CHEMICAL KINETICS & NUCLEAR CHEMISTRY

Fill in the blanks

1. An element ZA M undergoes an emission followed by two successive emissions. The

element formed is (1982-1 Mark)

2. The rate of chemical change is directly proportional to(1985-1 Mark)

14
3. The number of neutrons in the parent nucleus which gives 7 N on beta emission is
(1985-1 Mark)

4. The hydrolysis of ethyl acetate in medium is a order

reaction. (1986-1 Mark)

5. A radioactive nucleus decays emitting one alpha and two beta particles; the daughter
nucleus is of the parent. (1989-1 Mark)

6. For the reaction, N2 (g) 3H2 (g)

2NH3 (g)
Under certain conditions of temperature and partial pressure of the reactants, the rate of
formation of NH3 is 0.001 kg h1. The rate of conversion of H2 under the same condition is
kg h1. (1994-1 Mark)

7. In the Arrhenius equation, k AeE a / RT

, A may be termed as the rate constant at
(1997-1 Mark)

True/False:

1. For a first order reaction, the rate of the reaction doubles as the concentration of the
reaction(s) doubles. (1986-1 Mark)

2. Catalyst makes a reaction more exothermic. (1987-1 Mark)

3. Catalyst does not affect the energy of activation in a chemical reaction. (1989-1 Mark)

4. In emission from a nucleus the atomic number of the daughter element decreases by
one. (1990-1 Mark)

5. The rate of an exothermic reaction increases with increasing temperature. (1990-1 Mark)

Multiple Choice Questions with ONE correct answer:

1. If uranium (mass number 238 and atomic number 92) emits, an particle, the product has
mass no. and atomic no.
(a) 236 and 92 (b) 234 and 90
(c) 238 and 90 (d) 236 and 90 (1981-1 Mark)

2. The rate constant of a reaction depends on

(a) temperature (b) initial concentration of the reactants
(c) time of reaction (d) extent of reaction (1981-1 Mark)

3. The specific rate constant of a first order reaction depends on the

(a) concentration of the reactant (b) concentration of the product
(c) time (d) temperature (1983-1 Mark)
 Chemical Kinetics & Nuclear 2
Chemistry

4. A catalyst is a substance which

(a) increases the equilibrium concentration of the product
(b) changes the equilibrium constant of the reaction
(c) shortens the time to reach equilibrium
(d) supplies energy to the reaction (1993-1 Mark)

5. The radiations from a naturally occurring radioactive substance, as seen after deflection by a
magnetic field in one direction, are:
(a) definitely alpha rays (b) definitely beta rays
(c) both alpha and beta rays (d) either alpha or beta rays (1984-1 Mark)

6. The half-life period of a radioactive element is 140 days. After 560 days, one gram of the
element will get reduced to:
1 1
(a) g (b) g
2 4
1 1
(c) g (d) g (1986-1 Mark)
8 16

7. Read the following statement and explanation and answer as per the options given below:
Assertion: For each ten degree rise of temperature the specific rate constant is nearly
doubled.
Statement: Energy-wise distribution of molecules in a gas is an experimental function of
temperature.
(a) If both assertion and statement are correct and statement is an explanation of assertion.
(b) If assertion is correct and statement is wrong, statement is not an explanation of
assertion.
(c) If assertion is wrong and statement is correct, statement is not an explanation of
assertion.
(d) If both assertion and statement are wrong and statement is not explanation of assertion.
(1989-2 Marks)

8. The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction
at 25C are 3.0 x 104 s1, 104.4 kJ mol1 and 6.0 1014 s1respectively. The value of the rate
constant as T is,
(a) 2.0 x 1018 s1 (b) 6.0 1014 s1
(c) infinity (d) 3.6 x l030 s1 (1996-1 Mark)

27 29
9. 13Al is a stable isotope, 13 Al is expected to disintegrate by
(a) emission (b) emission
(c) positron emission (d) proton emission (1996-1 Mark)

139 94
10. The number of neutrons accompanying the formation of 54 Xe and 38 Sr from the absorption
235
of a slow neutron by 92 U , followed by nuclear fission is,
(a) 0 (b) 2
(c) 1 (d) 3 (1999-1 Mark)

11. The rate constant for the reaction, 2N2O5 2 O2 , is 3.0 105 sec1. If the rate is
4NO
2.40 x 105 mol litre1 sec1, then the concentration of N2O5 (in mol litre1) is
(a) 1.4 (b) 1.2
(c) 0.04 (d) 0.8 (200-Scr.)
12. If I is the intensity of absorbed light and C is the concentration of AB for the photochemical
process, AB h AB , the rate of formation of AB* is directly proportional to
(a) C (b) I
 Chemical Kinetics & Nuclear 3
Chemistry

(c) I2 (d) C.I (2001-Scr.)

13. Consider the chemical reaction, N2 (g) 3H2 (g) 2NH3 (g) . The rate of this reaction can
be expressed in terms of time derivative of concentration of N 2(g), H2(g) or NH3(g). Identify
the correct relationship amongst the rate expressions.
(a) Rate d[N2 ] / dt 1/ 3 d[H2 ] / dt 1/ 2d[NH3 ] / dt
(b) Rate d[N2 ] / dt 3 d[H2 ] / dt 2d[NH3 ] / dt
(c) Rate d[N2 ] / dt 1/ 3 d[H2 ] / dt 1/ 2d[NH3 ] / dt
(d) Rate d[N2 ] / dt d[H2 ] / dt d[NH3 ] / dt (2002-Scr.)

14. In a first order reaction the concentration of reactant decreases from 800 mol/dm 3 to 50
mol/dm3 in 2 104 sec. The rate constant of reaction in sec1 is:
(a) 2 x 104 (b) 3.45 x 105
4
(c) 1.386 x 10 (d) 2 x l04 (2003-Scr.)

24
15. 23
Na is the more stable isotope of Na. Find out the process by which 11 Na can undergo
radioactive decay.
(a) emission (b) emission

(c) emission (d) K electron capture (2003-Scr.)

16. The reaction, X Product, follows first order kinetics, in 40 minutes the concentration of X
changes from 0.1 to 0.025 M. The rate of reaction, when concentration of X is 0.01 M is
(a) 1.73 x 104 M min1 (b) 3.47 x 105 M min1
4 1
(c) 3.47 x 10 M min (d) 1.73 x 105 M min1 (2004-Scr.)

17. Which one of the following statement for order of reaction is not correct?
(a) Order can be determined experimentally
(b) Order of reaction is equal to sum of the powers of concentration terms in differential rate
law.
(c) It is not affected with the stoichiometric coefficient of the reactants
(d) Order cannot be fractional. (2005-Scr.)

Multiple Choice Questions with ONE MORE THAN ONE correct answer:

1. A catalyst:
(a) increases the average kinetic energy of reacting molecules
(b) decreases the activation energy
(c) alters the reaction mechanism
(d) increases the frequency of collisions of reacting species (1984-1
Mark)

2. The rate law for the reaction:

RCI + NaOH (aq.) ROH + NaCI
is given by, Rate = k1 [RCl]. The rate of the reaction will be
(a) doubled on doubling the concentration of sodium hydroxide
(b) halved on reducing the concentration of alky halide to one half
(c) increased on increasing the temperature of the reaction
(d) unaffected by increasing the temperature of the reaction. (1988-1 Mark)

3. Nuclear reactions accompanied with emission of neutron(s) are: (1988-1 Mark)

(a) 13 Al 2H
(B) 6 C 1H

17 4 30 12 1 13
15 P 7 N

(c)
30
15 P
14
30
Si 0
e
1 (d)
241
96 Am 24He
Bk
224
97
0
e
1
 Chemical Kinetics & Nuclear 4
Chemistry

4. For a first order reaction, (1998-2 Marks)

(a) the degree of dissociation is equal to (1-ekt)
(b) a plot of reciprocal concentration of the reactant vs time gives a straight line.
(c) the time taken for the completion of 75% reaction is thrice the t1/2 of the reaction
(d) the pre-exponential factor in the Arrhenius equation has the dimension of time, T1.

5. The following statement(s) is (are) correct:

(a) A plot of log Kp versus 1/T is linear
(b) A plot of log [X] versus time is linear for a first order reaction, X P.
(c) A plot of p versus 1/T is linear at constant volume
(d)A plot of p versus 1/V is linear at constant temperature (1999-3 Marks)

Subjective Problems:

1. Rate of a reaction A B Products, is given below as a function of different initial

concentrations of A and B:
[A] (mol/litre) [B] (mol/litre) Initial rate (mol/litre/min)
0.01 0.01 0.005
0.02 0.01 0.010
0.01 0.02 0.005
Determine the order of the reaction with respect to A and with respect to B. What is the half-
life of A in the reaction? (1982-4 Marks)

2. A first order reaction is 20% complete in 10 minutes. Calculate (i) the specific rate constant
of the reaction, and (ii) the time taken for the reaction to go to 75% completion.
(1983-2 Marks)

3. Radioactive decay is a first order process Radioactive carbon in wood sample decays with a
half life of 5770 years. What is the rate constant (in years 1) for the decay? What fraction
would remain after 11540 years? (1984-3 Marks)

4. While studying the decomposition of gaseous N 2O5 it is observed that a plot of logarithm of
its partial pressure versus time is linear. What kinetic parameters can be obtained from this
observation? (1985-2 Marks)

234 206
5. 90 Th disintegrates to give 82 Pb as the final product. How many alpha and beta particles
are emitted during this process? (1986-2 Marks)

6. A first order reaction has K = 1.5 106 per second at 200C. If the reaction is allowed to run
for 10 hours, what percentage of the initial concentration would have changed in the
product? What is the half life of this reaction? (1987-5Marks)

7. A first order reaction is 50% complete in 30 minutes at 27C and in 10 minutes at 47C.
Calculate the reaction rate constant at 27C and the energy of activation of the reaction in
kJ/mole. (1988-3 Marks)

8. An experiment requires minimum beta activity product at the rate of 346 beta particles per
minute. The half life period of 99
42 Mo , which is a beta emitter is 66.6 hours. Find the minimum
99
amount of 42 Mo required to carry out the experiment in 6.909 hours. (1989-5 Marks)

9. In the Arrhenius equation for a certain reaction, the value of A and Ea (activation energy) are
4 1013 s1 and 98.6kJmol 1 respectively. If the reaction is of first-order, at what temperature will
its half-life be ten minutes? (1990-3 Marks)
 Chemical Kinetics & Nuclear 5
Chemistry

10. The decomposition of N2 O5 according to the equation, 2N2 O5(g) 4NO2 g O2 g is first order
reaction. After 30 min from the start of the decomposition in a closed vessel, the total
pressure developed is found to be 284.5 mm of Hg and on complete decomposition, the total
pressure is 584.5 mm of Hg. Calculate the rate constant of the reaction. (1991-6 Marks)

1l. Two reactions (i) A products and (ii) B products, follow first-order kinetics. The
rate of the reaction (i) is doubled when the temperature is raised from 300 K to 310 K. The
half life for this reaction at 310 K is 30 minutes. At the same temperature B decomposes
twice as fast A. If the energy of activation for the reaction (ii) is half that of reaction (i),
calculate the rate constant of the reaction (ii) at 300K. (1992-3 Marks)

12. The nucleidic ratio, 13 H to 11H in a sample of water is 8.0 x 10 18 : 1. Tritium undergoes decay
with a half life period of 12.3 years. How many tritium atoms would 10.0 g of such a sample
contain 40 years after the original sample is collected? (1992-4 Marks)

13. A first-order reaction, A B , requires activation energy of 70 kJ mol 1 . When a 20%

solution of A was kept at 250 C for 20 minutes, 25% decomposition took place. What will be
the percent decomposition in the same time in a 30% solution maintained at 400 C ? Assume
that activation energy remains constant in this range of temperature. (1993-4Marks)

14. The gas phase decomposition of dimethyl ether follows first-order kinetics:
CH3 O CH3 g
4 g
CH 2 g
H CO g
The reaction is carried out in a constant volume container at 5000 C and has a half life of
14.5 minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere. What
is the total pressure of the system after 12 minutes? Assume ideal gas behaviour.
(1993-4 Marks)

15. The progress of the reaction, A nB, with time, is presented in figure given below.
Determine
-+

B
Conc. mol / l

0.5

0.3 A

0.1

1 3 5 7
Time / Hour
(i) The value of n
(ii) The equilibrium constant, K and
(iii) The initial rate of conversion of A. (1994-3 Marks)

16. From the following data for the reaction between A and B
A /molL-1 B /molL-1 Initial rate/ /molL-1s-1 ,at
300 K 320 K
4 5 4
I 2.5 10 3.0 10 5.0 10 2.0 10 3
II 5.0 10 4 6.0 10 5 4.0 10 3 -------
III 1.0 10 3 6.0 10 5 1.6 10 2 --------
 Chemical Kinetics & Nuclear 6
Chemistry

Calculate:
(i) the order of the reaction with respect to A and with respect to B,
(ii) the rate constant at 300K,
(iii) the energy of activation, and
(iv) the pre-exponential factor. (1994-5Marks)

17. One of the hazards of nuclear explosion is the generation of 90 Sr and its subsequent
incorporation in bones. This nuclide has a half life of 28.1 years. Suppose one microgram
was absorbed by a new born child, how much 90 Sr will remain in his bones after 20 years?
(1995-2 Marks)

18. At 3800 C , the half-life period for the first order decomposition of H2 O2 is 360 min. the energy
of activation of the reaction is 200 kJ mol- 1 . Calculate the time required for 75%
decomposition at 4500 C. (1995-4 Marks)

227
19. Ac has a half life of 22 years w.r.t. radioactive decay. The decay follows two parallel
paths, one leading to 227 Th and the other leading to 223 Fr. The percentage yields of these two
daughter nuclides are 2% and 98% respectively. What is rate constant (year 1 ) for each of
the separate paths? (1996-2 Marks)

20. The ionization constant of NH4 in water is 5.6 10- 10 at 250 C . The rate constant for the
reaction of NH4 and OH to form NH3 and H2O is 3.0 1010 Lmol1 s 1 .Calculate the rate constant
for proton transfer from water to NH3 . (1996-3 Marks)

21. The time required for 10% completion of a first order reaction at 298 K is equal to that
required for its 25% completion at 308 K. If pre-exponential factor for the reaction is
3.56 109 s 1 , calculate its rate constant at 318 K and also the energy of activation.
(1997-3Marks)

22. The rate constant for the first order decomposition of a certain reaction is described by the
equation:
1.25 10 4 K

log10 k s1 14.3
T
(i) What is the energy of activation for this reaction?
(ii) At what temperature will its half life period be 256 minutes? (1997-5 Marks)

23. Write a balanced equation for the reaction of 14

N with particle. (1997-1 Mark)

24. The rate constant of a reaction is 1.5 107 s1 at 500 Cand 4.5 10 7 s 1 at100 0 C. Evaluate
Arrhenius parameters A and Ea. (1998-5 Marks)

25. The rate constant for an isomerisation reaction, A Bis4.5 10 3 min1 . If the initial
concentration of A is 1 M, calculate the rate of the reaction after 1 hour. (1999-4Marks)

26. 238
92 U is radioactive and it emits and particles to form 206
82 Pb. Calculate the number of
and particles emitted in this conversion. An ore of 238
92 U is
238
found to contain 92 U and
206 238
82 Pb in the weight ratio of 1 : 0.1. The half life period of 92 U is 4.5 109 years. Calculate
the age of the ore. (2000-5 Marks)
 Chemical Kinetics & Nuclear 7
Chemistry

27. A hydrogenation reaction is carried out at 500K. If the same reaction is carried out in the
presence of a catalyst at the same rate, the temperature required is 400K. Calculate the
activation energy of the reaction if the catalyst lowers the activation barrier by 20 kJ mol1 .
(2000-3Marks)
28. The rate of a first order reaction is 0.04 mol L s at 10 minutes and 0.03 molL1s1 at 20
1 1

minutes after initiation. Find the half-life of the reaction. (2001-5 Marks)

29. The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm Hg
respectively. In a flask 10 moles of (A) is mixed with 12 moles of (B). However, as soon as
(B) is added, (A) starts polymerizing into a completely insoluble solid. The polymerization
follows first-order kinetics. After 100 minutes, 0.525 mole of a solute is dissolved which
arrests the polymerization completely. The final vapour pressure of the solution is 400 mm of
Hg. Estimate the rate constant of the polymerization reaction. Assume negligible volume
change on mixing and polymerization and ideal behaviour for the final solution.
(2001-10 Marks)

30.
64
Cu T50 12.8h decays emission (38%), emission (19%) and electron capture (43%).
Write the decay products and calculate partial half-lives for each of the decay processes.
(2002-5 Marks)

31. For the given reactions, A + B

Products, following data were obtained
Initial conc. (mol/L). Initial conc. (mol/L) Initial rate [molL-1s-1 ]
[A]0 [B]0
0.1 0.2 0.05
0.2 0.2 0.10
0.1 0.1 0.05
(a) Write the rate law expression.
(b) Find the rate constant. (2004-2Marks)

32. Complete and balance the following reactions.

(i) 92 Th 7 2
He 4 6 1 o
234
............... (2004-1 Mark)
(ii) 92
235
U 0n
1

............... 52
137
Te 40 Zr 92
(2005-1 Mark)
(iii) 34 Se
86
2 1e o
............... (2005-1 Mark)

33. At constant temperature and volume, X decomposes as (2005-4 Marks)

2X(g)
3Y(g) 2Z(g)
Px is the partial pressure of X.
Observation number Time (in minute) Px (in mm of Hg)
1 0 800
2 100 400
3 200 200
(i) What is the order of reaction with respect to X?
(ii) Find the rate constant.
(iii) Find the time for 75% completion of the reaction.
(iv) Find the total pressure when pressure of X is 700 mm of Hg.
 Chemical Kinetics & Nuclear 8
Chemistry

ANSWERS

A 4
A 1. Z M 2. product of active masses 3. 8
4. acidic, first (or basic, second) 5. isotope 6. 1.765 103 kg/hr
7. very high temperature or zero activation energy

B 1. T 2. F 3. F 4. F 5. F

C 1. (b) 2. (a) 3. (d) 4. (c)

5. (d) 6. (d) 7. (a) 8. (b)
9. (b) 10. (d) 11. (d) 12. (b)
13. (c) 14. (c) 15. (a) 16. (c)
17. (d)

D 1. (b, c) 2. (b, c) 3. (a, d) 4. (a, d)

5. (a, b, d)

E 1. 1, 0, 1.386 min 2. 0.02231 min1, 62.07 min

3. 1.2 104 yrs1, 1/4 4. first order 5. 6
6. 5.2%, 128.33 hours 7. 0.0231 min1, 43.848 kJ mol1
8. 3.451 1018 mol 9. 311.35 K
10. 5.2 103 min1 11. 3.267 102 min1
12. 5.624 105 atoms 13. 67.17 %
14. 0.749 atm 15. (i) 2, (ii) 1.2 M, (iii) 0.1 mol/l/hr
16. (i) 2.1, (ii) 2.66 108 mol2l2s1. (iii) 5.54 104J, (iv) 1.175 1018
17. 0.061 g 18. 20.34 min
19. 3.81 104 yr1, 3.14 102 yr1 20. 6.07 105
21. 9.22 104 sec1, 18.33 kcal mol1 22. (i) 239 kJ mol1, (ii) 669 K
24. 5.42 1010 sec1, 2.2 104 mol1 25. 3.4354 103 M min1
26. 7.097 108 yrs 27. 100 kJ mol1
28. 24.14 min 29. 1.005 104 min1
31. (a) R0 = k[A0]; (b) 0.5 sec1
33. (i) 1, (ii) 6.93 103 min1 (iii) 200 min, (iv) 950 mm Hg