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Answer Key

2017-2018
Class: 12 Worksheet Number:12/Chem/04/AK
Subject: Chemistry Chapter 04: Chemical Kinetics

Section A
Each question carries 1 mark :
1. Define order of a reaction.
The sum of powers of the conc. Of reactants in the rate law expression is known as the order of
Reaction.
Rate = K[A]x [B]y . . . order = x+y
2. What is meant by an elementary reaction?
A reaction which takes place in one step is called elementary reaction.
3. Define rate of a reaction?
Change in concentration of reactant or product per unit time is known as rate of reaction.
4. Give an example of pseudo first order reaction.
Hydrolysis of ester :- CH3COOC2Hsaq + H2O (l)  CH3COOHaq + C2H5OHaq
Each question carries 2 marks :
5. Distinguish between order and molecularity of a reaction. When could order and molecularity
of a reaction be the same?
ORDER MOLECULARITY
1) It is the sum of powers of conc of the 1) It is the number of reactant species (atoms,
raction in the rate law expression. ions & molecules)
Taking part in an elementary reaction which
must collides simultaneously in order to
having about a chemical change.
2) Order can be a whole number or a fraction 2) Molecularity cannot be zero or non-integer.
or zero
3) Order can be applied to both elementary 3) Moleuclarity can be applied only to
and complex reaction. elementary reaction.
4) It is determined experimentally 4) It is a theoretical concept

Order and molecularity are same for elementary reactions.


6. Define Threshold energy and activation energy. How they are related?
Threshold Energy: It is the minimum amount of energy which the reactant molecules must possess
for the effective collision in forming the products.
Activation Energy: It is the excess energy required by the reactants to undergo chemical reaction.
Activation energy = Threshold energy – Average kinetic energy of molecules.
a. Section A
b. Each question carries 1 mark :
7. State a condition under which a bimolecular reaction is kinetically first order reaction.
Bimolecular reaction becomes kinetically first order when one of the reactants is in excess
8. For a reaction A + B ⎯→ Products, the rate law is — Rate = k [A][B]3/2
Can the reaction be an elementary reaction? Explain.
During an elementary reaction, the number of atoms or ions colliding to react is referred to as
molecularity. Had this been an elementary reaction the order of reaction with respect to B would
have been 1, but in the given rate law it is 3 /2. This indicates that the reaction is not an elementary
reaction
9. In some cases, it is found that a large number of colliding molecules have energy more than
threshold energy, yet the reaction is slow. Why?

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For collisions to be effective, activation energy is not the only factor, they must also be properly
oriented.
10. What is the source of activation energy in a photochemical reaction?
Photochemical reactions require a light source that emits wavelengths. In the case of photochemical
reactions, light provides the activation energy.
11. Why does the rate of a reaction not remain constant throughout the reaction process?
Rate of reaction depends on the conc. Of reactant. As time proceeds, concentration of reactant
decreases.
12. The specific rate of reaction is 4.2×10-3mol L-1 s-1. What is the order of reaction?
From the units of rate constant we find it to be Zero order reaction
13. Is there any reaction for which reaction rate does not decrease with time?
Zero order reaction
14. The t1/2 of two samples are 0.1 and 0.4 s and concentrations are 200 and 50 mol L-1 respectively.
What is the order of the reaction?
2ndorder because t1/2 is inversely related to concentration for a second order reaction.
t 1/2 α [A0]-1
Each question carries 2 marks :
15. The rate constant for a reaction of zero order in A is 0.0030molL-1s-1. How long will it take for the
initial concentration of A to fall from 0.01 M to 0.0075 M?
Zero Order R xn
K = 0.0030 mol L-1 S-1
Initial conc = 0.01 M
Final conc. = 0.0075 M
Applying zero order rate expression
T =ʃR]o – [R] = (0.01 - 0.0075) mol L-1 = 0.83 sec.
-1 -1
K 0.0030 mol L s
16. Express the rate of the following reaction in terms of different reactants and products:
4 NH3 (g) + 5O2 � 4NO (g) + 6H2O(g)
If the rate of formation of NO is 3.6 x 10-3 mol-1s-1,calculate
(a) The rate of disappearance of NH3
(b) The rate of formation of H2O
(c) Rate of reaction.
4 NH3(g) + 5O2(g)  4 NO + 6 H2O (e)
Rate = r NO = 3.6 x 10-3 mol-1S-1

Rate = -1[NH3] = - 1d [O2] = 1 d[NO] = 1 [H2O]


4 d 5 d 4 dt 6 dt

d[NH3] = 3.6 x 10-3 mol-1s-1


dt
d[H2O] = 6/4[3.6x 10-3] = 5.4 x 10-3mol L-1s-1
dt
Rate = 1/4 [3.6 x 10-3 ] = 9 x 10-4mol L-1s-1
17. For the reaction 2N2O5 (g) → 4NO2 (g) + O2 (g) the rate of formation of NO2 is 2.8 x 10-3 Ms-1. Calculate
the rate of disappearanceof N2O5.

Rate = ¼ ∆ [NO2]/ ∆t = -1/2 ∆ [N2O5]/∆t


¼ (2.8 x 10-3) = -1/2 ∆ [N2O5]/∆t
Rate of disappearance of N2O5 (- [N2O5]/∆t) = 1.4 x10-3 M/s
18. What is the effect of catalyst on activation energy? Why?
Catalyst reduces the activation energy for the reaction by providing an alternate mechanism for

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reaction.

19. What will be the effect of temperature on rate constant?


The effect of temperature on the rate constant is given by the Arrehenius equation
K=Ae-Ea/RTwhere k is the rate constant, Ea is the energy of activation ,A is the collision
frequency, and T the temperature.

20. Plot a graph showing variation of potential energy with reaction .coordinate?

21. List the factors that determine the rate of a chemical reaction.
Factor that determine the rate of reaction
Nature of reaction species
Surface area of reactant
Presence of catalyst
Pressure
Light
22. What do you understand by the rate law and rate constant of a reaction? Identify the order of a
reaction if the units of its rate constant are : (i) L-1mol s-1 (ii) L mol-1 s-1
The representation of rate of reaction in terms of concentration of the reactants is known as rate law.
It is also called as rate equation or rate expression.
Rate constant may be defined as the rate of the reaction when the concentration of each reactant is
taken as unity.
(i) Zero order reaction
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(ii) Second order reaction
23. For a certain chemical reaction variation in the concentration log[R]0/[R] vs. time(s) plot is given
below
For this reaction write/draw
(i) What is the order of the reactions?
(ii) What are the units of rate constant k?
(iii) Give the relationship between k and t1/2.
(iv) What does the slope of above line indicate?

(i)1st Order (ii) s-1 (iii) k = 0.693


(iv) k __
2.303
Each question carries 2/3 marks :
24. Show that the time required for first order reaction 99.9% completion is 10 times that required for
half of the reaction to take place.
[Ro] = 100
[R] = 100-99.9= 0.1

kt = 2.303 log Ro
R
kt = 2.303 log 100
0.1
= 2.303 log 1000
kt = 2.303 x log 103
kt = 2.303 x 3 log 10.
t99.9 = 2.303 x 3
k
t ½ = 0.693
K
. . . t99.9 = 6.909
t½ k
0.693
k
t99.9 = 6.909
t½ 0.693

. . . t99.9 = 9.9697

. . . t99.9 = 10 t ½
25. From the fig.
(a) Calculate ∆H for the reaction and activation energy for forward reaction in absence of catalyst.
(b) Identify the curve for catalyzed reaction.
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(c) What is the energy of activation in the presence of catalyst?

From the figure-


Energy of reactions Er= 100KJ/Mol
Energy of products, Ep= 25 Kj/Mol
Change in energy, ΔH = ΔHP – ΔHR
= 25-100 = -75KJ/Mol
Threshold energy, Er= 350 KJ/Mol
Activation energy, Ea= Et – Er
= 350-100
= 250 kJ/ mol.
(b) The curve B is for catalysed reaction.
( C) In the presence of catalysts ,
Threshold energy Er= 200KJ/Mol
Activation energy, Ea= 200-100
= 100 kJ/mol.
26. Derive an expression for first order reaction.
For 1st order reaction.
Rate = k[R]
-d [k] = k x R
dt

. . . d [k] = = kdt
R

Integrating both the sides

ʃ d [R] = ʃ -kdt
R
ln [R] = - kt+o

At t = o, R = Ro.

C = ln [Ro]

Substituting
In [R] = -kt = ln[Ro}

Kt =ln [Ro]
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R

. . . kt = 2.303 log [Ro]


R
27. A first order reaction is 15% completed in 20 minutes. How long will it take to complete 60%?

k =2.303 log10[R]o
t [R]

k = 2.303 log10 100


20 85 I

k= 2.303 log10100 II
t 40

From eq 7& 8 II

2.303 log10 100 = 2.303 log10100


20 85 t 40

1[ log100- log85] = 1 [log100 – log 40]


20 t

1 [2-1.9294] = 1[2-1.602]
20 t
1 [0.0706] = 1[0.398]
20 t

... t =0.398 x 20 = 112.73 min


0.0706
28. The thermal decomposition of HCO2H is a first order reaction with a rate constant of 2.4x 10-3 s-1 at a
certain temperature. Calculate how long will it take for three-fourth of initial quantity of HCO2H to
decompose. (log 0.25 = -0.6021)
K = 2.303 log [Ro]
t [R/4]

K = 2.303 [log1 – log 0.25]


t
t= 2.303[0-(-0.6021)]
2.4 x10-3

= 2.303 x 0.6021 x 103


2.4
= 577s= 9.627 min
29. Consider a reaction A→ Products with k =2.0×10-2s-1. Calculate the conc. of A remaining after
100s if the initial conc. of is 1.0 mol L-1.
Reaction is 1storder K = 2.0 x 10-2 S-1, t = 100s
Rate = K [A] Ro = 1.0 mol L-1
Kt = 2.303 log Ro
R

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2x10-2 x 100 = 2.303 log 1


R
-2
2 x 10 x 100 = log 1
2.303 R
Antilog 2 = 1
2.303 R

Antilog [0.868] = 1
R
R= 1
Al[0.868]

R = 0.135 mol L-1


= 0.135molL-1
30. The half-life for decay of radioactive 14C is 5730 years. An archaeological artifact containing wood
had only 80% of the 14C activity as found in a living tree. Calculate the age of the artifact.
Ro = 100 R = 80
t ½ = 5730 years
t=?
K= 2.303 log10Ro
t R
K =0.693

0.693 = 2.303 log10100
5730 t 80
t= 2.303 x 5730 log 10100
0.693 80
t = 2.303 x 5730 x 0.09
0.693
t = 1844.64 years
31. For zero order reaction prove that half life is directly proportional to initial concentration.
K= Ro-R
t
At t = t ½ K= Ro
2
.
. . K= Ro-[Ro/2]

.
. . K x t ½ =Ro
2
. . . t ½ = Ro
2k
. . . Half life period directly proportional to Ro
32. The rate of a particular reaction doubles when the temperature changes from 295Kto 305K.
Calculate the activation energy of such reaction.
Ans.51.855 KJ/mol
T1 = 295 K K2 = 2K1
T2 = 305 K.Ea = ?

Formula log K2 = Ea (T2 - T1)


K1 2.303R T1T2

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Log 2 K1 = Ea 1 -1_
K1 2.303 x 8.314 295 305

Log 2 = Ea___ 305 - 295_


2.303 x 8.314 295 x 305

0.3010 x 2.303 x 8.314 x 295 x 305= Ea


10
Ea = 51855 J = 51.855 KJ mol-1
33. The rate of a reaction increases four times when the temperature changes from 300 K to 320 K.
Calculate the energy of activation of the reaction, assuming that it does not change with temperature.
(R= 8.314 JK-1 mol-1) Ans. 55.3 KJ/mol
log K2 = Ea 1 - 1
K1 2.303R T1 T2

Log 4 K1 = Ea 1 - 1
K1 2.303x 8.314 300 320

Ea = 55327.5815 J = 55.327 KJ
34. The decomposition of phosphine,
4PH3(g) → P4(g) + 6 H2 (g) has the rate law, Rate = k [PH3]
The rate constant is 6.0 x 10 s at 300 K and activation energy is 3.05 x 105J .Calculate the rate
-4 -1

constant at 310K Given : R = 8.314 JK-1 mol-1


4 Ph3 (g)  P4 (g) + OH2 (g)
Rate law :- Rate = [Ph3]
-4 -1
K1 = 6.0 x 10 S
T1 = 300K R = 8.314 J K-1mol-1
5
Ea = 3.05 x 10 J
T2 = 310 K
K2 = ?

Log k2=Ea T2 - T1
k12.303K T1T2

Log k2= 3.05 x 105 310 - 300


6x 10-4 2.303 x 8.314 x 310 x 300

Log k2 = 1.7128
-4
6x 10
k2 = A.L [1.7128]
6x 10-4
k2 = 51.6179 x 6 x 10-4
k2 = 0.03097 s-1
= 3.097 x10-2 s-1
35.
A first order decomposition reaction takes 40 minutes for 30 % of decomposition. Calculate t1/2 value
for it. K=8.9x10-3 min-1 t 1/2= 77.9 min
t 1/2= 77.9 min
k= 2.303 log a
t a-x

= 2.303 log 100

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40 100-30

= 2.303 log 100


40 70

k =2.303 log 1.4285


40

k =2.303 x 0.1549
40
k = 8.91 x 10-3
t ½ = 0.693 = 0.693
k 8.91 x 10-3

t 1/2= 77.9 min


36. The data given below is for the reaction,
2N2O5 (g) → 4NO2 (g) + O2 (g) at 298K :

S.No. [N2O5]
(molL-1)
Rate of disappearance of
N2O5 (mol L-1 min-1)
1. 0.0113 34x10-5
2. 0.0084 25 X 10-5
3. 0.0062 18 x10-5
Determine for this reaction :
(i) order of reaction
(ii) rate constant
(i) rate law
2 N2O5  4 No2(g) + O2 (g)
Rate = K x [A]x
-34 x10-5 = k x [0.0113] x I
-5
- 25 x 10 = k x [0.0084] x II

1.8 x 10-5 = k x [0.0062] x III


Eqn.I÷eq II
-34 x 10-5 = k x [0.0113] x
- 25 x 10-5 = k x [0.0084] x
x
1.36 = [1.34]
Diveq II by III
- 25 x 10-5 = k x [0.0084] x
-5
- 1.8 x 10 = k x [0.0062] x
1.38 = [1.35]x
. .. 1.36 = 1.34 x
1.38 1.35
x = 1
Order = 1
34 x10-5= k x [0.0113]1

k =34 x 10-5
0.0113
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k = 0.03008 S -1
(iii) Rate = 3.008 x 10-2 [N2O5]

37. Three experimental runs were carried out for the reaction between Cl2 and NO.
Cl2(g) + 2NO(g) � 2NOCl(g)
The following data were obtained
Run Initial conc Initial conc Initial rate
-1 -1
(molL ) (molL ) [NO] (mol L-1s-1)
[Cl2]
1. 0.020 0.010 2.40x10-4
2. 0.020 0.030 2.16 X 10-3
3. 0.040 0.030 4.32 x10-3
Determine the order of reaction and write the rate law equation for this reaction.

38. The following results have been obtained at 300 K during the kinetic studies of the reaction:
2A + B → C + D
Calculate the rate of formation of D when [A] = 0.5 mol L-1and [B] = 0.2 mol L-1 .

Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of


No formation of
–1 –1
D/mol L min
1 0.1 0.1 6.0 x 10-3
2 0.3 0.2 7.2 x 10-2
3 0.3 0.4 2.88 x 10-1
4 0.4 0.1 2.4 x 10-2

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Ans. Order w.r.t A=1, Order w.r.t B=2 Rate=0.12molL-1min-1
Ans. Order w.r.t A=1, Order w.r.t B=2 Rate=0.12molL-1min-1
2A + B  C+D
Rate of formation of D = ?

Rate = k [A]x [B]y
. . . 6 x 10-3 = k [0.1]x [0.1]y
. . . 2.4 x 10-2 = k [0.4]x [0.1]y
6 x 10-3=k [0.1]x [0.1]y
2.4 x 10-2 k [0.4]x [0.1]y
1 =1 x
4 4

7.2 x 10-2 = [0.3]x [0.2]y
2.88 x 10-1 = [04]x [0.1]y
1 =1 y
4 2
12 = 1 y
2 2
.
.Y=2

Rate = k [A]1 [B]2
. . . 6 x 10-3 = k [0.1]x [0.1]y
. . . k = 6 x 10-3 = 6
1 x 10-3
Rate = 6 x [0.5] [0.2]2
= 0.12 mol L-1S-1
39. Rate of reaction A + B � P is given below as a function of different initial concentrations of A and
B:
[A] [B] Initial rate
-1 -1
Mole litre Mole litre Mole litre-1 second-1
0.01 1.0 2.1x 10-3
0.02 1.0 8.4 x 10-3
0.02 2.0 8.4 x 10-3
Determine order of reaction w.r.t (A) and (B) and overall order of the reaction?
A+B  P

2.1 x 10-3= k [0.01]x [1]y I

8.4 x 10-3 = k [0.02]x [1]y II

8.4 x 10-3 = k [0.02]x [2.0]y III

EqI ÷eq II

2.1 x 10-3= k[0.01]x [1]y .


8.4 x 10-3 k[0.02]x [1]y
x
1 = 1
4 2

.. . = 2
Eq II÷eq III

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8.4 x 10-3= k [0.01]x[1]y
8.4 x 10-3 k [0.02]x [2]y
y
1 = 1
2

Y=0
. . . Order of reaction = 2+0 = 2
40. The following data were obtained for the reaction
2 A + 2B � products.
Expt Initial conc Initial conc Initial rate mol
[A] [B] L-1min-1

I 0.01 0.01 0.005


II 0.02 0.01 0.020
III 0.02 0.03 0.060
Determine the order of reaction and write the rate law equation for this reaction.
Ans. 3,Rate =K[A]2[B]
2 A + 2B  Product
Rate = k [A]x [B]y
0.005 = k [0.1]x [0.1]y I
0.020= k [0.02]x [0.01]y II
EqI÷eq II
1= 1
4 2
X = 2
0.060 = k[0.02]x [0.03]y III
Eq II by III
1 = 1 y
3 3
Y = 1
Rate = k[A]2 [B]1
Order = 3
41. The half-life for a first order reaction is 5x 104 s. What percentage of the initial reactant will react in
2 hours ?
t ½ = 5 x 104 s
T = 2 hr
Kt = 2.303 log 10 [Ro]
R
K = 0.693

K =0.693
5 x 104
0.693 x 2 x60 x 60 = 2.303 log 100
5 x 104 R

Antilog (0.04333) = 100


R
1.1049 = 100
R

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R= 100 = 90.50%
1.1049
% of initial reactant will react = 100-90.5 = 9.5
42. The first order rate constant for the decomposition of ethyl iodide
by the reaction
C2H5I(g) → C2H4 (g) + HI(g)
at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol.
Calculate the rate constant of the reaction at 700K. Ans. 6.36 × 10–3 s–1
We know that log k2 – log k1 = Ea/2.303R[1/T1 − 1/T2]
log k2 = log k1 + Ea/2.303R[1/T1 − 1/T2]
= log (1.60 × 10−5) + 209000 J mol L−1/2.303 × 8.314 J mol L−1K−1 [1/600K − 1/700K]
log k2 = – 4.796 + 2.599 = – 2.197
k2 = 6.36 × 10–3 s–1
43. A first order reaction is 20 % completed in 10 minutes. How long will it take to complete 75%?
K= 2.303 log a
t a-x

k =2.303 log 100


10 80  I

k= 2.303 log 100


t 25  II

From eq. I & II

2.303 log 1.25 = 2.303 log 4


10 t

2.303 x 0.09691 = 2.303 x 0.6021


10 t

t = 0.6021x 10 = 62.06min
0.09691

44. A first order reaction takes 20 minutes for 25% decomposition. Calculate the time when 75% of the
reaction will be completed.
K= 2.303 log a
t a-x
k =2.303 log 100
20 75  I

k= 2.303 log 100


t 25  II

From eq. I & II

2.303 log 1.33 = 2.303 log 4


20 t

2.303 x 0.1248 = 2.303 x 0.6021


20 t

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t = 96.49 min
45. The rate constant for the first order decomposition of H2O2 is given by thefollowing equation: log k
= 14.34 – 1.25 × 104K/T.Calculate Ea for this reaction and at what temperature will its half-period
be 256 minutes?

46. For a certain chemical reaction


A + 2B � 2C + D
The experimentally obtained information is tabulated below
Experiment [A]0 [B]0 Initial rate of
reaction
1. 0.30 0.30 0.096
2. 0.60 0.30 0.384
3. 0.30 0.60 0.192
4. 0.60 0.60 0.768

For this reaction


(i) derive the order of reaction w.r.t both reactants A and B. Ans. 2,1
(ii) Write the rate law. Rate=K[A]2[B]
(iii) Calculate the value of rate constant. 3.5 mol-2L2S-2
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(iv) Write the expression for the rate of reaction in terms of A and C.
A +2B  2C + D

Rate = k [A]x [B]y


0.096 = k [0.3]x [0.30]y I

0.384 = k [0.6]x [0.3]y II

0.192 = k [0.30]x [0.60]y III

0.768 = k [0.60]x [0.60]y IV

EgI÷eg III

0.096 = k [0.3]x [0.3]y .


0.092 k[0.3]x [0.6]y

11 = 1 y

2 2

Y =1
Eq III÷ Eq IV

0.192 =K [0.30]x [0.60]y .


0.768K[0.60]x [0.60]y

1  1x
4 2

1 = 1x
22 2

.. . X = 2
(ii) Rate = k [A]2 [B]
(iii) 0.096 = k [0.30]2 [0.30]

k = 0.096= 3.5 mol-2 L2S-2


0.30 x0.30 x0.3

(iv) Rate =- d [A] = 1 d [c]


2 dt dt
47. The following data were obtained for the reaction
2 NO2 (g) + F2 (g) � 2NO2F (g)
Expt Initial conc. Initial conc. Initial rate mol lit-
1
[NO2] [F2] min-1
I 0.20 0.05 6.0 x 10-3
II 0.40 0.05 1.2 x 10-2
III 0.80 0.10 4.8 x1 0-2
Determine the order of reaction and write the rate law equation for this reaction.
Ans. Order w.r.t NO2=1, F2=1.5
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2NO2 (g) + F2(g)  2 No2 F(g)
6 x 10 = k [0.20]x [0.05]y I
-3

1.2 x10-2 = k [0.40]x [0.05]y II

4.8x 10-2 = k [0.8]x [0.10]y III


Eq .I÷eq II
6 x 10-3 =k [0.20]x [0.05]y
1.2 x10-2 k [0.40]x [0.05]y

11 = 1x
2 2

X=1

Eg.II÷eg III

1.2 x10-2 = K [0.40]x [0.05]y


4.8x 10-2 = K [0.8]x [0.10]y
x y
1= 1 1
4 2 2
Y
1= 1 1
4 2 2

2= 1y
9 2
y
1 = 1
2 2 ... Y=1

Order of reaction = 2, Rate law = K[NO2] [F2]


48. (i)What is the order of reaction?
(ii) What are the units of rate constant?
(iii) What is slope equal to?
(iv) What is y - intercept?

(i) 1st order (ii) s-1 (iii) Slope =K (iv) ln [Ro]

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49. In a hydrolysis reaction, 5g ethyl acetate is hydrolyzed in presence of dilute HCl in 300 minutes. If
the reaction is of first order and the initial concentration of ethyl acetate is 22g/L, Calculate the rate
constant of the reaction. Ans. 8.36 x 10-4 min-1
1st Order R x n
T = 300 min
Ro = 22 gm / lit
R = 17 gm / lit

kt = 2.303og10Ro
R

= 2.303 log1022
300 17
= 2.303 log1.2941
300
k =2.303 log1.2941
300
k =2.303 x 0.1119
300
k = 8.59 x 10-4 min-1
50.
The decomposition of phosphine , PH3, proceeds according to the following equation:
4PH3 (g) → P4 (g) + 6H2 (g)
It is found that the reaction follows the following rate equation:
Rate = k [PH3].
The half life of PH3 is 37.9 s at 120oC.
(i) How much time is required for 3/4 th of PH3 to decompose? Ans. 75.8
min
(ii) What fraction of the original sample of PH3 remains behind after 1 minute? Ans 0.334
(i) It may be defined as charge in conc. Of reaction or product in unit time

(ii) It is the minimum extra energy required by the reactant molecule to cross the energy barrier i.e
threshold energy.

b) 4 PH3  P4(g) + 6 H2(g)

Rate = k [PH3]
t ½ = 37.9 sec
= 120 C = 393 K
(i) = t ¾ = 2 t ½
t ¾ = 2 x 37.9
= 75.8 min
(ii) t = 1 min = 60 sec t ½ = 37.9 sec

kt = 2.303 log Ro
R
0.693 x t = 2.303 log Ro
k½ R
0.693 x 60 = log Ro
37.9 2.303 R
Al(0.4764) = Ro
R

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Answer Key
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2.995 = Ro
R
R = 1 = 0.333
Ro 2.995
51. A first order reaction is 50% completed in 40 minutes at 300K and in 20 minutes at 320K. Calculate
the activation energy of the reaction.
K2 = 0.693/20 K1 = 0693/40
log K2 = Ea (T2 - T1)
K1 2.303R T1T2
Log 2 = Ea 320-300
2.303x 8.314 320 x 300
Ea = 27.66 kJ/mol
Section C
Each question carries 1 mark :
52. Why in the redox titration of KMnO4 vs oxalic acid, we heat oxalic acid solution before starting the
titration?
The reaction between KMnO4 and oxalic acid is very slow and hence by raising the temperature, we
can enhance the rate of reaction.
53.

At high pressure the following reaction is zero order.


2NH3(g) at 1130Kand Pt catalyst ⎯⎯⎯→ N2(g) + 3H2(g)
Which of the following options are correct for this reaction?
(i) Rate of reaction = Rate constant
(ii) Rate of the reaction depends on concentration of ammonia.
(iii) Rate of decomposition of ammonia will remain constant until ammonia
disappears completely.
(iv) Further increase in pressure will change the rate of r
Ans: (i), (iii), (iv)
54. The reaction between H2(g) and O2(g) is highly feasible yet allowing the gases to stand at room
temperature in the same vessel does not lead to the formation of water. Explain.
This is because activation energy for the reaction is very high at room temperature
55. If the activation energy of a reaction is zero, will the rate of reaction still depend on temperature?
k = A e-Ea/RT
When Ea = 0
k = A e -0/RT
k= A. e0
k=A
Rate of reaction will not depend upon the temperature if activation energy is zero.
56. For the reaction 2X → X2, the rate of reaction becomes 3 times when the concentration of X is
increased 27 times. What is the order of the reaction?
Order of reaction = 1/3
57. What do you mean by the term- collision frequency?
The number of collisions persecond per unit volume of the reaction mixture is known as collision
frequency (Z)
58. A catalyst does not alter Gibbs energy, ΔG of a reaction. Comment
The statement is true as catalyst catalyses the spontaneous reactions but does not catalyse non-
spontaneous reactions. It only alters the rate of a reaction by providing an alternate pathway.
59. A reaction is 50% complete in 2hours and 75% complete in 4 hours. What is the order of the
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Answer Key
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reaction?
t ½ = 2hr, t ¾ = 4 hr, t 8/2 = 2 t ½
This shows that t ½ is independent of initial conc., so it is 1st order reaction.
60. What is the effect of adding a catalyst on
(i)Activation energy(Ea)
(ii)Gibbs energy (ΔG)
(i)A catalyst decreases the activation energy by providing the alternative path of the mechanism.
(ii)There will be no change in ΔG.
Each question carries 2 marks :
61. An increase of 10 K in temperature rarely doubles the K.E. of particles but this increase in
temperature may be enough to double the rate of reaction. Explain.
For every 10o rise in temp. the rate constant nearing doubles. This is called temperature
coefficient,I .
I = Rate constant at T + 10o C
Rate constant at ToC

Increasing the temperature of the substance increases the fraction of molecules, which collide with
energies greater than Ea. It is clear from the diagram that in the curve at (t + 10), the area showing the
fraction of molecules having energy equal to or greater than activation energy gets doubled leading
to doubling the rate of a reaction
62. Explain the following graph between reaction co-ordinate and potential energy.

In uncatalysed reactions the Ea is very high. In catalysed reactions , the Ea is lowered and many
molecules are able to cross the energy barrier as it provides an alternate pathway.
63. For a first order reaction, time taken for half of the reaction to complete is t1 whereas that for 3/4th of
the reaction to complete is t2.How are t1 and t2 related to each other?
For a first order reaction, t1/2 is independent of initial concentration.
t1/2= 0.693/k .Hence if t1 is for 50% decomposition, For 75% it will be 2t1.
64. Following reaction takes place in one step
2NO (g) + O2(g) � 2NO2(g)
How will the rate of the above reaction change if the volume of the reaction vessel is diminished to
1/3rd of its original volume? Will there be any change in the order of the reaction with the reduced
volume?
2 NO + O2 (g)  2NO2 (g) ( As it is elementary reaction)

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Answer Key
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Let X be mole of NO
Y be mole of O2

V be the volume of vessel.

Rate 1= k [NO] [O2]1

X2 Y 1

Rate2 = k --- ---


V V

If volume reduce to V/3


3x 2 3y 1
Rate2 = k --- ---
V V
r2 = 27
r1
Rate become 27 time. Order remain same
65. Two reactions have identical values of Ea. Does this ensure that they will have the same rate constant
if run at the same temperature? Explain.
Having the same activation energy does not ensure that the reaction rates will be the same. many
reactions have 2 or more steps. activation energy is the energy required for the reaction to proceed, it
doesn't mean that this will solely determine reaction rate .
66. Rate constant k of reaction varies with temperature according to the equation:
Log k= constant- Ea/2.303R x1/T,
When a graph is plotted for log k versus 1/T, a straight line with a slope -6670 K is obtained?
Calculate energy of activation for this reaction. State the units.
Slope of line =-Ea = -6670K
2.303R
Ea = -6670 x 2.303 x8.314
Ea = 127711.43 J =127.7 KJ/mol
67. For the decomposition reaction:
N2O4(g) � 2NO2(g)
The initial pressure of N2O4 falls from 0.46atm to 0.28 atm in 30 minutes. What is the rate of
appearance of NO2?
Rate of disappearance of N2O4= [ 0.463028]
80
= - 0.18
30
= 6 x 10-3

-d (N2O4) = 1d [NO2] = rate


dt 2 dt

d [NO2]
dt = 2 x rate=2 x 6 x 10-3=12 x 10-3mol L-1 S-1
=1.2x10-2atm/min
68. The following reaction was studied in a closed vessel
2N2O5 (g) � 4NO2 (g) + O2(g)
It was found that the concentration o NO2 increases by 2.0 x 10-2mol L-1 in five seconds. Calculate

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Answer Key
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(a)The rate of reaction (b)The rate of change of concentration of N2O5(c)Rate of formation of NO21
2 N2O5 � 4NO2(g) + O2 (g)

Rate = -1d[ N2O5] = - 1d [NO2] = d [O2]


2 dt 4 dt dt
-2 -2
c) d[NO2] = 2 x 10 = 0.4 x 10 M/s.
dt
d) Rate of reaction = 1 x 0.4 x 10-2= 10-3 M/s.
b) Rate of change of concentration of N2O5 = 2 x Rate of reaction.
=2 x 10-3 M S-1
69. The activation energy of a reaction is 75.2KJmol-1 in the absence of a catalyst and 50.14 KJmol -1
with a catalyst. How many times will the rate of reaction grow in the presence of the catalyst if the
reaction proceeds at 25 �C? (R = 8.314 J K-1 mol-1) Ans. k2/k1=29960
-75.2/RT
In absence of catalyst k1 = Ae
k = Ae– Ea / RT
In presence of catalyst k2 =Ae-50.14 /RT
k1 = Ae-75.2/RT
k2 Ae-50.14 /RT
= e-75.2/RT - 50.14 /RT
k1= e-25.06/RT
k2
In k1 = -25-06
k2 RT
In k2 = 25-06
k1 RT
2.303 log k2 = -25-06 x 103
k1 8.314 x 298
Log k2 = -25-06 x 103
k1 8.314 x 298 x 2.303
k2= antilog [4.391984]
k1
k2 = 24660.39
k1
70. The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5s–1 at 546 K. If the energy of
activation is 179.9 kJ/mol, what will be the value of pre-exponential factor.

71. The time required for 10% completion of a first order reaction at 298K isequal to that required for its
25% completion at 308K. If the value of A is4 × 1010s–1 .Calculate k at 318K and Ea.

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Answer Key
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72. The activation energy for the reaction


2 HI(g) → H2 + I2 (g)
is 209.5 kJ mol–1 at 581K.Calculate the fraction of molecules of reactants having energy equal to or
greater than activation energy? Ans. 1.471 x 10 -19
Given that
Activation energy, Ea = 209.5 kJ mol−1
Multiply by 1000 to convert in j
Ea= 209500 J mol−1
Temperature, T = 581 K
Gas constant, R = 8.314 JK−1 mol−1
According to Arrhenius equation
K = A e –Ea/RT
In this formula term e –Ea/RT represent the number of molecules which have energy equal or more than
activation energy
Number of molecules = e –Ea/RT
=e-209500/8.314x581
=e-43.3708
Let y = e-43.4
Therefore ln y = ln e-43.3708
= (-43.3708) ln e ……..(ln e=1)
=(-43.3708)
2.303 log10 y = (-43.3708
log10 y = -18.8323
Y = Al(-18.8323)
= Al(---
19.15)
= 1.471 x 10-19

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Answer Key
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73. The reaction, N2 + O2→ 2NO contributes to air pollution whenever a fuel is burnt in air at a high
temperature . At 1500K equilibrium constant K for it is 1.0 x 10-5. Suppose in a case
[N2] = 0.8 mol L-1 and [O2 ]= 0.20mol L-1 before any reaction occurs . Calculate the equilibrium
concentrations of the reactants and the product after the mixture has been heated to 1500K.
Ans.[NO] = 1.2649 x 10 -3mol L-1 ,[ N2] = 0.79936 mol L-1[O2] =0.19936 mol L-1
N2 + O2 2NO
N2 + O2  2NO

T = 1500 K

K = 1 x 10-5
[N2] = 0.8 mol /L

[O2] = 0.2 mol /L

Let x mol/L of N2 and O2are decomposed at equilibrium. Equilibrium concentration of N2 = 0.8 –


x, O2 = 0.2 – x and No = 2x

[NO]2 = 1 x 10-5
[N2] [O2]

[2x]2 = 1 x 10-5
(0.8) (0.2)

2x2= 1.6 x 10-5


x2 = 8 x 10-7
x = 8 x 10-7
log x = log (8 x 10-7 ) ½
= ½ [log 8 + log 10-7 ]

= ½ [0.9031 – 7]

= ½ -6.0969]

Log x = - 3.0485

X = AL[-3.0485]

= AL [-3-1 +1 +1 -0.0485]

= AL [-4 +0.9515]

= AL [-4.9515]

X = 1.11 x 10-5
[N2] = 0.8 -1.11 x 10-5
= 0.7999
[O2] = 0.2 - 1.11 x 10-5=0.1999
[NO2] = 2.22 x 10-5
74. The decomposition of a hydrocarbon has value of rate constant as 2.5 x 10 4 s-1 at 270C. At what
temperature would rate constant be 7.5 x 104 s-`1 if energy of activation is 19.147 x 103 J mol-1?

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Answer Key
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(Given: log 2 = 0.3010, log 3 = 0.4771, log 5 = 0.6990)

75. Write a condition under which a bimolecular reaction is kinetically first order. Give an example of
such a reaction.
When one of the reactants is in excess.
CH3COOCH3 + H2O(excess) ---- CH3COOH + CH3OH

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