LS - 0 - 2 - 2d3125 - 024aeff931964-Chemical Kinetics

CHEMISTRY
Assignment
Home Work DPP
Chemical Kinetics (2)
Kinetics of different order reactions

1. For the reaction 2X3 = 3X2, the rate of formation of X2 is: [GATE : 2008]
1 1 3
(a) 3  d  X 3  / dt  (b)
2
 d  X 3  / dt  (c)
3
 d  X 3  / dt  (d)
2
 d  X 3  / dt 
2. For the reaction P + Q + R  S, experimental data for the measured initial rates is given below.
[GATE: 2007]
Initial conc. P Initial conc. Q Initial conc. R Initial rate
Expt.
M M M 
Ms 1 
5
1 0.2 0.5 0.4 8.0 10
2 0.4 0.5 0.4 3.2 104
3 0.4 2.0 0.4 1.28 103
4 CHEM ACADEMY
0.1 0.25 1.6
The order of the reaction with respect to P, Q and R respectively is:
4.0 10 5
(a) 2, 2, 1 (b) 2, 1, 2 (c) 2, 1, 1 (d) 1, 1, 2

th
3. For a given first order reaction, the reactant reduces to 1/4 its initial value in 10 minutes. The rate
constant of the reaction is: [GATE 2011]
(a) 0.1386 min–1 (b) 0.0693 min–1
(c) 0.1386 mol L–1 min–1 (d) 0.0693 mol L–1 min–1
4. The concentrations of a species A undergoing the reaction AP is 1.0, 0.5, 0.33, 0.25 mol dm–3 at
t = 0, 1, 2 and 3 seconds respectively. The order of the reaction is: [NET June 2013]
(a) two (b) one (c) zero (d) three
5. The half – life of first order decomposition of NH4NO2 is NO2 is allowed to decompose. The time
required for NH4NO2 to decompose 90% and the volume of dry N2O produced at this point mea-
sured at STP are respectively: [GATE: 1998]
(a) 6.978 hr., 2.016 L (b) 0.319 hr, 2.15 L (c) 0.319 hr, 2.016 L (d) None of these
6. For a first order homogenous gaseous reaction, A  2B + C then initial pressure was Pi while total
pressure after time ‘t’ was Pt. The write expression for the rate constants k in terms of P1, Pt and t is:
[GATE: 1999]
2.303  2Pi  2.303  2Pi 

(a) k  log   (b) k  log  
t  3Pi  Pt  t  2Pt  Pi 
2.303  Pi 
(c) k  log   (d) None of these
t  Pi  Pt 
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7. The half life of a zero order reaction (A  P) is given by (k = rate constant):
[NET June 2011]
 A 0 2.303  A 0 1
(a) t 1  (b) t 1  (c) t 2  (d) t 2 3  k  A 
2 2k 2 k 3 k 0
8. The decomposition of gaseous acetaldehyde at T(K) follows second order kinetics. The half – life
of this reaction is 400 s when the initial pressure is 250 torr. What will be the rate constant (in Torr–
1 –1
s ) and half – life (in s) respectively, if the initial pressure of the acetaldehyde is 200 Torr at the
same temperature? [NET June 2011]
5 –5 –4
(a) 10 and 500 (b) 10 and 400 (c) 10 and 400 (d) 10–5 and 500
9. The concentration of a reactant undergoing decomposition was 0.1, 0.08 and 0.067 mol L–1 after
1.0, 2.0 and 3.0 hr respectively. The order of the reaction is [NET Dec. 2011]
(a) 0 (b) 1 (c) 2 (d) 3
10. A substance A is consumed by a reaction of unknown order. The initial concentration is 1mM, and
concentrations at later times are as shown: [TIFR 2012]
Time (min) [A] (mM)
1 0.83
2 0.72
4 0.56
8 0.38
16 CHEM ACADEMY
0.24
What is the order of the reaction?
(a) zero (b) first – order (c) second – order (d) pseudo – first order
11. The method of initial rates is used to determine the rate law for the reaction given below.
2NO(g) + 2H2(g)  N2 (g) + 2H2O (g)
The following initial rates were determined at the given partial pressures (p) of reactants.
pNO (mmHg) pH2(mmHg) Initial rate (M/min) [TIFR 2013]
200 400 0.46
400 200 0.92
400 400 1.85
These data imply which of the following rate laws?
2 2 2 2
(a) rate  kp NO p H2 (b) rate  kp NO p H2 (c) rate  kp NO p H 2 (d) rate =  kp NOp H2
12. For the reaction: Br2  g   BF2  g   2BrF3  g  , the equilibrium constant at 2000 K and 1.0 bar is
5.25. When the pressure is increased by 8-fold, the equilibrium constant. [GATE 2001]
(a) Increase by a factor of 1.86 (b) Decreases by a factor of 1.86
(c) Remains same (d) Increased by a factor of 8
13. The half-life (t1/2) for the hydrolysis of an ester varies with the initial concentration of the reactant
([E]0) as follows: [GATE 2009]
[E]0 /10–2 mol L–1 5.0 4.0 3.0
T1/2 /s 240 300 400
The order of the reaction is:
(a) 0 (b) 1 (c) 2 (d) 3
14. Identify the figure which depicts a first order reaction.
Log Concentration
12 12
(Concentration)1
10 10
8 8
6 6
4 4
(a) 2 (b) 2
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time Time
12 12
–1
(Concentration)
Concentration
10 10
8 8
6 6
4 4
(c) 2 (d) 2
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time Time
15.
CHEM ACADEMY
If the concept of half-life is generalized to quarter-life of a first order chemical reaction, it will
be equal to. [NET Dec. 2012]
(a) n 2 / k (b) n 4 / k (c) 4 / k (d) 1/ 4k
16. A bacterial colony grows most commonly by cell division. The change in the population due to cell
division in an actively growing colony is dN=gN dt. The population of bacterial colony at time ‘t’
is  N 0  N(t  0) . [NET Dec. 2012]
2
(a) N 0  g t (b) N 0 exp   g t  (c) N 0 exp   g t  (d) N 0   g t 
17. In the reaction between NO and H2 the following data are obtained [NET Dec. 2013]
Experiment I: PH 2 = constant Experiment II: PNO = constant
PNO  mm of Hg  359 300 152 PH2  mm of Hg  289 205 147

dPNO dPH2
1.50 1.03 0.25 1.60 1.10 0.79
dt dt
The orders with respect to H2 and NO are

(a) 1 with respect to NO and 2 with respect to H2
(b) 2 with respect to NO and 1 with respect to H2
(c) 1 with respect to NO and 3 with respect to H2
(d) 2 with respect to NO and 2 with respect to H2
  A t 
18. For a first order reaction A  products, the plot of ln  A  vs time, where  A 0 and  A t refer
  0 
to concentration time t = 0 and t respectively, is [NET June 2014]
(a) a straight line with a positive slope passing through origin
(b) a straight line with a negative slope passing through origin.
(c) an exponential curve asymptotic to the time axis
  A t 
(d) a curve asymptotic to the In  A  axis.
  0 
19. The half-life time for a reaction at initial concentration of 0.1 and 0.4 mol–1 are 200s and 520s
respectively. The order of the reaction is [GATE 2000]
(a) 0 (b) 1 (c) 2 (d) 3
20. Sucrose is converted to a mixture of glucose and fructose in a pseudo first order process under
alkaline conditions. The reaction has a half life of 28.4 min. The time required for the reduction
of a 8.0 mM sample of sucrose to 1.0 mM is [GATE 2007]
(a) 56.8 min (b) 170.4 min (c) 85.2 min (d) 227.2 min
21. Statement: For the reaction of NO + O2  2NO2 the rate constant is observed to decrease with
temperature.
Reason: As per proposed mechanism, the first step is the dimerization of nitric oxide which is
exothermic.
CHEM ACADEMY
Assertion: Rate law = k2K.[NO]2[O2]
(a) Both Reason and Assertion are correct (b) Both Reason and Assertion are wrong
[GATE 2005]
(c) Reason is correct but Assertion is wrong (d) Reason is wrong but Assertion is correct
24. The combustion of ethane (C2H6) is represented by the following reaction:
2C2H6(g) + 7O2 (g)  4 CO2 (g) + 6 H2O (1)
Which of the following is TRUE for the above reaction? [TIFR 2015]
(a) The rate of consumption of ethane is seven times faster than the rate of consumption of oxygen
(b) Water is formed at a rate equal to two – third the rate of formation of CO2
(c) The rate of consumption of oxygen equals the rate of formation of water
(d) CO2 is formed twice as fast as ethane is consumed
25. Which of the following is the curve x = y2. [TIFR 2015]
(i) (ii)
(iii) (iv)
(a) i (b) ii (c) iii (d) iv

26. For a reaction, 2A  B  3Z , if the rate of consumption of A is 2 × 10–4 mol dm–3 s–1 the rate of
formation of Z (in mol dm–3 s–1) will be [NET June 2015]
4
(a) 3 × 10–4 (b) 2 × 10–4 (c)  104 (d) 4 10 4
3
27. The concentration of a reactant R varies with time for two different reactions as shown in the
following plots: [NET Dec. 2015]
CHEM ACADEMY[R] 1/[R]
time time
(I) (II)
The order of these two reactions I and II, respectively are
(a) zero and one (b) one and zero (c) zero and two (d) two and zero
28. If the rates of a reaction are R1 and R2 at concentrations C1 and C2 of a reactant respectively, the
order of reaction, ‘n’ (assuming that the concentrations of all other reactants and T remain constant)
with respect to the reactant is given by [NET June 2016]
log R1  log R 2 log C1  log C 2
(a) n  log C  log C (b) n  log R  log R
1 2 1 2
log C1  log R1 log C2  log R 2

(c) n  log C  log R (d) n  log C  log R
2 2 1 1
29. Experimentally determined rate law for the chemical reaction, [NET June 2016]
2NO2 F  2NO2  F2 is R  k  NO 2F

The rate determining step consistent with the rat law is
(a) 2NO2 F  2NO2  F2 (b) NO 2 F  F  NO 2  F2
(c) NO 2 F  NO 2  F2 (d) NO 2  F  NO 2 F
30. Half – life t1/2 for a third order reaction 3C  products, where C0 is the initial concentration of C,
will be [NET June 2016]
3 3 3 3
(a) 2kC2 (b) kC (c) 2kC (d) 3kC2
0 0 0 0
31. The fraction of groups condensed at time t in any stepwise condensation polymerization (overall
second order) reaction is [NET Dec. 2014]
1 kt  A 0 1  kt  A 0
(a) 1  kt  A 0 (b) 1  kt  A  (c) 1  kt A (d)
0  0 kt  A 0
32. The graph below plots the progress of a dimerization reaction involving species A. It depicts a
straight line with slope k (the rate constant). What is the value of the intercept, c in the graph?
[TIFR 2017]
CHEM ACADEMY
(a) [A(0)] (b) [A (0)]2 (c) [A(0)]–1 (d) k x[A(0)]2
33. In kinetic study of a chemical reaction, slopes are drawn at different times in the plot of concentra-
tion of reactants versus time. The magnitude of slopes with increase of time
[NET June 2017]
(a) remains unchanged (b) increases
(c) decreases (d) increases and decreases periodically
34. The rate constant of a reaction is 1.25 × 10 mol L–1 s–1. If the initial concentration of the reactant
–4
is 0.250 mol L–1, the total time (in second) required for complete conversion is __________.
[GATE 2017]
35. Reaction between A and B is carried out for different initial concentrations and the corresponding
half-life times are measured. The data listed in the table: [NET Dec. 2017]
Entry  A0   M   B0  M  t1/2  sec 

1 500 10 60
2 500 20 60
3 10 500 60
4 20 500 30
The rate can be represented as
2 2 2
(a) k  A  B (b) k  A  (c) k  A   B (d) k  A  B
36. If the unit of the rate constant of a reaction is L3mol–3s–1, the order of the reaction is
[NET June 2018]
(a) 1 (b) 2 (c) 3 (d) 4
37. For a second-order reaction, the straight line among the following plots is
[NET Dec. 2018]
(a) [X] versus time (b) 1/[X] versus time
(c) log[X] versus 1/time (d) log[X] versus time
38. The first order reaction is 90% complete is 30 min. How long will it take to be 99.9% completed?
[TIFR 2019]
(a) 33.3 min (b) 1.5 hr (c) 55 hr (d) None of these
39. If the half – life of a reaction is inversely proportional to the square of the square of the concentra-
tion of the reactant, the order of the reaction is [NET June 2019]
(a) 0 (b) 1 (c) 2 (d) 3
Kinetics of reversible, parallel and series reactions

1. In a consecutive first order reaction, A k1
 B  k2
C
(where k1 and k2 are the respective rate constants) species B has transient existence. Therefore,
(a) k1  k2
CHEM ACADEMY
(b) k1 = 2k2 (c) k1 >> k2
[GATE 2003]
(d) k1 << k2
2. H2 and Br2 react to give HBr by the following steps [GATE 2003]
k1

Br2  M   2Br  M  fast  , (K = k1 / k–1)
k2
k2
Br  H 2   HBr  H  slow 
k3
H  Br2   HBr  Br  fast 
The probable rate law for the above sequence is:
1
(a) rate  k 2  H 2  Br2  2 (b) rate  k 2  H 2  Br2 
1 1 1 1
(c) rate  k 2  K  2
 H2  Br2  2 (d) rate  k 2  K  2
 H 2  Br  2
Common data for Q. 3 and Q. 4
k1

For the opposing reaction, A  B  C  D
k 2
The forward reaction has values Ea = 100 kJ mol–1 and A = 1.0 × 1010 M–1s–1. The equilibrium
concentration of A, B, C and D are 1.0 M, 2.0 M, 5.0 M and 4.0 M respectively, at 700 K.
3. The values of k1 and k–1, respectively, at this temperature are [GATE 2003]
–1 –1 –1 –1 –1 –1 –1 –1
(a) 20 M s and 2.0 M s (b) 345 M s and 34.5 M s
(c) 34.5 M–1s–1 and 3.45 M–1s–1 (d) 200 M–1s–1 and 20 M–1s–1
4. The rate constant (k1) for the forward reaction at 1000 K is: [GATE 2003]
(a) 5.98 × 104 M–1 min–1 (b) 5.98 × 102 M–1 s–1
(c) 1.00 × 103 M–1 s–1 (d) 5.98 × 104 M–1 s–1
3 –1
5. k1
For the reaction of the type P  k2
 Q   R, given that  P 0  1.0M;k1  110 s and
k 2  1 10 4 s 1, the time at which the concentrations of Q and R are 0.5966 M and 0.0355 M,
respectively, is [GATE 2004]
(a) 500 s (b) 750 s (c) 1000 s (d) 1500 s
6. 
Consider an exothermic reaction A 
1 k
 I as the temperature increases
k 1
[GATE 2006]
(a) k1 , k 1 , and k1 / k 1 increases

(b) k1 increases, k–1 decreases, and k1/k–1 increases.
(c) k1, k–1 increases and k1/k–1 decreases
(d) k1 and k–1 decrease, and k1/k–1 increases.
Linked Answer Q. 7 and Q. 8
7. A reaction proceeds through the formation of an intermediate B in an unimolecular reaction
k1 kb
A   B  C
CHEM ACADEMY
The integrated rate law for this reaction is [GATE 2006]
(b)  A    A 0  e a  e b 
k t k t
(a)  A    A 0 e  ka t
 A 0 1  k a e kb t  k b eka t 
(c)  A     (d)  A    A 0 1  e  k a t  e  k bt 
2  ka  kb 
8. If ka >> kb , then concentration vs. time plot for the above reaction is:
[GATE 2006]
B B
Concentration
Concentration
A A
(a) (b)
C C
Time Time
A B
A
Concentration
Concentration
(c) (d)
C C
Time Time
9. 
1
For a reaction of the type X 
k
 Y , the correct rate expression is ([X]0 and [X] corresponds to
k2
the concentration of X at time t = 0 and t = t, respectively) [GATE 2013]
d X d X
(a)   k1  X 0   k1  k 2   X  (b)    k1  k 2   X   k 2  X 0
dt dt
d X d X
(c)    k1  k 2   X 0  k1  X  (d)    k1  k 2   X   k1  X 0
dt dt
10. For the parallel first order reaction shown below [GATE 2009]
Y
kl
X
k2
Z
–4 –1
the value of k1 is 1×10 s . If the reaction starts from X, the ratio of the concentrations of Y
 Y 1
and Z at any given time during the course of the reaction is found to be Z  4 The value of
 
k2 is:
(a) 1×10–4s–1 (b) 2.5×10–5s–1 (c) 4×10–4s–1 (d) 4×104s–1
CHEM ACADEMY
Linked Answer Q.11 and Q.12:
The decomposition of ozone to oxygen 2O3(g)  3O2(g) occurs by mechanism
k1
(i) M  g   O3  g    O2  g   O  g   M  g  Ea, 1
k2
(ii) O 2  g   O  g   M  g    M  g   O3  g  , Ea, 2
k3
(iii) O  g   O3  g    2O 2  g  , Ea, 3
where, M is the catalyst molecule.
ki' are rate constants and Ka,i's the activation energies for the elementary steps,
11. Under the steady state approximation for the intermediates, the rate of decomposition of ozone,
d  O3 
 , is [GATE 2011]
dt
2 2
2k1k 3  O 3   M  2k1k 3  O3   M 
(a) (b)
k 2  O 2  M   k 3  O3  k 2  O 2  M   k 3 O3 
2
2k1k 3  O3  M  2k1k 2  O3   M 
(c) k O M  k O (d)
2  2   3  3 k 2  O 2  M   k 3 O3 
12. Assuming k3[O3] >> k2[O2][M], the activation of the overall reaction is
[GATE 2011]
E a ,1E a,3
(a) Ea ,2 (b) E a ,3  E a ,1  E a,2 (c) Ea,2 (d) Ea,1
13. For a reaction involving two steps given below [GATE 2012]
First step: G  2H
Second step: G+HP
assume that the first step attains equilibrium rapidly. The rate of formation of P is proportional to
1/2 2 3/2
(a) G  (b)  G  (c)  G  (d)  G 
14. An example of a relaxation method of measuring rates is: [NET Dec. 2011]
(a) Spectroscopic monitoring of product concentration.
(b) Stopped flow technique
(c) Temperature jump experiments
(d) Measurements of spectral line widths
15. The overall rate of the following complex reaction, [NET Dec. 2011]
K

1
2A  A2 (fast equilibrium)
K2

A  B C (fast equilibrium)
k
3  P  2A
A 2  C  (slow)
by steady state approximation would be
(a) K 1K2k3[A]3[B] (b) K2K1k3[A][B]3 (c) K1K2k3[A][B]2 (d) K1K2k3[A][B]
16. The reversible reaction S  P is catalyzed by a catalyst. The equilibrium constant Keq = [P]/[S] is
CHEM ACADEMY
2 × 103. The forward rate constant was found to be 5 × 104 sec–1 and 4 × 10–6 sec–1 in the presence
and in the absence of the catalyst respectively. What is the expected rate constant for the reverse
reaction in the absence of the catalyst? [TIFR 2012]
8 –1 –9 –1 –10 –1
(a) 5 – 10 sec (b) 2 × 10 sec (c) 0.8 × 10 sec (d) 5 × 10–9 sec–1
17. The rate equation for the reaction 2AB + B2  2 AB2 is given by [NET June 2013]
rate = k[AB] [B2]
A possible mechanism consistent with this rate law is
 A 2 B2 (fast)
AB  AB 
slow
(a) 2AB  B2   2AB2 (b) slow
A 2 B2  B2   2AB2
slow
AB  B2   AB3  AB3 (fast)
AB  B2 
(c) fast (d) fast
AB3  AB  2AB2 AB3  AB  2AB2
18. For the first order consecutive reaction, P  Q  R, under steady state approximation to [Q], the
variation of [P], [Q] and [R] with time are best represented by
[GATE 2013]
[P] [Q] [P]

Concentration
Concentration
[R] [Q] [R]
(a) (b)
Time Time
[P] [P]
Concentration
Concentration
[R]
[R]
(c) (d) [Q]
[Q]
Time Time
19. Examine the following first order consecutive reactions. The rate constant (in s–1 units) for each
step is given above the arrow mark [NET June 2014]
5 8 5 3
10 10 10 10
(a) P   Q  R (b) P   Q  R
7 7 2 6
10 10 10 10
(c) P   Q  R (d) P   Q  R
20. Formation of Z from X is theoretically expected to obey the following kinetic scheme.
k1 k2

X  
Y  
Z

k 1 k 2
An experimentalist wants to verify the above scheme, but can observe and measure the concentra-
tion of only X or Z . Is it possible that under certain conditions, the measurements of [X] or [Z] as
function of time would lead the experimenter to conclude that the kinetic scheme is as given below,
and that the species Y is absent? [TIFR 2015]
(a) No, that is not possible

CHEM ACADEMY 
X 
k
obs 
Z
k  obs
(b) Yest, if k–1 >> k1 and k–2 << k2

k1 k2
(c) Yes, if k  k
1 2
(d) Yes, if [Y] attains a steady – state concentration during the experiment.
21. For the following reaction, [NET Dec. 2015]
k d  B

1 
A  k2
 2B; B   C, , is given by
k 1 dt
2 2
(a) k1  A  k 1  B  2k 2  B (b) 2k1  A   k 1  B  k 2  B
1 1 2 2
(c) k1  A   k 1  B  k 2  B (d) 2k1  A   2k 1  B  k 2  B
2 2
22. The reaction, A  B , is first order in both the directions. The forward and reverse rate constants
are 4.2 104 s 1 and 1.04×10–3s–1, respectively. The relaxation time for this reaction, in seconds, in
a temperature jump experiment is ___________ [GATE 2016]
23. For the following reaction,
k 105 L mol1s1
 
1
k 2 10s
A  B 
1
k 104 s 1
 I  P
1
if steady state approximation can be applied on [I], the observed rate constant of product formation,
in L mol–1 s–1, will be __________ [GATE 2016]
24. A reaction goes through the following elementary steps [NET Dec. 2016]
k1

A  B  
 2C  fast 
k 1
k
2 D
A  B   slow 
Assuming that steady state approximation can be applied to C, on doubling the concentration of A,
the rate of production of D will increase by (assuming k2[A]<<k–1[C])
(a) 2 times (b) 4 times (c) 8 times (d) 2 2 times
25. Photochemical decomposition of HI takes place with the following mechanism
HI  hv  Ia   H  I [NET June 2017]
k
1 H  I
H  HI  2
k
2I  M
I  I  M  2
Considering hydrogen (H) and iodine (I) atoms as intermediates, the rate of removal of HI is
(a) Ia/2 (b) Ia (c) 2Ia (d) Ia2

26.
CHEM ACADEMY
For the following consecutive first order reactions
K1 2.0 s
X 
1 K 2 0.1 s
 Y 
1
Z
[GATE 2017]
the time (in seconds) required for Y to reach its maximum concentration (assuming only X is
present at time t = 0) is __________ (up to two decimal places)
27. A reaction involving chemical species “R”, “G”, “P” and “H” has the observed stoichiometry:
[TIFR 2018]
2R + G  P + H
The experimentally observed rate equation for this reaction is rate = k[R]2. Which of the following
is a possible mechanism for the above reaction?
(a) R + G  I (fast); I + R  P + H (slow)
(b) R + R  I (fast); I + G  P + H (slow)
(c) R + R  I (slow); I + G  P + H (fast)
(d) R + G  I (slow); I + R  P + H (fast)
28. Elementary steps of a reaction are as follows [NET June 2018]
k1

A  B  
 2C ; k2
k 1 2C  D
If steady state approximation is applicable to C, the rate of product formation in the reaction is
(a) Proportional to [A] [B] (b) Proportional to [A]2 [B]2
(c) Proportional to [A]1/2 [B]1/2 (d) Independent of [A] [B]
29. The decomposition mechanism of ozone is [NET Dec. 2018]
k1

O3  
 O2  O
k 1
k
2  2O
O3  O  2
If k 1  O 2   k 2  O3  , then the order of the reaction with respect to ozone is

(a) zero (b) one (c) two (d) complex
30. The gas phase decomposition of A at 1000 K follows two decomposition paths
Elementary process Rate constant

i  A  BC 3 s 1
 ii  A  PQ 5 s 1
The maximum theoretical percentage yield of P at 1000 K is [NET June 2019]

(a) 62.5 (b) 60 (c) 166 (d) 37.5
31. Consider the following parallel irreversible first order reaction at temperature T,
Q
k1
P
k2
R
where k1 and k2 are the rate constants and their values are 5 × 10–2 and 15 × 10–2 min–1, respectively,
CHEM ACADEMY
at temperature T. If the initial concentration of the reactant (P) is 4 mol L–1, then the concentration
of product (R) after 10 min of reaction is ____________ mol L–1. (Round off to two decimal places)
[GATE 2019]
(Assume only P is present at the beginning of the reaction)
Arrhenius Equations
1. The rate law for one of the mechanism of the pyrolysis of CH3CHO at 520ºC and 0.2 bar is
1/ 2
 k 
Rate   k 2  1  [CH3CHO]3/2 [NET June 2012]
 2k 4 
The overall activation energy E, in terms of the rate law is:
1
(a) Ea (2)  E a (1)  2Ea (4) (b) E a (2)  E a (1)  E a (4)
2
1 1 1 1
(c) E a (2)  E a (1)  E a (4) (d) E a (2)  E a (1)  E a (4)
2 2 2 2
2. The half-life of a first order reaction varies with temperature according to
[GATE 2002]
(a) In t ½  1/ T (b) In t ½  T (c) t ½  1/T 2 (d) t ½  T 2
3. A certain reaction proceeds in a sequence of three elementary steps with the rate constants k1,
½
k2 and k3. If the observed rate constant (kobs) of the reaction is expressed as k obs  k 3  k1 / k 2  ,
the observed activation energy  E obs  of the reaction is
[GATE 2004]
½
1  E1  E 3  E1  E1  1
(a) 2  E   E 3 (b) E (c) E 3   (d) E3   E1  E 2 
 2 2  E2  2
4. The rate constant of two reactions as temperature T are k1(T) and k2(T) and the corresponding
activation energies are E1 and E2 with E2 > E1. When temperature is raised from T1 and T2, which
one of the following relations is correct? [GATE 2007]
k1  T2  k 2  T2  k1  T2  k 2  T2  k1  T2  k 2  T2  k1  T2  k 2  T2 
(a) k T  k T (b) k T  k T (c) k T  k T (d) k T  k T
1 1 2  1 1 1 2  1 1 1 2  1 1 1 2  1
Statement for Linked Q. 5 and Q. 6:

k1 .E A,l

In the reaction mechanism given, X  Y   Z 
k 3 ,E A.3
k 2 ,E A,2 
P
'k' s represent rate constants, 'EA's represent activation energies, and k2>>k3
5. The overall rate constant (koverall) for the formation of P can be expressed as
[GATE 2009]
(a) k1k3/k2 (b) k1 (c) k1/(k2+k3) (d) k1|(k2–k3)
6. The overall activation energy (EA,overall) for the formation of P can expressed as
[GATE 2009]
E A,l .E A,3 E A,l
(a) E (b) E A,l (c) E A,l  E A,3  E A,2 (d) E  E
7.
A,2
CHEM ACADEMY
The activation energy for the decomposition of H2O2 is 76 kJ/mol at room temperature and the
A,2 A,3
decomposition is very slow. When a little iodide is added, the activation energy decreases to 57 kJ
mol –1. The rate coefficient increases approximately by a factor of
[GATE 2002]
(a) 500 (b) 1000 (c) 2000 (d) 50
12000
8. The specific rate constant of decomposition of compound is represented by  n k  5.0  .
T
[GATE 2010]
The activation energy of decomposition for this compound at 300 K is
(a) 24 kcal/mole (b) 12 kcal/mole (c) 24 cal/mole (d) 12 cal/mole
9. For a reaction, the rate constant k at 27ºC was found to be k = 5.4 × 1011 e–50
The activation energy of the reaction is [NET June 2012]
(a) 50 J mol–1 (b) 415 J mol–1 (c) 15,000 J mol–1 (d) 125,000 J mol–1
10. According to Arrhenius equation (K = rate constant and T = temperature)
[NET Dec. 2013]
(a) ln K decreases linearly with 1/T (b) ln K decreases linearly with T
(c) ln K increases linearly with 1/T (d) ln K increases linearly with T
11. A first order gaseous reaction is 25% complete in 30 minutes at 2270C and in 10 minutes at 2370C.
The activation energy of the reaction is closest to (R = 2 cal K–1 mol–1)
(NET Dec. 2013]
–1 –1 –1
(a) 27 kcal mol (b) 110 kcal mol (c) 55 kcal mol (d) 5.5 kcal mol–1
12. Which of the following plots represent (s) the Arrhenius rate equation, k = Ac–Ea/RT with A = 3 ×
107s–1 and Ea = 3 × 104 J/mol.
(i) (ii)
(iii)
(a) (i) (b) (ii) (c) (iii) (d) (i) and (ii)
13. The temperature-dependence of a reaction is given by k  AT 2 exp(E 0 / RT) . The activation en-
1
(a) E 0  RT
2
CHEM ACADEMY
ergy (Ea) of the reaction is given by
(b) E0 (c) E0  2RT

[NET June 2015]
(d) 2E 0  RT
14. A reaction A + B + C  D follows the mechanism [NET Dec. 2014]
A  B  AB
AB  C  D
in which first step remains essentially in equilibrium. If H is the enthalpy change for the first
reaction and E0 is the activation energy for the second reaction, the activation energy of the overall
reaction will be given by
(a) E0 (b) E0 – H (c) E0 + H (d) E0 + 2H
15. The activation energy for the bimolecular reaction A + BC  AB + C is E0 in the gas phase. If
the reaction is carried out in a confined volume of 3, the activation energy is expected to
[NET Dec. 2012]
(a) remain unchanged (b) increase with decreasing 
(c) decrease with decreasing . (d) oscillate with decreasing .
16. For a reaction with an activation energy of 49.8 kJ mol–1, the ratio of the rate constants at 600 K and
300 K, (k600/k300), is approximately (R = 8.3 J mol–1 K–1)
(a) ln (10) (b) 10 (c) 10 + e (d) e10
[NET Dec. 2016]
17. If the pre – exponential factor in Arrhenius equation is 1.6 × 1012 s–1, the value of the rate constant
at extremely high temperature will be close to [NET June 2017]
(a) 1.6 × 1012 s–1 (b) 4.2 × 1012 s–1 (c) 2.4 × 109 s–1 (d) 1.2 × 106 s–1
18. Arrhenius equations for two chemical reactions are: k1  A1e  E1 /RT , k 2  A 2e  E 2 /RT . If E1  E 2 ,
then at a given temperature T, [NET June 2017]
k1 A1 k 2 A2
(a) k  A (b) k  A (c) k1k 2  A1A 2 (d) k1  k 2  A1  A 2
2 2 1 1
19. The dependence of rate constant k on a temperature T (in K) of a reaction is given by the expression
[GATE 2017]
ln k = [(–5000 K)/T] + 10
The activation energy of the reaction (in kJ mol–1) is __________ (up to two decimal places)
20. Difference between activation energies of the reverse and forward steps of a reversible reaction is
9:212RT. If the pre-exponential factor of the forward reaction is double that of the reverse reaction
at the same temperature, the equilibrium constant for the reaction at that temperature will be (ln10
= 2.303) [NET June 2018]
(a) 1 × 104 (b) 2 ×104 (c) 1 ×10–4 (d) 2 × 10–4
21. The activation energy of a reaction reduces by 12 kcal mol–1 in the presence of an enzyme at 300 K.
Assuming pseudo – first order kinetics, calculate the factor by which the reaction rate is increased.
[Given: R = 2 cal K–1 mol–1]
(a) 2 × 10–9 (b) 1.02 (c) 8.7 × 10–6 (d) 5 × 108
23. The Arrhenius rate expression k = Aexp (–Ea/RT) is only an approximation as one finds that that the
pre – exponential factor. A is not completely temperature independent. Assume that it weakly de-
CHEM ACADEMY
pends on temperature as A = BTm. Then the rate expression becomes k = BTm exp (–Eb/RT). Under
these circumstances the relation between Ea and Eb is given by
(a) Ea – Eb = mRT (b) Ea = Eb + (RTm) (c) Eb = Ea = +(RTm) (d) Eb – Ea = mRT
Collision Theory, Activated Complex Theory and Theory of Unimolecular reactions


1. For the reaction, A  B  X   P, Ea  20.0 kJ mol 1 at 300 K. The enthalpy change for the for--
mation of the activated complex from the reactants in kJ mol–1 is
[GATE 2004]
(a) 12 (b) 15 (c) 23 (d) 25
2. Consider the reaction, H 2  C 2 H 4  C 2 H 6
The molecular diamesters of H2 and C2H4 are 1.8Å and 3.6Å respectively. The pre – exponential
1
factor in the rate constant calculated using collision theory in m 3  mole  s 1 is approximately..
1
 8k T  2 1
(For this reaction at 300 K,)  B  N A  1.11 1027 m  mole  s 1 , where the symbols have their
  
usual meanings) [GATE 2012]
(a) 2.5 × 108 (b) 2.5 × 1014 (c) 9.4 × 1017 (d) 9.4 × 1023
3. The rate constant of a unimolecular reaction was 2.66 × 10–3 s–1 and 2.2 × 10–1 s–1 at T = 120 K and
360 K respectively. The rate constant (in s–1 units) at 240 K would be
[NET Dec. 2011]
(a) 2.4 × 10–2 (b) 2.4 × 10–1 (c) 4.8 × 10–2 (d) 1.8 × 10–3
4. According to conventional transition state theory, for elementary bimolecular reactions, the molar
entropy of activation S# is: [GATE 2011]
(a) Positive (b) Zero (c) Negative
(d) Positive for endothermic and negative for exothermic reactions.
5. One of the assumptions made in the conventional activated complex theory is:
[NET June 2012]
(a) Equilibrium is maintained between reactants and the activated complex
(b) Equilibrium is maintained between the reactants and the products.
(c) Equilibrium is maintained between the products and the activated complex
(d) Equilibrium is maintained between the reactants, the activated complex and the products.
6. The Arrhenius parameters for the thermal decomposition of NOCI, 2NOCl(g)®2N(g)+Cl2(g), are
A = 1013M–1s–1, Ea = 105 kJ mol–1 and RT = 2.5 kJ mol–1. The enthalpy (in kJ mol–1) of the
activated complex will be [NET Dec. 2012]
(a) 110 (b) 105 (c) 102.5 (d) 100
7. According to Eyring state theory for a bimolecular reaction, the activated complex has
(a) no vibrational degree of freedom
(b) vibrational degrees of freedom but they never participate in product formation
(c) one high frequency vibration that leads to product formation
(d) one low frequency vibration that leads to product formation
8.
CHEM ACADEMY
Oberve the following statements [NET June 2013]
(I) in the H2 – O2 reaction, explosion occurs when the rate of chain branching exceeds that of chain
termination.
3
(II) The order of the reaction, nA  products, is 2.5. For this reaction, t 1 2   A 0 2
(III) Unimolecular gas phas reactions are second order at low pressure but becomes first order at
high pressure.
Which of the following is correct?
(a) I, II and III are correct (b) Only II is correct
(c) Only III is correct (d) I and II are correct
9. In the Lindemann mechanism of unimolecular reactions, the observed order at low concentration is
[NET June 2013]
(a) 0.5 (b) 1 (c) 1.5 (d) 2
10. For a gas phase unimolecular reaction at tempeature 298K, with a pre-exponential factor of
2.17×1013s–1, the entropy of activation (JK–1 mol–1) is ____________ [NET June 2015]
11. Species A undergoes a unimolecular reaction as follows:
k
1
A  A   A * A
k 1
k2
A *  P
For this reaction, the first order rate constant at high pressure is k  .The first order the constant
k
becomes when pressure of A is [A]1/2. [NET Dec. 2014]
2
k
First order rate constant

k/2
[A]1/2 PA
The value of k1 will be
k  A 1/2
(a)  A  (b) k   A 1/2 (c) k    A 1/2 (d)
1/2 k
12. The first order rate constant for a unimoleclar gas phase reaction A  products that follows
Lindemann mechanism is 2.0 s–1 at pA = 1 atm and 4.0 s–1 at pA = 2 atm. The rate constant for the
activation step is [NET Dec. 2015]
(a) 1.0 atm 1s 1 (b) 2.0 atm 1s 1 (c) 4.0 atm 1s 1 (d) 8.0 atm 1s 1
13. For an elementary bimolecular gas phase reaction, activation energy is 5.5 kJ mol–1. Enthalpy of
activation, in kJ mol–1, at 300K is ________. (R = 8.314 JK–1 mol–1)
[GATE 2016]
14.
CHEM ACADEMY
If experimentally observed rate constant is greater than the maximum value of rate constant ob-
tained using hard – sphere model of collision theory, then relation between the impact parameter
(b) and sum of the radii of two reactants is [NET June 2016]
(a) b = r1 + r2 (b) b < r1 + r2 (c) b > r1 + r2 (d) b < r1 + r2
H #
15. According to the transition state theory, the plot with slope equal to is
R
[NET Dec. 2016]
k k 1 1
(a) ln k vs. T (b) ln   vs. T (c) ln   vs. (d) ln k vs.
T T T T
16. For two reactions, [NET Dec. 2016]
X  g   Y  g   Z  g  1
M  g   N g   P  g   2
According to the collision theory, the ratio of squares of pre – exponential factors of reactions 2
2
 A2 
(A2) and 1(A1) at the same temperature,   , is
 A1 
Species Mass  g / mol  Diameter  nm 

X 5 0.3
Y 20 0.5
M 10 0.4
N 10 0.4
(a) 4/5 (b) 5/5 (c) 5/3 (d) 3/5
17. kuni is the effective first – order rate constant of the following unimolecular reaction
k1

A  M   *
A M [NET Dec. 2018]
k 1
k2
A  P
The slope and intercept of the plot of 1/kuni vs. 1/[M] are 4×106 and 8×1011, respectively. The value
of k–1/k2 is
(a) 2 × 105 (b) 0.5 × 105 (c) 32 × 105 (d) 2 × 10–5
18. For a bimolecular gas phase reaction, P + Q  R, the pre – exponential factor is 1 × 1013 dm3 mol–
1 –1
s . The standard entropy of activation at 25ºC is_________ JK–1 mol–1. (Round off to two decimal
points).
(The standard concentration cº = 1 mol dm–3, Planck constant h = 6.62 × 10–34 J s, Boltzmann
constant kB = 1.38 × 10–23 JK–1, Gas constant R = 8.31 J mol–1 K–1).
ANSWER KEY
Kinetics of different order reactions
1. d 2. c 3. a 4. a 5. a 6. a 7. a
8. d 9. c 10. c 11. b 12. c 13. c 14. b
15. b 16. c 17. b 18. b 19. c 20. c 21. ( )
22. d
29. c
23. a
30. a
CHEM ACADEMY
24. d
31. c
25. c
32. c
26. a
33. c
27. c 28. a
34. (1999 to 2001)
35. c 36. d 37. b 38. b 39. d
Kinetics of reversible, parallel and series reactions
1. d 2. b 3. b 4. c 5. c 6. c 7. a
8. b 9. b 10. c 11. a 12. d 13. d 14. c
15. a 16. b 17. c 18. c 19. d 20. d 21. b
22. (666.67 to 685.00) 23. (99.85 to 99.95) 24. d 25. b
26. (1.56 to 1.60 27. c 28. a 29. b 30. a
31. (2.50 to 2.65)
Arrhenius Equations
1. c 2. a 3. d 4. d 5. a 6. c 7. c
8. a 9. d 10. a 11. c 12. d 13. c 14. c
15. c 16. d 17. a 18. a 19. (41.15 to 41.60)
20. b 21. (289.6) 22. d 23. d
Collision Theory, Activated Complex Theory and Theory of Unimolecular reactions
1. b 2. a 3. d 4. c 5. a 6. d 7. d
8. a 9. d 10. (2.65 to 3.15) 11. a 12. b
13. (0.50 to 0.52) 14. c 15. c 16. a 17. a
18. (–12.90 to – 12.40)

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CHEMISTRY

Chemical Kinetics (2)

Kinetics of different order reactions

(a) 2, 2, 1 (b) 2, 1, 2 (c) 2, 1, 1 (d) 1, 1, 2

2.303  2Pi  2.303  2Pi 

PNO  mm of Hg  359 300 152 PH2  mm of Hg  289 205 147

The orders with respect to H2 and NO are

(a) i (b) ii (c) iii (d) iv

CHEM ACADEMY[R] 1/[R]

log C1  log R1 log C2  log R 2

2NO2 F  2NO2  F2 is R  k  NO 2F

Entry  A0   M   B0  M  t1/2  sec 

The rate can be represented as

Kinetics of reversible, parallel and series reactions

(a) k1 , k 1 , and k1 / k 1 increases

the concentration of X at time t = 0 and t = t, respectively) [GATE 2013]

[P] [Q] [P]

[R] [Q] [R]

(a) No, that is not possible

(b) Yest, if k–1 >> k1 and k–2 << k2

(a) Ia/2 (b) Ia (c) 2Ia (d) Ia2

If k 1  O 2   k 2  O3  , then the order of the reaction with respect to ozone is

Elementary process Rate constant

The maximum theoretical percentage yield of P at 1000 K is [NET June 2019]

the observed activation energy  E obs  of the reaction is

Statement for Linked Q. 5 and Q. 6:

(b) E0 (c) E0  2RT

Collision Theory, Activated Complex Theory and Theory of Unimolecular reactions

First order rate constant

Species Mass  g / mol  Diameter  nm 

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