1.chemical Kinetics

FIITJEE
SUBJECT: CHEMISTRY CHEMICAL KINETICS
NAME…………………….. ENROLL NO……………. BATCH…………………
SECTION I (ONLY ONE CORRECT)

1. Which of the following expression(s) can correctly estimate the number of half-lives (n) of 1 st order
nuclear reaction?
(A) elt = 2n (B) t1 2 = n �t
-n
(C) N0 = Nt �2 (D) All of the above
2. Which of the following graphs is correct for zero order reaction?
(A) (B)
Rate
Rate
Conc
Conc
(C) (D)
Rate
Rate
2 3
(Conc)
(Conc)
3. For the reactions: Reaction-I A �� B and Reaction:II

C �� D, the following curves are plotted. Identify the correct
1M [A]
statements.
(A) ( t100% ) of reaction-I = 2/3 ( t100% ) of reaction-II
0.5M
[ C] at t = 3 minutes
(B) [ A ] =[C]
4
(C) 60
When [B] 30 = [A] at that time [C]= [D]
O (D) If [ A 0 ] = [ C0 ] Time
= 1M then ( t 80% ) of reaction-I=1/3 ( t80% ) of
reaction-II
3.
4. In the Arrhenius equation k = Ae -Ea RT , the rate constant k become equal to the Arrhenius constant
(A), when
(A) The temperature becomes infinite
(B) 50% reactants are converted to product
(C) The fraction of the molecules crossing the energy barrier is unity
(D) There is no need of activation energy to reactants for undergoing chemical change
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4.
5. For a 1st order reaction
A ( g) �� B ( s ) + 2C ( g )
the half life is 20 min. The reaction is carried out taking certain mass of A(g) in a closed vessel at
27C. The initial pressure of A(g) is 200 mm. The total pressure of the reaction mixture after one
hour is
(A) 550 mm (B) 425 mm
(C) 375 mm (D) 25 mm
6. Rate constant for a first order reaction is 2.303 min –1. For a reaction A �� B + C . The initial
concentration of A is 1 mol litre–1. The rate of reaction after 1 min would be
(A) 2.303 M min–1 (B) 0.693 M min–1
–1
(C) 0.2303 M min (D) 0.0693 M min-1
7. The chemical in a lightstick give off light as they react. When that lightstick is placed in warm
water the glow increases. This is because the
(A) Activation energy for the process is lowered.
(B) Average kinetic energy of the reactants increases.
(C) Higher temperature catalyzes the reaction
(D) Higher temperature changes the wavelength of light emitted.
8. A zero order reaction would definitely be
(A) exothermic (B) endothermic
(C) elementary (D) complex
Order � Molcularity implies a complex reaction.
Hydrogen exists as 3 isotopes –H, D, T and oxygen exists as 2 isotopes - O, O. How many
16 18
9.
radioactive water molecules are possible
(A) 8 (B) 9
(C) 12 (D) 15
10. A gaseous compound A reacts by three independent first order processes with rate constants
2 �10 -3 ,3 �10 -3 and 1.93 �10 -3 sec -1 for products B, C and D respectively. If initially pure A was
taken in a closed container with P = 8 atm, then the partial pressure of B (in atm) after 100 sec
from start of experiment
K1 B ( g)
K2
A ( g) C ( g)
K3
D ( g)
(A) 0.288 (B) 0.5277 (C) 1.154 (D) none of these

11. For a first order reaction its frequency factor is 2 �1012 s-1 and threshold energy is 110.8 kJ/mole.
At what temperature the half-life period will be 38.5 mins, if the average energy of reactants is
20.3 kJ/mole.
(A) 200 K (B) 270 K
(C) 370 K (D) 300 K
12. Heptene decompose according to following reaction
D
C7H14 �� 2C2H4 + C3H6
Rate constant was found to be 1�10-4 sec -1 . In what time (approximately) molar ratio of Heptene
to ethene in they reaction mixture will attain the value 1?
[log 2 = 0.3010, log 3 = 0.4771]
(A) 68 min (B) 4055 min
(C) 1738 min (D) 228 min
13. An adiabatic container filled with a movable adiabatic piston (operating at 1 atm) is filled with 2
litre of 2M H2O2 solution at 300 K. If H2O2 dissociates following first order decay with half life of
10 min then change in internal energy in first 20 min will be....(Given R = 2 cal/mol–K)
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(A) 900 cal (B) 450 cal
(C) 1800 cal (D) 225 cal
14. A substance A (s) undergoes following reaction:-
K1 = 1min-1, K 2 = 4min -1 �
�
� �
The mole fraction of D in the final mixture will be

(A) 0.25 (B) 0.2
(C) 0.5 (D) 0.4
15. A tangent drawn on the curve obtained by plotting concentration of product (mole L-1 ) of a first
order reaction vs. Time (min) at the point corresponding to time 20 minute makes an angle to 30º
with concentration axis. Hence the rate of formation of product after 20 minutes will be
-1 -1 -1 -1
(A) 0.580 mole L min (B) 1.723 mole L min
-1 -1 -1 -1
(C) 0.290 mole L min (D) 0.866 mole L min
16. In the first order reaction, the concentration of the reactants is reduced to 25% in one hour. The
half life period of reaction is
(A) 2 hrs (B) 4 hrs
(C) 1/2 hr (D) 1/4 hr
17. For a first order reaction: AnB (with possibly fractional), the concentration of the product varies
with time as (A0 is the concentration of A at time t = 0).
(
(A) [ B] = nA 0 1 - e
-2kt
) (B) [ B] = nA 0 t
(C) [ B] = nA 0 ( 1- e )
- kt
(
(D) [ B] = nA 0 e
- kt
)
18. A certain reaction A + B �� P is of first order with respect to each reactant. If
[ A ] 0 - 0.1M[ B] 0 = 5M and the second order rate constant K is 6 �10-3 M-1S -1, the half life of the
reaction (in sec.) is
(A) 23.5 (B) 27.7
(C) 33.3 (D) 115.5
19. Which of the following is most likely to show K-electron capture

(A) elements higher than the zone of stability and high atomic number
(B) elements lower than the zone of stability and low atomic number
(C) elements higher than the zone of stability and low atomic number
(D) elements lower than the zone of stability and high atomic number
20 From the following data for the reaction
H2 + I2 �� 2HI
T.K 1/TK–1 Log10K
769 1.310 2.9
667 1.510 1.1
The activation energy for the reaction (cal/mol) is
(A) 4  104 (B) 8  104
(C) 2  10 4
(D) 3  104
21. A first order reaction has a half life period of 69.3 sec. At 0.10 mol/litre reactant concentration, rate
will be
-4 -1 -3 -1
(A) 10 Msec (B) 10 Msec
-1 -1 -1 -1
(C) 10 Msec (D) 6.93 �10 Msec
22. The pH at which water is maximum dissociated is (at 25C)
(A) 2 (B) 7
(C) 10 (D) 14
12
K �K �
23. If over all rate constant for the following process is given by K = 2 � 1 � , then find out the
K 3 �K 5 �
overall activation energy
K
K1
A �� K2
B �� K3
C ��
D ��
4 K5
�E ��
� F
K -1
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The activation energies of first, second, third and fifth steps are 40, 60, 50, and 10 KJ mole
respectively.
(A) 25 (B) 45
(C) 50 (D) 60
24. For the given elementary parallel 1st order reaction
B ( g)
K1
A ( g)
K2
C ( g)
The rate constant K1 and K 2 are 2 �10 -2 sec -1 and 4.93 �10 -2 sec -1 respectively. If initially pure
A ( g) is taken in a closed container with pressure of 4 atm, then the partial pressure of B after 10
sec from, the start of experiment will be
(A) 1.423 atm (B) 1 atm
(C) 0.577 atm (D) 1.154 atm
25. In a parallel chemical reaction A reactant change into products B, C and D by using following
Stoichiometry and 1st order chemical kinetics, what will be the overall rate of disappearance of A
K1
A �� B
K2
2A �� C
K3
3A �� D
Where K1,K 2 ,K 3 are first order rate constants respectively?
dA dA
= ( K1 + K 2 + K 3 ) [ A ] = K1 [ A ] + K 2 [ A ] + K 3 [ A ]
2 3
(A) - (B) -3
dt dt
dA 1 1 dA
(C) - = K1 [ A ] + K 2 [ A ] + K 3 [ A ] (D) - = ( K1 + 2K 2 + 3K 3 ) [ A ]
dt 2 3 dt
26. A zero order reaction would definitely be
(A) exothermic (B) endothermic
(C) elementary (D) complex
Hydrogen exists as 3 isotopes –H, D, T and oxygen exists as 2 isotopes - O, O. How many
16 18
27.
radioactive water molecules are possible
(A) 8 (B) 9
(C) 12 (D) 15
28. A mixture of 2 gases –A (reactive) and X(inert) is kept in a closed flask when A decomposes as
per the following reaction at 500 K:
(A) A ( g) �� 2B ( g ) + 3C ( l ) + 4D ( s )
Pº = 210mmHg
Pt ( 10mins.) = 330mmHg
P� = 430mmHg
Vapour press of C ( l ) at 500 K is 20 mm Hg
Calculate the half life for A
(A) 5 mins (B) 10 mins
(C) 12 mins (D) given data is not sufficient to answer
29. Consider the following reaction occuring in gas phase

Cl2 ( g) + CHCl3 ( g) ��
�HCl ( g ) + CCl4 ( g )
The reaction is experimentally found to obey the following rate law
R = k [ CHCl3 ] [ Cl2 ]
12
Step 1: Cl2 ( g) ��2Cl ( g)

��
�
Step 2: Cl ( g) + CHCl3 ( g) ��
�HCl ( g) + CCl3 ( g)
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Step 3: Cl ( g) + CCl3 ( g ) ��
� CCl4 ( g )
Based on this information, what conclusion can be drawn about this proposed mechanism
(A) Step 1 is RDS (B) Step 2 is RDS
(C) Step 3 is RDS (D) RDS cannot be identified
k1
30. � � � �
Consider an exothermic reaction A ��B as the temperature increases
k -1
(A) k1,k -1, and k1 k -1 increases

(B) k1 decrease, k -1, increases, and k k -1 decreases
(C) k1,k -1 and k1 k -1 decreases
(D) k1 and k -1 increases, and k1 k -1 decreases
For a gaseous reaction CH3 CHO ( g) �� CO ( g ) + CH4 ( g ) initial pressure is 80 mm of Hg and
D
31.
total pressure at the end of 20 minutes is 120 mm of Hg. The rate constant of the reaction
assuming first order kinetics is
(A) 3.465 �10 -2 min-1 (B) 34.65 min–1
–1
(C) 3.465 min (D) 0.3465 min–1
32. The following reversible reaction starts only with A;
��
( )
K1 sec -1
A ��
��
� ��
�B;
1 �
-
K2 ( sec )
What is the time taken by the reaction to achieve equilibrium
1 �K1 � 1 �K �
(A) l n � + 1� (B) l n � 1 + 1�
K1 �K 2 � K 2 K
�2 �
1 �K 2 + K 1 � 1 �K �
(C) l n� � (D) l n � 2 + 1�
K1 � K1 � K 2 �K1 �
33. A certain reactant A n+ is getting converted to A ( n+ 4) + in solution. The rate constant of this reaction
is measured by titrating a volume of the solution with a reducing agent which only reacts with A n+
and A ( n+ 4) + . In this process, it converts A n+ A ( n- 2) + and A ( n+ 4) + to A ( n-1) +
Time 0 minute 10 minutes

Volume of reagent consumed 30 ml 45 ml
Calculate the rate constant (in the units of min ) of the conversion of A n+ to A ( n+ 4) + , assuming it
–1
to be a first order reaction.

[Given: n-factor of reagent remain same when it reacts with A n+ and A ( n+ 4) + .
In 3 = 1.099 ln 2 = 0.699]
(A) 0.1099 (B) 0.0699
(C) 0.02 (D) 0.04
34.
RP
A first order reaction occurring at 27ºC. If 10 -2% molecules are in activated state. Find the
maximum rate constant
(A) 3.4 �10 -2 (B) 3.4 �102
-4
(C) 10 (D) can’t be determined
35. Arrhenius equation can be used in

(A) zero order (B) first order
(C) second order (D) radioactivity
36. Aqueous AB st
2 decompose according to the 1 order reaction
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AB2 ( aq) ��
� A ( g) + 2B ( l )
After 20 min the volume of A ( g) collected during such a reaction is 20 ml, and that collected after
a very long time is 40 ml. The rate constant for the reaction is
-2 -1 -2 -1
(A) 1.435 �10 min (B) 3.466 �10 min
-2 -1 -1
(C) 3.46 �10 min (D) 6.96 min
K1 K2
37. For a complex reaction, A �� B �� C and K1 = 5K2, then which of the following graph is
�
most appropriate for the given reaction?
(A) (B)
(C) (D)
38. A radioactive element ‘A’ decays by the sequence given below and half life given below:
-a -2b
A ��30min
� B ��
2 days
�C
Which is/are correct
(A) After 2 hr, A will be less than 10% of the initial amount
(B) Amount of B present at any time is less than 50% of initial amount of A.
(C) Atomic number of A and C are same
(D) The mass number of B is greater than A.
39. For the reaction

A �� k
�B + C
Following data are obtained
Conc. of A(in M) 2 0.5 0.25 0.0625
Time (in min) 0 20 30 50
What will be the rate of reaction (in mol L–1 min–1), when conc of ‘A’ is 3 M.
(A) 2.079 �10 -3 (B) 6.75 �10 -1
-2
(C) 7.5 �10 (D) none of these
40. Two reactions r1 and r2 proceed at 25C at the same rate. The temperature coefficient of the
second reaction is 2.5 times of temperature coefficient of the first reaction. The ratio of rates of
these reactions at 96C will be ( r2 r2 ) , approx
(A) 10: 1 (B) 5: 1
(C) 15: 1 (D) 25: 1
Kf
41. ��
A �� B
�� is an exothermic reaction, then on increasing temperature
Kb
(A) K f K b , K f and K b all increases

(B) K f , K b increases and K f K b decreases
(C) K f decreases, K b increases, K f K b remains same
(D) K f , K D increases and K f K b remains same
42. For a first order reaction: A nB(with n-possibly fractional), the concentration of the product
varies with time as (A0 is the concentration of A at time t = 0).
(
(A) [ B] = nA 0 1 - e )
-2kt
(B) [ B] = nA 0 t
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(
(C) [ B] = nA 0 1 - e
- kt
) (
(D) [ B] = nA 0 e
- kt
)
43. .At 100C, the gaseous reaction A ( g ) �� 2B ( g ) + C ( g ) is found to be first order. Starting with
pure A, if at the end of 10 min, the total pressure the of the system is 176 mm and after a long
time the final pressure is 270 mm. The partial pressure of A at the end of 10 min is
(A) 94 mm (B) 73 mm
(C) 47 mm (D) 176 mm
\ Partial pressure of A after 10 min = 90 – 43 = 47 min
44. In the first order reaction, the concentration of the reactants is reduced to 25% in one hour. The
half life period of reaction is
(A) 2 hrs (B) 4 hrs
(C) 1/2 hrs (D) 1/4 hr.
45. A reaction takes place in three steps with activation energy Ea1 = 1800kJ mol,
Ea2 = 80kJ mol and Ea3 = 50kJ mol respectively. Overall rate constant of the reaction is
23
�
KK �
K = �1 2 �
�K 3 �
The activation energy of the reaction will be
(A) 140 kJ/mol (B) 150 kJ/mol
(C) 43.44 kJ/mol (D) 100 kJ/mol
k1
46. For the reversible reaction, A ��
��
� B, K 1 = 0.02min -1
, K 2 = 0.03min-1 . The reaction is tarted
k2
with A only. The half life of such reaction is defined as the time in which half of the equilibrium
amount of B is formed. What is half life of reaction ( l n2 = 0.693 )
(A) 34.65 min (B) 32.10 min
(C) 13.86 min (D) �
47. When the temperature of a reaction is increase from 37ºC to 47ºC, the rate increases by 3 times
then the activation energy of the reaction in the temperature range will be (log30 =1.477)
(A) 45.4 kJ (B) 90.55 kJ
(C) 25.5 kJ (D) 72.5 kJ
48. The catalyst decrease the Ea from 100 K mol-1 to 80 kJ mol-1 . At what temperature the rate of
reaction in the absence of catalyst at 500 K will be equal to rate reaction in presence of catalyst.
(A) 400 K (B) 200 K
(C) 625 K (D) None of these
49. Which of the following factor alters the rate of a reaction irrespective of order of the reaction?
(A) concentration of reactant (B) Temperature
(C) pH of medium (D) Concentration of product
50. A solid particle having spherical shape is assumed to react only on its surface. However the
amount of reactant contained in its is determined by its volume. Consider the following rate law for
a solid particle shrinking due to reaction:
dV
- = kS ( S = surface area )
dt
The order of the above reaction will be:
(A) 0 (B) 1
(C) 2 3 (D) 3 2
51. Reaction at the very first instant of their life,. i.e. shortly after start, follow
(A) Pseudo zero order kinetics (B) Pseudo first order kinetics
(C) Pseudo second order kinetics (D) Pseudo third order kinetics
SECTION II (ONE OR MORE THAN ONE)

1. According to Arrhenius the relationship between rate constant K and temperature can be given by
K Ea � T2 - T1 �
(A) K = Ae -Ea RT (B) log 2 = � �
K1 2.303R �T1T2 �
Ea
(C) log K = log A - (D) DG�= -2.303RTlogK
2.303RT
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2. B
-1
K1 = x1 sec ,Ea1 = y1kJ
C
K 2 = x 2 sec -1,Ea2 = y 2kJ
(Given that y1 > y 2 )
Choose the correct statements regarding above chemical reaction:
(A) Overall rate of reaction is equal to sum of formation of B and C.

x1 y 1 + x 2 y 2
(B) Overall activation energy of the reaction Ea =
x1 + x 2
l n2
(C) Half life of reaction is
x1 + x 2
(D) As the temperature decreases rate of reaction of both reactions decreases but ratio of rate of
reaction A �� C decreases more than A �� B.
3. Select the correct statement(s)

(A) On bombarding, N14 nuclei with a a-particle, the nuclei of the product formed after release
17
of proton would be 8 O
(B) Decay constant is not dependent on temperature.
(C) Nuclide and its decay product after a-emission are called isodiapheres.
(D) Half-life of radius is 1580 years, its average life will be 1097.22 years.
4. Two first order reaction have rate constant ratio 1 : 16 respectively. Then choose the correct
options in the following regarding these reaction:
(A) t 75% for these reaction is in the ratio 16 : 1 respectively
(B) t 99% = 2log90% for both the reaction
(C) t 25% for first reaction and t 75% for second reaction is in the ratio 1: 301
(D) degree of dissociation for these reaction at any point of time ‘t’ can have the ratio
e -k1t :e -k 2 t where K1 : K 2 = 1: 16
5. Collision theory explains, how chemical reactions occurs. Using this theory and kinetic molecular
model, which of the following influence the rate of reaction?
(A) Temperature of the system
(B) The geometry or orientation of collision
(C) The velocity of the reactants at the time of collision
(D) Concentration o reactants
6. For the first order reaction
2NO2 O5 ( g ) �� 4NO2 ( g ) + O2 ( g )
Which of the following statement/s is/are correct?
(A) The concentration of the reactant decreases exponentially with time
(B) The half-life of the reaction decreases with increasing temperature.
(C) The half-life of the reaction depends on the initial concentration of the reactant
(D) The reaction proceeds to 99.6% completion in eight half-life duration
7. Radio active element ‘X’ decays by the sequence and with half lives given below
a decay b- decay
X ��
t1 2 = 30min
�� Y ��
t1 2 = 2days
Z
Which of the following statements about this system are correct?
(A) After 30 min the no. of moles of Y present is less than the no. of moles of X left.
(B) Maximum moles of Y present at any time is less than 50% of the initial moles of X
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(C) Option B is certainly correct if t1 2 of Y is less than 30 min and that of X is 30 min
(D) X and Y are iso-diaphers.
8. At 280 K, the following data is given for the reaction
F2 + 2ClO2 �� 2FCIO2
d [ F2 ] � F2 � � ClO2 �
-
dt
(
�103 moldm-3 S -1 ) �( mol dm ) � �( mol dm ) �
3 3
�
� ��
� � �
�
1.2 0.10 0.01
4.8 0.10 0.04
2.4 0.20 0.01
Then which of the following is true regarding the above reaction?
(A) overall order of reaction is 2
-4 -3 - 1
(B) rate of disappearance of F2 is 2.4 �10 mol dm s
-4 -3 -1
(C) rate of formation of FClO2 is 4.8 �10 mol dm s
(D) order w.r.t. to F2 is zero
9. A radioactive element ‘A’ decay by the sequence given below and half life given below:
-a -2b
A ��
30min
� B ��2 days
�C
Which is/are correct?
(A) After 2 hr, A will be less than 10% of the initial amount.
(B) Amount of B present at any time is less than 50% of initial amount of A.
(C) Atomic number of A and C are same
(D) The mass number of B is greater than A
10. Arrhenius equation can be used in
(A) zero order (B) first order
(C) second order (D) radioactivity
SECTION III (PARAGRAPH)

Peroxycetyl nitrate (PAN) is an air pollutant produced in photochemical smong by the reaction of
hydrocarbon, oxies of nitrogen and sunlight. It dissociate as
O O
H3 C - C - OONO2  H3 C - C - O - O + NO2

( PAN)
A sample of plluted air is analysed for its PAN content which is reported as molecules PAN per litre of air
at 25C?
Time ( min ) Molecules �10 -14 L air
0.0 5.0
10.0 4.0
20.0 3.2
3.0 2.6
40.0 2.1
1. What is order of PAN decomposition reaction?
(A) 0 (B) 1
(C) 2 (D) 3
2. Rate constant of the reaction is
(A) 0.0231 min–1 (B) 0.009 min–1
–1 –1 –1 –1
(C) 0.0231 L mol min (D) 0.009 L mol min
3. Half life of the reaction is
(A) 10 min (B) 20 min
(C) 30 min (D) 60 min
KA KB
4. A �� TA
�
� product, B ��TB
product. Two reactions with half life periods TA , TB (in mins) and
(
K A min-1 ) ( -1 -1
)
and K B min litre min . If half life periods are equal at the start of reaction, the
(
reaction rate ratio at the start of reaction would be assumin g [ A ] 0 = [ B] 0 )
(A) K A TA (B) 0.693
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(C) both A and B (D) 0.0693
5. In vessel of capacity 1 litre at 27ºC for the first order decomposition of
C2H5Br ( g) � C2H4 ( g ) + HBr ( g ) , the initial pressure of 200 mm of Hg changes to 390 mm of Hg
after infinite time, where all the reactant is consumed. If at 10 min, 0.2 g of NaOH was required to
react completely with reaction mixture, then find out the half life of reaction?
(A) 8 min (B) 10 min
(C) 15 min (D) Data insufficient
SECTION-IV (MATRIX MATCH)
1. Match Column I with Column II

Column-I Column-II
(A) One a-particle (p) Isobar
(B) One a-and two b-particle (q) Isotope
(C) One b-particle (r) Isodiapher
Atomic number reduced by two and mass

(D) b-radiation (s)
number by four
(t) Nuclear de-excitation
CHEMICAL KINETICS
2. Following are the reaction and conclusions related to radioactive disintegration with initial
moles of each species being 10.
Column-I Column-II
The reaction can be represented by

-a -b
X ��
� Y ��
�Z
slow fast
(A) t1 2 = 69.3hr (p)
Time of reaction = 23.03 hr.
+b
A ��
t1 2 = 693hr
B The rate of reaction increases with
(B) (q)
time of reaction = 230.3 hr temperature
K -captue -a
P �� R �� S
fast slow The moles of the starting element after the
(C) t1 2 = 69.3hr. (r)
given time = 100.9
Time of reaction = 23.03 hr
The reaction can be represented by:
-b -a
L M �� N
(D) t1 2 = 6.93hr fast
(s)
slow
Time of reaction = 2.303 hr.
The rate of reaction decreases with

(t)
decreases in temperature
SECTION V (INTEGER)
1. Iodine-131 is a radioactive isotope. If 1 mg of 131I has an activity of 4.6 �1012 Bq. What is half-life
of 131I (in days)?
2. If a nuclei 87X loses 2a and 4b particles, then the new group no. for X in periodic table will be....
FIITJEE
3. There are two radioactive nuclei A & B, A is a-emitter and B is b-emitter, their decay constants are
in the ratio of 1 : 2. What should be the number of atoms of each nuclei at time t = 0, so that
probability of getting of a and b-particles are same at time = 0.
At time = 0
The radio, activity of both are same.
l1N1 = l 2N2
l A NA = l aN8
l A N8
=
lB NA
\NA : N8 = 2 : 1
4. For chemical reaction,

A B, the third half-life is four times of initial half-life. Find the order of reaction
5. For zero order reaction A3B plot of concentration vs time is as follows
Find half the period in minutes if the initial conc. of A be 1 M.

6. K + CH3I �� KI + CH3
Ea = 46.06 Cal/mol at 500 K for the above reaction potassium and methyl iodide molecules are
collided by the following two way
H
K + I C H Kl + CH3
H 0.2  1018 collision sec
H
K + H C I No reaction
H
0.8  1018 collision sec
2 x half-life period of the above reaction is = y. What is the approximate value of y/100.
7. The first order gaseous decomposition of N2 O4 in to NO2 has a rate constant value
K = 4.5 �103 s -1 at 1ºC and energy of activation 58 kJ mol –1. What should be the rise in
temperature in (ºC) to get the value of K = 1.00 �10 s ( log2.2 = 0.3424 )
4 -1
8. The half life period and the initial concentration for a reaction are as follows. The order of reaction
is
Initialconcentration 350 540 158
t1 2 425 275 941
9. In a reaction, the time required to complete half of the reaction was found to increases “16” times,
when the initial concentration of the reactant was reduced to 1/4 th. Then the order of the reaction
is.
1
10. A reaction X2 ( g) �� Z ( g) + Y ( g) exhibits an increases in pressure from 150 mm to 170 mm
2
in 10 min. The rate of disappearance of X2 in mm per min...................
FIITJEE
11. If initial concentration of the reactants A and B of the following process are increased by factors 4
and 2 respectively then by what factor the rate of reaction will increases?
1 2
� C ( aq ) ; r = K [ A ] 2 [ B ]
A ( aq) + B ( aq ) ��
12. For a hypothetical elementary reaction
2B
K1
K1 1
where =
A K2 2
K2 2C
Initially 2 moles of A are present, than total number of moles of A, B and C at the end of 50%
reactions is
13. The velocity of a reaction is tripled for every 10ºC rise in temperature. If temperature is raised by
x
120ºC then the velocity increases by x times. Where is equals to
9049
Temperature coefficient = 3 so an increasing 120ºC rate = 3 12
14. If lactobacillus bacteria (which coverts milk to curd) multiply in milk as per the data given
Time(minute) 0 15 45 75
No. of bacteria 100 200 800 3200
100 g milk to curd requires 4  109 such bacteria. Atleast how many hours it will required to
convert 1 kg milk if initially 100 bacteria were mixed in it.
15. For a radioactive decay reaction

XY+q a (where q is the number of stoichiometric
coefficient) Following graph was observed
In the ratio of the volume of emitted helium gas at different
time t1 and t 2 be 1 2 . Find the value of q.
ANSWER
SINGLE CORRECT
1. A 7. B 13. A 19. 25. D
2. A 8. D 14. D 20. A 26. D
3. 9. B 15. B 21. B 27. B
4. 10 C 16. C 22. B 28. B
5. C 11. B 17. C 23. A 29. B
6. C 18. A 24. C 30. D
12. A
FIITJEE
31. A 36. B 41. B 46. C 51. A
32. A 37. B 42. C 47. B
33. D 38 43. C 48. A
34. B 39. D 44. C 49. B
35. 40. B 45. A 50. C
ONE OR MORE THAN ONE
1. A,B,C 4. A, B,C,D 8. ABC
2. A,B,C 5. ABCD 9. AC
3. A, B, C 6. ABD 10. BC
7. ACD
PARAGRAPH
1. B 2. A 3. C 4. C 5. B
MATRIX MATCH
1. Ar,s; Bq, Cp; Dt
2. Ap, r; Br, Cr, s; Dp, r
INTEGER TYPE
1. 8 5. 8 11. 8
2. 3 6. 7 12. 3
7. 9 13. 9.
3. 2
8. 2 14. 8.
4. 2. 9. 3 15. 3
10. 4
SOLUTIONS
SINGLE CORRECT
1. A
For 1st order kinetics
Nt = N0 e -lt and N0 = Nt �2n
� e-lt = 2-n � ekt = 2n
2. A
In zero order reaction rate is independent of concentration
FIITJEE
3.
4.
5. C
A ( g) ��
�B ( s ) + 2C ( g )
t1 2 = 20min
60
No. of half lives = =3
20
200
Pressure of A after 60 min
2n
200
= = 25mm
23
Pressure of C after 60 min = 175  2 = 350 mm
Total pressure = PA + PC = 25 + 350 = 375
6. C
2.303 [ A] 0
K= log
t [ A]
2.303 1
2.303 = log
1 [ A]
1
log = 1, [ A ] = 0.1
[ ]
A
Rate = K [ A ]
= 2.303 �0.1 = 0.2303 Mmin-1 .
7. B
8. D
9. B
15 18
�
H2 O, H2 O �
15 18 �
Water constaining only one isotope of H = D2 O D2 O �6
15 18 �
T2 O, T2 O �
�
Waters containing more than one isotope of H = C2 � C1 = 5
3 2
\ Total possible waters = 6 +6 = 12

15 18 15
of which H2 O,D2 O HOD are non readiactive.
10 C
-3 -1
Overall rate constant K = K1 + K 2 + K 3 = 6.93 �10 sec
0.693
t1 2 = = 100 sec.
6.93 �10 -3
After half life, PB + PC + PD = 4atm
PB K1 200
Or, = =
PB + PC + PD K1 + K 2 + K 3 693
200
\ PB = 4 � = 1.154 atm
693
11. B
K = Ae -Ea/RT
Ea = Threshold energy – energy of reactant = 90.5
Ea
logK = logA–
2.303RT
FIITJEE
0.693 90500
log = 12.3 -
38.5 �60 2.303 �8.314 �T
4728.55
log3 �10 -412.3 -
T
4276.55
T= = 270
15.8
12. A
C7H14 � 2C2H4 + C3H8
a 0 0
a-x 2x x
e-x a
= 1, x =
2x 3
2.303 a
1�10-4 = log
t 2a 3
t = 67.59min.
13. A
Initial moles of H2O2 = 2 �2 = 4
1
Moles of H2O 2 left after 20 min ( 2 �t1 2 ) = 4 � 2 = 1
2
Moles of H2O 2 decomposed in 20 min = 4 – 1 =3
1
H2 O2 ( l ) ��H2 O ( l ) + O2 ( g)
2
Thus 3 moles H2 O2 will produce 3 2 mole O2 in 20 min.
3
�R �T
Volume change = nRT 2
=
P P
For adiabatic process q = 0 and DU = W
3
DU = W = -Pext DV = -1� �2 �300 = -900 cal.
2
14. D
[ B ] = K1 , XD =
K2
=
4
= 0.4
In final mixture [B] = [C] and [E] = [D] and
[ D] K 2 2K1 + 2K 2 10
15. B
Tangent makes an angle of 30º with concentration axis so it must make an angle of 60º with the
time axis (–ve direction). The slope of the tangent will be tan 60º i.e., 1.723
\( B )
16. C
2.303 a
K= log
t ( a - x)
2.303 100
= log = 2 �0.693
1 25
0.693 0.693 1
t1 2 = = = hr
K 2 �0.693 2
17. C
18. A
For 2nd order reactions
2.303 [ B] [ A ]
K= log 0
{
t [ A ] - [ B]
0 0 } [ A ] 0 [ B]
When t = t1 2 ,[ A ] =
[ A] 0 0.1
= = 0.05
2 2
FIITJEE
At that time, [ B] = 5 - 0.05 = 4.95
2.303 5 �0.05
\ t1 2 = log
6 �10 ( 0.5 - 5 )
-3
0.1�4.95
2.303 1
= log �23.5 sec
6 �10 ( -4.9 )
-3
2
19.
20. A
Ea
2.9 = LogA -
2.303R769
Ea
1.1 = LogA -
2.303R667
Ea = 4.17 �10 4 cal mol-1
21. B
rate = K[A]
0.6931
= [ 0.1]
69.3
= 10 -2 �
10 -1 �
� �
= 10-3
22. B
At 25C H+ ions = OH ion ions = 10–7
26. D
Order � Molcularity implies a complex reaction.
27. B
15 18
�
H2 O, H2 O �
15 18 �
Water constaining only one isotope of H = D2 O D2 O �6
15 18 �
T2 O, T2 O �
�
Waters containing more than one isotope of H = C2 � C1 = 5
3 2
\ Total possible waters = 6 +6 = 12

15 18 15
of which H2 O,D2 O HOD are non readiactive.
28. B
A ( g) ��
� 2B ( g ) + 3C ( l ) + 4D ( s ) Inert gas
t=0 P 0 0 0 i mm Hg
t = 10 mins P–x 2x 20 0 i mm Hg
t= � 0 2P 20 0 i mm Hg
P + i = 210
P–x+2x+20+i=330
2P+20+i=430
On solving; P = 200; x = 100
Hence 10 mins must be t1 2 29. B
If Step 2 were RDS
[ Cl]
2
R = k [ Cl] [ CHCl3 ] K C =
[ Cl2 ]
R = k K C [ Cl2 ]
12 12
(given rate law)
\ Step-2 is RDS.
30. D
� K1 �
DH = - ve so as T increases K c �= �decreases although rate const increases k = Ae (
- Ea RT
)
� K -1 �
31. A
FIITJEE
CH3 CHO ( g) � CH4 ( g ) + CO ( g )
80 0 0
after 20min 80 - x x x
Ptotal = 80 + x = 120
\ t1 2 = 20min;
0.693
\K = min-1 = 3.465 �10 -2 min -1
20
32. A
[ A ] t = [ A ] 0 e-K1t ;[ B] t = [ A ] 0 - [ A ] 0 e-K1t
d[ A ] d[ B]
- = K1 [ A ] t ; = K 2 [ B] t
dt dt
At equilibrium
d[ A ] d[ B]
- =
dt dt
1 �K1 �
On solving t = l n � + 1�
K1 �K 2 �
33. D
� A( )
n+ 4 +
A n+ ��
t=0 a0mol. 0
t = 10min a0 - x mol x mol
n-factor for A n+ = 2
n-factor for A ( n+ 4 ) + = 5
So, 2  a0 = 30  N ........(1)
2 ( a0 - x ) + 5 ( x ) = 45 �N .......... (2)
From (1) and (2)
a0 3
=
a0 - x 2
�a �
k ( 10 ) = ln � 0 �
�a0 - x �
4
k= = .04min-1
10
34. B
A is the maximum rate constant
35.
36. B
AB2 ( aq) 1st order

�� A ( g) + 2B ( l )
t �0 a 0 0
t � 0min ( a - x) x 2x x �20 ( at cos t.andvolumemole �pressure )
t �� 0 a 2a a � 40
1 �a �
K = ln �
t �a - x ��
1 �40 �
= ln
20 � �
�20 �
37. B
[A] decreases sharply and [B] increases sharply but decreases slowly as37. B
K
[A] decreases sharply and [B] increases sharply but decreases slowly as 2 < K 1
38
39. D
Q The half life period of ‘A’ is independent of concentration
FIITJEE
\ Reaction is first order with t1 2 = 10 min
0.693
\k = = 6.93 �10-2
10
-2 -1 -1
Rate (R) = k [A] = 6.93 �10 �3 = 0.2079mol L min
40. B
41. B
42. C
43. C
A ( g ) �� 2B ( g) + C ( g)
Initial Pº 0 0
After10min Pº -P 2P P
After longtime 0 2Pº Pº
\ 3Pº = 270, Pº = 90mm
\ Pº -P - 2P + P = 176
86
90 + 2P + 176, P = = 43mm
2
44. C
2.303 a
K= log
t ( a - x)
2.303 100
= log = 2 �0.639
1 25
0.693 0.639 1
t1 2 = = = hr
K 2 �0.693 2
45. A
23
�
KK �
The rate constant of reaction is K = � 1 2 �
�K 3 �
Activation energy of reaction will be
2
Ea = � Ea + Ea2 - Ea3 �
3� 1 �
2
= [ 180 + 80 - 50 ]
3
= 140kJ / mol.
46. C
47. B
K Ea �1 1 �
log 2 = � - �
K1 2.30R �T1 T2 �
Ea
log3 =
�1 1 �
2.303 �8.31� - �
�310 320 �
0.477 �2.303 �8.31�310 �320
= Ea = 90.55kJ
10
48. A
( Ea1 - Ea 2 ) Ea �1 1 �
= � - �
2.303RT 2.30R �T1 T2 �
2000 100000 �1 1 �
= � - �
T1 1 �T1 500 �
1 500 - T1
=
5T1 T1 500
500 = 2500 –5T1++
5T1 = 2000
FIITJEE
T1 = 400K
49. B
Factors mentioned in ( A ) , ( C ) and (D) may or may not alter the rate depending upon order of
reaction and role of H+ as catalyst.
50. C
dV
=k S
dt
dV
- = k ( 4pr 2 )
dt
dV
- = k 'r 2 ( k ' = 4pk )
dt
23
dV �3V � � 4 �
- = k '� � �Q V = pr 3 �
dt �4p � � 3 �
dV � �3 �
23
�
- = k " V2 3 �
k" = k'� � �
dt � �4p � �
� �
\ order = 2/3
51. A
ONE OR MORE THAN ONE

1. A,B,C
2. A,B,C
d [ A ] d [ B ] d [ C]
(A) - = +
dt dt dt
(B) K [ A ] = K1 [ A ] + K 2 [ A ]
Where K is overall rate constant.
K = K1 + K 2
dK dK1 dK 2
or = +
dT dT dT
Ea Ea Ea
-�Ea � - 1 � Ea � - Ea �
�
Ae �
RT
2 �
= A1e RT � 12 �+ A 2 e RT � 22 �
�RT � � RT � RT �
�
or K.Ea = K 1Ea1 + K 2Ea 2
K1Ea1 + K 2Ea2 x1y1 + x 2 y 2

or Ea = =
K x1 + y 2
l n2 l n2
(C) t1 2 = =
K x1 + x 2
K ' Ea �1 1 �
(D) l n = � - �
K R �T1 T2 �
3. A, B, C
(A) 7 N + 2 He ��
�8 O17 +1 H1
14 4
(B) for first order kinetics, l is independent of temperature
�p - 2 Y (
a- 2 ) + ( b- 2 )
(C) p X �� + 2 He 4
Isodiapheres are those, which have same difference with neutrons and protons, So,
X and Y are isodiapheres.
4. A, B,C,D
For 1st order reaction I75% = 2t 50% � t 50% ratio 16 : 1
Hence, t 75% ratio 16: 1
FIITJEE
t 25% 16 ln ( 4 3 ) 16 �.125 2 1
� For first order reaction t 99% ===޴ =
2t 90%�
t 75% 1 ln ( 4 ) .602 602 301
5. ABCD
6. ABD
7. ACD
8. ABC
d [ F2 ]
rate = - = l [ f2 ] [ ClO2 ] Over all order = 2
dt
Rate of disappearance of F2
d [ F2 ]
- = k [ F2 ] [ ClO2 ] = 1.2 �0.01�0.02 = 2.4 �10 -4
dt
Rate of formation of FClO2 = twice the rate at which F2 disappear
= 2 �2.4 �10 -4
= 4.8 �10-4 moldm-3 s-1
9. AC
b
a A ��-a
��ba--14 B ��
-2b
�ba - 4 C
t = 2hr
i.e. four half lives
1 [ A] 0
[ A] = [ A] 0 = = 6.2% of [ A ] 0
24 16
10. BC
PARAGRAPH
1. B
2. A
3. C
4. C
KA KB
A ��
TA
�
�product, B ��
TB
product
-d [ A ]
= KA [ A] ...(1)
dt
-d [ B ]
= KB [ B]
2
...(2)
dt
1
TB =
KB [ B] 0
Equation (1) is divided by (2)
0.693
-d [ A ] dt K A [ A ] 0 TA
[ A]0
= = = 0.693
-d [ B] dt K B [ B] 2 1
[ B] 0
2
[ B] 0 �TB
0
- d [ A ] dt KA [ A] 0 KA [ A] 0 KA [ A] 0
= = =
or -d [ B] dt K B [ B] 0
2
[ B] 0 [ B] 0
TB TA
5. B
C2H5Br ��
� C2H4 +HBr
at t = 0 Pº 0 0
at t = � 0 Pº Pº
Let Pº be the initial pressure of C2H5Br and pressure of inert gas = a0
Then, Pº +a0 = 200
At � time, 2Pº = aº = 390
� Pº 190 mm Hg, aº = 10mmHg
At time 10 min,
FIITJEE
0.2
Moles of NaOH = Moles of HBr = 0.005
40
On applying,
PV = nRT
P �0.005 �0.0821�300
PHBr = 95 mm of Hg
� PC2H5Br = 95mm of hg = half of initial pressure.
MATRIX MATCH
1. Ar,s; Bq, Cp; Dt
2. Ap, r; Br, Cr, s; Dp, r
Sol. All radioactive disintegrations are first order.
slow fast
X �� k1
� Y ��
k2
�Z
k1 and k 2 are rate constants.
1� �
[ Z] = [ X] 0 �1 -
k - k
( )
k 2 e -k1t - k 1e -k2 t �
� 2 1
k
Give 2 > k 1
[ Z ] @ [ X] 0 ( 1 - e - k t )
1
Qualitatively, we can say that the moment Y is formed

from, it immediately transforms to C.
Similarly in the following reaction also
slow fast
L �� M �� N
For these two cases the graph is
k1 k2
P ��fast
� R ��
fast
�S
1� �
[ S] = [ P] 0 �1 - k 2 e -k1t � ( )
� k 2 - k1
Given k1 > k 2
[ S ] = [ P] 0 ( 1 - e -k t )
1
All radioactive reactions re temperature independent

X �� Y �� Z
t1 2 = 69.hr
2.303 �[ x ] �
k1 = log � 0 �
t �[ x ] �
� t �
0.693
k1 = , t = 23.03 hr,[ x ] 0 = 10 moles
69.3
0.693 2.303 �10 �
= log � �� [ x ] t = 100.9
69.3 23.03 �[ X] �
� t�
A �� B
t1 2 = 693hr
0.693
k= ,t = 230.3hr,[ A ] 0 = 10moles
693
0.693 2.303 �10 �
= = log � �� [ A ] t = 100.9
693 230.3 �[ A ] �
� t�
P �� R �� S
0.693
t1 2 = 69.3hr,k1 = ,t = 23.03hr [ P ] 0 = 10 moles
69.3
\ [ P] t = 100.9
L ��
�M ��
�N
FIITJEE
0.693
t1 2 = 6.93hr, k = , t = 2.303hr.[ L ] 0 = 10moles
6.93
\ [ L ] t = 100.9
INTEGER
1. 8
2. 3
3. 2
4. 2.
5. 8
A � 3B
1- x 3x
at t = 4, 1–x = 3x
x=¼
for zero order reaction
C1 = C0 - kt
3
= 1 - k �4
4
1 1 C
4k = ; k = and t1 2 = o .
4 16 2k
1
t1 2 = =8
1
2�
16
6. 7
7. 9
�10 �103 � 58 �103 �T2 - 274 �
log � 3 �
= � �
�4.5 �10 � 2.303 �8.314 �274T2 �
� T2 = 283K = 10º C
\ Rise in temperature = 10 - 1 = 9º C
8. 2
t1 2 �( a )
1- n
where ‘n’ is order of reaction
425 �( 350 )
1- n
.......(1)
275 �( 540 )
1- n
.......(2)
941�( 158 )
1-n
.......(3)
1- n
425 �350 �
By (1) and (2), =
275 � �540 �
�
425 �350 �
Taking long, log = ( 1 - n ) log � �
275 �540 �
�n = 2
9. 3
n -1
t 2 �a1 �
=� �
t1 �a2 �
n -1
�1 �
16 = � � �\ n = 3
�14�
10. 4
1
X2 ( g) ��
� Z ( g) + Y ( g)
2
to 150 0 0
10min 150 - x x x 2
FIITJEE
x x
Total pressure = 150 - x + x + = 150 + = 170
2 2
X = 40min
40
Rate of disappearance of X2 = = 4 mm min
10
11. 8
12. 3
[ B] =
K1 1 x
= =
[ C] K2 2 y 2B ( 2x )
A
[ A] - ( x + y)
on 50% completion
2C ( 2y )
x 1
2 - ( x + y ) = 1 and =
y 2
1 1
\x = &y =
3 3
4
\ [ B ] = 2x =
3
2
[ C] = 2y = 3
4 2 9
Total moles + + 1 = = 3
3 3 3
13. 9.
14. 8.
As the bacteria are growing with first order kinetics
-2.303 a
K= log
t a+x
= 0.0462 min–1
2.303 a + x 2.303 4 �1011
t= log = log = 480mins
0.00462 a 0.462 100
So, 8 hrs
15. 3
X � Y + qa
at t1 a-x x qx
at t 2 a-y y qy
at t1 a - x = qx
a = qx + x
a = x ( q + 1)
a
x=
q+1
at t 2 , a - y = y
a
y=
2
Volume of the gas � no. of moles of the gas
qx x a q + 1
= =
qy y a2
x 2
� =
y q +1
FIITJEE
x 1 2 1
Given: = \ = �q=3
y 2 q +1 2

1.chemical Kinetics

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1.chemical Kinetics

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FIITJEE

SUBJECT: CHEMISTRY CHEMICAL KINETICS

NAME…………………….. ENROLL NO……………. BATCH…………………

SECTION I (ONLY ONE CORRECT)

3. For the reactions: Reaction-I A �� �B and Reaction:II

(A) 0.288 (B) 0.5277 (C) 1.154 (D) none of these

The mole fraction of D in the final mixture will be

19. Which of the following is most likely to show K-electron capture

29. Consider the following reaction occuring in gas phase

Step 1: Cl2 ( g) ���2Cl ( g)

(A) k1,k -1, and k1 k -1 increases

Time 0 minute 10 minutes

to be a first order reaction.

35. Arrhenius equation can be used in

39. For the reaction

(A) K f K b , K f and K b all increases

SECTION II (ONE OR MORE THAN ONE)

(A) Overall rate of reaction is equal to sum of formation of B and C.

3. Select the correct statement(s)

SECTION III (PARAGRAPH)

H3 C - C - OONO2  H3 C - C - O - O + NO2

SECTION-IV (MATRIX MATCH)

1. Match Column I with Column II

(A) One a-particle (p) Isobar

(B) One a-and two b-particle (q) Isotope

(C) One b-particle (r) Isodiapher

Atomic number reduced by two and mass

The reaction can be represented by

Time of reaction = 2.303 hr.

The rate of reaction decreases with

4. For chemical reaction,

Find half the period in minutes if the initial conc. of A be 1 M.

H 0.2  1018 collision sec

15. For a radioactive decay reaction

2. Ap, r; Br, Cr, s; Dp, r

\ Total possible waters = 6 +6 = 12

\ Total possible waters = 6 +6 = 12

AB2 ( aq) 1st order

ONE OR MORE THAN ONE

K1Ea1 + K 2Ea2 x1y1 + x 2 y 2

(B) for first order kinetics, l is independent of temperature

Qualitatively, we can say that the moment Y is formed

All radioactive reactions re temperature independent

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3. For the reactions: Reaction-I A �� B and Reaction:II

Step 1: Cl2 ( g) ��2Cl ( g)