4.

Chapter 4
INTEXT EXERCISE: 1
1. Rate of reaction generally decreases with time with - dN 2 - 1 dH 2 1 dNH3
7. dt = 3 dt = 2 dt
the decrease in the concentration of reactants.
2. According to law of mass action : R activity. The d NH3 1 - d H2 3 1
d t = 17 mol/hr & d t = 2 × 17 mol/hr
activity of aqueous substances is approximated by
Molarity. dH 3 1 2
or, - dt 2 = 2 × 17 × 1000 kg/hr
3. At a constant temperature,
= 1.76 × 10 4 kg/hr
Rate [concentration of reactant]order
dc
8. - dt refers as decrease in concentration of the
4. Rate of reaction = dt = : 10 D = 10
dx 0.2 - 0.1 0.1
reactant with time.
= 0.01 mol dm 3 min 1.
1 d [A] d [B] d [C] d [D]
- d (N 2) 1 d (H 2) 1 d (NH 3) 3 9. - 3 dt =- dt = dt = dt
5. dt =- 3 dt = 2 dt = 2 ×40×10 -3
10. Increase in concentration of B = 5 × 10 3 mol L 1

= 60 × 10 3
Time = 10 sec
6. ‘A’ will disappear at twice the rate at which ‘B’ will Increase of conc. B
Rate of appearance of B = Time taken
that of B. 5×10 -3 mol 1 -1
= 10 sec = 5×10 -4 mol L-1 Sec -1

INTEXT EXERCISE: 2
2.303 a 0.693 0.693
1. k = t log10 a - x ; 5. t1/2 = k = 6.2×10 -4 = 1117.7 sec
t = 2 × 102, a = 800, a x=50 2.303 a
6. k = t log a - x
2.303 2.303
k= log10 24 = × 4 × 0.301
2×10 2 2×10 4 0.693 2.303 100
t = 30 log 100 - 30
1

= 1.38 × 10 2 s 1 2

2. p0 = 500 atm t 1
2 = 58.2 min.
2.303 p0 7. For Ist order reaction half life is independent of
k = t log10 p t concentration.
2.303 500 dx
3.38×10 -5 = 10×60 log p t 8. For zero order reactions dt = k [A] o
500 500 0.693 2.303 10
or, 0.00880 = log p t & 1.02 = 490 atm 9. k = 24 hr -1 = 96 log a - x
2.303 a 10
3. k = t log a - x or log a - x = 1.2036 or 1 log (a x) = 1.2036
2.303 0.5
(a - x) = 0.05 mol L-1, 6 =
t log 0.05 or log (a x) = 0.2036 = 1.7964
2.303 0.5 2.303 or (a x) = antilog 1.7964 = 0.6258 gm
or t = 6 log 0.05 = 6 = 0.384 min
10. 0.08 mol 1 1 to 0.01 mol 1 1 involves 3 half life. So
4.
the t is 30 minutes.
reaction.
4.2 Chemistry
INTEXT EXERCISE: 3
1. 1.6 × 10 = k (0.5) (0.5)
4 p q
... (1) 6. t1/ a01 n
2
20 b 0.5 l & ^ 2 h = b 1 l
1-n 1-n
3.2 × 10 4 = k (0.5)p (1.0)q ... (2) =
14.14 1 2
3.2 × 10 4 = k (1.0)p (1.0)q ... (3)
n 1 = 0.5 n = 1.5
Dividing Eq (3) by Eq (2) p=0
1
Dividing Eq (2) by Eq (1) q=1 7. We know, t1/2 ao1 n. So, t = ka for second order
1
2
o
reactions.
Rate = k [B2]
8. Unit of rate constant for nth order reaction is
2. 2A + B Products
mol(n 1)
lit(n 1)s 1.
According to question : rate is doubled when [B] is
doubled. d ln k 3 H o
9. By Vant’s Hoff equation, dT = RT 2 .
Rate of reaction [A]p [B]1 Hence (a) is correct (b) is also correct as plot of log
As rate increase in rate is 8 times when concentration (X) vs time is linear. (c) is wrong because p \ T at
of both reactant is doubled. It means that overall constant volume. (d) is correct by Boyle’s law.
order of reaction is 3 and overall rate should be 10. aA xP
R = k [A] [B]
2
Rate of reaction = [A]a
3. The rate of reaction does not change with time for Order of reaction = a
zero order reaction.
[A]1 = 2.2 mM, r1 = 2.4 m M –1
s
...(i)
4. r = k[A] , 100r = k[10A]
n n
100 = 10
n
n=2 2.4
[A]2 = 2.2/2 mM, r1 = 0.6 m M –1s
or, 4 ...(ii)
5. For Ist order reaction
On reducing the concentration of A to half, the rate
kt of reaction is decreased by four times.
log (a x) = loa a 2.303
y = c + mx Rate of reaction = [A]2
Order of reaction = 2.
INTEXT EXERCISE: 4

8. log b k 400 l = 2.303

1. The increase in collision frequency brings in an k Ea : 1 1 D k 400
increase in effective collisions and thus rate of 200 R 200 - 400 & k 200 = 10
reaction increases. 2.303 × 400R
Ea = 1 = 921.2 R
2. Greater fraction of molecules are able to overcome
Ea : 1
T1 - T2 D
k 1
the activation energy barrier. So, the number of 9. log k2 = 2.303R
1
effective collisions increase. k
If k2 = 2
3. Activation energy is the energy needed by reactant 1

molecules to gain threshold energy level. Ea

log2 = 2.303×8.314 : 1 - 1 D
300 310
4. All other are different forms of Arrhenius equation.
Ea = .3010×2.303×8.314 b 10
300×310 l
5. Number of collision depend upon pressure,
concentration and temperature. = 53598.59 Jmol 1 = 54 kJ.
6. H = Ef Er 10. When k increases, rate of reaction also increases,
for exothermic reaction H < O pZ
k = E/RT for k to increase p, z, T should increase
Ef Er < O Ef < Er e
7. and E should decrease. ( e . 2.7 ).
 4.3
INTEXT EXERCISE: 5
1. As Z for Po is greater by 2 than Z for Pb, it is two -a
6. 92
X238 Y(n = 234
234
90
90 = 144)
positions on the right of Pb.
7. Uranium is an f Block element and so is Thorium,
2. Both and
hence both belong to Group III B.
8. 60
27 Co is radioactive due to high n/p ratio (33/27).
3. decay occurs by the nuclear change n
1
0
1
+1
p + e.
0
1 9. Balance the A and Z separately to get 178O.
4. 42
20
Ca 42
21
Sc + 0
1 10. As mass number of U increases, its radioactivity
5. t1/ = ln2/ and tavg = 1/ decreases.
2
INTEXT EXERCISE: 6

6. [B] at any time = k 1+ k0 ^1 - e -]k + k gth and

1. 3000 yrs = Two half lives. kA 1 2

1 1 2
Amount left = 4 th = 0.25g
[C] at any time = k + k 1 - e -]k + k gth
k2 A0 ^ 1 2

0.693 6390 1 2
2. t = = 2.31 = 3000 yrs.
5B? k1
1

2.31×10 -4
2
k 1
2.303 a 2.303 5C? = k2 which in this case is 2k = 2
3. m = 96 log a/8 = 96 log28
k1 k2
7. For a series reaction A B C
2.303 0.693
= 32 log = 32 mim -1 ln ^k2 /k1h
[B] is maximum at t = k - k .
0.693 2 1
t =1 = 32min.
2
m Now, since value of k1 and k2 are not given and only
or directly 1/8 th remains after 3 half lives Total ratio is given, therefore it cannot be determined.
time = 96 min. Hence one half life = 32 min. A A 1 1
0.693 2.303 N N 8. 16o = no or n = 4
4. m = 60 min -1 = 90 log No or log No 2 2 2
n = 4 i.e. no of half lives = 4
= 0.4514 or No/N = 2.828 or N = 600/2.828 = 1 1 1 1
9. 16 = n or 4 = n or n = 4
212 200. 2 2 2
Required time = 4 × t1/2 = 120 min = 2 hrs.
90
5. Half lives, n = 30 = 3 , Amount left 1 1 t1/2 1580
10. Average life (x) = = 0.693/t = 0.693 = 0.693
N 600 m 1/2
(N) = no = 3 = 75 atoms
2 2 = 2.279 × 103 years

EXERCISE 1

1 d [A] 1 d [B] 5. Rate of reaction decreases with time, increases with

1. 3A 2B. Rate = - 3 dt =+ 2 dt . concentration of reactant and increases with increase
d [B] 2 d [A] in temperature.
Hence + dt =- 3 dt
1 d [X] d [Z]
2. 6. Rate = - 2 dt =+ dt = 0.05 mol L 1 min 1
3. The rate of reaction is same irrespective of any d [X]
reactant or product, whose concentration change is - dt = 2 × 0.05 = 0.1 mol L 1 min 1
measured. d [H 2]
1 7. dt = 0.3 × 10 Ms
4 1

4. A2(g) — B(g) + 2 C(g)

1 d [H 2] 1 d [NH3]
100 0 0 Rate = - 3 dt =+ 2 dt
1
100 p p 2p d [NH3] 2 d [H 2] 2
1 Hence dt =- 3 dt =- 3 × ( 0.3 ×10 4)
100 p + p + 2 p = 120 or p = 40 mm
= 0.2 × 10 4 Ms 1
dp A 40
- dt = 5 = 8 mm min 1
2
4.4 Chemistry
8. As rate = k [RCl], on decreasing the concentration 2.303 a
24. k = t log a - x
of RCl to half, the rate will also be halved.
9. 2p = 4, 3p = 9 p = 2 = order. a kt 2.2×10 -5 ×60×90
or log a - x = 2.303 = 2.303 =0.0516
10. Rate of zero order reaction is independent of the a a-x
Hence a - x = 1.127 or a = 0.887
concentration of the reactant.
x
11. Units os rate constant k are : M1 n s 1. or, 1 - a = 0.887
x
12. Rate = K[NO]2[O2]. Initially rate = Ka2b. If volume or a = 0.112 = 11.2 %.
is reduced to half, concentration are doubled so that
2.303 a 2.303 a
new rate = k(2a)2 (2b) = 8ka2b i.e. 8 times. 25. k = t log aot = 24 log a/8
13. Initially, rate = k [A][B] = kab 2.303
k = 24 log 8 min -1
When volume of the vessel is reduced to one fourth,
concentrations become 4 times. Hence new rate = k 26. Rate = k[N2O5] = 6.25 × 10 4 × 1.25
(4a) (4b) = 16 kab i.e. it becomes 16 times. = 7.75 × 10 4 mol L 1s 1.
14. Rate = k[N2O5] (Order predicted from untis of k). 0.6 3
27. In case I, fraction of A reacted = 0.8 = 4
Hence 2.4 × 10 5 = 3.0 × 10 5 [N2O5] or [N2O5] = 0.8 0.675 3
mol L 1 In case II, fraction of A reacted = 0.9 = 4

15. Product of concentrations in moles L 1 are highest in

fraction of reaction is independent of initial
(b).
concentration.
dx Conc. 1
16. dt = k (Conc.)n or k = Time × 28. For zero order reactions : at = ao kt
(Conc.) n
= (Conc.) 1 n
time = (mol L )
1 1 1 n
sec 1 at completion at = 0
a
= mol1 nLn 1 sec 1
tcompletion = ko
17. As half life period remains constant, order = 1. x
Hence x = kt or t = k .
18. t1/2 of 1st order reaction is independent of ‘a’. a
For completion, x = a, Hence t = k .
19. As it is a reaction of 1st order, t1/2 does not depend
P, k = t ; [A] - [A] E
1 1 1
upon initial conc. 29. For 2nd order reaction, 2A
o
2.303 a
20. k = t log a - x Hence (1) is correct, (2) is wrong.
1 1
kt Further t1/2 = k [A] . Hence (3) is correct.
means 2.303 = log a log (a x) o

kt 30. From 1 and 3, keeping [B] const, [A] is doubled,

or, log (a x) = - 2.303 log a
rate remains unaffected. Hence rate is independent
-k of [A]. From 1 and 4, keeping [A] constant, [B] is
hence, slope = 2.303 .
doubled, rate becomes 8 times. Hence rate \ [B]3.
k
So, magnitude = 2.303 31. As doubling the initial conc. doubles the rate of
reaction, order =1.
21. Rate constant of reaction increases with increase in
temperature. 32. A straight line plot of [A] vs t with negative slope is
for a reaction of zero order.
[A o]
22. For zero order reactions, t1/2 = 2k t a1o- n
]ao/2g1 - n
1 1 33. t \ a1o- n &
1
= & 2 = 21 - n
t/ 2
2

When [Ao] is reduced to 4 th, t1/2 will become 4 th

1 n = 0.5 n = 0.5
23. 0.08 mol L 1 to 0.01 mol L 1 involves 3 half lives.
1 34. t1/2 a1 n. Hence t1/2 1 / a3
After n half lives concentration becomes n times.
2
Since 1 n = 3
n = 4.
 4.5
35. Earlier rate = Kan bm
46.
New rate = k (2a) b 2 l
n b m

New rate 2n an bm am
Earlier rate = a n b m = 2n. 2 m
= 2n m

36. 0.46 = k (0.1)p (0.2)q ... (1)

1.84 = k (0.2)p (0.2)q ... (2)
0.92 = k (0.2)p (0.1)q ... (3)
Solving we get p = 2 and q = 1
Rate = k [A]2 [B]
2.3 × 10 6 = k(.01)2 (1)1 47. Since order is not equal to stoichiometric
k = 2.3 × 10 2
1
37. [A] is kept constant, [B] is doubled, rate is doubled. =12 .
Hence rate [B] is kept constant, [A] is doubled, 48. A straight line is obtained when log k is plotted
rate becomes 4 times. Hence rate [A]2 against 1/T.
rate law is Rate = k[A]2 [B] 49. The activation energy for the reverse reaction can be
less than or more than Ea depending upon whether
Rate 1.15×10 -4
k= = 2.30 × 10 2
the reaction is endothermic or exothermic.
[A] [B] (0.5) 2 (0.02)
2

2.303 ao 2.303 800 50. Factual. Ho = c

38. k = t log a t = 2×10 4 log 50
51. Molecularity of a chemical reaction is never
2.303
= log2 4 = 1.386×10 -4 s -1 fractional.
2×10 4
39. From the units of k, it is a reaction of 2nd order. In
1
general, t1/2 \ n - 1 .
a
1 1
For 2nd order, t1/2 = ka = 0.5×0.2 = 10 min .
52.
40.
as rate of reaction is doubled. It may be noted that
in presence of acid, hydrolysis of ethyl acetate is a
pseudo unimolecular reaction but the actual value
of k depends upon the concentration of H+ ions,
otherwise rate constant of a reaction is constant at
53. 100 increase has been made 6 times, the rate will
constant temperature.
increase 26 = 64 times.
2.303 V3
41. k = t log V3 - Vt , gives constant value of k. 54. At T1 = 200 K if k1 = k, then at
Hence it is 1st order reaction. T2 = t00 K, k2 = 10 k
10k Ea b 500 - 200 l
42. Higher the activation energy, lower is the rate log k = 2.303R 500×200 or Ea = 767.67R
constant.
k Ea b T2 - T1 l
43. With increase in temperature, population of activated 55. log k2 = 2.303R T1 T2
1
molecules increases.
= 2.303×8.3 b 300×305 l = 0.1667
58300 5
44. A catalyst alters the reaction mechanism.
45. A reaction with two reactants cannot be unimolecular. k2
k 2 = antilog 0.1667 = 1.468 . 1.5.
4.6 Chemistry
56. Nuclei which are most stable and abundant have 68. 232 220
X " 89 Y, a = (232 - 220) /4 = 3
92
even no. of protons and neutrons because their spins
= 89 (92 3 × 2) = 3
tend to pair up.
2.303 10000 -2 -1
57. On emitting particle Z decreases by 2 and A 69. m = 50 log 2500 = 2.77×10 day
decreases by 4. 0.693
70. t1/2 = i.e. t1/2 ×m = 0.693 or x × x = 0.693
58. Rate of decay of radioactive elements is independent m
of temperature. This is how radioactive decay is i.e. x2 = 0.693 or x = (0.693)1/2.
different from 1st order chemical reactions. 71. Activity decreases by 90% when conc. decreases by
90%.
59. In (c) both n and p are even and n/p ratio is minimum
2.303 a
m = 10 log a - 0.9a = 0.2303 yr -1,
60. 14
7 N + 11 H " 15 0
8 O + 0c
0.693
61. U on losing 2 particles becoms
235
92
Ra and that
227
88
t1/2 = 0.2303 . 3yrs .
belongs to Group II A.
2.303 a 2.303
72. m = 2 log 3 = 2 log 4.
62. Some mass is lost which is converted into energy. a- 4a
63. (a) emits two neutrons. (b) emits (c) & (d) emit one 0.693
= 2.303 log2 = 0.693 hr -1 t = T 1
2

electron each.
73. Activity (ds 1) = N
64. Emission of particle leads to decrease of 2 units
of charge and decrease of 4 units of mass in the Activity = 6.023 curie = 6.023 × 3.7 × 107 d s 1

nucleus. 6.023 × 3.7 × 1010 = 3.7 × 104 × N

65. On balancing, product nucleus is 146 C. N = 6.023 × 106 atoms = 10 17
moles.
mass = 10 17
× 100 = 10 g15
66. t1/ = ln 2/ , = 1/ . × 0.6932 = t1/
2 2
74. Equal no. of atoms of U and Pb means half of U has
67. 228
Th Bi + x 24 + y
212 0
.
90 88 1 disintegrated, as 1 U atom produces 1 Pb atom.
228 = 212 + 4x or 4x = 16 or x = 4
Time taken = t1/2.
90 = 83 + 2x –y = 83 + 8 – y or y = 1 0.693 2.303 15.2
75. m = 5760 yr -1, t = 0.693/5760 log 7.6

EXERCISE 2

1. x A — YB d [NO]
(2) - dt = 2k1[NO] [H2] = k1’ [NO] [H2]
-1 d 1 d
x dt [A] = y dt [B] k1’ = 2k1
d [H 2]
-d x d (3) - dt 2k1[NO] [H2] = k1” [NO] [H2]
& dt [A] = y dt [B]
k1” = 2k1
log c m = log c x mc m
- d [A] + d [B]
y d 100
dt dt 3. dt [SO3] = 100 gram / min = 80 mole / min

log dt [A] = log dt [B] + log c y m

-d d x = 1.25 mole/min.
-1 d -d 1 d
log c y m = 0.3
x x 2
& y =1 & x:y 2 :1 2 dt [SO 2] = dt [O 2] = 2 dt [SO3]
-d 1.25 1.25
dt [O 2] = 2 mole/min = 2 ×32 gram/min
2. 2NO (g) + 2H2 (g) — N2 (g) + 2H2O (g)
= 20 gram/min
1 d [NO] 1 d [H 2] d [N 2]
Rate =- 2 dt =- 2 dt = dt 4. Rate of reaction at any instant is the slope of
1 d [H 2 O] the concentration vs time graph at that instant
= 2 dt = k1 [NO] [H 2]
d [P] 15 - 5 -1
d [H 2 O] dt = 20 - 0 = 0.5 MS
(1) dt = 2k1[NO] [H2] = k [NO] [H2]
So k = 2k1
 4.7
5. Rate law for: Ist order IInd order IIIrd order 13. Ct = C0 e–Kt
Rate = k[A]1 R2 = k[A]2 R3 = k[A]3 According to question
if [A] = 1 then r1 = r2 = r3 CA = CB
t t
if [A] < 1 then r1 > r2 > r3 CA e -k A t
= C B e -k B t
0 0

if [A] > 1 then r3 > r2 > r1

CA e -k t CA B

6. CB =0
& C = e(k 0 A - k B)t
0e -k t B A
0

for non elementary reactions.

ln4 = : 5 - 15 D t
ln2 ln2
7. A + B — product
ln (2) 2 = : 5 - 15 D t
r = k[A] [B]2 = 1 × 10 2 (k = 1 × 10 2)
1 ln2 ln2

r1 = k : 2 D : 2 D = 1×10 -2 × 8 = 1.25×10 -3
1 1 2 1
2ln2 = : 5 - 15 D t
ln2 ln2

2 = : 5 - 15 D t
8. aA + bB — Product 1 1
dx a b
dt = k [A] [B] 2
(i) As on doubling concentration of A rate become 2 = 15 × t
four times so a = 2. t = 15 minute.
(ii) On four time concentration of B rate become
1
double so b = 2 .
1
So, Given equation: 2a + 2 b $ Product
14. slope of graph at 20 sec
1 d [A] d [B] dy 0.35
- 2 dt =- 2 dt = dx = 50 = 7×10 -3
d [A] d [B]
- dt =- 4 dt
60
9. From units of k, we get that it is a zero order reaction. 15. t1/2 = 10 No. of Half life = 10 = 6 half life

C t = On = O6 = b 64O l
Total time for drop to disappears C C C
(ao at) = kt at = 0 (2) (2)
3.0×10 -6 16. From uni units of k, order is zero.
= t100% t100% = 6 × 10 9 sec
(0.05×10 -3) ×1.0×107
(A0 At) = kt for zeroth order
10. 2A + B — Product
(0.50 At) = 0.025 × t
d [A]
- dt = k [A] 0.50 At = 0.025 × 15
d [A] At = 0.125 M
- dt = k [a - x]
17. From the unit of k, it is evident that it is a second
Ct = C0 e Kt order reaction.
1
Ct = C0 e -k× k 1 d [NO 2] d [O 2]
-2 dt = dt
Ct = C0 e 1
d [NO 2] d [O 2]
C - dt = 2× dt = 2× 1.5 × 10 4 = 3 ×10 4
Ct = e0
11. From given graph x = kt 3 ×10 -4 = k [NO 2] 2 = 3 ×10 -3 [NO 2] 2
it is a zero order reaction 1
[NO2] = = 0.316.
10
d [A]
- dt = k 1 1
18. C t = C0 + kt
12. Reaction is zero order (unit of k)
1 1
[B] = 2 × moles of A reacted 0.04 = 0.2 + 0.002 × t
[B] = 2 × kt = 0.2 mol lit–1. 20
25 = 5 + 0.002 × t t= = 10,000 sec
2×10 -3
4.8 Chemistry
19. left
= [B]formed = n × [A]decayed 26. A — 2B + C
A0 e= n × A0 1 et t t=0 P0 0 0 P0
n t=t (PO – x) 2x x P0 + 2x = 176
e = n+1
t
P 3P0= 270 P0 = 90
0 0
[B]formed = n × A0 × :1 - n + 1 D = n + 01
n nA
2x = 176 – 90 = 86
20. It is property of Ist order Rxn and other all are x = 43
properties of IInd order. Pressure of A after 10 minute = Po x = 90 – 43 = 47
21. Now, t \ a1o- n & logt = log c + (1 - n) log a o
1
2
1
2
27. A (g) — B (g) + C(g) + D(g)
a Slope = 1 1 n=1 n=0
Initially Pi 0 0 0
As t 1
2 = ao/2k and t 1
2 = ao here, k = 1/2
At time t (Pi – Px) Px Px Px
22. t1/2 = Ca(1– n), n being order and C = constant
total pressure at time t = (Pi + 2Px) = Pt
log t1/2= log C + (1 – n) log a
So Px = b
Pt - Pi l 3P - P
1 – n = –1
2 & Pi - Px = i 2 t
n=2
k = t log b P -i P l = t log b 3P -i P l
2.303 P 2.303 2P
23. r1 = k[0.01]a [0.01]b = 6.93 × 10–6 i x i t

r2 = k[0.02]a [0.01]b = 1.386 × 10–5 28. A(s) — 2B(g) + C(g)

r3 = k[0.02] [0.02] = 1.386 × 10
a b –5 t=0 a
From data a = 1, b=0 t = 20 a x 2x x
Overall order = 1 ; k = 6.93 × 10 sec –4 –1 2a a
1 A 3a 225 a 75
6.93 × 10–4 = 50×60 ln A0
t
3x 150 x 50 (a x) 25
0.5
3 × 0.693 = ln A 75 75
t k . 20 = ln 25 a-y \ 9
At = 0.0625
75×8 75×8
rate of reaction=6.93 × 10–4×0.0625=4.33×10–5 Ms–1. y \ 9 & Ptot \ 3y = 3 = 200 mm.

24. Rate = k [A]3 29. Initial pressure 65 105 y 185

0.01 = k (0.012) 3
Half life 290 x 670 825
1
]1.2g3
k= ×10 4 Initial pressure of gas Initial moles of gas in above
question.
When [A] = [B] = 0.1
290 825
10 4 ]0.1g3 10 Half life Initial pressure as 65 . 185
]1.2g3
Rate k [A]3 = × =
1.23 So, it must be zero order reaction
Rate = 5.78
C P
t1/2 = 2ko = 2ko
25. This is parabolic graph
65
290 = 2k
65
k = 2×290 = 0.112 mm of Hg/sec
of y x2 105×2×290 y×2×290
x= 2×65 = 468 sec 670 = 2×65
So, This the graph of second order
dc y = 150 mm of Hg
as - dt = kc 2
1 r -r
30. k = 10×60 ln r3 - r0
3 t

1 - 10 - 40 1
= 10×60 ln - 10 - 15 = 10×60 ×ln 2
1

y2 \ x y\x 2
0.0693
= 60 = 1.15×10 -3 sec -1
- dC 1

dt = k [C] 2 order = 1/2.

 4.9

31. kt = ln kt = ln b Co l 40. log k = : 2.303R

C - Ea D 1
× T + log A
t

at Y axis : T D = 0
2N2O5 — 2 N 2O 4 + O2 1
T=3
t=0 200 cm 3
0 0
at X axis log k=0
t=0 20 cm3 180 cm3 90 cm3 - Ea 1 E
2.303R × T = log A T = R lna A
t=0 0 cm3 200 cm3 100 cm3
Initial volume of N2O5 = 200 cm3 41. H2 (g) + Br2 (g) 2HBr (g)

because Max. volume of O2 = 100 cm3 r = k[H2] [Br2] 1/2

Molecularity
k × 500 = ln b 20 l
200 ln 10 2.303
k = 500 = 500 elementary reactions.
32. NH4NO2 (aq) — N2 (g) + 2H2 ( ) 1 3
order = 1 + 2 = 2 .

t log b V3 - Vt l & V0 = 0
k=
2.303 V3 - Vo " , E 1
42. ln k = ln A - Ra × T

k = 20×60 log b 70 - 40 l
2.303 70 - 0 E - 8.3×103
Slope =- Ra = 8.3 =- 1000

= 20×60 log b 30 l & k = 1200 log 3 sec -1

2.303 70 2.303 7 Ea 1
43. log k =- 2.303 R T + constant
33. Since A is not optically active, hence r0 = 0. Ea -3 10
3

r -r
=- 2.303 R ×10 × T + constant
Now using kt = ln r0 - r3
t 3
Ea ×10 -3 4
1 0 - 100 thus, slope of graph will be - 2.303 R =- 0.4
k = 10 ln 50 - 100 = 0.0693 min -1
Ea = 2.303 × 1.98 × 104 = 45600 cal
34. V0 become zero in the expression
44. Radioactivity is a nuclear property, affected by n/p
kt = ln b V3 - V0 l
V -V
3 t ratio.
35. t1/2 45. Tavg = 1.44 t1/2 = 1.44 × 138.5 = 199.86 day
order reaction
46. Half life of radioactive substances does not depend
x Vt (= 5 L at t = 20 minutes)
upon initial concentration.
a Vf
C C
2.303 a 2.303 50 47. C3 = 30 = 80
k = t log a - x = 20 log 45 2
36. k = A × e– Ea/RT = A × e –Ea/R×3 = A = 6.0 × 1014 s–1. C3 1
C0 = 8
37. log b k2 l = 2.303R
k Ea (T2 - T1)
48. N = N 0 b 2 l
1 n
1 T1 T2
65×103 × (298 - 273)
b xv l = (x) ×200 b 1 l
4
= 2.303×8.3×298×273
20 2
k
Solving we get k2 = 11 V = 250 mL
1
So added volume of water = 50 mL.
38. k1 = A1 e -E /RT and k2 = A 2 e -E /RT
1 2

k1 A1 (E - E )/RT 49. u — Pb + 8
k 2 = A 2 ×e ; A1 and A2 are not given.
2 1

a x x
39. For reaction, A — B. 3a 1
Given x = 3 (a x) x= 4 u left = 4 of initial
Ea = 10 kJ/mole, H = 5 kJ/mole time = 2t 1
2 = 9 × 109 years.
Rxn endothermic because H (+) 256 256
50. = 64 = 4
H = Ea – Eb 26
A A
51. Activity after ‘n’ half lives = n0 so, 0.01 = 60
5 = 10 – Eb 2 2
Hence A0 = 0.64 Ci.
Eab = 10 – 5 = 5 kJ/mole. Then [B].
4.10 Chemistry
55. Rate = K [X] [Y2]
52. mt = n ; E
nx + ny
nx [X] 2
K eq = [X ]
t = 0.693 ×2.303 log10 : 1 D
0.693×109 1+7 2

[X] = K eq ×[X 2] 1/2

= 2.079 × 10 years
10

Rate Rate = K× K eq [X 2] 1/2 [Y2]

53. For complex reactions, rate determining step is
slowest step So the order of overall reaction is 1.5
Then in 1st Mechanism 56. H2(g) + 2ICl(g) — 2HCl (g) + I2(g)
Proposed mechanism
Rate = k [NO2] [O3] .....(i) slow
Mechanism: H2(g) + ICl(g) HCl(g) + HI (g)
But 2nd Mechanism
K a fast
O3 kb
O 2 + [O] .....(a) Ea k1 + Ea k 2
slow 57. We know, Eaov = 1

(k1 + k 2)
2

NO 2 + O NO3 .....(b)
NO3 + NO 2
fast
N 2 O5 .....(c) [1.0×10 -2 ×60 + 3×10 -2 ×70]
=
[1.0×10 -2 + 3.0×10 -1]
Then for Rxn (a)
ka [O 2] [O] Ea = 67.5 kJ/mole
k b = [O3] = k eq .....(d)
58. 1 mole of A will form 2 moles of B and C after
by Rxn (b) completion of reactions when 75% of A converted into
Rate = k [NO2] [O] .....(ii) B and C then total number of moles = 0.5 + 2 × 1.5 = 3.5
put value of [O] from (d) to (ii) moles.
keq [O3] k ×100 1.26×10 -4 ×100
Rate = k [O ] × [NO 2] 59. % of B = k1 + k =
2 1 2 12.6×10 -5 + 3.8×10 -5
k1 [NO 2] [O3] = 76.83%
Rate = [O 2]
k ×100 3.8×10 -5 ×100
It is 1st order wrt NO2 and O3 in both mechanisms. % of C = k2 + k =
1 2 12.6×10 -5 + 3.8×10 -5
dc = 23.17 %
54. From Rxn I : dt = 2k1 [A] [B]
60. [B] + [C] = 2 M
dc
From Rxn II : - dt = 2k2 [B] [C]
[B] 2k1 4 8 18
dc [C] = 3k 2 = 9 [B] = 13 and [C] = 13
From Rxn III : - dt = 2k3 [A] [C]
Combining we get :
dc
- dt = k2 [B][C] + k3 [A][C] 2k1 [A][B]

EXERCISE 3
1. I represents kinetic but II represents equilibrium e–2 = e– kt
region because at equilibrium the concentration 2
remains constant. t= k
0.693 1 t = 2 × natural life time.
2. Activity = N0 = mN 0 = t1/2 × 226 ×N A
5. Equation: Ag+ 2NH3 [Ag(NH3)2+]
0.693×6.02×10 23
A = 1600×365×24×60×226 dx
Given, dt = 2 × 107 L2 mol 2 s 1
A = 2.19 × 1012 dpm
[Ag+] [NH3]2 1 × 10 2 s 1 [Ag(NH3)2+]
3. H0 = EP ER dx
For equilibrium dt = 0
From given diagram H0 = y – z = x.
2 × 107 [Ag+] [NH3]2 1 × 10 2 [Ag(NH3)2+] = 0
4. Ct = C0 e– kt
[Ag (NH3) 2+] 2×107
1 2 = = 2×109 L2 mol -2
e2
× C0 = C0 e–kt [Ag ] [NH3]
+
1×10 -2
 4.11
]r3 - r0g
dx
6. dt = k [A] 2 2 = ]r3 - rtg
]r3 - r0g = 2r3 - 2rt
r0 = 2rt - r3

log b dt l = log k + 2 log [A]

dx 13. A + B C+D
: dx D = 0
Slope = 2 dt
Intercept = log k. k1 [A] [B] – k2[C] [D] = 0
7. A (aq) — B (aq) + C (aq) k1 [A] [B] = k2[C] [D]
t=0 a 0 0 [A] [B] = [C] [D]
t=t a–x x x
0.4 × 0.25 = 0.2 × 0.5
t= 0 a a
(a – x) + 2x + 3x \ n1 1 = 1.
a + 4x \ n1 .....(i) 14. There is an error of 3dps (already exist)
2a + 3a \ n2 Then N0 = (23 – 3) = 20 dps
n
a \ 52 .....(ii) Nt = 10 dps
k = t ln : a - x D
1 a The half life = 10 minutes
In next 10 minute Nt = 5 dps
b n2 l 4 (n 2)
1 5 1 Then value with error = (5 + 3) = 8 dps.
& k = t ln = t ln 5 (n - n )
b n 2 - n1
l 2 1
15. We have
4
5B?t 4k1 16
5C?t = 3k 2 = 9
8. pH = 5 pH =6
[H+] = 10–5 [H+] = 10–6
k 4
On decreasing [H+] concentration by 10 times, so, k1 = 3
2
the half life of reaction increases by 10 times that
Now k = k1 + k 2 = :2×10 -3 + 4 ×2×10 -3D sec -1
means reaction rate has been decreased by 10 times. 3
Therefore, we can say that the order of reaction with
7 7×10 -3 ×60
respect to [H+] concentration is one. = 2 ×10 -3 sec -1 = 2 min -1
9. We know ln2 693
so t1/2 = min = 7×30 = 3.3 min
tav = 1.44 × t50% 7×30×10 -3
and t75% = 2 t50% ln2
16. k1 + k 2 = 12
Then t50% < tav < t75%
10. Slowest step is the rate determining step. B 4 2 k
= 6 = 3 = k1
C 2
11. As only A is optically active. 5 ln2
So conc. of A at t = 20 min 40° 2 k1 = 12
While concentration of A at t = 50 min 10° ln2
k1 = 30 t1/2 = 30 hr.
1
so t1/2 = 15 min. (As rotation becomes th in 2t1/ ) 17. (1) is Ea
4 2
So volume consumed of H2O2 at t = 15 min = t1/ , is (2) is
2
according to 50% production of B.
(3) is Ea for second step and
at t=60 min. production of B=94.75% (four half lives)
(4) is H overall from the graph
So volume consumed = (40 ml) + b 2 l ml + b 4 l
40 40
18. H2O + O — 2OH H = 72 kJ/mole
ml + b 8 l ml = 75 ml.
40
and Ea = 77 kJ/mole
12. Given ]r3 - r0g = a , ]r3 - rtg = ]a - xg Then we know H = Eat – Eba
At 50% Inversion 72 = 77 – Eba
a
2 = (a - x) Eba = 5 KJ/mole
4.12 Chemistry
19. A + B — C 27. From the given graph it is clear that the concentration
t=0 a = 0.1 M b = 0.2 M 0 decrease linearly with time, therefore zero order
Reaction and A 3B type, as Pb
t = 100s a x b x x A
initially.
From question, r = k [A][B] and hence
- dC A CA
1 a (b - x)
kt = b - a ln b (a - x)
28. dt = K1 1 + K 2 C A if CA vis small
then 1 + K2CA = 1
1 0.1 (0.2 - x) - dC A
or 10 -3 ×100 = 0.2 - 0.1 ×2.303×log 0.2 (0.1 - x) dt = K1 .C A
log k = log A + b 2.303a R l × T
x . 0.002 E -E 1
29. K = Ae - RTa
[A] = 0.1 x = 0.098 M Also, the reaction which has more Ea, is the more
20. nA — B temperature sensitive.
a 30. We know
x
a x n t1/ = 24 min Rate = k [conc.]
2
x 3a Given Rxn catalysed by HA and HB
at t = 48 a x = n and x = 4
Rate constant kA = k1 [H+]HA
a 3a
4 = 4n or, n = 3. kB = k1 [H+]HB
d [C] Then relative strength of acids A and B is
21. In given sequence of Rxn dt = k 2 [B] - k3 [C]
k A 6H +@HA
k B = 6H +@HB
k1 k
22. A + A A + A* A* + A 2A
2

Rate of decomposition of A = k1[A]2 2 6H +@HA 5Acid HA?

Rate of formation of A = k2[A] [A*] 1 = 6H +@HB = strength of 5Acid HB?
At equilibrium 31. For bimolecular reaction, order = 2. As molecularity
rate of decomposition = rate of formation
if order = 2 we cannot be sure that the reaction is
k1[A]2 = k2[A][A*] bimolecular.
k
[A*] = k1 [A] 32. (b) Half life period independent of conc. of Zn then
2
order w.r.t. Zn is 1. So, Rate = k [Zn][H+]n
f = b1 - c l then c0 = ]1 - f g
c c
23. Given we can write,
0
Rate 2 [Zn] ;1×10 -2 En 100
- dt = k 5c ? Rate1 = [Zn] 1×10 -3 = 1
df 1 dc dc
- dt = c dt
0
Given n=2
1 5c ?
then dt = k ]1 - f g
df df
dt = c0 k Then Rate = k [Zn][H+]2

24. Given Rxn (c) Conc. of Zn four times and H+ ion is halved

Rate = k 54×Zn?: H2 D
+ 2
N 2 + 3 H2 2 NH3
dx
dt = 1 × 10 [N2] [H2] 1 × 10 [NH3]
2 3 3 2
Rate = k[Zn][H+]2
dx [N 2] [H 2] 3 Rate remins same.
When dt = 0 then = 10 -5
[NH3] 2
Hence the reaction will be at equilibrium at the (d) Similarly if conc. of H+ doubled and [Zn]
given instant. constant
Then Rate2 = k[Zn] [2H+]2
25. 2NO2(g) + F2(g) 2NO2F(g)
t = 0 2 atm 1 atm 0 Rate2 = 4 k[Zn] [H+]2
t= 3 0 0 2 atm Rate2 = 4 × Rate1
k1 a 6 -k t -k t
@ 33. Overall rate of a reaction can never be negative.
26. [B] = k - k1 e - e
1 2

2
3 conc
d [B] The rate of a reaction wrt a reagent is the 3 time of
dt = 0 when [B] is maximum. that reagent.
- k1 e -k t + k 2 e -k t = 0
1 2 Average and instantaneous rates may or may not be
k equal and rate of reaction is governed by the physical
1
So, t max = k - k ln k1 state of reactants.
1 2 2
 4.13
34. 3 A(g) — 2 B(g) + 2C (g) dk Ea
t=0 P0 dT = k $ RT 2
2x 2x
t = 20 P0 – x 3 3 ]dk/dTg Ea
k = fractional increase in k =
2P0 2P0 RT 2
t= 3 3 3 Larger the value of Ea more rapid is the increase
2P in k with temperature.
2 × 30 = 4
P0 = 3 atm 41.
x 42. A(g) — 2B(g) + C(g)
P0 + 3 = 3.5
x = 1.5 t=0 400 0 0
t50% = 20 is the half life t = 20 min 400 – p 2p p
t75% = 2 × 20 = 40 min Given 400 – p + 2p + p = 1000
t87.5%= 3 × t50%= 3 × 20 = 60 min 400 + 2p = 1000 p = 300 mm.

t99% = b ln2 l ×ln b 1 l = log2 ×log100 = 3 min

t 1
100 20 400 1 400 1
2
k = 20 ln 400 - 300 = 20 ln4;

35. For second order reactions, order is 2. ln2

k = 10 min–1
36. 2A — Product T1/2 = 10 min; Value of k = 0.0693 min–1
1 1
5A?t - 5A?0 = kt
1 1
5A?t = 5A?0 + kt
37. 2A + B — C
After 30 min Partial Pressure of A is 50 mm, After
t=0 2a a 0 30 min Partial Pressure of B is 700 mm
t=t 2a 2x a x x After 30 min Partial Pressure of C is 350 mm , After
d 5C? 30 min total pressure become 1100 mm
dt = k (2 (a x) (a x) 1) = 2k
2000
43. (c) Given, log k (min 1) = - T (k)
# d [c] = # 2k dt
Compare this with
[C] = 2 kt
Ea
unit of k = Ms 1 log k = log A - 2.303 RT(k)
[A] = 1 (a x) and [C] = x 5

[B] = (a x) Ea
k1 6CH 4@6Br2@
(d) - 2.303 R =- 2000
1 + k 2 5HBr?/ 6Br2@
38. Rate =
Ea = 9.212 k cal.
If [HBr] . 0 Rate = k1 [CH4][Br2]2. n=2 44. By using Maxwell’s velocity distribution curve
It is not a single step reaction as indicated by the the rise in temperature, increases the number of
complicated rate law and hence molecularity is not activated molecules to form the product therefore
rate of reaction increases.
k1 6CH 4@6Br2@2 45. Acidic hydrolysis of ester and inversion of cane sugar
k2 5HBr?
Rate . when [Br2] 0
are examples of pseudo unimolecular reactions.
order wrt CH4 = 1, Br2 = 2, HBr = 1 46. Use K = Ae Ea/RT

Overall order = 2. E
and lnK = lnA - RTa
39. We know Ea = (T - T1) 2 log b k2 l
2.303 RT T k
Ea 1
2 1 1 2.303 log K = 2.303 log A - 2.303R T
40. k = Ae Ea/RT
A=k T 3 Ea = 0
k = Ae Ea/RT

b - Ea l -E /RT $ c - 2 m
dk 1
dT = A $ R $ e
a

T
4.14 Chemistry
d 1
47. dt [NH2CONH2] = k4[NH3][HNCO] from (iii) P0 + PC + 2p = 2 [3P0 + PC]
Applying steady state approximation to HNCO or 3P0 1: P0 D
NH3 2 + 2p = 2 3P0 + 2
d 5HNCO?
3P0 1 1
= 0 = k3 [NH4NCO] – k4[NH3][HNCO] 2 + 2p = 2 × 2 ×7P0
dt 7 3P
k3 6NH3@5HNCO? 2p = 4 P0 - 2 0
k 4 = 6NH 4 CNO@ P
2p = 40
d 5urea?
= k 4 × 6NH3@5HNCO? = k 4 × k 3 6NH 4 NCO@
k
dt P
4 P = 80
k1 6
Also, [NH4NCO] = k × NH 4 CNO@ P3 = 3P0 + PC = 35
2
d 5urea? k1 6 P
dt = k3 × k × NH 4 CNO@ = k 6NH 4 CNO@ = 3P0 + 20 = 35
2
7P
= 2 0 = 35
48. Over all order of Rxn = b1 - 2 l =+ 2
1 1
P0 = 10 bar
As SO3 order wrt is - 1 so, Rate of Rxn slows P 10
2 54. PB = 2p = 40 = 4 = 2.5 bar
down, as [SO3] increases.
2.303 P
K1 K3 55. k = t1 log P -0 p
49. K = K 0
2
E1 E3 64 2.303 10
A1 e - RT ×A3 e - RT
- (Ea) overall log 49 = t1 log 10 - 1.25
Ae RT = E 2

A 2 e - RT t1 = 1.15 sec.
Ae RT = b A
- (E )
A1 A3 l - 6E +RT
a overall E -E @
1 3 2
56. Rate constant depends only on temperature.
e
2
(Ea)overall = E1 + E3 E2 = 30 KJ/mole 1:1:1
K1
2A K2
A* + A [Fast]
K1 6A*@5A? 6 *@ K1 5 ? 57.
K 2 = 5A?2 or A = K 2 A
k k
R = k3[A*] = k3 1 [A]
2
50. Rate of radioactive disintegration (–dN/dt) is also t=0 a
t=t x y a
5 ? 5C?
known as Activity or Radioactivity.
51. Greater is the temperature greater is the rate constant. 5A?0 = 5A?t + B2 t + 3 t
52. Activation energy is independent of temperature. 2x 3y
a = a-x-y+ 2 + 3
53. At higher temperature value of ‘k’ is more.
a=a
54. 55. 56.
A(g) — 2B(g) + C(g)
t=0 P0 PC 58.
t=t P0 – p 2p PC + p
t= 3 0 2P0 P 0 + PC 5X?t
1 5Y?t + 5Z?t
PC = 3 [P0 + PC]
ae - (k + k )t 1 2

3 PC = P0 + PC = k1 a 6 - (k + k )t
@ + k 2 a 61 - e - (k + k )t@
k1 + k 2 1 - e
1 2 1 2

2PC = P0 (k1 + k 2)
P ae - (k + k )t 1 2

PC = 20 =
PT = P0 – p + 2p + PC + p 61 - e - (k + k )t@; k1 a + k 2 a E
1 2

k1 + k 2
= P0 + PC + 2p e - (k + k )t
1 2

=
P3 = 2P0 + P0 + PC 1 - e - (k + k )t 1 2

1 1
6e - 1@ 6e kt - 1@
= 3P0 + PC = (k + k )t
1 2
= [where k = k1 + k2]
1
PT = 2 P3 (given)
 4.15
59. Fraction of acetic acid reacting Since Half is independent of the Initial conc. of A
k 3 3 Hence a = 1
= k +1 k = 3 + 4 = 7
1 2
First order w.r.t. A.
5B?ot 3k1
60.
5C?t = 4k 2 which depends only on temperature Now k’ is First order rate constant
not on time. 0693
k1 = t1/2
2.303 100
61. For 99% completion, t99% = k ×log 100 - 99 (i)
]T50g1 k'2 k 6H +@2b
]T50g2 k1' 6H +@1b
= =
2.303 100
For 90% completion, t90% = k ×log 100 - 90 (ii)
& b 10 l = c -5 m & b = 1
100 10 -4 b
t log 100
By Eqs. (i) and (ii) t99% = log 10 = 2 10
5 ?
90%
t99% = 2 × t90% So
-d A
5 ?6 +@1
dt = k A H Ans. ( 1 + 1 ) = 2
62. t : 0 5 15 35
67. Let a = 100
[A] : 1 0.5 0.25 0.125 a x = 80 (amount left)
t \ ]a og-1 & 1 - n =- 1 & n = 2
1
2
Q
Amount left = n [n = number of half lives]
2
Second order reaction.
100 10
80 = n & 2n = 8
63. Reaction zero order w.r.t. to A then. 2
n log2 = log 10 3 log2 = 1 3 × 0.3 = 0.1
when half of A reacted
0.1 0.1 1
A + B + C — Product n = log 2 = 0.3 = 3
at t = 0 a0 a0 a0 1
a0 a0 a0 n= 3
at t = 1000 sec. 2 2 2
Then we know for zero orders Rxn (a0 at) = kt t (time for 80% amount left or 20% decomposed)
= t (time for 50% amount left or decomposed)
1/2
a
given a t = 20 t1/2 = 3t.
a 68. Suppose order of Rxn is n
Then k×t = 20
a0 a0 a0 Then
t1/2 \ b P l
k = 2×t = 2×1000 = 2000 1 n
0
at t = 2000 sec.
a0 ]t1/2g1 d ]P0g2 nn
a0 - a t = 2000 ×2000 ]t1/2g2
=
]P0g1
at = 0 zero fraction left From (i) and (ii) data.
b 3.52 l = b 100 l
64. We know n-1

Rate = K [conc]n for nth order Rxn. 1.82 50

1.934 = (2)(n 1)
Then, Rate2 = b conc2 l
Rate conc n (1.9569) = (2)(n 1)
1 1
given, Rate2 = Rate1, conc2 = (conc1 × 1.5) n = 2 IInd order Rxn.
2.25 = (1.5)n 3163
69. log10 K = T + 12
n = 2 second order Rxn at T = (273 + 43.3) = 316.3 K
65. C At = b 2 l and C Bt = b 2 l
C 1 3 C 1 2 3163
A0 B0
log10 K = 316.3 + 12
C C 1 C 1 3 3 log10 K = (10 + 12) = 22
or CAt × C B0 = 2 or CAt = 2 × 2 = 4 = 0.75
Bt A0 Bt K = 1022
Ans. 75. Then half life period
- d 5A? 5 ?a 6 +@b t1/2 = b K×a l = 22
1 1 1
= 10 -19
dt = k A H
66. The Rate equation =
10 ×.001 1019
During any experiment pH is constant t1/2 = 10 19
- d 5A? 5 ?a
dt = k' A where k’ = k [H ]
+ b Ans. 10 19
minute.
4.16 Chemistry
70. N2 + 3H2 — 2NH3 A 0 ]Xg 4 A X
A 0 ]Yg 1 A Y
= ; =1
d ]N 2 g
73.
d 6H 2@ d 6NH3@
- dt =- 3dt = 2dt
]A0gY A X
m Y - m X = t ln < F
1
d 6N 2@ 1 d 6NH3@ 1 ]A0gX × A Y
- dt = 2 × dt = 2 ×2.0×10 -4
= 10 -4 mol L-1 S -1 = 1×10 -4 mol L-1 S -1 ]m Y - m Xgt = ln 14
71. We know for IInd order Rxn. ln 2
where m y = 30 and t = 120
k = t ; ]a - xg - a E (because concentration of
1 1 1
ty1/2 = 30 minutes.
both reactants are equal)
74. t1 = k ln b a 1 l
1 a+x
when Rxn completed 20% = ]a - xg = 100 × 5a ?
80

t 2 = k ln b a 2 l
Then 1 a+x
1 1
k = 500 > 80a - a H
1
100 ]t 2 - t1g = 1k ln b aa +
+ x1 l
x2

k = 500 : 80a - a D
1 100 1
k = t - t ln b a + x2 l
1 a+x
2 1 1

k = 500×a : 80 - 1D
1 100
k = 10 ln b 48 l
1 72

1 20 1 1 1 1
500 × 80 × a = 500×4 × a = 2000a k = 10 ln b 2 l
1 3
1
k = 2000a
k =b
ln3 - ln2 l
For 60% completed 10
]a - xg = b a - 100
60 l 40a
a = 100 ln2
= b ln310 ln2 l
-
]t1/2g
Then
0.30 0.48 - 0.30
1 1 ]t1/2g
1 =
k = t > 40a - a H 10
100 0.30 0.18
]t1/2g
= 10
1 1 :100 D
2000a = a×t 40 - 1 t1/2 =
30×10
18 = 17 minutes (Approx)
1 1 : 60 D
2000 = t 40 75. Molarity of original H2O2 =
Vol. Str. 20
11.2 = 11.2 =1.786
t = 3000 sec Ans. 3000/60 = 50 min. For titration,
-k1 t
72. At A0 e ...(i) [M1V1] V.F1 = [M2V2] V.F2
Bt B0 e -k t 2
...(ii) M1 × 10 × 2 = 0.025 × 25 × 5
A0 B0 M1 = 0.15625
Now molarity of diluted solution = 0.15625
At 4Bt
So molarity of original solution = 1.563
by (i) / (ii)
So, k = t ln b C0 l
1 C
4B t d B0 e -k t n 1
t
B t = B0 e -k t 2

k = 6×3600 log b 1.563 l s -1

2.303 1.786
]k 2 - k1gt
k = 80 sec 1

4=e
ln 4 = (k2 k1) t
ln4 ln4
t=
]k 2 - k1g ]k 2 - k1g
=

ln4
= 0.6932 0.6932 = 54 min
18 - 54
 4.17
d 5A? d 5B?
- dt =- dt = k3
d 5A? d 5C?
- dt = dt
(D) 2 A + B — 2 C + 3D
76.
r = K3 [A]º [B]º
unit of K = mol lt–1 time–1
1 d 5A? 1 d 5C? d 5A? d 5C?
- 2 dt =- 2 dt - dt = dt
1
]initial conc.gorder - 1
n 78. t1/2 \
/ ki Ei
i=1
E overall = n
79. (A) for zero order reaction C = C0 – kt
/ ki
i=1 k
2
(B) for frist order reaction log C = log C0– 2.303 ×t
kE + 4kE + 9kE + 16kE + .....n kE
= k + 2k + 3k + ..... - dc
(C) for zero order reaction dt vs C equal to zero
61 + ]2g2 + ]3 g2 + ..... ]ng2@E ]2n + 1g E
= = - dc b - dc l
1 + 2 + 3..... 3 dt = kc, log dt
21 = log k + log c
Eoverall = 3 E = 7E.
Hence plot of log against log c (abscissa) will have
77.
slope equal to unity
(A) r = k [A] [B]
80. (A) 2.303 log10 k2 = Ra : T
k E T2 - T1 D k 2
i.e. IInd order reaction & k = 11
1 2 T1 1
unit of k = mol–1 lt time–1
T2 = 298 K; T1 = 273 K, Ea = 65000 J, R = 8.314
d 5A? d 5B? J/(mol K)
- dt =- dt = k [A] [B]
d 5A? d 5C? 2.5 1 b 1 ln
20 = 8 = 2 & n = 3
- dt = dt (B)
(t1/2)A = (t1/2)B if A and B are taken in stoichiometric 0.693
ratio. & t = 3× 0.0693 = 30

(B) A + B — C + D a 0.693
(C) Zero order : t1/2 = 2k I order : t1/2 = k
r = k2 [B]º[A] = k2[A]
a 0.693 ak1
unit of k = time–1 does not have concentration unit. 2k0 = k1 & k 0 = 2 × 0.693
d 5A? d 5B?
- dt =- dt = k2[A] R ka
& R first = k1 = 2×0.693
d 5A? d 5C?
zero 0
- dt = dt ' "
(D) t1/2 \ ]a g1 - n
logt1/2 - log1/2
or ]1 - ng
log a' - loga"
(C) A + B — C+D
& 240 = b 0.136 l
1 480 0.0677 n - 1
r = k3 [A]º [B]º t1/2 \ n-1
a
unit of k = mole litre–1 time–1 n=0

1. Taking exp. I and II, we get order of [B] Overall order = 0 + 1 = 1

b 0.20 l = 6.93 # 10 -3
x -3
Now, rate = k[A][B]0
0.25 6.9.3 # 10 6.93 × 10–3 = k[0.10]
1x = 10 x = 0
Also, taking exp. II and III, we get order of [A] 6.93 # 10 -3
k= 0.10 = 0.0693 min
b 0.10 l · b 0.25 l = 6.93 # 10 -2
y 0 -3

0.20 0.30 0.693 0.693

1.386 # 10 t1/2 = k = 0.0693 = 10 min
b l = &y=1
1 1 10
y

2 2 To consume half of A it becomes 2 = 5 min

4.18 Chemistry
2. If concentration of [A] is doubled, rate will be 0.693 -3
rH O = 25 ×0.05 = 1.386×10
doubled, so order of A is 1. 2 2

Again if concentration of A and B both were doubled, 2H2O2 2H2O + O2

the rate will increase 8 times. 1
rO = 2 ×rH O
2 ; rO = 0.693×10 -3
2 2 2

Rate = [2A] [2B]2 = 8[A] [B]2

It means order of B is two. rO = 6.93×10 -4 mol/minute × litre
2

Hence, overall order is 3. 7. H = Eaf – Eab

3. According to Arrhenius equation, k = Ae–Ea/RT On –40 = 2x – 3x
increasing the value of Ea, k is decreasing. So, curve Eaf = 80 kJ/mol
I is correct.
Eab = 120 kJ/mol
On increasing temperature (T), k is increasing. So,
8.
curve II is also correct.
on doubling concentration of B, while keeping
4. Initially: concentration of A as same.
P0 = 363 torr 9. 2N2O5(g) 4NO2(g) + O2(g)
when 5% reacted, 95% is left. t=0 50 0 0
t = 30 50 – 2x 4x x
P1 = 363 × 0.95 = 344.85 torr
87.5 = 50 + 3x
R1 = 1 torr s-1
3x = 37.5 x = 12.5
∵ R1 = k P1n 1 = k (344.85)n
PN O after 30 min = 50 – 25 = 25
2 5
when 33% reacted, 67% is left
t1/2 = 30 min.
P2 = 363 × 0.67 = 243.21 torr
Hence after 60 min, (two half lives), PN O remaining
2 5

R2 = 0.5 torr s-1 50

= 4 = 12.5 torr.
0.5 = k (243.21)n
Hence decrease in PN O = 50 – 12.5 = 37.5 torr.
1 b 344.85 l
n 2 5

0.5 = 243.21 PNO = 2 × 37.5 = 75 torr

2

2 = (1.41) n 37.5
PO = 2 = 18.75 torr
2
1
we know 2 2
= 1.41 Ptotal = 12.5 + 75 + 18.75
2 = ]2g
n
2
= 106.25 torr.
n
2 =1 n=2 10. Higher order (> 3) reactions are rare due to low
5. From Arrhenius equation probability of simultaneous collision of all the
-Ea reacting species.
k = A.e RT
k - Ea b 1 1 l
So, k1 = A.e -E a1 /RT
...(1) 11. log k2 = 2.303R T2 - T1
1

k 2 = A.e -E /RT
...(2)
a2
k2
k2 ]E - E g a1 a2
k1 = 2; T2 = 310 K T1 = 300 K
so, equation (2) / (1) k1 = e
RT
- Ea
& log2 = 2.303×8.134 b 1 - 1 l
(As per exponential factors of both reactions is 310 300
same) Ea = 53598.6 J / mol = 53.6 KJ/mol
ln b k2 l = RT = 8.314×300 = 4
k Ea - Ea 10000
1 2
Rate at 50 o C ]2g3TT ]2g10
50
1 12. = = = 25 = 32 times
Rate at T1o C
1

1
6. In 50 minutes, concentration of H2O2 becomes 4 of 13.
initial.
t log b 100 - x% l
2.303 100
k=
2 × t1/2 = 50 minutes

t1/2 = t log b 100 - 99 l

t1/2 = 25 minutes 0.693 2303 100
0.693 0.693 2.303×2
k = 25 per minute
6.93 = t
So, t = 46.06 min.
 4.19

1. M — N P
= 30
r = K [M]x
t=t P0 x 2x x
as [M] is doubled, rate increases by a factor of 8.
i.e. 8 r = K [2M]x So, Pt = P0 x + 2x + x = P0 + 2x
8 = (2)x x=3 or 2x = Pt P0
1 P0
2. ] t = k ln
]P0 - xg
+

R HA 6H @HA+
1 P0 1 2P0
R HX = 6H +@HX t = k ln
]Pt - P0g k ln 2P0 - Pt + P0
or =
P0 -
1 6 +@ 2
100 = H HA 2P
HA H+ + A or Kt = ln 3P -0 P , Kt = ln 2P0 - ln (3P0 - Pt)
0 t
1 0.01 0.01 0.01
or ln (3P0 - Pt) =- Kt + ln 2P0
.1
0.01×0.01 Graph between ln(3P0 Pt) vs ‘t’ is a straight line
Ka = 1 = 10 -4 with negative slope.
3. For P, if t50% = x So (a) is correct option.
1 P0 1
then t75% = 2x t1/3 = K ln = ln 3
^P0 /3h K
It is independent of

with respect to P is 1. initial concentration.

So (b) is wrong option.
For Q, the graph shows that concentration of Q
decreases linearly with time. So rate, with respect to As rate constant is a constant quantity and
Q, remains constant. Hence, it is zero order wrt Q. independent of initial concentration.
So, overall order is 0 + 1 = 1. So Graph (d) is correct.
9. EA does not is depend on steric factor.
4. k = Ae–Ea/RT k
P = k actual Aactual > Atheoretical
So, variation will be theoretical

At T = 3 , k = A 10. Ct = C0e–kt
1
t1/2 \ k , k - on increasing T.
5. For Ist order reaction For zero order reaction After eight half lives,
,n2 0.693 C 1.386 C
k1 = t1/2 = 40 second -1 k0 = 2t 0 = 2×20 C = 8o C
1/2 2 C0 - 80
2 ×100 = 99.6%
k1 0.693 % completion = C
k0 = 1.386 = 0.5
0

6. aG + bH — products 11.
Rate = k[G]x [H]y 2N2O5 2N2O4 + O2
R = K [G]0x [H]0y (Let initial conc. are [G]0 & [H]0) t=0 1 0 0
8R = K[2G]0x [2H]0y = K2x.2yR t=t 1 P P P/2
so 2x + y = 8 x+y=3 P
1 P + P + 2 = 1.45
7. X1 = X2 = P
X3 = X = 2 = 0.45, p = 0.9
2.303 1
t= log 1 - P
8. A(g) 2B(g)+C(g) 2 # 5 # 10 -4
V=constant,T=300K 2.303 1
y # 10 -3 = log 1 - 0.9
2 # 5 # 10 -4
t=0 P0
2.303
log 10
t = t1/3 b P0 - 3 0 l
2P 4P0 2P0 =
2 # 5 # 10 -4
3 3
Y = 2.30
4.20 Chemistry
12. Rate k[A]x [B]y [C]z 16. Using integrated rate law method suppose order of
reaction = 0.
By exp. No. 1 & 2 y = 0
a -a 1 - 0.75 0.25
By exp. No. 1 & 3 z = 1 k1 = 0 t t = 0.05 = 0.05 = 5
0.75 - 0.40 0.35
By exp. No. 1 & 4 x = 1 k2 = 0.07 = 0.07 = 5
Rate = k[A]1 [B]0 [C]1 So, reaction must be of zero order.
From Exp. No.1 6×10 5 = k (0.2)(0.1) 17. 2X(g) — 3Y(g) + 2Z(g)
t=0 800 – –
k = 3×10 3
t 800 – 2x 3x 2x = (800 + 3x)
Now for [A] = 0.15 [B] = 0.25 [C] = 0.15 from given data in time 100 min the partial pressure
Rate = k [A] [B] [C]
1 0 1
of X decreases from 800 to 400 so t1/2 100 min. Also
= 3×10 3 × 0.15×1× 0.15 in next 100 min Px decreases from 400 to 200 to
again t1/2 = 100 min. Since half left is independent of
3×0.0225 × 10 3
6Y
.75 × 10 5 mol L sec initial concentration so reaction must Ist order with
Y
13. A(g) + B(g) AB(g) respect to X.
E a = e a + 2RT & Af = 4 Ab ,n2
b f Rate constant K = t1/2 = 6.93 × 10–3 min–1.
Now, Rate constant of forward reaction Time taken for 75% completion = 2 × t1/2 = 200 min.
k f = A f e -Ea /RT
f

Now when Px = 700 = 800 – 2x so x = 50 mm of Hg

Rate constant of reverse reaction K b = A b e -E ab /RT
so total pressure = 800 + 3x = 950 mm of Hg
Equilibrium constant
18. Rate of exchange of 14C between atmosphere and
K A
K eq = K f = A f e - (E af - E ab)/RT
living organism is so fast that an equilibrium is set
b b
up between the intake of 14C by organism and its
= 4e +2 = 4e2 exponential decay. Remember t of decay = 5770
1
2

Now, Go = RT ln Keq = 2500 ln (4e2) years.

= 2500 (ln 4 + ln e2) 19. Fossil has 6000 year age for the determination of
= 2500 (1.4 + 2) = 2500 × 3.4 = 8500 J/mole the age of old organism, as 6 years is too less time
14
C and it is given in passage
“Absolute value = 8500 J/mole”
that the method is not applicable for periods over
14. 8H+ + MnO4 + [Fe(H2)2 (ox)2]2 30,000 years.
Mn2+ + Fe3+ + 4CO2 + 6H2O 20. At nearby place :
rate of change of ]H g +
1 Co
rate of change of 6MnO -4 @
=8 m = T ln C
1 1

At far away place :

15. kt1/8 = ln ' C O/8 1 = ln8
C
O
1 Co
m = T ln C
kt1/10 = ln ' C /10
CO 1 2
= ln10 2

1 & Co
ln C - ln C 0
O
Co
t1/8 ln8 log8 T2 T1 =
then t1/10 ×10 = ln10 ×10 = log10 ×10 = 9 m 2 1

T1 = ln b C1 l
1 C
T2
m 2