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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

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

4 d 5 d 4 dt 6 dt

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.

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.

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?

t½

(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

t½

. . . 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?

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

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

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]

20 85 I

k= 2.303 log10100 II

t 40

From eq 7& 8 II

20 85 t 40

20 t

1 [2-1.9294] = 1[2-1.602]

20 t

1 [0.0706] = 1[0.398]

20 t

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]

t

t= 2.303[0-(-0.6021)]

2.4 x10-3

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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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]

= 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

t½

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]

T½

.

. . 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 = ?

K1 2.303R T1T2

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Log 2 K1 = Ea 1 -1_

K1 2.303 x 8.314 295 305

2.303 x 8.314 295 x 305

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

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

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

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40 100-30

40 70

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

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

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 .

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

EqI ÷eq II

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

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

t½

K =0.693

5 x 104

0.693 x 2 x60 x 60 = 2.303 log 100

5 x 104 R

R

1.1049 = 100

R

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Answer Key

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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

10 80 I

t 25 II

10 t

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

t 25 II

20 t

20 t

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Answer Key

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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?

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

(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

0.096 = k [0.3]x [0.30]y I

EgI÷eg III

0.092 k[0.3]x [0.6]y

11 = 1 y

2 2

Y =1

Eq III÷ Eq IV

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]

0.30 x0.30 x0.3

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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Answer Key

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2NO2 (g) + F2(g) 2 No2 F(g)

6 x 10 = k [0.20]x [0.05]y I

-3

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

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

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?

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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.

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.

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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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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Let X be mole of NO

Y be mole of O2

X2 Y 1

V V

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

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)

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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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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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

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)

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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(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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