Class Room Problems: Page # 44 Chemical Kinetics

Page # 44 CHEMICAL KINETICS
Class Room Problems

Ex.1 The oxidation of iodide ion by peroxy disulphate
ion is described by the equation :
3I– + S2O82– → I3– + 2SO42–
∆[S2O82– ]
(a) If – = 1.5 × 10–3 Ms–1 for a particular
∆t
∆[I– ]
time interval, what is the value of – for the same Ex.3 The stoichiometric equation for the oxidation of
∆t
bromide ions by hydrogen peroxide in acid solution is
time interval ?
2Br– + H2O2 + 2H+ → Br2 + 2H2O
(b) What is the average rate of formation of SO42–
during that time interval ? Since the reaction does not occur in one stage, the
rate e quat i on does not c orre sp ond to t hi s
Sol.
stoichiometric equation but is
rate = k[H2O2] [H+] [Br–]
(a) If the concentration of H2O2 is increased by a
factor of 3, by what factor is the rate of consumption
of Br– ions increased ?
(b) If, unde r ce rtai n condi ti ons, the rate of
consumption of Br– ions is 7.2 × 10–3 mole dm–3 s–1,
what is the rate of consumption of hydrogen peroxide
? What is the rate of production of bromine
(c) What is the effect on the rate constant k of
increasing the concentration of bromide ions ?
(d) If by the addition of water to the reaction mixture
the total volume were doubled, what would be the
effect on the rate of change on change on the
concentration of Br– ? What would be the effect on
the rate constant k ?
Ex.2 In the following reaction 2H2O2 → 2H2O + O2 Sol.
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 ?
Sol.
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CHEMICAL KINETICS Page # 45
Sol.
Ex.4 For a reaction 2P + Q → S ; following data were

collected. Calculate the overall order of the reaction.
Also find out the reaction rate constant.
P(mole/L) Q(mole/L) Rate
1. 6 × 10–3 1 × 10–3 0.012
2. 6 × 10–3 2 × 10–3 0.024
Ex.6 The rate of a reaction A + B → products is
3. 2 × 10–3 1.5 × 10–3 0.0024 studied to give following data.
4. 4 × 10–3 1.5 × 10–3 0.0096
Sol. Initial [A] in mol/L Initial [B] in mol/L rate (mol/L/min)
0.01 0.01 0.005
0.02 0.01 0.010
0.01 0.02 0.005
What is the rate law ? What is the half-life of A in the

reaction
Sol.
Ex.5Given the following steps in the mechanism for a

chemical reaction :
A + B – fast → C
B + C – slow → D + E
D + F – fast → A + E
(a) What is the stoichiometric equation for the reaction ?
(b) Which species, if any, are catalysts in this reaction ?
Ex.7 For the reaction :
(c) Which species, if any, are intermediates in this
reaction ? 2A + B + C → A2B + C
(d) Write the rate law for the rate-determinig step. the rate = k[A][B]2 with k = 2.0 × 10–6 M –2 s–1 .
Calculate the initial rate of the reaction when [A] =
(e) At any time [C] is directly proportional to [A].
0.1 M, [B] = 0.2 M and [C] = 0.8 M. If the rate of
Write the rate law for this reaction so that includes
reverse reaction is negligible then calculate the rate
only reactants and products, not intermediates.
of reaction after [A] is reduced to 0.06 M.
(f) What is overall order of the reaction ?
Sol. Ex.8The rate of a first order reaction is 0.04 mol lit–1

s–1 at 10 minutes after initiation and 0.02 mol lit–1 s–1
at 30 minutes. Find the half-life of the reaction.
Sol.
Ex.7 A & B are two different chemical species

undergoing 1st order decomposition with half lives equal
to 0.231 & 0.3465 sec respectively. If the initial conc.
[A]
of A & B are in the ratio 3 : 2. Calculate after
[B]
theree half lives of 'A'.
Sol.
Ex.9A solution of A is mixed with an equal volume of a

solution of B containing the same number of moles,
and the reaction A + B → C occurs. At the end of 1h,
A is 75% reacted. How much of A will be left unreacted
at the end of 2h if the reaction is (a) first order in A
and zero order in B ; (b) first order in both A and B ;
and (c) zero order in both A and B ?
Sol.
Ex.11 Inversion of sucrose is studied by measuring

angle of rotation at any time t.
C12H22O11 (sucrose) + H2O 
→ C6H12O6 (glucose)
+ C6H12O6 (fructose)
It is found that are (r0 – r ∞ ) ∝ a and (rt – r ∞ ) ∝ (a
- x) where r0, rt and r ∞ are the angle of rotation at
the start, at the time t and at the end of the respec-
tively. From the following values calculate the rate
constant and time at which solution is optically inac-
tive.
Time/ min. 0.0 46.0 ∞
Rotation of Glucose
& Fructose 24.1 10.0 –10.7
Sol.
Ex.10 A → B + C
Time T ∞
Volume of reagent V2 V3
Reagent reacts with all A, B and C and have 'n' factors

in the ratio of 1 : 2 : 3 with the reagent. Find k.
Sol.
Ex.12 The first order reaction :sucrose  → Glu-

cose + Fructose takes place at 3080 K in 0.5 NHCl. At
time zero the initial total rotation of the mixture is
32.40 C. After 10 minutes the total rotation is 28.80.
If the rotation of sucrose per mole is 850, that of
glucose of the glucose is 740 and fructose is -86.040.
Calculate half life of the reaction.
Sol. Ex.14 When the catalyst is removed from a reaction

at 5000K the rate decreases upto 4 times and activa-
tion energy is increased by 20%. Find the ratio of
velocity constants at temperature 3200K and 3000K
in the absence of catalyst. Assume activation energy
is independent to temperature.
Sol.
Ex.13 At room temperature (200C) milk turns sour in

about 65 hours. In a refrigerator at 30C milk can be
stored three times as long before its sours. Estimate
: (a) Activation energy of the reaction that causes
the souring of milk, (b) How long should it take milk to
sour at 400C.
Sol.
COMPREHENSION
For a reaction, if effective rate constant k’ is given
1/ 5
2k 2  k 1 
by k =   where k , k , k , k are rate
k 3  k 5  1 2 3 5
constants for different steps of the reaction
Ex.15 The effective activation energy is
1 1
(a) E' a = Ea2 – Ea3 + Ea – Ea
5 1 5 5
(b) E' a = Ea1 + Ea2 + E a3 + Ea5
(c) E' a = Ea1 + Ea2 – E a3 – Ea5
(d) E' a = Ea2 + Ea3 – E a5 – Ea1
Ex.17 Which one is correct ?

Sol.
A 2 A 11/5 {
 – Ea2 + Ea3 + 1/ 5Ea1 – 1/ 5Ea5  }
(a) k ' = 2 exp  
A 3 A 51/ 5  RT 
A 2 A 11/5 { }
 – Ea1 + E a3 + 1/ 5E a2 – 1/ 5Ea5 
(b) k ' = 2 exp  
A 3 A 51/ 5  RT 
A 2 A 51/5 { }
 – E a1 + E a2 + E a3 + E a5 
(c) k ' = 2 exp  
A 3 A 11/ 5  RT 
(d) none of these.
Sol.
Ex.16 The effective frequency factor

2 1/ 5
A 2  A1   2A 2   A1 
(a) A ' =   (b) A ' =    
A 3  A 5   A3   A5 
1/ 5
 A1   A3 
(c) A’= A1 × A2 × A3 × A4 (d) A ' =    
 A2   A5 
Sol.
Ex.18 For the reaction A → B, the rate law expression

d[A]
is – =K[A]1/2 . If initial concentration of A is A0.
dt
Calculate :
(a) integrated form of the rate expression.
(b) nature of plot of [A]1/2 vs. time
(c) half life period.
Sol. Ex.20 An organic compound A de composes following

two parallel first order mechanisms :
k1
B
k1 1
A ; k = 10 and k1 = a hr –1.
k2 2
C
Calculate the concentration ratio of C to A after one
hour from the start of the reaction, assuming only A
was present in beginning.
Sol.
B
k1
k2
A C
Ex.19 For a parallel first order reaction
k3
D
where k1 = x hr–1 and k1 : k2 : k3 = 1 : 10 : 100.
[B] [C] [D]

Calculate [A ] , [A ] and [A ] = ...................
t t t
Sol.
Ex.21. The reaction
k1
cis – Cr(en)2 (OH)+2 trans – Cr(en)2 (OH)+2
k2
is first order is both directions. At 25°C the equilibrium
constant is 0.16 and the rate constant k1 is 3.3 × 10–

4 –1
s . In an experiment starting with the pure cis form,
how long would it take for half the equilibrium amount
of the trans isomer to be formed ?
Sol.
Ex.23 For a reaction A2 + B2 → 2AB, evaluate the

energy of activation from the following data:
1 –1
T (in K) (K ) log10 K
T
500 2×10–3 3.0
200 5×10–3 2.0
Sol.
Ex.22 Two reactions (i) A → products (ii) B →

products, follow first order kinetics. The rate of the
reaction (i) is doubled when the temperature is raised
from 300 K to 310 K. The half life for this reaction at
310 K is 30 minutes. At the same temperature B
decomposes twice as fast as A. If the energy of
activation for the reaction (ii) is half that of reaction
(i), calculate the rate constant of the reaction (ii) at
300 K.
Sol.
Ex.24 A reaction proceeds five times more at 60ºC as

it does at 30ºC. Estimate energy of activation.
Sol. Sol.
Ex.26 A first order reaction A → B requires activation

energy of 70 kJ mol–1. When a 20% solution of A was
kept at 25ºC for 20 minute, 25% decomposition took
place. What will be the percent decomposition in the
same time in a 30% solution maintained at 40ºC? As-
sume that activation energy remains constant in this
range of temperature.
Sol.
Ex.25 For the reaction A B, ∆E for the reaction is

–33.0 kJ mol–1. Calculate :
(a) equilibrium constant KC for the reaction at 300 K
(b) If Ef and Eb are in the ratio 20 : 31, calculate Ef, Eb
at 300 K. Assuming pre-exponential factor same for
forward and backward reactions.
Ex.28 The energy of activation for a reaction is 100

kJ mol–1. Presence of a catalyst lowers the energy of
activation by 75%. What will be effect on rate of
Ex.27 At 380ºC, the half life period for the first order
reaction at 20ºC; other things being equal?
decomposition of H2O2 is 360 min. The energy of acti-
vation of the reaction is 200 kJ mol–1. Calculate the Sol.
time required for 75% decomposition at 450ºC.
Sol.
Ex.29 The progress of the reaction A nB with Ex.30A 22.4 litre flask contains 0.76 mm of ozone at
time is presented in the figure. Determine: 25ºC. Calculate
(i) the value of n, (i) the concentration of oxygen atom needed so that
(ii) the equilibrium constant, K and the reaction O + O3 → 2O2 having rate constant equal
(iii) the initial rate of conversion of A. to 1.5 × 107 litre mol–1 sec–1 can proceed with a rate
of 0.15 mol litre–1 sec–1.
0.6
Conc. mol/1
(ii) the rate of formatiuon of oxygen under this condi-

tion.
0.3
Sol.
1 3 5 7
Time/hour
Sol.
Exercise - I (Only one option is correct)
1. The rate of a reaction is expressed in different ways 4. Consider the following first order competing reac-
as follows : tions :
k and k
1 d[C] 1 d[D] 1 d[ A] d[B] X 
1
→A +B Y 
2
→C +D
+ =– = + =–
2 dt 3 dt 4 dt dt if 50% of the reaction of X was completed when 96%
The reaction is : of the reaction of Y was completed, the ratio of their
(A) 4A + B → 2C + 3D (B) B + 3D → 4A + 2C  k2 
(C) A + B → C + D (D) B + D → A + C rate constants  k  is
 1
Sol.
(A) 4.06 (B) 0.215 (C) 1.1 (D) 4.65
Sol.
2. 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 5. Units of rate constant for first and zero order
reactions in terms of molarity (M) are respectively.
(C) 1.5 × 1010 L mol–1 s–1 (D) 1.5 × 10–11
(A) sec–1, M sec–1 (B) sec–1, M
Sol.
(C) M sec–1, sec–1 (D) M, sec–1
Sol.
3. Reaction A + B → C + D follow's following rate law :

rate = k[ A ] +1/ 2 [B]1/ 2 . Starting with initial conc. of 1 M
of A and B each, what is the time taken for concen-
tration of A of become 0.25 M.
Given : k = 2.303 × 10–3 sec–1.
6. For the reaction A + B → C; starting with different
(A) 300 sec (B) 600sec
initial concentration of A and B, initial rate of reaction
(C) 900 sec (D) none of these were determined graphically in four experiments.
Sol.
S.NO. [A]0/M (Initial conc.) [B]0/M (Initial conc.) rate / (M sec–1)
–3 –2 –3
1 1.6 × 10 5 × 10 10
–3 –2 –3
2 3.2 × 10 5 × 10 4 × 10
–3 –1 –3
3 1.6 × 10 10 2 × 10
–3 –1 –3
4 3.2 × 10 10 8 × 10
Rate law for reaction from above data is

(A) r = k[A]2[B]2 (B) r = k[A]2[B]
(C) r = k [A][B]2 (D) r = k[A][B]
Sol. 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 [ H 2 O ] / d t } =
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 = k1 k"1
Sol.
7. For a reaction pA + qB → products, the rate law

expression is r = k[A]l[B]m, then :
(A) (p + q) < (1 + m)
(B) (p + q) > (1 + m)
(C) (p + q) may or may not be equal to (I + m)
(D) (p + q) = (1 + m)
Sol.
8. In the reaction : A + 2B → 3C + D, which of the

following expression does not describe changes in the 10. At certain temperature, the half life period in the
conc. of various species as a function of time : thermal decomposition of a gaseous substance as fol-
(A) {–d[C]/dt} = {3/2d[B]/dt} lows :
(B) {3d[D]/dt} = {d[C]/dt} P (mmHg) 500 250
(C) {3d[B]/dt} = {–2d[C]/dt} t1/2 (in min) 235 950
(D) {2d[B]/dt} = {d[A]/dt} Find the order of reaction [Given log (23.5) = 1.37 ;
Sol. log (95) = 1.97]
(A) 1 (B) 2 (C) 2.5 (D) 3
Sol.
11. A first order reaction is 50% completed in 20 13. The rate constant, the activation energy and
minutes at 27°C and in 5 min at 47°C. The energy of the Arrhenius parameter (A) of a chemical reaction at
activation of the reaction is 25°C are 3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 10–4s–1
(A) 43.85 kJ/mol (B) 55.14 kJ/mol respectively. The value of the rate constant at T → ∞ is
(C) 11.97 kJ/mol (D) 6.65 kJ/mol (A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1
Sol. (C) infinity (D) 6 × 10–4 s–1
Sol.
14. The following mechanism has been proposed for

the exothermic catalyzed complex reaction.
fast k1 k2
A+B I AB  → AB + I  → P+A
If k1 is much smaller than k2 . The most suitable
qualitative plot of potential energy (P.E.) versus
reaction coordinate for the above reaction.
12. For the first order reaction A → B + C, carried

out at 27°C if 3.8 × 10–16% of the reactant mol-
P.E.
P.E.
ecules exists in the activated state, the Ea (acti- AB+I A+P

A+B
vation energy) of the reaction is (A) A+B IAB (B) IAB
A+P
(A) 12 kJ/mole (B) 831.4 kJ/mole AB+I
(C)100 KJ/mole (D) 88.57 kJ/mole Reaction coordinate Reaction coordinate
Sol.
P.E.
P.E.
(C) A+B (D) A+B

AB+I A+P IAB AB+I A+P
IAB
Reaction coordinate Reaction coordinate
Sol.
F.R.
16. Consider A B + heat, If activation energy
B.R.
for forward reaction is 100 kJ/mole then activation
energy for backward reaction and heat of reaction is
:
(A) 100, 200 (B) 80, 20
(C) 120, 220 (D) 140, 40
Sol.
15. Choose the correct set of identifications.

Potential energy
(4)
(2) (3)
(1)
Reaction coordinate
(1) (2) (3) (4)
(A) ∆E for Ea for ∆Eoverall Ea for
E + S → ES ES → EPfor S → P EP → E + P
(B) Ea for ∆E for Ea for ∆Eoverall
E + S → ES E+S → ES ES → EP for S → P
(C) Ea for Ea for ∆Eoverall ∆E for
ES → EP EP → E + P for S → P EP → E + P
(D) Ea for Ea for Ea for ∆Eoverall 17. In a reaction, the thershold energy is equal to :
E + S → ES ES → EPEP → E + P for S → P (A) Activation energy + normal energy of reactants
(E) ∆E for ∆EOverall ∆E for Ea for (B) Activation energy – normal energy of reactants
E + S → ES for S → P EP → E + P EP → E + P (C) Activation energy
Sol. (D) Normal energy of reactants.
Sol.
18. The first order rate constant k is related to tem- 20. The rate constant, the activation energy and the
perature as long k = 15.0 – (106/T). Which of the frequency factor of a chemical reaction at 25°C are 3.0 ×
following pair of value is correct ? 1
–2 –1
0 s , 104.4 KJ mol–1 and 6.0 × 1014 s–1 respectively.
(A) A = 1015 and E = 1.9 × 104 KJ The value of the rate constant as T → ∞ is :
(B) A = 10–15 and E = 40 KJ (A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1
(C) A = 1015 and E = 40 KJ (C) infinity (D) 3.6 × 1030 s–1
(D) A = 10–15 and E = 1.9 × 104 KJ Sol.
Sol.
21. The rate data for the net reaction at 25°C for
the reaction X + 2Y → 3Z are given below :
[X0] [Y0 ] Time required for [Z] to increase by
0.005 mol per litre.
0.01 0.01 72 sec
0.02 0.005 36 sec
19. When a graph between log K and 1/T is drawn a
straight line is obtained. The point at which line cuts 0.02 0.01 18 sec
y-axis and x-axis. The intial rate (as given by Z) is :
(A) 0, Ea/2.303 R log A (B) ∞, Ea/(R ln A) (A) First order in both X and Y
(C) 0, log A (D) None of these (B) Second order in X and first order in Y
Sol. (C) First order in X and second order in Y
(D) None of the above
Sol.
22. The rate of production of NH3 in N2 + 3H2 → 2NH3 24. For a first order reaction, the concentration of
is 3.4 kg min–1. The rate of consumption of H2 is : reactant :
(A) 5.1 kg min–1 (B) 0.01 kg sec–1 (A) is independent of time
(C) 0.6 kg hr–1 (D) None of these (B) varies linearly with time
Sol. (C) varies exponentially with time (D) None
Sol.
25. Graph between conc. of the product and time of

the reaction A → B is of the type. Hence graph be-
– d[ A ]
tween and time will be of the type :
dt
1
x
time
23. For a given reaction of first order it takes 20 min. [–d[A]/dt] [–d[A]/dt]
for the conc. to drop from 1.0 M to 0.60 M. The time
required for the conc. to drop from 0.60 M to 0.36 M
(A) (B)
will be :
(A) more than 20 min (B) 20 min time time
(C) less than 30 min (D) cannot tell.
Sol. [–d[A]/dt] [–d[A]/dt]
(C) (D)
time time
Sol.
26. Mathematical representation for t1/4 life for first

order reaction is over is given by :
(A) t1/4 = [(2.303)/(K)] log 4
(B) t1/4 = [(2.303/(K)] log 3
(C) t1/4 = [(2.303)/(K)] log(4/3)
(D) t1/4 = [(2.303)/(K)]log(3/4)
Sol. Sol.
27. For a reaction A → Products, the conc. of reac-

tant C0, aC0, a2C0, a3C0............ after time interval 0, k
29. A reaction 2A + B  → C + D is first order with
t, 2t ............ where 'a' is constant. Then :
respect to A and 2nd order with respect to B. Initial
(A) reaction is of 1 st order and K = (1/t) ln a
conc. (t = 0) of A is C0 while B is 2C0. If at t = 30
(B) reaction is of 2nd order and K = (1/tC0)(1 – a)/a
minutes the conc. of C is C0/4 then rate expression at
(C) reaction is of 1st order and K = (1/t) ln (1/a)
t = 30 minutes is :
(D) reaction is of zero order and K = {(1 – a)}C0/t
Sol. 7C 30k 27C 30 k
(A) R = (B) R =
16 32
247C 30k 49 k C 30
(C) R = (D) R =
64 32
Sol.
∆ / Cu
28. N2Cl Cl + N2 Half-life
is independent of conc. of A. After 10 minutes volume
N2 gas is 10 L and after complete reaction 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
30. 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 conc. of
acid
(C) The change in pH of the solution will not affect
the rate
32. For a certain reaction of order 'n' the time for
(D) Doubling the conc. of H+ ions will increase the
half change t1/2 is given by t1/2 = [(2 – √2)/K] × C01/2,
reaction rate by 4 times.
where K is rate constant and C0 is the initial concen-
Sol. tration. The value of n is :
(A) 1 (B) 2 (C) 0 (D) 0.5
Sol.
33. Two first order reaction have half life in the ratio 3
: 2. Calculate the ratio of time intervals t1 : t2. The time
t1 and t2 are the time period for 25% and 75% comple-
tion for the first and second reaction respectively :
31. The decomposition of a gaseous substance (A)
(A) 0.311 : 1 (B) 0.420 : 1
to yield gaseous products (B), (C) follows first order
(C) 0.273 : 1 (D) 0.119 : 1
kinetics. If initially only (A) is present and 10 minutes
after the start of the reaction the pressure of (A) is Sol.
200 mm Hg and that of over all mixture is 300 mm Hg,
then the rate constant for 2A → B + 3C is
(A) (1/600) 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
Sol.
34. A reaction proceeds in three stages, The first 36. Following mechanism has been proposed for a re-
stage is a slow second order reaction, the second actions, 2A + B → D + E ; A + B → C + D .....(Slow) ; A
stage is fast and of first order, the third stage is fast + C → E .......(fast). The rate law expression for the
and is a third order reaction. The overall order of the reaction is :
reaction is : (A) r = K[A]2 (B) r = K[A]2[B]
(A) First order (B) Second order (C) R = K[A]2 (D) r = K[A] [B]
(C) Third order (D) Zero order. Sol.
Sol.
k1
37. For the reaction H2 + I2 2HI. The rate
k2
law expression is :
(A) [(+1/2) d[HI]/dt] = k1 [H2] [I2]
(B) [(+1/2) d[HI]/dt] = {k1 [HI]2 / k2 [H2][I2]
(C) [(+1/2) d[HI]/dt] = k1 [H2][I2] – k2[HI]2
35. A reaction of the type A + 2B + C → D occurs by
following mechanism (D) [(+1/2) d[HI]/dt] = k1 k2 [H2][I2]
A + B → X rapid equilibrium Sol.
X + C → Y Slow
Y + B → D Fast
What is the order of the reaction :
(A) 1 (B) 2 (C) 3
(D) Non determinable
Sol.
38. A subtance undergoes first order decomposition.

The decomposition follows two parallel first order re-
actions as : and K1 = 1.26 × 10–4 sec–1; K2 = 3.8 ×
10–5 sec–1. The percentage distribution of B and C are
(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
Sol.
k1 Question No. 42 to 43 (2 questions)

39. For 2A k2
B + 3C, 2C 
k–1 → 3D. Which of Oxidation of metals is generally a slow electrochemi-
cal reaction involving many steps. These steps in-
the following is correct : volve electron transfer reactions. A particular type of
(A) d[C]/dt = 3k1[A]2 – 3k-1[B][C]3 – 2K2[C]2 oxidation involve overall first order kinetics with re-
(B) d[B]/dt = k1 [A]2 spect to fraction of unoxidised metal (1 – f) surface
(C) d[A]/dt = 2K-1[B][C]3 – 2K1 [B][C]3 thickness relative to maximum thickness (T) of oxidised
(D) None. surface, when metal surface is exposed to air for con-
siderable period of time.
Sol.
0 200 hrs
t
–3
ln (1 – f)
df x
Rate law : = k(1 – f ) , where f = , x = thickness
dt T
of oxide film at time 't' & T = thickness of oxide film at
t = ∞ A graph of ln (1 – f) vs t is shown in the
adjacent figure.
41. The time taken for thickness to grow 50% of 'T' is
(A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs
Sol.
40. For 2A  → B →

k k
1 2
3C. k1=2×10-4 sec-1 and
-4
k2 = 3×10 l/mol-sec. {d[B]/dt} equal to:
(A) k1 [A] – k2 [B] (B) k1 [A]2 – k2 [B]
(C) k1 [A] – k2 [B]2
(D) k1[A]2 – k2 [C]3
Sol.
42. The exponential variation of 'f' with t(hrs) is given by

(A) [1 – e –3 t / 200 ] (B) e –3 t / 200 – 1
(C) e –3 t /200 (D) e3 t / 200

Sol.
COMPREHENSION - I
Question No. 44 to 45 (2 questions)
The rate of a reaction increases significantly with in-
k1 2B crease in temperature. Generally, rates of reaction
For a hypothetical elementary reaction A are doubled for every 10º rise in temperature.
k2 Temperature coefficient gives us an idea about the
C change in rate of a reaction for ev ery 10º
k1 1
where k = 2 change in temperature.
2
Rate constant of ( T + 10)º C
Initially only 2 moles of A are present. Temperature coefficient µ =
Rate constant at T º C
43. The total number of moles of A, B & C at the end
Arrhenious gave an equation which describes rate con-
of 50% reaction are
(A) 2 (B) 3 (C) 5 (D) None stant k as a function of temperature is k = A −Ea / RT
Sol. where k is a rate constant
A is frequency factor or pre exponential factor
Ea is activation energy
T is temperature in kelvin and
R is universal gas constant
Equation when expressed in logarithmic form becomes
Ea
log10 k = log10 A −
2.303 RT
45. For a reaction Ea = 0 and k = 3.2 × 105 s–1 at 325 K.

The value of k at 335 K would be
(A) 3.2 × 105 s–1 (B) 6.4 × 108 s–1
(C) 12.8 × 108 s–1 (D) 25.6 × 108 s–1
Sol.
44. Number of moles of B are 46. For which of the following reactions k310/k300 would
(A) 2 (B) 1 (C) 0.666 (D) 0.333 be maximum ?
Sol.
(A) P + Q → R ; E a = 10kJ (B) E + F → D ; E a = 21kJ
(C) A + B → C ; E a = 10.5 kJ (D) L + M → N; E a = 5 kJ

Sol.
47. Activation energies of two reaction are Ea and E′a

with Ea > E′a. If the temperature of the reacting sys-
tems is increased from T1 to T2 (k′ are rate constants
at higher temperature).
k1′ k ′2 k 1′ k ′2
(A) = (B) <
k1 k 2 k1 k 2
k1′ k ′2 k1′ 2k ′
(C) > (D) > 2
k1 k 2 k1 k2
Sol.
COMPREHENSION - II
The rate and mechanism of chemical reactions are

studied in chemical kinetics. The elementary reac-
tions are single step reactions having no mechanism.
The order of reaction and molecularity are same for
elementary reactions. The rate of forward reaction
aA + bB → cC + dD is given as :
 dx  1 d[A] 1 d[B] 1 d[C] 1 d[D]

rate =   =– =– = = or rate =
 dt  a dt b dt c dt d dt
K[A]a[B]b. In case of reversible reactions net rate ex-
pression can be written as : rate = K1[A]a[B]b –
K2[C]c[D]d. At equilibrium, rate = 0. The constants K,
K1, K2, are rate constants of respective reaction. In
case of reactions governed by two or more steps re-
actions mechanism, the rate is given by the solwest
step of mechanism.
49. The rate of formation of SO3 in the following re-
action : 2SO2 + O2 → 2SO3 is 10 g sec–1. The rate of
disappearance of O2 will be :
(A) 5 g sec–1 (B) 100 g sec–1
48. For the reactions, following data is given (C) 20 g sec (D) 2 g sec–1
Sol.
 − 2000 
P→Q k 1 = 1015 exp .  
 T 
 − 1000 
C→D k 2 = 1014 exp .  
 T 
Temperature at which k1 = k2 is
(A) 434.22 K (B) 1000 K (C) 2000 K (D) 868.44 K
Sol.
50. For the reaction : aA → bB ;
 – dA   dB 
log  = log  + 0.6 , then a : b is :
 dt   dt 
52. For the reaction : A + 2B AB2 ; the rate of
(A) 3.98 (B) 2.18 (C) 1.48 (D) 0
dx
Sol. forward reaction is = 1 × 105[A][B]2 – 1 × 104[AB2].
dt
The rate constants for forward and backward reac-
tions are :
(A) 1 × 105 L2 m–2 s–1, 1 × 104 sec
(B) 1 × 105 sec–1, 1 × 104 L2 m–2 s–1
(C) 1 × 105 L2 m–2 s–1, 1 × 104 sec–1
(D) 1 × 105 L m–1 s–1, 1 × 104 sec
Sol.
53. At the point of intersection of the two curves

51. For a reaction, 2ND3 → N2 + 3D2 ; shown for the reaction
– d[ND 3 ] d[N2 ]
= K 1 [N D 3 ] ; = K 2 [ND 3 ] ;
dt dt
d[D 2 ]
= K 3 [ND 3 ] , then :
conc
dt
(A) K1 = K2 = K3 (B) 3K1 = 6K2 = 2K3
(C) K1 = 2K2 = K3 (D) K1 = K2 = 2K3 time
A → nB
the concentration of B is given by :
nA 0 A0 nA 0 (n – 1)
(A) (B) (C) (D) A0
2 n–1 n+1 (n + 1)
Sol.
56. For a gaseous reaction, the rate is expressed in

dP dC dn
terms of in place of or , where C is con-
dt dt dt
54. For a hypothetical reaction aA + bB → Product,
centration, n is number of moles and 'P' is pressure of
the rate law is : rate = K[A]x[B]y. then :
reactant. The three are related as :
(A) (a + b) = (x + y) (B) (a + b) < (x + y)
(C) (a + b) > (x + y) (D) Any of these  dP  RT  dn   dC 
(A)   =  = 
Sol.  dt  V  dt   dt 
1  dF  1  dn   dC 
= =
RT  dt  V  dt   dt 
(B)
 dP   dn   dC 
(C)   =   =   (D) None of these
 dt   dt   dt 
Sol.
55. For the reaction : 2NO + Br2 2NOBr; the

mechanism is given in two steps :
Fast
(1) NO + Br2 NOBr2
(2) NOBr2 + NO  Slow

→ 2NOBr..
The rate expression for the reaction is :
(A) r = K[NO]2[Br2] (B) r = K[NO][Br2]
(C) r = K[NO][Br2]2 (D) r = K[NOBr2]
Sol.
COMPREHENSION - III 59. For an endothermic reaction, which one is true if

∆H is heat of reaction and Ea is energy of activation :
 dx 
The rate of a reaction   varies with nature, physi- (A) Ea > ∆H (B) Ea < ∆H
dt
( C ) E
a
>< ∆H (D) Ea = 0
cal state and concentration of reactants, tempera-
ture, exposure to light and catalyst, whereas rate Sol.
constant (K) varies with temperature and catalyst
only. The rate constant K is given as K = Ae –Ea /RT
where A is Arrhenius parameter or pre-exponential fac-
tor and Ea is energy of activation. The minimum en-
ergy required for a reaction is called threshold energy
and the additional energy required by reactant mol-
ecules to attain threshold energy level is called en-
ergy of activation.
57. For a reaction, A → B; if
. × 10 4
125
log10K(sec–1) = 14 – K, the Arrhenius pa-
T
rameter and energy of activation for the reaction are
:
(A) 1014 sec–1, 239.34 kJ (B) 14,57.6 kcal 60. For a chemical reaction : A → Product, the rate
(C) 10 14 –1
sec , 23.93 kJ (D) 1014 sec, 5.76 kcal of disappearance of A is given by :
Sol. –dC A CA
= K1
dt 1 + K 2 C A . At low CA, the order of reaction
and rate constants are respectively :
K1 K1 K1
(A) I, K (B) I, K1 (C) II, K (D) II, K + K
2 2 1 2
Sol.
58. At what conditions exponential factor is zero for

a reaction :
(A) Infinite temperature
(B) Free radical combination
(C) Energy of activation + Threshold energy
(D) All of these
Sol.
61. For a reversible reaction, A + B C + D ;

∆H = – A kcal. If energy of activation for the forward
reaction is B kcal, the energy of activation for back-
ward reaction in kcal is :
(A) – A + B (B) A + B (C) A – B (D) – A – B
Sol. REASONING TYPE

Directions : Read the following questions and
choose
(A) If both the statements are true and state-
ment-2 is the correct explanation of satement-1.
(B) If both the statements are true and state-
ment-2 is not the correct explanation of
satement-1.
(C) If statement-1 is True and statement-2 is
False.
–E / RT
62. The quantity –Ea/RT in K = Ae a is referred as (D) If statement-1 is False and statement-2 is
(A) Boltzman factor (B) Frequency factor True.
(C) Activation factor (D) None of these
Sol. 66. Statement-1 : Rate of a chemical reaction in-
creases as the temperature is increased.
Statement-2 : As the temperature is increased frac-
tion of molecules occupying ET or more increases.
(A) (A) (B) (B) (C) (C) (D) (D)
Sol.
63. How much faster would a reaction proceed at

25°C than at 0°C if the activation energy is 2 cal :
(A) 2 times (B) 16 times
(C) 11 times (D) Almost at same speed
Sol.
66. Statement-1 : For the molecules to react, they
must collide with each other.
Statement-2 : Bond breaking and formation occurs
during the collision.
(A) (A) (B) (B) (C) (C) (D) (D)
Sol.
67. Statement-1 : An α-decay, followed by 2β– de-

cays lead to the formation of an isotope.
64. The temperature coefficient of reaction I is 2 Statement-2 : Protons and neutrons keep on chang-
and reaction II is 3. Both have same speed at 25°C ing into one another by emission or absorption of π
and show I order kinetics. The ratio of rates of reac- mesons.
tions of these two at 75°C is : (A) (A) (B) (B) (C) (C) (D) (D)
(A) 7.6 (B) 5.6 (C) 6.6 (D) 8.6 Sol.
Sol.
68. Statement-1 : Catalyst does not change the

∆H value of the reaction.
Statement-2 : Catalyst are generally added in very
small quantities and not stoichiometrically.
(A) (A) (B) (B) (C) (C) (D) (D)
Sol.
69. Statement-1 : The order of the reaction

C12H22O11 + H2O C 6H12O 6 + O 6H12 O 6 is 2.
Statement-2 : The molecularity of this reaction is 2.
(A) (A) (B) (B) (C) (C) (D) (D)
Sol.
71. Consider the following energy diagram for the re-

action.
A2 + B2 2AB
MATCH THE FOLLOWING
Note : Each statement in column I has one or mores 50

than one match in column II. 40
Energy
(j mol–1)
30
70. 20
Column I Column II 10
(A) CH3 COOCH3 + H2O CH3COOH + CH3OH

Column I Column II
(P) molecularity = 1 (A) Ea(f) (P) –10 kJ mol–1
(B) Ea(b) (Q) 40 kJ mol–1
(B) C12H22O11 + H2O C 6H12O 6 + C 6H12 O 6 (C) ∆Hr (R) 30 kJ mol–1
(D) ET (S) 50 kJ mol–1
Sol.
(Q) molecularity = 2
(C) CH3 COOC2H5 + NaOH CH3 COONa + C 2H5 OH
(R) order = 1
(D) 2NO 2 + F2 2NO 2F
(S) order = 2
Note : Each statement in column I has only one match

in column II.
Sol.
Exercise - II (one or more than one option correct)

Sol.
1. Ozone decomposes according to the equation
2O3(g) → 3O2(g) Mechanism of the reaction is
Step I : O3(g) O2(g) + O(g) (fast)
Step II : O3(g) + O(g) → 2O2(g) (slow)

Which of the following is correct ?
(A) for step I, molecularity is 2 (B) for step II,
molecularity is 1
(C) step II is rate determining step
(D) Rate law expression for the overall reaction is
3. A substance undergoes first order decomposition.
d The decomposition follows two parallel first order
– [O 3 ] = k[O 3 ] 2 [O 2 ] –1
dt reactions as
Sol.
k1
B k1=1.26 × 10–4s–1
A k =3.8 × 10–5s–1
k2 C 2
The % distribution of B and C is ................ and

.................. respectively.
(A) 76.83% B (B) 23.17% C
(C) 23.17% (D) 76.83%C
Sol.
2. Consider the following case of competing 1st order 4. In the equation k = Ae –Ea/RT , A may be termed as
reactions the rate constant at
After the start of the reaction at t = 0, with only P, (A) very low temperature
concentration (B) very high temperature.
of Q is equal to R at all times. The time in which all (C) zero activation energy
Q (D) Boiling temperature of the reaction mixture.
k1
Sol.
the three P
k2 R
concentration will be equal is given by
2.303 2.303
(A) t = 2k 1
log10 3 (B) t = 2k log10 3
2
2.303 2.303
(C) t = 3k log10 2 (D) t = 3k log10 2
1 2
5. Which of the following concepts are correct

(A) If for, A → B ∆H = +q cal
then for, B → A ∆H = – q cal
(B) If for, A B equilibrium constant = K
1
then for, B A equilibrium constant =
K
(C) If for, A → B rate constant = k 8. For a reaction : 2A + 2B → products, the rate law
then for, B → A rate constant ≠ k expression is r = k[A]2 [B]. Which of the following is/
(D) If for, A → B energy of activation = E are correct?
then for, B → A energy of activation = – E (A) The reaction is first order w.r.t. B
Sol. (B) The reaction is of second order w.r.t. A
(C) The reaction is of third order, overall
(D) Slowest step of the reaction is given as A + B → AB
Sol.
6. The basic theory behind Arrhenious equation is that

(A) the activation energy and pre exponential factor
are always temperature independent.
(B) the number of effective collisions is proportional 9.
Et Et Et
to the number of molecules above a certain threshold
energy. H Cl + OH– H OH, OH H
(C) as the temperature increases, so does the number
of molecules with energies exceeding threshold energy. Me Me Me
(D) rate constant is a function of temperature.
(I) (II)
Sol.
Which of the following statements are correct ?
(A) It is SN 1 if (I) or (II) is formed.
(B) It is SN1 if equimolar mixture of (I) and (II) is
formed.
(C) It is SN2 if (I) or (II) is formed.
(D) It is SN2 if (II) is formed.
7. Which of the following statements are correct about Sol.
half life period ?
(A) It is proportional to initial concentration for a zero
order reaction.
(B) Average life = 1.44 times half life for a first order
reaction.
(C) Time of 75% reaction is thrice of half life period in
second order reaction.
(D) 99.9% reaction which is first order, takes place in 100
minutes if the rate constant of the reaction is 0.0693 min–1.
Sol. 10. Rate constant k varies with temperature by
2000
equation log10k(min–1) = 5 – . We can conclude
T
(A) pre exponential factor A is 105
(B) Ea is 2000 k cal
(C) Ea is 9.212 k cal
(D) pre exponential factor A is 5
Sol. 13. Following data is given for the reaction be-

tween A and B
Expt. [A] [B] Initial rate
(mol L–1) (mol L–1) (mol L–1 s–1)
(I) 2.5 × 10–4 3.0 × 10–5 5.0 × 10–4
(II) 5.0 × 10–4 6.0 × 10–5 4.0 × 10–4
(III) 1.0 × 10–3 6.0 × 10–5 1.6 × 10–2
Which of the following is correct ?
(A) Order w.r.t. A is 2
(B) Order w.r.t B is 1
(C) Value of rate constant is 2.67 × 108 L2 mol–2 s–1
(D) Order of the reaction is 4
11. A reaction is catalysed by H+ ion. In presence Sol.
of HA, rate constant is 2 × 10–3 min–1 and in presence
of HB rate constant is 1 × 10–3 min–1. HA and HB being
strong acids, we may conclude that
(A) HB is stronger acid than HA
(B) HA is stronger acid than HB.
(C) relative strength HA and HB is 2.
(D) HA is weaker than HB and relative strength is 0.5.
Sol.
14. Half life for which of the following varies with

initial concentration [A0]
(A) zero order (B) first order
(C) second order (D) third order
Sol.
12. The potential energy diagram for a reaction R →

P is given below
Which of the following is true ? 15. In which of the following, Ea for backward
(A) Ea (forward) = y z reaction is greater than Ea for forward reaction ?
(B) Ea (backward) = z y Ea =50kcal
x (A) a → b ∆H = −10kcal
(C) ET = x + y
(D) ∆Hr = x R Ea = 60 kcal
(B) a → b ∆H = −20kcal
Sol.
Ea =50kcal
(C) a → b ∆H = +10kcal
Ea = 60kcal
(D) a → b ∆H = +20kcal
Sol.
Exercise - III Subjective Level-I
Q.1 For the reaction

2NH3 → N2 + 3H2
a curve is plotted between [NH3] is time as shown
0.6 Q.3 Dinitropentaoxide decomposes as follows :

[NH3]
0.4 1
N2O5(g) → 2NO2(g) + O 2 ( g)
2
0.2 – d[N2 O 5 ]
Given that = k 1[N2 O 5 ]
dt
5 10 15 20 d[NO 2 ] d[O 2 ]
Time (sec.) = k 2 [N2 O 5 ] = k 3 [N2 O 5 ]
dt dt
What is the relation between k1, k2 and k3 ?
Calculate Sol.
(a) rate of disappearance between 5 to 10 sec
(b) rate of disappearance between 10 to 20 sec
Sol.
Q.4 The reaction 2A + B + C → D + E is found to be

first order in A second order in B and zero order in C.
(i) Give the rate law for the reaction in the form of
differential equation.
(ii) What is the effect in rate of increasing concen-
trations of A, B, and C two times ?
Sol.
Q.2 For the reaction 3BrO – → BrO 3– + 2Br – in an alka-
line aquesous solution, the value of the second order
(in BrO–) rate constant at 80°C in the rate law for
∆[BrO – ]
– was found to be 0.056 L mol–1s–1. What is
∆t
the rate of constant when the rate law is written for
∆[BrO 3– ] ∆[Br – ] Q.5 For the elementary reaction 2A + B2 → 2AB. Cal-
(a) , (b) ?
∆t ∆t culate how much the rate of reaction will change if
Sol. the volume of the vessel is reduced to one third of its
original volume?
Sol.
Sol.
Q.6 Ammonia and oxygen reacts at higher tempera-

tures as
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O (g)
In an experiment, the concentration of NO increases
by 1.08 × 10–2 mol litre–1 in 3 seconds. Calculate.
(i) rate of reaction.
(ii) rate of disappearance of ammonia
(iii) rate of formation of water.
Sol.
ZERO ORDER
Q.9 In the following reaction, rate constant is

1.2 × 10–2 Ms–1 A → B. What is concentration of B
after 10 and 20 min., if we start with 10 M of A.
Sol.
Q.7 In the following reaction 2H2O2 → 2H2O + O2

rate of formation of O2 is 3.6 M min–1.
(a) What is rate of formation of H2O ?
(b) What is rate of disappearance of H2O2 ?
Sol.
Q.10 For the fol lowi ng data for the reaction

A → products. Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M
Sol.
Q.8 The reaction A(g) + 2B(g) → C(g) + D (g) is an

elementary process. In an experiment, the initial par-
tial pressure of A & B are PA = 0.6 and PB = 0.8 atm, if
PC = 0.2 atm then calculate the ratio of rate of reac-
tion relative to initial rate.
Sol.
Q.11 The rate constant for a zero order reaction is

2 × 10–2 mol L–1 sec–1, if the concentration of the
reactant after 25 sec is 0.25 M, calculate the initial
concentration.
Sol.
FIRST ORDER
Q.14 A first order reaction is 75% completed in 72

min. How long time will it take for
(i) 50% completion (ii) 87.5% completion
Sol.
Q.12 A drop of solution (volume 0.10 ml) contains 6

× 10–6 mole of H+, if the rate constant of disappear-
ance of H+ is 1 × 107 mole litre–1 sec–1. How long
would it take for H+ in drop to disappear ? Q.15 A first order reaction is 20% complete in 10
Sol. min. Calculate (i) the specific rate constant, (ii) the
time taken for the reactions to go to 75% completion.
Sol.
Q.13 A certain substance A is mixed with an equimo-

lar quantity of substance B. At the end of an hour A is Q.16 Show that in case of unimolecular reaction, the
75% reacted. Calculate the time when A is 10% time required for 99.9% of the reaction of take place in
unreacted. (Given : order of reaction is zero) ten times that required for half of the reaction.
Sol. Sol.
Q.17 A first order reaction has a rate constant is Q.20 Consider the reaction : A → B + C. Initial con-
1.5 × 10–3 sec–1. How long will 5.0 g of this reactant centration of A is 1 M. 20 minutes time is required for
take to reduce to 1.25 g. d[B]
completion of 20% reaction. If = k[ A], then calcu-
Sol. dt
late half life (t1/2) of reaction.
Sol.
Q.18 A drug is known to be ineffective after it has

decomposed 30%. The original concentration of a
sample was 500 units/ml. When analyzed 20 months Q.21 The reaction SO2Cl2(g) → SO2(g) + Cl2(g) is a
later, the concentration was found to be 420 units/ first order gas reaction with k = 2.2 × 10–5 sec–1 at
ml. Assuming that decomposition is of I order, what 320° C. What % of SO2Cl2 is decomposed on heating
will be the expiry time of the drug? this gas for 90 min.
Sol. Sol.
ORDER OF REACTION & RATE LAW
Q.22 At 800° C the rate of reaction

Q.19 A viral preparation was inactivated in a chemi- 2NO + H2 → N2 + H2O
cal bath. The inactivation process was found to be Changes with the concentration of NO and H2 are
first order in virus concentration. At the beginning of
the experiment 2.0% of the virus was found to be 1 d[NO]
[NO] in M [H2] in M – in M sec–1
inactivated per minute. Evaluate k for inactivation pro- 2 dt
cess.
(i) 1.5 × 10–4 4 × 10–3 4.4 × 10–4 Q.24 The catalytic decomposition of N2O by gold at
(ii) 1.5 × 10 –4
2 × 10–3
2.2 × 10–4 900° C and at an initial pressure of 200mm is 50%
complete in 53 minutes and 73% complete in 100 min-
(iii) 3.0 × 10–4 2 × 10–3 8.8 × 10–4
utes.
(a) What is the order of this reaction ?
(i) What is the order of the reaction ?
(b) What is the rate equation for the reaction ? (ii) Calculate the velocity constant.
(c) What is the rate when (iii) How much of N2O will decompose in 100 min. at
[H2] = 1.5 × 10–3 M and [NO] = 1.1 × 10–3 M ? the same temperature but at initial pressure of
Sol. 600 mm?
Sol.
Q.23 The data below are for the reaction if NO and

Cl2 to form NOCl at 295 K
Concentration of Cl2[M] Concentration of NO Initial Q.25 The following data are for the reaction A + B
Rate (Ms–1) → products :
Conc. A Conc. B Initial Rate
0.05 0.05 1 × 10–3
(M) (M) (mol L–1 s–1)
0.15 0.05 3 × 10–3 0.1 0.1 4.0 × 10–4
0.05 0.15 9 × 10–3 0.2 0.2 1.6 × 10–3
(a) What is the order w.r.t NO and Cl2 in the reaction. 0.5 0.1 2.0 × 10–3
(b) Write the rate expression 0.5 0.5 1.0 × 10–2
(i) What is the order with respect to A and B for the
(c) Calculate the rate constant
reaction ?
(d) Determine the reaction rate when concentration (ii) Calculate the rate constant.
of Cl2 and NO are 0.2 M & 0.4 M respectively. (iii) Determine the reaction rate when the concentra-
Sol. tions of A and B are 0.2 M and 0.35M, respectively.
Sol.
Q.26 The pressure of a gas decomposing at the sur- (a) What is the order ?
face of a solid catalyst has been measured different (b) Write rate law
times and the results are given below (c) Calculate rate constant
t (sec) 0 100 200 300 (d) Calculate the rate of decomposition when the
Pr. (Pascal)4 × 103 3.5 × 103 3 × 103 2.5 × 103 acetone concentration is 1.8 × 10–3 M
Determine the order of reaction, its rate constant. Experiment Initial [CH3COCH3] Rate M s–1
Sol. 1. 6.0 × 10–3 M 5.2 × 10–5
2. –3
9.0 × 10 M 7.8 × 10–5
3. 1.8 × 10–3 M ?
Sol.
Q.27 The half life period of decomposition of a com-

pound is 50 minutes. If the initial concentration is
halved, the half life period is reduced to 25 minutes.
What is the order of reaction ?
Sol.
HALF LIFE
Q.29 The half life period of a first order reaction is

50 min. In what time will it go to 90% completion ?
Sol.
Q.30 A first order reaction has k = 1.5 × 10–6 per

second at 200°C. If the reaction is allowed to run for
10 hrs., what percentage of the initial concentration
Q.28 At 600°C, acetone (CH3COCH3) decomposes to
would have changed into the product ? What is the
ketene (CH2 = C = O) and various hydrocarbons. Given
half life of this reaction ?
the initial rate data in the table :
Sol.
Q.33 A flask contains a mixture of compounds A and

B. Both compounds decompose by first-order kinet-
ics. The half-lives are 54.0 min for A and 18.0 min. for
B. If the concentartions of A and B are equal initially,
how long will it take for the concentration of A to be
four times that of B ?
Q.31 Show that in case of a first order reaction, the
Sol.
time required for 93.75% of the reaction to take place
is four times that required for half of the reaction.
Sol.
Q.34 Two substances A (t1/2 = 5 mins) and B (t1/2 =

15 mins) follow first order kinetics are taken in such a
way that initially [A] = 4[B]. Calculate the time after
which the concentration of both the substance will
be equal.
Sol.
Q.32 The half time of the first order decomposition
of nitramide is 2.1 hour at 15°C.
NH2NO2(aq.) → N2O (g) + H2O (l)
If 6.2 g of NH2NO2 is allowed to decompose, calculate
(i) time taken for NH2NO2 to decompose 99%, and (ii)
volume of dry N2O produced at this point, measured
at 1 atm & 273 K.
Sol.
CONCENTRATION REPLACED BY OTHER QUANTI-

TIES IN FIRST ORDER INTEGRATED RATE LAW
Q.35 In this case we have

A → B + C
Time t ∞
Total pressure of A + B + C P2 P3
Find k.
Sol. Q.38 A → 2B + 3C
Time t ∞
Volume of reagent v2 v3
Reagent reacts with all A, B and C. Find K.
Sol.
Q.36 A → B + C
Time t ∞
Total pressure of (B + C) P2 P3
Find k.
Sol.
Q.39 S → G + F
Time t ∞
Rotation of Glucose & Fructose rt r∞
Find k.
Q.37 A → B + C
Sol.
Time 0 t
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k.
Sol.
Q.40 At 27°C it was observed during a reaction of

hydrogenation that the pressure of hydrogen gas de-
creases from 2 atmosphere to 1.1 atmosphere in 75
minutes. Calculate the rate of reaction (in M sec–1)
and rate of reaction in terms of pressure.
Sol. Q.43 The decomposition of N2O5 according to the

equation 2N2O5 (g) → 4 NO2(g) + O2 (g) is a first order
reaction. After 30 min. from start of decomposition in
a closed vessel the total pressure developed in found
to be 284.5 mm Hg. On complete decomposition, the
toal pressure is 584.5 mm Hg. Calculate the rate con-
stant of the reaction.
Sol.
Q.41 At 100° C the gaseous reaction A → 2B + C

was observed to be of first order. On starting with
pure A it is found that at the end of 10 minutes the
total pressure of system is 176 mm. Hg and after a
long time 270 mm Hg. From these data find (a) initial
pressure of A (b) the pressure of A at the end of 10 Q.44 The thermal decomposition of dimethyl ether
minutes (c) the specific rate of reaction and (d) the as measured by finding the increase in pressure of the
half life period of the reaction ? reaction.
Sol. (CH3)2 O(g) → CH4(g) + H2(g) + CO (g)
At 500° C is as follows :
Time (sec.) 390 1195 3155 ∞
Pre. increase (mm Hg) 96 250 467 619
the initial pressure of ether was 312 mm Hg. Write
the rate equation for this reaction and determine the
rate constant of reaction.
Sol.
3
Q.42 The reaction AsH3(g) → As(s) + H2 ( g) was
2
followed at constant volume at 310°C by measuring
the gas pressure at intervals Show from the following
figures that reaction is of first order.
Time (in hrs) 0 5 7.5 10
Total pressure (in mm) 758 827 856 882
Sol.
Q.45 From the following data show that decomposi- Sol.

tion of H2O2 in aqueous solution is first order.
Time (in minutes) 0 10 20
Volume (in c.c. of KMnO4) 22.8 13.3 8.25
Sol.
Q.46 A definite volume of H2O2 under going sponta-

neous decomposition required 22.8 cc. of standard
permanganate solution for titration. After 10 and 20
minutes respectively the volumes of permanganate
required were 13.8 and 8.25 c.c.
Q.48 In the hydrolysis of propyl acetate in the pres-
(a) Find order of reaction. How many the result be
ence of dilute hydrochloric acid in dilute aqueous so-
explained ?
lution the following data were recorded :
(b) Calculate the time required for the decomposition
Time from start in minutes 60 350
to be half completed.
Percentage of ester decomposed 18.17 69.12
(c) Calculate the fraction of H2O2 decomposed after
25 minutes. Calculate the time in which half the ester was decom-
posed.
Sol.
Sol.
Q.49 Hydrogen peroxide solution was stored in a mild

steel vessel. It was found, however, that the hydro-
gen peroxide decomposed on the walls of the vessel
Q.47 The following data were obtained in experi-
ment on inversion of cane sugar. (a first order reaction). An experiment with 100 ml of
a solution gave 10.31 ml oxygen (corrected to 1 atm
Time (minutes) 0 60 120 180 360 ∞
& 273 K) after 5.1 days under similar storage condi-
Angle of +13.1 +11.6 +10.2 +9.0 +5.87 –3.8 tions. Find how long the peroxide can be stored be-
rotation (degree) fore the loss of 20.00 ml oxygen occurs (per 100 ml
Show that the reaction is of first order. After what solution) if complete decomposition of the sample to
time would you expect a zero reading in polarimeter ? H2O2 gave 46.34 ml oxygen.
Sol. Sol.
k1 B
A
Q.52 k1 = x hr–1 ; k1 : k2 = 1 : 10. Calcu-
k2 C
[ C]
late after one hour from the start of the reaction.
[A]
Assuming only A was present in the beginning.
Sol.
Q.50 The reaction given below, rate constant for
disappearance of A is 7.48 × 10–3 sec–1. Calculate the
time required for the total pressure in a system con-
taining A at an initial pressure of 0.1 atm to rise to
0.145 atm and also find the total pressure after 100
sec. 2A (g) → 4B(g) + C (g)
Sol.
Q.53 A substance undergoes first order decomposi-

tion. The decomposition follows two parallel first or-
k1 B
A
der reactions as ; k1 = 1.26 × 10–4 sec–1
k2 C
and k2 = 3.6 × 10–5 sec–1. Calculate the % distribution
of B & C.
Sol.
PARALLEL AND SEQUENTIAL REACTION

k1 y
Q.51 For a reaction x , calculate value of ra-

k2 z
[ x] t
tio, at any given instant t.
[ y] + [ z]
Q.54 For a reaction A → B → C t1/2 for A & B are 4 Q.56 The energy of activation of a first order reac-
and 2 minutes respectively. How much time would be tion is 104.5 kJ mole–1 and pre-exponential factor (A) is
required for the B to reach maximum concentration. 5 × 10–13 sec–1. At what temperature, will the reaction
Sol. have a half life of 1 minute ?
Sol.
Q.57 The specific rate constant for a reaction in-

creases by a factor of 4, if the temperature is changed
from 27°C to 47°C. Find the activation energy for the
reaction.
Sol.
TEMPERATURE DEPENDENCE OF RATE (ACTIVA-
TION ENERGY)
Q.55 In gaseous reactions important for understand-

ing the upper atmosphere, H2O and O react bimolecu-
larly to form two OH radicals. ∆H for this reaction is
72 kJ at 500 K and Ea = 77 kJ mol–1, then calculate Ea
for the bi ol ec ul ar rec om bi nati on of
2 OH radicals to form H2O & O at 500 K
Sol.
Q.58 The energy of activation and specific rate con-

stant for a first order reaction at 25°C are 100 kJ/
mole and 3.46 × 10–5 sec–1 respectively. Determine
the temperature at which half life of the reaction is 2
hours.
Sol.
Q.61 Given that the temperature coefficient for the

saponification of ethyl acetate by NaOH is 1.75. Cal-
culate activation energy for the saponification of ethyl
acetate.
Sol.
Q.59 A first order reaction is 50% complete in 30

minutes at 27°C and in 10 minutes at 47°C. Calculate
the
(a) rate constant for the reaction at 27°C & 47° C and
(b) energy of activation for the reaction.
Sol.
Q.62 At 380°C, the half-life period for the first order

decomposition of H2O2 is360 min. The energy of acti-
vation of the reaction is 200 kJ mol–1. Calculate the
time required for 75% decomposition at 450°C.
Sol.
Q.60 A catalyst lowers the activation energy for a

certain reaction from 75 kJ to 25 kJ mol–1. What will
be the effect on the rate of reaction at 25°C, after
things being equal.
Sol.
MECHANISM OF REACTION
1  d[NO 2 ]  2
  = K [NO] [O 2 ]
Q.63 The reaction 2NO + Br2 → 2NOBr, is supposed 2  dt 
to follow the following mechanism
Sol.
(i) NO + Br2 fast NOBr2
(ii) NOBr2 + NO slow 2NOBr

Suggest the rate of law expression.
Sol.
Q.66 Deduce rate law expressions for the conver-

sion of H2 and I2 to HI at 400°C corresponding to each
of the following mechanisms :
(a) H2 + I2 → 2HI (one step)
(b) I2 2I
2 I + H2 → 2HI (slow)
(c) I2 2I
Q.64 For the reaction 2H2 + 2NO → N2 + 2H2O, the I + H2 I H2
following mechanism has been suggested :
IH2 + I → 2 H I (slow)
2NO N2O2 equilibrium constant K1 (fast)
(d) Can the observed rate law expression rate =
N2O2 + H2 K2 → N2O + H2O (slow) k[H2][I2] distinguish among these mechanisms ?
(e) If it is known that ultraviolet light causes the
N2O + H2 K

3
→ N2 + H2O (fast) reaction of H2 and I2 to proceed at 200° C with the
Establish the rate law for given reaction. same rate law expression, which of these mechanisms
becomes most improbable ? Are any of these mecha-
Sol.
nisms proved ?
Sol.
Q.65 Reaction between NO and O2 to form NO2 is

2NO + O2 → 2NO2 follows the following mechanism
K1
NO + NO N2O2 (in rapid equilibrium)
K–1
N2O2 + O2 K2 → 2NO2 (slow)
Show that the rate of reaction is given by
Fill in the blanks Q.2 True or False Statements :

1. The half-life period of radioactive element if 75% of 1. Order of a reaction can be written from the bal-
it disintegrates in 40 min is ___________. anced chemical equation.
2. For collision to be effective the energy possessed
by the colliding molecules should be equal to or greater 3
2. For a reaction having order equal to , the units
than the _______________ 2
3. In the reaction, H2 + I2 → 2HI, the rate of disap- for rate constant are sec–1.
pearance of H2 is _________ the rate of appearance 3. In a complex reaction the rate of overall reaction is
of HI. governed by the slowest step.
4. For an endothermic process, the minimum value of 4. t1/2 for a first order reaction is 6.93 s, the value of
activation energy can be ________. rate constant for the reaction would be 10s–1.
5. The rate of a reaction is ______________ to the t1/ 2
collision frequency. 5. The ratio t for a first order reaction is equal to
7 /8
6. The rate constant for the zero order reaction has
1/3
the dimensions __________________.
6. The rate of an exothermic reaction increases with
7. The reactions with molecularity more than three
the rise in temperature.
are ________________.
7. Molecularity of a reaction is always whole number.
8. A catalyst increases the rate of the reaction by
_____________ activation energy of reactants. 8. The reactants which are thermodynamically unstable
9. If activation energy of reaction is low, it proceeds are always kinetically unstable also.
at _______________ rate. 9. Order and molecularity of a single step reaction
10. In a multistep reaction, the ____________ step may or may not be same.
is rate determining. 10. The activation energy of a catalysed reaction is
11. R at e cons tant of a re ac ti on, ge ne ral l y more than the activation energy of the uncatalysed
______________ with increase in temperature. reaction.
12. The ratio t 7 / 8 / t1/ 2 for a first order reaction would 11. For a zero order reaction t 3 / 4 is related to t1/ 2 as
be equal to _____________ t 3 / 4 = 1.5 t1/ 2
13. For a zero order reaction, the rate of the reac-
12. A nuclide having one proton and one neutron is
tion is equal to the _________________of the reac-
tion. represented as 11H .
14. The value of temperature coefficient is generally
13. A radioactive element decays by emitting one α
between _____________________.
and two β-particles. The daughter element formed is
15. For a certain reaction, xM → yL, the rate of re- an isotope of the parent element.
action increases by 4 times when the concentration
14. The daughter product formed by the emission of
of M is doubled. The rate law is ______________.
α-particle has mass number less by 4 units than the
16. The rate equation r = k[ A ][B]1/ 2 suggests that or- parent nuclide.
der of overall reaction is ____________. 27 29
15. 13 Al is a stable isotope while 13 Al is expected to
17. 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 disintegrate by β-emission.
________. 16. Half-life period of a radioactive substance can
18. [Eactivated complex – Ereactants] = _______________. be changed by using some suitable catalyst.
19. In the Arrhenius equation k = Aexp (– E/RT), A 17. Emission of a β-particle by a radioactive nuclide
may be t erme d as t he rat e cons tant at N
______________ results in decrease in ratio.
P
20. For a ________________ order reaction the half-
life (t1/2) is independent of the initial conc. of the 18. Positron has same mass as that of an electron.
reactants. 19. 14
and 16
are isotones.
9 N 8 O
21. For a first order reaction a graph of log[A] vs t
has a slope equal to ____________ 20. The S.I. unit of activity is Curie (Ci).
22. Av erag e l i fe ti me of a nucl ei ,
Tav = ________________ t1/2.
Exercise - IV Subjective Level-II

1. The approach to the following equilibrium was ob- NO2 + H2O obeys the rate law for pseudo first order
served kinetically from both directions : kinetics in the presence of a large excess of hydrox-
ide ion. If 1% of nitro ethane undergoes reaction in
PtCl2–
4 + H2O [Pt(H2O)Cl3– ] + Cl– at 25°C, it was half a minute when the reactant concentration is 0.002
found that M, What is the pseudo first order rate constant ?
∆
– [PtCl24– ] = [3.9 × 10–5 sec–1] [PtCl24– ] – [2.1 × 10–
∆t 6. The decomposition of a compound P, at tempera-
3 – – ture T according to the equation
L.mol –1 –1
sec ] × [Pt(H2 O)Cl3 ] [Cl ] What is the value
of equilibrium constant for the complexation of the 2P( g) → 4Q ( g) + R( g) + S( l ) is the first order reaction. Af-
fourth Cl– by Pt(II) ? ter 30 minutres from the start of decomposition in a
closed vessel, the total pressure developed is found
2. A solution of A is mixed with an equal volume of a to be 317 mm Hg and after a long period of time the
solution of B containing the same number of moles, total pressure observed to be 617 mm Hg. Calculate
and the reaction A + B = C occurs. At the end of 1h, the total pressure of the vessel after 75 mintute, if vol-
A is 75% reacted. How much of A will be left unreacted ume of liquid S is supposed to be negligible. Also calculate
at the end of 2 h if the reaction is (a) first order in A the time fraction t 7 / 8 .
and zero order in B; (b) first order in both A and B ;
Given : Vapour pressure of S(l) at temperature T =
and (c) zero order in both A and B ?
32.5 mm Hg
3. If a reaction A → Products, the concentrations of

7. A certain reactant Bn+ is getting converted to B(n+4)+
reactant A are C0, aC0, a2C0, a3C0,................ after
in solution. The rate constant of this reaction is mea-
ti me i nt erval
sured by titrating a volume of the solution with a
0, t, 2t, 3t,.................. where a is a constant. Given
reducing reagent which only reacts with Bn+ and B(n +
0 < a < 1. Show that the reaction is of first order. Also
4)+
. In this process, it converts Bn+ to B(n–2)+ and B(n+4)+
calculate the relation in k, a and t.
to B(n–1)+. At t = 0, the volume of the reagent con-
sumed is 25 ml and at t = 10 min, the volume used up
4. The complex [CO(NH3)5F]2+ reacts with water ac- is 32 ml. Calculate the rate constant of the conver-
cording to the equation.
sion of Bn+ to B(n+ 4 )+ assuming it to be a first order
[Co(NH3 ) 5 F] 2+ + H2O → [Co(NH3 )5 (H2O)] 3 + + F –
reaction.
The rate of the reaction = rate const. × [complex]a
× [H+]b. The reaction is acid catalysed i.e. [H+] does
8. Decomposition of H2O2 is a first order reaction. A
not change duri ng the reacti on. Thus rate =
k[Complex]a where k' = k [H+]b, calculate 'a' and 'b' solution of H2O2 lebelled as "16.8 V" was left open.
given the following data at 25°C. Due to this, some H2O2 decomposed. To determine
the new volume strength after 2.303 hours, 20 mL of
[Complex] M [H+] M T1/ 2hr T3 / 4 hr
this solution was diluted to 100 mL. 25 mL of this
0.1 0.01 1 2 diluted solution was titrated against 37.5 mL of 0.02
0.2 0.02 0.5 1 M KMnO4 solution under acidic conditions [Given : STP
is 1 atm and 273 K] Calculate the rate constant (in
5. The reaction CH3 – CH2 – NO2 + OH– → CH3 – CH –
hr–1) for decomposition of H2O2.
9. A metal slowly forms an oxide film which completely 14. Two reactions (i) (A) → products (ii) B → prod-
protects the metal when the film thickness is 3.956 ucts, follow first order kinetics. The rate of the reac-
thousand ths of an inch. If the film thickness is 1.281 tion (i) is doubled when the temperature is raised from
thou. in 6 weeks, how much longer will it be before it 300 K to 310 K. The half life for this reaction at 310 K
is 2.481 thou? The rate of film formation follows first is 30 minutes. At the same temperature B decom-
order kinetics. poses twice as fast as A. If the energy of activation
for the reaction (ii) is half that of reaction (i), calcu-
10. An optically active compound A upon acid late the rate constant of the reaction (ii) at 300 K.
catalysed hydrolysis yield two optically active com-

15. A certain organic compound A decomposes by
pound B and C by pseudo first order kinetics. The
two parallel first order mechanism
observed rotation of the mixture after 20 min was 5°
B
k1
while after completion of the reaction it was –20°. If
A If k1 : k2 = 1 : 9 and k1 = 1.3 × 10–5 s–1.
optical rotation per mole of A, B & C are 60°, 40° & – k2
C
80°. Calculate half life of the reaction.
Calculate the concentration ratio of C to A, if an ex-
periment is started with only A and allowed to run for
11. A vessel contains dimethyl ether at a pressure of
one hour.
0. 4 at m. D i m et hy l et he r de comp os es as
CH3 OCH3 (g) → CH4 (g) + CO(g) + H2 ( g) . The rate constant 16. The reaction
k1
of decomposition is 4.78 × 10–3 min–1. Calculate the cis − Cr(en) 2 (OH) + 2 trans-Cr(en)2 (OH)+2
k2
ratio of initial rate of diffusion to rate of diffusion
is first order in both directions. At 25°C the equilib-
after 4.5 hours of initiation of decomposition. Assume
rium constant is 0.16 and the rate constant k1 is 3.3
the composition of gas present and composition of
× 10–4s–1. In an experiment starting with the pure cis
gas diffusing to be same.
form, how long would it take for half the equilibrium
amount of the trans isomer to be formed ?
12. At room temperature (20°C) orange juice gets
k1
spoilt in about 64 hours. In a referigerator at 3°C
17. For a reversible first-order reaction A B
juice can be stored three times as long before it gets k2
[B]eq
spoilt. Estimate (a) the activation energy of the re- k1 = 10–2 s–1 and [ A] = 4. If [A]0 = 0.01 mole L–1 and
eq
action that causes the spoiling of juice. (b) How long
[B]0 = 0, what will be the concentration of B after 30 s ?
should it take for juice to get spoilt at 40° C ?
18. For the system A(g) B(g), ∆H for the for-

13. A first order reaction, A → B, requires activation
ward reaction is –33 kJ/mol (Note : ∆H = ∆E in this
energy of 70 kJ mol–1. When a 20% solution of A was
[B]
kept at 25°C for 20 minutes, 25% decomposition took case). Show that equilibrium constant K = = 5.572
[ A]
place. What will be percent decomposition in the same × 105 at 300 K. If the activation energies Ef & Eb are
time in a 30% solution maintianed at 40°C? Assume in the ratio 20 : 31, calculate Ef and Eb at this tem-
that activation energy remains constant in this range perature. Assume that the pre-exponential factor is
of temperature. the same for the forward and backward reactions.
19. (a) The reaction A proceeds in parallel channels 23. The catalytic decomposition of formic acid may
B take place in two ways.
A Although the A → C branch is thermodynami- (a) HCOOH = H2O + CO
C
cally more favorable than the branch A → B, the prod- (b) HCOOH = H2 + CO2.
uct B may dominate in quantity over C. Why may this The rate constant and activation energy for reaction
be so ? (a) are 2.79 × 10–3 min–1 at 237°C and 12.0 kcal mole–
1
respectively and for reaction (b) are 1.52 × 10–4
(b) In the above problem, suppose the half life val-
min–1 at 237°C and 24.5 kcal mole–1 respectively. Find
ues for the two branches are 60 minutes and 90 min-
the temperature which will give a product made up of
utes, what is the overall half-life value?
equimolar quantities of water vapour, carbon monox-
ide, hydrogen and carbon dioxide.
k1
20. For the two parallel reactions A  → B and
24. For the following first order gaseous reaction
k2
A  → C , show that the activation energy E' for the
k1
2B(g)
disappearance of A is given in terms of activation
A(g)
energies E1 and E2 for the two paths by
C(g)
k E + k 2E2 k2
E' = 1 1
k1 + k 2 The initial pressure in a container of capacity Vlitres
is 1 atm. Pressure at time t = 10 sec is 1.4 atm and
k1 after infinite time it becomes 1.5 atmosphere. Find
21. For the mechanism A + B C; k
k2 C 
3
→D the rate constant k1 and k2 for the appropriate reac-
(a) Derive the rate law using the steady-state ap- tions.
proximation to eliminate the concentration of C.
(b) Assuming that k3 < < k2, express the pre-expo- 25. The gaseous reaction : n1A(g) → n2B(g) is first
nential factor A and Ea for the apparent second-order order with respect to A. It is studied at a constant
rate constant in terms of A1, A2 and A3 and Eal, Ea 2 pressure, with a0 as the initial amount of A.Show that
and Ea 3 for the three steps. the volume of system at the concentration of A at
time 't' are given by the expressions.
22. The reaction of formation of phosgene from CO
and Cl2 is CO + Cl2 → COCl2 The proposed mechanism  n   n  
V = V0  2  –  2 – 1 exp(–n1kt) ;
is  n1   n1  
k1
(i) Cl2 2 Cl (fast equilibrium)  
k –1  
k2  exp(–n1kt) 
[ A] t = [ A]0  
(ii) Cl + CO COCl (fast equilibrium)  
  n 2  –  n 2  – 1 exp(–n kt) 
  n1   n1  
k –2 1

(iii) COCl + Cl2 K    
3
→ COCl2 + Cl (slow)
Show that the above mechanism leads to the follow-
d [COCl2 ]
i ng rat e l aw = K [CO][Cl2 ]3 / 2 Where
dt
1/ 2
k 2  k1 
K = k3.  
k − 2  k − 1
Exercise - V JEE-Problems
OBJECTIVE PROBLEM 3. If I is the intensity of absorbed light and C is the
concentration of AB for the photochemical process
1. Which of the following statement(s) is (are) correct AB + hv → AB*, the rate of formation of AB* is
1 directly proportional to [JEE SCR 2001]
(A) A plot of log Kp versus is linear
T (A) C (B) I (C) I2
(D) CI
(B) A plot of log [X] versus time is linear for a first Sol.
order reaction, X → P
1
(C) A plot of log P versus is linear at constant
T
volume.
1
(D) A plot of P versus is linear at constant
V
temperature. [JEE 1999]
Sol.
4. Consider the chemical reaction, N2(g) + 3H2(g) →

2NH3(g). The rate of this reaction can be expressed in
term of time derivative of concentration of N2(g), H2(g)
or NH3(g). Identify the correct relationship amongst
the rate expressions. [JEE SCR 2002]
d[N2 ] 1 d[H2 ] 1 d[NH3 ]

(A) Rate = – =– =
dt 3 dt 2 dt
d[N2 ] 3d[H2 ] 2d[NH3 ]

(B) Rate = – =– =
2. The rate constant for the reaction dt dt dt
2N2O5 → 4NO2 + O2
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
is 3.0 × 10–5 sec–1. If the rate is 2.4 × 10–5 mol litre–1 (C) Rate = = =
dt 3 dt 2 dt
sec–1, then the concentration of N2O5 (in mol litre–1) is
[JEE SCR 2000] d[N2 ] – d[H2 ] d[NH3 ]
(A) 1.4 (B) 1.2 (C) 0.004 (D) 0.8 (D) Rate = = =
dt dt dt
Sol. Sol.
5. In a first order reaction the concentration of Sol.

reactant decreases from 800 mol/dm3 to 50 mol/dm3
in 2 × 104 sec. The rate constant of reaction in sec–1
is : [JEE SCR 2003]
(A) 2 × 104 (B) 3.45 × 10–5
(C) 1.3486 × 10–4 (D) 2 × 10–4
Sol.
8. 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 2006]
6. The reaction, X → Product follows first order (A) 0 (B) 1 (C) 2 (D) 3
kinetics. In 40 minutes the concentration of X changes Sol.
from 0.1 M to 0.025 M. Then the rate of reaction
when concentration of X is 0.01 M [JEE SCR 2004]
(A) 1.73 × 10–4 M min–1 (B) 3.47 × 10–5 M min–1
–4
(C) 3.47 × 10 M min –1
(D) 1.73 × 10–5 M min–1
Sol.
9. Under the same reaction condi ti ons, i ni ti al

7. Which of the following statement is incorrect about concentration of 1.386 mol dm–3 of a substance
order of reaction ? [JEE 2005] becomes half in 40 seconds and 20 seconds through
(A) Order of reaction is determined experimentally first order and zero order kinetics, respectively. Ratio
(B) It is the sum of power of concentration terms in  k1 
the rate law expression   of the rate constants for first order (k ) and
 k0  1
(C) It does not necessarily depend on stoichiometric
zero order (k0) of the reactions is [JEE 2008]
coefficients.
(A) 0.5 mol–1 dm3 (B) 1.0 mol dm–3
(D) Order of the reaction can not have fractional value.
(C) 1.5 mol dm–3 (D) 2.0 mol–1 dm3
Sol. [JEE 2010]

Sol.
12. For the first order reaction [JEE 2011]

2N2O5(g) → 4NO2(g) + O2(g)
10. For a first order reaction A → P, the temperature (A) The concentration of the reactant decreases ex-
(T) dependent rate constant (k) was found to follow ponentially with time.
the equation log k = – (2000) 1/T + 6.0. The pre- (B) The half-life of the reaction decreases with in-
exponential factor A and the activation energy Ea, creasing temperature.
respectively, are
(C) The half-life of the reaction depends on the initial
(A) 1.0 × 106s–1 and 9.2 kJ mol–1
concentration of the reactant.
(B) 6.0 s–1 and 16.6 kJ mol–1
(D) the reaction proceeds to 99.6% completion in
(C) 1.0 × 106 s–1 and 16.6 kJ mol–1 eight half-life duration.
(D) 1.0 × 106 s–1 and 38.3 kJ mol–1 [JEE 2009]
Sol.
Sol.
SUBJECTIVE PROBLEM
13. The rate constant for an isomerisation reaction

A → B is 4.5 × 10–3 min–1. If the initial concentration
of A is 1M. Calculate the rate of the reaction after 1
11. Plots showing the variation of the rate constant
h. [JEE 1999]
(k) with temperature (T) are given below. The plot
that follows Arrhenius equation is Sol.
k k
(A) (B)
T T
k k
(C) (D)
T T
14. A hydrogenation reaction is carried out at 500 K. 16. 2X(g) → 3Y(g) + 2Z(g)
If the same reaction is carried out in the presence of Time (in Min) 0 100 200
a catalyst at the same rate, the temperature required Partial pressure of X 800 400 200
is 400 K. Calculate the activation energy of the reaction
(in mm of Hg)
if the catalyst lowers the activation barrier by 20 kJ
mol–1. [JEE 2000] Assuming ideal gas condition. Calculate
Sol. (A) Order of reaction
(B) Rate constant
(C) Time taken for 75% completion of reaction
(D) Total pressure when Px = 700 mm. [JEE 2005]
Sol.
15. The rate of 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. 17. The concentration of R in the reaction R→ P was
[JEE 2001] measured as a function of time and the following data
Sol. is obtained:
[R] (molar) 1. 0 0.75 0.4 0 0.1 0

t(min.) 0. 0 0.05 0.12 0.18
[JEE 2010]
The order of the reaction is
Sol.
Answer-Key
Exercise-I
1. B 2. D 3. B 4. D 5. A 6. B
7. C 8. D 9. B 10. D 11. B 12. C
13. D 14. A 15. B 16. D 17. A 18. A
19. B 20. B 21. B 22. B 23. B 24. C
25. C 26. C 27. C 28. B 29. D 30. D
31. D 32. D 33. A 34. B 35. C 36. D
37. C 38. B 39. A 40. C 41. B 42. A
43. D 44. C 45. A 46. B 47. C 48. A
49. D 50. A 51. B 52. C 53. C 54. D
55. A 56. B 57. A 58. D 59. A 60. B
61. B 62. A 63. D 64. A 65. A 66. B
67. B 68. B 69. D
70. A → Q,R, B → Q,R, C → Q,S, D → S 71. A → R, B → Q, C → P, D → S
Exercise-II
1. C,D 2. A,B 3. B 4. B,C 5. A,B,C 6. B,C,D

7. A,B,C,D 8. A,B,C 9. B,D 10. A,C 11. B,C 12. A,B,D
13. A,B,C 14. A,C,D 15. A,B
Exercise-III
RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT
1. (a) 0.04 (b) 0.02 2. (a) 0.019 mol L–1 s–1, (b) 0.037 mol L–1 s–1
dx
3. 2k1 = k2 = 4k3 4. (i) = k[A] [B]2, (ii) rate increases by 8 times
dt
5. rate increase by 27 times
1 d[NO]
6. (i) r = = 9 × 10 –4 mol litre–1 sec–1, (ii) 36 × 10–4 mol litre–1 sec–1, (iii) 54 × 10–4 mol litre–1 sec–1
4 dt
1
7. (i) 7.2 mol litre–1 min–1, (ii) 7.2 mol litre–1 min–1 8.
6
ZERO ORDER
9. (i) 7.2 M, (ii) 10 M 10. K = 0.01 M min–1 11. 0.75 M 12. 6 × 10–9 sec
13. 1.2 hr
FIRST ORDER
14. (i) 36 min, (ii) 108 min. 15. (i) 0.0223 min–1, (ii) 62.17 min 17. 924.362 sec.
18. expiry time = 41 months 19. 3.3 × 10–4 s–1 20. 62.13 min 21. 11.2 %
ORDER OF REACTION & RATE LAW
22. (a) Third order, (b) r = k [NO]2 [H2], (c) 8.85 × 10–3 M sec–1
23. (a) order w.r.t NO = 2 and w.r.t Cl2 = 1, (b) r = K [NO]2 [Cl2], (c) K = 8 L2 mol–2 s–1
(d) rate = 0.256 mole L–1 s1
24. (i) first order (ii) k = 1.308 × 10–2 min–1 (iii) 73%
25. (i) rate = [A][B] ; (ii) k = 4 × 10–2 M–1 s–1 ; (iii) rate = 2.8 × 10–3 M s–1
5Pa
26. (i) Zero order, (ii) K = 27. Zero order
s
dx
28. (a) n = 1, (b) = k[CH3COCH3], (c) 8.67 × 10–3 s–1, (d) 1.56 × 10–5 M s–1
dt
HALF LIFE
29. 166.6 min 30. 5.26%, 4.62 × 105 sec 32. (i) t = 13.96 hrs, (ii) 2.2176 litre
33. 54 min 34. 15 min
CONCENTRATION REPLACED BY OTHER QUANTITIES IN FIRST ORDER INTEGRATED RATE LAW
1 P3 1 P3 1 V1
35. K = ln 36. K = ln 37. K = t ln (2V – V )
t 2(P3 – P2 ) t (P3 – P2 ) 1 2
1 4 V3 1 r∞
38. K = ln K = ln
t 5( V3 – V2 ) 39. t (r∞ – r1 ) 40. 8.12 × 10–6 Ms–1, 0.012 atm min–1
41. (a) 90 mm, (b) 47 mm, (c) 6.49 × 10–2 per minutes, (d) 10.677 min.
42. First order 43. k1 = 2.605 × 10–3 min–1
44. (i) r = K[(CH3)2O], 0.000428 sec–1 45. First order
46. (a) first order, (b) 13.75 minutes, (c) 0.716
47. 966 min 48. 206.9 min 49. 11.45 days 50. 0.180 atm, 47.69 sec.
PARALLEL AND SEQUENTIAL REACTION
1 [C] 10 11x
51. 52. = (e – 1) 53. 77.7, 22.3 54. t = 4 min
e(K 1 +K 2 ) t – 1 [ A ] 11
TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)
55. 5 kJ mol–1 56. 349.1 k 57. 55.33 kJ mole–1 58. 306 k
59. (a) 2.31 × 10–12 min–1, 6.93 × 10–2 min–1, (b) 43.85 kJ mole–1
60. rate of reaction increases 5.81 × 108 times
61. 10.272 k cal mol–1 62. t = 20.4 minutes
MECHANISM OF REACTION
63. r = K′ [NO]2 [Br2] 64. r = K [NO]2 [H2], where K = k2 × K1

66. (d) No, (e) mechanism (a) is incorrect
PROFICIENCY TEST
Q.1
1. 20 min. 2. threshold energy 3. half 4. equal to ∆H
5. directly proportional 6. mol L–1 s–1 7. rare 8. lowering
9. faster 10. slowest 11. increases 12. 3
13. rate constant 14. 2 and 3 15. rate = k [M]2
1
16. 1 17. –k 18. Activation energy
2
k
19. infinte temp. or zero Ea 20. first 21. – 22. 1.44
2.303
Q.2
1. False 2. False 3. True 4. False 5. True
6. True 7. True 8. False 9. False 10. False
11. True 12. False 13. True 14. True 15. True
16. False 17. True 18. True 19. False 20. False
Exercise-IV
2.303 1
1. (a) 6.25 ; (b) 14.3 ; (c) 0% 2. 53.84 3. K = log 4. a = b = 1
t a
5. 2 × 10–2 min–1 6. Pt = 379.55 mm Hg, t7/8 = 399.96 min 7. 0.0207 min–1

8. 0.60 9. 15.13 week 10. 20 min 11. 0.26 : 1
12. –1
(a) 43.46 kJmol , (b) 20.47 hour 13. % decomposition = 67.21%
14. k = 0.0327 min–1 15. 0.537 16. 4.83 mins 17. 0.0025 m
18. Ef = 6 × 104 J; Eb = 9.3 × 104 J 19. (b) t1/2 = 36 min
d(D) k 1k 3 ( A)(B) A 1A 3
21. (a) =
k 2 + k 3 ; (b) Ea = Ea 1 Ea 3 – Ea2.A = A 2
+
dt
23. 399° C ; R = 1.987 Kcal. mol–1 K–1 24. 0.0805
Exercise-V
OBJECTIVE PROBLEM
1. A,B,D 2. D 3. B 4. A 5. C 6. C
7. D 8. D 9. A 10. D 11. A 12. ABD
SUBJECTIVE PROBLEM
13. 3.435 × 10–3 M/min 14. 100 kJmol–1 15. t1/2 = 24.14 min
16. (B) 1 (B) 6.93 × 10–3 min (C) 200 min (D) 950 mm 17. 0

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Page # 44 CHEMICAL KINETICS

Class Room Problems

3I– + S2O82– → I3– + 2SO42–

Ex.4 For a reaction 2P + Q → S ; following data were

0.01 0.01 0.005

0.02 0.01 0.010

0.01 0.02 0.005

What is the rate law ? What is the half-life of A in the

Ex.5Given the following steps in the mechanism for a

Sol. Ex.8The rate of a first order reaction is 0.04 mol lit–1

Ex.7 A & B are two different chemical species

Ex.9A solution of A is mixed with an equal volume of a

Ex.11 Inversion of sucrose is studied by measuring

Reagent reacts with all A, B and C and have 'n' factors

Ex.12 The first order reaction :sucrose  → Glu-

Sol. Ex.14 When the catalyst is removed from a reaction

Ex.13 At room temperature (200C) milk turns sour in

constants for different steps of the reaction

Ex.15 The effective activation energy is

(b) E' a = Ea1 + Ea2 + E a3 + Ea5

(c) E' a = Ea1 + Ea2 – E a3 – Ea5

(d) E' a = Ea2 + Ea3 – E a5 – Ea1

Ex.17 Which one is correct ?

Ex.16 The effective frequency factor

Ex.18 For the reaction A → B, the rate law expression

Sol. Ex.20 An organic compound A de composes following

[B] [C] [D]

Ex.21. The reaction

is first order is both directions. At 25°C the equilibrium

constant is 0.16 and the rate constant k1 is 3.3 × 10–

of the trans isomer to be formed ?

Ex.23 For a reaction A2 + B2 → 2AB, evaluate the

Ex.22 Two reactions (i) A → products (ii) B →

Ex.24 A reaction proceeds five times more at 60ºC as

Ex.26 A first order reaction A → B requires activation

Ex.25 For the reaction A B, ∆E for the reaction is

Ex.28 The energy of activation for a reaction is 100

(ii) the rate of formatiuon of oxygen under this condi-

Exercise - I (Only one option is correct)

2. The rate constant for the forward reaction

3. Reaction A + B → C + D follow's following rate law :

Rate law for reaction from above data is

Sol. 9. For the reaction, 2NO(g) + 2H2(g) → N2(g) + 2H2O

7. For a reaction pA + qB → products, the rate law

8. In the reaction : A + 2B → 3C + D, which of the

14. The following mechanism has been proposed for

12. For the first order reaction A → B + C, carried

ecules exists in the activated state, the Ea (acti- AB+I A+P

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

15. Choose the correct set of identifications.

25. Graph between conc. of the product and time of

26. Mathematical representation for t1/4 life for first

27. For a reaction A → Products, the conc. of reac-

30. In acidic medium the rate of reaction between

38. A subtance undergoes first order decomposition.

k1 Question No. 42 to 43 (2 questions)

40. For 2A  → B →

42. The exponential variation of 'f' with t(hrs) is given by

(C) e –3 t /200 (D) e3 t / 200

45. For a reaction Ea = 0 and k = 3.2 × 105 s–1 at 325 K.

(C) A + B → C ; E a = 10.5 kJ (D) L + M → N; E a = 5 kJ

47. Activation energies of two reaction are Ea and E′a