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CHAPTER-3-CHEMICAL KINETICS

CHEMICAL KINETICS

CHAPTER – 3 – CHEMICAL KINETICS


ASSIGNMENT for IIT – JEE (MAINS & ADVANCE)

2020 – 2021
Electrochemistry

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CHAPTER-3-CHEMICAL KINETICS

Chemical Kinetics

Contents
Topic Page No.

Exercise - 1 03 - 20

Exercise - 2 21 - 29

Exercise - 3 30 - 34

Answer Key 35 - 36

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

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PART - I : OBJECTIVE QUESTIONS


*Marked Questions are having more than one correct option.
Section (A) : Rate of Reaction
A-1. For a hypothetical reaction A  L, the rate expression is -
dC A
rate = –
dt
(A) Negative sign represent that rate is negative
(B) Negative sign indicates to the decrease in the concentrations of reactant
(C) Negative sign indicates the attractive forces between reactants
(D) None of the above is correct

d[ A ] d[B] d[C]
A-2. xA + yB  zC. If  =  = 1.5 = then x,y and z are :
dt dt dt
(A) 1,1, 1 (B) 3, 2, 3 (C) 3, 3, 2 (D) 2, 2, 3

A-3. In the following reaction : xA  yB

 d[ A ]   d[B] 
log  dt  = log  dt  + 0.3
   
where –ve sign indicates rate of disappearance of the reactant. Thus, x : y is :
(A) 1 : 2 (B) 2 : 1 (C) 3 : 1 (D) 3 : 10

A-4. In the formation of sulphur trioxide by the contact process,


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

A-5. Rate of formation of SO3 in the following reaction 2SO2 + O2  2SO3 is 100 g min–1. Hence rate of disappearance
of O2 is :
(A) 50 g min-1 (B) 40 g min–1 (C) 200 g min–1 (D) 20 g min–1

A-6. A reaction follows the given concentration (M)–time graph. The rate for this reaction at 20 seconds will be:

0.5
0.4
0.3
0.2
0.1

0 20 40 60 80 100
Time/second

(A) 4 × 10–3 M s–1 (B) 8 × 10–2 M s–1 (C) 2 × 10–2 M s–1 (D) 7 × 10–3 M s–1

A-7. For the reaction : N2 + 3H2  2NH3. If the rate of disappearance of hydrogen is 1.8 × 103. What is the
rate of formation of ammonia. (mole per litre per sec.)
(A) 1.8 × 103 (B) 1.2 × 103 (C) 2.7 × 103 (D) 0.9 × 103

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A-8. The rate of a reaction is expressed in different ways as follows ;


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

(C) 4A + 2B  2C + 3D (D) B + (1/2) D  4A + 3

A-9. ln the reaction; A + 2B  3C + D, which of the following expression does not describe changes in the
concentration of various species as a function of time :
(A) {d [C] / dt} = – {3d [A] / dt} (B) {3d [D] / dt} = {d [C] / dt}
(C) {3d [B] / dt} = – {2d [C] / dt} (D) {2d [B] / dt} = {d [A] / dt}

A-10. For a chemical reaction 2X + Y  Z, the rate of appearance of Z is 0.05 mol L–1 per min. The rate of
disappearance of X will be -
(A) 0.05 mol L—1 per hour (B) 0.05 mol L—1 per min
(C) 0.1 mol L —1 per min (D) 0.25 mol L—1 per min

Section (B) : Rate Law

B-1. What is the order of a reaction whose


rate = KCA3/2 CB–1/2 ?
(A) 2 (B)1 (C)– 1/2 (D) 3/2

dA
B-2. The rate of certain hypothetical reaction A + B + C  products, is given, by r = – = K [A]½ [B]1/3
dt
[C]1/4. The order of reaction is given by :
(A) 1 (B) 1/2 (C) 2 (D) 13/12

B-3. The rate constant of nth order has units :


(A) Litre1–n mol1-n sec–1 (B) Mol1–n litre1-n sec
2 2
(C) Mol1 n litre n sec–1 (D) Mole1–n litren-1 sec–1

B-4. The rate constant of reaction changes when :


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

B-5. For which of the following, the units of rate constant and rate of the reaction are same -
(A) First order reaction (B) Second order reaction
(C) Third order reaction (D) Zero order reaction

B-6. For a chemical reaction, 2A + 2B  C + D, the order of reaction is one with respect to A and one with
respect to B. The initial rate of the reaction is 4 × 10–2 mol L–1 s–1. When 50% of the reactants are converted
into products, the rate of the reaction would become-
(A) 2 × 10–2 mol L–1s–1 (B) 1 × 10–2 mol L–1s–1
(C) 4 × 10 mol L s
–2 –1 –1 (D) 2 × 10–1 mol L–1 s–1

B-7. For a gaseous reaction the rate equation is v = k[A][B]. If the volume of the gaseous system is suddenly
reduced to 1/3 of initial volume. The rate would become –
(A) 1/9 times (B) 9 times (C) 1/6 times (D) 6 times

B-8. aA + bB  Product, dx/dt = k [A]a [B]b . If concentration of A is doubled, rate is four times. If concentration
of B is made four times, rate is doubled. What is relation between rate of disappearance of A and that of B ?
(A) – {d [A] / dt} = – {d [B] / dt} (B) – {d [A] / dt} = – {4 d [B] / dt}
(C) – {4 d [A] / dt} = – {d [B]/ dt} (D) None of these

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B-9. For the reaction, 2NO(g) + 2H2(g)  N2(g) + 2H2O(g) the rate expression can be written in the following
ways :
{d [N2] / dt} = k1 [NO][H2] ; {d[H2O] / dt} = k[NO][H2] ; {– d[NO] / dt} = k1 [NO] [H2] ; {–d[H2] / dt} = k1 [NO][H2]
The relationship between k, k1 , k1 and k1. is :
(A) k = k1 = k1 = k1 (B) k = 2k1 = k1 = k1
(C) k = 2k1 = k1 = k1 (D) k = k1 = k1 = 2 k1

B-10. For rate constant is numerically the same for three reactions of first, second and third order respectively.
Which of the following is correct :
(A) if [A] = 1 then r1 = r2 = r3 (B) if [A] < 1 then r1 > r2 > r3
(C) if [A] > 1 then r3 > r2 > r1 (D) All

B-11. In acidic medium the rate of reaction between (BrO3)¯ and Br¯ ions is given by the expression.
– [d (BrO3–) /dt] = K [BrO3– ] [Br¯] [H+]2 It means :
(A) Rate constant of overall reaction is 4 sec–1
(B) Rate of reaction is independent of the concentration of acid
(C) The changes in pH of the solution will not affect the rate
(D) Doubling the concentration of H+ ions will increase the reaction rate by 4 times.

B-12. For the irreversible process, A + B  products, the rate is first–order w.r.t. A and second–order w.r.t. B. If 1.0
mol each of A and B introduced into a 1.0 L vessel, and the initial rate was 1.0 × 10–2 mol L–1 s–1 , rate when half
reactants have been turned into products is :
(A) 1.25 × 10–3 mol L–1 s–1 (B) 1.0 × 10–2 mol L–1 s–1
(C) 2.50 × 10–3 mol L–1 s–1 (D) 2.0 × 10–2 mol L–1 s–1

Section (C) : The integrated rate laws


C-1. A first order reaction follows the expressions
k 1t C0 Ct
(A) Cte = C0 (B) Ct = C0 e k 1t (C) ln = –k 1t (D) ln = k 1t
Ct C0

C-2. Which of following statement is false


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

C-3. Half life period of a zero order reaction is –


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

C-4. Wrong data for the first order reaction is –


(A) t0.5 =100s, t0.75 = 200s (B) t0.75 = 32 min t0.5 = 16min
(C) Both the above (D) t0.5 = 100s, t0.75 = 150s

C-5. What is the half life of a radioactive substance if 75% of any given amount of the substance disintegrates
in 60 minutes –
(A) 2 Hours (B) 30 Minutes (C) 45 Minutes (D) 20 Minutes

C-6. For an elementary reaction X (g)  Y (g) + Z (g) the half life periods is 10 min. In what period of time
would the concentration of X be reduced to 10% of original concentration -
(A) 20 Min. (B) 33 Min (C) 15 Min (D) 25 Min

C-7. 99% of a first order reaction was completed in 32 min. When will 99.9% of the reaction complete –
(A) 50 Min (B) 46 Min (C) 49 Min (D) 48 Min

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C-8. In the presence of an acid, the initial concentration of cane sugar was reduced from 0.20 to 0.10 molar
in 5 hours and from 0.2 to 0.05 molar in 10 hours. The reaction is of –
(A) Zero order (B) First order (C) Second order (D) Third order

C-9. For a second order reaction, if the conc. of a reactant decreases from 0.08M to 0.04M in ten minutes,
what would be the time taken for the conc. to decreases to 0.01M –
(A) 20 minutes (B) 30 minutes (C) 50 minutes (D) 70 minutes

C-10. The rate constant for a second order reaction 8.0 × 10–4 litre mol–1min–1. How long will it take a 0.5M
solution to be reduced to 0.25M in reactant –
(A) 8.665 × 102 min (B) 8.0 × 10–4 min (C) 2.50 × 103 min (D) 4.0 × 10–4 min

C-11. A radioactive isotope decomposes according to the first order with half life period of 15 hrs. 80% of the
sample will decompose in -
(A) 15 × 0.8 hr. (B) 15 × (log 8) hr.
(C) 15 × (log5 / log2) hr. (or 34.83) hr. (D) 15 × 10/ 8 hr.

C-12. Radioactive decay follows -


(A) Zero order kinetics (B) Second order kinetics
(C) First order kinetics (D) Pseudo first order kinetics

C-13. The t0.5 for the first order reaction,


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

C-14. The rate constant of reaction 2 A + B  C is 2.57 × 10–5 It mole–1 sec–1 after 10 sec. 2.65 × 10–5 It.
mole–1 sec–1 after 20 sec. and 2.55 × 10–5 It. mole–1 sec–1 after 30 sec. The order of the reaction is:
(A) 0 (B) 1 (C) 2 (D) 3

C-15. For a first order reaction, the plot of log C against ‘t’ (logC vs 't') gives a straight tine with slope equal to :
(A) (k / 2.303) (B) (– k / 2.303) (C) (ln k / 2.303) (D) – k.

C-16. In a certain reaction, 10% of the reactant decomposes in one hour, 20 % in two hours, 30% in three hours and
so on the dimensions of the rate constant is :
(A) hour–1 (B) mole litre–1 sec–1 (C) litre mole–1 sec–1 (D) mole sec–1

C-17. In presence of HCl, sucrose gets hydrolysed into glucose and fructose. The concentration of sucrose was found
to reduce from 0.4 M to 0.2 M in 1 hour and to 0.1 M in total of 2 hours. The order of the reaction is :
(A) zero (B) one (C) two (D) None of these

C-18. In a first order reaction the reacting substance has half-life period of ten minutes. What fraction of the substance
will be left after an hour the reaction has occurred ?
(A) 1/6 of initial concentration (B) 1/64 of initial concentration
(C) 1/12 of initial concentration (D) 1/32 of initial concentration

K1 K2
C-19. In the following first order reactions (A) 
 Product, (B)  Product, the ratio k1 /k2 if 90% of (A) has
been reacted in time 't' while 99% of(B) has been reacted in time 2t is :
(A) 1 (B) 2 (C) 1/2 (D) None of these

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

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C-21. If a I-order reaction is completed to the extent of 60% and 20% in time intervals, t1 and t2, what is the ratio,
t1 : t2 ?
(A) 6.32 (B) 5.58 (C) 4.11 (D) 8.33

C-22. For a reaction A  Products, the concentration of reactant are C0 , aC0 , a2C0, a3C0 ........... after time interval
0, t, 2t ........where 'a' is constant. Then :
(A) reaction is of 1st order and K = (1/1) ln a (B) reaction is of 2nd order and K = (1/tC0)(1–a)/a
1  1 1  1
(C) reaction is of 1st order and K = ln  a  (D) reaction is of zero order and K = ln  
t   t a

C-23. The rate constant for the reaction A  B is 2 × 10–4 It. mol–1 min–1. The concentration of A at which rate of the
reaction is (1/12) × 10–5 M sec–1 is :
(A) 0.25 M (B) (1/20) 5 / 3 M (C) 0.5 M (D) None of these

C-24. Graph between concentration of the product and time of the reaction A  B is of the type Hence graph

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


(–d[A]/dt)
(A) (B) (C) (D)
Time

C-25. A graph plotted between log t50% vs. log concentration is a straight line. What conclusion can you draw from this
graph.

(A) n = 1 ; t1/2  a (B) n = 2, t1/2  1/a


(C) n = 1 ; t1/2 = (0.693 / k) (D) None of these

C-26. What will be the order of reaction and rate constant for a chemical change having log t50% vs log concentration
of (A) curves as :
(A) 0, 1/2 (B) 1, 1 (C) 2, 2 (D) 3, 1

C-27. A drop of solution (volume 0.05 mL) contains 3.0 × 10–6 moles of H+. If the rate constant of disappearance of H+
is 1.0 × 107 mole litre–1 sec–1. How long would it take for H+ in drop to disappear :
(A) 6 × 10–8 sec (B) 6 × 10–7 sec (C) 6 × 10–9 sec (D) 6 × 10–10 sec

Section (D) : Methods to determine The rate law


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

D-2. The data for the reaction A + B  C is


Exp. [A]0 [B]0 initial rate
1 0.012 0.035 0.10
2 0.024 0.035 0.80
3 0.012 0.070 0.10
4 0.024 0.070 0.80
(A) r = k [B]3 (B) r = k [A]3 (C) r = k [A] [B]4 (D) r = k [A]2 [B]2 .

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dx
D-3. A + B  Product, =k [A]a [B]b
dt
 dx 
If   = k, then order is :
 dt 
(A) 4 (B) 2 (C) 1 (D) 0

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

D-5. In the reaction : A + 2B + C  D + 2E


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

D-6. The following data pertain to reaction between A and B :


S.No. [A] [B] Rate
mol.l–1 mol.l–1 mol.l–1sec–1
I 1 × 10–2 2 × 10–2 2 × 10–4
II 2 × 10–2 2 × 10–2 4 × 10–4
III 2 × 10–2 4 × 10–2 8 × 10–4
Which of the following inference(s) can be drawn from the above data –
(a) Rate constant of the reaction 10–4
(b) Rate law of the reaction is k[A][B]
(c) Rate of reaction increases four times on doubling the concentration of both the reactant,
Select the correct answer –
codes :–
(A) a,b and c (B) a and b (C) b and c (D) c alone

D-7. Using the data given below the order and rate constant for the reaction : CH3CHO(g)  CH4(g) + CO(g) would
be –
Experiment no. Initial conc. Initial rate
[mol/] [mol.lit–1sec 1]
I 0.10 0.020
II 0.20 0.080
III 0.30 0.180
IV 0.40 0.320
Answer is –
(A) 2,[k = 2.0 /mol sec] (B) 0,[k = 2.0 mol/ sec]
(C) 2,[k = 1.5 /mol sec] (D) 1,[k = 1.5 sec–1]

D-8. For the reaction 2A + 3B  products, A is in excess and on changing the concentration of B from 0.1 M to
0.4 M, rate becomes doubled, Thus, rate law is :
dx dx dx dx
(A) = k[A]2 [B]2 (B) = k[A] [B] (C) = k[A]0 [B]2 (D) = k[B]1/2
dt dt dt dt

d [A]
D-9. For the reaction A  Products, – = k and at different time interval, [A] values are :
dt

Time 0 5 min 10 min 15 min


[A] 20 mol 18 mol 16 mol 14 mol
At 20 minute, rate will be :
(A) 12 mol /min (B) 10 mol/min (C) 8 mol/min (D) 0.4 mol/min

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 dx  dx 
D-10. A  Product and   = k[A]2 . If log   is plotted against log [A], then graph is of the type :
 dt   dt 

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

D-11. If a is the initial concentration of reaction, then the half life period of a reaction of nth order is directly
propotional to -
(A) an (B) an–1 (C) a1–n (D) an+1

D-12. The half-life period for a reaction at initial concentrations of 0.5 and 1.0 moles litre-1 are 200 sec and 100
sec respectively. The order of the reaction is -
(A) 0 (B) 1 (C) 2 (D) 3

D-13. Consider a reaction A   B + C. If the initial concentraton of A was reduced from
4 M to 2 M in 1 hour and from 2 M to 1 M in 0.5 hour, the order of the reaction is-
(A) One (B) Zero (C) Two (D) Three

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

E-1. Consider the reaction 2A(g)  3B(g) + C(g). Starting with pure A initially, the total pressure doubled in 3 hrs.
The order of the reaction might possibly be
(A) zero (B) first (C) second (D) unpredictable from this data

E-2. Formation of NO2F from NO2 and F2 as per the reaction 2NO2(g) + F2(g)  2NO2F(g) is a second order
reaction, first order with respect to NO2 and first order with respect to F2. If NO2 and F2 are present in a closed
vessel in ratio 2 :1 maintained at a constant temperature with an initial total pressure of 3 atm, what will be the
total pressure in the vessel after the reaction is complete?
(A) 1atm (B) 2 atm (C) 2.5 atm (D) 3 atm

E-3. In a gaseous state reaction, A2 (g)  B(g) + (1/2)C (g), The increase in pressure from 100 mm to 120 mm
is notices in 5 minutes. The rate of disapearance of A2 in mm min–1 is :
(A) 4 (B) 8 (C) 16 (D) 2

E-4. The decomposition of a gaseous substance (A) to yield gaseous products (B), (C) follows First order kinetics.
If initially only (A) is present and 10 minutes after the start of the reaction the pressure of (A) is 200 mm Hg and
that of over all mixture is 300 mm Hg, then the rate constant for 2A  B + 3 C is :
(A) (1/1200) ln 1.25 sec–1 (B) (2.303 /10) log 1.5 min–1
(C) (1/10) ln 1.25 sec –1 (D) None of these

E-5. In the reaction NH4NO2 (aq.)  N2 (g) + 2 H2O (l) the volume of N2 after 20 min and after a long time is 40 ml and
70 ml respectively. The value of rate constant is :
(A) (1/20) In (7/4) min–1 (B) (2.303 /1200) log (7/3) sec–1
(C) (1/20) log (7/3) min–1 (D) (2.303 / 20) log (11/7) min–1

E-6.  / Cu
–N2Cl  –Cl + N2 Half-life is independent of concentration of reactant. After 10 minutes
 
volume of N2 gas is 10 L and after complete reaction it is 50 L. Hence rate constant is:
(A) (2.303 /10) log 5 min–1 (B) (2.303 /10) log 1.25 min–1
(C) (2.303 /10) log 2 min–1 (D) (2.303 /10) log 4 min–1

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Section(F) : Effect of Temperature


F-1. The activation energies of the forward and backward reactions in the case of a chemical reaction are 30.5
and 45.4 KJ/mol respectively. The reaction is –
(A) Exothermic (B) Endothermic
(C) Neither exothermic nor endothermic (D) Independent of temperature

F-2. Chemical reaction occurs as a result of collisions between reacting molecules. Therefore, the reaction rate
is given by -
(A) Total number of collisions occurring in a unit volume per second
(B) Fraction of molecules which possess energy less than the threshold energy
(C) Total number of effective collisions
(D) None of the above
F-3. The chemical reactions in which reactants require high amount of activation energy are generally -
(A) Slow (B) Fast (C) Instantaneous (D) Spontaneous

F-4. For a reaction for whi ch the activation energies of forward and reverse reactions are equal -
(A) H = 0 (B) S = 0 (C) The order is zero (D) There is no catalyst

F-5. The activation energy of reaction is equal to-


(A) Threshold energy for the reaction
(B) Threshold energy + Energy of the reactants
(C) Threshold energy – Energy of the reactants
(D) Threshold energy + Energy of the products
F-6. Which of the following explains the increase of the reaction rate by catalyst -
(A) Catalyst decreases the rate of backward reaction so that the rate of forward reaction increases
(B) Catalyst provides extra energy to reacting molecules so that they may reduce effective collisions
(C) Catalyst provides an alternative path of lower activation energy to the reactants
(D) Catalyst increases the number of collisions between the reacting molecules.

F-7. The activation energy of the reaction


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

F-8. Rate of which reactions increases with temperature :


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

F-9. For a zero order reaction. Which of the following statement is false :
(A) the rate is independent of the temperature of the reaction.
(B) the rate is independent of the concentration of the reactants.
(C) the half life depends upon the concentration of the reactants.
(D) the rate constant has the unit mole It–1 sec–1.

F-10. A large increase in the rate of a reaction for a rise in temperature is due to
(A) increase in the number of collisions (B) the increase in the number of activated molecules
(C) The shortening of mean free path (D) the lowering of activation energy

F-11. The first order rate constant k is related to temp. as log k = 15.0 – (106 /T) Which of the following pair of value is
correct ?
(A) A = 1015 and E = 1.9 × 104 KJ (B) A = 10–15 and E = 40 KJ
(C) A = 1015 and E = 40 KJ (D) A = 10–15 and E = 1.9 × 104 KJ.

F-12. The decomposition of N2O into N2 & O2 in presence of gaseous argon follow second order kinetics with
41570 K

k = (5.0 × 1011 L mol1 s1) e T (K stands for Kelvin units). The energy of activation of the reaction is :

(A) 5.0 x 1011 J (B) 41570 J (C) 5000 J (D) 345612.98 J

Page 10 of 36
CHAPTER-3-CHEMICAL KINETICS

F-13. How much faster would a reaction proceed at 25°C than at 0°C if the activation energy is 65 kJ?
(A) 2 times (B) 5 times (C) 11 times (D) 16 times

F-14. The rate constant, the activation energy and the frequency factor of a chemical reaction at 25°C are
3.0 × 10–4 s–1, 104.4 KJ mol–1 and 6.0 × 1014 s–1 respectively. The value of the rate constant as T   is :
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1 (C) infinite (D) 3.6 × 1030 s–1

F-15. For a given reaction, energy of activation for forward reaction (Eaf) is 80kJ.mol1. H = 40kJ.mol1 for the
reaction. A catalyst lowers Eaf to 20 kJ.mol1. The ratio of energy of activation for reverse reaction before and
after addition of catalyst is :
(A) 1.0 (B) 0.5 (C) 1.2 (D)2.0

Section (G) : Mechanism of reactions


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

dc
G-2. For the reaction NO2 + CO  CO2 + NO the experimental rate expression is – = k[NO2]2 the number of
dt
molecules of CO involves in the slowest step will be -
(A) 1 (B) 2 (C) 3 (D) depends on mechanism

G-3. The reaction of hydrogen, and iodine monochloride is represented by the equation :
H2(g) + 2Cl(g) 2HCl(g) + 2(g)
This reaction is first–order in H2(g) and also first–order in Cl(g). Which of these proposed mechanism
can be consistent with the given information about this reaction ?
Mechanism  : H2(g) + 2Cl(g) 2HCl(g) + 2(g)
Slow
Mechanism  : H2(g) + Cl(g)   HCl(g) + H(g)
fast
HI(g) + Cl(g)   HCl(g) + I2(g)
(A)  only (B)  only (C) both  and  (D) neither  nor 

G-4. The reaction, X + 2Y + Z  N occurs by the following mechanism


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

G-5. In the Lindemann theory of unimolecular reactions, it is shown that the apparent rate constant for such a
k1C
reaction is kapp = where C is the concentration of the reactant k1 and  are constants. Calculate the
1  C
value of C for which kapp has 90% of its limiting value at C tending to infinitely large values, given  = 9 x 105.
(A) 106 mole/litre (B) 104 mol/litre (C) 105 mole/litre (D) 5 x 105 mol/litre

G-6. Trimolecular reactions are uncommon because


(A) the probability of three molecules colliding at an instant is very low.
(B) the probability of three molecules colliding at an instant is high.
(C) the probability of three molecules colliding at an instant is zero.
(D) the probability of many molecules colliding at an instant is high.

G-7. Select the correct statements :


(A) the molecularity of an elementary reaction indicates how many reactant molecules take part in the step.
(B) the rate law of an elementary reaction can be predicted by simply seeing the stoichiometry of reaction.
(C) the slowest elementary step in sequence of the reactions governs the overall rate of formation of product.
(D) a rate law is often derived from a proposed mechanism by imposing the steady state approximation or
assuming that there is a pre-equilibrium.

Page 11 of 36
CHAPTER-3-CHEMICAL KINETICS

Section (H) : Complications in first order reactions


 dx 
H-1. For an elementary reaction, net rate is  dt  = k[A]2 – k'[C] [B]2 then, select the correct statement :
 

2
d[ A ]2 d [B] d[C]
(A) – = = is the relation among (B) 2A 2B + C is the required reaction
dt dt dt

(C) both are correct (D) none is correct

H-2. Consider the elementary reaction sequence shown in figure. Which of the following
equations are correct ?

d[A] d [ C]
(A) = k1[A] + k4[D] (B) = k2[B]  k3[C]
dt dt

d [D]
(C) = k4[D] + k3[D] (D) Nothing can be said about order of reactions in this problem
dt

H-3. For an elementary reaction of reversible nature, net rate is :

 dx 
  = k [A]2 [B]1 – k [C], hence, given reaction is :
 dt  1 2

1
(A) 2A + C (B) 2A + B C (C) 2A C + B–1 (D) None of these
B

H-4. At a given temperature, k1 = k2 for the reaction


A+B C+D

 dx 
If  dt  = k1 [A] [B] – k2[C] [D] in which set of the concentration reaction ceases?
 

[A] [B] [C] [D] [A] [B] [C] [D]


(A) 0.1 M 0.2 M 0.3 M 0.4 M (B) 0.4 M 0.25 M 0.2 M 0.5 M
(C) 0.2 M 0.2 M 0.3 M 0.2 M (D) 0.2 M 0.2 M 0.4 M 0.2 M

H-5. The substance undergoes first order decomposition. The decomposition follows two parallel first order reactions
as :

K1 = 1.26 × 10–4 sec–1 and K2 = 3.8 × 10–5 sec–1

The percentage distribution of B and C


(A) 80% B and 20% C (B) 76.83% B and 23.17%C
(C) 90% B and 10% C (D) 60% B and 40% C

H-6. The rate constant for two parallel reactions were found reactions were found to be 1.0 × 10–2dm3 mol-1 s–1 and
3.0 × 10–2 dm3 mol–1 s–1. If the corresponding energies of activation of the parallel reactions are 60.0 kJ mol–1
and 70.0 kJ mol–1 respectively, what is the apparent overall energy of activation ?
(A) 130.0 kJ mol–1 (B) 67.5 kJ mol–1 (C) 100.0 kJ mol–1 (D) 65.0 kJ mol–1

Page 12 of 36
CHAPTER-3-CHEMICAL KINETICS

PART - II : MISCELLANEOUS QUESTIONS

COMPREHENSION
Comprehension # 1

A(g)  2B(g) + C(g)


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

1. At t = t1 pressure of gas B is :
(A) 2.5 bar (B) 1.25 bar (C) 5.0 bar (D) data is insufficient

2. Rate constant (k) = (log 64 – log 49) s–1. Value of t1 in seconds is :


(A) 2.15 s (B) 1.5 s (C) 2.3 s (D) 1.15 s

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


(A) 2 : 3 : 4 (B) 1 : 1 : 1 (C) 1 : 3 : 5 (D) 1 : 3 : 5

Comprehension # 2

4. For the (Set-1) :


(A) if T1 > T2, k1 > k2 always (B) if T1 > T2, k1 > k2 (for exothermic reaction)
(C) if T1 > T2, k1 < k2 (for endothermic reaction) (D) Ea1  Ea2

5. For the (Set-1) :


(A) Ea1 > Ea2 if T1 > T2 (B) Ea1 < Ea2 if T1 > T2
(C) Ea1 = Ea2 (D) Ea1 = 0.5 Ea2

6. Comparing set-I and II :


(A) k4 > k3 & k2 > k1 , if T2 > T1 (endothermic) (B) k4 < k3 & k2 > k1 , if T2 < T1 (endothermic)
(C) k4 > k3 & k2 > k1 , if T2 < T1 (exothermic) (D) k4 < k3 & k2 < k1, if T2 > T1 (exothermic)

Page 13 of 36
CHAPTER-3-CHEMICAL KINETICS

Comprehension # 3
A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Let us consider a
reaction
A(g)  B(g) + C(g)
At t = 0 a 0 0
At time t a–x x x
dx
The rate of reaction is given by the expression = k(a – x) and integrated rate equation for a given reaction is
dt

1  a 
represented as k = ln   where a = initial concentration and (a – x) = concentration of A after time t.
t ax

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

8. Consider a reaction A(g)  3B(g) + 2C(g) with rate constant 1.386 × 10–2 min–1. Starting with
2 moles of A in 12.5 litre vessel initially, if reaction is allowed to takes place at constant pressure & at 298K then
find the concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these

Comprehension # 4
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example, toluene can be
nitrated at the ortho, meta, or para positions, We shall consider the simplest case, that of two competing
irreversible first-order reactions :
k k2 D
A 1  C and A  
where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
 d[A] 
  = – k1[A] – k2[A] = – (k1 + k2) [A]  [A] = [A]0 e (k1 k 2 )t .
 dt 

 d [C] 
For C, we have   = k1[A] = k1[A]0 e (k1 k 2 )t . Multiplication by dt and integration from time 0
 dt 
k [A] ( k  k ) t
(where [C]0 = 0) to an arbitary time t gives [C] = 1 0 (1  e 1 2 )
k1  k 2

 d [D]  k 2 [ A ]0
Similarly, integration of   gives [D] = (1 – e (k 1  k 2 )t )
 dt  k1  k 2
The sum of the rate constants k1 + k2 appears in the exponentials for both [C] and [D].
[C] k1
At any time we also have = k
[D] 2

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

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

Page 14 of 36
CHAPTER-3-CHEMICAL KINETICS

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

1
(A) Independent of time (B)
(e kt  1)
(C) Depends upon initial concentration of X (D) [A]0 (ekt –1)

11. At high temperature acetic acid decomposes into CO2 & CH4 and simultaneously into CH2CO (ketene) and H2O
1 1
(i) CH3COOH   CH4 + CO2
k1 3s (ii) CH3COOH   CH2CO + H2O
k 2  4s

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


3 3 4
(A) (B) (C) (D) none of these
4 7 7

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

(A) Independent of time (B) Independent of temperature


(C) Depends upon initial concentration of A (D) Independent of mechanism of reaction

Comprehension # 5

For the given sequential reaction


1 k 2 k
A  B  C
the concentration of A, B & C at any time 't' is given by
k1[ A ]0
[A]t = [A]0 e  k1t ; [B]t = e  k1t  e  k 2 t
 
( k 2  k1 )
[C]t = [A0] – ( [A]t + [B]t )

13. The time at which concentration of B is maximum is


k1 1 k 1 k k2
(A) (B) ln 1 (C) ln 1 (D)
k 2  k1 k 2  k1 k 2 k1  k 2 k 2 k 2  k1

14. Select the correct option if k1 = 1000 s–1 and k2 = 20 s–1.

[C]t
[C]t
conc.

Conc.

(A) (B)
[B]t
[A]t
[B] t [A]t
time
time

[C]t [C]t
Conc.

Conc.

(C) (D)
[B]t

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

time time

Page 15 of 36
CHAPTER-3-CHEMICAL KINETICS

MATCH THE COLUMN


15. The polarimeter readings in an experiment to measure the rate of inversion of cane suger (1st order reaction)
were as follows
time (min) : 0 30 
angle (degree) : 30 20 – 15
Then match the following. (Use : log 35 = 1.54, log 3 = 0.48, log 2 = 0.3)

Column - I Column - II

(A) The half life of the reaction (p) 120 min.


(B) The solution is optically inactive at (q) 7.5°
(C) The equimolar mixture of the products (r) 75.2 min.
(D) The angle at half time (s) laevorotatory

16. Match the following :


Column - I Column - II

(A) A + B  C + D (p) Unit of rate constant possess concentration


r = k1 [A] [B] unit

(B) A + B  C + D (q) Rate constant for the reaction of both


r = k2 [A] [B]º the reactants are equal

(C) A + B  C + D (r) Rate of consumption of at least one of the


r = k3 [A]º [B]º reactants is equal to rate of production of at
least one of the products
(D) 2A + B  2C + 3D (s) If both reactants are taken in stoichiometric
r = k3 [A]º [B]º ratio, half life for both reactants are equal

17. For the reaction of type A(g)  2B(g)


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

d[ B]  d[A ]
(A) vs for first order (p)
dt dt

(B) [A] vs t for first order (q)

(C) [B] vs t for first order (r)

(D) [A] vs t for zero order (s)

Page 16 of 36
CHAPTER-3-CHEMICAL KINETICS

18. Match the following :


Column-I Column-II
(A) If the activation energy is 65 kJ then how much time (p) 2
faster a reaction proceed at 25°C than at 0°C

(B) Rate constant of a first - order reaction is 0.0693 min–1. (q) Zero
If we start with 20 mol L–1, it is reduced to 2.5 mol L–1
in how many minutes

(C) Half - lives of first - order and zero order reactions (r) 11
are same. Ratio of rates at the start of reaction is
how many times of 0.693 Assume initial concentration to
be same for the both.

(D) The half-life periods are given , (s) 30


[A]0 (M) 0.0677 0.136 0.272
t1/2 (sec) 240 480 960
order of the reaction is

ASSERTION / REASON
Directions :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
19. Statement-1 : A fractional order reaction must be a complex reaction.
Statement-2 : Fractional order of RDS equals to overall order of a complex reaction.

20. Statement-1 : The time of completion of reactions of type A  product (order <1) may be determined.
Statement-2 : Reactions with order  1 are either too slow or too fast and hence the time of completion can
not be determined.

21. Statement-1 : Temperature coefficient of an one step reaction may be negative.


Statement-2 : The rate of reaction having negative order with respect to a reactant decreases with the
increase in concentration of the reactant.

22. Statement-1 : The overall rate of a reversible reaction may decrease with the increase in temperature.
Statement-2 : When the activation energy of forward reaction is less than that of backward reaction, then the
increase in the rate of backward reaction is more than that of forward reaction on increasing
the temperature.

23. Statement-1 : In a reversible endothermic reaction, Eact of forward reaction is higher than that of backward
reaction
Statement-2 : The threshold energy of forward reaction is more than that of backward reaction

24. Statement-1 : A catalyst provides an alternative path to the reaction in which conversion ofreactants into
products takes place quickly
Statement-2 : The catalyst forms an activated complex of lower potential energy, with thereactants by which
more number of molecules are able to cross the barrier per unit of time.

Page 17 of 36
CHAPTER-3-CHEMICAL KINETICS

25. Statement-1 : In the reaction, 2 + 2S2O32–  S4O62– + 2– , the rate of disappearance of thiosulphate ions is
twice the rate of disappearance of 2.
Statement-2 : The rate of disappearance of 2 is twice the rate of disappearance of S2O32– ions.

26. Statement-1 : For A + 2B  C (rate= K[A]1[B]0), the half life time of reaction is only defined when conc.
of A and B are in stoichiometric ratio
Statement-2 : For above given order half life of reaction is directly proportional to conc. of A and not to conc.
of B due to its zero order.

27. Statement-1 : Many reactions occurring on solid surface are zero order reactions.
Au
Statement-2  N2 (g)  1/ 2O 2 ; rate = k[N2O]0 = k = constant is a zero order reaction.
: N2 O(g) 

28. Statement-1 : Half life of a certain radioactive element is 100 days. After 200 days, fraction left undecaye
will be 25%.
n
Ct  1 
Statement-2 :    , where symbols have standard meaning.
C0  2 

29. Statement-1 : Time taken for the completion of 75% of a st order reaction is double than its t½.
Statement-2 : Time taken for completion of any fraction of a st order reaction is a constant value.

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

TRUE / FALSE

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

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

33. If t1/2 for a first order reaction is 6.93 s, the value of rate constant for the reaction would be 10s–1.

34. Molecularity of a reaction is always whole number.

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

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

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

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

39. Partial orders are never negative.

40. Order of reaction may be change with change in practical conditions

41. The rate of reaction is uniform in zero order reaction.

Page 18 of 36
CHAPTER-3-CHEMICAL KINETICS

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

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

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

45. Molecularity defined only for RDS.

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

47. Activated complex is an intermediate product.

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

49. All collisions between reactants yield the desired product.

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

 d[A] 
51. The rate of the reaction A  B having the rate law   dt  k [ A ] [B]  when plotted against time will exhibit a
 

maximum at some time.

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

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

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

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

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

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

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

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

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

Page 19 of 36
CHAPTER-3-CHEMICAL KINETICS

FILL IN THE BLANKS


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

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

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

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

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

66. The reactions with molecularity more than three are _________.

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

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

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

70. Rate constant of a reaction __________ with increase in temperature.

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

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

73. The value of temperature coefficient is generally between _________.

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

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

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

77. [Eactivated complex – Ereactants] = ____________.

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

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

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

81. A catalyst is chemically ____________ at the end of a reaction

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

Page 20 of 36
CHAPTER-3-CHEMICAL KINETICS

PART - I : MIXED OBJECTIVE

Single Choice Type


1. Consider the reaction :
A  B + C
Initial concentration of A is 1 M. 20 minutes time is required for completion of 20 % reaction.
d[ B]
If = k[A], then half life (t1/2 ) is
dt
(A) 55.44 min. (B) 50 min (C) 62.13 min (D) None of these

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

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

3. For the first order decomposition of SO2Cl2(g),


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

-1–

-2–

-3–

(A) 0.2 (B) 4.6 × 10–1 (C) 7.7 × 10–3 (D) 1.15 × 10–2

4. The rate constant for the forward reaction A (g) + 2B(g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of A and 100
moles of B are present in a 10 litre vessel at equilibrium then rate constant for the backward reaction at this
temperature is :
(A) 1.50× 104 L mol–1 s–1 (B) 1.5 × 1011 L mol–1 s–1
10
(C) 1.5 × 10 L mol s–1 –1 (D) 1.5 × 10–11L mol–1 s–1
1 1

5. Reaction A + B  C + D follows following rate law : rate = k [A] 2 [ B] 2 . Starting with initial conc. of 1 M of

A and B each, what is the time taken for concentration of A of become 0.25 M.
Given : k = 2.303 × 10–3 sec–1.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) 1200 sec.

6. The reaction A (g)  B(g) + 2C (g) is a first order reaction with rate constant 3465 × 10–6 s–1. Starting with
0.1 mole of A in 2 litre vessel, find the concentration of A after 200 sec., when the reaction is allowed to take
place at constant pressure and temperature.
(A) 0.05 M (B) 0.025 M (C) 0.0125 M (D) None of these

Page 21 of 36
CHAPTER-3-CHEMICAL KINETICS

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

Concentration(M) 
1.5

1.2
1
0.8 Experiment-1
Experiment-2
0.6
5 10 15 20
time(min.) 

(A) 0.08 M min–1 (B) 0.036 M min–1 (C) 0.13 M min–1 (D) 1 M min–1

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

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


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

10. The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are
3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 1014s–1 respectively. The value of the rate constant at T   is
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1 (C) infinity (D) 3.6 × 1030 s–1

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

12. For the first order reaction A — B + C, carried out at 27 ºC if 3.8 × 10–16 % of the reactant molecules exists
in the activated state, the Ea (activation energy) of the reaction is [log 3.8 = 0.58]
(A) 12 kJ/mole (B) 831.4 kJ/mole (C) 100 kJ/mole (D) 88.57 kJ/mole

( 2  2 ) 1/ 2
13. For a certain reaction of order n, the time for half change, t1/2, is given by t1/2 = xC0 where k is
k
constant and C0 is the initial concentration. What is n?
(A) 1 (B) 2 (C) 0 (D) 0.5

 
1  1 1 
14. Given that for a reaction of order n, the integrated form of the rate equation is k =  where C0
t(n  1)  Cn 1 Cn1 
 0 

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

Page 22 of 36
CHAPTER-3-CHEMICAL KINETICS

15. In three different reactions, involving a single reactant in each case, a plot of rate of the reaction on the yaxis,
versus concentration of the reactant on the xaxis, yields three different curves shown below.

(i) (ii) (iii)

What are the possible orders of the reactions (i), (ii), (iii).
(A) 1, 2, 3 (B) 2, 1, 1/2 (C) 0, 1, 2 (D) 0, 1, 1/2

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

k
17. A reaction 2A + B  C + D is first order with respect to A and 2nd order with respect to B. Initial conc.
(t = 0) of A is C0 while B is 2C0. If at t as 30 minutes the conc. of C is C0 /4 then rate expression at t = 30 minutes is :
(A) R = 7 C03 k/16 (B) R = 27 C03 k / 32 (C) R = 247 C03 k / 64 (D) R = 49 k C03 / 32

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

19. In a I order reaction A  products, the concentration of the reactant decrease to 6.25% of its initial value in 80
minutes. What is (i) the rate constant and (ii) the rate of the reaction, 100 minutes after the start, if the initial
concentration is 0.2 mole/litre?
(A) 2.17 × 102 min1, 3.47 × 104 mol.litre1 min1
(B) 3.465 × 102 min1, 2.166 × 104 mol.litre1 min1
(C) 3.465 × 103 min1, 2.17 × 103 mol.litre1 min1
(D) 2.166 × 103 min1, 2.667 × 104 mol.litre1 min1

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

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

22. The reaction [Co (NH3)5Br]2 + H2O  [Co(NH3)5(H2O)]3+ + Br  is followed by measuring a property of the
solution known as the optical density of the solution which may be taken to be linearly related to the concentration
of the reactant. The values of optical density are 0.80, 0.35 and 0.20 at the end of 20 minutes, 40 minutes and
infinite time after the start of the reaction which is first order. Calculate the rate constant.
(A) 6.93 x 103 min1 (B) 3.51 x 102 min1 (C) 6.93 x 102 min1 (D) 3.51 x 103 min1

23. The inversion of cane sugar proceeds with half life of 50 minute at pH = 5 for any concentration of sugar. However
if pH = 6, the half life changes to 500 minute of any concentration of sugar . The law expression for sugar
inversion can be written as :
(A) r = K [sugar]2 [H+]0 (B) r = K [sugar]1 [H+]0 (C) r = K [sugar]1 [H+]1 (D) r = K [sugar]0 [H+]0.

Page 23 of 36
CHAPTER-3-CHEMICAL KINETICS

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

25. For the reaction 3A  Products the value of k = 1 × 10–3  / (mol–min) the value of – d[A] / dt in
mol/lt-sec when [A] = 2M is :
(A) 6.67 × 10–3 (B) 1.2 × 10–2 (C) 2 × 10–4 (D) 4 × 10–3

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

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

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

29. A  B KA = 1015 e–2000/T ;


CD KC = 1014 e–1000/T
Temperature T K at-which (KA = KC) is :
(A) 1000K (B) 2000K (C) (2000 / 2.303) K (D) (1000 / 2.303) K.

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

31. For the reaction A + 2B  products(started with concentrations taken in stoichiometric proportion), the
d [A]
experimentally determined rate law is – = k [A] [B] . The half time of the reaction would be :
dt
0.693 0.693 0.693
(A) (B) (C) (D) not defined
k 1/ k 2k

d[ A ] 1
32. For a reaction 2A + B  product, rate law is – = k[A]. At a time when t = , concentration of the reactant
dt k
is : (C0 = initial concentration)
C0 C0 1
(A) (B) C0e (C) 2
(D)
e e C0

1 1
33. Concentration of the reactant in first-order is reduced to after : (Natural life = )
e2 K
(A) one natural life-time (B) two-natural life-time
(C) three natural life-time (D) four natural life-time
34. If for a reaction in which A(g) converts to B(g) the reaction carried out at const.
V & T results into the following graph.
(A) then the reaction must be A(g)  3B(g) and is a first order reaction.
(B) then the reaction must be A(g)  3B(g) and is a second order reaction.
(C) then the reaction must be A(g)  3B(g) and is a zero order reaction.
(D) then the reaction must be A(g)  3B(g) and is a first order reaction.

Page 24 of 36
CHAPTER-3-CHEMICAL KINETICS

35. The instantaneous rate of disappearance of the MnO4– ion in the following reaction is 4.56 × 10–3 ms–1. Then the
rate of appearance of 2 is :
2MnO4– + 10 – + 16H+  2Mn2+ + 52 + 8H2O
2MnO4– + 10 – + 16H+  2Mn2+ + 52 + 8H2O
(A) 1.14 × 10–3 Ms–1 (B) 5.7 × 10–3 Ms–1 (C) 4.56 × 10–4 Ms–1 (D) 1.14 × 10–2 Ms–1

catalyst
36. Consider the following reactions at 300 K. A  B (uncatalysed reaction). A   B (catalyst reaction)
The activation energy is lowered by 8.314 KJ mol for the catalysed reaction. How many times the rate of this
–1

catalysed reaction greater than that of uncatalysed reaction ? (Given e3.33 = 28)
(A) 15 times (B) 38 times (C) 22 times (D) 28 times

37. The conversion of vinyl allyl ether to pent-4-enol follows first-order kinetics.
The following plot is obtained for such a reaction. The rate constant for the
reaction is
(A) 4.6 × 10–2 s–1
(B) 1.2 × 10–2 s–1
(C) 2.3 × 10–2 s–1
(D) 8.4 × 10–2 s–1

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

39. A simple mechanism for enzyme-catalyzed reaction is given by the following set of equations
E + S ES
(enzyme) (reactant) (intermediate-1)
ES EP
(intermediate-1) (intermediate-2)
EP E + P
(intermediate-2) (enzyme) (product)
This is known as the Michaelis–Menten mechanism. The potential energy diagram is shown in the fig. Which
of the following sets of identifications is correct ? (Assume that the temperature and pressure are constant).
(1) (2) (3) (4)
(A) E + P. EP ES E+S
(B) ES Activated complex EP Activated complex
(C) EP Activated complex ES Activated complex
(D) E+S ES EP E+P

More than one choice Type

d[A ]
40. For the reaction A  B, the rate law expression is  = k [A]1/2. If initial concentration of [A] is [A]0, then
dt

2 1/ 2
(A) The integerated rate expression is k = ( A  A1 / 2 )
t 0

(B) The graph of A Vs t will be


K
(C) The half life period t1 / 2 =
2[A]10/ 2

[A]0
(D) The time taken for 75% completion of reaction t 3 / 4 =
k

Page 25 of 36
CHAPTER-3-CHEMICAL KINETICS

41. Select incorrect statement(s):


(A) Unit of pre-exponential factor (A) for second order reaction is mol L–1 s–1.
(B) A zero order reaction must be a complex reaction.
(C) Molecularity is defined only for RDS in a complex reaction.
(D) Decay constant () of radioactive substance is affected by temperature.

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

43. Which of the following is/are correct statement?


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

44. Which of the following statement is incorrect ?


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

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

Reaction H Rate constant Energy of activation

PA HA kA EA

PB HB kB EB

Which of the following is(are) true?


(A) a = EB (B) b = EA (C) HA = b  d (D) HB = c  a

PART - II : SUBJECTIVE QUESTIONS

1. The oxidation of iodide ion by peroxy disulphate ion is described by the equation :
3– (aq) + S2O82– (aq)  3– (aq) + 2SO42– (aq)

[S2O82  ] [  ]
(a) If – = 1.5 × 10–3 Ms–1 for a particular time interval, what is the value of – for the same time
t t
interval ?
(b) What is the average rate of formation of SO42– during that time interval ?

2. In the following reaction 2H2O2 (aq)  2H2O () + O2 (g) rate of formation of O2 is 36 g min–1 ,
(a) What is rate of formation of H2O.
(b) What is rate of disappearance of H2O2.

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

Page 26 of 36
CHAPTER-3-CHEMICAL KINETICS

4. For the reaction 3BrO(aq)   BrO3 (aq) + 2Br (aq) in alkaline solution, the value of rate constant at
0
80 C in the rate law for [BrO ]/t was found to be 0.057 L.mol1.s1. What is the rate constant when the rate

law is written for (a) [BrO3]/t (b) + [Br ] / t ?

5. The rate law of a chemical reaction given below :


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

6. Decomposition of ammonia on platinum surface follow the change,


2NH3 (g)  N2 (g) + 3H2 (g)

(a) What does  d [NH 3 ] denote ?


dt

d [N2 ] d [H2 ]
(b) What does and denote?
dt dt
(c) If the decomposition is zero order then what are the rate of production of N2 and H2 if k = 2.5 × 10–4 Ms–1 ?
d [NH3 ] k1 [NH3 ]
(d) If the rate obeys – = 1  k [NH ] , what will be the order for decomposition of NH3 if (i) [NH3] is very
dt 2 3
very less and (ii) [NH3] is very very high K1 and K2 are constant.

7. Substance A reacts according to a first order rate law with k = 5 x 105 s1.
(a) If the initial concentration of A is 1.0 M, what is initial rate .
(b) What is the rate after 1.0 hour. (Given e–0.18 = 0.84)

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

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

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

11. (a) The half life period and initial concentration for a reaction are as follows. What is order of reaction?
Initial concentration 350 540 158
t1/2 425 275 941
(b) The half-life period for the thermal decomposition of PH3 at three different pressures are given below
Initial pressure (mm Hg) 707 79 37.5
Half--life (seconds) 84 84 83
What is the order of the reaction ?

Page 27 of 36
CHAPTER-3-CHEMICAL KINETICS

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

31 7
[Given : n = 0.869, e1.58 = 4.858] CI2O7(g) 
 CI2 (g) + O (g)
13 2 2

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

14. The kinetic of hydrolysis of methyl acetate in excess dilute HCl at 25°C were followed by withdrawing 2 mL of the
reaction mixture at intervals of (t), adding 50 mL water and titrating with baryta water. Determine the velocity
constant of hydrolysis.
t (in minute) 0 75 119 259 
Titre value (in mL) 19.24 24.20 26.60 32.23 42.03

22.79 22.79 22.79


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

15. D
A  B+C

Time 0 t 
Volume of reagent V1 V2 V3

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

16. A first order reaction, A  B, requires activation energy of 70 kJ mol1. When a 20% solution of A was kept at
250C for 20 minutes, 25% decomposition took place. What will be the percent decomposition in the same time
in a 30% solution maintained at 40 0C? Assume that activation energy remains constant in this range of
temperature.

17. The thermal decomposition of N2O5 occurs in the following steps.


slow
Step -  N2O5   NO2 + NO3

fast
Step -  N2O5 + NO3   3NO2 + O2

2N2O5 
 4NO2 + O2

suggest the rate expression.

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

(i) NO (g) + Br2 (g) NOBr2 (g)


Slow
(ii) NOBr2 (g) + NO (g)   2NOBr (g)
Suggest the rate expression.

Page 28 of 36
CHAPTER-3-CHEMICAL KINETICS

19. Given the following steps in the mechanism for a chemical reaction :
A + B 
 C (fast)

B + C 
 D + E slow)

D + F 
 A + E fast)
At any time [C] is directly proportional to [A].

(a) What is the stoichiometric equation for the reaction ?

(b) Which species, if any, are catalysts in this reaction ?

(c) Which species, if any, are intermediates in this reaction?

(d) Write the rate law for the rate-determining step.

(e) Write the rate law for this reaction.

(f) What is overall order of the reaction ?

20. The forward reactions rate for the nitric oxide-oxygen reaction
2NO + O2  2NO2 has the rate law ; rate = K [NO]2 [O2] .
Assume the mechanism:

2NO N2O2 , (rapid equilibration) ;


k'
N2O2 + O2  2 NO2 [slow step].

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

21. Experiment shows that the equilibrium constant of the reaction :


C2H5OH + CH3COOH CH3COOC2H5 + H2O
is 2.8 at room temperature, and the velocity constant of the forward reaction is 0.002. When a catalyst is added
this velocity constant is increased to 0.0045. What is now the velocity constant of the backward reaction?

22. For a first order reversible reaction A B , the initial concentration of A and B are [A]0 and zero

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

Page 29 of 36
CHAPTER-3-CHEMICAL KINETICS

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


* Marked Questions are having more than one correct option.

1. The rate constant for the reaction,2N2O5  4NO2+ O2, is 3 ×10–5 s–1. If the rate is 2.4 × 10–5 mol L–1 s–1, then
the concentration of N2O5 (in mol L–1) is : [JEE-2000, 1/35]
(A) 1.4 (B) 1.2 (C) 0.04 (D) 0.8

2. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a catalyst
at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction if the catalyst
lowers the activation barrier by 20 kJ mol–1. [JEE-2000, 3/100]

3. If '' is the intensity of absorbed light and 'C' is the concentration of AB for the photochemical process,
AB + hv  AB * , the rate of formation of AB * is directly proportional to [JEE-2001, 1/35]
(A) C (B)  (C) 2 (D) C.

4. The rate of a first order reaction is 0.04 mole litre–1 s–1 at 10 minutes and 0.03 mol litre–1 s–1 at 20 minutes after
initiation. Find the half life of the reaction. [JEE-2001, 5/100]

5. Consider the chemical reaction,


N2(g) + 3H2(g)  2NH3(g)
The rate of this reaction can be expressed in terms of time derivatives of conc. of N2(g) , H2(g) or NH3(g). Identify
the correct relationship amongst rate expressions : [JEE-2002, 3/90]
d [N2 ] 1 d [H2 ] 1 d [NH3 ] d [N2 ] d [H2 ] d [NH3 ]
(A) Rate =    (B) Rate =  3 2
dt 3 dt 2 dt dt dt dt

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


(C) Rate =   (D) Rate =   
dt 3 dt 2 dt dt dt dt

6. In the biologically-catalysed oxidation of ethanol, the concentration of ethanol decreases in a first order reaction
from 800 mol dm–3 to 50 mol dm–3 in 2 ×104 s. The rate constant (s–1) of the reaction is : [JEE-2003, 3/84]
(A) 3.45 × 10–5 (B) 1.38 × 10–4 (C) 1.00 × 10–4 (D) 5.00 × 10–5

7. Given X  product (Taking 1st order reaction)


conc 0.01 0.0025
(mol/lit)
time (min) 0 40
Initial rate of reaction is in mol //min. [JEE-2004, 3/84]
(A) 3.43 × 10–4 (B) 1.73 × 10–4 (C) 3.43 × 10–5 (D) 1.73 × 10–5

8. Initial rates, r0, of the A + B  P at different initial concentrations of A and B ([A]0 and [B]0) are given below:
––––––––––––––––––––––––––––––––––––––––––––
[A]0 [B]0 r0
(mol L–1) (mol L–1) (mol L–1 s–1)
––––––––––––––––––––––––––––––––––––––––––––
0.1 0.1 0.05
0.2 0.1 0.10
0.1 0.2 0.05
––––––––––––––––––––––––––––––––––––––––––––
(a) Write the rate equation.
(b) Calculate the rate constant of the reaction. [JEE-2004, 2/60]

Page 30 of 36
CHAPTER-3-CHEMICAL KINETICS

9. For a reaction 2X(g)  3Y(g) + 2Z(g) the following data is obtained.

Px (mm of Hg)
Time (min)
(Partial pressure of X)
0 800
100 400
200 200

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

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

11. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half in 40

 k1 
seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio   of the rate
 k0 
constant for first order (k1) and zero order (k0) of the reaction is. [JEE-2008, 3/82]
(A) 0.5 mol–1 dm3 (B) 1.0 mol dm–3 (C) 1.5 mol dm–3 (D) 2.0 mol–1 dm3

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

(C) 1.0 × 106 s–1 and 16.6 kJ mol–1 (D) 1.0 × 106 s–1 and 38.3 kJ mol–1

13. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is : [JEE-2010, 3/163]

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

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

[R](molar ) 1.0 0.75 0.40 0.10


t(min.) 0.0 0.05 0.12 0.18
The order of the reaction is :

235 142 90
15. The number of neutrons emitted when 92 U undergoes controlled nuclear fission to 54 Xe and 38 Sr is :
[JEE-2010, 3/163]

Page 31 of 36
CHAPTER-3-CHEMICAL KINETICS

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

(A) Proton, neutron, position (B) Neutron, position, proton


(C) proton, positron, neutron (D) positron, proton, neutorn

17. For the first order reaction [JEE-2011, 4/163]


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

18. An organic compound undergoes first-order decomposition. The time taken for its decompositionto 1/8 and 1/10
[ t 1/ 8 ]
of its initial concentration are t1/8 and t1/10 respectively. What is the value of × 10? (take log10 2 = 0.3).
[ t1 / 10 ]
[IIT-JEE-2012]

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)

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

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

3. The differential rate law for the reaction H2 + I2  2HI is : [AIEEE- 2002]
dH2  d[I ] d[HI] dH2  d[I2 ] 1 d[HI]
(1)   2  (2)  
dt dt dt dt dt 2 dt

1 dH2  1 d[I2 ] d[HI] dH2  d[I ] d[HI]


(3)   (4)  2  2 2  
2 dt 2 dt dt dt dt dt

4. The rate law for a reaction between the substances A and B is given by rate = k [A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the reaction
will be as [AIEEE- 2003]
1
(1) (2) (m + n) (3) (n – m) (4) 2(n – m).
mn
2

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

Page 32 of 36
CHAPTER-3-CHEMICAL KINETICS

6. In the respect of the equation k = Ae –Ea/RT in chemical kinetics, which one of the following statements is correct :
[AIEEE- 2003]
(1) k is equilibrium constant (2) A is adsorption factor
(3) Ea is energy of activation (4) R is Rydberg constant.

7. In a first order reaction, the concentration of the reactant, decreases from 0.8 M to 0.4 M in 15 minutes. The time
taken for the concentration to change from 0.1 M to 0.025 M is : [AIEEE- 2004]
(1) 30 minutes (2) 15 minutes (3) 7.5 minutes (4) 60 minutes

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

relation to this reaction is that the : [AIEEE- 2004]


(1) unit of k must be sec–1
(2) t1/2 is a constant
(3) rate of formation of C is twice the rate of disappearance of A
(4) value of k is independent of initial concentrations of A and B.

9. The half - life of a radioisotope is four hours. If the initial mass of the isotope was 200 g, the mass remaining after
24 hours undecayed is : [AIEEE- 2004]
(1) 1.042 g (2) 2.084 g (3) 3.125 g (4) 4.167 g.

10. Consider an endothermic reaction X  Y with the activation energies Eb and Ef for the backward and forward
reaction, respectively. In general [AIEEE- 2005]
(1) Eb < Ef (2) H = U (3) H < U (4) H > U

11. A reaction involving two different reactants can never be : [AIEEE- 2005]
(1) unimolecular reaction (2) first order reaction
(3) second order reaction (4) bimolecular reaction

12. A reaction was found to be second order with respect to the concentration of carbon monoxide. If the concentration
of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will be : [AIEEE- 2006]
(1) remain unchanged (2) tripled
(3) increased by a factor of 4 (4) doubled

13. The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr.
NO (g) + Br2 (g) NOBr2 (g) ; NOBr2 (g) + NO (g)  2NOBr (g) (slow step)

If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
[AIEEE- 2007, 3/120]
(1) 1 (2) 0 (3) 3 (4) 2

14. The energies of activation for forward and reverse reactions for A2 + B2 2AB are 180 kJ mol–1 and
200 kJ mol–1 respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse)
reactions by 100 kJ mol–1. The enthalpy change of the reaction (A2 + B2 2AB) in the presence of catalyst will be
(in kJ mol–1). [AIEEE- 2007, 3/120]
(1) 280 (2) 20 (3) 300 (4) 120

Page 33 of 36
CHAPTER-3-CHEMICAL KINETICS

15. A radioactive element gets spilled over the floor of a room. Its half-life period is 30days. If the initial activity is ten
times the permissible value, after how many days will it be safe to enter the room :
[AIEEE- 2007, 3/120]
(1) 10 days (2) 100 days (3) 1000 days (4) 300 days

1
16. For a reaction A  2B, rate of disappearance of 'A' related to the rate of appearance of 'B' by the
2

expression. [AIEEE- 2008, 3/105]

d [ A ] 1 d [B] d [ A ] d [B] d[A] d [B] d [ A ] 1 d [B]


(1)   (2)   (3)  4 (4)  
dt 4 dt dt dt dt dt dt 2 dt

17. The half life period of a first order chemical reaction is 6.93 minutes. Time required for the completion of 99% of
the chemical reaction will be (log 2 = 0.301) : [AIEEE - 2009, 8/144]
(1) 23.03 minutes (2) 46.06 minutes (3) 460.6 minutes (4) 230.3 minutes

18. The time for half life period of a certain reaction A  Products is 1 hour. When the initial concentration of the
reactant ‘A’, is 2.0 mol L–1 , how much time does it take for its concentration to come from 0.50 to 0.25 mol L–1. If
it is a zero order reaction? [AIEEE - 2010, 8/144]
(1) 4 h (2) 0.5 h (3) 0.25 h (4) 1 h

19. Consider the reaction [AIEEE - 2010, 4/144]


Cl2 (aq) + H2S(aq)  S(s) + 2H+ (aq) + 2Cl– (aq)
The rate equation for this reaction is
rate = k [Cl2][H2S]
Which of these mechanisms is/are consistent with this rate equation?
A. Cl2 + H2S  H+ + Cl– + Cl+ + HS– (slow)

Cl+ + HS–  H+ + Cl– + S (fast)


B. H2S  H+ + HS– (fast equilibrium)

Cl2 + HS–  2Cl– + H+ + S (slow)

(1) B only (2) Both A and B (3) Neither A nor B (4) A only

20. The rate of a chemical reaction doubles for every 10° C rise of temperature. If the temperature is raised by 50° C,
the rate of the reaction increases by about : [AIEEE-2011]
(1) 10 times (2) 24 times (3) 32 times (4) 64 times

21. For a first order reaction, (A)  products, the concentration of A changes from 0.1 M to 0.025 M in 40
minutes. The rate of reaction when the concentration of A is 0.01 M, is [AIEEE-2012, 4/120]
(1) 1.73 × 10 M/min
–3
(2) 3.47 × 10 M/min
–4
(3) 3.47 × 10 M/min
–5
(4) 1.73 × 10–4 M/min

Page 34 of 36
CHAPTER-3-CHEMICAL KINETICS

EXERCISE # 1
PART # I
A-1. (B) A-2. (C) A-3. (B) A-4. (A) A-5. (D) A-6. (D) A-7. (B)
A-8. (B) A-9. (D) A-10. (C) B-1. (B) B-2. (D) B-3. (D) B-4. (C)
B-5. (D) B-6. (B) B-7. (B) B-8. (B) B-9. (B) B-10. (D) B-11. (D)
B-12. (A) C-1. (A) C-2. (D) C-3. (B) C-4. (D) C-5. (B) C-6. (B)
C-7. (D) C-8. (B) C-9. (D) C-10. (C) C-11. (C) C-12. (C) C-13. (B)
C-14. (C) C-15. (B) C-16. (B) C-17. (B) C-18. (B) C-19. (A) C-20. (B)
C-21. (C) C-22. (C) C-23. (C) C-24. (C) C-25. (C) C-26. (A) C-27. (C)
D-1. (B) D-2. (B) D-3. (D) D-4. (D) D-5. (A) D-6. (C) D-7. (A)
D-8. (D) D-9. (D) D-10. (C) D-11. (C) D-12. (C) D-13. (B) E-1. (A)
E-2. (B) E-3. (B) E-4. (A) E-5. (B) E-6. (B) F-1. (A) F-2. (C)
F-3. (A) F-4. (A) F-5. (C) F-6. (C) F-7. (D) F-8. (A) F-9. (A)
F-10. (B) F-11. (A) F-12. (D) F-13. (C) F-14. (B) F-15. (D) G-1. (C)
G-2. (D) G-3. (B) G-4. (D) G-5. (C) G-6. (A) G-7.* (ABCD) H-1. (B)
H-2. (B) H-3. (B) H-4. (B) H-5. (B) H-6. (B)

PART # II
1. (A*) 2. (D*) 3. (B*) 4. (A*) 5. (C*) 6. (A*) 7. (C*)
8. (C*) 9. (C*) 10. (B*) 11. (B*) 12. (A*) 13. (C*) 14. (C*)
15. (A) r ; (B) p ; (C) s; (D) q 16. (A) p, q, r, s ; (B) q, r, s ; (C) p, q, r, s ; (D) p, r, s
17. (A) s, (B) r, (C) p, (D) q 18. (A) r ; (B) s ; (C) p ; (D) q
19. (C) 20. (C) 21. (D) 22. (A) 23. (C) 24. (A) 25. (C)
26. (A) 27. (B) 28. (A) 29. (A) 30. (B) 31. F 32. T
33. F 34. T 35. F 36. F 37. T 38. T 39. F
40. T 41. T 42. T 43. F 44. F 45. F 46. T
47. T 48. T 49. F 50. T 51. T 52. T 53. F
54. T 55. T 56. F 57. F 58. T 59. T 60. F
61. threshold energy 62. half 63. equal to H 64. directly proportional
65. mol L–1s–1 66. rare 67. lowering 68. fast 69. slowest
70. increases 71. 3 72. rate constant 73. 2 and 3
1
74. rate = k[M]2 75. 1 76. –k 77. Activation energy for forward reaction
2
k
78. infinte temp. or for zero Ea 79. first 80.  81. unchanged
2.303
82. sum, exponents

EXERCISE # 2
1. (C) 2. (C) 3. (C) 4. (D) 5. (B) 6. (B) 7. (A)
8. (D) 9. (C) 10. (B) 11. (B) 12. (C) 13. (D) 14. (A)
15. (B) 16. (B) 17. (D) 18. (D) 19. (B) 20. (B) 21. (D)
22. (C) 23. (C) 24. (D) 25. (C) 26. (A) 27. (A) 28. (B)
29. (D) 30. (C) 31. (C) 32. (A) 33. (B) 34. (C) 35. (D)
36. (D) 37. (C) 38. (C) 39. (D) 40. (AD) 41. (ACD) 42. (AC)
43. (ABC) 44. (CD) 45. (ABC)
SUBJECTIVE
1. (a) 4.5 × 10–3 M sec–1 (b) 3.0 × 10–3 M sec–1 2. (a) 40.5 gm min–1 (b) 76.5 gm min–1
3. 4.32 × 10–4 M sec–1 4. (a) 0.019 M1 s1 , (b) 0.038 M1 s1
5. 64
6. (a) Rate of decomposition of NH3. (b) Rate of formation of N2 and rate of formation of H2
(c) 2.5 × 10–4 M sec–1 , 7.5 × 10–4 M sec–1 (d) (i) 1 , (ii) 0
7. (a) 5 × 105 M/s (b) 4.2 × 105 M/s

Page 35 of 36
CHAPTER-3-CHEMICAL KINETICS

8. (i) 2nd order, (ii) 1st order, (iii) Third order, (iv) r = K[A]2[B] (v) k = 3.33 × 105 mole–2 +2 sec–1
9. order with respect to A = 1, order with respect to B = 0
10. 3 11. (a) n = 2, (b) First Order

(2 P0  P)2
12. 1.58 × 10–2, 2.33 atm. 13. 2P0  14. 3.27 × 10–3 min–1
P0

1 ( V3  V1)
15. ln ( V  V ) 16. % decomposition = 67.10% 17. k [N2O5]
t 3 2
18. Rate = k [NO]2 [Br2] 19. (a) 2 B+F  2E; (b) A; (c) C,D; (d) rate = k [B][C]; (e) rate = k'[A][B] (f) 2.
0.693
21. 0.001607 22. t=
K f  Kb
EXERCISE # 3
PART-I
1.1 (D) 1.2 EA = 100 KJ/mol 1.3 (B) 1.4 t1/2 = 24 min. 1.5 (A) 1.6 (B)
1.7 (A) 1.8 (a) R0 = k[A0], (b) 0.5 sec–1.
1.9 2X(g)  3Y(g) + 2Z(g)
t=0 800 – –
t=0 800 – 2x 3x 2x = (800 + 3x)
from given data in time 100 min the partial pressure of
X decreases from 800 to 400
so t1/2 100 min. Also in next 100 min Px decreases
from 400 to 200 to again t1/2 = 100 min. Since half left
is independent of initial concentration so reaction must
Ist order with respect to X.
n2
Rate constant K = = 6.93 × 10–3 min–1.
t1/ 2
Time taken for 75% completion = 2 × t1/2 = 200 min.
Now when Px = 700 = 800 – 2x so x = 50 mm of Hg
so total pressure = 800 + 3x = 950 mm of Hg
1.10 (D) 1.11 (A) 1.12 (D) 1.13 (A) 1.14 0 1.15 3
1.16 (A) 1.17 (A, B, D) 1.18 9

PART-II
2.1 (1) 2.2 (1) 2.3 (4) 2.4 (4) 2.5 (3) 2.6 (3) 2.7 (1)
2.8 (4) 2.9 (3) 2.10 (1) 2.11 (1) 2.12 (3) 2.13 (4) 2.14 (2)
2.15 (2) 2.16 (1) 2.17 (2) 2.18 (3) 2.19 (4) 2.20 (3) 2.21 (2)

Page 36 of 36

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