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 Chemical Kinetics

10 Years ' KCET Topicwise Trend at a Glance

No. of Questions
NCERT Topic
2014 2015 2016 2017 2018 2019 2020 2021 2022 2023

3.1 Rate of a Chemical Reaction 1 1 1 1

3.2 Factors Influencing Rate of a Reaction 1 1 1 2 2 1

3.3 Integrated Rate Equations 1 2 1 1 1 1 3 1

3.4 Temperature Dependence of the Rate of a

1 1 1 1 2
Reaction

3.5 Collision Theory of Chemical Reactions 1 1

Introduction Negative sign shows decrease in concentration

with time and positive sign shows increase in
Chemical kinetics is a branch of chemistry which deals concentration with time.
with the study of rate of reaction, mechanism and the
factors which affects the rate of reactions. Average and Instantaneous Rate of Reaction

Study of rate of reaction helps to predict how quickly The rate of change in concentration of any reactant or
product for a given interval of time is known as average
a reaction approaches the equilibrium. The rate of
rate of reaction. Consider the reaction :
reaction also provides information of mechanism of
RP
reaction .
—
R₂ − R₁ A[R]
By studying the reaction rate we can find out that in rav
t2- t1 ΔΙ
how many steps the reaction is taking place and which
Concentration

step is rate determining step . By knowing this we can

[R]o-
control the rate of a reaction as well. Factor affecting
reactants

the rate of reaction helps us to increase the rate of our

desired reaction.
of

[R₁ ]
AR Rav -^[R] __ -{ [R₂] − [R₁ ]}
3.1 Rate of a Chemical Reaction ΔΙ (t2- t₁)
d[R]
The rate ofreaction is the change in the concentration [R₂] K-At->
of any one of the reactants or products per Rinst = -d[R] slope
dt
unit time . dt
Decrease in conc. of reactant
Rate :=
Time taken t1 t2 t Time
Increase in conc. of product
where, R2 and R₁ are the concentrations of R at time t₂
Time taken
and t₁ respectively. The rate of change in concentration
Consider the hypothetical reaction : of any reactant or product at a particular instant of time
is known as instantaneous rate of reaction .
A B

Δ[Α] A[B] d[R] _d [P]

Rate = =+ Tinst
ΔΙ ΔΙ dt dt
Chemical Kinetics 111

d[P]
rinst =
dt
= slope (i) rate of appearance of Q
(P) (ii) rate of reaction.
stcudorpf Soln.: (i) Rate of appearance of Q
d[P]
d [Q] = 2 x10-2
[P2]
dt . x10-2 mol L-1 s-1
= 04
o dt 5
nnioetcanrot ∆[P] (ii) Rate of reaction
[P1] ∆[P] = [P2] −[P1] 1 d [Q] 1
∆t rav =
∆t (t21
−t ) x 04. x10-2 = 01.x10-2 mol L-1 s-1
C 4 dt = 4
The reciprocals of coefficients are written for the
t1 t2 t expression of rate of reaction.
Time
Units of rate of reaction : Illustration : How are the rates of formation of NO
and H2O related to the rate of consumption of NH3?
Concentration mol/litre
Rate = = = mol litre–1sec–1 1 d[ NO] = 1 d[HO2 ] = − 1 d[NH3 ]
Time sec Soln.:
Partial
Time
pressure 4 dt 6 dt 4 dt
In gaseous reaction = = atm s−1 d[NO] d[NH3 ]
\ =-
dt dt
Illustration : In a chemical reaction 2P → 4Q + R,
d[H2O] 6 d[NH3 ] d[NH3 ]
the concentration of Q is found to be increased by =- =-15.
2.0 × 10–2 mol L–1 in five seconds. Calculate dt 4 dt dt

Self Test - 1
1. For a reaction P + Q → 2R + S. Which of the d[ A] d[B ] d[dtA] = ]1
2 d[B
(a) - =4 (b) -
following statements is incorrect? dt dt dt
(a) Rate of disappearance of P -d[ A] = ]1
d[B d[ A] = d[B]
(c) (d) -
= Rate of appearance of S dt 4 dt dt dt
(b) Rate of disappearance of Q =
4. 2SO2rate
The + O2of→disappearance
2SO3 is 1.28 ×of10–5
SOM2 in the reaction,
2 × Rate of appearance of R s–1. The rate of
(c) Rate of disappearance of P = appearance of SO3 is
Rate of disappearance of Q (a) 0.64 × 10–5 M s–1 (b) 0.32 × 10–5 M s–1
(d) Rate of disappearance of Q = (c) 2.56 × 10–5 M s–1 (d) 1.28 × 10–5 M s–1
1 × Rate of appearance of R 5. The rate of formation of ammonia by the reaction :
2 N2 + 3H2 2NH3
2. In
of
is the
therate
formation
reaction, NO2O
of change
of 2N 2of
i5s[N
→ ] at
0.0072
2O54NO
molthe
2 L–1
+same
O2s–1.
, the
time?
rate d[]NH 3 = 2.5 × 10–4 mol L–1 s–1
What expressed as
dt
The rate of consumption expressed in terms of H2
(a) 0.0018 (b) 0.0144 −d[]H2
dt
(c) 0.0036 (d) 0.0072 as will be

3. For a reaction rate of disappearance of A is related (a) double (b) three times
to the rate of appearance of B by the expression (c) same
1 (d) one and a half time of that expressed in terms
A →2B
2 of NH3.

3.2 Factors Influencing Rate ofa Reaction

Rate of reaction depends upon number of factors : concentration of reactants, as the concentration of
1. Concentration reactants decreases (or that of products increases) with
Rate of reaction is directly proportional to the due course of time, rate of reaction also decreases.
112 Objective Karnataka CET | Chemistry

2. Temperature Reaction Order Units of rate constant

Rate of reaction increases with increase of temperature
Zero order 0
and usually becomes double for 10°C rise of temperature. mol L-1 1
reaction x =mol L–1 s–1
3. Catalyst s (mol L-1)0
Catalyst generally increases the speed of reaction by First order 1 mol L−1 1
lowering the energy barrier i.e., activation energy. reaction × = s–1
s (mol L−1)1
4. Surface Area of Reactant
Second 2 mol L−1 1
Greater the surface area (i.e., smaller particle size), ×
order 2 =mol–1 L s–1
faster will be the reaction. reaction s (mol L−1)
5. Nature of Reactant
Different reactants undergo similar kind of reaction Molecularity of a Reaction
with different rates because the energy factor involved • The minimum number of reacting particles
with different bonds are different. (molecules, atoms, or ions) that come together or
6. Presence of Light collide in a rate determining step to form product
Light provides the necessary activation energy for or products is called molecularity of reaction. It may
photochemical reactions. be unimolecular, bimolecular and trimolecular, etc.
NH4NO2 → N2 + 2H2O (unimolecular)
Rate Expression and Rate constant NO + O3 → NO2 + O2 (bimolecular)
• For the reaction, aA + bB cC + dD
Rate ∝ [A]x [B]y where exponents x and y may or 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4 (trimolecular)
• The molecularity is equal to the sum of number of
may not be equal to the stoichiometric coefficients
molecules of the reactants involved in a balanced
(a and b) of the reactants.
d[R] = k[A]x [B]y equation. The molecularity of such reactions is
Rate = – determined by the slowest step. Molecularity
dt
where k is a proportionality constant called rate depends upon the mechanism of the reaction.
constant and this equation is called rate law or rate Difference between molecularity and order of
expression. reaction
• Rate law is the expression in which reaction rate is S. Molecularity of Order of reaction
given in terms of molar concentration of reactants No. reaction
with each term raised to some power, which may or 1. It is the number It is the sum of
may not be same as the stoichiometric coefficient of of molecules of powers raised on
the reacting species in a balanced chemical equation. reactants taking part concentration terms in
in elementary step of a the rate expression.
Order of Reaction reaction.
Order of reaction is the sum of the exponents (powers)
2. It is a theoretical The values are derived
to which molar concentrations are raised in the rate law.
r = K[A]x [B]y concept. from rate expression.

Order of reaction (n) = (x + y) 3. Its value cannot be Its values can be zero
Order of a reaction can be 0, 1, 2, 3 zero or fractional. or fractional.
It can be zero, whole number, fractional or even
negative. 4. In a multistep reaction, In a multistep reaction
each step reaction
individual molecularity.
has its the order is determined
Units of rate constant : by slowest step.
Rate concentration 1
k = [A]x [B y = × ;
] time (concentration)n Illustration : For a reaction A + B → P, the rate law is
given by, r = k[A]1/2 [B]2
(where [A] = [B]) ( n = x + y)
What is the order of this reaction?
Taking SI units of concentration, mol L–1 and time,
Soln.: A + B → Product
s, the units of k for different reaction order are listed
Rate law, r = k[A]1/2 [B]2
below :
Chemical Kinetics 113

Order of reaction is sum of the powers of concentration Illustration : For the reaction, 2A + B₂ →→→
→ 2AB,
terms, following observations were obtained :
1 5
:: Order of reaction ——
= + 2 = − = 2.5 Rate of disappearance ofB₂ [A] [B2]
2 2 (mol L- ¹s-¹) (mol L- ¹) (mol L-¹)
Illustration : A reaction is of second order with 1.8 × 10-³ 0.015 0.15
respect to its reactant. How will its reaction rate be 1.085 × 10-2 0.090 0.15
affected if the concentration of the reactant is (i) 5.4 × 10-3 0.015 0.45
doubled (ii) reduced to half? Find out the following :
Soln.: Let the concentration of the reactant [A] = a (a) order of reaction
Order of reaction ==
= 2 so that,
(b) rate constant
Rate of reaction = k [A]² ...(1) (c) rate of formation of AB, when [A] = 0.02 and [B2]
= ka² = 0.04 mol L -1

(i) Given that concentration of the reactant is doubled d[B2 ]

Soln.: (a) The rate of disappearance of B2 ==
so, that [A] = 2a, dt
or r = k[A]" [B2]"
Putting the value in equation (1) we get
then 1.8 x 10-3 = k[0.015 ]" [0.15 ]" ...(i)
New rate of reaction, R₁ = k(2a) ² = 4ka²
1.085 × 10−² = k [0.090] ™ [0.15] ” ...(ii)
Hence , rate of reaction will increase to 4 times.
5.4 × 10-³ = k [0.015 ]m [ 0.45 ] " ... (iii)
(ii) Given that concentration of the reactant is
From eqns . (i) and (ii),
reduced to half
m
So that, [A] = ( 1/2)a 1.8 × 10- 0.015
= ⇒ m =1
Putting the value in equation ( 1 ) , we get 1.085 × 107 0.090
New rate of reaction R₂ = k(( 1/2)a)²
From eqns. (i) and (iii) ,
= (1/4)ka²
n
Hence, rate of reaction will reduce to 1/4. 1.8 ×10-3 = 0.15
⇒n = 1
Illustration : How can the rate of simple reaction , 5.4 × 10-3 0.45
2NO + O2 → 2NO2 , be affected , if volume of the
Order of reaction = 1 + 1 = 2
reaction vessel is doubled?
(b) Rate of disappearance of B₂ = k[A] ' [B2] ¹
Soln.: Rate (r₁) = k [NO]² [O₂]
1.8 × 10 −³ = k [ 0.015 ] ¹ [0.15 ] ¹
If volume of reaction vessel is doubled, the
k = 0.8 L mol−1 sec-1
concentration of reactants becomes half, then,
1 d [ AB] d[B2 ]
1 (c) Now,
2 dt dt
Rate (r2) = k
[ NO] [ O₂ ] d [ AB]
= 2 × k [ A]¹ [ B₂ ]¹
= dt
2 k [ NO ]² [ 02 ] == n
4
th d[AB]
1 or = 2 × 0.8 × (0.02) ¹ (0.04 ) ¹
i.e., rate becomes of the initial rate. dt
8 = 1.28 × 10−³ mol L- ¹s¯¹
S

Self Test - 2

1. The order of reaction is decided by (a) remains same

(a) temperature (b) becomes 4 times
(b) mechanism of reaction as well as relative (c) becomes one -fourth
concentration of reactants
(d) doubles.
(c) molecularity
(d) pressure. 3. In which of the following cases , does the reaction

2. If initial concentration is reduced to 1/4th in a zero go farthest to completion?

order reaction, the time taken for half the reaction (a) k = 102 (b) k = 10-2

to complete (c) k = 10 (d) k= 1

 114 MtG Objective Karnataka CET | Chemistry

4. The rate of formation of a dimer in a second order 2H2S + O2 →→→ products

dimerisation reaction is 9.1 x 10-6 mol L-1 s-1 at would increase
0.01 mol L- ¹ monomer concentration. What will (a) 3 times (b) 9 times
be the rate constant for the reaction ?
(c) 12 times (d) 27 times .
(a) 9.1 x 10-2 L mol-¹ s-¹
8. For a reaction X + Y → Z, rate ∞ [X] . What is (i)
(b) 9.1 x 10-6 L mol-1 s-1
(c) 3 x104 L mol-1 s-1 molecularity and (ii) order of reaction?

(d) 27.3 × 10-2² L mol− ¹ s¯¹ (a) (i) 2 , (ii) 1 (b) (i) 2 , (ii) 2
(c) (i) 1 , (ii) 1 (d) (i) 1 , (ii ) 2
5. Rate constant of two reactions are given below.
Identifying their order of reaction . 9. The rate of the reaction :
(i) k = 5.3 × 10−² L mol−¹ s−¹ NaOH → CH3COONa +
CH3COOC2H5 + NaOH
(ii) S
k = 3.8 x 104 s-1 C2H5OH

(a) (i) second order, (ii) first order is given by the equation ,
= k [CH3COOC₂Hs ] [NaOH]
(b) (i) first order, (ii) second order
(i) zero order, (ii) first order If concentration is expressed in mol/L, the units
(c)
of k are
(d) (i) second order, (ii) zero order
(a) mol-2 L2 S
s−1 (b) mol L-1 s-1
6. The rate constant for a first order reaction is
(c) L mol-1 s-1 (d) s-¹
equal to the initial rate of reaction when the initial
concentration of the reactant is 10. Order of a reaction can not be obtained
(a) 100 M (b) 1 x 10-2 M (a) experimentally
(c) 1.0 M (d) 0.1 M (b) from stoichiometry of the reaction
7. On increasing the pressure three fold, the rate of (c) if the reactants are gases
the given reaction (d) ifthe reactants are in different physical states.

3.3 Integrated rate Equations

It means final concentration of reactant, [ A] = [ % ]
2
The equations which are obtained by integrating the and, t becomes t1/2,
differential rate laws and which give a direct relationship
1 [Ao
between the concentrations of the reactants and time then, k =
t1/2 2 }
{ [46 ] [40]
are called integrated rate laws.

[A ]
t1

Zero Order Reaction

/2

t1/2
2k
Intercept = [a] Conc .
Thus , half-life period of a zero order reaction is directly
Slope = -k
proportional to initial concentration of reactant.
i.e. , ох
t1/2 [40]
First order reaction : The reaction in which the rate
Time 'ť'
of reaction is directly proportional to the concentration
k = =- { [ 40 ] - [ A]} of reacting substance .
t •
In first order reaction , the rate is determined by the
where, k is rate constant change of one concentration term only.
t is reaction time For a reaction, A → product
[A。] is initial reactant concentration dx dx
r= = k(a − x) or = kdt
dt (a− x)
[A] is final reactant concentration .
in
On tegration , dx
=
Half-life period f a-x) Skdt

Half-life period (†1/2) is the time in which half of the i.e. -ln(a —− x) = kt + c where , c is integration constant,
reaction has been completed i.e. , half of the reactant when t = 0, x = 0 then -ln a = c
concentration undergoes the reaction . .. -ln(a - x) = kt - In a
Chemical Kinetics 115

a Integrated Rate Equation for First Order Gas

or kt = ln a – ln (a – x) or kt = ln Phase Reactions
1 a a−x
k = ln Let us consider the general first order gas phase reaction :
t (a - x ) ln[A0] k = –slope of the A(g) → B(g) + C(g)
2303. a straight line Suppose the initial pressure of A = P0 atm.
k= log
t a-x [
n After time t, suppose the pressure of A decrease by p
I
2.303 [ A0 ] atm.
or k = log Now, as 1 mole of a decomposes to give 1 mole of B
t [ A]
and 1 mole of C, pressure of B and C will increases by p
Unit of k is sec–1 or min–1. Time (t)
each. Hence, we have
0.693 A(g) → B(g) + C(g)
• For first order reaction, t1/2 =
k Initial pressure : P0 atm 0 0
1 Pressure after time, t : (P0 –p) p atm p atm
• In general, t1/2 ∝ n 1
, where n = order of reaction
[ A0 ]− Total pressure of the reaction mixture after time t,
• order
It is independent
reaction. of initial concentration for first Pt = (P0– p) + p + p = P0 + p atm \ p = Pt – P0
\ Pressure of A after time t (PA) = P
2P0 0––(P
Ptt– P0)

But initial pressure of A (P0) ∝ initial conc. of A, i.e., [A]

and Pressure of A after time t (PA) ∝ conc, of A at time
• General expression for the time taken for nth
t, i.e., [A]
fraction of reaction of first order. Substituting these values in the first order rate equation,
2303. a 2303. [A]0
t= log k= log , we get
k a-x t [A]
2.303 a 2.303 1 2303. P0
t1/n = log = log k= log
k a k 1 t 2P0 -Pt
a- 1-
n n
Examples :
2.303 n
t1/n = log . • Zero order
k n -1
2NH3 N2 + 3H2;
• Amount of substance left after n half-lives
n Rate = k[NH3]0 = k
A =1  T
where n =
A0 2 t1/ 2 H2 + Cl2 2HCl;
Graphical representation of half life Rate = k[H2]0[Cl2]0 = k
• Ist order
• The graph of concentration, [A]t of the reactant
versus time t can be represented as 2N2O5 4NO2 + O2;
Rate = k[N2O5]
NH4NO2 N2 + 2H2O;
Rate = k[NH4NO2]
• IInd order
2NO2 2NO + O2;
Rate = k[NO2]2
H2 + I2 2HI; Rate = k[H2][I2]
• IIIrd order
2NO + O2 2NO2;
Rate = k[NO]2[O2]
Rate =+k[NO]2[Cl
2NO Cl2 2NOCl;
2]
• Fractional order
• Each successive half life in which reactant CH
Rate3CHO
= k[CH3CHO]3/2
CH4 + CO;
concentration decreases to its half value is the same.
116 || MtG Objective Karnataka CET | Chemistry

• Integrated rate equations for reactions of

2.303 a 2.303 Vo
different orders : k= = log
log
t a -x t Vt
Reaction Order Rate law Rate constant
In the present case, Vo = 46.1 cm³
R→ Products 0 [R] - [R]
Rate = k[R] k The value of k at each instant can be calculated as
t
follows:
2.303 Vo
k 2.303 [R]o k= log
R → Products 1 Rate = k[R] log t(min) V t
t [R] V₁t
2.303 46.1
10 29.8 k = log = 0.0436 min - 1
Pseudo first order reactions 10 min 29.8
•
Reactions which have higher order true rate law but 46.1
2.303
are found to behave as first order are called pseudo 20 19.3 k = log
= = 0.0435 min - 1
20 min 19.3
first order reactions .
Examples : Thus, the value of k comes out to be nearly constant.
Hence, it is a reaction of the first order.
▸ Acid hydrolysis of ethyl acetate :
H+ Illustration : The rate constant for an isomerisation
CH3COOC2H5 + H₂O ·
reaction, A →→→→→ B is 4.5 x 10-3 min¹ . If the initial
CH3COOH + C2H5OH
concentration of A is 1 M, calculate the rate of
Rate = k' [ CH3COOC2H5] [H₂O] reaction after 1 h.
= k[ CH3COOC₂H5 ] where k = k'[H₂O]
Soln.: Rate constant in min¹ shows that it is a
‣ Acid catalysed inversion of cane sugar : reaction of 1st order.
H+
C12H22O11 + H2O· → C6H12O6 + C6H12O6 ; 2.303 [A]o = 2.303 1
Cane sugar Fructose k= log log
Glucose [ A]t [A]t
t 60 min
Rate = k [C12H22O11]
= 4.5 x 103 min¹ or log [4] , = -0.1172
.. [A] = 0.7635 mol L- ¹
Info This is the concentration after 1 hr.
Shots
Rate of reaction after 1h = k[A]t
Reaction Order Rate law Rate constant = 4.5 x 10-3 x 0.7635 mol L-¹ min-1
X 10-3 mol L-¹ min-1
= 3.44 ×
1 1 1
2R→Products 2 Rate = k[R]2 k == Illustration : The decomposition of Cl₂O, at 400 K
t \ [ R] [ R]o in the gas phase to Cl2 and O2 is of 1st order. After 55
sec at 400 K, the pressure of Cl2O7 falls from 0.062 to
1 2.303
= 0.044 atm , calculate
A+B→ t ([A] - [ B]o )
2 Rate = k[A] [B] (a) the rate constant
Products (b) pressure of Cl₂O, after 100 sec.
[B] [ A]
log
[ A] [ B]
Soln.: C1207 Cl, +
202
3R→ Products 3 1 1 1 Mole at t = 0 a 0 0
Rate = k[R]3 k= Mole at t = 55 se
sec (a - x) x 7x/2
2t [R] [R
(a) Since, pressure of Cl2O7 is given so , a ∞ 0.062
2.303 a 2.303 0.062
Illustration : From the following data, show that the k= log10 = log10
decomposition of hydrogen peroxide is a reaction of t a- x 55 0.044
first order : k = 6.24 × 10-3 sec-1
t 0 10 20 (b) At t = 100 sec, (a - x) ох
∞ Pt
X 46.1 29.8 19.3
2.303 0.062
where, t is the time in minute and x is the volume .. 6.24x10 = log10
100 Pt
of the standard KMnO4 solution in cm³ required for
titrating the same volume of the reaction mixture . 0.062 6.24x10-1 0.062
log10 = = 0.270⇒ = 1.86
Soln.: Volume of KMnO4 solution used amount of 2.303
Pt Pt
H₂O2 present. Hence, if the given reaction is of the
first order, it must obey the equation : .. Pt = 0.033 atm
Chemical Kinetics 117

Self Test - 3
1. The reaction, X product, follows first order (c) 0.72 x 10–3 s–1 (d) 2.88 x 10–3 s–1
kinetics. In 40 minutes the concentration of X
6. If 'a' is the initial concentration of the reactant,
changes from 0.1 M to 0.025 M. Then the rate of
the time taken for completion of the reaction, if it
reaction when concentration of Xis 0.01 M will be
is of zero order, will be
(a) 1.73 x 10–4 M min–1
a a
(b) 3.47 x 10–5 M min–1 (a) (b)
k k2
(c) 3.47 x 10–4 M min–1
(d) 1.73 x 10–5 M min–1 2a k
(c) (d)
k a
2. The expression to calculate time required for
7. A first order reaction has a rate constant
completion of zero order reaction is
1.15 × 10–3 s–1. How long will 5 g of this reactant
[R
(a) t = 0 ] (b) t = [R] – [R0] take to reduce to 3 g?
k (a) 444 s (b) 400 s (c) 528 s (d) 669 s
k [R0[R [R]
(c) t = (d) t = 8. The half-life of a first order reaction is 10
[R0 ] ]-0 ] minutes. If initial amount is 0.08 mol/litre and
3. Half-life period of 2nd order reaction is
concentration at some instant is 0.01 mol/litre,
(a) proportional to initial concentration of then t =
reactants (a) 10 minutes (b) 30 minutes
(b) independent of initial concentration of (c) 20 minutes (d) 40 minutes.
reactants
(c) inversely proportional to initial concentration 9. The decomposition of N2O5 is a first order reaction
of reactants represented
15 minutes the
by N2O5
volume of O2
N2O4
produced
+ 12O2is. 9After
(d) inversely proportional to square of initial mL
concentration of reactants.
and at the end of the reaction 35 mL. The rate
4. The rate constant is numerically the same for constant is equal to
three reactions of first, second and third order 1 35 15
1 44
respectively. Which one is true for rate of three (a) ln (b) ln
15 26 35
reactions, if concentration of reactant is greater
than 1 M? 1 35 1 44
(c) ln (d) ln
(a) r1 = r2 = r3 (b) r1 > r2 > r3 15 44 15 26
(c) r1 < r2 < r3 (d) All of these 10. In a bimolecular reaction, if one of the reactants is
5. The rate constant of a first order reaction whose in large excess, then order of reaction is said to be
half-life is 480 s is (c) second
(a) zero (b) pseudo first
(a) 1.44 x 10–3 s–1 (b) 1.44 s–1 (d) third.

3.4 Temperature Dependence of a rate of a reaction without itself undergoing any

permanent chemical change.
Rate of Reaction
► Catalyst provides an alternate pathway or
• For a chemical reaction with rise in temperature by
reaction mechanism by reducing the activation
10°, the rate constant is nearly doubled.
energy between reactants and products and
• The ratio of the rate constant at 308 K to that at 298
hence lowering the potential energy barrier as
K is called temperature coefficient of the reaction.
shown in figure.
Arrhenius equation ► A catalyst does not alter Gibbs energy, AG and
• k = Ae–Ea/RT AH of a reaction. It catalyses the spontaneous
► Effect of catalyst on the rate of reaction : reactions but does not catalyse non-spontaneous
A catalyst is a substance which increases the reactions.
118 MtG Objective Karnataka CET | Chemistry

Reaction path Illustration Temperature coefficient for the

Reaction
rgyial

without catalyst saponification of an ester by NaOH is 1.75 . Calculate

eneent

path with
Energy of the activation energy.
Pot

catalyst Energyof activation

activation without k2
Reactants Soln.: Temperature coefficient i.e. , = 1.75
with catalyst catalyst k1
In general practice, T₁ is taken as 25 ° C i.e. , 298 K
Products and T½ as 35°C i.e. , 308 K
Ea
T₂ - T₁
Thus , log 2 =
k 2.303R TIT₂
Reaction coordinate
Effect of catalyst on activation energy Ea 10
log 1.75 X
▸ A catalyst does not change the equilibrium 2.303 × 1.987 308 × 298
constant of a reaction rather, it helps in attaining
Ea = 10.207 kcal mol- ¹
the equilibrium faster.
Illustration : In general, it is observed that the rate
Calculation of Activation Energy of a chemical reaction doubles with every 10° rise
in temperature. If this generalization holds for a
The minimum energy that the reacting molecule
must possess before undergoing a reaction is called reaction in the temperature range 295 K to 305 K.
activation energy. What would be the value of activation energy for this
reaction ?
k = Ae-Ea/RT (Arrhenius equation)
Ea Soln.: T₁ = 295 K, k₁ = k (say)
2.303logk = 2.303logA -
RT T₂ = 305 K, k₂ = 2k, Ea = ?
Ea
logk = logA Using Arrhenius equation
× 301

2.303R - Ea
Slope = 2.303R
When log k is plotted against k Ea T2 - Ti
log =
Ea Intercept
= logA k₁ 2.303 R T₁T₂
1 /T, slope
2.303R
1/T E
E = -2.303R × slope 2k a 305 - 295
log
Alternatively, let k₁ and k₂ are the rate constants for k 2.303 × 8.314 295 × 305
the reaction at two different temperatures T₁ and T₂
respectively. 2.303 × 8.314 × 295 × 305 × log 2
Ea =
E.a 10
logk₁ = log A -
2.303RT
2.303 × 8.314 × 295 × 305 × 0.3010
Ea k₂ Ea 1 1 =
logk₂ = log A ; log. 10
2.303RT2 k₁ 2.303R T T
== 51855.2 J mol¹ = 51.855 kJ mol- ¹
By solving this , one can calculate activation energy.

Self Test - 4
→ yial

1. The potential energy

Potent

increases by a factor greater than two

energ

(b)
diagram for the reaction (c) decreases by a factor lesser than two
R→→→→ P is given below : b
(d) is also increased by a factor of two .
AH° of the reaction
R 3.
corresponds to the energy Which of the following statements is incorrect?
(a) a (b) b (a) Activation energy for the forward reaction
Reaction coordinate-
(c) c (d) a +b equals activation energy for the reverse
reaction.
2. By increasing the temperature by 10°C, the rate
of forward reaction at equilibrium is increased by (b) For a reversible reaction , an increase in
temperature increases the reaction rate for
a factor of2. The rate of backward reaction by this
increase in temperature both the forward and the backward reaction.

(a) remains unaffected (c) Larger the initial reactant concentration for
Chemical Kinetics 119

a second order reaction, the shorter is its half temperature

life. evaluating rate constant at two different
(c)
(d) When At is infinitesimally small , the average temperatures
rate equals the instantaneous rate . (d) by doubling concentration of reactants.
4. The activation energy for a simple chemical 6. Which ofthe following statements is incorrect?
reaction A → B is E, in forward direction. The
activation energy for reverse reaction (a) The catalyst does not affect the equilibrium
of a reaction .
(a) is always less than Ea
(b) is always double of E (b) Reaction with higher activation energy has

(c) can be less than or more than Ea higher rate constant.

(d) is negative of Ea· (c) In an exothermic reaction , the activation

5. energy of the reverse reaction is higher than

The activation energy of a reaction can be
that of the forward reaction .
determined by
(a) changing the concentration of reactants (d) Half- life period of a first order reaction is
(b) evaluating rate constant at standard independent of initial concentration.

3.5 Collision Theory of Chemical Reactions

Collision Theory
•
Reactions occur when molecules collide with appropriate orientation and sufficient energy, not all molecular
collisions result successfully in the formation of product.
• For any successful collision :
► Particles must collide with sufficient energy > Ea•

They need to have correct alignment (collision geometry) to keep E, as low as possible.
► To account for effective collision , another factor P, called orientation factor or steric factor or probability
factor is introduced .
k = PZABe Ea/RT

where, ZAB represents the collision frequency of reactants A and B.

HS+
Improper 8-
H - C - Br + OH¯ — → No products
orientation
H、 8+
H
H- C- Br + OH— H H
H δ T 8-
Proper
.... Br
HO .... C .. → HO - C - H + Br¯
orientation
A
H H H

Self Test - 5

1. The rate constant is given by the equation be hard spheres and ignores their structural
k = PZe Ea/RT. Which factor should register features.

a decrease for the reaction to proceed more (b) Number of effective collisions determines
the rate of reaction.
rapidly?
(a) T (b) Z (c) Collision of atoms or molecules possessing

(c) E (d) P sufficient threshold energy results into the

product formation .
2. Which of the following statements is incorrect
(d) Molecules should collide with sufficient
about the collison theory of chemical reaction?
threshold energy and proper orientation for
(a) It considers reacting molecules or atoms to the collision to be effective.
 CHEMICAL KINETICS

CONCEPT Chemical kinetics helps us to determine the rate of a chemical reaction and also describe the conditions by which
the reactions rates can be altered . It also provides evidence for the mechanisms of chemical processes. Knowledge of
reaction mechanisms is of practical use in deciding what is the most effective way to cause a reaction to occur. The word
MAP kinetics is derived from the greek word ' kinesis ' meaning movement . Thermodynamics tells only about the feasibility of
a reaction whereas chemical kinetics tells about the rate of a reaction .

Rate of Reaction Order and Molecularity Integrated Rate Equation

of Reaction

For Zero Order

It is defined as the change in Order of Reaction
concentration of any one of It is defined as the sum of the
the reactants or products per powers of the concentration K = t [ 40] - [ 4]}
unit time. terms in the rate law. For a Where, k = rate constant,
given reaction, t = time,
Average rate and mA +nB → Product [A]。 = initial reactant
instantaneous rate rate = k [A]™ [B]” concentration,
.. order of reaction = m + n [A] = final reactant
The rate measured over a long
time interval is called average • It can be zero order, first concentration at
rate and the rate measured for order and so on. It can also time 'ť'
an infinitesimally small time be fractional.
interval is called instantaneous For First Order
rate.
Molecularity of Reaction a
K
t log (
2.303 )
It is defined as the number of
Rate Constant molecules of reactants taking
part in a chemical reaction .
It is equal to the rate of reaction For nth Order
It can be 1 , 2 , 3 ... but can
when the concentration of neither be zero or fractional.
each of the reactants is unity. 1 1 1
K=
an-l
t(n − 1) | ( a − x)”—1
where,
Temperature Dependence
Factors affecting rate k = rate constant,
of reactions of Rate of Reaction
a = initial concentration ,
Concentration of reactants : n = order of reaction ,
Greater the concentration , Collision Theory
x = concentration of reactant
faster is the reaction . k= PZeaIRT decomposed in time t.
Presence oflight: It provides where
the necessary activation . P = steric factor
energy and the reaction starts Z = collision frequency
(photochemical reactions) . Half Life Period
• Catalyst: It increases the Concept of activation energy
speed of reaction by lowering
The excess energy which must Time during which the
the energy barrier. i.e. , a new be supplied to the reactants to concentration of a reactant is
path is followed with lower undergo chemical reactions is reduced to half of its initial
activation energy. called activation energy (E ). concentration.
Surface area: Greater the E = E(threshold) -
E (reactants)
surface area, faster is the General expression for 11/2
reaction.
Arrhenius Equation a
• Temperature : Generally, Forzeroorderreaction, 1/2 =
the rate of reaction becomes Arrhenius proposed a 2k
• For first order reactions ,
almost double for every 10°C quantitative relation ship
between rate constant and 0.693
rise in temperature . The t1/2 =
temperature coefficient is temperature as k
defined as the ratio of rate k = Ae-Ea/RT Timerequiredforth fractional
Ea 2.303 . 1
constant at 308 K to that at change (t1/n) = -log- 1
In k = ln A- k
298 K. RT
Kt (308 K Ea n
log10 k = log10 A- Amount of substance left after
Temp. coefficient = 2.303RT
K a
(298 K) k2 Ea T₂ - Ti n half lives
(Value lies generally between log == 2n
2 and 3.) k₁ 2.303R T - T₂ • For zero order t3/4 = 1.5t1/2
Chemical Kinetics 121

3.1 Rate of a Chemical Reaction 10 minutes. What is the rate of reaction during
this interval?
1. When a chemical reaction takes place, during the (a) 5 × 10–3 M min–1
course of the reaction the rate of reaction (b) 2.5 × 10–3 M min–1
(a) keeps on increasing with time (c) 5 × 10–2 M min–1
(b) remains constant with time (d) 2.5 × 10–2 M min–1
(c) keeps on decreasing with time
7. In a reaction 2X → Y, the concentration of X
(d) shows irregular trend with time. decreases from 3.0 moles/litre to 2.0 moles/litre in
d[ A] indicates the 5 minutes. The rate of reaction is
2. The minus signinrate = -
dt (a) 0.1 mol L–1 min–1 (b) 5 mol L–1–1 min–1
_____ in concentration of the _____ with time. (c) 1 mol L–1 min–1 (d) 0.5 mol L min–1
The rate of a reaction is always _____ quantity.
The rate of reaction increases with _____ in 8. For the reaction, R→P, the concentration of
concentration of reactants. The blanks in the a reactant changes from 0.03 M to 0.02 M in 25
question corresponds to min. Calculate the average rate of reaction using
(a) decrease, products, positive, increase units of time in seconds.
(b) increase, reactants, negative, decrease (a) 6.66 × 10–5 (b) 6.6 × 10–6
(c) decrease, reactants, positive, increase (c) 5.67 × 10–5 (d) 7.26 × 10–6
(d) increase, products, positive, increase 9. HIadecreases
In reaction 2HI
from→0.7
H2mol
+ I2L
, the–1 concentration of
to 0.4 mol L–1 in
3. For a reaction R → P, the concentration of a
10 minutes. What is the rate of reaction during
reactant changes from 0.05 M to 0.04 M in 30
this interval?
minutes. What will be the average rate of reaction
(a) 1.5 × 10–2 M min–1 (b) 2.5 × 10–3 M min–1
in minutes?
–4
(a) 4 × 10 M min–1 (c) 5 × 10–2 M min–1 (d) 2.5 × 10–2 M min–1
(b) 8 × 10–4 M min–1 10. Nitrogen dioxide decomposes to nitric oxide and
(c) 3.3 × 10–4 M min–1 molecular oxygen as
(d) 2.2 × 10–4 M min–1 2NO2(g) → 2NO(g) + O2(g)
The concentration - time data for the consumption
4. For the reaction A + B → C + D, the variation of NO2 at 300° C are as follows:
of the concentration of the reactant with time is
given by the curve Time/s 0 100 200 300
(a) I NO2
[NO2. ]/M 8.4 × 10–3 5.6 ×10–3 4.3 × 10–33.0 × 10–3
(b) II Calculate the average rate of decomposition of
(c) III
(d) IV (a) –1.3 × 10–5 M/s (b) 1.3 × 10–5 M/s
5. In a reaction, X → Y, the concentration of X (c) 2.5 × 10–5 M/s (d) –2.5 × 10–5 M/s
decreases from 0.50 M to 0.38 M in 10 min. What 11. For the reaction, 2X + 3Y4Z, the rate of
is the rate of reaction in M s–1 during this interval? reaction may be represented as
(a) 2 × 10–4 (b) 4 × 10–2
(a) rate = − 1 d[X ] = 1 d[Y ] = 1 d[Z ]
(c) 2 × 10–2 (d) 1 × 10–2 2 dt 3 dt 4 dt
6. In
HIadecreases
reaction 2HI
from→0.5
H2mol
+ I2L
, the
–1 concentration 1 d[X ] 1 d[Y ] 1 d[Z ]
–1 of (b) rate = - =- =
to 0.4 mol L in 2 dt 3 dt 4 dt
122 Objective Karnataka CET | Chemistry

(c) rate = 1 d[X ] = 1 d[Y ] = 1 d[Z ] (b) -

1 d[H2]
=+
1 d[NH3]
2 dt 3 dt 4 dt 2 dt 3 dt
2 d[dtX ]
1 1 d[Y ] 1 d[Z ] 1 d[H2] 1 d[NH3]
(d) rate = =- =- + =-
3 dt 4 dt (c)
2 dt 3 dt
12. For the reaction 4A+ B → 2C + 2D, which of
1 d[H2] 1 d[NH3]
the following statement is not correct? (d) + =-
(a) The rate of disappearance of B is one fourth 3 dt 2 dt
of the rate of disappearance of A. 18. Nitrogen dioxide (NO2) dissociates into nitric
(b) The rate of formation of C is one-half of the 2NO (NO) and oxygen (O2) as follows:
oxide
2 → 2NO + O2
rate of consumption of A.
If the
6.0 × 10
rate
–12of
mol
decrease
L of. What
concentration of NO
will be the rate2 of
is
(c) The rate of appearance of D is half of the rate –1
–1 s
of disappearance of B.
increase of concentration of O2?
(d) The rates of formation of C and D are equal.
(a) 3 × 10–12 mol L–1 s–1
In
13. Consider
0.0125
the reaction
molthe
L reaction,
. 2What
is being
2N2
isOformed
5 → at 4NO
the2rate
+ O2. (b) 6 × 10–12 mol L–1 s–1
NO
s of (c) 1 × 10–12 mol L–1–1 s–1
–1 –1
the rate of reaction at
(d) 1.5 × 10 mol L s–1
–12
this time?
(a) 0.0018 mol L–1 s–1 19. In the formation of sulphur trioxide by the Contact
(b) 0.0031 mol L–1 s–1 process,
2SO2(g) + O2(g) → 2SO3(g)
(c) 0.0041 mol L–1 s–1
The rate of reaction is expressed as
(d) 0.050 mol L–1 s–1
d(O2) 25. 10-4
14. For the reaction, 2A → 3C, the reaction rate is - = x mol L–1 sec–1
dt
equal to The rate of disappearance of (SO2) will be
–1 –1
d[ A] 1 d[ A] –4
(a) - (b) - (a) 5.0 × 10 mol L s
dt 2 dt (b) 2.25 × 10–4 mol L–1 s–1
(c) -
1 d[ A]
(d)
d[ A] (c) 3.75 × 10–4 mol L–1 s–1
3 dt dt (d) 50.0 × 10–4 mol L–1 s–1.
15. In the reaction A + 3B → 2C, the rate of 20. For the reaction 4NH3 + 5O2 → 4NO + 6H2O,
formation of C is mol
if s–1of disappearance of NH3 is 3.6 × 10–3
theLrate
(a) the same as rate of consumption of A –1
, what is the rate of formation of H2O?
(b) the same as the rate of consumption of B (a) 5.4 × 10–3 mol L–1 s–1
(c) twice the rate of consumption of A (b) 3.6 × 10–3 mol L–1s–1
(d) 3/2 times the rate of consumption of B. (c) 4 × 10–4 mol L–1 s–1
16. The rate expression for the following reaction (d) 0.6 × 10–4 mol L–1 s–1
in terms of rate of consumption of reactants and 21. For the reaction, 2N2O5 →104NO–42 + O2 rate and
formation of products is rate constant are 1.02 × mol L–1 s–1 and
F2(g) + 2ClO2(g) → 2FClO2(g) 3.4 × 10–5s–1 respectively. The concentration of
d[]F2 1 d[]ClO2 N2O5 in mol L–1 will be
(a) (b) (a) 3.4 × 10–4 (b) 3.0
dt 2 dt
(c) 5.2 (d) 3.2 × 10–5
d[]FClO
2 1 d[]FClO2
(c) −2 (d)
dt 2 dt 22. For the reaction,
+ 3+ 2+
5Fe(aq) +MnO4(aq)
– +8H(aq) →5Fe(aq)+Mn(aq) +4H2O
17. For
the the
rate reaction
of reaction+
N2 expressions
3H2 → 2NH3, how are
the 2+
instantaneous rate of the reaction is
inter-related
d[H2] d[NH3 ] ? 1 d[]H
+ d[]MnO-4
and (a) (b)
dt dt 8 dt dt
1 d[H2] 1 d[NH3 ] 3+ 2+
1 d[]Fe 1 d[]Fe
(a) - =+ (c) (d)
3 dt 2 dt 5 dt 5 dt
Chemical Kinetics 123

23. For the reaction, 2N2O5-4NO2 + O2, the rate (a) pressure (b) temperature
of reaction can be expressed in terms of time and (c) concentration (d) catalyst .
concentration by the expression:
29. For the reaction, A½ + B + C →→ AC + AB, it is
d[ N2O5 ] 1 d[ NO₂ ] = 1 d[ O₂ ]
(a) Rate found that tripling the concentration ofA2 triples
dt 4 dt 2 dt
the rate, doubling the concentration of C doubles
1 d[ N2O5 ] =
_ 1 d[ NO₂ ] _ d[O₂ ] the rate and doubling the concentration of B has
(b) Rate
2 dt 4 dt dt no effect. What is the rate law?

(a) k [42 ]² [ C] (b) k [B] 1/2 [C]

1 d[ N2O5 ] _ 1 d[ NO2 ] _ d[ O₂ ]
(c) Rate (c) k [42] [ C] (d) k [42]³ [B]² [C]
4 dt 2 dt dt

1 d[ N2O5 ] =
_ 1 d[ NO2 ] _ 1 d[ O₂ ] 30. The rate of a gaseous reaction is given by the
(d) Rate =
2 dt 2 dt 2 dt expression k[A] [B]³ . The volume of the reaction .
vessel is reduced to one half of the initial volume.

24. Consider the reaction 2N2O4 4NO2 and What will be the reaction rate as compared to the
original rate a?
-d[N2O4 ] == k and d[NO2 ] = k' , then
given that
dt dt 1 1
(a) -a (b) -a
(a) 2k' = k (b) k' = 2k 8 2

(c) k =k (d) none of these . (c) 2a (d) 32a

25. The rate of reaction is expressed in different ways 31. In the reaction, A + 2B - Products, doubling
as follows : the concentration of B (keeping the concentration
1 d[C] = 1 d[D] 1 d[A] d[B] ofA constant) increases the rate
+ =+
2 dt 3 dt 4 dt dt (a) 2 times (b) 4 times
The reaction is (c) 3 times (d) 6 times .
(a) 4A + B2C + 3D Y , the rate
32. For a chemical reaction, X →→→→
(b) B + 3D → 4A + 2C
of reaction increases by a factor of 27 when the
(c) A+ B C +D concentration of X is increased by 3 times, the
(d) B + DA + C order of the reaction with respect to X is
(a) 1 (b) 3 (c) 2 (d) 2.5
26. For a reaction P + Q → 3R + S. Which of the
following statements is incorrect? 33. Consider the following reaction :
(a) Rate of disappearance of P = Rate of 2A +B + C —→→→ Products
appearance ofS How will the rate of reaction change when the
(b) Rate of disappearance of Q = 2 x
× Rate of concentration of A is doubled and that of B is
appearance ofR tripled while C is taken in excess?
(c) Rate of disappearance of P = Rate of (a) The rate reduces to 8 times of its original
disappearance of Q value.
1 (b) The rate reduces to 12 times of its original
(d) Rate of disappearance of Q = × Rate of
value.
3
appearance ofR
(c) The rate increases by 8 times of its original
3.2 Factors Influencing Rate of a Reaction value.

(d) The rate increases by 12 times of its original

27. According to law of mass action, rate of chemical value.
reaction is proportional to
34. The rate of a gaseous reaction is given by k [A] [B] .
(a) concentration of reactants
If the volume occupied by the reacting gases is
(b) molar concentration of reactants
suddenly reduced to half the original volume, the
(c) concentration of products rate of the reaction relative to the initial rate will
(d) molar concentration of products. be

28. The rate of reaction that does not involve gases (a) 1/8 (b) 1/4
does not depend upon (c) 8/1 (d) 4
124 Objective Karnataka CET | Chemistry

35. Rate of a reaction can be expressed by following (a) [A] × 2; [B] × 2 (b) [A] × 2; [B] × 4
rate expression, Rate = k[A]2 [B], if concentration (c) [A] × 1; [B] × 4 (d) [A] × 4; [B] × 1
of A is increased by 3 times and concentration of
43. Order of reaction is
B is increased by 2 times, how many times rate of
reaction increases? (a) never zero
(a) 9 times (b) 27 times (b) never fractional
(c) 18 times (d) 8 times (c) always equal to number of molecules taking
part in reaction
36. The rate of the reaction, A → product
(d) an experimentally determined quantity.
is 1.25 × 10–2 M/s when concentration of A is
0.45 M. Determine the rate constant if the reaction 44. Consider the following reaction,
is second order in A.–1 2H2 + O2 → 2H2O
–2 The rate law expression, r = k [H2 n for the
above
(a) 6.173 × 10 M s–1
–1 –1
]
(b) 6.89 × 10–4 M –1s is doubled,
reaction.
the When
rate of the
reaction
concentration
is found of
to H2
(c) 5.182 × 10–5 M s–1 be
–1 quadrupled. The value of n is
(d) 2.37 × 10–2 M s–1
(a) 0 (b) 1
37. carried
The reaction,
out in a2SO
1 dm
2(g)3 +vessel
O2(g)and
→ 2SO3(g) is
2 dm3 (c) 2 (d) 3
vessel
separately. The ratio of reaction velocities will be 45. What is the order of a reaction which has a rate
(a) 1 : 8 (b) 1 : 4 (c) 4 : 1 (d) 8 : 1 expression, rate = k [A]3/2 [B]–1?
(a) 32 (b)
1
38. The rate constant of a reaction depends upon
2
(a) temperature of the reaction
(b) extent of the reaction (c) 0 (d) 1
(c) initial concentration of the reactants 46. ForareactionA+B → C+D,ifconcentrationofA
(d) the time of completion of reaction. is doubled without altering that of B, rate doubles.
39. For the reaction A + B → products, it is found If concentration of B is increased nine times
that orders of the reaction in A and B are 1 and 2 without altering that of A, rate triples. Order of
respectively. When the conc. of A is halved and the reaction is
that of B is doubled, the rate increases by a factor 1 1
For a1reaction
47. (a) (b)I 1 (c) 2 (d) 1
2

(a) 2 (b) 8 (c) 4 (d) 16 3

–
40. The rate law for the reaction,
2
+ OCl–→IO– + Cl–, in an
2NOBr
The rate
(g) →
constant
2NOfor
(g) +the
Br2(g)
reaction
is rate =atk [NOBr]
a certain
. aqueous medium, the rate of the reaction is given
–1
d[IO− ] = [ I− ][OCl− ]
temperature is 1.62 M s–1. If the concentration by k . The overall order of
of NOBr at a certain time is 2.00 × 10–3 M, what dt [OH − ]
will be the rate of reaction? the reaction is
–1
(a) 4.40 × 10–6 M s–1 (b) 4.50 × 10–6 M s (a) –1 (b) 1 (c) 0 (d) 2
(c) 6.44 × 10–6 M s–1 (d) 6.48 × 10–6 M s–1 48. The rate of an elementary reaction A → B,
increases by 100 when the concentration of A is
41. A reaction in which reactants (R) are converted
into products (P) follows second order kinetics. If increased ten folds. The order of the reaction with
concentration of R is increased by four times, what respect to A is
will be the increase in the rate of formation of P? (a) 1 (b) 2
(a) 9 times (b) 4 times (c) 10 (d) 100
(c) 16 times (d) 8 times 49. 2A → B + C would be a zero order reaction
42. The rate expression for the reaction, when
A(g) + B(g) → C(g) is rate = K[A]2 [B]1/2. What (a) the rate of reaction is proportional to square
changes in the initial concentrations of A and B of concentration of A
will cause the rate of reaction to increase by a (b) the rate of reaction remains same at any
factor of eight? concentration of A
Chemical Kinetics 125

(c) the rate remains unchanged at any [A] moles/ L d [Product]/dt(moles/L/sec)

concentration of B and C
0.003 10.0 × 10–5
(d) the rate of reaction doubles if concentration
0.006 5.0 × 10–5
of B is increased to two times.
0.012 2.5 × 10–5
50. Which of the following is an example of a fractional (a) 1 (b) –2 (c) –1 (d) 2
order reaction? (All are elementary reactions.)
(a) X + Y → Z 58. The rate of reaction A + B + C → products, is
1 1
(b) P + 3Q→2R
given as: rate = k[ A]2 [B]3[C ]. The order of the
(c) S + T→4Q reaction is
(d) 1/2 A + B → C (a) 1 (b) 3
51. For the reaction, A + B → P. If [B] is doubled 5 11
at constant [A], the rate of the reaction doubles. (c) (d)
6 6
If [A] is tripled and [B ] is doubled, the rate of the
reaction increases by a factor of 6. What is the 59. The conversion of molecules x to y follows second
overall order of the reaction? order kinetics. If concentration of x is increased to
three times, the rate of formation of y will
(a) 1 (b) 3 (c) 0.5 (d) 2
(a) increase by three times
52. The rate of reaction, A + B → Products is given (b) decrease by three times
by the equation r = k[A][B]. If B is taken in large (c) increase by nine times
excess, the order of the reaction would be
(d) decrease by nine times.
(a) 2 (b) 1
(c) 0 (d) Unpredictable. 60. The decomposition of dimethyl ether is a
fractional order reaction. The rate of reaction is
53. The order of reaction is decided by given by rate = k(pCH3COCH3)3/2. If the pressure
(a) temperature is measured in bar and time in minutes, then what
(b) mechanism of reaction as well as relative are the units of rate and rate constant?
concentration of reactants (a) bar min–1, bar2 min–1
(c) molecularity (b) bar min–1, bar–1/2 min–1
(d) pressure. (c) bar–1/2 min–1, bar2 min–1
54. The rate of the reaction A + 2B → C + 2D is (d) bar min–1, bar1/2 min–1
a6 × 10–4 M/s when [A] = [B] = 0.3 M. What is the
overall 61. Match the rate law given in column I with the
given order of the is 2 × 10if–3the
temperaturereaction s rate constant at dimensions of rate constants given in column II
–1
. and mark the appropriate choice.
(a) 2.0 (b) 3.0
Column I Column II
(c) 1.0 (d) 4.0
(A) Rate = k[NH3]0 (i) mol L–1 s–1
55. For the reaction, aA → xP, when [A] = 2.2 mM the
rate was found to be 2.4 mM sec–1. On reducing (B) Rate = k[H2O2][I–] (ii) L mol–1 s–1
concentration
–1 of A to half, the rate changes to (C) Rate = (iii) s–1
0.6 mM sec . The order of reaction with respect k[CH3CHO]3/2
to A is –1
(D) Rate = k[C2H5Cl] (iv) L1/2 mol–1/2 s
(a) 1.5 (b) 2.0 (c) 2.5 (d) 3.0
(a) (A) → (iv), (B) → (iii), (C) → (ii), (D) → (i)
56. A reaction involves two reactants. The rate
of reaction is directly proportional to the (b) (A) → (i), (B) → (ii), (C) → (iii), (D) → (iv)
concentration of one of them and inversely (c) (A) → (ii), (B) → (i), (C) → (iv), (D) → (iii)
proportional to the concentration of the other. (d) (A) → (i), (B) → (ii), (C) → (iv), (D) → (iii)
The overall order of reaction will be 62. The unit of rate constant for the reaction,
(a) one (b) two 2H2
= k[H2][NO]
+ 2NO → 2H2O + N2 which has rate
(c) zero (d) none of these. 2 is
,
57. Calculate the order of reaction, A → Product, (a) mol L–1s–1 (b) s–1 –1
from the following data : (c) mol–2 L2 s–1 (d) mol L
 126 || MtG Objective Karnataka CET | Chemistry

63. In a reactionA+2B- products, the molecularity 70. The reaction A + 2B + CZ, occurs by the
of the reaction is following mechanism :
(a) 3 (b) 2 (c) 1 (d) zero . (i) A+ B X (Fast)
true (ii) X + CY (Slow)
64. Among the following statements , the
statement is (iii) Y + BZ (Very fast)
Rate law for this reaction is
(a) the order of a reaction changes with the
temperature (a) k [ C] (b) k [A] [B]² [ C]
(b) the molecularity and the order ofthe reaction (c) k [Z] (d) ] [Z]
k [X] [Y
are always equal
3.3 Integrated Rate Equations
(c) the molecularity and the order ofthe reaction
can be determined experimentally
71. A substance reacts with initial concentration of
(d) only the order and not the molecularity of a -3
a mol dm according to zero order kinetics. The
reaction can be determined experimentally.
time it takes for the completion of the reaction is
65. For a chemical reaction , (k = rate constant)
(a) the molecularity may be zero or fractional k a a 2k
(a) (b) (c) (d)
(b) the order is always equal to the molecularity a 2k k a
(c) the order is always different from the 72. The reaction X + W → Y + Z would be zero order
molecularity reaction when
(d) the order and the molecularity may be the (a) _rate remains unchanged at any concentration
same or different. of Y and Z

66. In a multistep reaction, the overall rate of reaction (b) rate ofreaction doubles if concentration ofY
is is doubled.

(a) equal to the rate of slowest step (c) rate of reaction remains same at any
concentration of X and W
(b) equal to the rate of fastest step
(c) equal to the average rate of various steps (d) rate of reaction is directly proportional to
square of concentration of X.
(d) equal to the rate of the last step.
dc
67. The reaction between H2 (g) and ICl®) occurs in 73. The rates of a certain reaction at different
the following steps : dt
times are as follows :
(i) H₂ + IC1 →→ HI + HCl
Time(s) Rate (mol L-¹ s-¹)
(ii) HI + ICl →→→ I₂ + HCl
0 2.8 × 10-2
The reaction intermediate in the reaction is
10 2.78 × 10-2
(a) HCl (b) HI
20 2.81 × 107
(c) 12 (d) ICI 30 2.79 × 10-2

68. For a reaction , 2NO + 2H2 → N2 + 2H2O , the The reaction is

possible mechanism is (a) first order (b) second order
2NO ⇒ N2O2 zero order (d) third order.
(c)
slow
N2O2 + H2 > N2O + H_O 74. The rate constant for a zero order reaction is
N₂O + H2O fast > N₂ + H₂O coct
со k=
What is the rate law and order of the reaction? (a) k= (b)
2t t
(a) Rate = k [N2O2] , order = 1 CO Ct со
(c) k = ln (d) k = £0
(b) Rate = k [N2O2 ] [H2 ] , order = 2 2t Ct
(c) Rate = k [N2O2 ]² , order = 2 75. For a general reaction
(d) Rate = k [N2O2]² [H2 ] , order = 3
X-

X → Y, the plot of conc.

Conc
o. f

69. Select the intermediate in the following reaction of X vs time is given in the
mechanism : figure. What is the order of
+ + → 202 the reaction and what are the
3(g)
(a) O3(g) (b) units of rate constant? Time →
(c) O2 (g) (d) none of these . (a) Zero, mol L s
Chemical Kinetics 127

(b) First, mol L-¹ s¯¹

S 81. Mathematical expression for t1/4 i.e. , when (1/4)th
(c) First, s- 1 reaction is over following first order kinetics can

Concentration
(d) Zero , L mol˜¯¹ s¯¹
S be given by
2.303
76. reactant (a) t1/4 = log 4
k
of

a 2.303
(b) tv
/4 = log 2
k
k = - Slope 2.303 4
(c) t1/4 = log
k 3
2.303 3
(d) t1/4 = log
k 4
82. The decomposition of dinitrogen pentoxide
Time
(N2O5) follows first order rate law. What will be
The above plot is for order reaction to
the rate constant from the given data?
calculate value of rate constant.
At t = 800 s , [N2O5 ] = 1.45 mol L
(a) second (b) first
At t = 1600 s, [N2O5 ] = 0.88 mol L-¹
(c) zero (d) first and zero (a) 3.12 ×X 10-4 s-1
S (b) 6.24 x 104 s−1
S

77. For a zero order reaction, the plot of conc. of (c) s-1
2.84 x 104 S (d) 8.14 x 104 s-1
S
products vs time is a straight line with 83. A reaction is of first order when
(a) + ve slope and zero intercept (a) the amount of product formed increases
(b) ve slope and zero intercept linearly with time
(c) + ve slope and non- zero intercept (b) the rate decreases linearly with time
(d) ve slope and non- zero intercept. (c) the rate is linearly related to the concentration
of the reactant
78. What is the two third of a first order reaction
(d) the concentration of the reactant decreases
having k = 5.48 × 10−14 s−1 ?
linearly with time .
(a) 2.01 x 1011 s (b) 2.01 Х
× 1013 S
(c) 8.08 x 1013 S 16.04 x 1011 S 84. Which of the following represents the expression
(d)
for 3/4th life of a first order reaction?
79. The decomposition of a substance follows first k 4 2.303 10 3
order kinetics. If its concentration is reduced to (a) log (b) log8 4
2.303 3 k
1/8th of its initial value in 24 minutes, the rate
2.303 2.303
constant of the decomposition process is (c) log4 (d) log 3
k k
1
(a) min−1 85. Unit of rate constant in case of first order reaction
24
is
0.692
min (a) inversely proportional to the concentration
(b)
24 units

1 (b) independent of concentration units

2.303
(c) log min¯¹
24 8 (c) directly proportional to concentration units
(d) inversely proportional to the square of
2.303 8 concentration units.
(d) log min- 1
24 01
86. The first order reaction was started with a
80. Rate constant in case of first order reaction is decimolar solution of the reactant. After 8 minutes
(a) inversely proportional to the concentration and 20 seconds, its concentration was found to be
units M/100 . The rate constant of the reaction is

(b) independent of concentration units (a) 2.303 x 10-5 sec-1 (b) 2.303 × 10 sec
ec
(c) directly proportional to concentration units (c) 4.606 x 10-3s -1
4.606 × (d) 2.606 x 104 sec

(d) inversely proportional to the square of 87. The rate constant of a first order reaction is given
concentration units. by
128 MtG Objective Karnataka CET | Chemistry

a in 200 seconds. The rate constant for the reaction is

(a) k = 2.303 xtx log10 -1 -4 S
(a− x)
(a) 1.01386 s (b) 2 × 10 s-1
(c) 1.3 86 ×
X 10− 2 s−1
S (d) 3. ×4 X 10-4sS-1
k a
(b) = 2.303log10
t (a− x) 96. A radioactive isotope having a half life period of
2.303 l 1 3 days was received after 12 days. It was found that
(c) k= og10 there were 3 g of the isotope in the container. The
t (a - x) initial amount of the isotope when packed was
2.303 a
(d) log10 (a) 36 g (b) 48 g
k=
t (a− x) (c) 12 g (d) 24 g

88. If 60% of a first order reaction was completed in 97. A first order reaction is 20% complete in 10
60 minutes , 50% of the same reaction would be minutes. What is the specific rate constant for the
reaction?
completed in approximately
(a) 40 minutes (b) 50 minutes (a) 0.0970 min (b) 0.009 min¯¹

(c) 45 minutes (d) 60 minutes (c) 0.0223 min¯¹ (d) 2.223 min- 1

[log 4 = 0.60, log 5 = 0.69 ] 98. Decomposition of a compound is known to

be a first order reaction . Three-fourths of the
89. A reaction is 50% complete in 45 minutes and 75 %
complete in 90 minutes . The order of reaction is compound taken had decomposed at the end of

(a) 1 (b) 2 3 two hours. The quantity left over at the end of the
(c) (d) 0
next three hours will be about
90. The reaction A -→→→→ B follows first order kinetics .
(a) 1% (b) 2% (c) 3% (d) 4%
The time taken for 0.8 mole of A to produce 0.6
99. A first order reaction has a rate constant
mole of B is 1 hour. What is the time taken for
conversion of 0.9 mole ofA to produce 0.675 mole 1.15 x 103 Ss¹ . How long will 5 g of this reactant
of B? take to reduce to 3 g?

(a) 1 hour (b) 0.5 hour (a) 444 s (b) 400 s

(c) 0.25 hour (c) 528 s (d) 669 s

(d) 2 hours
100. For the first order reaction , half-life is 14 s. The
91. A first order reaction is 80 % complete in 10
minutes. What is the specific reaction rate per time required for the initial concentration to
second? 1
reduce to of its value is
(b) 0.0027 s-1 8
(a) 0.510 s (a) 28 s (b) 42 s (c) (14)³s (d) (14)² s
(c) 0.161 s-1 (d) 0.2 s-1
101. The integrated rate equation for first order reaction
92. The rate constant of a first order reaction is A products, is given by
15 × 10−3 s¯¹ . How long will 5.0 g of this reactant
take to reduce to 3.0 g? (a) k = 2.303 In [A]o
t [A]t
(a) 34.07 s (b) 7.57 s
1 [A]t
(c) 10.10 s (d) 15 s (b) k In
t [A]o
93. If 60% of a first order reaction was completed in
2.303
log10 [ A]t
60 minutes, 30% of the same reaction would be (c) k=
t [ A]o
completed in approximately
(a) 50 minutes (b) 23.3 minutes 1 [A]t
(d) k = ¹In [4]
(c) 60 minutes (d) 40 minutes. t [A]o

94. In a first order reaction, 75% of the reactants 102. A reaction is 50% complete in 2 hours and 75 %
disappeared in 1.386 hours . What is the rate complete in 4 hours, the order of reaction is
constant ? (a) O (b) 1 (c) 2 (d) 3.
(a) × 10-3 sec
3.6 X (b) 2.7 × 10 sec-1
103. In a first order reaction , reactant concentration ' C '
(c) 72 x 10-3 sec−1 (d) 1.8 x 10-³ sec-1 varies with time ' t' as
95. In a first order reaction the concentration of 1
(a) C decreases with
reactant decreases from 400 mol L- ¹ to 25 mol L- ¹ t
Chemical Kinetics 129

(a) -k (b) -k/2.303

(b) log C decreases with
t (c) k/2.303 (d) k
1
(c) increases linearly with t 111. The slope of a graph In [A] versus t for a first order
C
reaction is −2.5 × 10-3 S • The rate constant for
(d) log C decreases linearly with t.
the reaction will be
104. A radioactive element gets spilled over the floor of (a) 5.76 x 10-3 s-1 (b) 1.086 x 10-3
10¯ s-1
a room . Its half-life period is 30 days. If the initial (c) -2.5 x 10-3 Ss−1 2.5 × 10-³ s−1
S
(d)
activity is 10 times of the permissible value , after
how many days it will be safe to enter the room? 112. A plot of log(a - x) against time t is a straight line.
This indicates that the reaction is of
(a) 1000 days (b) 300 days
(a) zero order (b) first order
(c) 10 days (d) 100 days
(c) second order (d) third order.
105. Given t1/2 = 3 hours, then how many gram of a
113. Observe the given graphs carefully.
substance will remain after 18 hours from 300
gram of a substance? |In[R]o
k = - slope

log
(a) 4.6 gram (b) 5.6 gram

([R
Slope = k/2.303

]0/
K

In
[R
(c) 9.2 gram (d) 6.4 gram.

]
106. Thermal decomposition of a compound is 1st order 0 t
reaction. If a sample of compound decomposes (i)
50% in 120 minutes, how much time will it take Which of the given orders are shown by the graphs
for 90% decomposition ? respectively?
(a) About 240 minutes (b) About 560 minutes (i) (ii)
(a) Zero order First order
(c) About 45 minutes (d) About 400 minutes
(b) First order Zero order
107. Rate constant for a reaction is 10-3 s- ¹ . Time to
(c) First order First order
leave 25 % reaction is
(d) Second order Zero order
(a) 693 s (b) 1386 s
(c) 6930 s (d) 2029 s 114. In the following plot, for a first order reaction ,
slope is equal to
108. The rate constant for a first order reaction is
60 S
s¯¹ . How much time will it take to reduce the -loge a
loge

initial concentration of the reactant to its 1/ 16th

)-x
a
(

value? Slope
(a) 0.046 s (b) 0.025 s
(c) 0.098 s (d) 0.060 s
Time
109. A graph corresponding to a first order reaction is
k
(a) -k (b)
2.303
Rate 2.303
Conc. (c) (d) -k x 2.303
(a) (b) k

115. A substance A decomposes in solution following

t Conc. the first order kinetics . Flask I contains 1 litre of
1 M solution of A and flask II contains 100 ml of
0.6 M solution ofA. After 8 hours the concentration
Rate Rate of A in flask I becomes 0.25 M. What will be the
(c) (d)
time for concentration of A in flask II to become
0.3 M?

Conc. Conc. (a) 0.4 hours

110. The slope of the straight line obtained by plotting (b) 2.4 hours
rate versus concentration of reactant for a first (c) 4.0 hours
order reaction is (d) Unpredictable as rate constant is not given .
130 || MtG Objective Karnataka CET | Chemistry

116. For a zero order reaction A → P, t1/2 is A is 0.5 M then the half-life is
(k is rate constant) In 2 0.693
(a) (b)
[A]o 0.693 k 0.5k
(a) (b)
2k k
log2 log2
1 In 2 (c) (d)
(c) (d) k k√0.5
k[A]o [A]。 k 126. For a first order reaction A B, the reaction
117. The half-life period of a zero order reaction is rate at reactant concentration of0.01 M is found to be
given by 2.0 × 10-5 mol L- ¹ sec¹ . The half - life period of the
[A]o 2.303k reaction is
(a) (b)
k [A]o (a) 220 seconds (b) 30 seconds
(c) 300 seconds (d) 347 seconds .
[A]o 2[A]o
(c) (d)
2k k 127. If the rate constant of a first order reaction is

118. When the concentration of a reactant in the zero 1.3 × 10˜² min‍¹ , then its half-period in seconds is
order reaction is doubled, the half-life period is (a) 53.3 (b) 3200 (c) 1.247 (d) 0.888
(a) halved (b) doubled
128. If the half- time for a particular reaction is found
(c) remains same (d) tripled . to be constant and independent of the initial
concentration of the reactants, then the reaction
119. Which ofthe following relation is correct for zero
is of
order reaction?
(a) first order (b) zero order
(a) t3/4 = 2t1/2 (b) t3/4 = 1.5 t1/2
1 1 (c) second order (d) none of these .
(c) t3/4 = t1/2 (d) t3/4 = 3¹1/2
129. For the reaction A →→→→ B, the rate law expression
120. In a first order reaction , the concentration of the is, rate = k [A] . Which of the following statements
reactants is reduced to 25 % in one hour. The half- is incorrect?
life period of the reaction is (a) The reaction follows first order kinetics.
(a) 2 hr (b) 4 hr (b) The t1/2 of reaction depends on initial
(c) 1/2 hr (d) 1/4 hr. concentration of reactants.

121. The half - life of a certain first order reaction is 60 (c) k is constant for the reaction at a constant
minutes. How long will it take for 80% reaction to temperature.
occur? (d) The rate law provides a simple way of
(a) 139.39 minutes (b) 19.9 minutes predicting the conc . of reactants and products
at any time after the start of the reaction.
(c) 199.39 hours (d) 40 minutes.

122. The half-life of a first order reaction is 10 minutes . 130. Half-life period of a first order reaction is 10 min .
Ifinitial amount is 0.08 mol/litre and concentration What percentage of the reaction will be completed
in 100 min?
at some instant is 0.01 mol/litre, then t is
(a) 10 minutes (b) 30 minutes (a) 25% (b) 50%

(c) 20 minutes (d) 40 minutes. (c) 99.9% (d) 75%

131. The rate of a first order reaction is 1.5 x 10-2 mol L-¹
123. For a first order reaction , the ratio of the time for
99.9% completion of the reaction to half of the min¹ at 0.5 M concentration of the reactant. The
reaction to complete is half-life of the reaction is

(a) 2 (b) 4 (c) 10 (d) 8 (a) 7.53 minutes (b) 0.383 minutes
(c) 23.1 minutes (d) 8.73 minutes .
124. The half-life period of a first order reaction is 15
minutes. The amount of substance left after one 132. What fraction of a reactant remains after 40 min if
hour will be t1/2 is 20 min for a first order reaction?
(a) one half (b) one fourth 1 1
14118

(a) (b)
(c) one eighth (d) one sixteenth . 2

125. In a first-order reaction A → B, if k is rate 1

(c) (d)
constant and initial concentration of the reactant 6
Chemical Kinetics 131

133. The half-life of the reaction X → Y, following 142. The first order rate constant for the decomposition of
first order kinetics, when
–1 the initial concentration N2O5 is 6.2 × 10–4 sec–1 . The t1/2 of decomposition is
of X is 0.01 mol L and initial rate is 0.00352 (a) 1117.2 (b) 111.72
mol L–1 min–1 will be (c) 223.4 (d) 160.9
(a) 19.69 min. (b) 1.969 min. 143. Which of the following expressions is correct
(c) 7.75 min. (d) 77.5 min. for first order reaction? (a0 refers to initial
134. The decomposition of N2O5 occurs as, concentration of reactant)
kinetics,
2N 2O5 4NO2 + O2, and follows first order (a) t1/2 ∝ a00 (b) t1/2 ∝a–20
–1
(c) t1/2 ∝ a0 (d) t1/2 ∝ a0.
(a) hence the reaction is bimolecular 144. Which of the following is not correct?
(b) the reaction is unimolecular (a) Rate of zero order reaction depends upon
(c) t1/2 ∝ [A]0 initial concentration of reactant.
(d) t1/2 ∝ [A]2 (b) Rate of zero order reaction does not depend
135. In a first order reaction, the concentration upon initial concentration of reactant.
of reactant is reduced to 1/8 of the initial (c) t1/2 of first order reaction is independent of
concentration in 75 minutes at 298 K. What is the initial concentration of reactant.
half-life period of the reaction in minutes? (d) ti1/2
nitial
of zero order reaction is dependent of
(a) 50 min. (b) 15 min. concentration of reactant.
(c) 30 min. (d) 25 min. 145. The inversion of cane sugar is represented by
C12H22O11 + H2O —H→—
136. The half-life of a substance in a certain enzyme- + C6H12O6 + C6H12O6.
catalysed reaction is 140 s. The time required for It is a
the concentration of the substance to fall from (a) second order reaction
1.28 mg L–1 to 0.128 mg L–1 is (b) unimolecular reaction
(a) 465 s (b) 388 s (c) 560 s (d) 700 s (c) pseudo-unimolecular reaction
137. Half-life period of a first order reaction is 10 min. (d) none of these.
What percentage of the reaction will be completed 146. In pseudo unimolecular reactions,
in 20 min? (a) both the reactants are present in low
138. (a)
A first
25% order(b)reaction
50% takes(c) 99.9%
40 min(d)for75%30% concentration
(b) both the reactants are present in same
concentration
decomposition. What will be t1/2?
(c) one of the reactants is present in excess
(a) 77.7 min (b) 52.5 min
(d) one of the reactants is non-reactive
(c) 46.2 min (d) 22.7 min
147. In a pseudo first order hydrolysis of ester in water,
139. The rate constant for a first order reaction is the following results were obtained.
2 × 10–2 min–1. The half-life period of reaction is
t/s 0 30 60 90
(a) 69.3 min (b) 34.65 min –1 0.55 0.31 0.17 0.085
(c) 17.37 min (d) 3.46 min Ester/mol L
What will be the average rate of reaction between
140. What will be the half-life of the first order reaction
the time interval 30 to 60 seconds?
for which the value of rate constant is 200 s–1?
–2 (a) 1.91 × 10–2 s–1
(a) 3.46 × 10 s (b) 3.46 × 10–3 s
(b) 4.67 × 10–3 mol L–1 s–1
(c) 4.26 × 10–2 s (d) 4.26 × 10–3 s
(c) 1.98 × 10–3 s–1
141. For a first-order reaction P → Q, if k is rate (d) 2.07 × 10–2 s–1
constant and initial concentration of the reactant
Pis 1.5 M, then the half-life is 3.4 Temperature Dependence of the Rate of a
log 2 Reaction
log 2
(a) (b)
k k0.5 148. For every 10° rise in temperature rate of reaction
ln 2 0.693 (a) doubles (b) becomes 4 times
(c) (d)
k 0.5k (c) becomes 8 times (d) becomes 10 times
132 Objective Karnataka CET | Chemistry

149. If the rate of a reaction at 50 °C is 2.6 × 10–3 157. The activation energy of exothermic reaction
mol L–1 s–1, then what will be rate of reaction at A B is 80 kJ. The heat of reaction is 200 kJ
80 °C? (For every 10° rise in temperature rate mol–1. The activation energy for the reaction B
doubles) –2 A in kJ/mol will be
(a) 2.08 × 10 (b) 7.025 × 10–3 (a) 80 (b) 120 (c) 280 (d) 200
(c) 7.8 × 10–3 (d) None of these 158. The activation energy for the forward reaction
150. Effect of temperature on reaction rate is given by X Y is 80 kJ/mol and DH is – 20 kJ/mol.
(a) Claisen-Clapeyron equation Calculate the activation energy for reverse
(b) Arrhenius equation reaction.
(c) Gibb’s-Helmholtz equation (a) 40 kJ/mol (b) 100 kJ/mol
(d) Kirchoff’s equation. (c) 80 kJ/mol (d) 120 kJ/mol

151. The rate of reaction is doubled for 10°C rise of 159. For an endothermic reaction, DH represents the
temperature. The increase in the reaction rate as a enthalpy of the reaction in kJ mol–1. The minimum
result of temperature rise from 10°C to 100°C is amount of activation energy will be
(a) 112 (b) 512 (a) less than zero (b) equal to DH
(c) 1024 (d) 100. (c) less than DH (d) more than DH.

152. What happens when the temperature of a solution 160. Consider the following reaction profile :
is increased from 25°C to 65°C? For the reaction AB, the activation energy is
(a) The rate of the reaction remains unchanged
and the rate constant k decreases.
(b) The rate of the reaction increases and rate
constant k decreases.
(c) The rate of the reaction decreases and so
does the rate constant k.
(d) The rate of the reaction increases and so does
the rate constant k.
153. A chemical reaction was carried out at 300 K and (a) a (b) b (c) c (d) d
280
k2 respectively.
K. The rateThen
constants were found to be k1 and 161. Theactivationenergyforasimplechemicalreaction
energy
A B isreverse
→ for Ea in forward
reaction
direction. The activation
(a) k2 = 4 k1 (b) k2 = 2k1
(c) k2= 0.25 k1 (d) k2 = 0.5 k1 (a) is always less than Ea
154. Rate constant k of a reaction is dependent on (b) is always double of Ea
temperature as : (c) can be less than or more than Ea
k = Ae−Ea /RT (d) is negative of Ea.
k has the least value at 162. Energy profile of the reaction A + BC AB + C
(a) high T and high Ea is given in the figure
(b) high T and small Ea
(c) low T and low Ea
(d) low T and high Ea.
155. Energy of activation of an exothermic reaction is
(a) zero (b) negative
(c) positive (d) can't be predicted.
156. When the activation energies of the forward and
reverse reactions are equal, then Which of the following statement is true?
(a) DU = 0, DS = 0 (b) DU=∞, DS = 0 (a) Threshold energy of the reaction is 100 kJ.
(c) DG = 0, DU = 0 (d) only DU = 0 (b) Efis 60 kJ mol–1 while Er is 40 kJ mol–1.
Chemical Kinetics 133

(c) DH is + 20 kJ mol–1 and the reaction is (a) –X (b) Y – Y

endothermic. (c) Y–X (d) X + Y
(d) All are true.
170. By increasing the temperature by 10°C, the rate
163. The energy diagram of a reaction P + Q → R + S is of forward reaction at equilibrium is increased by
given. What are A and B in the graph? a factor of 2. The rate of backward reaction by this
increase in temperature
(a) remains unaffected
A
(b) increases by a factor greater than two
Energy R B (c) decreases by a factor lesser than two
P (d) also increases by a factor of two.
Reaction coordinate 171. Arrhenius equation is
(a) A → activation energy , B → heat of reaction (a) k = Ae–Ea/RT
(b) A → threshold energy, B → heat of reaction (b) k = AeEa/RT
(c) A → heat of reaction, B → activation energy (c) k = Ae–RT/Ea
(d) A → potential energy, B → energy of reaction (d) k = AeRT/Ea

164. For an exothermic reaction, DH –1 represents the 172. A reactant (A) forms two products
enthalpy of the reaction in kJ mol . The minimum A →k1
B, activation energy Ea1
amount of activation energy will be →
k2 C
A , activation energy Ea2
(a) can be predicted (b) equal to DH
If Ea2 = 2Ea1, then k1 and k2 are related as
(c) less than DH (d) more than DH.
2Ea RT
(a) k1 = 2k2e 1/
165. The rate constant is given by the equation
2Ea1 /RT
k = Ae −Ea /RT . Which factor should register a (b) k1 = k2e
decrease for the reaction to proceed more rapidly? 2Ea1 /RT
(c) k2 = ke
1
(a) T (b) Z (c) A (d) Ea
2Ea2 /RT
166. An exothermic reaction A B has an activation (d) k1 = Ak2e
energy of 17 kJ per mole of A. The heat of the 173. The activation energy in a chemical reaction is
reaction is 40 kJ. Calculate the activation energy defined as,
for the reverse reaction B A. (a) the difference in energies of reactants and
(a) 60 kJ (b) 57 kJ products
(c) 75 kJ (d) 90 kJ (b) the sum of energies of reactants and products
167. The rate constant, activation energy and the (c) the difference in energy of intermediate
Arrhenius parameter of a chemical reaction complex with the average energy of reactants
at 25°C are 3.0 × 10–4 s–1, 104.4 kJ mol–1 and and products
6.0 × 1014 s–1 respectively. The value of the rate (d) the difference in energy of intermediate
constant as T → ∞ is complex and the average energy of reactants.
(a) 2.0 × 1018 s–1 (b) 6.0 × 1014s–1 174. The activation energy necessary for a reaction,
(c) infinity (d) 3.6 × 1030 s–1 may be lowered by
168. For an endothermic reaction AB, the (a) decreasing the temperature
activation energy is 15 kcal mol–1. The heat of (b) increasing the temperature
reaction is 5 kJ. The activation energy for the (c) adding a catalyst
reaction BA is (d) reducing the potential energy.
(a) 10 kcal mol–1 (b) 20 kcal mol–1 175. The decomposition of A into product has values of
–1
(c) 40 kcal mol (d) 100 kcal mol–1 k as 4.5 × 103 s–1 at 10°C and energy of activation
169. An exothermic reaction A B has an activation as 60 kJ mol–1. At what temperature k would be
energy of X kJ mol–1 of A. If the energy change in 1.5 × 104 s–1?
the reaction is Y kJ, then the activation energy of (a) 273.15 K (b) 24.19°C
the backward reaction will be (c) 280.39 K (d) 45.29°C
134 Objective Karnataka CET| Chemistry

176. The potential energy diagram for a reaction 180. The temperature dependence of the rate constant
X → Y is given. A and C in the graph corresponding k is expressed as k = Ae–Ea/RT.
to When a plot between logk and 1/T is plotted we
get the graph as shown.

(a) A → activation energy, C → AH°

What is the value of intercept in the graph?
(b) A → energy of reactants, C → energy of
Ea
products (a) (b) log A
RT
(c) A → AH°, C → activation energy Ea Ea R
(d) A → activation energy, C → threshold energy (c) - log A (d) -
2303.RT 2303.T
177. The rate constant of a reaction 181. When
reaction,
a graph
a graph
of log
with slope
10K against
equal
1/T
tois–1plotted,
x 103 Kfor
(a) decreases with increasing Ea is
(b) decreases with decreasing Ea obtained. Hence the activation energy is
(c) is independent of Ea (a) 8.314 x 103 J mol–1 (b) 3.61 kJ mol–1
(d) decreases with increasing temperature. (c) 4.85 x 103 J mol–1 (d) 19.1 kJ mol–1
182. When a graph of log10k is plotted against 1/T, the
178. The temperature dependence
inverse of slope of the line is
of the rate constant k is Ea 2303.R
expressed as k = Ae–Ea/RT. (a) - (b) -
R Ea
When a plot between logk Ea
Ea
and 1/T is plotted we get the (c) - (d) -
graph as shown. 2303. 2303.R
183. Slope of the plot of log k versus 1/T is 5.64.
What is the value of slope in
Activation energy in J mol–1 will be
the graph?
(a) 108 (b) 98 (c) 118 (d) 138
Ea Ea
(a) (b) - 184. A reaction rate constant is–1given by
RT 2303.R
k = 1.2 x 1014 e–25000/RT s . It means that
Ea
(c) - log A (d) - 2303.Ea R (a) log k versus log Twill give a straight line with
2303.RT T a slope as –25000
179. The rate constant of a reaction is shown as (b) log k versus T will give a straight line with
k = 2.1 x 1010e–2700/RT slope as 25000
(c) log k versus log 1/T will give a straight line
It means that
with slope as –25000
I. log k vs 1/T will be a straight line with (d) log k versus 1/T will give a straight line
intercept on log k axis = log 2.1 x 1010.
185. What is the energy of activation of a reaction if its
II. Number of effective collisions are
rate doubles when the temperature is raised from
2.1 x 1010 cm–3 s–1. 290 K to 300 K?
III. Half-life of a reaction increases with increase (a) 12 kcal (b) 41 kcal
of temperature. (c) 13.8 kcal (d) 52 kcal.
IV. log k vs 1/T will be a straight line with slope
2700 186. The rate constants at 27°C and 67°C for
=- the dissociation
6.90 x 10–3 respectively.
of N2O5Whatare 3.45 x 10–5 and
2303.R
is the activation
Which of the above statement(s) is/are true? energy for the dissociation of N2O5?
(a) I and II (b) II and III (a) 112.3 kJ (b) 225 kJ
(c) III and IV (d) I and IV (c) 448 kJ (d) 285 kJ
Chemical Kinetics 135

187. The correct expression for activation energy is, (d) it fastens the attainment of equilibrium by
k1 Ea (T1 - T2) lowering activation energy.
(a) log10 =
k2 2.303R xT1 xT2 191. Which of the following statements about the
catalyst is true?
k2 Ea (T1 - T2 )
(b) log10 = (a) A catalyst makes the reaction feasible by
k1 2303
. R xT1 xT2
making AG more negative.
k2 Ea (T2 - T1 ) (b) A catalyst makes equilibrium constant more
(c) log10 =
k1 2303
. RxT1 xT2 favourable for forward reaction.
k2 = Ea (T2 - T1 ) (c) A catalyst accelerate rate of reaction by
(d) log10
k1 R xT1 x T2 bringing down the activation energy.
188. Which of the following statements about the (d) A catalyst always increases the rate of
catalyst is true? reaction.
(a) A catalyst accelerates the rate of reaction by 192. On increasing the temperature by 10 K the rate of
bringing down the energy of activation. reaction becomes double. Which of the following
(b) A catalyst does not participate in reaction is the most appropriate reason?
mechanism. (a) With increase of temperature, velocities
(c) A catalyst makes the reaction more feasible increase and hence the number of collisions is
by making AG more negative. appreciably increased.
(d) A catalyst makes equilibrium constant more (b) The activation energy decreases with increase
favourable for forward reaction. of temperature.
(c) The bonds between the atoms of the
189. The graph of the effect of catalyst on activation
reacting molecules become weak at higher
energy is given below. Fill up the blanks X and Y
temperature.
with appropriate statements.
(d) Higher the temperature, larger is the fraction
of colliding particles which can cross the
energy barrier.
193. If hydrogen and oxygen are mixed and kept in
the same vessel at room temperature, the reaction
does not take place to form water because
(a) activation energy for the reaction is very high
at room temperature
(a) X = energy of activation without catalyst, (b) molecules have no proper orientation to
Y = energy of activation with catalyst react to form water
(b) X = path of reaction with catalyst, Y = path of (c) the frequency of collisions is not high enough
reaction without catalyst for the reaction to take place
(c) X = energy of activation with catalyst, (d) no catalyst is present in the reaction mixture.
Y = energy of activation without catalyst
194. On increasing temperature of the reacting system
(d) X = energy of endothermic reaction, by 10 degrees the rate of reaction almost doubles.
Y = energy of exothermic reaction The most appropriate reasons for this is
190. When a catalyst is used in an equilibrium process, (a) collision frequency increases
(a) it increases the rate of forward reaction (b) activation energy decreases by increase in
(b) it decreases the rate of backward reaction temperature
(c) it decreases activation energy of forward (c) the fraction of molecules having energy equal
process and increases activation energy of to threshold energy or more increase
backward process (d) the value of threshold energy decreases.
136 MtG Objective Karnataka CET | Chemistry

3.5 Collision Theory of Chemical Reactions (c) the rate of reaction could be independent of
the energy
195. Rate of a general reaction A + B → products can (d) one of the reactants could be in excess .
be expressed as follows on the basis of collision
200. For effective collisions , colliding molecules must
theory.
have
Rate = ZAB e-Ea/RT

Which of the following statements is not correct (a) minimum potential energy

for the above expression? (b) sufficient kinetic energy

(a) Z is collision frequency and is equal to (c) sufficient potential energy

number of collisions per second per unit (d) maximum energy of activation.
volume of the reaction mixture .
201. According to collision theory of reaction rates
-Ea/RT is the fraction of molecules with
(b) e
(a) every collision between reactants leads to
kinetic energy equal to or greater than E
chemical reaction
(c) E is activation energy of the reaction .
(b) rate of reaction is proportional to velocity of
(d) All the molecules which collide with one molecules
other are effective collisions.
(c) all reactions which occur in gaseous phase
196. The rate constant is given by the equation are zero order reactions
k = P. Ze EdRT. Which factor should register a (d) rate of reaction is directly proportional to
decrease for the reaction to proceed more rapidly? collision frequency.
(a) T (b) Z (c) Ea (d) P 202. A chemical reaction proceeds following the
formula k = PZe Ea/RT. Which of the following
197. In the given diagram, ER, Ep and Ex represent the
processes will increase the rate of reaction?
energy of the reactants, products and activated
complex respectively. Which of the following is (a) Lowering of Ea
the activation energy for the backward reaction ? (b) Lowering of P

Ex (c) Lowering of Z
(d) Rate of reaction is independent of all the
Energy

A➡

above factors .
→

B
—Ep
203. According to collision theory,
collision rate = Z [reactants] where Z is
ER
(a) activation energy (b) packing frequency
Progress of reaction (c) collision frequency (d) potential energy.

(a) A (b) B (c) C (d) D 204. Orientation factor is directly proportional to

198. Collision theory is applicable to (a) collision frequency

(a) first order reactions (b) fraction of molecule

(b) zero order reactions (c) rate of reaction

(d) threshold energy.
(c) bimolecular reactions
(d) pseudo first order reactions. 205. Chemical reaction occurs as a result of collisions

199. For a certain reaction a large fraction of molecules between reacting molecules. Therefore, the
reaction rate is given by
has energy more than the threshold energy, still
the rate of reaction is very slow. The possible (a) total number of collisions occurring in a unit
reason for this could be that volume per second

(a) the colliding molecules could be large in (b) fraction of molecules which possess energy
size less than the threshold energy

(b) the colliding molecules must not be properly (c) total number of effective collisions
oriented for effective collisions (d) none ofthe above .
Chemical Kinetics 137

1. For the reaction 2NH3 → N2 + 3H2, 6. The rate constant, k of the reaction,
d[NH3] d[N 2 Which
N2O5(g)equation
→ 2NO O2(g)
describes
is 2.3 ×the
10–2
change
sec–1.
if − = k1[NH3], ] = k2[NH3 given
2(g)
dt dt 2
d[dt
H2 ] +below
1
= k3],
[NH3] of [N2O5] with time? [N2O5]0 and [N2O5] t,
then the relation between k1, k2 and k3 is at time t. to concentration of N2O5 initially and
correspond
(a) k1 = k2 = k3 (b) k21k1==3kk2 = 2k3
(c) 1.5k1 = 3k2 = k3 (d) 3k3 (a) [N2O5]t = [N2O5]0 + kt
(b) log10[N2O5]t = log10[N2O5]0 –kt
2. For two first order reactions, (i) A → products
constants.
and (ii) B The
→first
products,
reaction
k1 (i)
andis slower
k2 are the rate (c) [N2O5]0 = [N2O5]t ekt
than the [N2O5]0
second reaction (ii). The graphical observation (d) ln = kt
[N2O5]t
corresponding to this observation will be
7. For a general chemical change,
(ii) 2A + 3B Products, the rates with respect to
(i)
A
and
is r1
r2 and
are related as respect to B is r2. The rates r1
that with
(ii) (i)
(a) (b)
(a) 3r1 = 2r2 (b) r1 = r2
2
(c) 2r1 = 3r2 (d) r1 = 3r2

(ii) 8. Which of the following graphs will show the

variation
into NO2ofand
partial
O2 following
pressurethe
of N2
first
O5order
decomposing
(i)
kinetics?
(i)
(c) (d)

(ii) (a) (b)

3. A first order reaction takes 40 min for 30%

decomposition. What will be t1/2?
(a) 77.7 min (b) 52.5 min (c) (d)
(c) 46.2 min (d) 22.7 min
4. Consider the reaction : 2N2O4  4NO2
9. According to Arrhenius equation which of the
d[N 2O4 ] d[ NO2 ]
If - = k and = kj then following options represents the graph of ln k vs
dt dt
1
(a) 2k ′ = k (b) k ′ = 2k ?
T
1
(c) k ′ = k (d) k = kj
4
5. Cyclopropane rearranges to form propene (a) (b)

Thisfollowsfirstorderkinetics.Therateconstantis
2.714 × 10–3 sec–1. The initial concentration (c) (d)
of cyclopropane is 0.29 M. What will be the
concentration of cyclopropane after 100 sec? 10. For an exothermic chemical process occurring in
(a) 0.035 M (b) 0.22 M two steps as follows :
(c) 0.145 M (d) 0.0018 M (i) A + B → X(slow) (ii) X → AB (fast)
138 Objective Karnataka CET | Chemistry

the process of reaction can be best described by 14. Which of the following factors are responsible for the
increase in the rate of a surface catalysed reaction?
(i) A catalyst provides proper orientation for the
P.E
reactant molecules to react.
(a) A+B X (ii) Heat of adsorption of reactants on a catalyst
AB
helps reactant molecules to overcome
Reaction co-ordinate activation energy.
(iii) The catalyst increases the activation energy
X of the reaction.
P.E (a) (i) and (iii) (b) (i) and (ii)
(b) A+B
AB (c) (ii) and (iii) (d) (i), (ii) and (iii)
Reaction co-ordinate 15. The rate of first order reaction is 1.5 × 10–2
mol L–1 min–1 at 0.5 M concentration of the
reactant. The half-life of the reaction is
(a) 0.383 min (b) 23.1 min
P.E
(c) A+B X (c) 8.73 min (d) 7.53 min.
AB
Reaction co-ordinate 16. The rate of a reaction is expressed in different
ways as follows :
1 d[ A] 1 d[B] 1 d[C ] 1 d[D ]
− =+ =− =+
X m dt n dt p dt q dt
AB
(d) P.E The reaction is
A+B (a) nA + mB pC + qD
Reaction co-ordinate (b) pA + qB mC + nD
11. The rate constant (k') of one of the reaction is (c) pA + mB nC + qD
found to be double than that of the rate constant (d) mA + pC nB + qD
(k") of another reaction. Then the relationship
17. For a zero order reaction, rate constant is given by
between the corresponding activation energies of the
two reactions (E′a and E″a ) can be represented as (a) [A]t = kt + [A]0 (b) k = t ([A]0 – [A]t)
(a) E′a > E″a (b) E′a < E″a t
(c) k= (d) [A]t = – kt + [A]0
(c) E′a = E″a (d) E′a = 4E″a [ A]0 -[ A]t
18. A reaction is represented by A → k B
12. For a given reaction, presence of catalyst reduces 1 (slow)
and A + B →2
k
rate constants of two(fast)
C steps.where
The rate
k1 and
of production
k2 are the
the energy of activation by 2 kcal at 27°C. The
rate of reaction will be increased by
(a) eRT (b) e–RT/2 of C will be given by
(c) e 2/RT
(d) e–2/RT (a) k1[A] [B] (b) k1[A]
(c) k1k2 [A] (d) k2 [A] [B]
13. is
Inexpressed
the reaction
as 2N2O5 → 4NO2 + O2, the rate
19. The incorrect order indicated against the rate of
k
d[N 2O5 ] reaction : A + B →C is
(i) - = k1[N2O5 ] Rate Order
dt
d[C ]
d[NO2 ] (a) = k[ A] 1
(ii) = k2[N2O5 ] dt
dt
(b) d[C ] = kA [ ][ B] 2
d[O2] dt
(iii) = k3[N2O5]
dt -d[ A]
(c) = kA[ ][B] 1
Relation between k1, k2 and k3 is dt
(a) 2k1 = 4k2 = k3 (b) 2k1 = k2 = 4k3 -d[ A]
(d) = k[ A] 1
(c) 2k1 = k2 = 2k3 (d) k1 = 4k2 = 2k3 dt
Chemical Kinetics 139

20. Afirst order reaction takes 100 min for completion (a) 5 x 10-3 S
s-1 (b) 7.36 × 10-2 S
of 60% of reaction . The time required for 3.5 x 10-2 s-1 (d) 6.36 x 10-3 s-1
(c)
completion of 90% of the reaction is
(a) 150 min (b) 200 min 25. What is the time required for a first order reaction
to be 99% complete , compared to the time taken
(c) 220.9 min (d) 251.3 min
for the reaction to be 90% complete?
21. Which of the following graphs represents (a) There is no change.
endothermic reaction? (b) Time taken is double .
Activated complex (c) Time taken is triple.
Energy

(d) The time required is half the initial value.

(i) 26. A first order reaction is 20% complete in 20 min.

Reactants
Products Time taken to complete 60% of the reaction will
Reaction coordinate be
Activated complex (a) 42 min (b) 62 min
→ gy
Ener

(c) 72 min (d) 82 min

(ii)
Products 27. In the following first order competing reactions
Reactants where t₁
t1 = t2 :
Reaction coordinate k₁
A + Reagent → Product
Activated complex k₂
B + Reagent → Product
Energy

(iii) k1
The ratio of if only 50% of B and 94% of A
Reactants Products k2

Reaction coordinate have been reacted is

(a) (i) only (b) (ii) only (a) 4.06 (b) 0.246 (c) 2.06 (d) 0.06

(c) (iii) only (d) (i) and (ii) 28. For a chemical reaction Y½ +
+ 2Z → product,

22. The half life of a first order reaction is 6.0 h . How rate controlling step is Y + Z
long will it take for the concentration of reactant 2
to decrease from 0.8 M to 0.25 M? If the concentration of Z is doubled , the rate of
reaction will
(a) 9.06 h (b) 10.07 h
(a) remain the same (b) become four times
(c) 8.71 h (d) 5.45 h
(c) become √2 times (d) become double.
23. Which statement is not correct?

(a) For an endothermic reaction , heat of reaction 29. The following data pertains to reaction between
A and B.
is lesser than energy of activation .
S. [A] [B] Rate
(b) For an exothermic reaction, heat of reaction
No. mol L-1 mol L-1 (mol L- ¹ time¯¹)
is more than energy of activation.
(c) For an exothermic reaction energy of 1. 1.0 × 10-2 × 10-2
2.0 X 2.0 × 10-4
activation is lesser in forward reaction than 2. 2.0 × 10-2 2.0 x 10-2 4.0 × 10-4
in backward reaction. 8.0 × 10-4
3. 2.0 × 10-2 4.0 x 10-2
(d) For an endothermic reaction energy of
Which of the following inferences can be drawn
activation is more in forward reaction than in from the above data?
backward reaction .
I. Rate constant of the reaction is 1.0 × 10-4.
24. The first order rate constant for the decomposition II . Rate law of the reaction is : rate = k[A] [B]
of ethyl iodide by the reaction, III. Rate of reaction increases four times on
→→ doubling the
C2H5Ig C2H4(g) + HI(g) concentration of both the
at 600 K is 1.60 × 10-5 reactants .
-5 S
s- 1 . Its energy of activation is
209 kJ/mol . The rate constant of the reaction at (a) I, II and III (b) I and II only
700 K is (c) II and III only (d) III only
140 MtG Objective Karnataka CET | Chemistry

30. The half life of a first order reaction is 0.5 min at (b) (A) and (B) zero order, (E) first order
a certain temperature . Calculate the time required (c) (A) and (B) zero order, (C) and (E) first order
for 80% reactant to decompose. (d) (B) zero order, (C) and (E) first order.
(a) 69.7 s (b) 73.5 s → Products ,
34. In the reaction of aA + bB + cC
(c) 45.7 s (d) 1.05 s
(i) if concentration of A is doubled, keeping
31. The rate constant of a reaction is shown as conc. ofB and C constant, the rate of reaction
k = 2.1 × 10¹0 e-2700/RT becomes double
It means that (ii) if concentration of B is halved keeping conc.
I. log k vs 1 /T will be a straight line with of A and C constant, the rate of reaction
intercept on log k axis = log 2.1 x 1010. remains unaffected
II. Number of effective collisions are (iii) if concentration of C is made 1.5 times, the
-3 s-¹.
2.1 x 1010 cm³ rate of reaction becomes 2.25 times .

III. Half-life of a reaction increases with increase The order of reaction is

of temperature . (a) 1 (b) 2.5 (c) 3 (d) 3.5

IV. log k vs 1 /T will be a straight line with slope 35. In several experiments on the kinetics of reaction
2700 A+ B products , it is observed that
2.303R (i) On doubling the initial concentration of A,
the rate was increased by four times and
Which of the above statements are true?
(ii) On doubling the initial concentration ofB, the
(a) I and II only (b) II and III only rate was increased by two times .
(c) III and IV only (d) I and IV only The correct statement is

32. Which of the following statements is true? (a) the reaction is first order in A and second
order in B
(a) For first order reaction, straight-line graph
(b) the reaction is first order in both the reactants
of log C vs t is obtained , slope = − k/2.303 .
dx
(b) A plot of log k vs 1/T gives a straight-line (c) the rate equation is = k[ A] [ B]
dt
graph for which slope := - E /2.303R.
(d) Order of reaction is 3.
(c) Units of k for the first order reaction are
36. The rate constant for a first order reaction is
independent of concentration units.
7.0 × 104 s¯¹ . If the initial concentration of the
(d) All of these .
reactant is 0.080 M, what concentration will
33. For the following graphs remain after 35 minutes?
(a) 0.0765 M (b) 0.0456 M
(c) 0.0237 M (d) 0.0184 M
Concentration

(A) Rate (B) 1/2

Concentration

37. The following data were obtained during the

Time Initial conc. first order thermal decomposition of SO2Cl2 at a
constant volume .
SO2Cl2(g) → SO2(g) + Cl2(g)
(C) (D)
Experiment Time/s-1 Total pressure/
atm
Time Time
1 0 0.5
2 100 0.6

(E) Rate What is the rate of reaction when total pressure is

0.65 atm ?
Concentration- (a) 0.35 atm s-1
-1
Choose from the options given below, the correct (b) 2.235 x 10-3 atm s
one regarding order of reaction is (c) 7.8 x 104
10 atm s
(a) (B) and (D) zero order, (E) first order (d) 1.55 x 10 atm s-1
Chemical Kinetics 141

38. From the following data for the reaction between (iv) doubling the concentration of H+ ions will
A and B, increase the reactions rate by 4 times.

[A] [B] Initial rate (a) Only (ii) (b) Only (iii)
mol L-1 mol L-1 mol L-1 s-1 (c) Only (i) and (ii) (d) Only (iii) and (iv)
I 2.5 × 10-4 3.0 x 100-5 5.0 X
× 10-4 43. Time required for 99.9% completion of a first
II 5.0 ×
X 10-4 6.0 × 10-5 X 10-3
4.0 × order reaction is nearly
III × 10
1.0 X 6.0 × 10−5 × 10-
1.6 X
(a) 10 times that required for 25 % of the reaction
the order of reaction with respect to A is 2 and (b) 10 times that required for 50% ofthe reaction
with respect to B is 1 .
(c) 20 times that required for 50% of the reaction
Using the value of activation energy 55.3 kJ mol¯¹ ,
(d) 100 times that required for 90% of the
calculate the pre- exponential factor. reaction.
Given T = 27°C.
-
44. In a first order reaction A → B, 60% of the given
(a) 2.280 ×
X 1018 (b) 1.140 X
× 1018
sample of compound decomposes in 45 minutes .
(c) 2.280 × 1015 (d) 1.140 X
× 1015
What is the half life of the reaction?
39. Hydrolysis of cane sugar in presence of acid is a (a) 34 min (b) 56 min
first order reaction with half life time of 4 hours. (c) 48 min (d) 27 min
What fraction of sucrose undergoes hydrolysis in
11 hrs? 45. In a hypothetical reaction XY, the activation
energy for the forward and backward reactions
(a) 0.9345 (b) 0.6122
(c) 0.8511 (d) 0.412 are 15 and 9 kJ mol‍¹ respectively. The potential
energy ofX is 10 kJ mol¹ . Which of the following
40. A first order reaction has k = 1.5 × 10−6 per second statements is/are correct?
at 200°C. If the reaction is allowed for 10 hours,
(i) The threshold energy of the reaction is
what percentage of the initial concentration would
25 kJ mol¹ .
have changed in the product?
(ii) The potential energy of Y is 16 kJ mol¯¹ .
(a) 0.052 % (b) 52%
(iii) Heat of reaction is 6 kJ mol¯¹ .
(c) 5.20% (d) 2.6%
(iv) The reaction is endothermic .
41. Which of the following statements is not correct?
(a) Only (i) (b) Only (i) and (ii)
(a) For a zero order reaction, t1/2 is proportional
(c) Only (ii) and (iii) (d) All are correct.
to initial concentration .
46. An exothermic chemical reaction proceeds by two
(b) The relationship of variation of rate
stages .
constant with temperature is given by stage 1 Intermediate stage 2
Reactants → Products
= ET2 - T
log The activation energy of state 1 is 50 kJ mol¹ .
k₁ 2.303R TT½
The overall enthalpy change for the reaction is
(c) The unit of rate constant for a reaction is -100 kJ mol¹ . Which diagram could represent
moll-" L" -1s-1where n is order ofthe reaction . the energy level diagram for the reaction ?

(d) The unit of rate of reaction changes with 200 200+

150 150
order of reaction.
(a) E 100 (b) E 100
42. In acidic medium, the rate ofreaction between [BrO3 ] 50 50 R
and [Br ] ions is given by the expression Progress of reaction Progress of reaction
d[BrO3 ] = 200+ 200
= k[ BrO3 ] [ Br¯ ] [ H *† ]²
dt 150 R 150
It means (c) E 100 (d) 100
50 50
(i) rate constant of the reaction depends upon
the concentration of H+ ions Progress ofreaction Progress of reaction

(ii) rate of reaction is independent of the 47. The energy of activation for a certain second order
concentration of acid added reaction is 85.2 kJ mol¹ and its frequency factor is
(iii) the change in pH of the solution will affect 3.1 x 1011 L mol¹ s¹ S at 310 K. Calculate the rate
the rate of reaction constant ofthe reaction . (R = 8.314J K¹ mol¹)
 142 MtG Objective Karnataka CET | Chemistry

(a) 13.72 × 10−³ L mol− ¹ s−

S 1 constant in this range of temperature .
(b) 1.372 L mol−¹ s−1
(a) 39.08% (b) 32.83 %
(c) s¯¹
1.592 x 10-³ L mol¯¹ S
(c) 67.17% (d) 60.92%
(d) 1.372 × 10-³ L mol− ¹ s¯1
S
50. Fill up the following with suitable terms.
48. The progress of a reaction AnB, with time is
(i) Activation energy = Threshold energy-
presented in the figure, determine the value of n.
(ii) Half-life period of zero order reaction =
(iii) Average rate of reaction =
0.5
Conc
.mol

(iv) Instantaneous rate of reaction =

L

0.3
(i) (ii) (iii) (iv)
0.1 0.693 dx A[A]
(a) Potential energy
1 3 5 7 k dt At
Time/Hour
1 Δ[Α] dx
(a) 1 (b) 2 (c) 3 (d) 4 (b) Energy of reactants
k At dt
49. A first order reaction AB, requires activation
energy of 70 kJ mol¹ . When a 20% solution ofA logk Δ[Α] dx
(c) Energy of reaction
t At dt
was kept at 25° C for 20 min. 25 % decomposition
takes place . What will be the percent decomposition a dx
A[A]
at the same time in a 30% solution maintained (d) Average kinetic
2k At dt
at 40°C? Assume that activation energy remains energy of reactants

KCET Exam Archive / 10 Years ' PYQs ( 2014-2023)

(c) 0.0693 M min¯¹

1. A(g) P(g) + Q(g) + R(g) , follows first order
(d) 0.0693 x 3 M min-1 (2015)
kinetics with a half-life of 69.3 s at 500 ° C. Starting
5. The half-life period of a first order reaction is
from the gas 'A' enclosed in a container at 500°C
re of
and at a pressure of 0.4 atm, the total pressu 60 minutes. What percentage will be left over
the system after 230 s will be after 240 minutes?
(a) 1.15 atm (b) 1.32 atm (a) 6.25% (b) 4.25%
(c) 1.22 atm (d) 1.12 atm (2014) (c) 5% (d) 6% (2016)
2. 100 cm³ of 1 M CH3COOH was mixed with 6. For a chemical reaction ,
100 cm³ of 2 M CH3OH to form an ester . The mA → xB, the rate law is r = k[A]².
change in the initial rate if each solution is diluted
If the concentration of A is doubled, the reaction
with equal volume of water would be rate will be
(a) 4 times (b) 0.25 times
(a) doubled
(c) 2 times (d) 0.5 times. (2015)
(b) quadrupled
3. In a first order reaction, the concentration of the
reactant is reduced to 12.5 % in one hour. When (c) increased by 8 times

was it half completed? (d) unchanged . (2016)

(a) 20 min (b) 15 min d[B]

7. 3A 2B, rate of reaction, + is equal to
(c) 3 hr (d) 30 min (2015) dt
4. Half- life period of a first order reaction is 10 min. 3 d[ A] 2 d[A]
Starting with initial concentration 12 M, the rate (a) (b)
2 dt 3 dt
after 20 min is
(a) 0.693 x 3 M min (c) +2d
[A] 1 d [ A]
(d) (2016)
(b) 0.0693 x 4 M min-1 dt 3 dt
Chemical Kinetics 143

8. The activation energy of a chemical reaction can 13. The temperature coefficient of a reaction is 2 .
be determined by When the temperature is increased from 30 °C to
(a) evaluating rate constants at two different 90 °C, the rate of reaction is increased by
temperatures (a) 150 times (b) 410 times
(b) changing the concentration of reactants (c) 72 times (d) 64 times. (2018)
(c) evaluating the concentration of reactants at
14. The value of rate constant of pseudo first order
two different temperatures
reaction
(d) evaluating rate constant at standard
(a) depends only on temperature
temperature. (2016)
(b) depends on the concentration of reactants
1 present in small amounts
9. For a reaction A →→→→ 2B, rate of disappearance
(c) depends on the concentration of reactants
of A is related to rate of appearance of B by the
present in excess
expression
(d) is independent of the concentration of
-d [ A] =
_1d [ B] reactants. (2018)
(a)
dt 4 dt
15. The plot of t1/2 v/s [R]o for a reaction is a straight-
−d [A] = 4 d[B]
line parallel to x-axis. The unit for the rate constant
(b)
dt dt of this reaction is

-d [ A] _1d [ B]
== (a) mol L-¹s (b) mol L-1 s-1
S
(c) -1
dt 2 dt (c) L mol-1 s-1
S (d) s (2019)

-d [ A] =
_d [ B] 16. Which is a wrong statement ?
(d) (2017)
dt dt
(a) Rate constant, k = Arrhenius constant A : ifE₁ = 0
10. Which ofthe following statements is in accordance
(b) e E/RT gives the fraction of reactant molecules
with the Arrhenius equation ?
that are activated at the given temperature .
(a) Rate of a reaction increases with increase in
1
temperature. (c) Ink vs plot is a straight line.
T
(b) Rate of reaction does not change with
increase in activation energy. (d) Presence of catalyst will not alter the value
(c) Rate constant decreases exponentially with of Ea (2019)
increase in temperature .
17. 1 L of 2 M CH3COOH is mixed with 1 L of
(d) Rate of a reaction increases with decrease in
activation energy. 3 M C2H5OH to form an ester. The rate of the
(2017)
reaction with respect to the initial rate when each
11. Which of the following statements is incorrect? solution is diluted with an equal volume of water
(a) Molecularity is only applicable for elementary will be
reaction.
(a) 0.25 times (b) 2 times
(b) The rate law for any reaction cannot be
(c) 0.5 times (d) 4 times . (2019)
determined experimentally.
(c) Biomolecular reactions involve simultaneous 18. The time required for 60% completion of a first
collision between two species. order reaction is 50 min. The time required for
(d) Complex reactions have fractional order . 93.6% completion of the same reaction will be

(2017) (a) 83.8 min (b) 50 min

(c) 150 min (d) 100 min . (2020)
12. For the reaction, 2SO2 + O22SO3 , the rate
of disappearance of O2 is 2 × 10+ mol L- ¹ s¯¹ . The 19. For an elementary reaction,
2A + 3B → 4C + D the rate of appearance of
rate of appearance of SO3 is
(a) 2 X × 104 mol L-¹ Ss−1 C at time is 2.8 x 10-3 mol L- 1s- 1 . Rate of
(b) 4 × 104 mol L- ¹ S
s−1 disappearance ofB at 't' , t will be

(c) 1 × 10-¹ mol L-1 s-1

S 3 -1
(a) 2 (2.8 × 10 −³ ) mol L- ¹ S
(d) 6x 10 mol L- 1 s-1 (2018) 4
144 Objective Karnataka CET | Chemistry

(b) 2(2.8 × 10–3) mol L–1 s–1 25. A first order reaction is half completed in
45 min. How long it need 99.9% of the reaction
1 28
(c) ( . x 10-3 ) mol L-1 s-1 to be completed?
4
(a) 10 hours (b) 20 hours
4 28
(d) ( . x 10-3 ) mol L-1 s-1 (2020) (c) 5 hours (d) 7.5 hours (2022)
3
26. The rate of the reaction:
20. kThe rate constant of a reaction is given by
= PZe CH3COOC2H5 + NaOH →
–Ea/RT under standard notation. In order
CH3COONa + C2H5OH
to speed up the reaction, which of the following is given by the equation
factors has to be decreased? Rate = k[CH3COOC2H5][NaOH]
(a) Both Z and T (b) Ea If concentration is expressed in mol L–1, the unit
of k is
(c) T (d) Z (2020)
(a) L mol–1 s–1 (b) s–1
21. For a reaction A + 2B → Products, when (c) mol–2 L2 s–1 (d) mol L–1 s–1 (2022)
concentration of B alone is increased, half life 27. For nth order of reaction, half-life period is directly
remains the same. If concentration of A alone is proportional to
doubled, rate remains the same. The unit of rate (a) an – 1 (b) a1 – n
constant for the reaction is 1
–1 1
(a) s (b) L mol–1 s–1 (c) n−1
(d) a1n− (2022)
–1 –1 a
(c) mol L s (d) atm–1 (2021)
28. Half-life of a reaction is found to be inversely
22. If the rate constant for a first order reaction is k, proportional to the fifth power of its initial
the time(t) required for the completion of 99% of concentration, the order of reaction is
the reaction is given by (a) 5 (b) 6 (c) 3 (d) 4
(2022)
4606. 2303.
(a) t= (b) t= 29. In which one of the following reactions, rate
k k
constant has the unit mol L–1 s–1?
0693. 6909.
(c) t= (d) t= (2021) (a) Acid catalysed hydrolysis of CH3COOCH3
k k
(b) CHCl3 + Cl2 → CCl4 + HCl
23. The rate of a gaseous reaction is given by the (c) 2NO(g) + O2( )g → 2NO2(g)
expression, k[A][B]2. If the volume of vessel (d) Decomposition of HI on the surface of gold
is reduced to one half of the initial volume, the (2023)
reaction rate as compared to original rate is 30. For a reaction, the value of rate constant at 300 K
1 1 is 6.0 × 105 s–1. The value of Arrhenius factor A at
(a) (b) infinitely high temperature is
16 8
(a) 6× 105 × e–Ea/300R (b) e–Ea/300R
(c) 8 (d) 16 (2021)
6 x 10-5
24. Higher order (> 3) reactions are rare due to (c) (d) 6 × 105 (2023)
300
(a) shifting of equilibrium towards reactants due
31. reactions
The rate are
constants
1016 ×ke and k2and
for10t15
wo different
to elastic collisions 1–2000/T
× e–1000/T
(b) loss of active species on collision respectively. The temperature at which k1 = k2 is
(c) low probability of simultaneous collision of 2000
(a) K (b) 2000 K
all reacting species 2303.
(d) increase in entropy as more molecules are 1000
(c) K (d) 1000 K (2023)
involved. (2021) 2303.
Chemical Kinetics 145

Hints & Explanations

8. (a) : X + Y → Z
Self Test - 1 Rate ∝ [X] ; hence order of reaction = 1
1. (b) Molecularity of reaction = 2
1 d[N2O5 ] 1 d[NO2 ] dx
2. (c) : - = 9. (c) : For a second order reaction, = k[ A]2
2 dt 4 dt conc. dt
2
d[N2O5] 2 = k[ conc.]
=- x 00072
. =-00036
. mol L-1 s-1 time
dt 4
mol L-1 1
3. (c) : For this reaction, = k mol L-1 x mol L-
s
1
A —→— 2B k = L mol–1 s–1
2 10. (b) : Order of a reaction cannot be obtained from
1 d[ A] 1 d[B ] the balanced chemical equation of the reaction. It is an
Rate = − =
1/2 dt 2 dt experimentally dtermined quantity.
d[ A] = ]1d[B
⇒ −
dt 4 dt Self Test - 3
of SO3
4. (d) : The
formation rateare
ofsame.
disappearance of SO2 and the rate of
1. (c) : Given : t = 40 min, [X]0 = 0.1 M, [X] = 0.025 M
=
2.303 0.1
1 d[ NH3] 1 d[H 2 ] or - d[ H2 ] =3xd[ NH3] \ k log
5. (d) : =- t 0.025
2 dt 3 dt dt 2 dt
2.303 2.303
= xlog 4 = x 2 log 2
Self Test - 2 40 40
2303.x 2x03010.
1. (b) = 0.03467 min -1
40
2. (c) : t1/2 ∝ [A0] for zero order reaction \ Rate = k [X]
th
 14A   1 = (0.03467 × 0.01) M min–1
If A0 becomes  0  then, t1/2 also becomes   . = 3.467 × 10–4 M min–1 @ 3.47 × 10–4 M min–1
 4
of
3. (a) : Greater the value k, faster is the reaction. 2. (a) : [R] = [R0] – kt
For completion of reaction, [R] = 0
4. (a) : 2A→A2 [R
Rate of formation of dimer = k[A]2 or t = 0]
k
k=
Rate of formation of dimer 3. (c) : For nth order reaction, t1/2 ∝ [A0]1–n
2
[ A] For 2nd order, t1/2 ∝ [A0]–1i.e., t/ ∝ 1 .
12
91.x10-6 mol L-1 s-1 [ A0 ]
k= = 91.x10-2 L mol-1 s-1
(0.01 mol L 1)2
- 4. (c) : r1 = k[A] , r2 = k[A] , r3 = k[A]3
1 2

5. (a) : For second order, rate constant If [A] > 1M ; then r3 > r2 > r1
mol L-1 1 0.693 0.693 1
= x
2 = mol–1 L s–1 5. (a) : k = = = 1.44 x10-3s-
s t1/ 2 480
( mol L-1)
mol L-1 1 6. =1
For first order, rate constant = x = s-1 (a) : For zero order reaction, t {[ A]0 -[ A]}
s mol L-1 k
6. (c) : Rate = k [concentration]n When reaction is complete, [A] = 0
if [concentration]n = 1, rate = k [A a
Hence, t = 0 ] =
7. (d) : 2H2S + O2 Product k k
Rate = k pH22S× pO 2 = x 2.303 [R0 ] 2.303 5
7. (a) : t = log = log
On increasing the pressure three fold k [R] 103
1.15x - 3
Rate = k()3pH2S2 × 3pO2 = 2.00 × 103 log1.667 = 2 × 103 × 0.2219 = 444 s
= k × 9 pH22S 3×pO2 0.693 0.693
8. (b) : k
t1/2 10
= k × 27 × pH22S × pO2 = 27x 0.08
Amount left=after n half-lives,
= 0.01 =
2n
Hence, rate will increase 27 times.
 146 MtG Objective Karnataka CET | Chemistry

0.08 - A[ X]
2n = 8, n = 3 5. (a) : Rate of reaction =
0.01 ΔΙ
then, total time = 3 × 10 = 30 minutes. A[X] = X; -X = 0.50 -0.38 = 0.12 M
9. (a) : As at the completion of reaction 35 mL of O2 is 0.12
formed, hence 70 mL of N2O5 is present initially as from the Rate = = 2 × 10 M S
s¹
reaction we can see that, 10 × 60
1 A[R] 1 0.4-0.5
1 6. (a) :Average rate = = --X
N2O5 : N2O4 : 02 :: 1 : 1 : 2 At 2 10
2
1 0.1
= -X = 5 × 10-3 M min¯¹
N2O5N2O4 + 2 10
2
Initial 70 mL 0 0 1 A[X]
After 15 min. 70-18 mL 18 mL 9 mL 7. (a) : Rate =
2 At
For first order reaction
1 a 1 70 1 35 == 1 (3-2) == – 0.1 mol L- ¹ min¯¹
k = -ln == In or In 2 5
t a - x 15 52 15 26
Negative sign signifies the decrease in concentration .
10. (b) 8. (b) : For the reaction RP
Average rate of reaction
Self Test - 4 Change in concentration of reactant
Time taken
1. (c) : AH° of the reaction is the difference of energy of
products and reactants. -A[R] [ R₂ ] - [R₁ ]
2. t t
(d) : Increase in tempera i
ture ncreases the rate of both
forward and backwar reaction by equal factor to bring the Where, change in concentration of reactant,
d
equilibr fa . A[R] or [R2] - [R₁ ] = [0.02 − 0.03 ]
ium ster
Time, t = 25 min
3. (a) : Ef+ E,
Er (-0.01)M
(0.02-0.03)M =
4. (c) : Activation energy can be same or different for
(25×60)s (1500)s
forward and backward reaction .
= 6.66 × 10−6 Ms¯¹ (.. M = mol L- ¹)
5. (c) The activation energy of a reaction can be
1 ^[R] =--
1 X 0.4-0.7
determined by evaluating rate constant at two different 9. (a) : Average rate =
2 At 2 10
temperatures by using the following expression :
1 0.3
k, = Ea T₂ − T₁ = -X = 1.5 × 102 M min™ ¹
log 2 10
k 2.303 R T¡T₂
10. (b) : Average rate of decomposition of NO₂
6. (b) : Higher the activation energy, lower is the rate A[NO₂ ] 3.0 × 103 (M) -4.3 × 10˜³ (M)
constant. At 300(s) -200(s)
Self Test - 5 = 1.3 × 10 M/s
1 d[X] == 1 d[Y] = 1 d[ Z ]
1. (a) : Lower the activation energy, faster is the reaction . 11. (b) : Rate =
2 dt 3 dt 4 dt
2. (c) : Not only sufficient threshold energy of colliding
12. (c) : The rate of appearance of D is double the rate of
atoms or molecules but also the proper orientation for the
disappearance ofB.
collision is required for the formation of products .
1 d[NO₂ ] ==1 · × 0.0125 = 0.0031 mol L-1 s-1
S
13. (b) : Rate
KCET Connect 4 dt 4
1 d[A]
1. (c) : Rate of reaction ∞ conc. of reactants 14. (b) :
2 dt
As the reaction proceeds, concentration of the reactants
decreases hence the rate also keeps on decreasing with time. d[ A] 1 d[B] = 1 d[C]
15. (c) : Rate ==
dt 3 dt 2 dt
2. (c)
d[F2 ]
A[R] ([R]2 − [R]1 ) 16. (d) : Rate of consumption of F2 at time t = −
3. dt
(c) : Average rate = —
ΔΙ t2 - t1
d[CIO2 ]
Rate of consumption of ClO2 at time t =
(0.04 0.05) 0.01 dt
= 3.3 × 10 M min, −1
30 30
Rate of formation of FCIO , at time t = d[FCIO₂ ]
4. (a) : Concentration of reactants decreases with time. dt
Chemical Kinetics 147

d[]F2 [A2 [A2] 2,2 [B]

Let be
and
1initial
and
[C]2[C]
and
represent
1 represent
final rates
final
initial
ofconcentrations,
theconcentrations
reaction when
andand
Rate of reaction at time t = − , [B] let
dt 2
1 d[ClO2 ] = 1 d[FClO2 ] concentrations
R 1 and
] R1 the
=−
2 dt 2 dt are changed.
17. (a)
(i) If [A2]2 = 3[A2]1, R2 = 3R1
18. (a) : For the reaction, 2NO2 → 2NO + O2 R2 = k[ A2][2B][2
x y C]2z

1 d[NO2] 1 d[NO] = d[O2] R1 k[ A2][1xB][1yC]1z

− =
2 dt 2 dt dt If the concentrations of B and C remain constant, then
x
d[]NO R2 = ([3 A2 ])
- 2 = 6x10-12 mol L-1 s-1 1
= 3x
dt R1 [ A2 ]1
d[]O2 = 3x10-12
mol L-1 s-1 \ 3R1 = 3x
dt R1
19. (a) : 2SO2 + O2 2SO3 \ 3 = 3x \ x = 1
Rate of formation or disappearance are related (ii) [B2] = 2[B]1, R2 = R1
d[O2 ] = − 1 d[SO2] = 1 d[SO3] The concentrations of A and C remain constant.
∴ − y
dt 2 dt 2 dt R1 = [ B ]2 (2[B ]1 ) y = 2y
\ R2
y = [B
1 d[SO2 ] B ]1
−25×10−
. 4
=− \ 1=2y\]1y = 0
2 dt (iii) If [C]2 = 2[C]1, R2 = 2R1
d[SO2 ] z = (2[C
]) z
= 50.×10−4 mol L−1s−1 \ R2 = [C ]2 1 = 2z
dt R1 [C ]1z [C ]1z
1 d[NH3] 1 d[H2O] 2R1
20. (a) : − =+ \ = 2z \ z = 1
4 dt 6 dt R1
d[H2O] = 6 Hence, the rate law is :
x36.x10-3 = 54. x10-3 mol L-1 s-1 Rate = k[A2]x[B]y[C]z = k[A2]1[B]0[C]1 = k[A2][C]
dt 4
30. (d) : Rate = k[A]2 [B]3 = a
Rate 1.02x10-4 mol L-1 s-1 When volume is reduced to one half then conc. of reactants
21. (b) : [N2O5 ] = =
k . x10-5 s-1
34 will be doubled.
= 3 mol L–1 Rate = k[2A]2 [2B]3 = 32 k[A]2 [B]3 = 32a
31. (b) : (Rate)1 = k [A]x [B]y
22. (c) : 1 d[]Fe3 +
(Rate)2 = k [A]x [2B]y
5 dt
23.expressed
be (b) : Foras2N2O5 → 4NO2 + O2, the rate of reaction can (Rate)2 = 2y for an elementary process, the coefficient
(Rate)1
1 d[N2O5] = 1 d[NO2] = d[O2]
− in front of the reactant is the order with respect to the
2 dt 4 dt dt
reactant. \ y = 2.
24. (b) : 2N2O44NO2 \ (Rate)2 = (Rate)1 × (2)2 = 4 × (Rate)1
\ Rate should increase 4 times.
1 d[ NO
24 ] 1 d[NO2 ]
Rate = − =+ 32. (b) : Initially rate (r1) = k[X]n …(i)
2 dt 4 dt (let n be the order of reaction)
1 1 n
k = kj ⇒ k′ = 2k Dividing
Then, r1 ×
eqn.
27 =(ii)
k[3byX]
eqn. (i) …(ii)
2 4
25. (b) : Minus signs are for reactants and positive signs for 27 = [3]n
product. Dividing numbers are the coefficients. \ n=3
13 Thus, order of reaction is 3.
26. (b) : Rate of disappearance of Q = × rate of appearance
of R 33. (d) : 2A + B + C Products
r1 = k [A]2 [B]
27. (b) : According to law of mass action, rate of chemical
reaction is proportional to molar concentration of reactants. [ Cis taken in excess, rate does not depend upon C]
r2 = k [2A]2 [3B]
28. (a) : Only gaseous reactions depend upon pressure.
Non-gaseous reactions have no effect of pressure. ⇒ r2 = 12k [A]2 [B]
29. (c) : Given : A2 + B + C AC + AB r =12k[ A][
2 2 B]

The rate law may be represented as, r1 k[ A][2B]

Rate = k[A2]x[B]y[C]z ⇒ r2 = 12r1
148 Objective Karnataka CET | Chemistry

34. (d) : Given r1 = k [A]x [B]y ... (i) On dividing equation (ii) by (i), we get,
4 = 2n
On reducing the original volume to half, the concentrations
of reactants A and B will be doubled. (2)2 = (2)n
⇒ n=2
Let the new rate be r2. Then,
r2 = k[2A]x [2B]y 45. (b) : 3 -1 = 1
or r2 = k × 4 [A]x [B]y [ x = y = 1] ... (ii) 2 2
initialr2rate.
or = 4r1 The rate will become four times relative to the 46. (a) : Order of reaction with respect to A,
Rate (r1) ∝ [A]n
35. (c) : Given, R1 = k[A]2 [B] On doubling concentration of [A],
According to question, R2 = k[3A]2 [2B] Rate (r2) = 2r1 ∝ [2A]n
= k × 9 [A]2 2 [B] Thus, n = 1
= 18 × k [A]2 [B] = 18 R1 Order of reaction with respect to B,
Rate (r1) ∝ [B]n
36. (a) : For second order, rate law is, R = k [A]2
On increasing concentration of [B] nine times,
R 1.25×10−2 Rate (r2) = 3r1 ∝ [9B]n
∴k = = = 6.173 × 10–2 M–1 s–1
A[]2 (0.45)2 Thus, n = 1/2.

1
2
1
37. (d) : Rate (r1) = k[SO2]2 [O2] in 1 dm3 vessel Overall order of reaction = 1+ = 1
(Law of mass
In 2 dm3 vessel i.e., double volume, concentration becomes
action) 2
1
47. (b) : d[IO- ] = k [I-[]1[OCl- ]
half. dt OH - ]1
2
r2 = 1 SO2  1  =8
1 ][O
2 = 18 1 Order of reaction = 1 +1 – 1 = 1
Rate( ) k    2 O2  k[SO2 2] r
2 48. (b)
r1 =8 r2, i.e., 8 : 1 49. (b) : Zero order reaction is independent of concentration
38. (a) : Rate constant of a reaction depends on its of reactant.
temperature. 50. (d) : 12A + B →C
39. (a) : For the reaction, A + B products, the rate law
is Rate = k[A]1/2 [B]1
dx Order = 1.5
= r1 = kA[ ][B]2 ... (i)
dt 51. (d) : The rate law of the reaction is of the form,
rate1 = k[A]x [B]y
= k ⎡⎢⎣12A⎤⎢⎦[2B]2
r2 ... (ii) If [B] is doubled at constant [A], the new rate law is
rate2 = k[A]x {2[B]}y
or [ ][B ]2
r2 = k 1 x 22 kA ... (iii) x
rate 2 = k[ A][B y y
] 2
2 Hence,
x y
= 2y
rate1 k[ A][B ]
Dividing (iii) by (i)
rate2
r2 = 2kA[ ][B ]2 But = 2 because rate2 is twice of rate1
=2 ( r2 = 2r1 ) rate1
r1 [ ][ B ]2
kA Thus, 2 = 2y and hence y = 1
If [B] doubled and [A] is tripled, the rate law becomes
40. (d) : Rate = k[NOBr]2
rate3 = k {3[A]}x {2[B]}y and rate3 = 6 rate1
k = 1.62 M–1 s–1, [NOBr] = 2.00 × 10–3 M = k x 3x [ A]x x 2y [B y
Hence, rate = 1.62 (M–1 s–1) × (2 × 10–3)2 (M2) Therefore, rate3 ] = 3x x 2y
rate k[ A][x B y
]
= 6.48 × 10–6 M s–1
rate3
41. (c) : R→P Now, because 1 = 6 and y = 1
For a second order reaction, rate = k[R]2 rate1
If conc. of R is increased by four times, rate = k[4R]2 6 = 2 × 3x or 3 = 3x and hence x = 1.
Hence the rate of formation of P increases by 16 times. It follows that the reaction is first order with respect to A and
2 1/2 B each and second order overall.
42. (b) : Rate (r1) = k[A] [B]
52. (b) : r = k[A][B]
If [A] is doubled and [B] is increased four times,
2 2 1/2
If B is in large excess then rate becomes independent of [B]
Rate = k[2A] [4B]1/2 = 4 × 2k[A] [B] = 8 r1 and will depend only on [A].
43. (d) r = k[A]
(c) : r=kthe
44. doubling
On n
[Hconcentration of H2 ... (i) \ Order of reaction = 1
2]
, 53. (b) : Mechanism of reaction as well as relative
4r = k [2H2]n .... (ii) concentration of reactants decide that how many
Chemical Kinetics 149

concentration terms affect the rate of reaction i.e., order of rate

reaction. Units of rate constant =
(PCH₂OCH3 )3/2
54. (c) : The rate law for the reaction is of the form,
bar min
rate = k [A] [B] = bar -1/2 min −1
-1 bar3/2
rate = 6 × 104 M/s, k = 2 × 10-3 S 9 [A] = [B] = 0.3 M. 61. (d)
Hence, 6 × 10+ (M/s) = 2 × 10-3 (s¹ ) x (0.3 M) (0.3 My
62. (c) : Unit of rate constant for the reaction is
6 × 10 (M/s)
or = (0.3)x + y (Mx+y) rate mol L-1 s-1 -1
2 × 10-3(s-¹) k= = mol-² L² s¯¹
[H2 ][ NO]² (mol L- ¹)( mol L- ¹)²
or 0.3 (M) = (0.3) +y (M)x+y
63. (a) Molecularity of the reaction A + 2B →→→ P, is
It follows that x + y = 1. Hence, the overall order of the
1 + 2 = 3 , as one molecule of reactant A and two molecules of
reaction is 1 .
reactant B collide with each other.
55. (b) Rate = k [concentration]"
64. (d)
r₁ = 2.4 = k [2.2]" ...(i)
65. (d)
r₂ = 0.6
16 == k
k ...(ii) 66. (a) : Slowest step is the rate determining step .
"
1x2.2]
67. (b)
On solving equations (i) and (ii),
n = 2, i.e. , 2nd order reaction. 68. (b) : The slowest step of the reaction is rate determining
1 step .
56. (c) : Rate ∞ [ Conc . ] × N2O2 + H2 → N₂O + H₂O
[Conc. ] Rate of reaction = k [N2O2 ] [H2]
ох [Conc .]°. Hence, order = 0
i.e. , Rate ∞ Hence, order of reaction = 2
57. (c): From 1st reading, 69. (b) : The intermediate species is one which is formed
rate = 10.0 x 105 = k[0.003]" ...(i) and used up during the course of reaction .
M

(where, n is order of reaction)

From 2nd reading, 70. (a) : Slow step is the rate determining step of the
reaction. Only in step (ii) , the reactant ' C' is involved in the
rate = 5.0 × 10 = k[0.006] " ...(ii) slow step of the reaction .
Dividing eqn. (i) by (ii) ,
71. (c) x = kx t
10.0 × 10-5 k [ 0.003]” X
G

=
5.0 × 10-5 k[0.006]" k
a
Time for completion of reaction (when x = a), i.e. , t =
2= n = -1 k
2-H 72. (c) Rate of a zero order reaction is independent of the
1 1 11 concentration of reactants.
58. (d) : + +1=
2 3 6 73. (c) : The study of the data shows that the rate of reaction
does not vary with time. It is characteristic of a zero order
59. (c) : For second order kinetics, reaction .
rate = k [reactant]²
74. (b) : For zero order reaction integrated rate equation is
so make two equation first by taking initial rate and
concentration, second by taking tripled concentration and k = Co - ct
unknown rate (r' ) . Compare them to find a relation between t
心 み

r and r' . dx
For the reaction, x 75. (a) : For a zero order reaction , rate = k =
y dt
Reaction rate (r) = k [x]² 1 1
(i) Units of k = mol L S
If the concentration of x is increased three times, then
76. (c)
Reaction rate (r') = k [x]² = k × [3x]² (ii)
On dividing equation (ii), we get 77. (d) : -Intercept = [A ]

r' k × [9x² ]
9
r kx[x2 ] Slope = - k
[A]
It means that the rate of formation of y will increase by nine
times.
Time (t)
60. (b) : In terms of pressure,
78. (b) : For two-third of a reaction,
Rate = k(PCH3COCH3) 3/2 a
Units of rate = bar min−1 [ A]o = a, [A]; = =
3
 150 MtG Objective Karnataka CET | Chemistry

2.303 . ogo 0.693 0.693

= l For 50% completion, t1/2 =
t2/3
k [A]t k 0.0153 min-1
2.303 a 2.303 = 45.3 min = 45 min
= -log- log3
k a k 89. (a) : As t75% = 2 × t50% , the order of the reaction is one .
3 0.6 - 3
2.303 × 0.4771 90. (a) : In case I, fraction of A reacted =
t213 = 2.01 × 1013 s 0.8 4
5.48 × 10-14 0.675 3
In case II, fraction of A reacted
79. (d) : First order rate constant 0.9 4
a For a first order reaction , time taken for the same fraction of
k = 2.303 a = 1 ; a − x = 1/8
log reaction is independent of initial concentration.
t a-x
91. (b) : Given, a = 100 , x = 80 , when t = 10 min.
2.303 1
k= log min¯¹ Substituting these values in the first order rate equation
24 1/8 2.303 a
k= log we get
t a-x
2.303 log 8
or k= min1
24 2.303 100
k= log
10 × 60 100-80
80. (b) : In case of first order reaction rate constant 2.303 2.303
= log 5 = -x0.6989
(k) == sec 10×60
=
600
2.303 a -1 ≈
81. (c) : t = log k = 0.00268 s 0.0027 s¯¹
S
k a - x
2.303 a
If t = t1/4; x = a/4 92. (a) : t = log
k a -x
2.303 a 2.303 l 4
.. -log- og 2.303 5
t1/4 or t= log == 34.07 s
k (a - a/4) k
15 × 10 3
2.303 [4]
82. (b) : k = log 93. (b) : For 60% completion, a = 100 and a - x = 40 and
(t₂ - t₁) [42 ] time, t = 60 min
1.45 2.303 2.303 100 2.303
2.303 k: log
k= log = -× 0.2169 log 2.5 = 0.0153
0.88 800 60 40 60
(1600-800)
= 6.24 × 10-4s
S-1 2.303 100
t30% log = 23.3 minutes
0.0153 70
83. (c) : For a 1st order reaction, rate ∞ conc.
2.303 a 2.303 100
84. (c) : t = log 94. (b) : k = log
k a -x 1.386 × 60 × 60 100-75
3 За 2.303
for th life , x = -1.
log 4 = 2.7 x 104 sec-1
4 4 1.386 × 3600
2.303 a 2.303
t314 log log 4. (Time 1.386 hours need to be changed to seconds)
k a -3a /4 k
95. (c) : For first order reaction,
85. (b) : In case of first order reaction, rate constant, k = s¯¹ . 2.303 a 2.303 400
k log = log
2.303
a
86. (c) : k = t a-x 200 25
log
t a -x 2.303
= -1 -1
t = 8 minutes 20 seconds = 8 × 60 + 20 = 500 seconds - × 1.204 = 0.01386 S = 1.386 × 10-2 S
200
1
a == M [A]o
10 96. (b) : Amount of substance left after n half lives =
2n
1 Number of half lives = 4
(a− x) = M
100 [12 days = 4 half lives if t1/2 = 3 days]
2.303 1/10 :: [A]。 = 3 × 2″ = 3 × 24 = 48 g
k log 4.606 × 10-3 sec -1
500 1/100 80
97. (c) : a − x = · × a = 0.8a , t = 10 min
2.303 100
a
87. (d) : k - log10 2.303 a 2.303 a
t (a− x) k log log
t a -x 10 0.8a
2.303 a 2.303 1
88. (c) k= ·log -log- 10
60 min a -0.6a 60 0.4 k = 0.2303log = 0.2303(1-0.9030)
8
= 0.0153 min¯¹ = 0.2303 × 0.0970 = 0.0223 min¯¹
Chemical Kinetics 151

98. (c) : 3/4 or 75% completion from 100 → 50 — 25 in 107. (b) : Where, k = rate constant = 10-3 S
2 hours. Time means t₁/2 = 1 hour. a = initial amount = 100
0.693 a - x = amount left after time t = 25
k= hour
1 t = time to leave 25% reaction
After 3 more hours total time will be 5 hours. 2.303 100 2.303
.. t= log log 4
2.303 100 10 25 10-3
5= log
0.693 X 2.303 × 0.6020
= 1386 s
100 5 × 0.693 10-3
or log ·; x⇒ 3.16 ≈ 3%
x 2.303 2.303
108. (a) : t = log16
k
2.303 og o 2.303 5 2.303
99. (a) : t = l R = log t= × 1.204 = 0.046 s
k R 1.15 × 10 −³ 3 60
== 2.00 × 10³ log1.667 = 2 × 10³ × 0.2219 = 444 s 109. (b) 110. (d)
1 111. (d) : Slope of the graph In [A]t vs t will be equal to – k
100. (b) : For initial concentration to reduce to " no . ofhalf
hence, the value of rate constant is 2.5 × 10−³ s−1
lives = 3 .
1 112. (b) : First order reaction gives a straight line plot of
n [4]t
101. (b) : k = -¹lIn log (ax) and time.
t [A]o
102. (b) : t50% = 2 hours, t75% = 4 hours log a

if 1st order then, t75% = 2 × t50%

-k
4 = 2 × 2 , hence, 1st order reaction . log (a - x) slope
2.303
103. (d) : For a first order reaction
k.t
=
= log[ C ] - log[ C ]
2.303 113. (c)
k.t
or, log[C ] = log[C ] 114. (b)
2.303
Plot of log [C] vs t is a straight line with negative slope. 115. (c) : For flask I
Hence, log [C] decreases linearly with 't' . 2.303 1 2.303 2.303
k= log = log 4 = × 0.6021
104. (d) : A radioactive disintegration reaction is always of 8 0.25 8 8
1st order. [A] 0 = 10 [A] ; t₁/2 = 30 days
For flask II
0.693 0.693
k 2.303 0.6 2.303 × 8
t1/2 30 t = log = × 0.3010 = 4 hours
k 0.3 2.303 × 0.6021
2.303 [Alo = 2.303 10[A]
t= log × 30 × log
k Alternatively,
[A] 0.693 [A]
From concentration 0.6 M to 0.3 M it means t₁/2 has been
= 99.7 100 days
asked. Then
18
105. (a) : Number of half-lives = 0.693 × 8
3 t1/2 = = 4 hours .
2.303 × 0.6021
[A]o
Amount left after n half-lives == [40 ] 116. (a) : For zero order reaction, t1/2 =
2n 2k
300 117.(c)
Thus, amount left = = 4.6g .
26 118. (b) : For zero order reaction , t1/2 ∞ a.
106. (d) : Given t1/2 = 120 min 119. (b)
0.693
:: k= - min t1/250
120 120. (c) : 100 1 11/225, Thus t1/2 = 1/2 hr
hr hr
Now for 90% completion
2.303 a 2.303 0.693 0.693
k= log ... (ii) 121. (a) : k =
t 0.1a t t1/2 60
Comparing (i) and (ii) Time taken for 80% reaction to occur
0.693 2.303 a 2.303× 60 100
t = 2.303 Log log
120 t k a-x 0.693 100-80
2.303 × 120 2.303 × 60
t= min = 398.78 min ≈ 400 min.
0.693 ·log 5 = 139.39 minutes
0.693
 152 || MtG Objective Karnataka CET | Chemistry

0.693 0.693 dx
122. (b) : k = 133. (b) : = k[X] (For a first order reaction)
t1/2 10 dt
2.303 0.08 2.303 × 10 0.00352 = k × 0.01 ⇒ k = 0.352
t= log log 8 = 30 minutes 0.693 0.693
k 0.01 0.693 = 1.969 min.
t1/2
k 0.352
Alternatively,
0.08 134. (c) : For first order reaction, half life is independent of
Amount left after n half-lives, 0.01 = concentation .
0.08 2n
135. (d) : Let a = 1 , a - x = 1/8 , t = 75 min.
2n = =8
0.01 2.303 a 2.303 1 2.303×0.903 -1
k log log min.¯
n=3 t a -x 75 1/8 75
Then, total time = 3 × 10 = 30 minutes For first order reaction ,
123. (c) : t99.9% = 10 half lives. 0.693 0.693 × 75
t1/2 = = 24 · 99 ≈ 25 min.
1 1hr 60 k 2.303 × 0.903
124. (d) : Half-lives = n = = = =4
t1/2 15 min 15 0.693 2.303 a
136. (a) : k = and k log
t a-x
ʼn half lives = [ A]o =
Amount left after n _ [ A]o =
_ [ A]。 t1/2
2n 24 16
0.693 2.303 1.28
So, log ⇒t = 465 s
125. (a) : Half-life of a first order reaction does not depend 140 0.128
upon initial concentration .
0.693 2.303 -l a
137. (d) : og-
126. (d) : Rate = k [concentration]"
t1/2 t a -x
2.0×10-5
k= = 2 × 10-3 sec-1 0.693 2.303 100
0.01 log x= 75%
10 20 100 - x
0.693 0.693
t1/2 = 347 seconds 138. (a) : 30% decomposition means X = 30% of R。
k 2×10-3
or R = Ro − 0.3R。 = 0.7Ro
2.303 Ro
0.693 0.693 For first order, k = log
127. (b): t1/2 = t R
k 1.3 × 10-2
= 53.30 minutes = 3198.46 s≈ 3200 s 2.303 log 10 min− 1 =
= 8.918 × 10-3 min¯¹
40 7
128. (a) : For nth order reaction, 0.693 0.693
t1/2 77.7 min
1 k 8.918 × 10-3 min
t1/2 oc where n = order of reaction .
a(n-1) 0.693 0.693
1 1 139. (b) : t1/2 == 34.65 min
i.e. Ifn = 1 , ty/2∞ 1-1 t1/2 ∞ k 2×10-2
α 0.693
0.693
140. (b) : t1/2 = 3.46 × 10-3 s
i.e. independent of initial concentration.
M k 200
0.693
For first order reaction, †1/2 141. (c) : For a 1st order kinetics,
k 2.303 a
k= log10
129. (b) : As it is a reaction of 1st order, t1/2 does not depend t a --X
0.693 a
upon initial conc. as t1/2 == At t1/2, k = 2.303 log1
k 0
t1/2 a
0.693 2.303 a 2
130. (c) : log
t1/2 t a-x 2.303 In2
or t1/2 log10 2 =
0.693 2.303 . 100 k k
log x = 99.9 %
10 100 100 - x 0.693 0.693
142. (a) : 1/2 = = 1117.2 seconds .
k 6.2 × 104
131. (c) : Rate = k[concentration]
143. (a) : t1/2 for first order reaction is independent of initial
1.5 × 10-2 -1 concentration : . t1/2 ∞
k = 3 × 10−2 min¯
0.5
144.(a)
0.693 0.693
= = 23.1 minutes 145. (c) Inversion of cane sugar is a particular example of
t1/2 -2
k 3× 10- pseudo-unimolecular reaction.
t1/2 1 t1/2 1
132. (a) : 1 146. (c) : When one of the reactants is in excess the reaction
20 min 2 20 min 4 behaves as a first order reaction .
Chemical Kinetics 153

147. (b) : Average rate during the time interval 30-60 s. Energy of activation of forward reaction,
(0.17-0.31 ) = 0.14 Ef= 100-40 60 kJ
Rate == C2 - C1 Heat of reaction,
t2 -t1 60-30 30
AH = Energy of products – Energy of reactants
= 4.67 x 10-3 mol L- 1 S
s-1 == 60 – 40 = 20 kJ (Endothermic reaction)
148. (a) Energy of activation of reverse reaction,
E = Threshold energy - Average energy of products
149. (a) : For every 10° rise in temperature rate of reaction = 100-60 = 40 kJ.
double.
163. (a)
30° rise in temperature means 2 × 2 × 2 = 8 times rate .
new = 8 164. (a) : cannot be predicted
Told 165.(d)
New rate == 2.6 X 10-3 × 8 = 20.8 × 10−3
166. (b) : Ea(forward) + AE = Ea(reverse)
= 2.08 × 10-2 mol L-1 Ss-1
17 + 40 = Ea(reverse)
150. (b) : Arrhenius equation gives a quantitative idea about Ea(reverse) = 57 kJ
effect of temperature on reaction rates . 167. (b) : k = Ae Ea/RTAs T → ∞
151. (b) : Rise of temperature = 100 – 10 = 90 °C i.e. 9 × 10 . X 1014 s
k = A = 6.0 ×

For n × 10° increase of temperature rate increases 2" times . 168. (a) : AH = E - E. +5 = 15 - Er :. E = 10
Thus, increase in rate = 29 = 512.
169. (d) : Activation energy (E ) of backward reaction for an
152. (d) : Rate ∞ rate constant exothermic reaction.
153. (c) : For every 10°C rise of temperature rate constant = E₁ of forward reaction + heat of reaction
= X + Y.
becomes double. Thus for 20°C rise (280 K to 300 K) rate
constant becomes four times. 170. (d) : Increase in temperature increases the rate of both
1 forward and backward reactions by equal factor to bring the
-
i.e. k₁ = 4k½ or k₂ = — k₁ = 0.25 k₁ equilibrium faster.
171.(a)
154. (d) : We have, the Arrhenius equation ,
k = Ae-Ea/RT = ART/Ea 172. (b) : A kB, A_k2_C ,
By Arrhenius equation
k becomes least when Tis low and E is high.
k₁ = Ae-Ea₁ /RT
155. (c) : Activation energy is always positive .
-Ea2 / RT
156. (d) and k₂ = Ae (A is Arrhenius constant)

157. (c) : AH = Eƒ— Eb (Given, Ea₂ = 2E )

- 200 = 80 - Eb .. k₂ = Ae-2Ea1/RT
E = 200 + 80 = 280 kJ/mol Ae˜Eaa1 /RT
k1 = 2E../RT
158. (b) : Activation energy of reverse reaction = e a1
k₂ Ae-2E1/ RT
= Ea(f) - (AH) = 80 kJ/mol-(-20 kJ/mol)
= (80 + 20) kJ/mol = 100 kJ/mol :. k₁ = k₂e²Ea₁ /RT

159. (d) : For endothermic reaction , the minimum amount 173. (d)
ofactivation energy will be more than ΔΗ.
174. (c) : A catalyst lowers the activation energy.
160. (c) : Activation energy is the extra energy that the
175. (b) : According to Arrhenius equation
F

reactants must acquire in order to give products, on collisions.

k2 = E
a

T₂ - Ti
log X
161. (c) : Activation energy can be same or different for both k₁ 2.303R TT2
forward and backward reactions .
1.5 × 104 (60000 J mol¯¹ ) T - 283
162. (d) : 100tz log =
4.5 × 10 2.303 × (8.314 J mol− ¹ ) 283 T₂
80+ E60 kJ
Energy

|E₁ = 40 kJ
kJ-
in

60+ T2-283
ΔΗΙ AB + C log 3.333 = 3133.62
40+A + BC 283 T2
20+ T₂ = 297.19 K = (297.19-273.0) = 24.19°C
0 Temperature = 24.19°C
Progress ofthe reaction
176. (a) : AH° is the difference in energy of reactants and
From this energy profile it is clear that : products.
Threshold energy of the reaction = 100 kJ; average energy of Activation energy is the minimum energy of a reaction at
reactants = 40 kJ. which activated complex is formed.
 154 || MtG Objective Karnataka CET | Chemistry

177. (a) : According to Arrhenius equation rate constant 190. (d) : The equilibrium is attained faster in case of reaction
decreases with increasing E in which catalyst is used as it lowers the activation energy.
178. (b) 191. (c) 192. (d) 193. (a) 194. (c)
179. (d) : k = 2.1 × 1010e-2700/RT 195. (d) : Only those collisions in which molecules collide
-2700/RT
In k = ln 2.1 × 1010 + ln e to get sufficient energy, called threshold energy and proper
2700 orientation are effective collisions. Rest of the molecules
In k = ln 2.1 x 1010
RT collide and bounce back.
2700
log k = log 2.1 × 1010 196. (c) : Ea is activation energy. Lower activation energy
2.303RT
favours the reaction.
2700 1
log k == + log2.1 × 1010
2.303RT 197. (a) : For backward reaction, activation energy is from
On comparing it with straight line equation y = mx + c, we get product to activated complex.
2700 198. (c) : Collision theory is applicable to bimolecular
.. m (slope)
2.303R reactions only because three or more molecules can't collide
effectively.
and C = log 2.1 × 1010
180. (b) 199. (b) : Apart from energy considerations, the colliding
molecules should have proper orientation for effective
–Ea
181. (d) : Slope = collisions .
2.30
3R 200. (b)
-Ea
− 1 × 10³ =
.
2.303R 201. (d) : The increase in collision frequency brings an
increase in effective collisions and thus rate of reaction
E₁a = 2.303 × 8.314 × 103 = 19.1 kJ mol- ¹
increases .
182. (b)
202. (a) : Lowering of E , raises the value of k.
Eaα
183. (a) : slope 203. (c) 204. (c)
2.303R
Ea 205. (c) : More is the number of effective collisions more will
-5.64 = be reaction rate.
2.303R
Ea = 5.64 × 2.303 × 8.314 KCET Ready
= 107.9898 = 108 J mol¹
184. (d) : k = 1.2 x 1014e25000/RT -1 1. (c) : 2NH3 →→→→ N₂ + 3H₂
25000 1 d[NH3 ] = d[ N2 ] =
_1- d[ H2 ]
Rate =
log k = log( 1.2x10¹4) - log k 2 dt dt 3 dt
RT
25000
slope =
R ¹ k₁ [NH3 ] = k₂ [NH3 ] = = k3 [NH3 ]
Ea 1/T
k₂ = T₂ −T₁
185. (a) : log 1.5k₁ = 3k2 = k3
k 2.303R T T₂ 2. (b)
Ea
300-290
log 2 = 3. (a) : 30% decomposition means X = 30% of Ro
2.303× 2 290 × 300
or R = Ro − 0.3R。 = 0.7Ro
(k₂ = 2 k₁, R = 2 cal/K/mole) 2.303 Ro]
For first order, k = log !
Ea = 12062 calories ≈ 12 kcal. t R
Ea - 2.303 10
k₂
X T₂2 − T₁ log- min = 8.918 × 10-³ min¯−1
186. (a) log
40 7
k₁ 2.303 × R T₂T₁
0.693 0.693
= = 77.7 min
E

6.90 × 10 E 40 t1/2 =
a

log X k 8.918 × 10-3 min¯¹

3.45 × 10- 2.303 × 8.314 300 × 340
4. (b) : 2N2O4 — 4NO2
= 2.303 × 8.314 × 300 × 340 × log 200
:. Ea = 112.34 kJ 1 d[N2O4 ] 1 d[NO₂] or
40 Rate =+ =
2 dt 4 dt
k2.= Ea (T2 - Ti )
187. (c) log10 or k ' = 2k
k₁ 2.303 R × T₁ × T₂
188. (a) : A catalyst brings down the energy of activation . 2.303 a
5. (b) : k - log
t (a− x)
189. (c) : Energy of activation is lowered when a catalyst is
used. (a - x) is the concentration left after 100 sec.
Chemical Kinetics 155

2.303 0.29 [A] = 0.5 M

2.714 x 10-3 = log \ 1.5 × 10–2 = k × 0.5
100 (a - x )
15.×10−2
0.27 0.29 0.29 ∴ k= = 3×10−2 min −1
⇒ = log ⇒ 0.117 = log 0.5
2.303 (a − x) (a − x)
For first order reaction,
⇒ (a– x) = 0.22 M 0.693 0.693
Half-life period t1/2 = = = 23.1min
1 [N2O5]0 k 3x10-2
6. (d) : k = ln 16. (d): A and C are reactants as their concentration falls
t [ N2O5]t
with time hence, (minus sign).
[ N2O5]0 B and D are the products of the reaction because their
kt = ln
N2O5 ]t concentration increases with time hence (plus sign).
m and p are the stoichiometric coefficients of A and C while n
7. (a) : For the reaction 2A + 3B Products; and q are the coefficients of products B and D.
So, the equation of the reaction becomes :
1 ⋅ d[ A] d[B] mA + pC nB + qD.
− =− 1 ⋅
2 dt 3 dt
17. (d)
Given : − d[ A] d[B] k1
18. (b) : The slow step A → B, is the rate determining
= r1; − = r2
dt dt step of the reaction, Hence, rate of production of C, i.e.,
1
2 d[C ]
or r1 = 1 r2 or 3r1 = 2r2 = k1[ A].
3 dt -d[ A]
8. (c) : For first order, partial pressure or conc. of the 19. (c) : According to the expression [ ][ B ] the
= kA
order of reaction should be two. dt
reactant decreases exponentially with time.
9. (a) : Arrhenius equation, k = Ae–Ea/RT 20. (d)
Case I : : For the first order reaction, k = 2.303log
C
t C0t
Ea
ln k = ln A –
RT C0 = 100 M, Ct = 100 – 60 = 40, t = 100 min
This equation is of the form, y = mx + c, 2.303 100
i.e., the equation of a straight line. k= x log
100 40
10. (c) : First step is slow (require large activation energy) 2.303x0.3979
second step is fast (less activation energy) and overall reaction k= ... (i)
100
is exothermic. So, product energy level should be less as
Case II:
compared to reactants.
C0 = 100 M, Ct = 100 – 90 = 10 M
11. (b): As k' > k". 2303. 100
t= log
Greater the rate constant, lesser is the activation energy. k 10
∴ Ea′ < Ea′′ 2.303x100
12. (c) : k1 = Ae–Ea/RT
= = 251.3 min
2.303x 0.3979
... Substituting k from (i)
k2 = Ae–[Ea– 2]/RT
21. (b) : For an endothermic reaction,
-[Ea -2]
-[ Ea - 2]+ Ea 2 Ea(products) < Ea(reactants)
k2 e RT = eRT
= -Ea = e RT RT DH > DH
k1 (products) (reactants)
e RT 22. (b) : First we calculate the rate constant from t1/2,
1 d[N2O5 ] = 1 d[NO2 ] = d[O2] 0.693 0.693 −1
13. (b) : Rate = − k= = = 01155
. h
2 dt 4 dt dt t1/2 6( h )
1 2.303 [A
Rate = − k1[ NO
25 ] = 1 k2[ NO
25 ] = k3[ NO
25 ] Now, t = log10 ]0
2 4 k [ A]t
On dividing
get, 2k1 all the terms by [N2O5] and multiplying by 4 we [A]0 = 0.8 M, [A]t = 0.25 M, k = 0.1155 h–1
= k2 = 4k3 2.303 0.8(M )
Hence, t = log10
1 0.25(M)
14. (b) : The catalyst decreases the activation energy of the 0.1155 h -
reaction and thus increases the rate of reaction. 2303 2.303
0.1155
× 0.5051
= −1
log10 3.2 = h = 10.07 h
15. (b) : For the first order reaction, 01155
. . h
Rate = k [A]
23.are
all (b)
true. We
: For anhave
exothermic reaction Ea > DE. However, rest
Given that,
dx Ea( f) = EThreshold - E Reactant
= 15.x10-2mol L-1 min-1 and
dt
 156 Objective Karnataka CET | Chemistry

Eab() = EThreshold - E Product 29. (c) : Rate law : Rate = k[A]x [B]y
Doubling [A], rate is doubled. Hence, x = 1
Thus, Ea( f ) - Ea(b) = E Product - EReactant = AE Similarly, y = 1
\ Rate = k[A][B]
If ∆E = −ve then Ea( f ) < Eab
( )
-4
rate .20x10
If DE = + ve then Ea(b) < Ea(f ) k= = =1
[ A][B] 1x10-2 x 2x10-2
24. (d) : We know that
Ea  11 1 
2.303R (rate)2 = k(2[ A])(2[B])
logk2 − log k1 = =4
T − T  (rate)1 kA
[ ][B ]
 2
0.693 0.693
log k2 = log k1 +
Ea
2.303R  1 1  30. (a) : k = = = 1.386min−1
 T1 − T  t1/2 0.5(min)
 2
-1 2.303 [ A]0
8.314JJmol k= log10
= log(1.60x10-5) + 1
2.3032x09000 mol- 1K - t [ A]t

⎡ 1 1 ⎤ 2.303 [ A]0
or t= log10
⎢⎣ 600 K − 700 K ⎢⎦ k [ A]t
log k2 = – 4.796 + 2.599 = – 2.197 [A]0 = 100, [A]t = 100 – 80 = 20
k2 = 6.36 × 10–3 s–1
2303
. 100
Hence, t = log10
2.303 100 1386
. (min-1 ) 20
25. (b) : t99% = log …(i)
k 100 -99
2.303 2.303
2.303 100 = log10 5 = x 0.699
t90% = log …(ii) 1.386(min-1 ) 1.386 (min-1)
k 100 -90
t 99% log
log100
10 = 1.162 min = 69.7 s
Dividing equation (i) by (ii), = =2
t 90% 31. (d) : k = 2.1 × 1010 e–2700/RT
\ t99% = 2 × t90% ln k = ln 2.1 × 1010+ ln e–2700/RT
2303. a 2700
26. (d) : k = log ln k = ln 2.1 × 1010 −
t a-x RT
2700
2.303 100 log k = log 2.1 × 1010 −
k= log 2303.RT
20 100 − 20
2.303 100 2.303 log k = - 2700 1 + log 21.x1010.
= log = × 0.0969 = 0.01115min−1 2.303RT
20 80 20 On comparing it with straight line equation y = mx + c, we get
2.303 100
k= log = 0.01115 2700
t60% 100 −60 ∴ m (slope) = − and C = log 2.1 × 1010
2303.R
2.303
⇒ t60% = × 0.3979  82min Ea
0.01115 32. (d) : log k = − + log A
2.303 100 2303RT
.
27. (a) : k2 = log for 50% of B reacted Ea
t2 50 Straight line with slope = -
2303.R
2.303 100
k1 = log for 94% of A reacted
t1 6 First order reaction, k = 2303. log C
k2 t1 0.3010 t C -x
∴ = ×
k1 t2 1.2218 k
\ Straight line with slope = -
Since t2 = t1, because 50% B has reacted when 94% A has 2303.
Units of k for the first order reaction are independent of
reacted.
concentration units.
k2 = 0.3010 k1
∴ = 0.246 and = 4.06 33. (b) : Graph (A) is for zero order reaction as the rate
k1 1.2218 k2
1
remains constant at any time.
Graph (B) is for zero order reaction.
28. (c) : Rate1 = kY
[ ][Z]2
1
a
According to the formula, t1/2 2
Rate2 = k[Y ][]2Z2 So, t1/2 ∝ a = k
1 Graph (E) is for 1st order reaction as the rate of reaction is
1
\ Rate12 = k[Y ][2Z]2 = 2 2 = 2 directly proportional to concentration.
1 ( ) According to the equation, r = k[A]1t
kY
[ ][Z ]2 ⇒ r ∝[A]t
Chemical Kinetics 157

34. (c) : (i) R × ох [B]° (iii) R ∞

ос [A] (ii) R ∞ ox [ C]²
0.693 2.303 l a
og10
ос [A] [B] ° [C]²
Rate ∞ 11 a-x
4
.. Overall order = 3 .
a 0.693 × 11
.. log10 = = 0.827
35. (d) : The rate law of the reaction A + B · Products, a-x 2.303 × 4
as determined from its kinetics is, a = Antilog (0.827)
dx a -x
k[ A]² [B] · a-x
dt = fraction remaining unhydrolysed
So, the overall order of the reaction is 2 + 1 = 3 . a
a -x
2.303 lo [A]% 1 = fraction hydrolysed.
36. (d) : k = g10 a
t [A]
.. Fraction of sucrose that undergoes hydrolysis
[A]% kxt
or log10 = = 1 − 0.1489 = 0.8511
[A]t 2.303
40. (c) : For a first order reaction,
k = 7.0 × 10+ s t = 35 min = 2100 s , [A] 。 = 0.08 M 2.303 a
Hence, k= log
t a-x
0.08(M) 7.0 × 10 ( s¹ ) × 2100 (s) = Given : t = 10 × 60 × 60 sec
log = 0.6383
[4]t 2.303 Let initial concentration (a) be 1 ,
2.303 1
and 0.08(M) = antilog (0.6383) = 4.35 Then, k = log
10 × 60 × 60 (1 - x)
[A]t
0.08(M) = On putting value of k = 1.5 × 10-6 S¹ , we get
It follows that [A]t = = 0.0184 M
1 1
4.35 = 0.0234 or 1.055
⇒ log
The concentration that remains after 35 min is 0.0184 M. (1 - x) (1 - x)

37. (c): SO2Cl2 → SO2 + Cl2 On putting value of k = 1.5 x 106 s¹ , we get
Initial pressure Ро 0 0 1.055-1
or x= = 0.052 i.e. , 0.052 × 100 = 5.2 %
Pressure at time t Po -P P Р 1.055
Let initial pressure, po ох Ro
41. (d) : The unit of rate of reaction is mol L-¹ s¯¹ . It does
Pressure at time t, P = Po - p +p + p = Po + p
not change with order.
Pressure of reactants at time t, po -
− p = 2po − P₁ ∞ R
2.303 42. (d) : (i) is wrong because rate constant does not depend
k= -log- Ро upon the concentrations of the reactants.
t 2Po -Pt
(ii) is wrong because rate depends upon [H+]²
2.303 0.5 2.303 (iii) is correct because change in pH means change in [H*]
log log 1.25 ions
100 2 × 0.5-0.6 100
(iv) is correct because rate ∞ [H+]².
= 2.2318 × 10-³ s−1
S
Pressure of SO₂Cl₂ at time t (pso, cl,) 2.303 a
43. (b) : For first order reaction, t = log
== 2po - P₁t = 2 × 0.50 0.65 atm ==
= 0.35 atm k a -x
Rate at that time = k × pso₂Cl₂ 2.303 100 2.303
t99.9 log -x3
k 100-99.9 k
= (2.2318 X
× 103 ) X
× (0.35) = 7.8 x 10+ atm s
2.303 100 = 2.303 2.303
38. (b) : From experiment 1 , we have t50 log log2 = -x0.301
k 50 k k
Rate = k(2.5 × 10-4)2 (3.0 x10-5)
t99.9 = 10 approx.
5.0 ×10-4 -1
k 2.67 × 108 mol -2L²s¯¹ t50
(2.5 × 104) ( 3.0 × 10-5)
44. (a) : First we calculate rate constant of the reaction .
Ea 1 2.303
logk = X + log A k= log10 [A]%
2.303 R T t [ A]t
55.3 × 103 1
log 2.67 × 108 = - X + log A [A] 。 = 100, [A] t = 100 – 60 = 40 , t = 45 min
2.303 × 8.314 300 2.303 100 2.303
Hence, k = log10 =
or logA = 18.057 ⇒ A = 1.140 × 1018 × log10 2.5
45(min) 40 45(min)
2.303 lo a 2.303
39. (c) : k = g10 - × 0.3979 = 0.0204 min¯¹
t a-x 45(min)
0.693 2.303 log a 0.693 0.693
10 t1
/2 = 34 min
t1/2 11 a -x k 0.0204(min¹)
 158 MtG Objective Karnataka CET | Chemistry

45. (d) : Now, for % age decomposition at 40°C (313 K)

Et
Given, a = 100, (a − x) = ( 100 – x) ; t = 20 min; k = 0.0556
Energy 9 kJ mol-¹ 2.303 100
15 kJ mol-¹ Thus, k313 = -log-
20 (100 - x)
(i)
(iii) 2.303 100
10 kJ mol-¹ 0.0556 = log ⇒x = 67.169 or 67.17%
X 20 (100 - x)

Progress of reaction 50. (d)

46. (c) : 200+

↑ 150 KCET Exam Archive
E 100
1. (d) : t1/2 =€ 69.3 S, t = 230 s, a = 0.4 atm
50 For first order reaction ,
Progress of reaction 0.693 0.693
→ k= = 0.01 s-1
Diagram (c) represents exothermic reaction with t1/2 69.3

E₁ = 200 – 150 = 50 kJ mol¯¹ and 2.303 a 2.303 0.4

k log log
AH = 50 150 - 100 kJ mol¹ t a -x 230 0.4 - x

47. (d) : The logarithmic form of Arrhenius equation is 2.303 0.4 0.4
Ea 0.01 = log- = 0.01 log-
log10 k = log10 A- 230 0.4 - x 0.4 - x
2.303RT
Ea 0.01 0.4 0.4
A = log 1 = log
or log101 0.01 0.4 - x 0.4 - x
k 2.303RT
Ea 0.4 0.4
E₁ = 85.2 kJ mol¹ = 85.2 X × 103 J mol¹ , T = 310 K, Antilog of 1 = 10 = ⇒x = 0.36
A = 3.1 x 1011 L mol- 1 Ss-1 0.4 - x 0.4 -x
3.1 × 1011 85.2 × 103 For the given reaction ,
Hence , log10 == 14.354
k 2.303 × 8.314 × 310
A(g) P(g) + Q(g) + R(g)
3.1× 1011 Initial 0.4 0 0 0
That is = antilog (14.354) = 2.26 × 1014 Final 0.4-0.36 0.36 0.36 0.36
k
Total pressure = (0.4-0.36) + (3 x 0.36) = 1.12 atm
3.1 ×1011
and k = = 1.372 × 10−3 L mol− ¹ s-1 2. (b) : CH3COOH + CH3OH →→ CH3COOCH3 +H₂O
2.26× 1014 1M 2M
48. (b) : From the graph we can see that in 4 hours (1 to 5)
r₁ = k[CH3COOH] [CH3OH] = k(1 )(2) = 2k
concentration of A decreases to 0.3 M from 0.5 M whereas
When solution is diluted with equal volume of water,
concentration of B increases to 0.6 M from 0.2 M.
concentration is reduced to half.
Loss of conc. of A in 4 hours = (0.5 − 0.3 ) = 0.2 M
Gain in concentration of B in 4 hours = (0.6 – 0.2) = 0.4 M 2 k
r2 = k =
So, the increase in concentration of 'B' in the same time 00-
(4 hours) is twice the decrease in concentration of ‘A’.
71 = 2k = 4
Thus, n = 2 . r2 = = 0.25
r2 k/2 4
49. (c) : Given : a = 100 , (a – x) = 100 – 25 = 75 ; t = 20 min
Using the relation 3. (a) : For a first order reaction,
2.303 a
k log 2.303 lo [A] = 2.303 . log : 100 = 0.0346 min¯1
t (a - x) ' k g
t [A] 60 12.5
we get
2.303 100 Now t1/2 0.693 0.693
- = 0.014386 min¯¹ == 20 min
At 25°C (298 K) ; k₁ = · -log- k 0.0346
20 75
At 40 °C (313 K); k₂ = ? 4. (d) : 12 M t1/2 _6 M — 1/2 →→→ 3 M
k2 = E. T₂ -Ti Initial conc.
We know that log
k₁ 2.303 RT₁ × T₂ t1/2 = 10 min
0.693
k2 70 × 103 313-298 k == 0.0693 min -1
log = X 10
0.014386 2.303 × 8.314 298 ×313
As t1/2 is 10 min, after 20 minutes the concentration will be
k₂ 3 M.
or = 3.864 or k₂ = 0.0556
0.014386 Hence, Rate = 0.0693 × 3 M min¯¹
Chemical Kinetics 159

0.693 0.693 0.693 14. (a)

5. (a) : t1/2 = ==k =k
k t1/2 60 15. (d) : Plot of t₁/2 vs [R] 0 for a reaction is a straight line
k = 0.01155 min¯¹ parallel to x-axis, means t₁/2 is independent of [R] 。 hence, the
reaction is first order.
2.303 a :: Unit of rate constant := S
k= log
t a-x
16. (d)
Let the initial amount (a) be 100 .
17. (a) : r = k [CH3COOH] [ C2H5OH]
2.303 100
0.01155 min 1 = log r; = k[2 M] [3 M] ...(i)
240 min a -x
2 M3 M
=
0.01155 min x 24 min 100 rf = k ...(ii)
= log 2 2
2.303 a -x
On dividing (ii) by (i) , we get
1.204 = log 100 - log (a - x) 3
k[M] M
1.2042 - log (a - x) rf 2
= = 0.25
log (ax) = 2-1.204
Ꭲ; k[2 M ] [ 3 M ]
log (ax) = 0.796
or (ax) 6.25% .. The rate of reaction becomes 0.25 times of initial rate.

6. (b) : r = k[A]² 18. (c) : For first order reaction,

When concentration of A is doubled, 2.303 a
k log
r = k[2A]² ⇒rr = 4k[A] ² t a-x
1 d[A] 1 d[B] where, a = initial concentration of the reactant, a − x =
7. (b) : =+
3 dt 2 dt concentration of the reactant after time, t.
2 d[A] + d[B] For 60% completion of reaction,
=
3 dt dt 2.303 100
k= log
50 40
k E.a T₂ -Ti
8. (a) : log 2 = 2.303
k 2.303R T₁T₂ k= × 0.397 = 0.0183
50
9. (a) : A 2B
2 For 93.6% completion of reaction,
2.303 100
1 d [ A] 1 d[B] k log
1/2 dt 2 dt t 6.4
2d [ 4] - 1 d[B] −d[ A ] =
_ 1 d[B] 2.303 100
or 0.0183 = log
dt 2 dt dt 4 dt t 6.4
2.303
10. (a, d) : According to Arrhenius equation, t= X1.193
k = Ae Ea /RT 0.0183
n
On increasing temperature and decreasing activation energy t = 150 min
(E ), rate of reaction increases.
19. (a) : 2A + 3B 4C + D
11. (b) : The rate law for any reaction cannot be determined 1 d[B] 1 d[C]
=+
theoretically but it is determined experimentally. 3 dt 4 dt
12. (b) : 2SO₂ + O2 = 2SO3 d[B] = 3 d[C] ==3 1
Rate of reaction s¹
(2.8 × 10− ³) mol L¯¹ S
dt 4 dt 4
1 d[SO2 ] _ _ d[O₂ ] =
_ 1 d[ SO3 ]
2 dt dt 2 dt 20. (b) : k = PZe¯Ea/RT
Ea
-d[02 ] 1 d[SO₂ ] log k = log (PZ)
=+ RT
dt 2 dt
1 d[SO3 ] For k to increase , Ea should be small and that is possible
2× 104 = RT
2 dt
only when E,a is less or Tis more. So, for the reaction to speed
d[SO3 ] = 2x2x1044x10-4 mol L-1 s-1 up rapidly E,α should decrease.
S
dt
21. (a) : As [B] increase, t1 /2 remains same i.e. ,
13. (d) : Temperature coefficient 2 means rate of reaction 1st order with respect to B.
doubles at every 10°C rise in temperature . On doubling concentration of A, rate remains same, so it is
zero order w.r.t. A.
k90 °C
Thus , = 26 = 64
Rate = k [4] [B] ¹
k30°C Overall order = 1 .. Units of k = s−1
 160 MtG Objective Karnataka CET | Chemistry

2.303 ogo mol L

1
s
-1
22. (a) : t = l
log k= = mol¯¹ L s¯¹ or L mol¯¹ s¯¹
S
k [A] mol² L-2
2.303 4.606
= log 27. (b, c) : For nth order reaction,
k (100 k 1 ха1-n
t1/2 ∞
23. (c) : R = k[A] ' [B]² n
a -1
Volume is reduced to half means pressure is doubled . 1 1
28. (b) : For nth order : t1/2 °
R' = k [24] [2B]² an-1 a
R' = k [A] [B]² × 8 n- 1=5 ⇒ n = 5 +1 = 6
-1 -1
R' = 8R 29. (d) : mol L S is the unit of zero order rate constant .
.. Rate of reaction becomes 8 times the initial rate. Decomposition of HI on gold surface is a zero order reaction.
24. (c) : Higher order reactions are rare because there 30. (d) : k = Ae¯E /RT (Arrhenius equation )
is low probability of simultaneous collisions of all reacting A = keEa/RT
species, so the number of effective collisions becomes very 1
less (negligible). at T = ∞ ,
T
25. (d) : For first order reaction,
.. A = k
0.693 0.693 -1
= 0.693 k= min A = 6 × 10
t1/2
k t1/2 45
31. (c) Let the temperature be T'.
a
k - 2.3 log At T', k₁ = k₂
t 03 a -x
1016 хе -2000/T ' = 1015 хе -1000/T'
0.693 2.303 100 2.303× 3
log 2000 1000
45 0.1 -1000/T'
e T'10
or = 10 or e T'
448.6 -2000/T'
2.303 × 3 × 45 e
t= · min = 448.6 min = hours
0.693 60 1000
= 7.5 hours 1000
or e T' = 10 or = In 10
T'
26. (a) The rate of the given reaction is expressed in
mol L-1 s-1 . Hence, 1000 1000 1000
-1 -1 or T:= K
mol L-¹ s¹ = k [mol L- ¹]² In 10 2.303 log 10 2.303

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