CHEMICAL KINETICS

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[B] d[C ]
A-2. xA + yB  zC. If  d[ A ] =  = 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) + O 2 (g)  2SO 3 (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
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
(C) Mol1n litre n 2 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
–2
(C) 4 × 10 mol L s –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
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) Ct e = C0 (B) Ct = C0 e k1t (C) ln = –k1t (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
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
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 .
 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 –1sec1]
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
  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 f rom
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
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
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.
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
 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)