes.

172. Which of the following statement(s) is/are correct? 175. In a hypothetical reaction X → Y, the activation energy
for the forward and backward reaction is 15 and 9 kJ
(a) An increase in temperature increases the rate con-
mol–1 respectively. The potential energy of X is 10 kJ
stant as well as the equilibrium constant of an exo-
mol–1. Identify the correct statement(s).
thermic reaction.
(a) The threshold energy of the reaction is 25 kJ.
(b) Densities of diamond and graphite are x and y (x > y).
(b) The potential energy f Y is 16 kJ
Increase in pressure on the equilibrium favours
(c) Heat of reaction is 6 kJ.
backward reaction. C(diamond) ⇌ C(graphite)
(d) The reaction is endothermic.
(c) Solubility of a solute (s) is dependent upon tem-
perature as S = A.e–∆H/RT (Here ∆H is the enthalpy
of solution)
10.28 Chapter 10

Passage Based Questions

Passage-1 179. The effective activation energy is
When sucrose is hydrolysed, it produces dextrorotatory 1 1
“glucose” and laevorotatory “fructose” whereas the reac- (a) E a′ = E a - E a + E a - + E a
2 3
5 1
5 5

tant itself is a dextrorotatory compound. The above a con- (b) E ′a = E a1 + E a 2 + E a 3 + E a 5

version process follows first order kinetics. Similarly, an
optically active compound A is hydrolysed as follows. (c) E ′a = E a1 + E a 2 − E a 3 − E a 5
(d) E ′a = E a 2 + E a 3 − E a 5 − E a1
H+
A + H2O 2B + C
180. The effective frequency factor
The observed rotation of compound A, B and C are 60o,
50o and − 80o per mole respectively. The angles of rotation A 2  A1 
2

(a) A ′ =
A 3  A 5 
after 40 minutes and after the completion of reaction were
26o and 10o respectively. At 27oC activation energy for con- 1/ 5
version is 27kJ mol–1. (Use: log 1.25 = 0.0969, log 14.97 = 2A 2  A1 
(b) A ′ =
1.175) A 3  A 5 

176. The value of rate constant of the above reaction at (c) A′= A1 × A2 × A3 × A4 × A5
27oC is A1  A 3 
1/ 5

(d) A ′ =
(a) 1.94 × 10–3 min–1 A 2  A 5 
(b) 1.37 × 10–6 min–1
(c) 6.13 × 10–3 min–1 181. Effective rate constant K’ in terms of frequency factor
(d) 5.57 × 10–3 min–1 A and activation energy of Ea would be
177. The value of t1/2 for the above process at 127oC is  1 1 
- E a + E a + E a - E a 
(a) 1.2 hours 2A 2 A11/ 5 5 5
exp  
2 3 1 5

(b) 8.4 minutes (a) k ′ =

A 3 A1/5 5 RT
(c) 1.5 hours
(d) 5.68 minutes  1 1 
- E a + E a + E a - E a 
2A 2 A11/ 5 5 5
exp  
1 3 2 5

178. At what temperature half life of above process is equal (b) k ′ =

A 3 A1/5 5 RT
to 31.1 minutes?
(a) 490 K 1/ 5
(c) k ′ = 2A 2 A 5 exp {
- Ea + Ea + Ea + Ea
1 2 3 5
}
(b) 345 K 1/ 5
A 3 A1 RT
(c) 72 K
(d) 280 K (d) None of these

Passage-2
For a reaction if effective rate constant k’ is given by
1/ 5
2k 2  k1 
k′ = where k1, k2, k3, k5 are rate constants for
k 3  k 5 

different steps of the reaction.

 Chemical Kinetics 10.29

Match the Column Type

182. Match the following (d) Half life of (s) [A] = [A0]e− kt
Column–I zero order
reaction
(a) First order reaction
(b) Zero order reaction (t) e−Ea/RT
(c) Second order reaction
184. Match the following
(d) Fractional order reaction
Column–II
Column–I Column–II
(p) Catalytic reaction in which the catalyst is partially
covered with reactant.
(a) t 1/ 2 = 0.693 (p) Zero order
(q) k
a (q) First order
(b) t 1/ 2 =
2k

(c) t = 1 (r) Average life

k
(r) T1/2 α conc. of reactant.
(s) 1 (s) Second order
(d) t 1 =
2
ak
(t) Nuclear disintegration

(t) k is time−1. 185. Match the following

183. Match the following Column–I Column–II

(a) N2O5 2NO2 + ½ O2 (p) first order
Column–I Column–II
(a) Fraction of 1 2.303 [Co]
effective (p) k.A (b) H2O2 H2O + ½ O2 (q) k = log
0
t [C]
collisions
(b) Half-life of (c) H2 + Cl2 hv 2HCl (r) Zero order
-kt
second order (q) log[A] = + log[A 0 ]
2.303
reaction
C0
(c) Integrated rate (d) 2NH3 N2 + 3H2 (s) t 1/ 2 =
A0 2k
law for first (r)
2k
order reaction In2
(t) t 1/ 2 =
k

Assertion-Reason Type
186. Assertion: For a reaction A(g) → B(g) 187. Assertion: For a first order reaction, A (g) →
−rA = 2.5 PA at 400 K Product the time required to reduce successively the
−rA = 2.5 PA at 600 K concentration of reactant by a constant fraction is
Activation energy is always same.
4125 J/mol. Reason: At any instant, the rate of a first order reac-
Reason: Since for any reaction values of rate constant tion is given by k[A].
at two different temperatures is same therefore activa-
tion energy of the reaction is zero.
10.30 Chapter 10

Integer Type

188. The reaction 2NO + Br2 → 2NOBr follows the follow-
ing mechanism :
1. NO + Br2 NOBr2 (fast)
2. NOBr2 + NO → 2NOBr (slow)
If concentrations of both NO and Br2 are increased two
times, the rate of reaction would become ____ times.
189. The t1/2 for the decomposition of CH3CHO at constant
temperature and at initial pressure of 340 mm and 170
mm of Hg were 410 and 820 s respectively. The order
of the reaction is ___.
190. The rate of a first order reaction at 20 min is 0.55 mol
L–1 min–1 and 0.055 mol L–1 min–1 at 40 min after initi-
ation. Find half life of the reaction in minutes.
191. For the reaction A → Product, the following data were
got.
d[A]
[A]
dt
(i) 1 1
(ii) 2 8
(iii) 3 27
The order of the reaction is ______
192. In gaseous reactions important for understanding the
upper atmosphere, H2O and O react bimolecularly to
form two OH radicals. ∆H for this reaction is 72 kJ at
500 K and Ea = 77 kJ mol−1, then Ea for the bimolecu-
lar recombination of 2OH radicals to form H2O & O at
500 K is ____.
193. Given two separate reactions
(I) Products
(II) Products,
Reaction (I) follows first order kinetics while reaction
(II) follows second order kinetics. Both the reactions
have same half lives. When the initial concentration of
(A) is ‘n’ times that of (B), then the rate of reaction (I)
is 1.386 times that of reaction (II) at the start of reac-
tion. The value of n is ____.
194. Two first order reactions A and B have the same fre-
quency factor and activation energy of A exceeds
that of B by 10.46 kJ mol−1. If A is 30% complete in
60 min. at 100oC, how long will the B take for 70%
decomposition. [Given : log 3 = 0.4771, log 7 = 0.845,
antilog 0.4633 = 2.9]
195. The half life period and initial concentration of a reac-
tion are as follows. What is order of reaction?
Intitial cocentration 350 540 158
t1/2 425 275 941
196. How many of the following graphs are correct?
(a) (b)
(c) (d)
197. The inversion of cane sugar proceeds with a constant
half life of 500 minute at pH = 5, for any concentration
of sugar. However, the half life changes to 50 minutes.
What would be the order of reaction with respect to H+
at a given concentration of sugar?
198. A reaction, A(g) + 2B(g) 2C(g) + D(g) was
studied using an initial concentration of B which was
1.5 times that of A. But the equilibrium concentrations
of A and B were found to be equal. What is the value
of Kp for above equilibrium?

Previous Year’s Questions

199. Units of rate constant for the first and zero-order reac- 200. For a reaction A + 2B C, rate is given by
tions in terms of molarity Μ, units are respectively +d[C]/dt = k[A][B], hence the order of the reaction is
[2002] [2002]
–1
(a) s , Ms –1
(b) s , Μ
–1
(a) 3 (b) 2
(c) Μ s–1, s–1 (d) M, s–1 (c) 1 (d) 0
 Chemical Kinetics 10.31

201. Consider the following two reactions 207. The rate reaction for the reaction [2004]
A Product –d[A]/dt = k1 [A]0 2A + B C
B Product –d[B]/dt = k2 [B] is found to be rate = K[A] [B]
k1, and k2 are expressed in terms of molarity (mol L–1) The correct statement in relation to this reaction is that the
and time (s–1) as [2002] (a) unit of K must be s1
(a) s–1, Μ s–1 L–1 (b) Ms–1, Μ s–1 (b) value of A: is dependent of the initial concentra-
(c) s–1 M–1 s–1 (d) Μ s–1, L–1 s–1 tion of A
202. Rate constant of the first-order reaction when initial (c) Rate of formation of is twice the rate of disap-
concentration Co and concentration Ct at time t is given pearance of A
by equation (d) t½ is a constant
kt = log C0 – log Ct 208. Consider an endothermic reaction X Y with
Graph is a straight line if we plot [2002] the activation energies Eb and Ef for the backward and
(a) t vs log Co (b) t vs log Ct forward reactions respectively. In general, [2005]
(c) t–1 vs log Ct (d) log Co vs log Ct (a) Eb<Ef
(b) Eb>Ef
203. The rate law for a reaction between the substances
(c) Eb – Ef
A and is given by Rate = [A]n [B]m
(d) there is no definite relation between Eb and Ef
on doubling the concentration of A and halving
209. t¼ can be taken as the time taken for the concentration
the-concentration of B, the ratio of the new rate to the 3
of a reactant to drop to __4 of its initial value.
earlier rate of the reaction will be as [2003]
If the rate constant for a first order reaction is then t1/4
(a) l/2 (m + n) (b) (m + n)
can be written as [2005]
(c) (n – m) (d) 2(n–m)
(a) 0.1/k (b) 0.29/k
204. For the reaction system (c) 0.69/k (d) 0.75/k
2NO (g) + O2 (g) 2NO2 (g) 210. A reaction involving two different reactants can never
volume is suddenly reduced to half its value by be? [2005]
increasing the pressure on it. If the reaction is of first (a) Unimoleculur reaction
order with respect to O2 and second order with respect (b) Ist order reaction
to NO2, the rate of reaction will [2003] (c) IInd order reaction
(a) diminish to one fourth of its initial value (d) Bimoleculur reaction
(b) diminish to one eighth of its initial value
211. The following mechanism has been proposed for the
(c) increase to eight times of its initial value
reaction of NO with Br2 to form NO Br
(d) increase to four times of its initial value
NO(g) + Br2(g) NOBr2 (g)
205. In the respect of the equation k = Ae–Ea/RT in chemi-
cal kinetics, which one of the following statements is NOBr2(g) + NO(g) 2NOBr (g)
correct? [2003] If the second step is the rate determining step, the order
(a) k is equilibrium constant of the reaction with respect to NO (g) is [2006]
(b) A is adsorption factor (a) l (b) 0
(c) Eo is energy of activation (c) 3 (d) 2
(d) R is Rydberg constant
212. A reaction was found to be second-order with respect
206. In a first-order reaction, the concentration of the re- to the concentration of carbon monoxide. If the
actant, decreases from 0.8 Μ to 0.4 Μ in 15 minutes. concentration of carbon monoxide is doubled, with
The time taken for the concentration to change from everything else kept the same, the rate of reaction will
0.1 Μ to 0.025 Μ is [2004] [2006]
(a) 30 minutes (a) remain unchanged
(b) 60 minutes (b) triple
(c) 7.5 minutes (c) increase by a factor of 4
(d) 15 minutes (d) double
10.32 Chapter 10

213. Rate of a reaction can be expressed by Arrhenius 219. Consider the reaction:
equation as, k = Ae–E/RT Cl2 (aq) + H2S (aq) S (s) + 2H+ (aq) + 2Cl– (aq)
In this equation, Ε represents [2006] The rate equation for this reaction is
(a) the energy above which all the colliding molecules Rate = k[Cl2] [H2S]
will react Which of these mechanisms is/are consistent with this
(b) the energy below which colliding molecules will rate equation? [2010]
not react (1) Cl2 + H2S H+ + Cl– + Cl+ + HS– (slow)
(c) the total energy of the reacting molecules at a tem Cl+ + HS– H+ + Cl– + S (fast)
perature, Τ (2) H2S ⇔ H + HS (fast equilibrium)
+ –

(d) the fraction of molecules with energy greater than Cl2 + HS– 2Cl– + H+ + S (slow)
the activation energy of the reaction (a) 2 only (b) Both 1 and 2
(c) Neither 1 nor 2 (d) 1 only
214. The energies of activation for forward and reverse
reactions for A2 + B2 2AB are 180 kJ mol–1 220. The rate of a chemical reaction doubles for every
and 200 kJ mol–1 respectively. The presence of a cat- 10°C rise of temperature. If the temperature is raised
alyst lowers the activation energy of both (forward by 50°C, the rate of the reaction increases by about:
and reverse) reactions by 100 kJ mol–1. The enthalpy [2011]
change of the reaction (A2 + B2 2AB) in the (a) 16 times
presence of catalyst will be (in kJ mol–1) [2007] (b) 42 times
(a) 120 (b) 280 (c) 32 times
(c) 20 (d) 300 (d) 20 times
215. Consider the reaction, 221. For a first order reaction, (A) → products, the con-
2A + B Products centration of A changes from 0.10 M to 0.025 Min 40
When concentration of alone was doubled, the half life minutes. The rate of reaction when the concentration
did not change. When the concentration of A alone of A is 0.01 M, is: [2012]
was doubled, the rate increased by two times. The unit (a) 3.47 × 10 M/min
–5

of rate constant for this reaction is [2008] (b) 3.47 × 10–4 M/min
(a) no unit (b) mol L–1 s–1 (c) 1.73 × 10–5 M/min
(c) s–1 (d) L mol–1 s–1 (d) 1.73 × 10–4 M/min
216. For a reaction ½ A 2B, rate of disappearance 222. The rate of a reaction doubles when its temperature
of ‘A’ is related to the rate of appearance of ‘B’ by the changes from 300 K to 310 K. Activation energy of
expression [2008] such a reaction will be:
d [A] d [B] d [A] d [B] (R = 8.314 JK–1 mol–1 and log 2 = 0.301) [2013]
(a) – ____ 1 ____
__
dt = 2 dt (b) – ____ 1 ____
__
dt = 4 dt (a) 58.5 kJ mol–1
d [A] d [B] d [A] d [B] (b) 60.5 kJ mol–1
(c) – ____ ____
dt = dt (d) – ____ ____
dt = 4 dt (c) 53.6 kJ mol–1
217. The half life period of a first order chemical reac- (d) 48.6 kJ mol–1
tion is 6.93 minutes. The time required for the com- 223. Deomposition of H2O2 follows a first order reaction.
pletion of 99% of the chemical reaction will be In fifty minutes the concentration of H2O2 decreases
(log 2 = 0.301): [2008] from 0.5 to 0.125 M in one such decomposition. When
(a) 23.03 minutes (b) 46.06 minutes the concentration of H2O2 reaches 0.05 M, the rate of
(c) 460.6 minutes (d) 230.3 minutes formation of O2 will be: [2016]
–4 –1
218. The time for half life period of a certain reaction (a) 6.93 × 10 mol min
A products is 1 hour. When the initial concen- (b) 2.66 L min–1 at STP
tration of the reactant ‘A’, is 2.0 mol L–1, how much (c) 1.34 × 10–2 mol min–1
time does it take for its concentration to come from (d) 6.93 × 10–2 mol min–1
0.50 to 0.25 mol L–1 if it is a zero order reaction?
[2010]
(a) 4 h (b) 0.5 h
(c) 0.25 h (d) 1 h
 Chemical Kinetics 10.33

ANSWER KEYS
Single Option Correct Type
1. (a) 2. (b) 3. (a) 4. (b) 5. (a) 6. (a) 7. (d) 8. (c) 9. (b) 10. (c)
11. (c) 12. (d) 13. (a) 14. (d) 15. (c) 16. (b) 17. (a) 18. (a) 19. (d) 20. (c)
21. (c) 22. (c) 23. (b) 24. (d) 25. (b) 26. (c) 27. (b) 28. (d) 29. (c) 30. (c)
31. (c) 32. (c) 33. (a) 34. (a) 35. (c) 36. (c) 37. (d) 38. (c) 39. (a) 40. (c)
41. (d) 42. (a) 43. (a) 44. (a) 45. (b) 46. (a) 47. (c) 48. (d) 49. (a) 50. (c)
51. (d) 52. (a) 53. (d) 54. (a) 55. (b) 56. (c) 57. (d) 58. (b) 59. (b) 60. (a)
61. (b) 62. (c) 63. (a) 64. (b) 65. (a) 66. (b) 67. (c) 68. (b) 69. (a) 70. (b)
71. (b) 72. (b) 73. (d) 74. (a) 75. (b) 76. (a) 77. (c) 78. (d) 79. (c) 80. (c)
81. (a) 82. (c) 83. (a) 84. (b) 85. (b) 86. (c) 87. (b) 88. (c) 89. (c) 90. (d)
91. (d) 92. (a) 93. (c) 94. (c) 95. (a) 96. (d) 97. (a) 98. (b) 99. (a) 100. (a)
101. (a) 102. (a) 103. (a) 104. (b) 105. (b) 106. (a) 107. (d) 108. (c) 109. (b) 110. (d)
111. (c) 112. (c) 113. (b) 114. (c) 115. (c) 116. (a) 117. (a) 118. (a) 119. (b) 120. (c)
121. (d) 122. (c) 123. (b) 124. (c) 125. (d) 126. (c) 127. (a) 128. (a) 129. (a) 130. (d)
131. (b) 132. (a) 133. (d) 134. (b) 135. (a) 136. (b) 137. (b) 138. (a) 139. (c) 140. (c)
141. (a) 142. (b) 143. (b) 144. (b) 145. (a) 146. (b) 147. (d) 148. (b) 149. (a) 150. (b)
151. (a) 152. (d) 153. (d) 154. (a) 155. (c) 156. (c) 157. (c) 158. (a) 159. (b) 160. (b)
161. (a) 162. (b) 163. (a) 164. (c) 165. (c) 166. (d) 167. (c) 168. (c) 169. (b)

More than One Option Correct Type

170. (c) and (d) 171. (a) and (b) 172. (b), (c) and (d)
173. (c), and (d) 174. (b), (c), and (d) 175. (a) (b) (c) and (d)

Passage Based Questions

176. (d) 177. (b) 178. (b) 179. (a) 180. (b) 181. (d)

Match the Column Type

182. (a) → (s, t); (b) → r; (c) → (q),(s); (d) → (p, s) 183. (a) → t; (b) → p; (c) → (q, s); (d) → r
184. (a) → (q, t); (b) → p; (c) → (q), (r), (t); (d) → (s)
185. (a) → (p), (q), (t); (b) → (p), (q), (t); (c) → (r), (s); (d) → (r), (s)

Assertion-Reason Type
186. (d) 187. (b)

Integer Type
188. 8 189. 2 190. 6 191. 3 192. 5 193. 2 194. 7 195. 2 196. 3
197. 1 198. 4

Previous Year’s Questions

199. (a) 200. (b) 201. (d) 202. (b) 203. (d) 204. (c) 205. (c) 206. (a) 207. (b) 208. (a)
209. (b) 210. (a) 211. (d) 212. (c) 213. (b) 214. (c) 215. (d) 216. (b) 217. (b) 218. (c)
219. (d) 220. (c) 221. (b) 222. (c) 223. (a)
10.34 Chapter 10

HINTS AND SOLUTIONS

Single Option Correct Type

Rate mole L–1s–1 kZ
1. k1 = ____ __________
[A] = mole L–1 = s
–1
Fractional yield of Z =
___
kav
3.8 × 10–5
________
0.693 0.693 = 1.64 × 10–4 = 0.2317
9. t1/2 = _____ ___________
k = 6.2 × 10–4 s–1 = 1117.7 s
d[N2O5] __
_______ 1 d[NO2] _____
______ 2d[O2]
12. Catalyst decreases the activation energy of the system. 57. – dt = 2 – dt = dt
23. The rate of formation of AB• is directly proportional to the So, k1 [N2O5] = k2/2 [N2O5] = 2k3 [N2O5]
intensity of incident light (I).
that is, 2k1 = k2 = 4k3
25. It is a pseudo first-order reaction. Since r α RCl, so rate is
59. As it is a Ist order reaction so
halved when the concentration of alkyl halide is halved. 16 mm 32 mm
26. Lesser is the activation energy, faster is the reaction. 50% 75%
completion completion
27. No, it is not an elementary process.
60. As t0.75 = 2 t0.5
29. For an endothermic reaction, Ea will be more than ΔΗ, while
1
__ 1
__
for an exothermic reaction, Ea will be less than ΔH. Thus, t0.5 = 2 × t0.75 = 2 × 138.6
31. It is a characteristic constant of a particular reaction at a = 69.3 seconds
given temperature. It does not depend upon initial concentra-
Now, k = _____ 0.693
0.693 _____
t0.5 = 69.3 = 0.01 units
tion of the reactants, time of reaction and extent of reaction.
= 10–2 units
34. According to collision theory, rate of reaction depends on 1 n
__
the number of molecules whose energy is greater than the
62. [A] = [A0] 2 ( )
n
threshold energy. [A] / [A0] = 1/8 = 2 ( __1 )
41. Catalyst lowers the activation energy barrier and thus it 3 n

shortens the time taken to attain equilibrium. ( __12 ) = ( __12 )

n=3
n −1
1 1 The time in three half-lives = 3 × 14 s = 42 s
48. As t α   or ( a )
1− n

2  a  64. Since it is a first order reaction, therefore log (N2O5) vs time

gives a straight line graph with –ve slope (slope = k/2.303)
= k [a]1–n
0.693 0.693
log t 1 α = (1 – n) log a + log k 65. As for 1st order K 1 = = S
-1

t1 40
2
2
As t = mx + c
1 – n = tan 45° = 1 for zero order =
[ A ] = 1.386
0
mol dm–3 S–1
2t 2 × 20
Hence n = 0
k=1 K1 0.693 × 2 × 20 –1 3
= = 0.5 mol dm
54. It is a first-order reaction rate. At high temperature, rate K0 40 × 1.386
constant will be larger. The larger the value of k, the smaller 0.693 _____
_____ 0.693
66. k = t = 15 = 4.62 × 10–2 min–1
will be the half-life period of first-order reaction. 1/2

0.693
____ 67. Initial = [A0][B0]
t1/2 = Assuming that the volume of solvent = volume of solution,
k

56. For parallel path reaction (average) = k1 + k2 Initial rate = k × 2 M × 2 M = 4 k M2

k2
k (average) = k1 + k2
= 1.26 × 10–4 + 3.8 x 10–5
__
68. log10 k = 2.30 R T – T
1 2 1
_____
(
–Ea __
1 1
__
)
–9 × 1000 cal
________________
= 1.64 × 10–4sec–1 = = 0.1103
2.303 × 2 cal mol–1 K–1
kY
___
Also fractional yield of Y = k2
kav = 1289
1.26 × 10–4
________ k1
= 1.64 × 10–4 = 0.7683
Percentage increase = 28.9 %.
 Chemical Kinetics 10.35

69. Rate = k[A]1 92. r = k [A] = 60 × 10–4 × 0.01

= 3 × 10–6 × 0.1 = 3 × 10–7 Ms–1 1
___
= 60 × 10–4 × 102
70. The order of an elementary reaction is determined = 60 × 10–6 mol L–1 min–1
experimentally and therefore, statement 2 is not correct.
2.303
_____ [A]0
____
72. Rate = [N2O5]1 93. k = log
t A
[N2O5]1 = Rate/k 2.303
________ 800
___
= 2 × 10–4 s–1 log 50 = 1.386 × 10–4 s–1.
1.02 × 10–4
________
= 3.4 × 10–5 =3
94. Given Ea < Ea2
76. Pseudo-unimolecular reactions occur when one or more k1´ k2´
___ __
reactants is in excess. Usually such reactions occur in So, the ratio k ´ > k
1 2
solvents, which itself is one of the reactants.
77. The rate of reaction is given as 96. The stoichiometric coefficients of reaction has no relation to
d[A] ____
d[B] __ d[C] ____
d[D] the order of reaction.
____ 1 ____
– 2dt = dt = 3 dt = dt

78. Rate = k[A] (It is a first order reaction) 97.

(t )
1/ 2 1
 a2 
n -1

=
(t )  a 1 
r
___ 2.0 × 10–5 Ms–1
___________ 1/ 2 2
k = [A] = 0.01 M 50 n–1
___
2 × 10–5 s–1
________
( __12 )
100
=
= 10–2 = 2 × 10–3 s–1 1 n–1

0.693 ______
_____ 0.693
( ) ( __21 )
1
__
2
=
t1/2 = k = 2 × 10–3 s 1 1 1–n
( ) ( __12 )
__
2
=
= 346.5 s = 347 s 1–n=1
80. From the units of rate constant (10–3 min–1) it is found or n = 1 – 1 = 0 (zero order)
that it is a first order reaction.
r = [concentrated] 99. Rate = [A]x [B]1/Y [C]X/Y
= 10–3 × 0.2 Order = X + Y + Y
1
__ X
__
= 0.0002 mol dm–3 min–1
(1 + X)
______
1
__ 1
__ 1
__ 6+4+3
_______ =X+
Y
81. Order = 2 + 3 + 4 = 12
1
__
13
__ 100. Average life (Τ) =
= 12 λ
85. For a zero-order reaction, x = kt Here λ = Decay constant 0.693
0.693
_____
that is, = mx + c t½ = λ
as = 0, line passes through origin 0.693
_____
λ= t
87. k = Ae–Ea/RT (Arrhenius equation) ½

when Τ ∞ t 12 10s
k = A e0, or k = A T= = = 14.4S0
0.693 0.693
Thus k = 6 × 1014s–1
Ea _____
k2 _____
__ T2–T1
88. In the first case 102. log k = 2.303 T T
V α CA CB½ 1 1 2

or V = k CA 2CB½ (Ea = 1)
k__
In the second case 2
= 1 or k2 = k1 = 1.6 × 106s–1
V` = k 2CA (2CB)½ k1
Ea
________ 10
________
On dividing 103. log 2.5 = ×
2.303 × R 300 × 310
½
2CA(2CB)
V` ________
__ __
√ Ea 10
V = CA CB½ = 2 2 0.3979 = ×
2.303 × 8.314 300 × 310
89. Statement (l) is not correct because sum of powers raised
to concentration terms in the rate law denotes the order of Ea = 70.77 × 103 J = 70.8 kJ
reaction, which is 1 + 1 = 2 and not equal to unity. d[N2] d[H2]
____ 1 ____
__
90. In a zero-order reaction, the rate remains constant. 106. Rate = – dt = – 3 dt
d[C]
____ 52.5
____ 1 ______
__ d[NH3]
Rate of reaction, – dt = 2.5 =+2 dt
= 21 moles L–1 hour–1 107. r = k [N2 O5]1
In one hour, the amount of reactant consumed = 21 %. _r 2.40 × 10–5
________
[N2 O5] = = = 0.8
k 3 × 10–5
10.36 Chapter 10
n–1
80
___ 0.8
d[A] __
1 ____
__ d[B]
1 ____
113. Rate = – 3 dt = 2 dt 113
___
= 1.6 ( ) Taking logarithms,

d[A]
log 0.7 = (n – l) log 0.5
2 ____
__
= – 3 dt On solving,
n = 1.5
115. Rate = k [A]n = k (X)n
123. According to the rate law
6.25 × Rate = k (2.5 X)n Rate = k [A] [B]
6.25 × k (X)n = k (2.5 X)n From first experiment we have
(2.5 X/X)n = 6.25 2 × 10–4 = k (1 × 10–2) (2 × 10–2)
(2.5)n = (2.5)2 k=2
The rate law: Rate = k [A][B] shows that rate of reaction
i.e., n = 2
becomes four times the original rate, when the concentration
116. From expt (1) and (2), it is clear that when [B] is kept con- of each reactant is doubled.
stant and [A] is made 6 times, the rate also becomes 6 times, 124. a = 1 M, t = 60 min, k = 4.5 × 10–3 min–1
thus r α [A]1. Further from expt (1) and (3) when [A] is kept a–x=?
constant and [B2] is tripled, rate also becomes three times, 2.303
_____ a
____
k= t log a – x
Thus, r α [B2]1 a
____ _____
kt 4.5 × 10–3 × 60
___________
log a – x = 2.303 =
Hence r = k [A]1 [B2]1 2.303
Ea a
____
______ or log a – x = 0.1172
118. Slope = 2.303 R
a
____
Ea = – slope × 2.303 R a –x = antilog (0.1172) = 1.31
1
____
= – (–5000) × 2.303 × 8.314 a – x = 1.31
1
____
= 95700 JK–1 mol–1 a – x= 1.31 = 0.7633
= 95.7 kJ K–1 mol–1 After one hour, concentration of A is (a – x) = 0.7633
Rate of reaction after 1 hour = k (cone.)
Ea = 4.5 × 10–3 × 0.7633
119. log K = log A −
2.303RT = 3.43 × 10–3 Mmin–1
1 Ea
log K = 6 − ( 2000 ) 125. log k = log A –
T 2.303 RT
on solving log A = 6 so A = 106 S–1 22011
___________
log 1.5 × 107 = log A – 2.303 × 8.314
Ea 7 + log 1.5 = log A – 3.5591
= 2000 on solving Ea = 38.29 kJ/M log A – log 1.5 = 10.5591
2.303 R
A
_____
log 1.5 s–1 = 10.5591
120. For a first-order reaction, rate = k[C] A
_____
1.5 s–1
= anti-log (10.5591) = 3.615 × 1010
Initial rate = k [Ci]
0.65
____ Now, A = 3.615 × 1010 × 1.5
1
= k[100] = 5.4225 × 1010 s–1
k = 0.65/100 126. k1 1.5 × 107 s–1, k2 = 4.5 × 107 s–1
0.693 × 100
0.693 _________
_____
t½ = = min T1 = 50 + 273 = 323 K,
k 0.65
0.693 × 100
_________ T2 = 100 + 273 = 373 K
= 0.65 × 60 hour
k1 Ea T2 − T1
= 1.776 hour. log =
k2 2.303 T1 T2
2.303
_____ C 0 _____
2.303 0.1 M
______
121. k = t log = 40 min log 0.025 M 4.5 × 10 7
Ea 373 − 323
C t log =
7
2.303
_____ 2.303 × 0.6021
___________ 1.5 × 10 2.303 × 8.314 373 × 323
= 40 log 4 = 40
min–1 Ea × 50
______________
2.303 × 0.6021
___________ log3 = 19.147 × 373 × 323
Rate = k[Α] = 40
min–1 × 0.01 M
Ea × 50
______________
= 3.47 × 10–4 M/min or 0.04771 = 19.147 × 373 × 323

122.
(t )
1
2 1 80
___
= 113 = (p2/p1)n–1
on solving, Ea = 22.11 J/mole
≈ 2.2 × 104 J/mole
(t )
1
2 2
Here p2, p1 are the initial pressures
 Chemical Kinetics 10.37

127. ln k1 = ln A – 18/RT. 131. From experiment no. 2 and 3 it is clear that when [A]
ln k2 = ln A – 4/RT. is doubled keeping [B] constant, rate becomes four
ln k1 – ln k2 = –18/RT + 4/RT times, thus r ∝ [A]2
1
___ Now rate equation is r = [A]2 [B]”
= RT (4 –18)
14kJ
____ From experiment 1 and 2,
= – RT
5 × 10–4 = k [2.5 × 10–4]2 [3 × 10–5]n (i)
k1 14 × 10 3 4 × 10–3 = k [5 × 10–4]2 [6 × 10–5]n (ii)
log10 =− Divide (ii) and (i),
k2 2.303 × 8.314 × 300
4 × 10–3 k[5 × 10–4]2[6 × 10–5]n
k1 = 5 × 10–4 =
3 k[2.5 × 10–4]2[3 × 10–5]n
So, = 3.656 × 10 −
k2 8 = 22. 2n
128. Compare with the equation 2n = 8/4 = 21
n=1
Ea r = k[A]2 [B]1
ln k = ln A −
RT 132. ΔΕ° = Εa(f) – Εa(r).
Ea This holds good for uncatalyzed and catalyzed reactions.
Thus, = 1.25 × 104
R ΔΕ0 is the same for both these reactions.
and Ea = R × 1.25 × 104 For the uncatalyzed reaction, –30 kcal
1.98
____ = 28.0 kcal – Ea(r).
Ea = 1000 × 1.25 × 104
So, Ea(r) = 58.0 kcal
Ea = 24.75 kcal mol–1 For the catalyzed reaction, –30 kcal
129. At 450°C, = 10.5 kcal –Εa(r)
0.693
_____ 0.693
________
k = t½ = 10.17 min So, Ea(r) = 40.5 kcal
= 0.0681 min–1 133. A = 5 × 1011 × exp(–128000/RT)
Now for 75% decomposition = A. exp(– Ea/RT)
x = 75% of a = 0.75a Ea = 128000 J mol–1
For gaseous reaction
2.303
_____ a
____
t= k
log a – x Here Δη is change in the number of molecules, when
2.303
_________ a
_______ the activated complex is formed.
= 0.0681 min–1 log a – 0.75a
Here Δη = 0 (unimolecular reaction).
2.303
_________ 1
____ So, ΔΗ = 128000 – 8.314 × 448 J mol–1
= 0.0681 min–1 0.25
= (128000 – 3725) J mol–1
= 20.39 min = 124275 J mol–1
130. A (g) B (g) + 2C (g) = 124.3 kJ mol–1
At 320 seconds, x moles of A decomposes giving x moles of 135. R = k[conc.]n (i)
B and 2x moles of C.
2r = k[16 conc.]n (ii)
Total number of moles = a – x + x + 2x
Divide (ii) and (i)
= a + 2x 2r k[16cone.]n
__
So number of moles has increased by 2x. r = k[conc.]n

2x = 96 mm Hg 2 = 16n
x = 48 mm Hg 21 = 24n
1
__
For a first order reaction, 4n = 1 n=4
136. From graph it follows that at time 4 minute from the start of
2.303  a 
5.2 × 10–4 = log10 
 a − 48 
the reaction.
320
a
_____ [X] = [Y]
On solving, log a – 48 = 0.07225 3X Y
On solving, t=0 a
a = 313 mm of Hg t = 4 min a–x x/3
x
__
a–x=3
3a
___
x= 4
3a __
__ a
a–x=a– 4 =4
10.38 Chapter 10

137. This shows that, in 4 minutes, concentration of X has reduced 1/2

 A e -/RT
1

to 25% of the initial value therefore, t3/4 = 4 min. As t3/4 = 2 t1/2 =A3 e–E3/RT  1 -E /RT 
for a first-order reaction, so half-life of this reaction = 2 min. A
 2 e 2

αΑ xP
A 3 A1 E − E2 
× e −  3 + 1
E
Rate of reaction = [A]α =
A2  RT RT 
Order of reaction = α
[A]1 = 2.2 m M, r1 = 2.4 m Μ s–1 (i) kobs= Ae–Ea(obs)/RT
2.2
___ 2.4
___
[A]2 = 2 m M, r2 = 0.6 m Μ s–1 or 4 (ii) E E 
E obs =E 3 +  1 − 2 
On reducing the concentration of A to half, the rate of reac- 2 2 
tion is decreased by four times. 141. After 6 hour Meq of H2O2 in 10 ml diluted solution
Rate of reaction = [A]2
= 25 × 0.025 × 5
Order of reaction = 2.
= 3.125
138. Half life period (T) and initial conc. (a) are related as follows.
Meq of H2O2 in 100 ml conc. solution = 31.25
1 Meq of H2O2 in 10 ml of ‘x’ volume H2O2 present initially
Tα where n is the order of reaction.
a n-1 Volume strength × Volume of solution (ml)
=
1 5.6
T1 α n-1
a1 x
= × 10 = 1.79x
1 5.6
T2 α
a 2n-1 meq H 2 O 2,i
In =kt
n-1 meq H 2 O 2,t
T1  a 2 
=
T2  a 1  0.022 =
2.303
log
1.79x
6 31.25
Where a2 = 2a1, T2 = 2T1
2.303
Substituting in the above equation, =  log1.79 + log x − log 31.25 
6 
1 2.303
= (2)n−1 = 0.253 + log x − 1.495 
2 6 
Or 2−1 = 2n−1 2.303
=  −1.242 + log x 
n −1 = −1 or n = 0 6 
It is a zero order reaction. log x = 1.2993
139. ⇒ x = 20 Volume
142. rate = k [A] [B2]
2
[A]
K=
[A 2 ]
1/ 2
⇒ [A] = K [A 2 ]
For a zero order reaction, A → B,

Rate =
−d[A]
= k or − d[A] = k. dt rate = k K [A 2 ]1/ 2 [B 2 ]
dt
3
when t = 0, [A] = [A]0 and t = t, [A] = [A] Overall order =
[A] t=t
2
Hence − ∫[A]0
d[A] = ∫
t=o
dt 144. Time required to complete a definite fraction is independent
of initial concentration.
[A]0 − [A] = kt 145. Among option (B) and (D), rate would be less in (B) (HNO3
Or [A] = [A]0 − kt and HCl are both strong acids). Among (A), (B) and (C) , the
Thus the plot of [A] versus t is linear with negative slope and conc. of TA is same but the conc. of H+ will be 0.20 M in (B)
intercept [A]0. and less than 0.20 M in (A) and (C) each. As acetic acid is a
weaker acid than HCO2H, the least rate of hydrolysis will be
1/2
k  with 0.1 M in TA and 0.20 M in CH3CO2H.
140. kobs= k 3  1 
 k2  146. λA = λ1 + λ2 = 1.5 × 10− 5 + 5 × 10−6
= 20 × 10–6 s–1
 Chemical Kinetics 10.39

Also, Rate constant of the above reaction is given by

2.303 R – R∞
k= log ∞
t R∞ – Rt
2.303 100
= log = 0.069min –1
t 50
149. rA= k1 a; rB= k2 a2
[A]
Also, 2.303 log 0 =λ × t rB k 2 a 2 k 2 a
[A]t = =
rA k1 a k1
∴ 2.303 log 0.25 =20 × 10-6 × 5 × 60 × 60
[A]t 0.693
t 1/2 (A) = ;
0.25 k1
⇒ log = 0.1563
[A]t 1
t 1/2 (B) =
k2a
∴ [A]t = 0.1744M = 0.25 – [B]–[C]
∴ [B] + [C] = 0.25 – 0.1744 = 0.0756 M 0.693 1
= ;
λ2 k1 k2a
Fraction of C formed =
λ1 + λ2
k1
=0.693=2.303 log2
[C] k2a
=
[B]+[C] 150. Comparison of data at S. No. I and II shows that when [A]
⇒ [C] is doubled, the rate is doubled, hence order of reaction with
respect to A is first and comparison of data S.No. II and III
5 × 10−6 show that when [B] is doubled, the rate is also doubled hence
= (0.0756)
20 × 10−6 first order with respect to B. Therefore inferences 1 and 3 are
correct.
= 1.89 × 10–2 M
[A 0 ] 152. k1 = 3.46 × 10–5
147. Amount of A left in n1 half lives =
2 n1 T = 298 K

[B0 ] 0.0693
Amount of B left in n2 half lives = k2 = sec −1 =9.6 × 10−5 sec −1
2 n2 2 × 60 × 60
T=?
[A 0 ] [B0 ]
Now, = n 2 after ‘A’ decays for n1 halves and ‘B’ Using Arrhenius equation :
2 n1 2
k2 E  1 1
decays for n2 half lives. In =− a  − 
k1 R  T2 T1 
Now , since, [A0] = 4[B0]
4 = 2(n1–n2)
 9.6 × 10-5  100 × 103  1 1 
n1 – n2 = 2 2.303log  -5 
= −  − 
n2 = (n1 – 2)  3.46 × 10  8.314 T 298 
also, T = n1 × (t1/2)A and 1 8.314 1
T = n2 × (t1/2)B − × 2.303(log2.77) =
298 105 T
n1 × (t 1/2 ) A
=1 1
n 2 × (t 1/2 )B 3.355 × 10−3 − 8.48 × 10-5 =
T
n1 × 5 = n2 × 15 T= 306 K
n1
=3
n2 153. k = Ae–Ea/400R (i)
'
− E a / 400 R
On solving, n2 = 1 and n1 = 3 2k = Ae (ii)
So, after 15 min conc. of both A and B would be same. Dividing (a) by (1)
148. A → B + C 2 = e(Ea – E′a )/400R
o
Ro = 0, Rt = 50o and R∞ = 100
10.40 Chapter 10

E a − E a′ 0.693 k 2 a 2
ln 2 = In 2 Or × =
400R k1 1 1
Ea − E′a = 0.693 × 800 = 554.4
2k1 = 0.693 k2a
≃ 554 cal k1 = 0.3465 k2a
Initial rates are r1 = k1 (a) and r2 = k2(a)2
155. Sugar is Glucose + Fructose
r1 k1 (a) k 0.3465 k 2 (a)
Initial amount a 0 0 = = 1 = =0.3465
r2 k 2 (a)2 k 2 (a) k 2 (a)
Final amount a – x x x
x Rt – Ra Hence r1 : r2 = 0.3465 : 1
Degree of hydrolysis of sugar = =
a R∞ – R0 160. From slow step,
Rate = k[NOCl2] [NO] (i)
5 − 13.1 −8.1 From fast step
= = = 0.48
−37.5 − 13.1 −16.85
[NOCl 2 ]
Percentage hydrolysis of sugar = 48 % Equation constant K=
[NO][CL 2 ]
156. 2N2O(g) 2N2 (g) + O2(g)
Pi 0 0 Putting the value of [NOCl2] in (i)
Pi – 2P 2P P Rate = Kk′[NO]2 [Cl2]
For a first order reaction, Rate = k[NO]2 [Cl]
161. For (i) reaction slope is less than the slope of reaction (ii)
1 P hence k1> k2 and (t1/2)1 < (t1/2)2.
k= In i
t Pi -2P 162. at = a0 – x = a0 – kt
Where Pi = initial pressure of gas 0.2 + (2 × 10–2 × 10 ) = 0.4 mol/l = a0
Pi – 2P = pressure of gas at time t. -E /RT
k 305 e a (305)
Total pressure at t = Pi + P = Pf 163. = =2
k 295 e -Ea /RT(295)
P = Pf – Pi
∴ Pi – 2P = Pi – 2Pf + 2Pi ∆E  10 
ln 2 =  
= 3Pi – 2Pf 8.314 305 × 295 

n ∆P ∆E = 51851 J mol–1; 51.85 kJ mol–1

157. Change in molarity = =
v RT 1 1
166. t 1/2 a ;t =k n-1 ;
n-1 1/2
a a
3 − 2.18
= ln t1/2 = ln k – (n – 1)ln a
0.082 × 300
167. 3A → 2B
0.82 1 Initially no. of moles, a 0
= = = 0.033
0.82 × 30 30 At x, (a – 3x) 2x
a – 3x = 2x
Change in molarity
Rate of Reaction= a
time x=
5
3x 3a
0.033 % of A reacted = × 100 = × 100 = 60%
= mol L-1 sec -1 a 5a
40 × 60
= 1.375 × 10–5 mol L–1 sec–1. 168. r = k[A]x [B]y
0.693 1 2.4 × 10–3 = k(0.1)x(0.1)y (i)
159. For first order reaction, k1 = and k 2 = 4.8 × 10–3 = k(0.2)x(0.1)y (ii)
t 1/2 t 1/2 a
3.8 × 10–2 = k(0.1)x (0.4)y (iii)
0.693 1 On solving x = 1 and y = 2
In the problem, k1 = and k 2 =
t1 k2a Overall order of the reaction is 3.
0.693 1 Rate constant depends on activation energy of the reaction.
If t1 : t2 = 2: 1, then : =2:1 The stoichiometric coefficient of reactants may not be equal
k1 k 2 a
to order of reaction.
 Chemical Kinetics 10.41

More than One Option Correct Type

171. The order of a reaction may be zero, integer or fractional. The A
A1
Z1 X → Z1 −− 4Y 4
2YY+ 2 He
order of an elementary reaction is equal to its molecularity. 1

Inversion of cane sugar follows first order. There is no A1 – 4

Z1 – 2 Y→ A1 – 4
Z1 Z + 2 0–1 e
direct relation between order and molecularity for a particu-
lar reaction. 175. Eact(Forward) = 15 kJ mol–1, Eact(Backward)
172. Increase of pressure favours the side with increase in density. = 9 kJ mol–1,
N2O4 2NO2 Eth = Ereactant + Eact (Forward)
1–α 2α 10 kJ mol–1 + 15 kJ mol–1 = 25 kJ mol–1,
(1 - α )M N + 2αM NO MN Eproduct = Eth − Eact (backward)
2 O4 2 2 O4
M eq mix = M av = = = 25 kJ mol–1 – 9 kJ mol–1 = 16 kJ mol–1
1+ α 1+ α
ΔE = Eproducts – Ereactants = (16 − 10) kJ mol–1
0.693
175. λ = λ1 > λ2 = 6 kJ mol–1
t 1/ 2
As ΔE (or ΔH) is positive, the reaction is endothermic

Passage Based Questions

176. A 2B + C kt Ea  1 1 
t=0 a 0 0 log =  -  ; T=345 K .
k1 2.303R  300 T2 
t = 40 a–x 2x x
t=∞ 0 2a a Alternate solution:
(a – x) × 60 + 2x × 50 + x (− 80) = 26 0.693
t 1/2 at 27°C = =124.4
60a – 40 x = 26 (i) 5.57 × 10 –3
2a × 50 + a(−80) = 10 (ii) t1/2 at 127oC = 8.4
By (i) and (ii) Hence the temperature at which t1/2 = 31.14 min should lie
1 1 between 27oC to 127oC. In option (b) only the temperature is
a= ;x = in between 27oC to 127oC.
2 10
179. k' = Rate constant for overall reaction
2.303 1/ 2 k'= A'e − E'a/RT (i)
k 27°C = log
40 1 1 -E a1 /RT -E a 2 /RT
−
2 10 k1 =A1 e ; k 2 =A 2 e
-E a 3 -E a 5
k27°C = 5.57×10− 3 min− 1 (ii)
k 3 =A 3 e RT ; k 5 =A 5 e RT
k2 Ea 1 1 1/5
177. log =  −  2k 2  k1 
k ′= As this is given for us
k 3  k 5 
k1 2.303R  T1 T2 

k2 27 × 103  1 1  1/5
log =  300 − 400  2A 2 e
-E a1 /RT
 A1 e -Ea1 /RT 
5.57 × 10 -3
2.303 × 8.314   = -E a 3 /RT  -E /RT 
A3e  A 5 e a5 
k2 1/ 5
log =1.175 2A 2 A11/ 5 e a 2
-E / RT
 e -Ea1 / RT 
5.57 × 10-3 =  -Ea / RT 
A 3 A1/1 5 e -Ea 2 / RT  e 5 
k2
=14.97
5.57 × 10-3 1/ 5
(− Ea + Ea )  − Ea Ea 
1/ 5
A A 
=2 2  1 ×e 2 3
×e 1 5
 (iii)
(k2)127 = 83.36 × 10–3 A3  A5  RT  RT 
0.693
(t 1 )127 = =8.4 min -E a′ 1/ 5
 −Ea + Ea 
k2 2A 2  A1 
2
A ′e RT
= e 2 3

A 3  A 5   RT 
0.693
178. (k) t =
31.1
10.42 Chapter 10

1/ 5
 e - Ea + Ea  Ea Ea
× 1 5
 (iv) − E 'a = − E a + E a − 1
+ 5

 RT  2 3
5 5
Ea Ea
On comparing both side, we get E a′ = E a − E a + 1
− 5 (vi)
1/ 5
2 3
5 5
2A 3  A1 
A′ = (v)
A 3  A 5 

Match the Column Type

182. Except zero order reactions, conc. vs time gives a tions, when the surface of the catalyst is partially cov-
curve. But for zero order reactions, a straight line is ered, the order is fractional. For second order reaction,
obtained. Unit of k for first order is time−1. For zero t vs
order reactions, the half life is directly proportional
to initial conc. of the reactant. In heterogeneous reac-  1 
 a − x  is a straight line.

Assertion-Reason Type
187. A (g) → Product (i.e., Ao /4), would be
Let initial concentration of A is Ao A /2
2.303
Time required to make concentration of Ao to Ao/2, t= log 0
k A0 / 4
2.303 A0
t= log 2.303
k A0 / 2 log2 t= (ii)
k
2.303 (i) and (ii) are same, which signifies that time required to
log2 t= (i)
k reduce successively the concentration of reactant by half (or
by a constant fraction) is always same.
Time required to make concentration of Ao/2 half again

Integer Type

188. Rate = k[NOBr2] [NO] R 20 [A]20

=
[NOBr2] = k. K[NO]2 [Br2] R 40 [A]40
Rate = k. K[NO]2 [Br2]
0.55 [A]20
Rate = k′ [NO]2 [Br2] =
0.055 [A]40
When the concentrations doubled,
Rate = k′ [2NO]2 [2Br2] = 8 k’ [NO]2 [Br2] Also, [A]20 = [A]o e−20k
Rate increase by 8 times. [A]40 = [A]o e−40k

189. t1/2 α [CH3CHO]1 − n, where n is the order of the reaction e −20K 0.55
=
e −40K 0.055
1– n
410  340  e20k = 10
=
820  170 
2.303
k= min -1
 340  20
410
Log = (1 − n) log 
820  170  t 1/ 2 =
0.693
6.06 ; 6 min
k
Log ½ = (1 − n) log 2
191. Since the specific reaction rate k is the rate when the reactant
n=2
concentration is unity
190. The ratio of the rate of a first order reaction at 20 min and 40 d[A]
min is given be k = 1 as =1
dt
 Chemical Kinetics 10.43

From (ii) and (iii) EB

In k B = In B −
d[A] RT
= k[A]m
dt kB EA − EB 10.46 × 1000
8 = 1 . (2)m = (2)3; m = 3 So, ln = = = 3.37
kA RT 3.73 × 8.314
27 = 1 × (3)m; m = 3.
kB 3.37
192. As ∆H is positive, therefore reaction is endothermic. The Or log = = 1.4633
k A 2.303
energy profile diagram for an endothermic reaction can be
shown as: kB
= 29
kA
100 1 10
60k A = In ; kA = In
70 60 7
29 10
k B = 29k A = In
60 7
100
k B t = In
30
 10 
In  
 3 60 (1 - 0.4771) 60 0.5229
t= ;t = = ×
Now when the product is converted back to reactant, the 29 10 29 (1 - 0.845) 29 0.155
In
energy of activation is x kJ/mole as shown in the above 60 7
figure.
= 7 min.
x = Ea(f) − ∆H = (77 – 72) = 5 kJ mol−1
193. For (A), rate = kA[A] 195. t1/2 α (a)1 – n
For I 425 α (350)1 – n (i)
0.693
(t 1/ 2 )A = For II 275 α (540)1 – n (ii)
kA
For III 941 α (158)1 – n (iii)
For (B), rate = kB[B]2
1-n
425  350 
1 By equations (i) and (ii), =
(t 1/ 2 )B =
a ⋅ kB
, where a is the conc. of [B] at the start of 275  540 

reaction 425 350

Taking log, log =(1 − n) log
Since half lives are same 275 540
n=2
0.693 1
=
kA a ⋅ kB 196. (a) 1st order reaction
(b) Zero order reaction
kA (c) Incorrect plot of t1/2 vs. concentration.
=0.693a
kB (d) Explosive reaction
Since initial concentration of (A) is n times that of (B). 197. Let the order of reaction w.r.t. sugar be x and w.r.t. H+ be y.
[A] = na R = k[Sugar]x [H+]y
rA kA na rA Since, t1/2 remains constant for any concentration of sugar at
= × , given =1.386 a given pH, the order w.r.t. sugar will be 1.
rB kB a 2 rB
R = k[Sugar] [H+]y
na R = k’[Sugar] where k’ = k[H+]y
1.386= 0.693 a ×
a2 This is an example of pseudo 1st order reaction.
1.386 At pH = 5, t1/2 = 500 min and at pH = 4, t1/2 = 50 min.
n= =2
0.693 0.693
= k(10-5 )y (i)
EA 500
194. In k A = In A -
RT
10.44 Chapter 10

0.693 Initial conc. x 1.5 x 0 0

= k(10-4 )y (ii) At equil. x–y 1.5 x – 2y 2y y
50
Given : x – y = 1.5x – 2y; y = 0.5x.
Dividing (i) and (ii)
Thus, at equilib. [A] = 0.5x [B] = 0.5x [C] = x[D]
1 y
= (10 −1 ) y =1 = 0.5x
10
(x 2 )(0.5)
Order of reaction w.r.t. H+ = 1 kc = K p =
(0.5x)(0.5x)2
198. A (g) + 2B(g) ⇌ 2C(g) + D(g) =4

Previous Year’s Questions

203. Rate becomes xy times if concentration is made x times of a 207. 2A + B C
reactant giving yth order reaction. Rate = k [A][B]
Rate = [A]n [B]m It represents a second-order reaction.
Concentration of A is doubled, so x = 2, 208. For endothermic reaction, ∆H = + ve
y = n and rate becomes = 2n times ∆H = Ef – Eb, it means Eb < Ef
Concentration of is halved, so x = ½ and 2.303
_____ 0.29
4 ____
__
29. t1/4 = k
log 3 = k
y = m and rate becomes = (½)m times
Net rate becomes = (2)n (½)m times 210. Generally, molecularity of simple reactions is equal to the
= –(2)n – m times. sum of the number of molecules of reactants involved in the
balanced stoichiometric equation. So a reaction involving
204. (dx/dt) = k [NO]2 [O2]
two different reactants can never be unimolecular.
= k (nNO/V)2 (nO2/V)
211. r = k[NO][NOBr2]
dx
__ __
k
dt
= V3 (nNO)2 (nO2) [NOBr ]2
kc = [NO][Br2 ]
__ k (nNO)2 (nO2)
dx ___________ 2

dt
= (v/2)3 r = k [NO]2 [Br2] × kc = k [NO]2[Br2]
= 8 (dx/dt) Thus,order with respect to NO is 2.
206. Order 1 212. r1 = k[CO]2
Concentration changes from 0.8 Μ to 0.4 Μ (50%) in 15 r2 = k[2CO]2
minutes, this half-life is 15 minutes = T50 r2/r1 = 4
A change from 0.1 Μ to 0.025 Μ is 75% and for a first-order 213. Ε is activation energy.
reaction
If Ea + ER = Ethreshold energy. only then, the molecule may react.
T75 = 2 × T50 = 2 × 15 = 30 minutes
214. ΔΗ (Reaction) = Ef – Er
T50 = 15 minutes
= 80 – 100 = –20
2.303log2
________
k= T50 215. 2A + B Product
2.303 log 2 When concentration of B is doubled, the half-life did not
________
= 15 change, hence reaction is of first-order w.r.t. B. When con-
α = 0.1M centration of A is doubled, reaction rate is doubled, hence
reactions is of first-order w.r.t. A. So, over all order of
(α – x) = 0.025 M
reaction is 1 + 1 = 2
For first order
Therefore, unit of rate constant L mol–1 s–1.
2.303
_____ α
____
k= t log α – x 216. ½A 2B
2d [A]
_____ d [B]
1 ____
__
2.303 log 2 _____
________ 2.303 0.1
_____ – dt
= + 2 dt
15
= t log 0.025
d [A]
____ d [B]
1 ____
__
2.303
_____ – dt = 4 dt
= t log 4
2 × 2.303 log 2
2.303 log 2 ___________
________
= 0.6932
15 t 217. As λ =
t = 30 minutes. t1
2
 Chemical Kinetics 10.45

0.6932 221. 0.1 

20
→ 0.05 
→ 0.025 20

= min −1
6.93
t 1 = 20 min
2.303 [A 0 ] 2
As t = log
λ [A]
0.693
K=
2.303 × 6.93 100 20
So t = log
0.6932 1 r = K[A]
= 46.06 minutes. 0.693
= × 0.01
1 20
218. t1/2 for a nth order reaction is given by t1/ 2 α n −1
[A ]
0
= 3.465 × 10–4 M/min
t1/2 for a zero order reaction is given as t1/2 α [A0] 222. As

2M 1hr 1M 1/2hr 0.5M 1/4hr 0.25M k2 E a ( T2 − T1 )

log =
219. According to mechanism 1 the rate law expression is k2 2.303 ( T2 − T1 )
Rate = k[Cl2] [H2S]
E a × 10
According to mechanism (2) log 2 =
H2S  H+ + HS– (fast) (i) 2.303(8.314)(300)(310)
Cl2 + HS– 2Cl– + H+ + S (slow) (ii) on solving
Rate = k[Cl2] [HS–] Ea = 53.42 kJ/mole
Ea = 53.6 kJ/mole
 H +   HS- 
From (i), K=
[ H S] 2

K [ H 2 S]
Or [HS–] =
 H + 
Substituting this value in rate equation.

[H S] = K [Cl ].[H S]
Rate K [Cl 2 ] K
2 2 2

 H +   H + 
220. Rate = 2h = 25
= 32 times