Chemistry Question Bank

Batch : C C
CHEMICAL KINETICS
SINGLE CHOICE QUESTIONS

+
1. For the complex [Ag(NH3)2+]
, Ag + 2NH3
 dx 
  = 2 × 107 L2 mol–2 s–1 [Ag+] [NH ]2 – 1 × 10–2 s–1 [Ag(NH ) +]
 dt  3 3 2

Hence, ratio of rate constants of the forward and backward reactions is :

(A) 2 × 107 L2 mol–2 (B*) 2 × 109 L2 mol–2 (C) 1 × 10–2 L2 mol–2 (D) 0.5 × 10–9 L2 mol–2
Sol. Equation
Ag+ + 2NH3 [Ag(NH3)2+]
Given
dx
= 2 × 107 L2 mol–2 s–1 [Ag+] [NH3]2 – 1 × 10–2 s–1 [Ag(NH3)2+]
dt
dx
For equilibrium =0
dt
2 × 107 [Ag+] [NH3]2 – 1 × 10–2 [Ag(NH3)2+] = 0

[ Ag(NH3 )2 ] 2  10 7
 2 = = 2 × 109 , L2 mol–2.
[ Ag ][NH3 ] 1 10 2
2. In the reaction N2 + 3H2 2NH3

 dx  [N2 ] [H2 ] 3
  = 1 × 102 [N ] [H ]3 – 1 × 10–3 [NH ]2 and at some instant if = 10–5 M2
 dt  2 2 3 [NH3 ] 2

 dx 
then at this instant value of   is:
 dt 

(A*) 0 (B) 1 × 105 (C) 1 × 10–5 (D) 1 × 10–3

Sol. Given Rxn

N2 + 3 H2 2 NH3
dx
= 1 × 102 [N2] [H2]3 – 1 × 10–3 [NH3]2
dt

dx [N2 ][H2 ] 3
when =0 then = 10–5
dt [NH3 ] 2
Hence the reaction will be at equilibrium at the given instant.

3. In the following graphical representation for the reaction A  B there are two types of regions :

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 [B]

Conc.

[A]

I: II :

(A) I and II both represent kinetic region at different interval

(B) I and II both represent equilibrium regions at different time interval
(C) I represents kinetic while II represents equilibrium region
(D*) I represents equilibrium while II represents kinetic region
Sol. J represent kinetic but II represent equilibrium region
Because at equilibrium the concentration remains constant.

4. Rate law of the reaction A  Product is, rate = k[A]. Graphically it is represented as

Hence, rate constant is :

(A) 3 × 10–4 s–1 (B*) 1 × 10–2 s–1 (C) 3 × 10–2 s–1 (D) 1 × 10–4 s–1
(Rate ) 1 10 3 3  10 3
Sol. Rate constant K= = = = 1 × 10–2 sec–1
[conc.] .1 .3

5. For a given reaction A  Product, rate is 1 × 10–4 M s–1 when [A] = 0.01 M and rate is 1.41 × 10–4 M s–1 when
[A] = 0.02 M. Hence, rate law is :
d[A] d[A] d [A ] k d[A]
(A)  = k [A]2 (B)  = k[A] (C)   [A ] (D*)  = k[A]1/2
dt dt dt 4 dt
Sol. A  Product
We know Rate = K [conc.]n
1 × 10–4 = K [.01]n .....(i)
1.41 × 10–4 = K [.02]n .....(ii)
(i) / (ii)
n
1  1
=  
1.41  2 

1
n=
2
Then

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 – d(A )
= K [A]1/2
dt
k1
6. Following reaction can take place in both direction A B, For the forward reaction
k2

–1
Rate (M s )

and for the backward reaction

[A],M

[B] Rate
0.01 M 1 × 10–2 Ms–1
0.02 M 2 × 10–2 Ms–1
Hence, net reaction rate of B is :
(A) = k1 [A] – k2 [B] (B*) = k1 – k2 [B] (C) = k1 [A] – k2 (D) = k1 – k2

Sol. Rate of Rxn independent of conc. of A

Net Rxn Rate = K1 [A]0 – K2[B]1
order wrt B is 1 because rate doubles when conc. of B doubles
Then
Net Rxn Rate = k1 – k2 [B].

7. For the following reaction

 dx 
(CH3)3CCl + H2O  (CH3)3 COH + HCl ,   = k[CH3)3CCl], hence, rate determining step can be:
 dt 

(A*) (CH3)3CCl  (CH3)3C+ + Cl– (B) (CH3)3CCl + H2O  (CH3)3COH + HCl
(C) (CH3)3C+ + H2O  (CH3)3COH + H+ (D) H+ + Cl–  HCl
Sol. Rate depends only conc. of [(CH3)3CCl] hence rate determening
Step (CH3)3CCl  (CH3)3 C+ + Cl–

8. For the non-equilibrium process, A + B products, the rate is first-order w.r.t. A and second-order w.r.t. B. If
1.0 mole 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
–3 –1 –1
(C) 2.50 × 10 mol L s (D) 2.0 × 10–2 mol L–1 s–1
Sol. A + B  Product
Initial conc. 1 1
Initially
1.0 × 10–2 = K [1] [1]2
K = 1.0 × 10–2|
When half of reactant reacted
2
 1   1
–2
Rate = 1.0 × 10 2  
   2
Rate = 1.25 × 10–3

9. Select the correct statements out of I, II and III for zeroth order reaction
I : Quantity of the product formed is directly proportional to time
II : Larger the initial concentration of the reactant, greater the half-life period

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 III : If 50% reaction takes place in 100 minutes, 75% reaction take place in 150 minutes.
(A) I only (B) I and II only
(C) II and III only (D*) I, II and III
Sol. We know for zeroth order Rxn
For (I)
x = kt
For (II)
t1/2  [A0] [Initial concentration]

For (III)
A0
A0 – = k × 100 .....(i)
2
A0
A0 – =k×t .....(ii)
4

A0
2 k  100
=
 3 A0  kt
 
 4 

100  3
t=
2
= 150 minutes.

10. A certain zeroth order reaction has k = 0.025 M s–1 for the disappearance of A. What will be the concentration
of A after 15 seconds if the initial concentration is 0.50 M ?
(A) 0.50 M (B) 0.375 M (C*) 0.125 M (D) 0.060 M
Sol. Suppose At
We know (A0 – At) = kt for zeroth order
(.50 – At) = .025 × t
.50 – At = .025 × 15
At = 0.125 M

11. A reaction of first-order completed 90% in 90 minutes, hence, it is completed 50% in approximately :
(A) 50 min (B) 54 min (C*) 27 min (D) 62 min

2.303  100  2.303 2.303

Sol. K= log   = × log10 = min–1
90  100 – 90  90 90

.6932
t1/2 (50% completed) = × 90 = 27 minutes.
2.303

12. T50 (Half-life period) of first-order reaction is 10 minute. Starting with 10 mol L–1, rate after 20 minute is :
(A) 0.0693 mol L–1 min–1 (B*) 0.0693 × 2.5 mol L–1 min–1
–1 –1
(C) 0.0693 × 5 mol L min (D) 0.0693 × 10 mol L–1 min–1
2
 1
Sol. Conc. after at 2 half life (20 minute) =   × (Initial conc.)
2
2
 1
=   × 10 = 2.5 M.
2

.6932
Then Rate = k[at] = × 2.5
10
= .06932 × 2.5

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13. For the first-order reaction Tav (average life), T50 and T75 in the increasing order are :
(A*) T50 < Tav < T75 (B) T50 < T75 < Tav
(C) Tav < T50 < T75 (D) Tav = T50 < T75
Sol. We know
tav = 1.44 × t50%
and t75% = 2 t50%
Then t50% < tav < t75%

14. Which is not true for a second order reaction ?

(A) It can have rate constant 1 × 10–2 L mol–1 s–1
(B) Its half-life is inversely proportional to its initial concentration
(C*) Time to complete 75% reaction is twice of half-life
1
(D) T50 =
ka

Sol. C  It is properties of Ist order Rxn and other all are properties of IInd order..

15. Acid catalysed hydrolysis of ester is first-order reaction and rate constant is given by
2.303 V  V0
k= log V  V
t  t
where V0, Vt and V are the volume of standard NaOH required to neutralise acid present at a given time ; if
ester is 50% hydrolysed then :
(A) V = Vt (B) V = (Vt – V0) (C*) V = 2Vt – V0 (D) V = 2Vt + V0
Sol. If easter 50% hydrolysed then
a0
x=
2
a0
(a0 – x) =
2
We can write
a0  (V – V0)
(a0 – x )  (V – Vt)
V – V0
= (V – Vt)
2
V – V0 = 2 V – 2 Vt
V – V0 
Vt =
2
or V = 2 Vt – V0

16. If no catalyst (H+) is present in acid hydrolysis of ester (in above question) then rate constant K is :
2.303 V0 2.303 V
(A) log (B*) log
t ( Vt  V ) t ( V  Vt )

2 . 303 V 2.303 V
(C) log 0 (D) log
t Vt t ( Vt  V )

17. Inversion of sucrose (C12H22O11) is first-order reaction and is studied by measuring angle of rotation at different
instant of time
+
H
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
d d l
If (r – r0)  a and (r – rt)  (a – x) (where r, rt and r are the angle of rotation at the start, at the time t and t
the end of the reaction respectively, then there is 50% inversion when :

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 (A*) r0 = 2rt – r (B) r0 = rt – r (C) r0 = rt – 2r (D) r0 = rt + r
Sol. Given (r – r0) = a , (r – rt) = (a – x)
At 50% Inversion
a
= (a – x)
2
r – r0  = (r – r0 )
2
(r – r0 ) = 2r – 2rt
r0 = 2rt – r

18. In the above question solution is optically inactive when :

(A) rt = a (B*) rt = 0 (C) rt = x (D) rt = (a + x)
Sol. Above question solution optically inactive if.
rt = 0

N Cl
19. KI
 I2
COCH3
Kinetics can be studied by titration using :

(A*) Na2S2O3 (B) KMnO4 (C) H2C2O4 (D) OH

Sol. Na2S2O3 which react with I2 .

M M 8
20. Z A( g) Z 4 B(g)  (  particles) ( – particles are helium nuclei, so will form helium gas by
trapping electrons)
The radioactive disintegration follows first-order kinetics Starting with 1 mol of A in a 1-litre closed flask at
27ºC pressure set up after two half-lives is approximately :
(A) 25 atm (B) 12 atm (C*) 61.5 atm (D) 40 atm
M M 8
Sol. Z A( g) Z 4 B(g)  (  particles)

M M8
Z A ( g)  Z  4 B ( g )  2 ( 24 He ( g))
1 mole 0 0
 3 3 3
1 –  2×
 4 4 4
3
After two half life mole of A decomposes.
4

1 3 3
Total moles after 2 half life =    2  
4 4 4
= 2.5 mole
pV = nRT
p × 1 = 2.5 × .082 × 300
p = 61.5 atm

21. A.G.M. counter is used to study the radioactive process of first-order. In absence of radioactive substance A,
it counts 3 disintegration per second (dps). When A is placed in the G.M. counter, it records 23 dps at the
start and 13 dps after 10 minutes. It records x dps after next 10 minutes and A has half-life period y minutes.
x and y are :
(A*) 8 dps, 10 min (B) 5 dps, 10 min (C) 5 dps, 20 min (D) 5 dps, 5 min
Sol. There is an error of 3dps

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 Then No = (23 – 3) = 20 dps
Nt = 10 dps
The half life = 10 minutes
In next 10 minute Nt = 5 dps
Then value with error = (5 + 3) = 8 dps.

22. Saponification of ethyl acetate (CH3COOC2H5) by NaOH (Saponification of ethyl acetate by NaOH is second
order Rxn) is studied by titration of the reaction mixture initially having 1:1 molar ratio of the reactants. If 10
mL of 1 N HCl is required by 5 mL of the solution at the start and 8 mL of 1 N HCl is required by another 5
mL after 10 minutes, then rate constant is :
2.303 10 2.303 10
(A) k = log (B) k = log
10 8 10 2

1 1 1  1 1 1 
(C*) k =  (D) k = 
10  8 10  10  2 10 
Sol. Saponification of ethyl acetate by NaOH is second order Rxn

1 1 1
Then k=  – 
t  a t a0 

1 1 1 
k=  – .
10  8 10 

dx
23. For the reaction A (g) + 2B(g)  C(g) + D(g) = k [A] [B]2
dt
Initial pressure of A and B are respectively 0.60 atm and 0.80 atm. At a time when pressure of C is 0.20 atm,
rate of the reaction, relative to the initial value is :
dx 2
A (g) + 2B(g)  C(g) + D(g)
, dt = k [A] [B]
1 1 1 1
(A*) (B) (C) (D)
6 48 4 24
Sol. Initial Rate = k [A] [B]2
Rate 1 = k [.60] [.80]2 .....(i)
Rate 2 = k [At] [Bt]|2 .....(ii)
Given Rxn
A (g) + 2 B (g)  C (g) + D (g)
.60 atm .80 atm 0 0 t=0
(.60 – .2) (.80–.40) .20 .20 atm
.40 atm .40 atm .20 atm .20 atm t=t
Put value of pressure of t = t in rate equation (II)
Rate 2 = k [.40] [.40]2
Rate 2 k[.40][.40] 2
=
Rate1 k[.60][.80] 2

Rate 2 2 1 1
Rate1
= × =
3 4 6

 dx 
24. If   = k [H+]n and rate becomes 100 times when pH changes from 2 to 1. Hence, order is :
 dt 
(A) 1 (B*) 2 (C) 3 (D) 0
 dx 
Sol.   = k [H+]n
 dt 
Given
pH change from 2 to 1

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 Then H+ concentration change from 10–2 M to 10–1 M
Then

 dx 
 
 dt 1 k[10 2 ]n
=
 dx  k[10 1] n
 
 dt  2

n
Rate1 1  1
= =   , n=2
Rate 2 100  10 

25. Consider following reaction ,

Zn + 2 H+  Zn2+ + H2
Half–life period is independent of concentration of Zn at constant pH. At constant Zn concentration, half–life
is 10 minutes at pH = 2 and half–life is 100 minutes at pH = 3. Hence , rate law is :
(A*) k [Zn][H+] (B) k [Zn][H+]2 (C) k [Zn]0 [H+] (D) k [Zn]0 [H+]2
Sol. Half life period independent on conc.hence order is unity wrt Zn
Let order with respect to H+ ions is 'a'
Then the rate law will be Rate = k [Zn][H+]a
At pH = 2, [H+] = 10–2 So the rate law becomes Rate = (k[10–2]a )[Zn] = k1 [Zn]
ln 2 ln 2
so the half life will be T1/2 = k = = 10 min
1 k(10 2 )a
At pH = 3, [H+] = 10–3 So the rate law becomes Rate = (k[10–3]a )[Zn] = k2 [Zn]
ln 2 ln 2
so the half life will be T1/2 = k = = 100 min
2 k(10 3 )a

10 k(10 3 )a
so we have =
100 k(10 2 )a
which will give 10–1 = 10–a
Hence a = 1

26. Following are the values of Ea and H for three reactions carried out at the same temperature :
I : Ea = 20 kJ mol–1 , H = – 60 kJ mol–1
II : Ea = 10 kJ mol–1 , H = – 20 kJ mol–1
III: Ea = 40 kJ mol–1 , H = + 15 kJ mol–1
If all the three reaction have same frequency factor then fastest and slowest reactions are :
Fastest Slowest
(a) I II
(b*) II III
(c) I III
(d) can’t be predicted.
Sol. The rate of reaction is decided by value of rate constant which depends on energy of activation not on the
value of H, definitely the comparison of rate of reactions of backward reactions can be done if H values are
also given to us.
27. for a reaction A  B, Ea = 10 kJ mol–1 , H = 5 kJ mol–1 . Thus , potential energy profile for this reaction
is :

(A) (B*)

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 (C) (D)

Sol. For Rxn

A  B.
Ea = 10 kJ/mole , H = 5 kJ/mole
Rxn indothermic because H (+)
H = Ea – Eb
5 = 10 – Eb
Eab = 10 – 5 = 5 kJ/mole
Then [B].

28. Milk turns sour at 400C three times as faster as 00C. Hence Ea in cal of process of turning of milk sour is :

2.303  2  313  273 2.303  2  313  273  1

(A*) log3 (B) log  
40 40 3

2.303  2  40
(C) log3 (D) None of the above
273  313
Sol. Milk turn sour at 400C three times faster as 00C
Then
40º C ij nj rate at 40 º C k 40 0 C
= k 0
0º C ij nj rate at 0 º C 0 C

2.303 RT1T2  k 400 C 

 
Ea = log k 0 
(T2 – T1 )  0 C 

2.303  2  313  273 log(3)

Ea =
40
1
29. Graph between log k and (k is rate constant in s–1 and T is the temperature in K) is a straight line. If OX =
T
1
5 and slope of the line = – then Ea is :
2.303

2
(A) 2.303 × 2 cal (B) cal
2.303
(C*) 2 cal (D) None of these
Sol. We know
Ea
log K = log A – 2.303 RT

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 compare this by
y = mx + c
Ea
m = – 2.303 R slope of this

Ea 1
Given – 2.303 R = –
2.303
Ea = R = 2 cal

30. If the fermentation of sugar in an enzymatic solution that is 0.12 M , the concentration of the sugar is
reduced to 0.06 M in 10 h and to 0.03 M in 20 h. What is the order of the reaction ?
(A*) 1 (B) 2 (C) 3 (D) 0
Sol. In 1st order Rxn, decreases in % of concentration same in same interval of Time
 (.12 – .06) 
  100  = 50%
 12 

(.06 – .03)
 100 = 50%
.06
so reaction must be of first order.

31. A reaction is catalysed by H+ ion;and in the rate law the dependence of rate is of first order with respect to the
concentration of H+ ions, in presence 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 (both strong acids) have relative strength as :
(A) 0.5 (B) 0.002 (C) 0.001 (D*) 2
Sol. We know
Rate = k [conc.]
Given Rxn catalysed by HA and HB
Rate constant kA = k1 [H+]A
kB = k1 [H+]B
Then relative strength of acids A and B is
kA [H ] A
=
kB [H ]B

2 [H ] A [ Acid A ]
=  = strength of [ AcidB]
1 [H ] B

32. For the first-order reaction (C = C0 e k1t ) and Tav = k1–1. After two average lives concentration of the reactant is
reduced to :
100 100
(A) 25% (B) 75% (C) % (D*) %
e e2
Sol. Given
C = C0 e k1t
1
tav = k
1
Given
2
t = 2 tav = k
1

2
– k 1
k1
C = C0 e
C 100
 100 =
C0 e2

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33. Number of natural life times (Tav) required for a first-order reaction to achieve 99.9% level of completion is :
(A) 2.3 (B*) 6.9 (C) 9.2 (D) 0.105
Sol. We know
2.303 a
k= log
t (a – x)
99.9% completion
a = 100
a – x = (100 – 99.90) = .10
Then

2.303  100 
t= log  
k  .10 

 1
t = 2.303 × 3 ×  
k 
t = 6.9 × tav

34. The reaction of NO2 (g) and O3 (g) is first-order in NO2 (g) and O3 (g)
2 NO2 (g) + O3 (g)  N2O5 (g) + O2 (g)
The reaction can take place by mechanism :
slow
I : NO2 + O3   NO3 + O2
fast
NO3 + NO2    N2O5
ka fast
II : O3 [O2] + O
kb
slow
NO2 + O   NO3
fast
NO3 + NO2   N2O5
Select correct mechanism.
(A) I only (B) II only (C*) both I and II (D) None of I and II
Sol. For Rxn rate determining step is slowest step
Then in 1st Rxn
Rate = k [NO2] [O3] .....(i)
But 2nd Rxn
ka fast
O3 [O2] + O ....(a)
kb
slow
NO2 + O    NO3 ....(b)
fast
NO3 + NO2   N2O5 ....(c)
Then for Rxn (a)
ka [O 2 ] [O]
= [O ] = keq ....(d)
kb 3

by Rxn (b)
Rate = k [NO2] [O] ....(ii)
put value of [O] from (d) to (ii)
k eq [O 3 ]
Rate = k × [NO2]
[O 2 ]

k1 [NO 2 ] [O 3 ]
Rate = [O 2 ]
35. Match the graphical study with the order of the reactions :

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 I : Rate II : Half life

[initial conc]

III : (a – x)–1

I II III I II III
(A) A B C (B) B C A
(C) C B A (D*) C A B

Sol. Graph I – Rate independent of time zero order Rxn.

Graph II – Half life independent of time Ist order Rxn.
1
Graph III – between and time straight line second order Rxn.
(a – x)

36. The bromination of acetone that occurs in acid solution is represented by

CH3COCH3 (aq) + Br2 (aq)  CH3COCH2 Br (aq) + HBr (aq)
Given :

Initial Rate
Initial concentrations Disapperance of
Br2 , Ms–1
Br2 [CH3COCH3] M [H+]
0.050 0.30 0.050 5.7 × 10–5
0.10 0.30 0.050 5.7 × 10–5
0.10 0.30 0.10 1.2 × 10–4
0.050 0.40 0.20 3.1 × 10–4

Based on the above data , rate law is :

 dx 
(A)   = k [CH3COCH3] [Br2] [H+]
 dt 

 dx 
(B*)   = k [CH3COCH3] [H+]
 dt 

 dx 
(C)   = k [CH3COCH3] [Br2]
 dt 

 dx 
(D)   = k [CH3COCH3] [Br2] [H+]2
 dt 
Sol. According to above data.
suppose rate law
dx
= k [CH3COCH3]a [Br2]b [H+]c
dt

RESONANCE Page 12
 by data (i) and (ii) conc. of [Br2] increased 2 times and conc. of [CH3COCH3] and [H+] constant rate remains
same. Then zero order wrt Br2 .
Similarly conc. of [H+] increased 2 times rate increased 2 times, so first order wrt H+.
Similarly 1st order wrt CH3COCH3
Then
dx
= k [CH3COCH3] [H+]
dt

37. A(g)  B(g) + C(g)

d [ A]
– = k [A]
dt
At the start pressure is 100 mm and after 10 min , pressure is 120 mm. hence , rate constant (min–1) is :
2.303 120 2.303 100
(A) log (B) log
10 100 10 20
2.303 100 2.303 100
(C*) log (D) log
10 80 10 120
Sol. A (g)  B (g) + C (g)

d [ A]
– = k [A]
dt
A (g)  B (g) + C (g)
100 0 0 t=0
(100 – P) P P t = 10 min.
100 – P + P + P = 120
(100 + P) = 120
Then
2.303 100
k= log
10 (100 – P)

2.303  100 
k= log  
10  80 

38. The rate law for the dimerisation of NO2 is

d [NO 2 ]
– = k [NO2]2
dt
which of the following changes will change the value of the specific rate constant , k ?
(A) Doubling the total pressure on the system
(B*) Doubling the temperature
(C) Both of (A) and (B)
(D) None of the above
Sol. Rate constant change on changing temperature .

39. In the following reaction, how is the rate of appearance of the underlined product related to rate of disappear-
ance of the underlined reactant ?
BrO3– (aq) + 5 Br– (aq) + 6 H+ (aq)  3 Br2 () + 3 H2O ()
d [Br2 ] 5 d [Br – ] d [Br2 ] d [Br – ]
(A) =– (B) =–
dt 3 dt dt dt

d [Br2 ] d [Br – ] d [Br2 ] 3 d [Br – ]

(C) =– (D*) =–
dt dt dt 5 dt
Sol. We know

RESONANCE Page 13
 d (BrO3 ) 1 d(Br  ) 1 d (H ) d (Br2 )
– =– =– =+
dt 5 dt 6 dt dt
Then by this relation
d (Br2 ) 3 d (Br – )
=–
dt 5 dt

40. 3 A  B + C
It would be a zero order reaction when :
(A) the rate of reaction is proportional to square of concentration of A
(B*) the rate of reaction remains same at any concentration of A
(C) the rate remains unchanged at any concentration of B and C
(D) the rate of reaction doubles if concentration of B is increased to double
Sol. Rate = k [conc]n  Independent of conc. of A.

41. The potential energy diagram for a reaction R  P is given below :

H0 of the reaction corresponds to the energy –

(A*) x (B) y (C) z (D) (x+y)
Sol. By diagram
H0 = y – z = x

42. Read the following industrial methods for the preparation of H2SO4 and answer the question at the end.
Professor Molina of the Massachusetts Institute of Technology won the 1995 Nobel Prize in Chemistry for his
work or atmospheric chemistry. One reaction that he has studied in detail is the acid rain reaction which
produces H2SO4 in the atmosphere. He has proposed two possible stoichiometric reactions :
Proposal A : H2O (g) + SO3 (g)  H2SO4 (g)
Proposal B : 2 H2O (g) + SO3 (g)  H2SO4 (g) + H2O (g)

Using simple collision theory , what reaction orders would be expected for proposal B ?
Proposal B is thought to proceed by the following two-step process :

SO3 + 2 H2O SO3.2 H2O (fast)

k2
SO3.2 H2O   H2SO4 + H2O (slow)
(SO3.2 H2O is a complex which is stabilized by hydrogen bonds and k2 << k1 or k–1 ).
(A) k [H2O] [SO3] (B*) k [H2O]2 [SO3] (C) k [SO3] (D) k [H2O]
Sol. Rate determining step is slow step
Then
Rate = k2 [SO3 . 2 H2O] .....(i)
We know by fast equation
k1 [SO 3 .2 H2O]
=
k 1 [SO 3 ][H2O] 2
k1
[SO3. 2 H2O] = k [SO3] [H2O]2 ....(ii)
1
put the value of [SO3 . 2 H2O] from (ii) to (i)
k1
Rate = k2 × k [SO3 ] [ H2O]2
1
Rate = k [H2O]2 [SO3]

RESONANCE Page 14
43. Two reaction, A  products and B  products have rate constants Ka and Kb at temperature T and
activation energies Ea and Eb respectively. If Ka > Kb and Ea < Eb and assuming that A for both the reactions
is same then :
(A) At higher temperatures Ka will be greater than Kb
(B) At lower temperature Ka and Kb will differ more and Ka > Kb
(C) As temperature rises Ka and Kb will be close to each other in magnitude
(D*) All of the above

44. At room temperature, the reaction between NO and O2 to give NO2 is fast, while that between CO and O2 is
slow. It is due to :
(A) CO is smaller in size that of NO
(B) CO is poisonous
(C*) The activation energy for the reaction,
2NO + O2  2NO2 is less then
2CO + O2  2CO2
(D) None of the above

45. The rate law for a reaction between the substances A and B is given by rate = K[A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the
reaction will be as :
(A) 1/2m + n (B) (m + n) (C) (n – m) (D*) 2(n – m)
n m
Sol. Rate = K [A] [B]
given A increased two times
and B increased two times
B m
then Rate2 = K[2A]n [ ]
2
Rate2 = K[A]n [B]m x 2(n-m)
Ans. D

46. In gaseous reactions important for the understanding of the upper atmosphere H2O and O react bimolecularly
to form two OH radicals. H for this reaction is 72 kJ at 500 K and Ea is 77 kJ mol–1, then Ea for the
bimolecular recombination of two OH radicals to form H2O and O is :
(A) 3 kJ mol–1 (B) 4 kJ mol–1 (C*) 5 kJ mol–1 (D) 7 kJ mol–1
Sol. H2O + O  2 OH H = 72 kg/mole
and Ea = 77 Kg/mole
Then we know H = Ea – Eb
72 = 77 – Eb
Eb = 5 KJ/mole

47. A reaction takes place in three steps having rate constants K1, K2, K3 respectively. The overall rate constant
K 1K 3
K= . If energies of activations for the three steps are 40, 30, 20 kJ respectively, the overal energy of
K2
activation is :

(A) 10 (B) 15 (C*) 30 (D) 60

k1 k 3
Sol. given K =
k2
we know that for any reaction
1 dk E
.  a
k dT RT 2
so differentiating the given relation of k with k1, k2 & k3 with respect to temperature, we have
d dk 2
k2 (k 1 k 3 )  k 1 k 3
dk dT dT

dT K 22

RESONANCE Page 15
 1  dk 3 dk1  k1k 3 k 2 dk 2
= k k1 dT  k 3 dT  
2   k 22 dT

Ea k1 k 3 Ea3 k 3 k1 Ea1 k1 k 3 Ea2

k.  .  .  .
2 k 2 RT 2 k 2 RT 2 k 2 RT 2
RT
Ea = Ea 3  Ea1  Ea 2
= (20 + 40 – 30)
= 30 kJ/mol

Multiple choice questions

48. Table I (reactions) and table II (methods) have been matched

Correct matching is :
P Q R P Q R
(A) X Y Z (B*) Y X Z
(C*) Z X Y (D) Z Y X

Sol. P  y,z , Q  x , R  y, z.

49. Which of the following statements are correct about half–period.

(A*) It is proportional to initial concentration for zeroth order
(B*) Average life = 1.44 (half–life for first order reaction)
(C*) Time of 75% completion of reaction is thrice of half–life(initial half life) period in second order reaction
(D*) 99.9% reaction takes place in 100 minutes for the case when rate constant is 0.0693 min–1

50. Zn + 2 H+  Zn2+ + H2

Half–life period is independent of concentration of zinc at constant pH. For the constant concentration of Zn,
rate becomes 100 times when pH is decreased from 3 to 2. Hence ,

dx
(A) = k [Zn]0[H+]2
dt

 dx 
(B*)   = k [Zn][H+]2
 dt 
(C*) rate is not affected if concentration of zinc is made four times and that of H+ ion is halved
(D*) rate becomes four times if concentration of H+ ion is doubled at constant Zn concentration

Sol. Half life period independent of conc. of Zn than order W.R.T. Zn is 1st
Rate = k [Zn][H+]n we can write
by data
n
Rate 2 [ Zn]  1 10 2  100
=   =
Rate 1 [ Zn]  1 10 3  1
Given n = 2
Then Rate = k [Zn][H+]2 [B].
Conc. of Zn 4 times and H+ ion is halved

RESONANCE Page 16
 2
 H 
Rate = k [4 × Zn]  
 2 
Rate = k [Zn][H+]2
Rate remians and same [C].
Similarly
If conc. of H+ doubled and [Zn] constant
Then Rate2 = k [Zn] [2H+]2
Rate2 = 4 k [Zn] [H+]2
Rate2 = 4 x Rate1 [D].
2000
51. Rate constant k varies with temperature by equation , log k(min–1) = 5 – . We can conclude:
T(K )
(A) pre–exponential factor A is 5
(B) Ea is 2000 kcal
(C*) pre–exponential factor A is 105
(D*) Ea is 9.212 kcal
Sol. Given
2000
log k (min–1) = 5 – T (k )

Compare this with

Ea
log K = log A – 2.303 RT(k )

we find
A = 1 × 105 [C].
Ea
– 2.303 R = – 2000

Ea = 9.212 k cal [D].

52. Activation energy of a chemical reaction can be determined by :

(A) evaluating rate constant at standard temperature
(B*) evaluating velocities of reaction at two different temperatures
(C*) evaluating rate constant at two different temperatures
(D) changing concentration of reactants
Sol. We know
2.303 RT1T2  k2 
Ea = log  k 
(T2 – T1 )  1

53. Which of the following statements are correct ?

(A*) Law of mass action and rate law expressions are same for single step reactions.
(B*) Order of the slowest elementary reaction of a complex reaction gives the order of the complex reaction
(C*) Both order and molecularity have normally a maximum value of 3
(D) Molecularity of a complex reaction,
A + 2B  C is 3.
54. Which of the following statement are true regarding the log K vs. 1/T plot shown in the given diagram ?

K  Ar E a / RT

(A*) Plot P shows that the energy of activation is independent of temperature.

(B*) Plot Q describes the behaviour of temperature dependence of energy of activation
(C*) Arrhenius behaviour is described by P

RESONANCE Page 17
 Ea
(D*) The slope of curve P gives the value –
R
55. If the rate of reaction :
Pt
2SO2(g) + O2(g)  2SO3(g) is given by :

K[SO 2 ]
Rate =
[SO 3 ]1/ 2
which statements are correct ?
(A) The overall order of reaction is –1/2
(B*) The overall order of reaction is +1/2
(C*) The reaction slows down as the product SO3 is build up
(D) The rate of reaction does not depend upon concentration of SO3 formed
 1 1
Sol. Over all order of Rxn = 1 –  = + [B].
 2 2
as SO3 for Rate of Rxn slow down.
56. Which statements are correct about the two first order reactions if made with same initial concentrations ?
M  Product
N  Product
(A*) t1/2 for M is more than t1/2 of N
(B) t1/2 for M is less than t1/2 of N
(C) Rate constant for M is more than rate constant for N
(D*) Rate constant for M is less than rate constant for N
Sol. For second order Rxn
we know

1 1 – 1 
t=  
K  A A0 

1 1
= Kt + A
A 0
in which. The graph will show straight line with slope K and the graph will shows straight line with intercept
1
A 0  .
1
57. For a second order reaction plots are made for vs time for the reaction, 2A  Product. Pick up the
[A ]
correct sentences.
(A*) the graph will show straight line with slope K
(B) the graph will show straight line with intercept [A]0
(C*) the graph will show straight line with slope [A]0
1
(D) the graph will show straight line with intercept [ A ]
0

58. Select the correct statements :

(A*) the molecularity of an elementary reaction indicates how many reactant species 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

Match the columns

59. Match order of the reaction (in List – I) with the corresponding rate constant (in List – II) :
List I (order) List II (rate constant)

RESONANCE Page 18
 1  1 1
– 2
(A) Zeroth 1. k=  2
2t  (a – x ) a 

1  1 1
(B) First 2. k=  – 
t  (a – x ) a 
x
(C) Second 3. k=
t
1  a 
(D) Third 4. k= loge  
t  (a – x ) 

Ans. (A) 3 , (B) 4 (C) 2 (D) 1

Sol. (A )  (3) , (B)  (4) , (C)  (2) , (D)  (1)

60. Match order of the reaction (in List - ) with the unit of rate constant (in List-II) :
List I (order) List II (unit)
(A) Zeroth 1. L2 mol–2 s–1
(B) First 2. L mol–1 s–1
(C) Second 3. mol L–1 s–1
(D) Third 4. s–1

Ans. (A) 3 (B) 4 (C) 2 (D) 1

Sol. (A )  (3) , (B)  (4) , (C)  (2) , (D)  (1)

61. Match the given reaction of various order (in List I) with method of study of kinetics (in List II) :
List  (reaction) List II (method)
(A) 2N2O5(g)  2N2O4(g) + O2 (g) 1. Titration by Na2S2O3
(B) S2O82– + 2I–  2SO42– + I2 2. Titration by KMnO4
(C) 2H2O2  2H2O + O2 3. Titration by NaOH
(D) C12H22O11+H2O  C6H12O6+C6H12O6 4. Measuring pressure of the mixture in inert medium.
(E) CH3CHO(g)  CH4(g) + CO (g) 5. Measuring angle of rotation.
H
(F) CH3COOC2H5+H2O 
 CH3COOH + C2H5OH 6. Measuring pressure of the gas in CCl4 medium
(use the fact that N2O4 dissolves in CCl4 medium)

Ans. (A) 6 (B) 1 (C) 2 (D) 5 (E) 4 (F) 3

62. Match the order of reaction (in List I) with its property (in List II) :
List I (order) List II (Property)
1
(A) Zeroth 1. Half life 
a2
1
(B) First 2. Half life 
a
(C) Second 3. Half life is doubled on doubling the initial
concentration
(D) Third 4. 50% reaction takes same time even if con

RESONANCE Page 19
 -centration is halved or doubled.

Ans. (A) 3 (B) 4 (C) 2 (D) 1

Comprehensions # 1

Study the following experiment and answer the questions at the end of it.
The following reactions was studied at 250C in benzene solution containing 0.10 M pyridine
CH3OH + (C6H5)3 CCl  (C6H5)3 C . OCH3 + HCl
A B C
The following sets of data were observed :
Set Initial concentration time difference Final concentration [C]
[A]0 [B]0
I 0.10 M 0.05 M 25 min 0.0033 M
II 0.10 M 0.10 M 15 min 0.0039 M
III 0.20 M 0.10 M 7.5 min 0.0077 M

d [C]
63. Rates in sets I , II and III are respectively (in M min–1) :
dt
I II III
(A*) 1.30 × 10–4 2.6 × 10–4 1.02 × 10–3
(B) 0.033 0.0039 0.0077
(C) 0.02 × 10–4 0.04 × 10–4 0.017
(D) None of above

64. Rate law of the above experiment is :

(A) k [A] [B] (B*) k [A]2 [B] (C) k [A] [B]2 (D) k [A]2 [B]0

65. Rate constant of the above experiment is (L2 M–2 min–1)

(A) 1.3 × 10–1 (B) 2.6 × 10–2 (C*) 2.6 × 10–1 (D) 1.3 × 10–2
dc  c  .0033
Sol. 63-65 (I) Rate = =   = = 1.32 × 10–4
dt  t  25

dc  c  .0039
(II) Rate = =   = = 2.6 × 10–4
dt  t  15

 c  .0077
(III) Rate =   = = 1.02 × 10–3 Ans. [A]
  t  15
64 (II) Rate of Rxn = Rate of formation of C.
Then we say by I data.
Suppose [Rate = k [A]a [B]b] ....(i)
1.32 × 10–4 = k [.10]a [.05]b ....(ii)
2.6 × 10–4 = k [.10]a [.10]b ....(iii)
1.02 × 10–3 = k [.20]a [.10]b ....(iv)
By equation (ii) and (iii) we find b = 1
By (iii) and (iv) we find a = 2.
Then Rate = k [A]2 [B]1 Ans. [B].
65 (III) Rate 1.32 × 10–4 = k [.10]2 [.05]
k = 2.6 × 10–1 Ans. [C]

Comprehensions # 2
Study the two photochemical reactions and answer the question at the end.
For the overall reaction between A and B to yield C and D , two mechanisms are proposed :
I. A + B  AB*  C + D , k1 = 1 × 10–5 M–1 s–1
II. A  A*  E , k1 = 1 × 10–4 s–1

RESONANCE Page 20
 E + B  C + D , k2 = 1 × 1010 M–1 s–1
(species with * are short-lived)

66. Rate according to mechanism I when concentration of each reactant is 0.1 M will be:
(A*) 1 × 10–7 Ms–1 (B) 1 × 10–6 Ms–1 (C) 1 × 10–5 Ms–1 (D) 1 × 10–4 Ms–1

67. Rate according to mechanism II when concentration of each reactant is 1 M will be:
(A*) 1 × 10–4 Ms–1 (B) 1 × 1010 Ms–1 (C) 1 × 10–6 Ms–1 (D) 1 × 10–10 Ms–1

68. At what concentration of B, rates of two mechanism are equal :

(A) 1 M (B) 5 M (C) 7 M (D*) 10 M
Sol. 66-68 (I).
Rate law for mechanism I
Rate = k11 [A] [B]
Rate = 1 × 10– 5 [.1] [.1] = 1 × 10–7 m/sec .
67 (II).
Rate = 1 × 10–4 × [1] = 1 × 10–4

68 (III).
Rate I = Rate II
k11 [A] [B] = k1 [A]
k1
B= = 10 M
k 11

COMPREHENSION # 3
The thermal decomposition of N2O5 occurs as : 2N2O5  4NO2 + O2
Experimental studies suggest that rate of decomposition of N2O5, rate of formation of NO2 or rate of formation
of O2 all becomes double if concentration of N2O5 is doubled.

69. The correct mechanism for decomposition of N2O5 is :

Slow
(A*) N2O5  Fast
 NO2 + NO3 ; N2O5 + NO3  3NO2 + O2
Fast
(B) N2O5  Slow
 NO2 + NO3 ; N2O5 + NO3  3NO2 + O2

Fast
1
(C) N2O5   2NO2 + 2 O2

Slow Fast
1
(D) N2O5   NO + NO2 + 2O2 ; N2O5 + NO2  3NO2 + 2 O2

70. If rate constants for decomposition of N2O5, formation of NO2 and formation of O2 are K1, K2 and K3 respec-
tively, then :
(A) K1 = K2 = K3 (B*) 2K1 = K2 = 4K3 (C) K1 = 2K2 = K3 (D) K1 = K2 = 2K3

71. If rate of formation of O2 is 16 g/hr, then rate of decomposition of N2O5 and rate of formation of NO2 respec-
tively is :
(A) cannot be calculated with out knowing rate constants
(B*) 108 g/hr, 92 g/hr
(C) 32 g/hr, 64 g/hr
(D) 54 g/hr, 46 g/hr

72. The container of 2 litre contains 4 mole of N2O5. On heating to 100°C, N2O5 undergoes complete dissociation
to NO2 and O2. Select the correct answers if rate constant for decomposition of N2O5 is 6.2 x 10–4 sec–1.
1. The mole ratio before and after dissociation is 4 : 2.
2. Half life of N2O5 is 1117 sec and it is independent of temperature.
3. Time required to complete 40% of reaction is 824 sec.
4. If volume of container is doubled, the rate of decomposition becomes half of the initial rate :
(A) 1, 3, 4 (B) 1, 2, 3, 4 (C*) 3, 4 (D) 2, 3, 4

Sol. 70-72

RESONANCE Page 21
 (a) The rate of reaction is decided by the slowest step (I order) of reaction.
1 1 d [NO 2 ] d [O 2 ]
(b) Rate of reaction = – d(N2O5] = =
2 4 dt dt 0
d [N 2O 5 ] d [NO 2 ]
– = K1 [N2O5] ; + = K2[N2O5]
dt dt
d [O 2 ]
and = K3 [N2O5]
dt
K1 K
  2 = K3
2 4
d [O 2 ] 16
(b) = 16 g/hr = mol hr–1
dt 32
d [NO 2 ] 4 d [O 2 ] 16
dt = =4x = 2 mol hr–1 = 2 x 46 = 92 g hr–1
dt 32
 d [N2O 5 ] 2 d [O 2 ] 16
= =2x = 1 mol hr–1 1 x 108 = 108 g hr–1
dt dt 32
1
(c) N2O5  2NO2 + O
2 2
Initial mole   
moles after diss 0 8 2
4
 Mole ratio = = 2.5
10

0.693 0.693
t1/2 = = = 1117.7 sec but it depends upon temperature as K also depends upon tempear
K 6 .2  10 4

2.303 100
t40% = 4 log = 824 sec
6.2  10 60
Rate = K[N2O5] ; Thus r1 = K [N2O5]
If V is doubled the concentration becomes half
1
 r2 = K [N O ]
2 2 5
r1 2
 r =
2 1

COMPREHENSION # 4
The instantaneous rate of an elementary chemical reaction : aA + bB cC + dD can be given by :
rate = Kf[A]a [B]b – Kb [C]c [D]d where, Kf and Kb are rate constants for forward and backward reactions
respectively for the reversible reaction. If the reaction is an irreversible one, the rate is expressed as : rate =
K[A]a [B]b where K is rate constant for the given irreversible reaction and (a + b) is order of reaction. It is also
a
evident from the stoichiometry of reaction that rate of disappearance of A is times the rate of disappear-
b
ance of B. The variation of rate constant K with temperature is expressed in terms of Arrhenius equation :
Kf
K = Ae Ea / RT whereas the ratio K is expressed in terms of van’t Hoff isochore :
b

Kf
Kb
= Ae  H / RT , where Ea and H are energy of activation and heat of reaction respectively..

73. For a chemical reaction aA  bB ;

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  d[ A ]   d[B] 
log   = log   + 0.3,
 dt   dt 
then the ratio of a and b is approximately :
(A) 3 (B) 0.3 (C*) 2 (D) 0.5
1 d [ A ] 1 d [B]
Sol. (C) – 
a dt b dt
d [ A ] a d [B]
or  
dt b dt

 d [ A]  a d [B]
or log    log  log
 dt  b dt

a
 log = 0.3
b
a
 =2
b
Kf
74. The variation of K and K with temperature shows the following effects :
b

Kf
(i) For endothermic reaction K increase, K also increases
b

Kf
(ii) For endothermic reaction K decreases, K also decreases.
b

Kf
(iii) For exothermic reaction K and K both increases.
b

Kf
(iv) For exothermic reaction K increases and K decreases
b

Kf
(v) For exothermic reaction K and K both decreases.
b
(A*) i, v (B) iii, v (C) ii, iii (D) ii, iii, v
Sol. (A) Ea is always positive thus K increases with temperature.
Kf
H is –ve, K decreases with temperature.
b

Kf
H is +ve, K increases with temperature.
b

75. For a gaseous phase I order reaction : A(g)  B(g) + 2C(g) (rate constant K = 10–2 time–1), in a closed
vessel of 2 litre containing 5 mole of A(g) at 27°C, which of the following is incorrect ?
(A) Rate of appearance of C(g) is 5 x 10–2 mol L–1 t–1
(B) Rate of disappearance of A(g) is 6.15 x 10–3 atm t–1
(C) Rate of disappearance of A(g) is 5.0 x 10–2 mol t–1
(D*) Rate of appearance of B(g) is 5 x 10–2 mol L–1 t–1
d [A ] d [B] 1 d [ C]
Sol. (D) Rate or reaction = –  
dt dt 2 dt
Also rate of reaction,
d[A] 5
 = K [A]1 = 10–2 ×
dt 2

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 = 2.5 × 10–2 mol L–1 t–1
 P=CRT
d [A ] 1 d [P]
   .
dt RT dt
d [PA ] d[A]
   RT = 0.0821 × 300 × 2.5 × 10–2
dt dt
= 6.15 × 10–1 atm t–1
d[A] d[n]
 
dt V. dt

d[nA ] d[ A ]
   V. = 2 × 2.5 × 10–2
dt dt
= 5.0 × 10–2 atm t–1
  d[ A ] 
76. For an elementary reaction aA  product, the graph plotted between log   vs. time gives a
 dt 
straight line with intercept equal to 0.6 and showing an angle of 45° with origin, then :
(A*) rate constant = 3.98 time–1 and a = 1
(B) rate constant = 3.98 mol L–1 t–1 and a = 1
(C) rate constant = 1.99 time–1 and a = 1
(D) rate constant = 1.99 mol–1 L1 t–1 and a = 2
dC A
Sol. (A) Rate = – = K CaA
dt

 dCA 
 log  = log K + a log CA
 dt 
 log K = 0.6
K = 3.98 time–1 and a = 1 tan 45º

Second order W.R.T.A

1
Then t1/2 = ka
0

1
t1/2 = = 39.2 min.
.622  4.10  10 2

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