Answer Key Chemical Kinetics

Solutions Slot – 1 (Chemistry) Page # 1
CHEMICAL KINETICS
EXERCISE – I SINGLE CORRECT (OBJECTIVE QUESTIONS)

Sol.1 B
B + 3D = 2C + 4A Sol. 9 B
2NO + 2H2 → N2 + 2 H 2O
Sol.2 D 1 d[NO] 1 d[H2 ] d[N2 ] 1 d[H2O]
A(g) 2B(g) − =− = = .......(1)
2 dt 2 dt dt 2 dt
Kf = = 1.5 × 10–3 s–1
Multiplying eqn (1) by 2 gives
At eq.m, Rf = Rb
Kf [A] = Kb[B]2 d[NO] d[H2 ] 2d[N2 ] d[H2O]
− =− = =
On solving : Kb = 1.5 × 10–11 dt dt dt dt
Putting the value of in the given questions
Sol.3 B
A+B → C+D K1' [NO][H2 ] = K1" [NO][H2 ] = 2K1[NO][H2]
k = 2.303 × 10–3 sec–1 = K[NO][H2]
2.303 1 ⇒ K1' = K1" = 2K1 = K
t= log
k 0.25
2.303 100 Sol.10 D
= log
2.303 × 10 −3 25  1
n−1
= 103 × (0.605) t1/2 α  

a
= 600 sec
⇒ t1/2 α (a)1–n
Sol.4 D
2.303 100 2.303 0.6955 (t1/ 2 )1 a1
⇒ =
k1 =
t
log
50
=
t
log 2 =
t (t1/ 2 )2 a2
2.303 2.303 3.22 1−n

k2 = 2 log 5 = × 2 × 0.69 = 235  500 
t t t ⇒ = 
950  250 
k2 ⇒ log23.5 – log95 = (1-n)log2
=
k1 4.65 ⇒ n=3
Sol.5 A Sol.11 B
–1
sec , Msec –1 t1/2 = 20 min at 300 K
t’1/2 = 5 min at 320 K
Sol.6 B 0.693
From the above data, it is clear that on doubling t1/2 = −Ea = 20
the concentration of B, the rate is doubled hence or- A.e 300R
der w.r.t. B is 1
Similarly, Order w.r.t. A = 2 0.693
⇒ rate = K[A]2[B] t’1/2 = =5
−Ea
Sol. 7 C A.e 320R
pA + q B → Products
r = k[A]l[B]m −Ea
(p + q) may or may not be equal to (l + m ) t1/ 2 e R
320
(order may or may not be equal to stoichiometric coef- =4=
t'1/ 2 −Ea
ficient for a complex reaction. e R
300
Sol. 8 D Ea  1 1 
 − 
A+2B → 3C + D 4= R  300 320 
e
d[ A ] 1 d[B] 1 d[C] d[D]
− =− = =
dt 2 dt 3 dt dt
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Page # 2 Solutions Slot – 1 (Chemistry)
Ea  20  Ea= 100KJ
ln 4 =  
R  300 × 320 
On solving, Ea = 55303.12 J Reactant
= 55.3 KJ
Product
Sol. 12 C Only one option because

A→B+C Eb = Ea + ∆H.O. reaction
−Ea
3.8 × 10 −16
e RT = Sol. 17 A
100 In a reaction, the threshold energy is equal to :
−Ea Activation energy + Normal energy of reactants.
= 2.303 log(3.8×10–18)
RT
Sol. 18 A
Ea = 100 KJ/mol
10 6
Sol. 13 D log K = 15 –
T
At temperature = ∞
log A = 15
Rate constant = Arrhenious constant.
⇒ A = 1015
Ea
Also, = 106
Sol. 14 A 2.303R
A+ B Fast K1
IAB → K2 Ea = 1.9 × 104 KJ
 AB + I 
→ A + P
Sol. 19 B
Since
K1 <<< K2 = most Imp. peack will be higher
log K
P.E.
1/T
A+P
IAB
A+B AB+I When line cuts y axis
1
Reaction coordinate =0⇒ T=∞
T
When it cut X -axis
Sol. 15 B log K = 0
Ea
⇒ log A =
P.E. 2.303RT
Ea
⇒ T=
(4) R ln A
(1)
(2) (3)
Sol. 20 B
K = 3 × 10–2 s–1
Reaction coordinate
Ea = 104.4 KJ/mol
As ∆E overall = 4 A = 6 × 1014
So, first option is correct. Value of rate constant at T = ∞ will be equal to
frequency factor i.e. A = 6 × 1014 s–1
Sol. 16 D
F.R.
A B + heat
B.R.
Sol. 21 B
Eaf = 100 KJ/mol
Eab = ? 1
Rate α
heat of reaction = ? time
Since,
Rate becomes four times by doubling the concen-

tration of A Sol. 27 C
⇒ Order w.r.t A is 2 If we calculate K, it comes constant every time
Also, i.e. reaction is of first order.
by doubling the concentration of B, the rate
becomes double 2.303 C
Also, K = log 0
⇒ Order w.r.t. B is 1. t aC0
Sol. 22 B 1  1
= ln  
1 d[H2 ] 1 d[NH3 ] t a
− =
3 dt 2 dt
Sol. 28 B
d[H2 ] 3 d[NH3 ]
⇒ – = Ph – N2Cl  ∆ / Cu
→ Ph – Cl + N2

dt 2 dt
Half life is independent of concentration
3 ⇒ reaction is of first order
= × 3 .4
2 Ph – N2Cl → PhCl + N2
= 5.1 Kgmin-1 t=0 A0 0 0
t = 30 A0–x x x
Sol. 23 B t= ∞ 0 A0 A0
x α 10
2.303 a
K= log A0 α 50
t a−x ⇒ A0 – x α 40
2.303 1 2.303 A0
K= log log
20 0.6 K= t A0 − x
Also,
2.303 0.60 2.303 50
log = log
K= 10 40
t 0.36
Since, Rate constant will be equal 2.303
= log (1.25) min–1
2.303 1 2.303 0.60 10
log = log
20 0.6 t 0.36
On solving, t = 20 min Sol.29 D
2A + B k C + D
→
Sol. 24 C t=0 C0 2C0 0 0
For a first order reaction, the concentration of the t = 30 C0–2x 2C0 –x x x
reactant varies exponentially with time
(A = A0e–kt) C0
given, x=
4
Sol. 25 C
C0 C
Reaction is or zero order After 30 min, [A] = C0 – 2 × = 0
hence, Option C will be correct. 4 2
C0 7C0
Sol. 26 C [B] = 2C0 – =
4 4
1 th  C0   7C0 
t1/4 = time taken for decomposition.
4 r = K   
 2  4 
3 th
⇒ will be left 49 k C30
4 ⇒ R=
32
2.303 1
t1/ 4 = log =
K 3/4 Sol.30 D
2.303 4 d[BrO3 ]
= log − = k[BrO3][Br–][H+]2
K 3 dt
D option is correct.
Sol.31 D Sol.36 D
2A → B + 3C 2A + B → D + E
t=0 P0 0 0 A + B → C + D (Slow)
t = 10 P0–2p1 p1 3p1 A + C → E (Fast)
p0 – 2p1 = 200 .......(1) ⇒ Rate = K[A][B]
p0 – 2p1 + p1 + 3p1 = 300 [As slowest step is rate determing step].
p0 + 2p1 = 300 ......(2)
_____________________ Sol.37 C
(I) + (II) 2p0 = 500 ⇒ p0 = 250 K1
Pressure of A After 10 min H2 + I2 2HI
K2
= p0 – p1 = 200
1 250 1 d[HI]
K= ln = k1[H2][I2] – k2 [HI]2
2 × 10 200 2 dt
1 Sol.38 B
K= ln1.25
2 × 10 k1 = 1.26 × 10–4 k2 = 3.8 × 10–5
⇒ None is correct
k1
B = k + k × 100
Sol.32 D 1 2
2− 2  k1
  C = k + k × 100
t1/2 =  K  ×C01/2 1 2
 
⇒ t1/2 α C01/2
Sol.39 A
Also, t1/2 α C01–n (where n is the order of reaction )
K1
⇒ 1 – n = 1/2 ⇒ n = 0.5 2A B + 3C
K–1
Sol.33 A 2C k 3D
→

2
2.303 100
t1 = log 1 d[C]
3K 75 = k1 [A]2 – k–1[B][C]3
3 dt
2.303 100
t2 = log d[C]
2K 25 ⇒ = 3K1 [A]2 – 3K–1 [B][C]3 ............(I)
dt
t1 0.311 from 2nd reaction
⇒ =
t2 1 = 0.311 : 1
1 dC
– = K2[C]2
2 dt
Sol.34 B
Slowest step is rate determining step. dC
⇒ = – 2K2[C]2 ............(II)
dt
Sol.35 C From (I) & (II)
A+2B+C →D
d[C]
K1
A + B → = 3K1[A]2 – 3K–1 [B][C]3 – 2K2[C]2
 X (Rapid) ..........(1) dt
K
X + C 
→ Y (Slow) ..........(2)
Sol.40 C
Y + B → D (Fast) ..........(3) 2A →K1
 B 
K2 –4
→ 3C. K1 = 2 × 10 sec ,
–1
Rate = K[X][C] ............(4) K2 = 3 × 10–4 L/mol-sec.

Since X is not in the orginal reaction, hence it has From the unit of rate constant for the given se-
to be eliminated. quential reactions, it is clear that first reaction is of
[ X] first order & the second reaction is of second order.
from eqn (1), K1 = ⇒ [X] = K1[A][B] Hence, rate law is given as
[ A ][B]
Rate = K1[A] – K2[B]2
Putting this value in eqn (4)
Rate = KK1[A][B][C] Sol.41 B
Rate = K ' [A][B][C]
⇒ Order = 3
Sol.45 A
df
= K(1–f) Ea
dt
log k = log10A –
2.303RT
1 1
K= ln When Ea = 0, k = 3.2 ×105 & it does not depend on T
t 1− f
1 Sol.46 B
K= [ln1 − ln(1 − f )] When Ea = is max,
200
3 k 310
⇒K=
200 k 300 would be max
0.693 0.693
t1/2 = = Sol.47 C
K 3 / 200
t1/2 = 46.2 hrs  K1  Ea  1 1
log  K '  = 2.303 R  T − T  ....(1)
 1  1 2
Sol.42 A
1 – f = e–kt  K2  E'a  1 1
⇒ f = 1 – e–kt Also log  K'  = 2.303R  T − T  .....(2)
Putting the value of k in from eqn(1)  2  1 2
f = 1 – e–3t/200 eq. (1)/(2)
Sol.43 D K 
log 1 
B  K'1  = Ea
K1
2x  K  E'a
log 2 
A  K '2 
2-x-y K2
C
y K 
log 1 
2–x–y=1  K '1 
⇒ x + y = 1 ............(1) ⇒ >1 (Ea < E’a)
K 
log 2 
1 d[B]  K '2 
= K1[A]
2 dt
K1 K2
d[B] ⇒ K' > K'
= 2K1[A] 1 2
dt
d[C] Sol.48 A
Also, = K2[A]
dt
−2000 −2000 −1000
[B] = 2K1 1015
1 e T 1015 e T = 1014 e T
⇒ [C] K 2 = 2 × (Given K1 : K2 = 1 : 2 )
2 −1000 2000
10 = +
⇒ [B] = [C] e T T
⇒ 2x = y .............(2)
1000
Solving (1) and (2) 10 =
e T
1 2
x= ,y= 1000
3 3 ln 10 = T
Total moles after 50 % of the reaction
= 2 – x – y + 2x + y 1000
= 2 + x = 7/3 T=
2.303
T = 434.22 K
Sol.44 C
No. of Moles of B = 2x
Sol.49 D
= 2/3
2SO2 + O2 → 2SO3
= 0.666
⇒ A0 = x(n + 1)
d[SO3 ]
= 10g/sec–1 A0
dt =x
⇒
n +1
d[SO3 ] 1
= mol/sec nA 0
dt 8
⇒ Concentration of B(nx) =
n +1
−1 d[SO 2 ] d[O 2 ] 1 d[SO3 ]
As =– =
2 dt dt 2 dt Sol.54 D
d[O2 ] 1 Order of reaction has no relation with stoichiometric
⇒ – = mol/sec ⇒ coefficient. Therefore, it may or may not be equal to
dt 16
the order of reaction.
d[O2 ]
= 2g sec–1
dt Sol.55 A
2NO + Br2 2NOBr
Sol.50 A (1) NO + Br2 Fast
NOBr2
aA → bB
(2) NOBr2 + NO  Slow
1 d[ A ] 1 d[B] → 2NOBr
– = rate = K[NO][NOBr2]
a dt b dt
NOBr2 has to be eliminated as it is not in the original
 d[ A ]   d[B]  a reaction from eq. (1)
−  /  =
 dt   dt  b [NOBr2 ]
K1 = [NO][Br ]
 d[A]   d[B]  a 2
log  −  = log   + log   ⇒ [NOBr2] = K1[NO][Br2] ........(3)
 dt   dt  b
From (1) & (3)
a rate = K[NO]×K1[NO][Br2]
⇒ log   = 0.6 rate = K’[NO]2[Br2] (Where K K1 = K’)
b
a Sol.56 B
⇒ = 3.98 PV = nRT
b
P n
Sol.51 B = =C
RT V
2ND3 → N2 + 3D2
1 dP 1 dn dC
−d[ND3 ] dN2 1 d[D2 ] ⇒ = =
= = RT dt V dt dt
2 dt dt 3 dt
−1 1
K1[ND3] = K2[ND3] = × K3[ND3] Sol.57 A
2 3
A→B
k1 k
= k2 = 3 1.25 × 10 4
2 3 log10K = 14 – .........(1)
3 k1 = 6 k2 = 2 k3 (by multiplying with 6) T
Ea
Sol.52 C logK = logA – −
2.303RT
forward reaction is of third order and backward is of
Comparing
first order. Calculate the value of K according to the
logA = 14 ⇒ A = 1014sec –1
given information.
Also
Sol.53 C Ea 1.25 × 10 4
A → nB =
2.303RT T
A0 0
⇒ Ea = 2.39.34 KJ
A0 –x nx
Given
A0 – x = nx
⇒ A0 = x + nx
Sol.58 D
2 1 1 
Exponential factor = 0  − 
K2
when T = ∞ = e R  273 298 
K1
Free radical combination
Energy of activation + Threshold energy 2 25 
 
R  273×298 
K2 = K1 . e
Sol.59 A
K2 ≈ K1
For an endothermic reaction
So, almost at same speed
Sol.64 A
Temp coff. of I = 2
H of II = 3
Ea Ea > ∆H
25 32 1
Ratio of rates = = =
5 227 7.6
3
Sol.65 A
Sol.60 B I : Rate ↑ : Temp ↑
II : As Rate ↑ Temp ↑ because fraction of molecules
−dC A CA with higher speed in Maxwell curve increases.
= K1
dt 1 + K 2C A
Sol.66 B
K1 I : Molecules reaction only when thus get energy i.e.,
1 by collision.
+ K2
CA II : During collision bond break form occurs but i.e.,
due to random motion molecules collide.
1
As CA is very low ⇒ C is very high Sol.67 B
A
1 Sol.68 B
i.e., C >>> K2
A
Sol.69 D
−dC A K
= 1
dt 1 = K [C ]1 Sol.70 A-QR, B-QR, C-QS, D-S
1 A
CA (A) CH3COOCH3 + H2O CH3COOH + CH3OH
molecularity = 2; order = 1
⇒ Rate constant = K1
(B) C12H22O11+ H2O C6H12O6 + C6H12O6
and order of reaction = 1
molecularity = 2; order = 1
⇒ option B is correct
(C) CH3COOCH3 + H2O CH3COOH + CH3OH
Sol.61 B molecularity = 2; order = 2
(D) CH3COOCH3 + H2O CH3COOH + CH3OH
Sol.62 A order = 2
–Ea/RT in K A e −Ea / RT is Boltzmann’s factor Sol.71 A-R, B-Q, C-P, D-S

Sol.63 D From the figure it is clear that.
A2 + B2 2AB
K1 A.e −2 / 273R
= (A) Eat = 40 KJ/mol
K 2 A.e −2 / 298R (B) Eab = 50 KJ/mol
(C) ∆Hr = – 10 KJ/mol
2 2
K1 −
= e 298R 273R
K2
EXERCISE – II MULTIPLE CORRECT (OBJECTIVE QUESTIONS)

Sol.3 A,B
Sol.1 C,D
K1
2O3(g) 3O2(g) B
Slowest step is rate determing step A K2
C
rate = K[O3][O] .........(1)
Since, [O] is not in the original reaction hence it has K1 = 1.26 × 10–4 sec–1
to be eliminated. K2 = 3.8 × 10–5 sec–1
From first step
K1
[O 2 ][O] K1[O3 ] % B = K + K ×100 = 76.83 %
1 2
K1 = [O ] ⇒ [O] = [O ] .........(2)
3 2
K2
Putting the value of [O] in the eq. (1) % C = K + K ×100 = 23.17 %
1 2
[O 3 ]
rate = K1K [O3] [O ]
2
Sol.4 B,C
Rate = K[O3]2[O2]–1
At very high temp i.e., T = ∞
Sol.2 A,B
K = Ae–0
K1 Q K =A
⇒ A may be termed as the rate constant at high temp
P K2 and Ea = 0.
R
Since [Q] = [R] all the times, Sol.5 A,B,C

Energy of activation can never be negative
 K1 
(
[P] = P0 e −(K1+K 2 )t = P0  K + K  1 − e
−(K1+K 2 )t
) Option (D) is incorrect.
 1 2
As K1 = K2 Sol.6 B,C,D
Only ans will be given
− 2K t 1 1 −2K1t
⇒ e 1 = − e
2 2
Sol.7 A,B,C,D
3 −2K t 1
⇒ e 1 = (A) For zero order reaction
2 2
a0
1 t1/2 =
− 2K1t 2K
⇒ e =
3
⇒ t1/2 α a0 (initial concentration )
Taking ln of both side
(B) For first order reaction
–2K1t = – ln3
Average life = 1.44 × half life
ln 3 2.303 (C) For IInd order reaction
t = 2K = 2K log103
1 1 1
t1/2 = KC (Co = initial concentration)
As K1 = K2 0
1 1
2.303 Also Kt = C − C
t = 2K log103 0
2
1 1 1  Sol.11 B,C
t3 / 4 =  − 
t  C0 / 4 C0  +
H
A 
→ B
1 3 3 Rate = K[H+][A]
= K × C = KC = 3 × t1/ 2
0 0 Rate = K’[A]
⇒ t3/4 = 3 × t1/2 If K’ has greater value for HA
⇒ [H+] has to be large
2.303 100
(D) t = log ⇒ for that acid has be stronger
99.9 0.0693 0.1
⇒ [HA] is strongers that HB
t99.9 = 100 min Also Relative strength = 2
Sol.8 A,B,C Sol.12 A,B,D

Rate = K[A]2[B] From figure it is clear that Ea(forward) = y
Ea(backward) = Z
⇒ rate w.r.t B = 1
∆Hr = + x
Overall order of the reaction = 2 + 1 = 3
for a complex reaction the rate determing step is
Sol.13 A,B,C
determined experimentally.
From the given data, it is clear that
(A) keeping [B] constant, After doubling the concen-
Sol.9 B,D tration of [A] makes the rate of reaction four times.
In SN1 reaction, formation of carbocation takes place ⇒ reaction is of order two w.r.t. A.
which is planar. (B) Similarly order w.r.t. B = 1
⇒ equimolar mixture of (I) and (II) will be formed in (C) Rate = K[A]2[B]
case of SN1. In SN 2 reaction Nucleophile will 5 × 10–4 = K × (2.5 × 10–4)2 × 3.0 × 10–5
attack from the opposite to leaving group
⇒ K = 2.67 ×108 L2mol–2 s–1
⇒ Product (II) will be formed in case of SN2 reaction. (D) order = 2 + 1 = 3
Sol.10 A,C
Sol.14 A,C,D
2000
log10K(min–1) = 5 – t1/2 of (A) zero (C) second (D) third order varies with
T
concentration.
Ea
log K = log A – Sol.15 A,B
2.303 RT
Ea =50kcal
log A = 5 ⇒ A = 105 (A) A   → ∆H = – 10KCal
Ea (backward) = 60 KCal
Ea 2000
= Ea = 60kcal
2.303 RT T (B) A   → B ; ∆H = – 20KCal
Ea = 2000 × 2.303 × 8.314 cal Ea =50kcal
(C) A   → B ;∆H = +10KCal
Ea = 9.212 Kcal
Ea = 60kcal
(D) A   → B ;∆H = + 20KCal
EXERCISE – III SUBJECTIVE QUESTIONS

− ∆[NH3 ] −(0.4 − 0.6) 0 .2 Sol.8 A + 2B → C + D
Sol.1 (a) = = = 0.04
∆t 10 − 5 5 PP, t = 0 0.6 0.8
0 0
− ∆[NH3 ] −(0.2 − 0.4) 0 .2
(b) = = = 0.02 After reaction 0.6 – x 0.8 – 2x x x
∆t 10 10
Sol.2
=0.2
∆[BrO3 − ] 0.056 0.4 0.4
= [BrO–]2
∆t 3 We have
R1 = k [A] [B]2 = k × 0.6 × (0.8)2
− ∆[BrO − ] − ∆[BrO3 − ] ∆[Br − ] R2 = k [A] [B]2 = k × 0.4 × (0.4)2
⇒ = =
3∆t ∆t 2∆t
R2 1
⇒ K = 0.019 =
R1 6
∆[Br − ] 2
Also, = × 0.056[BrO–]2
∆t 3 Sol.9 A → B
⇒ K = 0.037 a–x x
−d[N2O5 ] d[NO2 ] 2d[O 2 ] [B] = x = kt
Sol.3 = = x1 = 1.2 × 10–2 × 10 × 60 = 7.2 M
dt 2dt dt
x2 = 1.2 × 10–2 × 20 × 60 = 14.4 M (Not possible)
1 d[O2 ]
K1[N2O5] = K2[N2O] = 2K3 ∴ [B] at t = 20 min = 10 M
2 dt
1 Sol.10 Time [A]
K1 = K = 2K3
2 2 0.0 0.10
x1 = 0.01
1.0 0.09 x2 = 0.02
dx
Sol.4 (i) = K[A][B]2 = r1
dt
2.0 0.08
(ii) r2 = K[2A][2B]2 = 8r1
x∝ t
Sol.5 r1 = k[A]2 [B2] Hence this is zero order reaction.
r2 = k [3A]2 [3B2] Now, x = kt
0.01 = kx 1
1
upon reducing volume rd k = 0.01
3
= 27 [A]2 [B2] = 27r1
Sol.11 A → B
∆[NO] 1 1.08 × 10 −2 t=0 a 0
Sol.6 [i] r = = ×
4∆t 4 3 t=t a–x x
= 9 × 10–4 mol l–1 s–1
∆[NH3 ] ∆[NO] x = kt
[ii] – = x = 2 × 10–2 × 25 = 0.50
4 ∆t 4∆t
Now, a – x = 0.25
−∆[NH3 ]
⇒ = 36 × 10–4 ⇒ a = 0.25 + 0.50 = 0.75 M
∆t
∆[H2O] ∆[NO] Sol.12 x = kt
[iii] = 6× = 54 × 10–4
∆t 4∆t we have x=a (initial concn of H+)
∆[H2O] ∆[O 2 ] a 6 × 10−2

Sol.7 [a] =2 = 2 × 3.6 = 7.2 ⇒ t= = = 6 × 10–9
∆t ∆t k 107
∆[H2O 2 ]
[b] − = 7.2
∆t
Sol.13 A → B
Sol.22 [a] keeping concn of H2 const, when
after reaction (1 – 0.75)
⇒ 0.75 = kt = k × 60 [NO] is doubled, the rate is 4 times.
keeping [NO] constant, when [H2] is doubled
0.75
k= the rate is doubled
60
∴ rate = k [NO]2 [H2]
when x = 0.9
∴ order of reaction = 3
0 .9
t= × 60 = 1.2 hour [b] rate = K [NO]2 [H2]
0.75
4.4 × 10 −4
Sol.14 t1/4 = 72 min = 2 half rives ⇒ K=
(1.5) × 10 −8 × 4 × 10 −3
2
t1/2 = 36 min
t1/8 = 3 half lives = 3.6 × 3 = 1.8 min [c] rate = K [NO]2 [H2] = 8.85 × 10–3 M sec–1
2.303 100 Sol.23 [a] order w.r.t. NO = 2

Sol.15 [i] k = log = 0.0223 min–1
10 80 order w.r.t. Cl2 = 1
[b] rate = K [NO]2 [Cl2]
[ii] t = 
2.303 100 
log  min = 62.11 sec.
 0.223 25 
1× 10 −3
[c] k = = 8 L2 mol2 s–1
(0.05 )2 (0.05 )
2.303 100
Sol.16 t1 = log [d] rate = K [Cl2] [NO]2 = 0.256
k 0 .1
2.303 100
t2 = log
k 50 0.693
Sol.24 k1 = = 0.013
53
t1 3
t 2 = log 2 = 10 2.303 100
k2 = log = 0.013
100 27
2.303 5 (i) As k1 = k2, the reaction is of the first order

Sol.17 t= log (ii) k = 0.013 min–1
1.5 × 10 −3 1.25
= 924.362 sec (iii) 73%
Sol.25 Rate = k [A]m [B]n

2.303 500
Sol.18 k= log 4 × 10–4 = k [0.1]m [0.1]n … (1)
20 420
2 × 10–3 = k (0.5)m (0.1)n … (2)
2.303 100
texp = log = 41 months Equation (2)/(1)
k 70
5 = (5)m
⇒ m=1
2.303 100
Sol.19 k= log = 3.3 × 10–4 sec Also, 2 × 10–3 = k (0.5)m (0.1)n … (3)
60 98
1 × 10–2 = k (0.5)m (0.5)n … (4)
Equation (4)/(3)
2.303 1
Sol.20 k= log 5 = (5)n
20 0.8
⇒ n=1
0.693 (ii) Rate = K [A] [B]
⇒ t1/2 = = 62.23 min
k
4 × 10 −4
K= = 4 × 10–2 M–1 s–1
0.1× 0.1
2.303 100
Sol.21 k= log = 2.2 × 10–5
90 × 60 100 − x (iii) Rate = 4 × 10–2 (0.2) × (0.35)
⇒ x = 11.2% = 2.8 × 10–3 M s–1
Sol.26 t 0 100 200 300

1 1
∆(Pr) 0.5 × 103 1 × 103 1.5 × 103 = 4
= = 6.25%
2 16
∆(Pr) ⇒ No of half lives = 4
0.5 × 10 0.5 × 10 0.5 × 10
t
∆(Pr) 0.693 0.693

As
t
= K (Constant) = 5 (Pa/s) Sol.32 t½ = =
k 2.1
the reaction of zero order
2.303 100
(i) t= log = 13.96 hrs
k 1
Sol.27 for zero order
t1/2 ∝ a (ii) NH2NO2 → N2O(g) + H2O(l)
Alternatively No. of moles 0.1 (1 – 0.99) 0.099 0.099
nRT 0.099 × 0.082 × 273
log( t ½ )2 − log( t ½ ) Volume of H2O = =
n = 1 + log(a ) − log(a ) P 1
0 1 0 2
= 2.219 L
Sol.28 Rate = K[A]n Sol.33 Time [A] [B]

Rate K (6 × 10–3)n = 5.2 × 10–5 .........(1) t=0 a a
K (9 × 10–3)n = 7.8 × 10–5 .........(2)
a a a
n t = 54 =
9  7.8  2 ( 2 )3 8
(2)/(1)   =  
 
6  5. 2  ∴ t = 54 min
(a) → n = 1
Sol.34 Time [A] [B]
(b) → Rate = K[A]
0 4a a
7.8 × 10 −5 1 a
(c) → K = = 8.67 × 10–3 s–1 4a × = a
9 × 10 −3 15
( 2)2 2 2
(d) → Rate 8.67 × 10–3 × 1.8 × 10–3 ∴ time = 15 min
= 1.56 × 10–5 Ms–1
Sol.35 A → B + C
0.693 t=0 P0 0 0
Sol.29 k= t=t P0 – p p p
50
t=∞ 0 P0 P0
0.303 100 Given
t= log = 166.6 min
k 10 and 2P0 = p3
P0 + p = p2
0.693 We have
Sol.30 t½ = = 4.62 × 105 sec
k 1 P 1 p3
k = ln 0 = ln
2.303 100 t P0 − p t 2(p3 − p2 )
k= log
10 × 3600 100 − x
⇒ x = 5.26% Sol.36 A → B + C
t=0 P0 0 0
0.693 t=t P0 – p p p
Sol.31 t½ = t=∞ 0 P0 P0
k
Given
2.303 100 and 2P0 = p3
t2 = log
k 6.25 2p = p2
t2 1 P 1 p3
t½
=4 k = ln 0 = ln
t P0 − p t (p3 − p2 )
Alternatively fraction left
Sol.37 A → B + C
∆P −(1.1− 2)
t=0 a 0 0 Sol.40 R(PP) = − =
∆t 75
t=t a–x x x
Now, V1 ∝ a = 0.012 atm min–1
V2 ∝ (a + x)
⇒ (2V1 – V2) ∞ (a – x) − ∆C −∆P
Also, RC = =
∆t (RT)∆t
1 V1
⇒ k = ln
t (2V1 − V2 )
P
As, C=
RT
Sol.38 A → 2B + 3C
t=0 a 0 0 −(1.1− 2)
∴ RC =
t=t a–x 2x 3x 0.082 × 75 × 60 × 300
t=∞ 0 2a 3a = 8.12 × 10–6 Ms–1
Now, V2 ∝ (a – x) + 2x + 3x
Sol.41 A → 2B + C
V2 ∝ (a + 4x) … (1)
t=0 P0 0 0
Also, V3 ∝ 5a … (2) t=t P0 – P 2P P
t=∞ 0 2P0 P0
From above equation Given 3P0 = 270 mm Hg
5V2 ∝ (5a + 20x) … (3) (a) P0 = 90 mm Hg
From equation (2) and (3)
Also, P0 + 2P = 176 mm Hg
5V2 – V3 ∝ 20x
⇒ 2P = 176 – 90
1 V ⇒ P = 43 mm Hg
x ∝ V2 – 3
4 20
V3 [b] P0 – P = 90 – 43 = 47 mm Hg
and, a∝ ,
5
2.303 90
[c] k= log = 0.0649 min–1
V V V 10 47
and (a – x) ∝ 3 + 3 − 2
5 20 4
0.693
[d] t½= = 10.677 min
5V3 − 5V2 k
∝
20
2.303 a 2.303 4V3 Sol.42 P0=758

∴ k= t
log
a−x
=
t
log
5(V3 − V2 ) at 5 P0 – x1+3/2=827 → x1=138
⇒ P0 –x1=758 – 138 = 620
at 10 P0–x2+3/2=882 → x=248
Sol.39 rt = k2x + k3x P0–x2= 510
r∞ = k2a + k3a
P0 758
r∞ rt ⇒ from 0 to 5 = = = 1.2
a= , x= P0 – x1 620
k2 + k3 k2 + k3
from 5 to 10
r∞ − rt
⇒ (a – x) = k + k p0 − x1 620
2 3 = =1..2
P0 – x2 510
1 r
⇒ k= ln ∞ ration is same
t r∞ − rt
first order
Sol.43 2N2O5 → 4NO2 because of 2 N2O5 Sol.46 Same as above question

[a] order = 1
1  A0 
K= ln 
2t  A t  [b] t½ =
0.693 0.693
= = 13.26 min
k 0.052
P0 –2x 4x x → P0+3x
5P0 2.303 100
o 2P0 P0/2 → [c] k= log
t 100 − x
2
P0+3x=284.5 equation (1)  100 
2.303
13.26 = log  100 − x 
5P0 25  
=584.5 → P0=233.8 → x=16.9
2
x
⇒ = 0.716
2.303 233.8 100
K= log =2.60×10–3 min–1
2 × 30 200
because reactant 2N2O5
2.303 r0 − r∞
Sol.47 k= log r − r
t t ∞
Sol.44 (CH3)2 O(g) → CH4(g) + H2(g) + CO(g)

t=0 312 0 0 0 2.303  13.1 + 3.8 
k1 = log  
Pressure 60  11.6 + 3.8 
at t = 390 s 312–p p p p
Given 312 + 2P = 312 + 96 2.303  13.1+ 3.8 
k2 = log  10.2 + 3.8 
P = 48 120  
2.303 P0 (13.1+ 3.8)

we have, k1 = log P − p 2.303
390 k3 = log (9 + 3.8)
0 180
2.303 312 (13.1+ 3.8)

= log = 4.28 ×10–4 2.303
390 312 − 48 k4 = log (5.87 + 3.8)
360
2.303 312 As, k ≈ k2 ≈ k3 ≈ k4, Calculate kavg
Similarly,k2 = log
1195 312 − 125 The reaction is of Ist order
= 4.28 × 10–4 At zero reading rt = 0
2.303 312
k3 = log 2.303 13.1+ 3.8
3155 312 − 233 .5 and kavg = log (3.8)
t
= 4.28 × 10–4
As k1 = k2 = k3 ⇒ t = 966 min
the reaction is of Ist order
Rate = k[(CH3)2 O]
2.303 100
and k = 4.28 × 10–4 sec–1 Sol.48 k= log
t 100 − x
v0 2.303 100
2.303 ⇒ k1 = log (100 − 18.17 )
Sol.45 k= log v 60
t t
2.303 22.8 2.303 100

k1 = log = 0.0539 k2 = log (100 − 69.12)
10 13.3 350
2.303 22.8 k1 + k 2
k2 = log = 0.0508 kavg =
20 8.25 2
kavg = 0.052
As k1 = k2, the reaction is of first order. 0.693
t½ = k
avg
1
Sol.49 H2O2 → H2O + O
2 2 [C] k 2 [ A ]0 [1− e −(k1+k 2 )t ]
Sol.52 =
t=0 a 0 [ A ] (k 1 + k 2 ) [ A ]0 e −(k1+k 2 )t
x
t=t a–x
2
a =
11
(e − 1)
10 11x
t=∞ 0
2
x ∝ volume of O2 liberated at time t
a ∝ volume of O2 liberated at time = ∞ k1 1.26
Sol.53 % B = (k + k ) × 100 = × 100
46.34 1 2 (1.26 + 0.36)
2.303
⇒ k= log ( 46.34 − 10.31)
5.1 = 77.77%
%C = 22.22%
2.303 46.34
⇒ t= log ( 46.34 − 20 )
k
= 11.45 days. k 
ln 2 
 k1 
Sol.54 tmax = (k − k ) = 4 min
Sol.50 2A(g) → 4B(g) + C(g) 2 1
t = 0 0.1 0 0
PP 0.693
where, k1 =
4
x
t = t 0.1 – x 2x
2 0.693
k2 =
2
3x
Given 0.1 + = 0.145
2
Sol.55 Ea(ƒ) – Ea(b) = ∆H
⇒ x = 0.03 Ea(b) = 77 – 72 = 5 kJ mol–1
− ∆[ A ]
Also, = 7.48 × 10–3 [A] Ea 1
∆t Sol.56 log k = log A – ×
2.303 T
2.303 0.1
We have, k= log 0.693
t 0.1 − x k= , A = 5 × 1013 sec–1
60
2.303 0.1 Ea = 104.5 × 103 J mol–1
7.48 × 10–3 = log
t 0.07
t = 47.69 second
K2 Ea  1 1
2.303 0.1 Sol.57 log K = 2.303R  T − T 
Also, 7.48 × 10–3 = log 1  1 2
100 0.1 − x
Calculate x,
Ea  1 1 
log4 =  300 − 320 
Total pressure = 0.1 +
3x
= 0.180 atm 2.303R  
2
Ea = 55.33 KJmol–1
Sol.51
0.693
[ x ]0 e −(k1+k 2 )t Sol.58 K2 = Sec–1
[ x]
= 2 × 3600
[ y ] + [ z] k 1[ x ]0
k1 + k 2
[ ]
k [ x]
[
1− e −(k1+k 2 )t + 2 0 1 − e −( k1+k 2 )t
(k 1 + k 2 )
] K1 = 3.46 × 10–5 sec–1
K2 100 × 103  1 − 1 
− ( k1+k 2 ) t We have log K =  
=
e
=
1 1 2.303R  298 T 
[1− e −(k1+k 2 )t ] [e(k1+k 2 )t − 1]
T = 306 K
0.693 slow
Sol.59 (a) K1 = K27ºC = [ii] NOBr2 + NO 2NOBr
30 k1
rate = k1 [NO] [NOBr2]

0.693
K2 = K47ºC =
10 [NOBr2 ]
keq = [NO][Br ]
2
K2 Ea  1 1 
(b) log K = 2.303R  −  [NOBr2] = keq [NO] [Br2]
1  300 320 
∴ rate = k1 keq [NO]2 [Br2]
⇒ Ea = 43.85 KJ mol–1 = keff [NO]2 [Br2]
Sol.64 rate = k2 [N2O2] [H2]

Sol.60 K1 = Ae −(Ea )1 / RT
[N2O 2 ]
K2 = Ae −(Ea )2 / RT keq = = k1
[NO]2
K2 ⇒ [N2O2] = k1 [NO]2
−(Ea2 −Ea1 ) / RT = e50000/(4.314 × 298)
K1 = e ∴ rate = k1k2 [NO]2 [H2]
= 5.81 × 108
Sol.65 rate = k2 [O2] [N2O2]
k1 N O
K 35 º Ea  1 1  = 2 2
k −1 [NO]2
Sol.61 log K =  298 − 308 
25 º 2 .303R  
k1
K 35 º [N2O2] = [NO]2
–1 –1 k −1
K 25 º = 1.75 , R = 2 Calorie mol K
⇒ Ea = 10.757 K cal mol–1 ∴ rate =

k 2k1
[O2] [NO]2
k −1
k2 Ea  1 1  d[NO2 ]
Sol.62 log k = 2.303R  T − T  ⇒ = k [NO]2 [O2]
1  1 2 2dt
T1 = 380 + 273 = 653 k
T2 = 723 k Sol.66 [a] rate = k [H2] [I2]
0.693
k1 = min–1 [b] rate = k [I]2 [H2]
360
Ea = 200 × 103 J mol–1 [I]2
keq = [I ]
Calculate k2 2
2.303 100 ∴ rate = k keq [I2] [H2]

& t= k 2 log 25 =’ [I2] [H2]
k
[c] rate = k [H2] [I2]

⇒ t = 20.4 mintues
[d] no
Sol.63 2NO + Br2 → 2NOBr
[e] Mechanism a is incorrect (As the reaction is
fast complex)
[i] NO + Br2 NOBr2
keq
EXERCISE – IV ADVANCED SUBJECTIVE QUESTIONS

Sol.1
A+B→C Kf
Keq for given reaction = K
b
−d[ A ]
(a) = K[A][B]º = K[A]
dt
Kb 2.1× 10 −3
Keq for reverse reaction = K = = 53.84
1 f 3.9 × 10 −5
fraction left = in 1 hr
( 2)2
No. of half lives = 2
Sol.3
1
∴ t1/2 = hr 2.303 C
2 K1 = log 0
t aC0
∴ The amt left after 2 hr (no. of t1/2 = 4 )
−d[ A ] 2.303 C
(b) = K[A][B] = K[A]2 K2 = log 0 = K
dt 2t a 2C0 1
for 2nd order as [A]0 = [B]0

Similarly K2 = K3 = K4
1 1 ∴ The reaction is of first order
∴ = + Kt
a−x a
2.303 1
& K= log
1 1 t a
= +K ×l
100 − 75 100
Sol.4
1 1 4 −1 3 The reaction is of first order as can be seen from the given
K= − = =
25 100 100 100 data
When t = 2 hr Also, Rate = K[H+][Complex]a
We have a = 1
1 1 1 6 7
= + 2K = + = and t1/2 α K[H+]b
100 − x 100 100 100 100
from give data
⇒ 700 – 7x = 100
1
600 (t1/2)1 α
⇒ x= = 85.7 % fraction left = 14.3 % b
7 K H+ 
 1
(C) For zero order
−d[ A ] 1
=K
dt ⇒1αK ..........(1)
K(0.01)b
for zero order
x = Kt 1
∴ 75 = K × t (t1/2)2 α
b
Also, x = K × 2 K H+ 
  2
⇒ x = 150 %
Hence the reaction is complete & fraction left
= 0% 1
⇒ 0.5 α ..........(2)
K(0.02)b
Sol.2 eqn (1) /eq. (2)
−
∆
∆t
[ ] [ ]
PtCl24− = Kf PtCl24− – Kb[Pt(H2O)Cl3]–[Cl–]  0.02 
2=  
b
 0.01 
b=1
Sol.5 Sol.7
Rate = K [CH3CH2NO2] Bn+ → B(n + 4) +
As [OH–] is in excess initial a 0
 2.303 100  2e + B → B(n–2)+

n+
∴ K =  log  min −1
 (1/ 2 ) 99  t = t (a – x) x
5e + B(n+4)+ → B(n–1) +
= 2 × 10–2 min–1
Let normality of reducing agent be N
thus at t = 0, a × 2 = N × 2S
Sol.6
2a = 25 N
2P(g) → 4 Q (g) + R(g) + S (l)
at
t=0 P0 0 0 32.5
t = t(a – x). 2 + x . 5 = 32 N
PP(mm Hg)
3x = 7 N
P
t = 30m P0–P 2P 32.5 7
2 x= N
3
P
t= ∞ 0 2P0 32.5 2.303 25 / 2N
2 log
Now K = 10  25 7
 − N
P0 5P0  2 3
Given, 2P0 + + 32.5 = 617 ⇒ = 584.5
2 2 = 2.07 × 10–2 min–1
⇒ 233.8 Sol.8
At t = 0
P 3P
& P0 – P + 2P + = P0 + = 317 – 32.5 ∵ 22400 mL O2 = 68 g H2O2
2 2
= 284.5 68 × 20
∴ 20 mL O2 = g H2O2 in 1 mL
22400
⇒ P = 33.8
P0 – P = 200 68 × 20 × 10
g H2O2 in 10 mL
22400
2.303 P0 ∴ Meq. of H2O2 in 10 mL of 20 valume H2O2 initially.
∴K= log
30 P0 − P 68 × 20 × 10 × 1000
= = 35.71
22400 × 17
2.303 233.8 At t = 6 hrs.
= log
30 200
Meq. of H2O2 in 10 mL diluted Sol.
= 0.0052 = 25 × 0.025 × 5 = 3.125
Also, When t = 75 min Meq. of H2O2 in 10 conc. Sol
= 3.125 × 10 = 31.25
2.303 233.8
K= log = 0.0052 2.303 25.71
30 233.8 − P' K= log = 0.022 hr–1
6 31.25
⇒ P’ = 75.5 mm Hg
Sol.9
3P'
∴ Total pressure= P0 + + 32.5 2.303 τ0
2 log
K= t ( τ0 − τ )
= 233.8 + 113.26 + 32.5
= 379.55 mm Hg 2.303 3.956
K= log
6 (3.956 − 1.281)
t = 15.13 weeks
Sol.10 Sol.12
A→ B + C K 293
= 3 , T = 293 K, T = 276 K
t=0 K 276 2 1
no. of moles a 0 0
t = 20 min a-x x x K2 Ea  T2 − T1 
(a) 2.303 log K = R  T T  (R = 2 cal)
t= ∞ 0 a a 1  1 2 
Optical rotation reaction no. of moles
Ea  293 − 276 
At t = ∞ ∴ 2.303 log 3 =  
2  293 × 276 
40 a – 40 a = – 20
Ea = 10453.95 cal = 10.454 Kcal
⇒ – 40 a = – 20
K3 Ea  T3 − T2 
1 (b) Also, 2.303 log K = R  T T 
a= 2  3 2 
2
At, t = 20 min This time, Ea = 10.454 K cal , T3 = 313 K, T2 = 293 K
60 (a – x) + 40 x – 80 x = 5 K3 10.454 × 103 313 − 293

∴ 2.303 log K =
60a – 100 x = 5 2 2 313 × 293
30 – 100 x = 5
K3
⇒ K = 3.12
25 1 2
x= =
100 4
K 3 t2
No. of moles of A is becoming half after Now, K = t
2 3
20 min
∴ t1/2 = 20 min 1
∵ Kα
time
Sol.11 Also, if juice is not spoilt upto 64 hr at 20ºC it will not
spoil upto 192 hr at 30ºC.
CH3 – O – CH3(g) →CH4(g) + CO(g) + H2(g)
Similarly, we can have
t=0 0.4 0 0
0 K2 1
t3 = t2 × K = 64 × = 20.5 hr
After 0.4 – x x x 3 3 . 12
x
2.303 0.4 Sol.13

time t K= log
t (0.4 − x ) For the change, A → B
20 % solution of A decomposes 25% in 20 minutes at
2.303 0.4 25ºC.
4.78 × 10–3 = log
4.5 × 60 A Let amount of solute undergoing decay = a = 20
0.4 – x = 0.110 ∴ amt of solute left (a – x) after 20 minutes
x = 0.4 – 0.110 = 0.290  75 

= 20 ×   = 15
 100 
0.11× 46 + 0.29 + 0.29 × 28 + 0.29 × 2
Mm =
0.98 2.303 a 2.303 20
∴ K25 = log = log
= 18.78 t a−x 20 15
= 1.44 × 10–2 min–1
r0 18.78 0.4
= ×
rm 46 0.98 K 40 Ea  T2 − T1 
∵ 2.303 log K = R  TT 
25  1 2 
= 0.261
K 40 70 × 1000  313 − 298   K 2 , 310 

2
∴ 2.303 log
8.314  313 × 298  = log  
= .............(viii)
0.0144
 K 2 , 300 
∴ K40 = 5.58 × 10–2 min–1
By eq. (ii) & (viii)
The reaction if carried out by 30% solution shows the
left amount (a – x) = min 20 min 2
 K 2 , 310 
  =2
2.303 a  K 2 , 300 
∵ K40 = = log
t a−x
By eq. (iii) & (iv)
2.303 30 2K1 , 310 =
5.58 × 10–2 = log 2 K2, 300
20 m
m = 9.83 or K2 , 300 = 2 K1, 300
\ % decomposition = [(a – m)/a] × 100 by eq. (i) & (x)
= [(30 – 9.83 )/30] × 100 K2, 300 = –2 –1
2 × 0.0231 = 3.27 × 10 min
= 67.2 %
Sol.15
Sol.14
The given changes are K2 −(K1 +K 2 )t
[C] = K + K [ A ]0 [1 − e ]
I A → Products, t1/2 at 310 K = 30 min 1 2
II B → Products [A] = [A]0 e −(K1 +K 2 )t

0.693
∴ K1 at 310 K = [C] K 2 [1 − e −(K1 +K 2 )t ]
30 ⇒ =
[A] K1 + K 2 e −(K1 +K 2 )t
= 0.0231 min–1 ..................(i)
K1 at 310 K2 −(K1+K 2 )t
Given, K at 300 = 2 ..............(ii) = K + K [e − 1]
1 1 2
K 2 at 310 K 2 / K1 −(K1 +K 2 )t
and K at 300 = 2 .................(iii) = 1 + K / K [e − 1]
1 2 1
Ea 2 9 −4
1 = [e(1.3×10 )×3600 − 1]
Also, given that E = ..........(iv) 1+ 9
a1 2
= 0.537
 K1 310  Ea1  310 − 300  As,
For I : 2.303 log  K 300  =
R  310 × 300 
.....(v)
 1  K2
K1 = 9
 K 2 310  Ea2  310 − 300 
For II : 2.303 log  K 300  = K2 = 9 × 1.3 × 10–5
R  310 × 300 
.....(vi)
 2 
On dividing (v) by eq (vi) Sol.16
Let at equilibrium degre of conversion be x.
 K , 310 
log 1 
 K1, 300  Ea1 x
= 0.16 ⇒ x = 0.138
 K , 310  = E = 2 ..............(vii) 1− x
log 2  a2
 K 2 , 300  K1
K 2 = 0.16 ⇒ K2 = 6.25 K1
 K1, 310   K 2 , 310 
or log  K , 300  = 2 log  K , 300  dx
 1   2  = K1(1–x) – K2x = K1(1–7.25x)
dt
Sol.19
dx
= K1. dt (b) Keff = K1 + K2
1 − 7.25 x
0.693 0.693
1 1 = ( t ) + (t )
⇒ ln = K1 t 1/ 2 1 1/ 2 2
7.25 1 − 7.25 x
0.693  1 1
For half equilibrium reaction +
( t1/ 2 )overall = 0.693  60 90 
1 1 (t1/2)overall = 36 min
ln
t = 7.25 K1 1 − 7.25 × x
2 Sol.20
= 290 Second B
K1
Sol.17 A
A → B K2
t=0 0.01 0 C
Keff = K1 + K2
At eq. 0.01–xeq x eq
−E / RT +
Ae −Ea / RT = A1e 1 A 2e −E2 / RT
[B]eq −2
10 Diff w.r.t = T
∴ KC = [ A ] = =4
eq Kb Ea A A1E1 A 2E2
e −Ea / RT = e −E1 / RT + e −E2 / RT
2 2
[ x]eq RT RT RT 2
EaKeff = E1K1 + E2K2
0.01 − [ x]eq
E1K1 + E2K 2
∴ Kb = 0.25 × 10–2 Ea = K1 + K 2
0.04
and [X]eq = = 0.008 Sol.21
5
K1
2.303 x eq A+B K2
C
t = (K + K ) log ( x − x )
f b eq K3
C 
→ D
2.3030 0.008 d[C]
⇒ 30 = log = K1[A][B] – K2[C] – K3[C]
−2 (0.008 − x ) dt
1.25 × 10
d[C]
0.008 At steady state =0
∴ = 1.455 dt
0.008 − x
∴ x = 2.5 × 10–3 ML–1 K1[ A ][B]
⇒ [C] = (K + K )
2 3
Sol.18 d[D] K1K 3 [ A ][B]

Also, = K3[C] = (K + K )
Given, ∆H = Ef – Eb = – 33 KJ dt 2 3
Kf = Ae −E f / RT K1K 3
Also, Keff = K 2 as (K2 >> K3)
Kb = Ae −Eb / RT
A1e −Ea / RT × A 3 e −Ea3 / RT
33×103 ⇒ Ae −Ea / RT =
Kf (E −E ) / RT A 2E −Ea2 / RT
∴ KC = K = e b f = e 8.314×300
b
A1A 3 −(Ea1−Ea3 +Ea2 ) / RT
= 5.572 × 105 at 300 K = e
A2
K f 20
(b) Given K = 31 and Ef – Eb = – 33 KJ Comparing LHS & RHS
b
A1A 3
21 A= A2
∴ Ef – Ef = – 33 KJ
20 and Ea = Ea1 + Ea3 – Ea2
33 × 20
∴ Ef = = 60 KJ
11
Sol.22
1
Rate = K3 [COCl][Cl2] ...........(i) ⇒ e −(K1 +K 2 )×10 = = 0.2
5
K1 [Cl]2 ⇒ – (K1+ K2) × 10 = ln (0.2)
= ............(ii)
K −1 [Cl2 ] ln(0.2)
⇒ K1 + K = = 0.16
− (10)
K2 COCl
& K = [CO][Cl] ∴ K1 = 0.5 × 0.16 = 0.0805
−2
from (i) & (iii)
Sol.25 n1A → n2B
K 3K 2 K1 t=0 a0 0
Rate = K Cl2 [CO][Cl2 ]
−2 K −1 n2
t=t a0–k n1 x
1/ 2
K 3K 2  K1 
=   [CO][Cl2 ]3 / 2 We have
K −2  K −1 
−d[ A ]
= K [CO][Cl2]3/2 = = n1K[A]
dt
Sol.23 [A]t = [A]0 e −n,kt

a = a0 e −n,kt
Sol.24
No. of moles α pressure of the system (As, T& V a0 – x = a0 e −n,kt
constant)
x = a0[1 - e −n,kt ]
K1 2B V α no. of moles
So,
A
K2
C n2 n 
a0 − x + x a0 +  2 − 1 x
Total pressure at t = 10 sec V n1 = V  n1 
= =
V0 a0 V0 a0
2K1[ A ]0
| A |0 e −(K1+K 2 )×10 + [1 − e −(K1 +K 2 )×10 ]
K1 + K 2 n2
a0 + a0 (1 − e −n,kt )( − 1)
K2 = n1
−(K1 +K 2 )×10
+ K + K | A |0 [1 − e ] = 1.4 a0
1 2
Also, t = ∞
 2K1 K2 
  n2 
(
= V0 1 +  n − 1 1 − e
−n,kt 
 )
+   1  
  [A] = 1.5
 K1 + K 2 K 1 + K 2  0
 n2  n2  −n,kt 
2K1 + K 2 K1 = V0 1 + n − 1 −  n − 1e 
+ 1 = 1.5   1  
K1 + K 2 = 1.5 ⇒ K1 + K 2
1
 n2  n2  −n,kt 
= V0  n −  n − 1e
K1 
⇒ K + K = 0.5  1  1  
1 2
Also, Also,
( 2K1 + K 2 )
e −(K1 +K 2 )×10 + [1 − e −(K1 +K 2 )×10 ] = 1.4  
K1 + K 2  ( −n,kt )

a0 − x  e 
[A]t = = [ A ]0  
⇒ e −(K1 +K 2 )×10 + 1.5 [1 − e −(K1+K 2 )×10 ] = 1.4 V  
 n2 −  n2  − 1e −n,kt 
 n1  n1   
⇒ 1.5 – 0.5 e −(K1 +K 2 )×10 = 0.1  
EXERCISE – V IIT-JEE PROBLEMS

= 1.386 × 10–4 M/min
Sol.1 A,B,D Sol.6 C
(A) is correct because on plotting a graph between log The concentration reduces from 0.1 M to 0.025 M in
1 40 minutes = 2t1/2
Kp vs It is a straight line. t1/ 2 t1/ 2
T 0.1  → 0.05  → 0.025
2t1/2 = 40 ∴ t1/2 = 20 min (40 min)
∆H 1
logKp = – +l
R T 0.693 0.693
K= t1/ 2 = 20
(B) For the Ist order reaction, plot a graph between log
(x) vs time, it is a straight line. Rate of reaction A → B
log(x) = log(x0) + Kt (A) = 0.01 M
y = c + mx 0.693
= K × [A] = × 0.01
1 1 20
(D) P vs or P ∝ or PV = costant is Boyle’s law.. = 3.465 × 10–4 M/min
V V
1 Sol.7 D
The plot of P vs is a straight line. The order of reaction can have values 0, 1,2, 3 or even
V
in a fraction. It is always determined experimentally.
Sol.8 D
Sol.2 D Let a moles of G combine with b moles of H forming
Rate constant (K) = 3 × 10–5 sec–1 the product
Rate of reaction = 2.40 × 10–5 mole litre –1 sec–1 aG + bH → Product
Rate of reaction = K × [Molar conc. of N2O5] Rate of reaction ∝ [G]a × [H]b
Rate (r) = K × (G)a × (H)b.............(1)
2.40 × 10 −5 When conc. of both G and H are doubled, the rate
[N2O5] = = 0.8 mol/litre
3 × 10 −5 becomes 8 times
8r = K × (2G)a × (2H)b
8r = K × 2a + b [G]a × [H]b .............(2)
Sol.3 B
Substitute the value of r in eq. (2)
In photochemical reactions, the rate of reaction is 8 × K × [G]a × [H]b = K × 2a + b [G]a × [H]b
dependent upon intensity of absorbed light i.e., rate ∝ 2a + b = 8 = 23
I. or a+b=3
The order of reaction = 3
Sol.4 A
N2(g) + 3H2(g) → 2NH3(g) Sol.9 A
For a first order reaction
d[N2 ] −1 d[H2 ] 1 d[NH3 ]
Rate = – = = K1 = Rate costant
dt 3 dt 2 dt
0.693
K1 = ...........(1)
−d[N2 ] −1 d[H2 ] 1 d[NH3 ] 40
Hence, A = Rate = = =
dt 3 dt 2 dt For a zero order reaction
A → B
Sol.5 C 1.386 mol/dm3
a = 800 mol/dm3 t = 2 × 104 sec 1.386
Half conc. = = 0.693 mol dm–3
a – x = 50 mol/dm3 2
2.303 a time = 20 sec
k= log for a first order reaction
t a−x dx 0.693
K0 = = ......(2)
dt 20
2.303 800 2.303 Divide eq. (1) by (2)
= log = × 4 × 0.3010
4
2 × 10 50 2 × 10 4
= (Ea = 20)
K1 0.693 20
= ×
at 400 K K = Ae −(Ea −20 ) / 400T ............(3)
–1 3
K0 40 0.693 = 0.5 mol dm
Since the rate is same at 500 K without catalyst and
Sol.10 D at 400 K with catalyst.
A → P, a first order reaction equation of first order Dividing Eq. (2) by (3)
Ea e −Ea / 500R
1=
e −(Ea −20 ) / 400R
log K = log10A –
2.303 RT
Given equation is (Ea −20 )
−
2000 e 400R = e −Ea / 500R
log K = 6.0 –
T
Ea − 20 Ea
Equating eqs. (1) and (2) =
log10A = 6 or A = 106 or 1.0 × 106 S–1 400 500
5Ea – 100 = 4 Ea
Ea Ea = 100 kJ/mol
= 2000
2.303 R
Ea = 2000 × 2.303 × R Sol.3 Rate = K × conc. of reactant = K × C
= 2000 × 2.303 × 8.314 × 10–3 kJ mol–1 r1 = K × 0.04
= 38.3 kJ mol–1 r2 = K × 0.03
Sol.11 A r1 C1 0.04
= =
A0 A r2 C2 0.03
Sol.12 A = = 0
28 256 t = 10 minutes
2.303 C
% completion =
255
× 100 K= log 1 = 2.303 × log 0.04
256 t C2 10 0.03
= 99.6%
2.303 4 2.303
K= × log = [log 4 – log 3 ]
10 3 10
SUBJECTIVE 2.303  (0.6021 − 0.4771) = 2.303 × 0.1250 
Sol.1 A → B rate costant = 4.5 × 10–3 sec–1 =  
10  10 
r = 60 sec, a = 1.0 M, conc. left = (a – x) = x
= 0.0287 min–1
2.303 a
4.5 × 10–3 = K = log 0.693 0.693
t a−x t1/2 = = = 24.14 min
K 0.0287
2.303 1
⇒Κ= log
60 a−x Sol.4 (i) The data show that pressure is reduced to half in
1 4.5 × 10 −3 × 60 1
log = 100 minutes and to th in 200 minutes showing it to
a−x 2.303 4
be a 1 st order reaction.
1 (ii) t1/2 = 100 min
= 1.310
a−x
0.693 0.693 0.693
K= = –3 –1
1 t1/ 2 100 = 6.93 × 10 min = 100
a–x= = 0.7634 M
1.31
Rate of reaction = Rate constant × conc. after 1 hr 2.303 100
(iii) t = log
= 4.5 × 10–3 × 0.7634 K 25
= 3.44 × 10–3 mol/litre/min
Sol.2 K = Ae −Ea / RT ........(1)

Arrhenius equation
at 500 K, K = Ae −Ea / 500 T ..........(2)
at 400 K, the lowering of activation energy

Answer Key Chemical Kinetics

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Solutions Slot – 1 (Chemistry) Page # 1

EXERCISE – I SINGLE CORRECT (OBJECTIVE QUESTIONS)

= 103 × (0.605) t1/2 α  

2.303 2.303 3.22 1−n

Sol. 12 C Only one option because

Rate becomes four times by doubling the concen-

Rate = K[X][C] ............(4) K2 = 3 × 10–4 L/mol-sec.

f = 1 – e–3t/200 eq. (1)/(2)

–Ea/RT in K A e −Ea / RT is Boltzmann’s factor Sol.71 A-R, B-Q, C-P, D-S

EXERCISE – II MULTIPLE CORRECT (OBJECTIVE QUESTIONS)

Since [Q] = [R] all the times, Sol.5 A,B,C

Sol.8 A,B,C Sol.12 A,B,D

EXERCISE – III SUBJECTIVE QUESTIONS

∆[H2O] ∆[O 2 ] a 6 × 10−2

2.303 100 Sol.23 [a] order w.r.t. NO = 2

2.303 5 (i) As k1 = k2, the reaction is of the first order

Sol.25 Rate = k [A]m [B]n

Sol.26 t 0 100 200 300

∆(Pr) 0.693 0.693

Sol.28 Rate = K[A]n Sol.33 Time [A] [B]

2.303 a 2.303 4V3 Sol.42 P0=758

Sol.43 2N2O5 → 4NO2 because of 2 N2O5 Sol.46 Same as above question

Sol.44 (CH3)2 O(g) → CH4(g) + H2(g) + CO(g)

2.303 P0 (13.1+ 3.8)

2.303 312 (13.1+ 3.8)

2.303 22.8 2.303 100

rate = k1 [NO] [NOBr2]

Sol.64 rate = k2 [N2O2] [H2]

⇒ Ea = 10.757 K cal mol–1 ∴ rate =

2.303 100 ∴ rate = k keq [I2] [H2]

[c] rate = k [H2] [I2]

EXERCISE – IV ADVANCED SUBJECTIVE QUESTIONS

for 2nd order as [A]0 = [B]0

 2.303 100  2e + B → B(n–2)+

60 (a – x) + 40 x – 80 x = 5 K3 10.454 × 103 313 − 293

2.303 0.4 Sol.13

x = 0.4 – 0.110 = 0.290  75 

K 40 70 × 1000  313 − 298   K 2 , 310 

II B → Products [A] = [A]0 e −(K1 +K 2 )t

Sol.18 d[D] K1K 3 [ A ][B]

Sol.23 [A]t = [A]0 e −n,kt

EXERCISE – V IIT-JEE PROBLEMS

Sol.2 K = Ae −Ea / RT ........(1)

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