CHEMICAL KINETICS

Solution to Subjective Problems

LEVEL – I

1. For first order reaction

2.303 1
k= log
t 1 x
Putting the different values,
2.303 1
1.5  10–6 s–1 = log
t 1 x
6
1 1.5  10  10  3600
or log 
1 x 2.303
= 0.0234
1
or  1.055
1 x
or x = 0.52 = 5.2%
Hence initial concentration changed into product = 5.2%
We know,
0.693 0.693
t1/2 = 
k 1.5  10  6 s1
= 4.62  105 s = 128.33 hours

2. k1 = 5.03  102 mol1 dm3 s1 at T1 = 289 K

k2 = 6.71 mol1 dm3 s1 at T2 = 333 K
 6.71  Ea  333  289 
log  =  
 5.03  10  2.303  8.314  333  289 
2

On solving we get, Ea = 88.914 kJ

The rate constant at 305 K may be determined from the relation:
k Ea  1 1
log 2    
k 1 2.303R  T1 T2 
 k2  88.914  1 1 
log  
2 
  
 5.03  10  2.303  8.314  298 305 
1 3 1
On solving we get, k2 = 0.35 mol dm s

3. For first order reaction,

0.693
K=
t1 / 2
0.693
K653 = = 1.925  10–3 min–1
360
K723 = ?

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RSM79Ph-IICKCH(H&S)2

Ea  T2  T1 
log K723 – log K653 =  
2.303R  T1T2 
log K723 – log 1.925  10–3 min–1
200  103 Jmol 1  723  653 
= 1 1
  
2.303  8.314 JK mol  723  653K 
log K723 – (0.2844 – 3) = 1.55
log K723 = 2.8344
K273 = 6.82  10–2 min–1
For first order reaction,
2.303 a 2.303 100
t= log = 2 1
log = 33.768 min log 4
K ax 6.82  10 min 100  75
= 33.768  0.602 = 20.33 min

K2 E [T  T1 ]
4. 2.303 log = a 2
K1 R T1T2
K2 2.37  10 4  458  413 
2.303 log =  458  413 
5.5  10  4 1.987  
K2 = 9.38  10 sec
–3 –1

For I131 time required to fall its activity to 1%

2.303 100
t= log = 53.17 days
0.693 1
8
2.303
For Sr90, time required to fall its activity to 1% be, = log100 = 59.8 days
0.693
9
Thus 90Sr which takes longer time to fall its activity to 1% is to be serious

2.303 
5. Time of maximum activity tmax = log d
d  p p
d  disintegration constant of daughter element
p  disintegration constant of parent elements
0.693
d = = 0.01145 min–1
60.5
0.693
p = = 0.00109 min–1
10.6  60
2.303  0.01146 
tmax = log 
(0.01145  0.00109)  0.00109 
tmax = 227 min

6. Since the plot of logarithms of partial pressure versus time is linear, hence the
reaction is of first order

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 RSM79Ph-IICKCH(H&S)3

The equation for first reaction is

2.303 a 2.303 a 2.303 2.303
k log or t = log =– log( a  x )  log a
t ax k ax k k
This is a straight line equation (y = mx + c) hence its slope is equal to – 2.303 / k
from which the specific rate reaction can be calculated. The intercept of this equation
2.303
log a: hence the value of ‘a’ can also be calculated by knowing the value of k.
t

7. i) A nB
The initial concentration of A = 0.6 M
The equilibrium concentration of A = 0.3 M
Hence concentration of A lost = 0.3 M
If x is the concentration of A lost, then more is the concentration, B obtained
Hence, B = nx = n  0.3 M
B is 0.6 M (from the graph)
0.6 M = n  0.3 M
n=2
[B]n [0.6]2
ii) K =  = 1.2
[A] 0.3
iii) When t = 0, [A] = 0.6 M
t = 1 hr, [A] = 0.5 M
 Rate of conversion = 0.5 – 0.6 = – 0.1 M hr–1

8. Given t1/2 = 28.1 years N0 = 10-6 g, t = 20 yrs

2.303 No 2.303 x28.1 10 6
t= log = log
 N 0.693 N
-7
N = 6.1 x 10 g

2.303 original activity 2.303 x 5500 1

9. t = log = log = 491.16 year
 recent activity 0.693 0.94
 the painting was done in the year (1999-491) = 1508 which was within the life
span of Raphael (1483-1520)
 It was not a forgery

10. Rate = k [NO]x [Cl2]y where x = order w.r.t. NO

x y
i.e. R = k [NO] [Cl2] y = Order w.r.t. Cl2
Case (1) 8R = k [2NO]x [2Cl2]y
Case (2) 2R = k [NO] x [2Cl2]y
Dividing the equation we have
4 = 2x  x = 2
Similarly 2R = k [NO] x [2Cl2]y
R = k [NO] x [Cl2]y
 2 = 2y  y =1
Overall order = x + y = 2 + 1 = 3

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RSM79Ph-IICKCH(H&S)4

LEVEL- II

1. i) According to Arrhenius equation

K = A.eEa / RT
or loge K = logeA + loge eEa / RT
Ea
log K = log A - …(i)
2.303RT
Given that
1.25  10 4 K
Log K(s–1) = 14.34 - …(ii)
T
On comparing equation (i) and (ii)we can say that,
E 1.25  10 4 K

2.303RT T
or Ea = 1.25  104 K  2.303  R
= 1.25  104 K  2.303  8.314 JK–1 mol–1 = 23.934  104 J mol–1
= 239.34 kJ mol–1
0.693 0.693
ii) K =  = 0.0000451 sec–1
t1 / 2 256  60
 log0.000451 sec–1
1.25  10 4
= 14.34   T = 669.16K
T

2. For second order reaction, when reactants have same concentration

1 x
K=
t (a  x )
1 x 
 t = t1/2;  x = a/2 or a - x = a/2 or log K = log  . 
 t a(a  x ) 
T = 373 + 43.3 = 316.3 K
3163  1 0.0005 
12 –  log  . 
T  t1 / 2 0.001  0.0005 
3163 1000 
12 –  log  
316 .2  t1 / 2 
2 = log 1000 – log t1/2
or log t1/2 = 1
or t1/2 = 10 minutes

3. CH3–OCH3(g)  CH4(g) + H2(g) + CO(g)

Initial 0.4 0 0 0
at time t = 0.4–p p p p
Suppose initial moles = a
and at any time number of moles = a – x
As ideal gas behaviour so moles  pressure
a  0.40 & (a-x)  (0.40 – p)

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 RSM79Ph-IICKCH(H&S)5

Now calculate P which is the pressure corresponding to the moles of reactant

decomposed. Total pressure is the summation of the pressure of entire system. Total
pressure = 0.4 – p + p + p + p = 0.4 + 2P
t1/2 = 14.5 min
K = 0.04779 min–1
2.303 0.4
0.04779 min–1 = log
12 0.40  P
 P = 0.175 atm
 Ptotal = 0.75 atm

50 0.50
4. Uranium present = g g atom = 2.1 x 10-3g atom
100 238
2.425 2.425
Pb present = g  g atom
100 100 x 206
2.425 x 93
Pb from Uranium decay = = 0.109 x 10-3g atom
100 x 206 x 100
N = 2.1 x 10-3g atom
N0 = (2.1 x 10-3 + 0.109 x 10-3)g atom = 2.2 x 10-3g atom
2.303 N 2.303 2.2 x 10 3
Now t = log 0 = log
 N 1.52 x 10 10 2.1x 10  3
 t = 3.3 x 108 yrs.

5. No. of -particles (or) He formed = 2.24  1013 min–1

 No. of He particles formed in 420 days = 2.24  1013  420  1440 = 1.355  1019
Also at 27°C and 750 mm; He = 0.5 mL
Using PV = nRT
750 0.5
 = n  0.0821  300  n = 2.0  10–5 moles
760 1000
2.0  10–5 moles of He = 1.355  1019 particles of He
1.355  1019
 1 mole of He = = 6.775  1023 particles
2.0  10  5
 Avogadro’s number = 6.775  1023 particles/mol

6. Let the order of the reaction is ‘n’

dC1 dC 2
  = KC1n ;  = KCn2
dt dt
 dC 1  dC 2 
or, log   = logK + nlogC1; log    = log K + n logC2
 dt   dt 
 dC1   dC 2 
log    log  
n=  dt   dt 
log C1  log C2
log 0.035  log 0.021  1.46  1.68 0.22
n= =  = 1.128
log 5  log 3.2 0.7  0.505 0.195
So order of the reaction is 1.128

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RSM79Ph-IICKCH(H&S)6

7. We know,
K Ea  T2  T1 
log 300   
K 280 2.303R  T2T1 
Ea = energy of activation
Given: Ea = 0
Ea  T2  T1 
   =0
2.303R  T2T1 
K 300
or log =0
K 280
K 300
or =1
K 280
Hence K300 = K280
Or K300 = 1.6  106 s–1

2.303 r r
8. K= log 0 
t rt  r
32.4
Total moles of sucrose =  0.38
85
Sucrose  Glucose + Fructose
0
t=0 0.38r1 0 0
t = 10 min 0.38 r10 -r10 r20 –r30
t= 0.38 r20
–0.38 r30
Total rotation at t = –4.7120
2.303 32.4  4.712 2.303
K= log = log 1.12
10 28.8  4.712 10
0.693
K = 0.0113 min–1 , t1/2 = = 61.16 min
K

9. For first order reactions,

2.303 N
t= log o
K N1
2.303 100
At 298 k; t = log
K 298 90
2.303 100
At 309 K; t = log
K 308 25
Since time is the same hence,
2.303 100 2.303 100
log  log
K 298 90 K 308 25
0.0458 0.1249 K 0.1249
or  or 308  = 2.73
K 298 K 308 K 298 0.0458
According to Arrhenius equation
K Ea  1 1 
2.303 log 308  
K 298 8.314  298 208 


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 RSM79Ph-IICKCH(H&S)7

Ea  10 
or 2.303 log 2.73 = = 76.65 kJ
8.314  298  308 

and K318 = 9.036  10–4 s–1

10. According to kinetic equation of first order

2.303 a
K= log
t ax
a = 5.0 mg/ml (a-x) = 4.2 mg/ml, t = 20 months
2.303 5 2.303
K= log =  0.07528
20 4 .2 20
K = 8.728  10–3 months–1
Suppose t months are sufficient for its 30% decomposition, therefore
2.303 100
8.728  10–3 = log
t 70
2.303 100
t= log = 263.86  0.1549 = 40.87 months
8.728  10  3 70
 41 months
0.693
Half life period = = 79.39 months
8.728  10  3
 80 months

Solution to Objective Problems

LEVEL – I

1. For 87.5% change there will be three half-changes. Hence half-time of the reaction
1 60
will be h = = 20 min, since half-time of a first order reaction is a constant
3 3
independent of initial concentration.
100%   50% 
20 min
 25% 
20 min
 12.5%
20 min
(un reacted)

0.693 0.693
k  = 0.0346 min–1
t1 / 2 20

96
2. Number of halflives = =4
24
10
Concentration remaining after 96 hrs = = 0.625 M
( 2) 4

3. This reaction is a zero order reaction

k 80
4.  2 5 = 32
k 30

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RSM79Ph-IICKCH(H&S)8

5. K = Ae–Ea/RT when T  
 value is 6  1014s–1

6. Order = + 3/2 – 1 = 1/2

K1 [B]
16. For parallel reaction 
K 2 [C]
[B] 1.14  10 4 3
 5
=
[C] 3.8  10 1
 % of B = 75
 and percentage of C = 25

17. Tangent makes an angle of 30° with concentration axis so it must make an angle of
60° with the time axis (–ve direction). The slope of the tangent will be tan60° i.e.,
1.723.

18. The rate data suggests the rate law as follows

Rate  A i.e., r  A1/2
 order = 0.5

19. Unit of the rate constant mole –1/2L1/2.min1/2 suggests that the reaction obeys kinetics
of 1.5 order.
Rate = k [CH3CHO]3/2
Rate moleL 1 min 1
or k =  = Mole–1/2, L1/2.min–1
[CH 3CHO ]3 / 2 (mole L-1 )3 / 2
So, by doubling the concentration of acetaldehyde the rate will increase 21.5 i.e.,
2.828 times.

20. Step II, being r.d.s.

Rate of overall reaction = rate of Step II = KII [O3][O]
Putting the value of [O] from the equilibrium of Step I,
K K [O ] 2
Rate = II C 3
[O 2 ]

21.

EP
E H
ER

Reaction coordinate

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