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Chemical Kinetics

Contents
Topic

Page No.

Theory

01 - 06

Exercise - 1

07 - 24

Exercise - 2

25 - 33

Exercise - 3

34 - 38

Exercise - 4

39 - 41

Answer Key

42 - 43

Syllabus
Chemical Kinetics :
Rates of chemical reactions; Order of reactions; Rate constant; First order reactions; Temperature
dependence of rate constant (Arrhenius equation).

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CHEMICAL KINETICS
Rate/Velocity of chemical reaction :
The rate of change of concentration with time of different chemical species taking part in a chemical reaction is
known as rate of reaction of that species.
c
mol / lit.
Rate =
=
= mol lit1 time1 = mol dm3 time1
t
sec
Rate is always defined in such a manner so that it is always a positive quantity.

Types of Rates of chemical reaction :


For a reaction R P
Average rate =

Total change in concentrat ion


c
[R]
[P]
=
=

=
Total time taken
t
t
t

Instantaneous rate : rate of reaction at a particular instant.


c
dc
d [R]
d [P]
Rinstantaneous = tlim
=
=
=
0
dt
dt
dt
t

Relation between reaction rates of different species involved in a reaction :


For the reaction : N2 + 3H2 2NH3
1d [H2 ]
d [N2 ]
1 d [NH3 ]
Rate of reaction =
= 3 dt =
dt
2 dt

Order of reaction :
Let there be a reaction m1A + m2B products.
Now, if on the basis of experiment, we find that
R [A]P [B]q
Where p may or may not be equal to m1 and similarly q may or may not be equal to m2.
p is order of reaction with respect to reactant A and q is order of reaction with respect to reactant B and
(p + q) is overall order of the reaction.

Integrated rate laws :


Zero order reactions :
For a zero order reaction
General rate law is, Rate = k [conc.] = constant
If C0 is the initial concentration of a reactant and Ct is the
concentration at time t then
Rate = k =

C0 Ct
' t'

or

kt = C0 Ct

or Ct = C0 kt

Unit of K is same as that of Rate = mol lit1 sec1.

First Order Reactions :


k=

C0
2.303
log C
t
t

Half life time (t1/2)


t1/2 =

2.303 log 2
ln2
0.693
=
=
k
k
k

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CHEMICAL KINETICS # 1

Second order reaction :


1
1

Ct
C 0 = kt

Pseudo first order reaction :


A second order (or of higher order) reactions can be converted into a first order reaction if the other reactant is
taken in large excess. Such first order reactions are known as pseudo first order reactions.
For A + B Products
[Rate = K [A]1 [B]1
2.303

b(a x )

k = t (a b) log a (b x )
Table : Characteristics of Zero, First, Second and nth Order Reactions of the Type A Products
Zero Order

Differential Rate law

First-Order

[ A ]
= k[A]
t

(Integrated Rate law) [A]t = [A]0 kt

[ A ]
= k[A]
t

In [A]t = kt + In [A]0

nth order

Second-Order

[ A ]
= k[A]2
t

1
1
=
kt
+
[A]t
[ A ]0

[ A ]
k [ A ]n
t
1

(A t )

n1

1
( A 0 )n 1

(n 1) kt

Linear graph

Half-life

[A]t v/s t

t1/2 =

In [A] v/s t

[ A ]0
2k

t1/2 =

(depends on [A]0)

0.693
k

(independent of [A]0)

1
v/s t
[A]

( A t )n1

1
t1/2 = k[ A ]
0

t 1/ 2

v/s

1
( A 0 )n1

(depends on [A]0)

Methods to determine order of a reaction :


By comparison of different initial rates of a reaction by varying the concentration
of one of the reactants while others are kept constant
r = k [A]a [B]b [C]c

if

[B] = constant
[C] = constant

then for two different initial concentrations of A we have

r01 = k [A0]1a

r02 = k [A0]2a
r01

r02

[A ]
0 1
[ A 0 ]2

Method of half lives :


The half lives of each order is unique so by comparing half lives we can determine order
for nth order reaction

t1/2

t1 / 2
t1' / 2

1
[R0 ]n1

(R '0 )n1
(R 0 )n1

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CHEMICAL KINETICS # 2

Methods to monitor the progress of the reaction :


Pressure measurement :
Progress of gaseous reaction can be monitored by measuring total pressure at a fixed volume & temperature.
Let there is a 1st order reaction
A(g)

k=

nB(g)

P0 (n 1)
2.303
log nP P
t
0
t

Final total pressure after infinite time = Pf = nP0


Formula is not applicable when n = 1, the value of n can be fractional also.
Do not remember the formula but derive it for each question.

By titration method :
By measuring the volume of titrating agent we can monitor amount of reactant remaining or amount of product
formed at any time. It is the titre value . Here the milliequivalent or millimoles are calculated using valence
factors.
V0 = vol. of titrant used at t = 0
Vt = vol. of titrant used at t
V = vol. of titrant used at t =
k=

[this is exclusively for HCl.]

V V0
2.303
log V V
t

Optical rotation measurement :


It is used for optically active sample. It is applicable if there is at least one optically active species involved
in chemical reaction.
where are r0, rt, r are angle of optical rotation at time
K=

t = 0, t = t and t =

Y Y0
2.303
log
t
r rt

Effect of temperature on rate of reaction :


In early days the effect of temperature on reaction rate was expressed in terms of temperature coefficient
which was defined as the ratio of rate of reaction at two different temperature differing by 10C (usually these
temperatures were taken as 25C and 35C)
T.C. =

K t 10
2 to 3 ( for most of the reactions)
Kt

Arrhenius theory of reaction rate :

Enthalpy (H)
HR

Ea1

Ea2

Threshold enthalpy
or energy

Reactants
H = Hp HR = Ea1 Ea2

HP

HR = Summation of enthalpies of reactants


HP = Summation of enthalpies of reactants
H = Enthalpy change during the reaction
Ea1 = Energy of activation of the forward reaction
Ea2 = Energy of activation of the backward reaction

Products

Progress of reaction (or reaction coordinate)

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CHEMICAL KINETICS # 3

T2

Fraction of
molecule

T2 > T1

T1
Ea

e E a / RT represents fraction of molecules K.E. having energy greater Ea

rate e E a / RT
dependence of rate on temperature is due to dependence of k on temperature.

k e Ea / RT
k Ae Ea / RT

[Arrhenius equation]

General characteristics of catalyst :


P.E.

A catalyst drives the reaction through a low energy path and


hence Ea is less. That is, the function of the catalyst is to
lower down the activation energy.
Ea = Energy of activation in absence of catalyst.
Ea = Energy of activation in presence of catalyst.
Ea Ea = lowering of activation energy by catalyst.

Ea
E'a

HR
HP

Products

Reaction Coordinate

Molecularity and Order :


The number of molecules that react in an elementary step is the molecularity of the elementary reaction.
Molecularity is defined only for the elementary reactions and not for complex reactions. No elementary reactions
involving more than three molecules are known, because of very low probability of near-simultaneous collision of
more than three molecules.
The rate law for the elementary reaction
aA + bB products

rate = k[A]a[B]b, where a + b = 1, 2 or 3.

For an elementary reaction, the orders in the rate law equal the coefficients of the reactants.

Mechanism of a reaction :
Reactions can be divided into
Elementary / simple / single step
Complex / multi-step
ELEMENTARY REACTION :
These reaction take place in single step without formation of any intermediate
T.S.

Ep

P.E.
Er
Reaction coordinates

For elementary reaction we can define molecularity of the reaction which is equal to no of molecules which
make transition state or activated complex because of collisions in proper orientation and with sufficient energy

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CHEMICAL KINETICS # 4

COMPLEX REACTION :
Reaction which proceed in more than two steps. or having some mechanism. ( sequence of elementary reaction
in which any complex reaction procceds)
T.S.

intermediate

E
Reaction coordinates

For complex reaction each step of mechanism will be having its own molecularity but molecularity of net
complex reaction will not be defined.
CALCULATION OF RATE LAW/ ORDER

MECHANISM IN WHICH R.D.S. GIVEN


If R.D.S. involves only reactant, product or catalyst on reactant side
rate law of R.D.S. = rate law of reaction
RDS is having intermediate on reactant side
To calculate order, we have to specify [ intermediate] in expression of rate law in terms of conc. of [R], [P] or
catalyst with the help of same equilibrium step given in mechanism.
MECHANISMS IN WHICH RDS NOT SPECIFIED :
STEADY STATE APPROXIMATION :
At steady state

d [intermediate ]
=0
dt

COMPLICATIONS IN 1st ORDER REACTION


PARALLEL 1st ORDER REACTION OR COMPETING FIRST-ORDER REACTIONS

1
1
1
Teff = T1 + T2

k1
[B]
= k
[C]
2

Ea

(remember)

(remember)

E a1k 1 E a 2 k 2
k1 k 2

REVERSIBLE 1ST ORDER REACTION ( both forward and backward )


A
t=0
t=t
t = teq.

a
a x
a xeq.

B
0
x
xeq.

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CHEMICAL KINETICS # 5

kfa
x = k k
f
b

kf + kb =

1 e

( k f k b ) t

(remember)

x eq.
1

n x x
t
eq.

(remember)

SEQUENTIAL 1ST ORDER REACTION OR CONSECUTIVE FIRST-ORDER REACTIONS


k

t=0
t

1
2

A
B
C
a
0
0
ax
y
z

k 1a
y = k k { e k1t e k 2 t }
2
1

all first order equation

(remember)

k1
1
tmax. = k k n k
1
2
2

CASE-

(remember)

k1 >> k2
k

CASE :

k2 >> k1

Conc
[C]

[B]

[A]

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CHEMICAL KINETICS # 6

PART - I : OBJECTIVE QUESTIONS


*Marked Questions are having more than one correct option.
Section (A) : Rate of Reaction
A-1.

For a hypothetical reaction A L, the rate expression is dC A


rate =
dt
(A) Negative sign represent that rate is negative
(B) Negative sign indicates to the decrease in the concentrations of reactant
(C) Negative sign indicates the attractive forces between reactants
(D) None of the above is correct

A-2.

xA + yB zC. If
(A) 1,1, 1

A-3.

d[C]
d[B]
d[ A ]
=
= 1.5
= then x,y and z are :
dt
dt
dt
(B) 3, 2, 3
(C) 3, 3, 2

In the following reaction :


d[ A ]

(D) 2, 2, 3

xA yB
d[B]

log dt = log dt + 0.3

where ve sign indicates rate of disappearance of the reactant. Thus, x : y is :


(A) 1 : 2
(B) 2 : 1
(C) 3 : 1
(D) 3 : 10
A-4.

In the formation of sulphur trioxide by the contact process,


2SO2 (g) + O2 (g) 2SO3 (g)
d(O 2 )
The rate of reaction is expressed as
= 2.5 x 104 mol L-1 sec-1
dt
The rate of disappearance of (SO2) will be (A) 5.0 x 104 mol L1 s1
(B) 2.25 x 104 mol L1 s1
4
1
1
(C) 3.75 x 10
mol L s
(D) 50.0 x 104 mol L1 s1

A-5.

Rate of formation of SO3 in the following reaction 2SO2 + O2 2SO3 is 100 g min1. Hence rate of disappearance
of O2 is :
(A) 50 g min-1
(B) 40 g min1
(C) 200 g min1
(D) 20 g min1

A-6.

A reaction follows the given concentration (M)time graph. The rate for this reaction at 20 seconds will be:
0.5
0.4
0.3
0.2
0.1
0

20 40 60 80 100
Time/second

(A) 4 103 M s1
A-7.

(B) 8 102 M s1

(C) 2 102 M s1

(D) 7 103 M s1

For the reaction : N2 + 3H2 2NH3. If the rate of disappearance of hydrogen is 1.8 103. What is the
rate of formation of ammonia. (mole per litre per sec.)
(A) 1.8 103
(B) 1.2 103
(C) 2.7 103
(D) 0.9 103

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CHEMICAL KINETICS # 7

A-8.

The rate of a reaction is expressed in different ways as follows ;


+ 1/2(d[C]/dt) = 1/3 (d[D]/dt) = + 1/4 (d[A]/dt) = (d[B]/dt) The reaction is :
(A) 4 A + B 2C + 3D

(B) B + 3D 4A + 2C

(C) 4A + 2B 2C + 3D

(D) B + (1/2) D 4A + 3

A-9.

ln the reaction; A + 2B 3C + D, which of the following expression does not describe changes in the
concentration of various species as a function of time :
(A) {d [C] / dt} = {3d [A] / dt}
(B) {3d [D] / dt} = {d [C] / dt}
(C) {3d [B] / dt} = {2d [C] / dt}
(D) {2d [B] / dt} = {d [A] / dt}

A-10.

For a chemical reaction 2X + Y Z, the rate of appearance of Z is 0.05 mol L1 per min. The rate of
disappearance of X will be (A) 0.05 mol L1 per hour
(B) 0.05 mol L1 per min
1
(C) 0.1 mol L
per min
(D) 0.25 mol L1 per min

Section (B) : Rate Law


B-1.

B-2.

B-3.

What is the order of a reaction whose


rate = KCA3/2 CB1/2 ?
(A) 2
(B)1

(C) 1/2

(D) 3/2

The rate of certain hypothetical reaction A + B + C products, is given, by r =


[C]1/4. The order of reaction is given by :
(A) 1
(B) 1/2

(C) 2

The rate constant of nth order has units :


(A) Litre1n mol1-n sec1

(B) Mol1n litre1-n sec

(C) Mol1 n litre n sec1

dA
= K [A] [B]1/3
dt

(D) 13/12

(D) Mole1n litren-1 sec1

B-4.

The rate constant of reaction changes when :


(A) Volume is changed
(B) Concentrations of the reactants are changed
(C) Temperature is changed
(D) Pressure is changed

B-5.

For which of the following, the units of rate constant and rate of the reaction are same (A) First order reaction
(B) Second order reaction
(C) Third order reaction
(D) Zero order reaction

B-6.

For a chemical reaction, 2A + 2B C + D, the order of reaction is one with respect to A and one with
respect to B. The initial rate of the reaction is 4 102 mol L1 s1. When 50% of the reactants are converted
into products, the rate of the reaction would become(A) 2 102 mol L1s1
(B) 1 102 mol L1s1
2
1
1
(C) 4 10 mol L s
(D) 2 101 mol L1 s1

B-7.

For a gaseous reaction the rate equation is v = k[A][B]. If the volume of the gaseous system is suddenly
reduced to 1/3 of initial volume. The rate would become
(A) 1/9 times
(B) 9 times
(C) 1/6 times
(D) 6 times

B-8.

aA + bB Product, dx/dt = k [A]a [B]b . If concentration of A is doubled, rate is four times. If concentration
of B is made four times, rate is doubled. What is relation between rate of disappearance of A and that of B ?
(A) {d [A] / dt} = {d [B] / dt}
(B) {d [A] / dt} = {4 d [B] / dt}
(C) {4 d [A] / dt} = {d [B]/ dt}
(D) None of these

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CHEMICAL KINETICS # 8

B-9.

For the reaction, 2NO(g) + 2H2(g) N2(g) + 2H2O(g) the rate expression can be written in the following
ways :
{d [N2] / dt} = k1 [NO][H2] ; {d[H2O] / dt} = k[NO][H2] ; { d[NO] / dt} = k1 [NO] [H2] ; {d[H2] / dt} = k1 [NO][H2]
The relationship between k, k1 , k1 and k1. is :
(A) k = k1 = k1 = k1
(B) k = 2k1 = k1 = k1
(C) k = 2k1 = k1 = k1
(D) k = k1 = k1 = 2 k1

B-10.

For rate constant is numerically the same for three reactions of first, second and third order respectively.
Which of the following is correct :
(A) if [A] = 1 then r1 = r2 = r3
(B) if [A] < 1 then r1 > r2 > r3
(C) if [A] > 1 then r3 > r2 > r1
(D) All

B-11.

In acidic medium the rate of reaction between (BrO3) and Br ions is given by the expression.
[d (BrO3) /dt] = K [BrO3 ] [Br] [H+]2 It means :
(A) Rate constant of overall reaction is 4 sec1
(B) Rate of reaction is independent of the concentration of acid
(C) The changes in pH of the solution will not affect the rate
(D) Doubling the concentration of H+ ions will increase the reaction rate by 4 times.

B-12.

For the irreversible process, A + B products, the rate is firstorder w.r.t. A and secondorder w.r.t. B. If 1.0
mol each of A and B introduced into a 1.0 L vessel, and the initial rate was 1.0 102 mol L1 s1 , rate when half
reactants have been turned into products is :
(A) 1.25 103 mol L1 s1
(B) 1.0 102 mol L1 s1
(C) 2.50 103 mol L1 s1
(D) 2.0 102 mol L1 s1

Section (C) : The integrated rate laws


C-1.

A first order reaction follows the expressions


(A) Cte

k 1t

= C0

(B) Ct = C0 e k 1t

(C) ln

C0
= k 1t
Ct

(D) ln

Ct
= k 1t
C0

C-2.

Which of following statement is false


(A) A fast reaction has a larger rate constant and short half-life
(B) For a first order reaction, successive half lives are equal
(C) For a first order reaction, the half-life is independent of concentration
(D) The half life of a reaction is half the time required for the reaction to go to completion

C-3.

Half life period of a zero order reaction is


(A) Independent of concentration
(B) Directly proportional to initial concentration
(C) Inversely proportional to concentration
(D) Directly proportional to the square of the concentration

C-4.

Wrong data for the first order reaction is


(A) t0.5 =100s, t0.75 = 200s
(C) Both the above

(B) t0.75 = 32 min t0.5 = 16min


(D) t0.5 = 100s, t0.75 = 150s

C-5.

What is the half life of a radioactive substance if 75% of any given amount of the substance disintegrates
in 60 minutes
(A) 2 Hours
(B) 30 Minutes
(C) 45 Minutes
(D) 20 Minutes

C-6.

For an elementary reaction X (g) Y (g) + Z (g) the half life periods is 10 min. In what period of time
would the concentration of X be reduced to 10% of original concentration (A) 20 Min.
(B) 33 Min
(C) 15 Min
(D) 25 Min

C-7.

99% of a first order reaction was completed in 32 min. When will 99.9% of the reaction complete
(A) 50 Min
(B) 46 Min
(C) 49 Min
(D) 48 Min
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CHEMICAL KINETICS # 9

C-8.

In the presence of an acid, the initial concentration of cane sugar was reduced from 0.20 to 0.10 molar
in 5 hours and from 0.2 to 0.05 molar in 10 hours. The reaction is of
(A) Zero order
(B) First order
(C) Second order
(D) Third order

C-9.

For a second order reaction, if the conc. of a reactant decreases from 0.08M to 0.04M in ten minutes,
what would be the time taken for the conc. to decreases to 0.01M
(A) 20 minutes
(B) 30 minutes
(C) 50 minutes
(D) 70 minutes

C-10.

The rate constant for a second order reaction 8.0 104 litre mol1min1. How long will it take a 0.5M
solution to be reduced to 0.25M in reactant
(A) 8.665 102 min
(B) 8.0 104 min
(C) 2.50 103 min
(D) 4.0 104 min

C-11.

A radioactive isotope decomposes according to the first order with half life period of 15 hrs. 80% of the
sample will decompose in (A) 15 0.8 hr.
(B) 15 (log 8) hr.
(C) 15 (log5 / log2) hr. (or 34.83) hr.
(D) 15 10/ 8 hr.

C-12.

Radioactive decay follows (A) Zero order kinetics


(C) First order kinetics

C-13.

(B) Second order kinetics


(D) Pseudo first order kinetics

The t0.5 for the first order reaction,


PCI5(g) PCI3(g) + Cl2(g)
is 20 min. The time in which the conc. of PCI5 reduces to 25% of the initial conc. is close to(A) 22 min
(B) 40 min
(C) 90 min
(D) 50 min

C-14.

The rate constant of reaction 2 A + B C is 2.57 105 It mole1 sec1 after 10 sec. 2.65 105 It.
mole1 sec1 after 20 sec. and 2.55 105 It. mole1 sec1 after 30 sec. The order of the reaction is:
(A) 0
(B) 1
(C) 2
(D) 3

C-15.

For a first order reaction, the plot of log C against t (logC vs 't') gives a straight tine with slope equal to :
(A) (k / 2.303)
(B) ( k / 2.303)
(C) (ln k / 2.303)
(D) k.

C-16.

In a certain reaction, 10% of the reactant decomposes in one hour, 20 % in two hours, 30% in three hours and
so on the dimensions of the rate constant is :
(A) hour1
(B) mole litre1 sec1
(C) litre mole1 sec1
(D) mole sec1

C-17.

In presence of HCl, sucrose gets hydrolysed into glucose and fructose. The concentration of sucrose was found
to reduce from 0.4 M to 0.2 M in 1 hour and to 0.1 M in total of 2 hours. The order of the reaction is :
(A) zero
(B) one
(C) two
(D) None of these

C-18.

In a first order reaction the reacting substance has half-life period of ten minutes. What fraction of the substance
will be left after an hour the reaction has occurred ?
(A) 1/6 of initial concentration
(B) 1/64 of initial concentration
(C) 1/12 of initial concentration
(D) 1/32 of initial concentration

C-19.

K1
K2
In the following first order reactions (A)
Product, (B)
Product, the ratio k1 /k2 if 90% of (A) has

been reacted in time 't' while 99% of(B) has been reacted in time 2t is :
(A) 1
(B) 2
(C) 1/2
C-20.

(D) None of these

Two substances A (t1/2 = 5 min) and B (t1/2 = 15 min) are taken in such a way that initially [A] = 4[B]. The time
after which both the concentration will be equal is : (Assume that reaction is first order)
(A) 5 min
(B) 15 min
(C) 20 min
(D) concentration can never be equal

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CHEMICAL KINETICS # 10

C-21.

If a I-order reaction is completed to the extent of 60% and 20% in time intervals, t1 and t2, what is the ratio,
t1 : t2 ?
(A) 6.32
(B) 5.58
(C) 4.11
(D) 8.33

C-22.

For a reaction A Products, the concentration of reactant are C0 , aC0 , a2C0, a3C0 ........... after time interval
0, t, 2t ........where 'a' is constant. Then :
(A) reaction is of 1st order and K = (1/1) ln a
(B) reaction is of 2nd order and K = (1/tC0)(1a)/a
(C) reaction is of 1st order and K =

C-23.

(D) reaction is of zero order and K =

1 1
ln
t a

The rate constant for the reaction A B is 2 104 It. mol1 min1. The concentration of A at which rate of the
reaction is (1/12) 105 M sec1 is :
(B) (1/20) 5 / 3 M

(A) 0.25 M

C-24.

1
1
ln a
t

(C) 0.5 M

(D) None of these

Graph between concentration of the product and time of the reaction A B is of the type

Hence graph

between d[A]/dt and time will be of the type :


(d[A]/dt)

(A)

(B)

(C)

(D)

Time

C-25.

A graph plotted between log t50% vs. log concentration is a straight line. What conclusion can you draw from this
graph.

(A) n = 1 ; t1/2 a
(C) n = 1 ; t1/2 = (0.693 / k)

(B) n = 2, t1/2 1/a


(D) None of these

C-26.

What will be the order of reaction and rate constant for a chemical change having log t50% vs log concentration
of (A) curves as :
(A) 0, 1/2
(B) 1, 1
(C) 2, 2
(D) 3, 1

C-27.

A drop of solution (volume 0.05 mL) contains 3.0 106 moles of H+. If the rate constant of disappearance of H+
is 1.0 107 mole litre1 sec1. How long would it take for H+ in drop to disappear :
(A) 6 108 sec
(B) 6 107 sec
(C) 6 109 sec
(D) 6 1010 sec

Section (D) : Methods to determine The rate law


D-1.

When concentration of reactant in reaction


A B is increased by 8 times, the rate increase only 2 times. The order of the reaction would be (A) 2
(B) 1/3
(C) 4
(D) 1/2

D-2.

The data for the reaction A + B C is


Exp.
[A]0
[B]0

initial rate

1
2
3
4

0.10
0.80
0.10
0.80

(A) r = k [B]3

0.012
0.024
0.012
0.024

0.035
0.035
0.070
0.070
(B) r = k [A]3

(C) r = k [A] [B]4

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(D) r = k [A]2 [B]2 .

CHEMICAL KINETICS # 11

D-3.

A + B Product,

dx
=k [A]a [B]b
dt

dx
= k, then order is :
dt

If

(A) 4

(B) 2

(C) 1

(D) 0

D-4.

One litre of 2M acetic acid and one litre of 3M ethyl alcohol were mixed. The esterification takes place
according to the reaction:
CH3COOH + C2H5OH CH3COOC2H5 + H2O
If each solution is diluted by one litre water the rate would become
(A) 4 times
(B) 2 times
(C) 0.5 times
(D) 0.25 times

D-5.

In the reaction : A + 2B + C D + 2E
Ther rate of reaction remains unchanged if the conc. of B is doubled and that of A and C is kept constant.
What is the order with respect to B.
(A) 0
(B) 1/2
(C) 1
(D) 3

D-6.

The following data pertain to reaction between A and B :


S.No.
[A]
[B]
Rate
mol.l1
mol.l1
mol.l1sec1
I
1 102 2 102 2 104
II
2 102 2 102 4 104
III
2 102 4 102 8 104
Which of the following inference(s) can be drawn from the above data
(a) Rate constant of the reaction 104
(b) Rate law of the reaction is k[A][B]
(c) Rate of reaction increases four times on doubling the concentration of both the reactant,
Select the correct answer
codes :
(A) a,b and c
(B) a and b
(C) b and c
(D) c alone

D-7.

Using the data given below the order and rate constant for the reaction : CH3CHO(g) CH4(g) + CO(g) would
be
Experiment no.
Initial conc.
Initial rate
[mol/]
[mol.lit1sec 1]
I
0.10
0.020
II
0.20
0.080
III
0.30
0.180
IV
0.40
0.320
Answer is
(A) 2,[k = 2.0 /mol sec]
(B) 0,[k = 2.0 mol/ sec]
(C) 2,[k = 1.5 /mol sec]
(D) 1,[k = 1.5 sec1]

D-8.

For the reaction 2A + 3B products, A is in excess and on changing the concentration of B from 0.1 M to
0.4 M, rate becomes doubled, Thus, rate law is :
(A)

D-9.

dx
= k[A]2 [B]2
dt

(B)

dx
= k[A] [B]
dt

For the reaction A Products,


Time
[A]

0
20 mol

5 min
18 mol

(C)

dx
= k[A]0 [B]2
dt

(D)

dx
= k[B]1/2
dt

d [A]
= k and at different time interval, [A] values are :
dt

10 min
16 mol

At 20 minute, rate will be :


(A) 12 mol /min
(B) 10 mol/min

15 min
14 mol

(C) 8 mol/min

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(D) 0.4 mol/min

CHEMICAL KINETICS # 12

D-10.

dx
dx
= k[A]2 . If log
is plotted against log [A], then graph is of the type :
dt
dt

A Product and

(A)

(B)

(C)

(D)

D-11.

If a is the initial concentration of reaction, then the half life period of a reaction of nth order is directly
propotional to (A) an
(B) an1
(C) a1n
(D) an+1

D-12.

The half-life period for a reaction at initial concentrations of 0.5 and 1.0 moles litre-1 are 200 sec and 100
sec respectively. The order of the reaction is (A) 0
(B) 1
(C) 2
(D) 3

D-13.

Consider a reaction A B + C. If the initial concentraton of A was reduced from


4 M to 2 M in 1 hour and from 2 M to 1 M in 0.5 hour, the order of the reaction is(A) One
(B) Zero
(C) Two
(D) Three

Section (E) : Methods to monitor the progress of reaction


E-1.

Consider the reaction 2A(g) 3B(g) + C(g). Starting with pure A initially, the total pressure doubled in 3 hrs.
The order of the reaction might possibly be
(A) zero
(B) first
(C) second
(D) unpredictable from this data

E-2.

Formation of NO2F from NO2 and F2 as per the reaction 2NO2(g) + F2(g) 2NO2F(g) is a second order
reaction, first order with respect to NO2 and first order with respect to F2. If NO2 and F2 are present in a closed
vessel in ratio 2 :1 maintained at a constant temperature with an initial total pressure of 3 atm, what will be the
total pressure in the vessel after the reaction is complete?
(A) 1atm

(B) 2 atm

(C) 2.5 atm

(D) 3 atm

E-3.

In a gaseous state reaction, A2 (g) B(g) + (1/2)C (g), The increase in pressure from 100 mm to 120 mm
is notices in 5 minutes. The rate of disapearance of A2 in mm min1 is :
(A) 4
(B) 8
(C) 16
(D) 2

E-4.

The decomposition of a gaseous substance (A) to yield gaseous products (B), (C) follows First order kinetics.
If initially only (A) is present and 10 minutes after the start of the reaction the pressure of (A) is 200 mm Hg and
that of over all mixture is 300 mm Hg, then the rate constant for 2A B + 3 C is :
(A) (1/1200) ln 1.25 sec1
(B) (2.303 /10) log 1.5 min1
1
(C) (1/10) ln 1.25 sec
(D) None of these

E-5.

In the reaction NH4NO2 (aq.) N2 (g) + 2 H2O (l) the volume of N2 after 20 min and after a long time is 40 ml and
70 ml respectively. The value of rate constant is :
(A) (1/20) In (7/4) min1
(B) (2.303 /1200) log (7/3) sec1
1
(C) (1/20) log (7/3) min
(D) (2.303 / 20) log (11/7) min1

E-6.

/ Cu
N2Cl

Cl + N2 Half-life is independent of concentration of reactant. After 10 minutes

volume of N2 gas is 10 L and after complete reaction it is 50 L. Hence rate constant is:
(A) (2.303 /10) log 5 min1
(B) (2.303 /10) log 1.25 min1
1
(C) (2.303 /10) log 2 min
(D) (2.303 /10) log 4 min1

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CHEMICAL KINETICS # 13

Section(F) : Effect of Temperature


F-1.

The activation energies of the forward and backward reactions in the case of a chemical reaction are 30.5
and 45.4 KJ/mol respectively. The reaction is
(A) Exothermic
(B) Endothermic
(C) Neither exothermic nor endothermic
(D) Independent of temperature

F-2.

Chemical reaction occurs as a result of collisions between reacting molecules. Therefore, the reaction rate
is given by (A) Total number of collisions occurring in a unit volume per second
(B) Fraction of molecules which possess energy less than the threshold energy
(C) Total number of effective collisions
(D) None of the above

F-3.

The chemical reactions in which reactants require high amount of activation energy are generally (A) Slow
(B) Fast
(C) Instantaneous
(D) Spontaneous

F-4.

For a reaction for whi ch the activation energies of forward and reverse reactions are equal (A) H = 0
(B) S = 0
(C) The order is zero (D) There is no catalyst

F-5.

The activation energy of reaction is equal to(A) Threshold energy for the reaction
(B) Threshold energy + Energy of the reactants
(C) Threshold energy Energy of the reactants
(D) Threshold energy + Energy of the products

F-6.

Which of the following explains the increase of the reaction rate by catalyst (A) Catalyst decreases the rate of backward reaction so that the rate of forward reaction increases
(B) Catalyst provides extra energy to reacting molecules so that they may reduce effective collisions
(C) Catalyst provides an alternative path of lower activation energy to the reactants
(D) Catalyst increases the number of collisions between the reacting molecules.

F-7.

The activation energy of the reaction


A + B C + D + 38 k.cal is 20 k.cal, What would be the activation energy of the reaction,
C + D A + B
(A) 20 k.cal
(B) 20 k.cal
(C) 18 k.cal
(D) 58 k.cal

F-8.

Rate of which reactions increases with temperature :


(A) of any
(B) of exothermic reactions
(C) of endothermic
(D) of none.

F-9.

For a zero order reaction. Which of the following statement is false :


(A) the rate is independent of the temperature of the reaction.
(B) the rate is independent of the concentration of the reactants.
(C) the half life depends upon the concentration of the reactants.
(D) the rate constant has the unit mole It1 sec1.

F-10.

A large increase in the rate of a reaction for a rise in temperature is due to


(A) increase in the number of collisions
(B) the increase in the number of activated molecules
(C) The shortening of mean free path
(D) the lowering of activation energy

F-11.

The first order rate constant k is related to temp. as log k = 15.0 (106 /T) Which of the following pair of value is
correct ?
(A) A = 1015 and E = 1.9 104 KJ
(B) A = 1015 and E = 40 KJ
(C) A = 1015 and E = 40 KJ
(D) A = 1015 and E = 1.9 104 KJ.

F-12.

The decomposition of N2O into N2 & O2 in presence of gaseous argon follow second order kinetics with
k = (5.0 1011 L mol1 s1) e
(A) 5.0 x 1011 J

41570 K
T

(B) 41570 J

(K stands for Kelvin units). The energy of activation of the reaction is :


(C) 5000 J

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(D) 345612.98 J

CHEMICAL KINETICS # 14

F-13.

How much faster would a reaction proceed at 25C than at 0C if the activation energy is 65 kJ?
(A) 2 times
(B) 5 times
(C) 11 times
(D) 16 times

F-14.

The rate constant, the activation energy and the frequency factor of a chemical reaction at 25C are
3.0 104 s1, 104.4 KJ mol1 and 6.0 1014 s1 respectively. The value of the rate constant as T is :
(A) 2.0 1018 s1
(B) 6.0 1014 s1
(C) infinite
(D) 3.6 1030 s1

F-15.

For a given reaction, energy of activation for forward reaction (Eaf) is 80kJ.mol1. H = 40kJ.mol1 for the
reaction. A catalyst lowers Eaf to 20 kJ.mol1. The ratio of energy of activation for reverse reaction before and
after addition of catalyst is :
(A) 1.0
(B) 0.5
(C) 1.2
(D)2.0

Section (G) : Mechanism of reactions


G-1.

For the reaction H2 (g) + Br2 (g) 2HBr (g) the experiment data suggested that r = k[H2][Br2]1/2
The molecularity and order of the reaction are respectively :
(A) 2, 3/ 2
(B) 3/2 , 3/2
(C) Not defined, 3/2
(D) 1,1/2

G-2.

For the reaction NO2 + CO CO2 + NO the experimental rate expression is


molecules of CO involves in the slowest step will be (A) 1
(B) 2
(C) 3

G-3.

dc
= k[NO2]2 the number of
dt

(D) depends on mechanism

The reaction of hydrogen, and iodine monochloride is represented by the equation :


H2(g) + 2Cl(g)
2HCl(g) + 2(g)
This reaction is firstorder in H2(g) and also firstorder in Cl(g). Which of these proposed mechanism
can be consistent with the given information about this reaction ?
Mechanism : H2(g) + 2Cl(g)
2HCl(g) + 2(g)
Slow

Mechanism : H2(g) + Cl(g) HCl(g) + H(g)


fast
HI(g) + Cl(g) HCl(g) + I2(g)
(B) only
(C) both and

(A) only
G-4.

G-5.

The reaction, X + 2Y + Z N occurs by the following mechanism


(i)
X+Y
M
very rapid equilibrium
(ii)
M+ZP
slow
(iii)
O+YN
very fast
What is the rate law for this reaction
(A) Rate = k[Z]
(B) Rate = k[X] [Y]2 [Z] (C) Rate = [N]

(D) neither nor

(D) Rate = k[X] [Y] [Z]

In the Lindemann theory of unimolecular reactions, it is shown that the apparent rate constant for such a
reaction is kapp =

k1C
where C is the concentration of the reactant k1 and are constants. Calculate the
1 C

value of C for which kapp has 90% of its limiting value at C tending to infinitely large values, given = 9 x 105.
(A) 106 mole/litre
(B) 104 mol/litre
(C) 105 mole/litre
(D) 5 x 105 mol/litre
G-6.

G-7.

Trimolecular reactions are uncommon because


(A) the probability of three molecules colliding at an instant is very low.
(B) the probability of three molecules colliding at an instant is high.
(C) the probability of three molecules colliding at an instant is zero.
(D) the probability of many molecules colliding at an instant is high.
Select the correct statements :
(A) the molecularity of an elementary reaction indicates how many reactant molecules take part in the step.
(B) the rate law of an elementary reaction can be predicted by simply seeing the stoichiometry of reaction.
(C) the slowest elementary step in sequence of the reactions governs the overall rate of formation of product.
(D) a rate law is often derived from a proposed mechanism by imposing the steady state approximation or
assuming that there is a pre-equilibrium.
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CHEMICAL KINETICS # 15

Section (H) : Complications in first order reactions


H-1.

dx

For an elementary reaction, net rate is dt = k[A]2 k'[C] [B]2 then, select the correct statement :

(A)

d[C]
d[ A ]2 d [B]
=
=
is the relation among (B) 2A
dt
dt
dt

(C) both are correct


H-2.

2B + C is the required reaction

(D) none is correct

Consider the elementary reaction sequence shown in figure. Which of the following
equations are correct ?

H-3.

(A)

d[A]
= k1[A] + k4[D]
dt

(B)

d [ C]
= k2[B] k3[C]
dt

(C)

d [D]
= k4[D] + k3[D]
dt

(D) Nothing can be said about order of reactions in this problem

For an elementary reaction of reversible nature, net rate is :


dx

= k [A]2 [B]1 k [C], hence, given reaction is :


1
2
dt

(A) 2A +

H-4.

1
B

(B) 2A + B

(C) 2A

C + B1

(D) None of these

At a given temperature, k1 = k2 for the reaction


A+B
If

H-5.

C+D

dx
dt = k1 [A] [B] k2[C] [D] in which set of the concentration reaction ceases?

[A]

[B]

[C]

[D]

[A]

[B]

(A)

0.1 M

0.2 M

0.3 M

0.4 M

(B)

0.4 M

0.25 M 0.2 M

[C]

[D]
0.5 M

(C)

0.2 M

0.2 M

0.3 M

0.2 M

(D)

0.2 M

0.2 M

0.2 M

0.4 M

The substance undergoes first order decomposition. The decomposition follows two parallel first order reactions
as :

K1 = 1.26 104 sec1 and K2 = 3.8 105 sec1


The percentage distribution of B and C

H-6.

(A) 80% B and 20% C

(B) 76.83% B and 23.17%C

(C) 90% B and 10% C

(D) 60% B and 40% C

The rate constant for two parallel reactions were found reactions were found to be 1.0 102dm3 mol-1 s1 and
3.0 102 dm3 mol1 s1. If the corresponding energies of activation of the parallel reactions are 60.0 kJ mol1
and 70.0 kJ mol1 respectively, what is the apparent overall energy of activation ?
(A) 130.0 kJ mol1

(B) 67.5 kJ mol1

(C) 100.0 kJ mol1

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(D) 65.0 kJ mol1

CHEMICAL KINETICS # 16

PART - II : MISCELLANEOUS QUESTIONS


COMPREHENSION
Comprehension # 1
A(g) 2B(g) + C(g)
Initially at t = 0 gas A was present along with some amount of gas (C). At t = 0 mole fraction of gas C is
1/3. After some time t = t1, total pressure is half of the final total pressure at t = tx (a very long time). Assume this
decomposition is a first order, at a constant temperature. It is also given at t = tx, final total pressure is 35 bar.
1.

At t = t1 pressure of gas B is :
(A) 2.5 bar

2.

(B) 1.25 bar

(D) data is insufficient

Rate constant (k) = (log 64 log 49) s1. Value of t1 in seconds is :


(A) 2.15 s

3.

(C) 5.0 bar

(B) 1.5 s

(C) 2.3 s

(D) 1.15 s

(C) 1 : 3 : 5

(D) 1 : 3 : 5

Ratio of rate constant at t = 0 to t = t1 to t = tx is :


(A) 2 : 3 : 4

(B) 1 : 1 : 1

Comprehension # 2

4.

For the (Set-1) :


(A) if T1 > T2, k1 > k2 always

(B) if T1 > T2, k1 > k2 (for exothermic reaction)

(C) if T1 > T2, k1 < k2 (for endothermic reaction) (D) Ea1 Ea2
5.

For the (Set-1) :


(A) Ea1 > Ea2

if T1 > T2

(C) Ea1 = Ea2


6.

(B) Ea1 < Ea2

if T1 > T2

(D) Ea1 = 0.5 Ea2

Comparing set-I and II :


(A) k4 > k3 & k2 > k1 ,

if T2 > T1 (endothermic) (B) k4 < k3 & k2 > k1 ,

if T2 < T1 (endothermic)

(C) k4 > k3 & k2 > k1 ,

if T2 < T1 (exothermic) (D) k4 < k3 & k2 < k1,

if T2 > T1 (exothermic)

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CHEMICAL KINETICS # 17

Comprehension # 3
A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Let us consider a
reaction
A(g) B(g) + C(g)
At t = 0
a
0
0
At time t
ax
x
x
The rate of reaction is given by the expression

represented as k =

dx
= k(a x) and integrated rate equation for a given reaction is
dt

1 a
where a = initial concentration and (a x) = concentration of A after time t.
ln
t
ax

7.

Thermal decomposition of compound X is a first order reaction. If 75% of X is decomposed in 100 min. How long
will it take for 90% of the compound to decompose?
Given : log 2 = 0.30
(A) 190 min
(B) 176.66 min
(C) 166.66 min
(D) 156.66 min

8.

Consider a reaction A(g) 3B(g) + 2C(g) with rate constant 1.386 102 min1. Starting with
2 moles of A in 12.5 litre vessel initially, if reaction is allowed to takes place at constant pressure & at 298K then
find the concentration of B after 100 min.
(A) 0.04 M
(B) 0.36 M
(C) 0.09 M
(D) None of these

Comprehension # 4
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example, toluene can be
nitrated at the ortho, meta, or para positions, We shall consider the simplest case, that of two competing
irreversible first-order reactions :

k
k2 D
A 1 C and A

where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
d[A]

= k1[A] k2[A] = (k1 + k2) [A]


dt

[A] = [A]0 e (k1 k 2 )t .

d [C]
For C, we have
= k1[A] = k1[A]0 e (k1 k 2 )t . Multiplication by dt and integration from time 0
dt
k [A]
( k k ) t
(where [C]0 = 0) to an arbitary time t gives
[C] = 1 0 (1 e 1 2 )
k1 k 2
d [D]
gives
Similarly, integration of
dt

[D] =

k 2 [ A ]0
(1 e (k 1 k 2 )t )
k1 k 2

The sum of the rate constants k1 + k2 appears in the exponentials for both [C] and [D].
At any time we also have

9.

k1
[C]
= k
[D]
2

starting initially with only A Which of the following is correct at time t

(A) [A]0 = [A]t +[B]t + [C]t


(C) [A]0 = [A]t +

[C] t
[B] t
+
3
2

(B) [A]0 = [A]t + 2 [B]t + 3 [C]t


(D) [A]0 =

2
[A]t +[B]t + [C]t
3

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CHEMICAL KINETICS # 18

10.

[ X] t
starting with only 'X', ratio [ Y ] [ Z]
t
t

11.

(A) Independent of time

(B)

(C) Depends upon initial concentration of X

(D) [A]0 (ekt 1)

(e kt 1)

At high temperature acetic acid decomposes into CO2 & CH4 and simultaneously into CH2CO (ketene) and H2O
1

k1 3s
(i) CH3COOH
CH4 + CO2

k 2 4s
(ii) CH3COOH
CH2CO + H2O

What is the fraction of acetic acid reacting as per reaction (i) ?


(A)

12.

3
4

(B)

For A

3
7

(C)

4
7

(D) none of these

starting with pure A ratio of rate of production of B to C is

(A) Independent of time


(C) Depends upon initial concentration of A

(B) Independent of temperature


(D) Independent of mechanism of reaction

Comprehension # 5
For the given sequential reaction
k

2
1
A
B
C
the concentration of A, B & C at any time 't' is given by

[A]t =

[A]0 e k1t

[B]t =

k1[ A ]0
e k1t e k 2 t
( k 2 k1 )

[C]t = [A0] ( [A]t + [B]t )


The time at which concentration of B is maximum is
(A)

(B)

1
k
ln 1
k 2 k1 k 2

(C)

1
k
ln 1
k1 k 2 k 2

(D)

k2
k 2 k1

Select the correct option if k1 = 1000 s1 and k2 = 20 s1.

[B]t
[A]t

(B)

[C]t

Conc.

(A)

[C]t

conc.

[B] t

time

[A]t

time

(C)

[C]t

(D)
[B]t

time

Conc.

14.

k1
k 2 k1

Conc.

13.

[C]t
[B]t
[A] t

[A]t

time

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CHEMICAL KINETICS # 19

MATCH THE COLUMN


15.

16.

17.

The polarimeter readings in an experiment to measure the rate of inversion of cane suger (1st order reaction)
were as follows
time (min)
:
0
30

angle (degree) :
30
20
15
Then match the following. (Use : log 35 = 1.54, log 3 = 0.48, log 2 = 0.3)
Column - I

Column - II

(A)

The half life of the reaction

(p)

120 min.

(B)

The solution is optically inactive at

(q)

7.5

(C)

The equimolar mixture of the products

(r)

75.2 min.

(D)

The angle at half time

(s)

laevorotatory

Match the following :


Column - I

Column - II

(A)

A + B C + D
r = k1 [A] [B]

(p)

Unit of rate constant possess concentration


unit

(B)

A + B C + D
r = k2 [A] [B]

(q)

Rate constant for the reaction of both


the reactants are equal

(C)

A + B C + D
r = k3 [A] [B]

(r)

Rate of consumption of at least one of the


reactants is equal to rate of production of at
least one of the products

(D)

2A + B 2C + 3D
r = k3 [A] [B]

(s)

If both reactants are taken in stoichiometric


ratio, half life for both reactants are equal

For the reaction of type A(g) 2B(g)


Column-I contains four entries and column-II contains four entries. Entry of column-I are to be matched
with ONLY ONE ENTRY of column-II
Column - I

Column - II

(A)

d[ B]
d[A ]
vs
for first order
dt
dt

(p)

(B)

[A] vs t for first order

(q)

(C)

[B] vs t for first order

(r)

(D)

[A] vs t for zero order

(s)

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CHEMICAL KINETICS # 20

18.

Match the following :


Column-I

Column-II

(A)

If the activation energy is 65 kJ then how much time


faster a reaction proceed at 25C than at 0C

(p)

(B)

Rate constant of a first - order reaction is 0.0693 min1.


If we start with 20 mol L1, it is reduced to 2.5 mol L1
in how many minutes

(q)

Zero

(C)

Half - lives of first - order and zero order reactions


(r)
are same. Ratio of rates at the start of reaction is
how many times of 0.693 Assume initial concentration to
be same for the both.

11

(D)

The half-life periods are given ,


[A]0
(M)
0.0677
t1/2
(sec) 240
order of the reaction is

30

(s)
0.136
480

0.272
960

ASSERTION / REASON
Directions :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
19.

Statement-1
Statement-2

: A fractional order reaction must be a complex reaction.


: Fractional order of RDS equals to overall order of a complex reaction.

20.

Statement-1

: The time of completion of reactions of type A product (order <1) may be determined.

Statement-2

: Reactions with order 1 are either too slow or too fast and hence the time of completion can
not be determined.

21.

Statement-1
Statement-2

: Temperature coefficient of an one step reaction may be negative.


: The rate of reaction having negative order with respect to a reactant decreases with the
increase in concentration of the reactant.

22.

Statement-1
Statement-2

: The overall rate of a reversible reaction may decrease with the increase in temperature.
: When the activation energy of forward reaction is less than that of backward reaction, then the
increase in the rate of backward reaction is more than that of forward reaction on increasing
the temperature.

23.

Statement-1

: In a reversible endothermic reaction, Eact of forward reaction is higher than that of backward
reaction
: The threshold energy of forward reaction is more than that of backward reaction

Statement-2
24.

Statement-1
Statement-2

: A catalyst provides an alternative path to the reaction in which conversion ofreactants into
products takes place quickly
: The catalyst forms an activated complex of lower potential energy, with thereactants by which
more number of molecules are able to cross the barrier per unit of time.

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CHEMICAL KINETICS # 21

25.

: In the reaction, 2 + 2S2O32 S4O62 + 2 , the rate of disappearance of thiosulphate ions is

Statement-1

twice the rate of disappearance of 2.

26.

Statement-2

: The rate of disappearance of 2 is twice the rate of disappearance of S2O32 ions.

Statement-1

: For A + 2B C (rate= K[A]1[B]0), the half life time of reaction is only defined when conc.
of A and B are in stoichiometric ratio

Statement-2

: For above given order half life of reaction is directly proportional to conc. of A and not to conc.
of B due to its zero order.

27.

28.

Statement-1

: Many reactions occurring on solid surface are zero order reactions.

Statement-2

Au
: N2 O(g)
N2 (g) 1/ 2O 2 ; rate = k[N2O]0 = k = constant is a zero order reaction.

Statement-1

: Half life of a certain radioactive element is 100 days. After 200 days, fraction left undecaye
will be 25%.
n

29.

30.

Ct 1
, where symbols have standard meaning.
C0 2

Statement-2

Statement-1

: Time taken for the completion of 75% of a st order reaction is double than its t.

Statement-2

: Time taken for completion of any fraction of a st order reaction is a constant value.

Statement-1 : If the activation energy of reaction is zero temperature will have no effect on the rate constant
Statement-2 : Lower the activation energy faster is the reaction

TRUE / FALSE
31.

Order of a reaction can be written from the balanced chemical equation.

32.

In a complex reaction the rate of overall reaction is governed by the slowest step.

33.

If t1/2 for a first order reaction is 6.93 s, the value of rate constant for the reaction would be 10s1.

34.

Molecularity of a reaction is always whole number.

35.

Order and molecularity of a single step reaction may or may not be same.

36.

The activation energy of a catalysed reaction is more than the activation energy of the uncatalysed reaction.

37.

For a zero order reaction t3/4 is related to t1/2 as t3/4 = 1.5 t1/2

38.

The rate of an exothermic reaction increases with the rise in temperature.

39.

Partial orders are never negative.

40.

Order of reaction may be change with change in practical conditions

41.

The rate of reaction is uniform in zero order reaction.

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CHEMICAL KINETICS # 22

42.

The rate law of the elementary reaction; 3A B must be r = k [A]3

43.

If the partial orders are equal to corresponding coefficients in the balanced reaction, the reaction must be
elementary.

44.

Every species that appears in the rate law of reaction must be a reactant or product in that reaction.

45.

Molecularity defined only for RDS.

46.

Product can form only when the required orientation and energy conditions are met.

47.

Activated complex is an intermediate product.

48.

The pre-exponential factor A has the same units for all reactions.

49.

All collisions between reactants yield the desired product.

50.

If the partial orders differ from the coefficients in the balanced reaction, the reaction must be complex.

51.

The rate of the reaction A B having the rate law dt k [ A ] [B] when plotted against time will exhibit a

d[A]

maximum at some time.


52.

For a firstorder reaction, the time required to reduce successively the concentration of reactant by a constant
fraction is always same.

53.

As a first order reaction proceeds at a constant temperature, the rate remains constant.

54.

If concentration of catalyst appear in rate law (rate = k [catalyst]1 [reactant]1) then it may becomes pseudo first
order reaction during the reaction.

55.

Larger the value of Ea , greater is the effect on the value of k for a given temperature change.

56.

A catalyst in a chemical reaction decreases the activation energy of the forward reaction and increases the
activation energy of the reverse reaction

57.

A catalyst in a chemical reaction increases the forward Ea and decreases the backward Ea

58.

A catalyst in a chemical reaction decreases both forward and backward Ea

59.

At lower temperature, increase in temperature cause more change in the value of k than at higher temperature.

60.

Molecularity of a reaction may includes the number of product molecules taking part in the reaction.

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CHEMICAL KINETICS # 23

FILL IN THE BLANKS


61.

For collision to be effective the energy possessed by the colliding molecules should be equal to or greater than
the ____________.

62.

In the reaction, H2 + I2 2HI, the rate of disappearance of H2 is _______ the rate of appearance of HI.

63.

For an endothermic process, the minimum value of activation energy can be _______.

64.

The rate of a reaction is ________ to the collision frequency.

65.

The rate constant for the zero order reaction has the dimensions___________.

66.

The reactions with molecularity more than three are _________.

67.

A catalyst increases the rate of the reaction by__________ activation energy.

68.

If activation energy of reaction is low, it proceeds at _______ rate.

69.

In a multistep reaction, the ________ step is rate determining.

70.

Rate constant of a reaction __________ with increase in temperature.

71.

The ratio t7/8 / t1/2 for a first order reaction would be equal to _________.

72.

For a zero order reaction, the rate of the reaction is equal to the ______ of the reaction.

73.

The value of temperature coefficient is generally between _________.

74.

For a certain reaction, xM yL, the rate of reaction increases by 4 times when the concentration of M is
doubled. The rate law is _________.

75.

The rate equation r = k [A][B]1/2 suggests that order of overall reaction is _______.

76.

A plot of [A] vs t for a certain reaction A B with r = k [A]0 will be a straight line with slope equal to ________.

77.

[Eactivated complex Ereactants] = ____________.

78.

In the Arrhenius equation k = Aexp (E/RT), A may be termed as the rate constant at __________.

79.

For a ______ order reaction the half-life (t1/2) is independent of the initial conc. of the reactants.

80.

For a first order reaction A P, a graph of log [A] vs t has a slope equal to __________.

81.

A catalyst is chemically ____________ at the end of a reaction

82.

The order of a reaction is the ________ of the _________ of all the concentration terms in the rate equation.

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CHEMICAL KINETICS # 24

PART - I : MIXED OBJECTIVE


Single Choice Type
1.

Consider the reaction :


A B + C
Initial concentration of A is 1 M. 20 minutes time is required for completion of 20 % reaction.
If

d[ B]
= k[A], then half life (t1/2 ) is
dt

(A) 55.44 min.


2.

(C) 62.13 min

(D) None of these

If decomposition reaction A (g) B (g) follows first order kinetics then the graph of rate of formation (R) of B
against time t will be

(A)

(B)

(C)

(D)

For the first order decomposition of SO2Cl2(g),


SO2Cl2(g) SO2(g) + Cl2(g)
a graph of log (a0 x) vs t is shown in figure. What is the rate constant (sec1)?
Time (min)
2
4 6 8 10
(0,0)
|
| | |
|
-1
log (a0 x)

3.

(B) 50 min

-2
-3

(A) 0.2
4.

(B) 4.6 101

(C) 7.7 103

(D) 1.15 102

The rate constant for the forward reaction A (g) + 2B(g) is 1.5 103 s1 at 100 K. If 105 moles of A and 100
moles of B are present in a 10 litre vessel at equilibrium then rate constant for the backward reaction at this
temperature is :
(A) 1.50 104 L mol1 s1
(B) 1.5 1011 L mol1 s1
10
1
1
(C) 1.5 10 L mol s
(D) 1.5 1011L mol1 s1

5.

Reaction A + B C + D follows following rate law : rate =

k [A]

1
1
2 [ B] 2 . Starting with initial conc. of 1 M of

A and B each, what is the time taken for concentration of A of become 0.25 M.
Given : k = 2.303 103 sec1.
(A) 300 sec.
(B) 600 sec.
(C) 900 sec.
(D) 1200 sec.
6.

The reaction A (g) B(g) + 2C (g) is a first order reaction with rate constant 3465 106 s1. Starting with
0.1 mole of A in 2 litre vessel, find the concentration of A after 200 sec., when the reaction is allowed to take
place at constant pressure and temperature.
(A) 0.05 M
(B) 0.025 M
(C) 0.0125 M
(D) None of these

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CHEMICAL KINETICS # 25

The variation of concentration of A with time in two experiments starting with two different initial concentration of
A is given in the following graph. The reaction is represented as A(aq) B(aq). What is the rate of reaction
(M/min) when concentration of A in aqueous solution was 1.8 M?

Concentration(M)

7.

1.5
1.2
1
0.8

Experiment-1
Experiment-2

0.6
5

10

15

20

time(min.)

(A) 0.08 M min1

(B) 0.036 M min1

(C) 0.13 M min1

(D) 1 M min1

8.

In respect of the equation k = A exp ( Ea / RT), which one of the following statements is correct?
(A) R is Rydberg's constant
(B) k is equilibrium constant
(C) A is adsorption factor
(D) Ea is the energy of activation

9.

Rate of a reaction can be expressed by Arrhenius equation as :


k = AeE/RT
In this equation, E represents
(A) The fraction of molecules with energy greater than the activation energy of the reaction
(B) The energy above which all the colliding molecules will react
(C) The energy below which colliding molecules will not react
(D) The total energy of the reacting molecules at a temperature, T

10.

The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25C are
3.0 104 s1, 104.4 kJ mol1 and 6.0 1014s1 respectively. The value of the rate constant at T is
(A) 2.0 1018 s1
(B) 6.0 1014 s1
(C) infinity
(D) 3.6 1030 s1

11.

A first order reaction is 50% completed in 20 minutes at 27C and in 5 min at 47C. The energy of activation of
the reaction is
(A) 43.85 kJ/mol
(B) 55.14 kJ/mol
(C) 11.97 kJ/mol
(D) 6.65 kJ/mol

12.

For the first order reaction A B + C, carried out at 27 C if 3.8 1016 % of the reactant molecules exists
in the activated state, the Ea (activation energy) of the reaction is [log 3.8 = 0.58]
(A) 12 kJ/mole
(B) 831.4 kJ/mole
(C) 100 kJ/mole
(D) 88.57 kJ/mole

13.

For a certain reaction of order n, the time for half change, t1/2, is given by t1/2 =
constant and C0 is the initial concentration. What is n?
(A) 1
(B) 2
(C) 0

14.

( 2 2 ) 1/ 2
xC0 where k is
k

(D) 0.5

Given that for a reaction of order n, the integrated form of the rate equation is k =

1 1
1

where C0
t(n 1) Cn 1 Cn1
0

and C are the values of the reactant concentration at the start and after time t. What is the relationship between
t3/4 and t1/2 where t3/4 is the time required for C to become 1/4 C0?
(A) t3/4 = t1/2 [2n1 + 1]
(B) t3/4 = t1/2 [2n1 1]
n+1
(C) t3/4 = t1/2 [2 1]
(D) t3/4 = t1/2 [2n+1 + 1]

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CHEMICAL KINETICS # 26

15.

In three different reactions, involving a single reactant in each case, a plot of rate of the reaction on the yaxis,
versus concentration of the reactant on the xaxis, yields three different curves shown below.

(i)

(ii)

(iii)

What are the possible orders of the reactions (i), (ii), (iii).
(A) 1, 2, 3

(B) 2, 1, 1/2

(C) 0, 1, 2

(D) 0, 1, 1/2

16.

The time elapsed of a certain between 33% and 67% completion of a first order reaction is 30 minutes. What is
the time needed for 25% completion?
(A) 150.5 minutes
(B) 12.5 minutes
(C) 180.5 minutes
(D) 165.5 minutes

17.

A reaction 2A + B C + D is first order with respect to A and 2nd order with respect to B. Initial conc.

(t = 0) of A is C0 while B is 2C0. If at t as 30 minutes the conc. of C is C0 /4 then rate expression at t = 30 minutes is :


(A) R = 7 C03 k/16

(B) R = 27 C03 k / 32

(C) R = 247 C03 k / 64

(D) R = 49 k C03 / 32

18.

For a certain reaction, a plot of {[C0 C] / [C]} against the time t, yields a straight line. C0 = initial conc. of the
reactant and C is the reactant concentration after time t. What is the order of the reaction :
(A) 3
(B) zero
(C) 1
(D) 2

19.

In a I order reaction A products, the concentration of the reactant decrease to 6.25% of its initial value in 80
minutes. What is (i) the rate constant and (ii) the rate of the reaction, 100 minutes after the start, if the initial
concentration is 0.2 mole/litre?
(A) 2.17 102 min1, 3.47 104 mol.litre1 min1
(B) 3.465 102 min1, 2.166 104 mol.litre1 min1
(C) 3.465 103 min1, 2.17 103 mol.litre1 min1
(D) 2.166 103 min1, 2.667 104 mol.litre1 min1

20.

At 373 K, a gaseous reaction A 2B + C is found to be of first order. Starting with pure A, the total pressure at
the end of 10 min. was 176 mm and after a long time when A was completely dissociated, it was 270 mm. The
pressure of A at the end of 10 minutes was :
(A) 94 mm
(B) 47 mm
(C) 43 mm
(D) 90 mm

21.

The reaction A(s) 2 B(g) + C(g) is first order. The pressure after 20 min. and after very long time are 150 mm
Hg and 225 mm Hg. The value of rate constant and pressure after 40 min. are :
(A) 0.05 In 1.5 min1, 200 mm
(B) 0.5 ln 2 min1 ,300 mm
1
(C) 0.05 In 3 min , 300 mm
(D) 0.05 In 3 min1 , 200 mm

22.

The reaction [Co (NH3)5Br]2 + H2O [Co(NH3)5(H2O)]3+ + Br is followed by measuring a property of the
solution known as the optical density of the solution which may be taken to be linearly related to the concentration
of the reactant. The values of optical density are 0.80, 0.35 and 0.20 at the end of 20 minutes, 40 minutes and
infinite time after the start of the reaction which is first order. Calculate the rate constant.
(A) 6.93 x 103 min1

23.

(B) 3.51 x 102 min1

(C) 6.93 x 102 min1

(D) 3.51 x 103 min1

The inversion of cane sugar proceeds with half life of 50 minute at pH = 5 for any concentration of sugar. However
if pH = 6, the half life changes to 500 minute of any concentration of sugar . The law expression for sugar
inversion can be written as :
(A) r = K [sugar]2 [H+]0

(B) r = K [sugar]1 [H+]0

(C) r = K [sugar]1 [H+]1

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CHEMICAL KINETICS # 27

24.

The reaction A Products, is zero order while the reaction B Products, is 1st order. For what initial
concentration of A the half lives of the two reactions are equal.
(A) 2 M
(B) ln 2 M
(C) 2 log 2 M

(D) 2 ln 2 M

25.

For the reaction 3A Products the value of k = 1 103 / (molmin) the value of d[A] / dt in
mol/lt-sec when [A] = 2M is :
(A) 6.67 103
(B) 1.2 102
(C) 2 104
(D) 4 103

26.

Two I-order reactions have half-lives in the ratio 3 : 2. Calculate the ratio of time intervals t1 : t2. Where t1 is the
time period for 25% completion of the first reaction and t2, for 75% completion of the second reaction.
(A) 0.311 : 1
(B) 0.420 : 1
(C) 0.273 : 1
(D) 0.199 : 1

27.

The Arrhenius relationship of two different reactions is shown below. Which reaction is
faster at a lower temperature and which is more sensitive to changes of temperature ?
(A) B faster, A more sensitive
(B) B in both cases
(C) A in both cases
(D) A faster, B more sensitive

28.

When a graph between log K and 1/T is drawn a straight line is obtained. The point at which line cuts y -axis and
x -axis respectively correspond to the temp :
(A) 0, Ea / 2.303 R log A
(B) , Ea / (R ln A)
(C) 0, log A
(D) None of these

29.

A B
KA = 1015 e2000/T ;
CD
KC = 1014 e1000/T
Temperature T K at-which (KA = KC) is :
(A) 1000K
(B) 2000K

(C) (2000 / 2.303) K

(D) (1000 / 2.303) K.

30.

The rate of a reaction gets doubled when the temperature changes from 7C to 17C. By what factor will it
change for the temperature change from 17C to 27C?
(A) 1.81
(B) 1.71
(C) 1.91
(D) 1.76

31.

For the reaction A + 2B products(started with concentrations taken in stoichiometric proportion), the
experimentally determined rate law is
(A)

32.

0.693
k

(B)

d [A]
= k [A]
dt

0.693
1/ k

For a reaction 2A + B product, rate law is

(C)

[B] . The half time of the reaction would be :

0.693

(D) not defined

2k

d[ A ]
1
= k[A]. At a time when t = , concentration of the reactant
dt
k

is : (C0 = initial concentration)


(A)

33.

C0
e

(B) C0e

C0
e

Concentration of the reactant in first-order is reduced to


(A) one natural life-time
(C) three natural life-time

34.

(C)

(D)

1
e2

1
C0

after : (Natural life =

1
)
K

(B) two-natural life-time


(D) four natural life-time

If for a reaction in which A(g) converts to B(g) the reaction carried out at const.
V & T results into the following graph.
(A) then the reaction must be A(g) 3B(g) and is a first order reaction.
(B) then the reaction must be A(g) 3B(g) and is a second order reaction.
(C) then the reaction must be A(g) 3B(g) and is a zero order reaction.
(D) then the reaction must be A(g) 3B(g) and is a first order reaction.

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CHEMICAL KINETICS # 28

35.

The instantaneous rate of disappearance of the MnO4 ion in the following reaction is 4.56 103 ms1. Then the
rate of appearance of 2 is :
2MnO4 + 10 + 16H+ 2Mn2+ + 52 + 8H2O
2MnO4 + 10 + 16H+ 2Mn2+ + 52 + 8H2O
(A) 1.14 103 Ms1
(B) 5.7 103 Ms1
(C) 4.56 104 Ms1
(D) 1.14 102 Ms1

36.

catalyst
Consider the following reactions at 300 K. A B (uncatalysed reaction). A
B (catalyst reaction)
1
The activation energy is lowered by 8.314 KJ mol for the catalysed reaction. How many times the rate of this
catalysed reaction greater than that of uncatalysed reaction ?
(Given e3.33 = 28)
(A) 15 times
(B) 38 times
(C) 22 times
(D) 28 times

37.

The conversion of vinyl allyl ether to pent-4-enol follows first-order kinetics.


The following plot is obtained for such a reaction. The rate constant for the
reaction is
(A) 4.6 102 s1
(B) 1.2 102 s1
(C) 2.3 102 s1
(D) 8.4 102 s1

38.

A substance A' decomposes in solution following the first order kinetics. Flask contains 1 L of 1 M solution of
A and flask contains 100 ml of 0.6 M solution. After 8 hr, the conc. of A in flask 1 becomes 0.25 M. What will
be time for cone. of A in flask to become 0.3 M ? :
(A) 0.4 hr
(B) 2.4 hr
(C) 4.0 hr
(D) unpredictable as rate constant is not given

39.

A simple mechanism for enzyme-catalyzed reaction is given by the following set of equations
E
+
(enzyme)

S
(reactant)

ES
(intermediate-1)

ES
(intermediate-1)

EP
(intermediate-2)

EP
E
+
P
(intermediate-2)
(enzyme)
(product)
This is known as the MichaelisMenten mechanism. The potential energy diagram is shown in the fig. Which
of the following sets of identifications is correct ? (Assume that the temperature and pressure are constant).
(1)
(2)
(3)
(4)
(A)
E + P.
EP
ES
E+S
(B)
ES
Activated complex
EP
Activated complex
(C)
EP
Activated complex
ES
Activated complex
(D)
E+S
ES
EP
E+P

More than one choice Type


40.

For the reaction A B, the rate law expression is

(A) The integerated rate expression is k =


(B) The graph of

d[A ]
= k [A]1/2. If initial concentration of [A] is [A]0, then
dt

2 1/ 2
( A A1 / 2 )
t 0

A Vs t will be

(C) The half life period t1 / 2 =

K
2[A]10/ 2

(D) The time taken for 75% completion of reaction t 3 / 4 =

[A]0
k

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CHEMICAL KINETICS # 29

41.

Select incorrect statement(s):


(A) Unit of pre-exponential factor (A) for second order reaction is mol L1 s1.
(B) A zero order reaction must be a complex reaction.
(C) Molecularity is defined only for RDS in a complex reaction.
(D) Decay constant () of radioactive substance is affected by temperature.

42.

E1
2
In a consecutive reaction system A
B
C when E1 is much greater than E2, the yield of
B increase with
(A) increase in temperature
(B) decreases in temperature
(C) increase in initial concentration of A
(D) decrease in initial concentration of A

43.

Which of the following is/are correct statement?


(A) Stoichiometry of a reaction tells about the order of the elementary reactions.
(B) For a zero order reaction, rate and the rate constant are identical.
(C) A zero order reaction is controlled by factors other than concentration of reactants.
(D) A zero order reaction is always elementary reaction.

44.

Which of the following statement is incorrect ?


(A) The order of reaction is the sum of powers of all the concentration terms in the rate equation.
(B) The order of reaction with respect to one reactant is the ratio of the change of logarithm of the rate of the
reaction to the change in the logarithm of the concentration of the particular reactant, keeping the concentrations
of all other reactants constant.
(C) Orders of reactions can not be fractional.
(D) The order of a reaction can only be determined from the stoichiometric equation for the reaction.

45.

Consider the decay of P to A and B by two parallel first order reactions as shown in Fig. Given

Reaction

Rate constant

Energy of activation

PA

HA

kA

EA

PB

HB

kB

EB

Which of the following is(are) true?


(A) a = EB
(B) b = EA

(C) HA = b d

(D) HB = c a

PART - II : SUBJECTIVE QUESTIONS


1.

The oxidation of iodide ion by peroxy disulphate ion is described by the equation :
3 (aq) + S2O82 (aq) 3 (aq) + 2SO42 (aq)
(a) If

[S2O82 ]
t

= 1.5 103 Ms1 for a particular time interval, what is the value of

[ ]
for the same time
t

interval ?
(b) What is the average rate of formation of SO42 during that time interval ?
2.

In the following reaction 2H2O2 (aq) 2H2O () + O2 (g) rate of formation of O2 is 36 g min1 ,
(a) What is rate of formation of H2O.
(b) What is rate of disappearance of H2O2.

3.

The reaction 2NO(g) + Cl2(g) 2NOCl(g) is second order in NO and first order in Cl2. In a volume of
2 dm3, 5 mole of nitric oxide and 2 mol of Cl2 were brought together, and the initial rate was 2.4 10 3 mole
dm3 s. What will be the rate when half of the chlorine has reacted ?
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CHEMICAL KINETICS # 30

4.

BrO3 (aq) + 2Br (aq) in alkaline solution, the value of rate constant at
For the reaction 3BrO(aq)
0

80 C in the rate law for [BrO ]/t was found to be 0.057 L.mol1.s1. What is the rate constant when the rate
law is written for (a) [BrO3]/t (b) + [Br ] / t ?

5.

The rate law of a chemical reaction given below :


2NO (g) + O2 (g) 2NO2 (g)
is given as rate = k [NO]2 [O2]. How will the rate of reaction change if the volume of reaction vessel is reduced to
1/4th of its original value?

6.

Decomposition of ammonia on platinum surface follow the change,


2NH3 (g) N2 (g) + 3H2 (g)
(a) What does d [NH 3 ] denote ?
dt

(b) What does

d [N2 ]
d [H2 ]
and
denote?
dt
dt

(c) If the decomposition is zero order then what are the rate of production of N2 and H2 if k = 2.5 104 Ms1 ?
(d) If the rate obeys

k1 [NH3 ]
d [NH3 ]
= 1 k [NH ] , what will be the order for decomposition of NH3 if (i) [NH3] is very
dt
2
3

very less and (ii) [NH3] is very very high K1 and K2 are constant.
7.

Substance A reacts according to a first order rate law with k = 5 x 105 s1.
(a)

If the initial concentration of A is 1.0 M, what is initial rate .

(b)

What is the rate after 1.0 hour.

(Given e0.18 = 0.84)

8.

Consider the following data on the hypothetical reaction between the reactants (A) and (B) give products
2A + 2B C + 3D
[A]
[B]
Rate r
[mol 1]
[mol 1]
[mol 1 s1]
1.
6.0 x 10-3
1.0 x 10-3
0.012
2.
6.0 x 10-3
2.0 x 10-3
0.024
-3
-3
3.
2.0 x 10
1.4 x 10
0.0020
4.
4.0 x 10-3
1.4 x 10-3
0.0080
If the reaction rate given by r = [A]a[B]b, then,
(i) What is the order of the reaction with respect to A.
(ii) What is the order of the reaction with respect to B.
(iii) What is the overall order.
(iv) Write the rate law equation.
(v) Calculate the rate constant.

9.

The reaction A + 2B C + 2D is run three times. In the second run, the initial concentration of A is double that
in the first run, and the initial rate of the reaction is double that of the first run. In the third run, the initial
concentration of each reactant is double the respective concentrations in the first run, and the initial rate is
double that of the first run. What is the order of the reaction with respect to each reactant?

10.

In a kinetic study of the reduction of nitric oxide with hydrogen, the initial pressure of 340 mm, an equimolar
mixture of gases was reduced to half the value in 102 seconds. In another experiment, the initial pressure of 288
mm, under the same conditions was reduced to half the value in 140 sec. Calculate the order of the reaction.

11.

(a)

The half life period and initial concentration for a reaction are as follows. What is order of reaction?
Initial concentration
350
540
158
t1/2
425
275
941

(b)

The half-life period for the thermal decomposition of PH3 at three different pressures are given below
Initial pressure (mm Hg)
707
79
37.5
Half--life (seconds)
84
84
83
What is the order of the reaction ?
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CHEMICAL KINETICS # 31

12.

The decomposition of Cl2O7 at 400 K in gaseous phase to Cl2 and O2 is of order reaction. After 55 sec at 400
K, the pressure of reaction mixture increases from 0.62 to 1.88 atm. Calculate the rate constant of given
reaction, also calculate the pressure of reaction mixture after 100 second.
[Given : n

13.

31
= 0.869, e1.58 = 4.858]
13

CI2 (g) +
CI2O7(g)

7
O (g)
2 2

For a homogeneous gaseous phase reaction 2A 3B + C the initial pressure was P0 while pressure after time
't' was P. Find the pressure after time '2t'. Assume first order reaction.

14.

The kinetic of hydrolysis of methyl acetate in excess dilute HCl at 25C were followed by withdrawing 2 mL of the
reaction mixture at intervals of (t), adding 50 mL water and titrating with baryta water. Determine the velocity
constant of hydrolysis.
t (in minute)

75

119

259

Titre value (in mL)

19.24

24.20

26.60

32.23

42.03

[ln

15.

22.79
22.79
22.79
= 0.2454, ln
= 0.39, ln
= 0.8439]
17.83
15.43
9. 8

D
A
B+C
Time

Volume of reagent

V1

V2

V3

The reagent reacts with only B, C and D. Find k.


16.

A first order reaction, A B, requires activation energy of 70 kJ mol1. When a 20% solution of A was kept at
250C for 20 minutes, 25% decomposition took place. What will be the percent decomposition in the same time
in a 30% solution maintained at 40 0C? Assume that activation energy remains constant in this range of
temperature.

17.

The thermal decomposition of N2O5 occurs in the following steps.


Step -

slow
N2O5

NO2 + NO3

Step -

fast
N2O5 + NO3
3NO2 + O2

4NO2 + O2
2N2O5

suggest the rate expression.

18.

The reaction 2NO (g) + Br2 (g) 2NOBr (g), obeys the following mechanism.
(i) NO (g) + Br2 (g)

NOBr2 (g)

Slow
(ii) NOBr2 (g) + NO (g)
2NOBr (g)

Suggest the rate expression.

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CHEMICAL KINETICS # 32

19.

Given the following steps in the mechanism for a chemical reaction :


C
A + B

(fast)

D + E
B + C

slow)

A + E
D + F

fast)

At any time [C] is directly proportional to [A].


(a) What is the stoichiometric equation for the reaction ?
(b) Which species, if any, are catalysts in this reaction ?
(c) Which species, if any, are intermediates in this reaction?
(d) Write the rate law for the rate-determining step.
(e) Write the rate law for this reaction.
(f) What is overall order of the reaction ?
20.

The forward reactions rate for the nitric oxide-oxygen reaction


2NO + O2 2NO2 has the rate law ; rate = K [NO]2 [O2] .
Assume the mechanism:
2NO

N2O2 , (rapid equilibration) ;


k'

N2O2 + O2 2 NO2 [slow step].


Show that the rate law can be explained, where in K = kk.
21.

Experiment shows that the equilibrium constant of the reaction :


C2H5OH + CH3COOH

CH3COOC2H5 + H2O

is 2.8 at room temperature, and the velocity constant of the forward reaction is 0.002. When a catalyst is added
this velocity constant is increased to 0.0045. What is now the velocity constant of the backward reaction?

22.

For a first order reversible reaction A

B , the initial concentration of A and B are [A]0 and zero

respectively. If concentrations at equilibrium are [A]eq. and [B]eq. derive an expression for the time taken by B to
attain concentration equal to [B]eq/2 .

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CHEMICAL KINETICS # 33

PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)


* Marked Questions are having more than one correct option.
1.

The rate constant for the reaction,2N2O5 4NO2+ O2, is 3 105 s1. If the rate is 2.4 105 mol L1 s1, then
the concentration of N2O5 (in mol L1) is :
[JEE-2000, 1/35]
(A) 1.4
(B) 1.2
(C) 0.04
(D) 0.8

2.

A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a catalyst
at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction if the catalyst
lowers the activation barrier by 20 kJ mol1.
[JEE-2000, 3/100]

3.

If '' is the intensity of absorbed light and 'C' is the concentration of AB for the photochemical process,
AB + hv AB * , the rate of formation of AB * is directly proportional to
(A) C
(B)
(C) 2

[JEE-2001, 1/35]
(D) C.

4.

The rate of a first order reaction is 0.04 mole litre1 s1 at 10 minutes and 0.03 mol litre1 s1 at 20 minutes after
initiation. Find the half life of the reaction.
[JEE-2001, 5/100]

5.

Consider the chemical reaction,


N2(g) + 3H2(g) 2NH3(g)
The rate of this reaction can be expressed in terms of time derivatives of conc. of N2(g) , H2(g) or NH3(g). Identify
the correct relationship amongst rate expressions :
[JEE-2002, 3/90]
(A) Rate =
(C) Rate =

d [N2 ]
1 d [H2 ] 1 d [NH3 ]

dt
3 dt
2 dt

d [N2 ]
1 d [H2 ] 1 d [NH3 ]

dt
3 dt
2 dt

(B) Rate =

d [N2 ]
d [H2 ]
d [NH3 ]
3
2
dt
dt
dt

(D) Rate =

d [N2 ]
d [H2 ] d [NH3 ]

dt
dt
dt

6.

In the biologically-catalysed oxidation of ethanol, the concentration of ethanol decreases in a first order reaction
from 800 mol dm3 to 50 mol dm3 in 2 104 s. The rate constant (s1) of the reaction is : [JEE-2003, 3/84]
(A) 3.45 105
(B) 1.38 104
(C) 1.00 104
(D) 5.00 105

7.

Given

X product (Taking 1st order reaction)

conc
0.01 0.0025
(mol/lit)
time (min) 0
40
Initial rate of reaction is in mol //min.
(A) 3.43 104
(B) 1.73 104
8.

[JEE-2004, 3/84]
(C) 3.43 105

(D) 1.73 105

Initial rates, r0, of the A + B P at different initial concentrations of A and B ([A]0 and [B]0) are given below:

[A]0
[B]0
r0

(a)
(b)

(mol L1)
(mol L1)
(mol L1 s1)

0.1
0.1
0.05
0.2
0.1
0.10
0.1
0.2
0.05

Write the rate equation.


Calculate the rate constant of the reaction.
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[JEE-2004, 2/60]

CHEMICAL KINETICS # 34

9.

For a reaction 2X(g) 3Y(g) + 2Z(g)


Time (min)
0
100
200

the following data is obtained.

Px (mm of Hg)
(Partial pressure of X)
800
400
200

Find order with respect to X, rate constant of the reaction, time taken for 75% completion and find the total
pressure when partial pressure of X, Px = 700 mm of Hg.
[JEE-2005, 2/60]
10.

Consider a reaction aG + bH Products. When concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when concentration of G is doubled keeping the concentration of H
fixed, the rate is doubled. The overall order of the reaction is :
[JEE-2007, 3/81]
(A) 0
(B) 1
(C) 2
(D) 3

11.

Under the same reaction conditions, initial concentration of 1.386 mol dm3 of a substance becomes half in 40

k1
seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio of the rate
k0
constant for first order (k1) and zero order (k0) of the reaction is.
(A) 0.5 mol1 dm3
(B) 1.0 mol dm3
(C) 1.5 mol dm3

[JEE-2008, 3/82]
(D) 2.0 mol1 dm3

12.

For a first order reaction A P, the temperature (T) dependent rate constant (k) was found to follow the equation
1
log k = (2000)
+ 6.0. The pre-exponential factor A and the activation energy Ea, respectively, are :
T
[JEE-2009, 3/80]
6 1
1
1
1
(A) 1.0 10 s and 9.2 kJ mol
(B) 6.0 s and 16.6 kJ mol
(C) 1.0 106 s1 and 16.6 kJ mol1
(D) 1.0 106 s1 and 38.3 kJ mol1

13.

Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is :

(A)

14.

[JEE-2010, 3/163]

(B)

(C)

(D)

The concentration of R in the reaction R P was measured as a function of time and the following data is
obtained :
[JEE-2010, 3/163]

[R](molar ) 1.0 0.75 0.40 0.10


t(min.)

0.0 0.05 0.12 0.18

The order of the reaction is :


15.

The number of neutrons emitted when

235
92 U

undergoes controlled nuclear fission to

142
54 Xe

and

90
38 Sr

is :

[JEE-2010, 3/163]

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CHEMICAL KINETICS # 35

16.

Bombardment of aluminum by -particle leads to its artificial disintegration into two ways, (i) and (ii) as shown.
Products X, Y and Z respectivey are :
[JEE-2011, 3/163]

(A) Proton, neutron, position


(C) proton, positron, neutron

(B) Neutron, position, proton


(D) positron, proton, neutorn

17.

For the first order reaction


2N2O5(g) 4NO2(g) + O2(g)
(A) the concentration of the reactant decreases exponentially with time
(B) the half-life of the reaction decreases with increasing temperature
(C) the half-life of the reaction depends on the initial concentration of the reactant
(D) the reaction proceeds to 99.6% completion in eight half-life duration

18.

An organic compound undergoes first-order decomposition. The time taken for its decompositionto 1/8 and 1/10
of its initial concentration are t1/8 and t1/10 respectively. What is the value of

[JEE-2011, 4/163]

[ t 1/ 8 ]
10? (take log10 2 = 0.3).
[ t1 / 10 ]
[IIT-JEE-2012]

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)


1.

Units of rate constant of first and zero order reactions in terms of molarity M unit are respectively
[AIEEE- 2002]
(1) sec1, M sec1
(2) sec1, M
(3) M.sec1, sec1
(4) M, sec1

2.

For the reaction A + 2B C, rate is given by R = [A] [B]2 then the order of the reaction is : [AIEEE- 2002]
(1) 3
(2) 6
(3) 5
(4) 7

3.

The differential rate law for the reaction H2 + I2 2HI is :


(1)
(3)

4.

1 dH2 1 d[I2 ]
d[HI]

2 dt
2 dt
dt

(2)

dH2 d[I2 ] 1 d[HI]

dt
dt
2 dt

(4) 2

dH2
d[I ]
d[HI]
2 2
dt
dt
dt

The rate law for a reaction between the substances A and B is given by rate = k [A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the reaction
will be as
[AIEEE- 2003]

(1)

2
5.

dH2
d[I ]
d[HI]
2
dt
dt
dt

[AIEEE- 2002]

mn

(2) (m + n)

(3) (n m)

(4) 2(n m).

For the reaction system: 2NO(g) + O2(g) 2NO2(g), volume is suddenly reduced to half its value by increasing
the pressure on it. If the reaction is of first order with respect to O2 and second order with respect to NO, the rate
of reaction will :
[AIEEE- 2003]
(1) diminish to one-fourth of its initial value
(2) diminish to one-eighth of its initial value
(3) increase to eight times of its initial value
(4) increase to four times of its initial value.
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CHEMICAL KINETICS # 36

6.

In the respect of the equation k = Ae Ea/RT in chemical kinetics, which one of the following statements is correct :
[AIEEE- 2003]

7.

(1) k is equilibrium constant

(2) A is adsorption factor

(3) Ea is energy of activation

(4) R is Rydberg constant.

In a first order reaction, the concentration of the reactant, decreases from 0.8 M to 0.4 M in 15 minutes. The time
taken for the concentration to change from 0.1 M to 0.025 M is :
(1) 30 minutes

8.

(2) 15 minutes

(3) 7.5 minutes

[AIEEE- 2004]
(4) 60 minutes

The rate equation for the reaction 2A + B C is found to be : rate = k[A] [B]. The correct statement in
relation to this reaction is that the :

[AIEEE- 2004]

(1) unit of k must be sec1


(2) t1/2 is a constant
(3) rate of formation of C is twice the rate of disappearance of A
(4) value of k is independent of initial concentrations of A and B.
9.

The half - life of a radioisotope is four hours. If the initial mass of the isotope was 200 g, the mass remaining after
24 hours undecayed is :
(1) 1.042 g

10.

[AIEEE- 2004]
(2) 2.084 g

(3) 3.125 g

(4) 4.167 g.

Consider an endothermic reaction X Y with the activation energies Eb and Ef for the backward and forward
reaction, respectively. In general
(1) Eb < Ef

11.

12.

(2) H = U

[AIEEE- 2005]
(3) H < U

(4) H > U

A reaction involving two different reactants can never be :


(1) unimolecular reaction

(2) first order reaction

(3) second order reaction

(4) bimolecular reaction

[AIEEE- 2005]

A reaction was found to be second order with respect to the concentration of carbon monoxide. If the concentration
of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will be : [AIEEE- 2006]

13.

(1) remain unchanged

(2) tripled

(3) increased by a factor of 4

(4) doubled

The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr.
NO (g) + Br2 (g)

NOBr2 (g) ; NOBr2 (g) + NO (g) 2NOBr (g) (slow step)

If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
[AIEEE- 2007, 3/120]
(1) 1
14.

(2) 0

(3) 3

(4) 2

The energies of activation for forward and reverse reactions for A2 + B2

2AB are 180 kJ mol1 and

200 kJ mol1 respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse)
reactions by 100 kJ mol1. The enthalpy change of the reaction (A2 + B2 2AB) in the presence of catalyst will be
(in kJ mol1).
(1) 280

[AIEEE- 2007, 3/120]


(2) 20

(3) 300

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(4) 120

CHEMICAL KINETICS # 37

15.

A radioactive element gets spilled over the floor of a room. Its half-life period is 30days. If the initial activity is ten
times the permissible value, after how many days will it be safe to enter the room :
[AIEEE- 2007, 3/120]
(1) 10 days

16.

(2) 100 days

For a reaction

(3) 1000 days

(4) 300 days

1
A 2B, rate of disappearance of 'A' related to the rate of appearance of 'B' by the
2

expression.
(1)

17.

[AIEEE- 2008, 3/105]

d [ A ] 1 d [B]

dt
4 dt

(2)

d [ A ] d [B]

dt
dt

(3)

d[A]
d [B]
4
dt
dt

(4)

d [ A ] 1 d [B]

dt
2 dt

The half life period of a first order chemical reaction is 6.93 minutes. Time required for the completion of 99% of
the chemical reaction will be (log 2 = 0.301) :
(1) 23.03 minutes

18.

(2) 46.06 minutes

[AIEEE - 2009, 8/144]


(3) 460.6 minutes

(4) 230.3 minutes

The time for half life period of a certain reaction A Products is 1 hour. When the initial concentration of the
reactant A, is 2.0 mol L1 , how much time does it take for its concentration to come from 0.50 to 0.25 mol L1. If
it is a zero order reaction?
(1) 4 h

19.

[AIEEE - 2010, 8/144]

(2) 0.5 h

(3) 0.25 h

(4) 1 h

Consider the reaction

[AIEEE - 2010, 4/144]

Cl2 (aq) + H2S(aq) S(s) + 2H+ (aq) + 2Cl (aq)


The rate equation for this reaction is
rate = k [Cl2][H2S]
Which of these mechanisms is/are consistent with this rate equation?
A.

Cl2 + H2S H+ + Cl + Cl+ + HS (slow)


Cl+ + HS H+ + Cl + S (fast)

B.

H2S H+ + HS (fast equilibrium)


Cl2 + HS 2Cl + H+ + S (slow)

(1) B only
20.

(2) Both A and B

(3) Neither A nor B

(4) A only

The rate of a chemical reaction doubles for every 10 C rise of temperature. If the temperature is raised by 50 C,
the rate of the reaction increases by about :
(1) 10 times

21.

(2) 24 times

[AIEEE-2011]
(3) 32 times

(4) 64 times

For a first order reaction, (A) products, the concentration of A changes from 0.1 M to 0.025 M in 40
minutes. The rate of reaction when the concentration of A is 0.01 M, is
(1) 1.73 10 M/min
3

(2) 3.47 10 M/min


4

(3) 3.47 10 M/min


5

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[AIEEE-2012, 4/120]
(4) 1.73 104 M/min

CHEMICAL KINETICS # 38

PART-NCERT QUESTIONS
1.

From the rate expression for the following reactions, determine their order of reaction and the dimensions of the
rate constants.
(i) 3NO(g) N2O (g)
Rate = k[NO]2

(ii) H2O2 (aq) + 3I (aq) + 2H 2H2O (l) + I3


Rate = k[H2O2] [I]
(iii) CH3CHO (g) CH4 (g) + CO(g)
Rate = k[CH3CHO]3/2
(iv) C2H5Cl (g) C2H4 (g) + HCl (g)
Rate = k[C2H5Cl]

2.

For the reaction :


2A + B A2B
the rate = k[A][B] 2 with k = 2.0 10 6 mol 2 L 2 s 1. Calculate the initial rate of the reaction when
[A] = 0.1 mol L1, [B] = 0.2 mol L1. Calculate the rate of reaction after [A] is reduced to 0.06 mol L1.

3.

The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of production of N2 and
H2 if k = 2.5 104 mol1 L s1?

4.

The decomposition of dimethyl ether leads to the formation of CH4, H2 and CO and the reaction rate is given by
Rate = k [CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in a closed vessel, so the rate can also be expressed in
terms of the partial pressure of dimethyl ether, i.e.,
Rate = k (PCH3OCH3)3/2
If the pressure is measured in bar and time in minutes, then what are the units of rate and rate constants?

5.

Mention the factors that affect the rate of a chemical reaction.

6.

A reaction is second order with respect to a reactant. How is the rate of reaction affected if the concentration of
the reactant is
(i) doubled
(ii) reduced to half ?

7.

What is the effect of temperature on the rate constant of a reaction? How can this effect of temperature on rate
constant be represented quantitatively?

8.

In a pseudo first order hydrolysis of ester in water, the following results were obtained :

(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
9.

A reaction is first order in A and second order in B.


(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?

10.

In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of
A and B as given below :

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


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CHEMICAL KINETICS # 39

11.

The following results have been obtained during the kinetic studies of the reaction :
2A + B C + D

Determine the rate law and the rate constant for the reaction.
12.

The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks
in the following table:

13.

Calculate the half-life of a first order reaction from their rate constants given below :
(i) 200 s1
(ii) 2 min1
(iii) 4 years1

14.

The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80%
of the 14C found in a living tree. Estimate the age of the sample.

15.

The experimental data for decomposition of N2O5


[2N2O5 4NO2 + O2] in gas phase at 318K are given below :

(i) Plot [N2O5] against t.


(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log[N2O5] and t.
(iv) What is the rate law ?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).
16.

The rate constant for a first order reaction is 60 s1. How much time will it take to reduce the initial concentration
of the reactant to its 1/16th value?

17.

During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1g of 90Sr was absorbed in the
bones of a newly born baby instead of calcium, how much of it will remain after 10 years and 60 years if it is not
lost metabolically.
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CHEMICAL KINETICS # 40

18.

For a first order reaction, show that time required for 99% completion is twice the time required for the completion
of 90% of reaction.

19.

A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.

20.

For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are obtained.
Calculate the rate constant.

21.

The following data were obtained during the first order thermal decomposition of SO2Cl2 at a constant volume.
SO2 Cl2 (g) SO2 (g) + Cl2 (g)
Calculate the rate of the reaction when total pressure is 0.65 atm.

22.

The rate constant for the decomposition of N2O5 at various temperatures is given below :

Draw a graph between ln k and 1/T and calculate the values of A and Ea. Predict the rate constant at 30 and
50C.
23.

The rate constant for the decomposition of hydrocarbons is 2.418 105 s1 at 546 K. If the energy of activation
is 179.9 kJ/mol, what will be the value of pre-exponential factor.

24.

Consider a certain reaction A Products with k = 2.0 102 s1. Calculate the concentration of A remaining after
100 s if the initial concentration of A is 1.0 mol L1.

25.

Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law, with
t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours ?

26.

The decomposition of hydrocarbon follows the equation k = (4.5 1011s1) e28000K/T. Calculate Ea.
k = (4.5 1011s1) e28000K/T

27.

The rate constant for the first order decomposition of H2O2 is given by the following equation :
log k = 14.34 1.25 104K/T
Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes?

28.

The decomposition of A into product has value of k as 4.5 103 s1 at 10C and energy of activation
60 kJ mol1. At what temperature would k be 1.5 104 s1?

29.

The time required for 10% completion of a first order reaction at 298K is equal to that required for its 25%
completion at 308K. If the value of A is 4 1010 s1. Calculate k at 318 K and Ea.

30.

The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the energy of
activation of the reaction assuming that it does not change with temperature.
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CHEMICAL KINETICS # 41

EXERCISE # 1
A-1.
A-8.
B-5.
B-12.
C-7.
C-14.
C-21.
D-1.
D-8.
E-2.
F-3.
F-10.
G-2.
H-2.

(B)
(B)
(D)
(A)
(D)
(C)
(C)
(B)
(D)
(B)
(A)
(B)
(D)
(B)

A-2.
A-9.
B-6.
C-1.
C-8.
C-15.
C-22.
D-2.
D-9.
E-3.
F-4.
F-11.
G-3.
H-3.

(C)
(D)
(B)
(A)
(B)
(B)
(C)
(B)
(D)
(B)
(A)
(A)
(B)
(B)

1.
8.
15.
17.
19.
26.
33.
40.
47.
54.
61.
65.
70.

(A*)
2.
(D*)
3.
(C*)
9.
(C*)
10.
(A) r ; (B) p ; (C) s; (D) q 16.
(A) s, (B) r, (C) p, (D) q 18.
(C)
20.
(C)
21.
(A)
27.
(B)
28.
F
34.
T
35.
T
41.
T
42.
T
48.
T
49.
T
55.
T
56.
threshold energy
62.
mol L1s1
66.
rare
increases
71.
3

74.

rate = k[M]2

78.

infinte temp. or for zero Ea

82.

sum, exponents

1.
8.
15.
22.
29.
36.
43.

(C)
(D)
(B)
(C)
(D)
(D)
(ABC)

75.

A-3.
A-10.
B-7.
C-2.
C-9.
C-16.
C-23.
D-3.
D-10.
E-4.
F-5.
F-12.
G-4.
H-4.

1
2

PART # I
A-4.
(A)
B-1.
(B)
B-8.
(B)
C-3.
(B)
C-10. (C)
C-17. (B)
C-24. (C)
D-4.
(D)
D-11. (C)
E-5.
(B)
F-6.
(C)
F-13. (C)
G-5.
(C)
H-5.
(B)

(B)
(C)
(B)
(D)
(D)
(B)
(C)
(D)
(C)
(A)
(C)
(D)
(D)
(B)

A-5.
B-2.
B-9.
C-4.
C-11.
C-18.
C-25.
D-5.
D-12.
E-6.
F-7.
F-14.
G-6.
H-6.

(D)
(D)
(B)
(D)
(C)
(B)
(C)
(A)
(C)
(B)
(D)
(B)
(A)
(B)

A-6.
B-3.
B-10.
C-5.
C-12.
C-19.
C-26.
D-6.
D-13.
F-1.
F-8.
F-15.
G-7.*

(D)
A-7.
(D)
B-4.
(D)
B-11.
(B)
C-6.
(C)
C-13.
(A)
C-20.
(A)
C-27.
(C)
D-7.
(B)
E-1.
(A)
F-2.
(A)
F-9.
(D)
G-1.
(ABCD) H-1.

PART # II
(B*)
4.
(A*)
5.
(C*)
6.
(A*)
7.
(B*)
11.
(B*)
12.
(A*)
13.
(C*)
14.
(A) p, q, r, s ; (B) q, r, s ; (C) p, q, r, s ; (D) p, r, s
(A) r ; (B) s ; (C) p ; (D) q
(D)
22.
(A)
23.
(C)
24.
(A)
25.
(A)
29.
(A)
30.
(B)
31.
F
32.
F
36.
F
37.
T
38.
T
39.
T
43.
F
44.
F
45.
F
46.
F
50.
T
51.
T
52.
T
53.
F
57.
F
58.
T
59.
T
60.
half
63.
equal to H
64.
directly proportional
67.
lowering
68.
fast
69.
slowest
72.
rate constant
73.
2 and 3
76.

77.

Activation energy for forward reaction

79.

first

80.

k
2.303

81.

unchanged

6.
13.
20.
27.
34.
41.

(B)
(D)
(B)
(A)
(C)
(ACD)

(B)
(C)
(D)
(B)
(B)
(B)
(C)
(A)
(A)
(C)
(A)
(C)
(B)

(C*)
(C*)

(C)
T
F
T
F
F

EXERCISE # 2
2.
9.
16.
23.
30.
37.
44.

(C)
(C)
(B)
(C)
(C)
(C)
(CD)

3.
10.
17.
24.
31.
38.
45.

(C)
(B)
(D)
(D)
(C)
(C)
(ABC)

4.
11.
18.
25.
32.
39.

(D)
(B)
(D)
(C)
(A)
(D)

5.
12.
19.
26.
33.
40.

(B)
(C)
(B)
(A)
(B)
(AD)

7.
14.
21.
28.
35.
42.

(A)
(A)
(D)
(B)
(D)
(AC)

SUBJECTIVE
1.
3.
5.
6.
7.

(a) 4.5 103 M sec1 (b) 3.0 103 M sec1


4.32 104 M sec1
64
(a) Rate of decomposition of NH3.
(c) 2.5 104 M sec1 , 7.5 104 M sec1
(a) 5 105 M/s (b) 4.2 105 M/s

2.
4.

(a) 40.5 gm min1 (b) 76.5 gm min1


(a) 0.019 M1 s1 , (b) 0.038 M1 s1

(b) Rate of formation of N2 and rate of formation of H2


(d) (i) 1 , (ii) 0

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CHEMICAL KINETICS # 42

8.
9.
10.

(i) 2nd order, (ii) 1st order, (iii) Third order, (iv) r = K[A]2[B] (v) k = 3.33 105 mole2 +2 sec1
order with respect to A = 1, order with respect to B = 0
3
11.
(a)
n = 2,
(b)
First Order

12.

1.58 102, 2.33 atm.

13.

2P0

15.

( V3 V1)
1
ln ( V V )
t
3
2

16.

% decomposition = 67.10%

18.

Rate = k [NO]2 [Br2]

19.

(a) 2 B+F 2E; (b) A; (c) C,D; (d) rate = k [B][C]; (e) rate = k'[A][B] (f) 2.

21.

0.001607

22.

t=

(2 P0 P)2
P0

14.

3.27 103 min1


17.

k [N2O5]

0.693
K f Kb

EXERCISE # 3
PART-I
1.1

(D) 1.2 EA = 100 KJ/mol

1.7

(A) 1.8 (a) R0 = k[A0], (b) 0.5 sec1.

1.9

2X(g) 3Y(g) + 2Z(g)


t=0
800

t=0
800 2x
3x 2x = (800 + 3x)
from given data in time 100 min the partial pressure of
X decreases from 800 to 400
so t1/2 100 min. Also in next 100 min Px decreases
from 400 to 200 to again t1/2 = 100 min. Since half left
is independent of initial concentration so reaction must
Ist order with respect to X.
Rate constant K =

1.10
1.16

1.3 (B) 1.4 t1/2 = 24 min.

1.5

(A)

1.6

(B)

1.14

1.15

(3)
(3)
(4)

2.6
2.13
2.20

(3)
(4)
(3)

2.7
2.14
2.21

n2
= 6.93 103 min1.
t1/ 2

Time taken for 75% completion = 2 t1/2 = 200 min.


Now when Px = 700 = 800 2x so x = 50 mm of Hg
so total pressure = 800 + 3x = 950 mm of Hg
(D)
1.11
(A)
1.12
(D)
1.13
(A)
(A)
1.17
(A, B, D)
1.18
9

PART-II
2.1
2.8
2.15

(1)
(4)
(2)

2.2
2.9
2.16

(1)
(3)
(1)

2.3
2.10
2.17

(4)
(1)
(2)

2.4
2.11
2.18

(4)
(1)
(3)

2.5
2.12
2.19

(1)
(2)
(2)

EXERCISE # 4
1.
3.
4.
5.

rav = 6.66 106 Ms1


Order of the reaction is 2.5
XY
Rate = k[X]2
The rate will increase 9 times
t = 444 s

9.

1.471 1019

2.

Rate of reaction = rate of diappearance of A = 0.005 mol litre1min1

6.

1.925 104 s1

8.

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Ea = 52.897 kJ mol1

CHEMICAL KINETICS # 43

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