Chemistry : Chemical Kinetics and Nuclear Chemistry

ASSIGNMENTS

SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I

1. The isomerism of cyclopropane to propene is of first order with k = 8.25 × 10–4 s–1 at 500°C. If
cyclopropane is enclosed in a heated tube at 500°C. What will be the minimum time needed to yield at
least 10% propene in resultant gas sample.
2. For a reaction, A  B + C, it was found that the end of 10 minutes from the start the total optical
rotation of the system ws 50° and when the reaction is complete, it was 100°. Assuming that only B
and C are optically active and dextro rotatory. What would be the rate constant of this first order
reaction.
3. At a given instant thee are 25% undecayed radioactive nuclei in a sample. After 10 seconds the
number of undecayed nuclei reduces to 12.5%. What is the time in which the number of undecayed
nuclei will further reduce to 6.25% of the reduced number.
4. Naturally occurring potassium consist of 0.01% K40, which has a half life of 1.28 × 109 yr. What would
be the activity of 1.0 g sample of KCl.
5. A catalyst lowers the activation energy of a reaction from 20 kJ mole–1 to 10 kJ mole–1. What is the
temperature at which the uncatalysed reaction will have the same rate as that of the catalysed at 27C.
6. For the first order reaction A(g)  2B(g) + C(g), the initial pressure is PA = 90 mm Hg, the pressure after
10 minutes is found to be 180 mm Hg. What is the rate constant of the reaction ?
7. The activity of a radioactive sample reduced from 20 Ci to 1.25 Ci in 2000 years. What are the half -
life of the sample and its decay constant.
k1 k2
8. In the sequential chain reaction A   B   C at the steady state, the half life of B is 30 seconds,
then what will be the half life of A? Given that at any time, the number of atoms of A is twice the
number of atoms of B.
9. What is the percentage fraction of the molecule crossing over the energy barrier at 27ºC. Given that
Ea(b) = 80 cal, H = 20 cal and antilog (0.072) = 1.181.
10. At 278C the half life period for the first order thermal decomposition of ethylene oxide is 363 min and
the energy of activation of the reaction in 52,00 cal/mole. From these data estimate the time required
for ethylene oxide to be 75% decomposed at 450C.
Chemistry : Chemical Kinetics and Nuclear Chemistry

LEVEL - II
1. For the following reaction, the rate law has been determined to be
rate = k[A][B]2 with k = 2  106 mol2 L2 sec1
2A + B + C  A2B + C
For this reaction the initial conc of the various species.
[A] = 0.1 mol L1; [B] = 0.2 mol L1; [C] = 0.8 mol L1. Determine the rate after 0.04 mol L1 of A has
reacted.
2. For the reaction process A + B —— products, the rate is first order w.r.t A and second order w.r.t
B. If 1 mol each of A and B were introduced into a 1 L vessel, and the initial rate were 1  10-2 (mol/
L)sec-1. Calculate the rate when half the reactants have been turned into products.
3. 10g atoms of an -active radioisotope are disintegrating in a sealed container. In one hour helium gas
collected at STP is 11.2 litre. Calculate the half-life of the radioisotope.
4. The gas phase decomposition of dimethyl ether follows first-order kinetics.
CH3OCH 3(g) 
 CH 4(g)  H 2(g)  CO(g)
The reaction is carried out at constant volume in a container at 500°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.
5. In the Arrhneius equation for a certain reaction, the value of A and Ea (activation energy) are 4 × 1013
s–1 and 98.6 kJ mol–1, respectively. If the reaction is of first order, at what temperature will its half-life
period be ten minutes?
6. The reaction 2NO(g) + 2H2  N2(g) + 2H2O(g) has been studied at 904°C

Sl. No. Initial Concentration Rate of appearance of N2 (mol litre–1 sec–1

NO H2
1. 0.42M 0.122M 0.136
2. 0.21M 0.122M 0.0339
3. 0.21M 0.244M 0.0678
4. 0.105M 0.488M 0.0339
Determine the reaction order
7. The decomposition of N2O5 according to the equation 2N2O2(g) + O2(g) is a first order reaction. After 30
min from start of decomposition in a closed vessel the total pressure developed is found to be 284.5 mm
Hg. On complete decomposition, the total pressure is 584.5 mm Hg. Calculate the rate constant of the
reaction.
8. A certain physiologically important first order reaction has an activation energy equal to 45.0 kJ/mol at
normal body temperature (37°C). Without a catalyst, the rate constant for the reaction is 5.0 × 10–4s–
1
. To be effective in the human body, where the reaction is catalysed by an enzyme, the rate constant
must be at least 2.0 × 10–2s–1. If the activation energy is the only factor affected by the presence of the
enzyme, by how much must the enzyme lower the activation energy of the reaction to achieve the
desired rate?
 Chemistry : Chemical Kinetics and Nuclear Chemistry

1
9. The half-life period for the reaction, N 2 O5 
 2NO 2  O2 is 2.4 hours at 30°C. What time would
2
10 8
be required to reduce 5 × 10 molecules of N2O5 to 10 molecules?
10. For a certain reaction, it takes 5 minutes for the initial concentration of 0.5 mole/L to become 0.25
mole/L and another 5 minutes to become 0.125 mole/L.What is the order and specific rate constant of
the reaction?

LEVEL - III
1. Two I order reactions having same reactant concentration proceed at 25°C at the same rate. The
temperature coefficient of the rate of the first reaction is 2 and that of second reaction is 3. Find the
also of the rates of these reactions at 75°C.
2. In a certain reaction Bm+ is getting converted to B(n+4)+ in solution. The rate constant of this reaction is
measured by titrating a volume of the solution with a reducing agent which reacts only with Bn+ and
B(n+4)+. In this process, it converts Bn+ to B(n–2)+ and B(n+4)+ to B(n-1)+. At t = 0, the volume of reagent
consumed is 25 mL and at t = 10 min, the volume used is 32 mL. Calculate the rate constant of the
conversion of Bn+ to B(n+4)+ assuming it to be a first order reaction.
3. For the reaction
2NO + H2  N2O + H2O

dp
the value of  was found to be 1.50 torr s–1 for a pressure of 359 torr of NO and 0.25 torr s–1 for
dt
a pressure of 152 torr, the pressure of H2 being constant. On the other hand, when the pressure of NO
dp
was kept constant,  was 1.60 torr s–1 for a hydrogen pressure of 289 torr and 0.79 torr s–1 for a
dt
pressure of 1.47 torr. Determine the order of the reaction.
4. Calculate the value of rate constant and time required for solution to become optically inactive.
Time/min 0.0 7.2 36.8 46.0 68 
Rotation of Polarized light /degree 24.1 21.4 12.4 10.0 5.5 –10.7
5. Decomposition of H2O2 is a first order reaction. A solution of H2O2 labelled as 20 volumes was left
open. Due to this some H2O­2 decomposed. To determine the new volume strength after 6 hours, 10 Ml
of this solution was diluted to 100 Ml. 10 Ml of this diluted solution was titrated against 25 Ml of 0.025
M KmnO4 acidified solution. Calculate the rate constant for decomposition of H2O2.
6. The inversion of the sugar proceeds with constant half life of 500 minute at Ph = 5 for any concentration
of sugar. However, if Ph = 6, the half life changes to 50 minute. Derive the rate law for inversion of
cane sugar.
7. Bi-cyclohexane was found to undergo two parallel first order rearrangements. At 730 K, the first order
rate constant for the formation of cyclohexane was measured as 1.26 × 10–4 s–1 and for the formation
of methyl cyclopentene the rate constant was 3.8 × 10 –5s–1 . What was the % distribution of the
rearrangement products.
Chemistry : Chemical Kinetics and Nuclear Chemistry

8. If a reaction A  Products, the concentrations of reactant A are C0, Ac0, a2C0, a3C0.. after time
interval 0, t, 2t, 3t, …. Where a is constant. Given 0  a  1. Show that the reaction is of I order. Also
calculate the reaction in K, a and t.
9. For a homogeneous gaseous phase reaction 2A  3B + C, the initial pressure was P0 while pressure
at time ‘t’ was P. Find the pressure after time 2t. Assume first order reaction.
10. The decomposition of a compound A, at temperature T according to the equation.

2P(g) 
 4Q (g )  R (g)  S(l)
is the first order reaction. After 30 minutes from the start of decomposition in a closed vessel, the total
pressure developed is found to be 317 mm Hg and after a long period of time the total pressure
observed to be 617 mm Hg. Calculate the total pressure of the vessel after 75 minutes, if volume of
liquid S is supposed to be negligible. Also calculate the time fraction t7/8.
Given: Vapour pressure of S(l) at temperature T = 32.5 mm Hg.
 Chemistry : Chemical Kinetics and Nuclear Chemistry

SECTION - II
SINGLE CHOICE QUESTIONS
1. The instantaneous rate of disappearance of the MnO 4 ion in the following reaction is
4.56 × 10–3 Ms–1.

2MnO 4  10I   16H  

 2Mn 2   5I2  8H 2 O
The rate of appearance of I2 is
(a) 1.14 × 10–3 M s–1 (b) 5.7 × 10–3 M s–2
(c) 4.56 × 10–4 M s–1 (d) 1.14 × 10–2 M s–1
2. The rate constant for a zero-order reaction is

C0 C0  C t
(a) k  (b) k 
2t t

C0  Ct C0
(c) k  ln (d) k  C
2t t

3. The rate expression for the reaction A(g) + B(g)  C(g) is rate = kC2A C1/B 2 . What changes in the initial
concentrations of A and B will cause the rate of reaction to increase by a factor of eight?
(a) CA × 2; CB × 2 (b) CA × 2; CB+ × 4
(c) CA × 1; CB × 4 (d) CA × 4; CB × 1
4. In an exothermic reaction X  Y, the activation energy is 100kJ mol–1 of X. The enthalpy of the
reaction is –140 kJ mol–1. The activation energy of the reverse reaction Y  X is
(a) 40 kJ mol–1 (b) 340 kJ mol–1
(c) 240 kJ mol–1 (d) 100 kJ mol–1
5. The rate constant, the activation energy and the pre-exponential factor of a chemical reaction at 25°C
are 8.0 × 10–4 s–1, 112 kJ mol–1 and 4 × 1015 s–1 respectively. The value of the rate constant as T  
is
(a) 8 × 1016s–1 (b) 4 × 104s–1
(c) 4 × 1015s–1 (d) 112 × 1012s–1
6. Two first order reactions have half-lives in the ratio 3:2. Calculate the ratio of time intervals t1 : t2; t1 is
the time period for 25% completion of the first reaction and t2 for 75% completion of the second
reaction.
(a) 0.311:1 (b) 0.420:1
(c) 0.273:1 (d) 0.119:1
7. Which of the following rate law has an overall order of 0.5 for the reactions involving substances x,y,z?
(a) Rate = k(Cx) (Cy) (Cz) (b) Rate = k (Cx)0.5 (Cy)0.5 (Cz)0.5
o
R  Cx  Cz 
1.5 –1 0
(c) Rate = k(Cx) (Cy) (Cz) (d) Rate = 2
 Cy 
Chemistry : Chemical Kinetics and Nuclear Chemistry

8. The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary process. In an experiment, the initial
partial pressure of A & B are PA = 0.60 and PB = 0.80 atm. When PC = 0.2 atm the rate of reaction
relative to the initial rate is
(a) 1/48 (b) 1/24
(c) 9/16 (d) 1/6
9. For a second order reaction of the type rate = k [A]2, the plot of [A]t versus t is linear with a
(a) positive slope and zero intercept
(b) positive slope and non zero intercept
(c) negative slope and zero intercept
(d) negative slope and non zero intercept
10. If concentration are measured in mole/lit and time in minutes, the unit for the rate constant of a 3rd
order reaction are
(a) mol lit–1 min–1 (b) lit2 mol–2min–1
(c) lit.mol–1 min–1 (d) min–1
11. Radioactivity is affected by
(a) Temperature (b) Pressure
(c) State of chemical combination (d) None
12. No. of  – particles emitted during the change a X b c Y d is

ad a d
(a) (b) c   b
4  2 

 bd a d
(c) c   a (d) c   b
 2   2 
A1
13. For two atoms Z1 X and Z2 X A 2 where Z1  Z 2 and A1  A 2 , A1 – 2Z1 = A2 – 2Z2, the species
would be called
(a) Isotonic (b) Isodiaphers
(c) Isoters (d) none
14. Which statement is true about N/P ratio
(a) It increases by  –emission (b) It increases by  –emission
(c) It increases by  –emission (d) None of these
15. How many  and  particles should be eliminated so that an isodipher is formed
(a) n  , n  (b) n  , (n + 1) 
(c) n  (d) n 

16. 92 U  0 n1 92 U 236  Pr oducts  x 0 n1  3.2  10 11 J . The energy released when 1 gm of
235
92 U
235

finally undergoes fission is

(a) 12.75 × 108 kJ (b) 16.4 × 107 kJ
(c) 8.2 × 107 kJ (d) 6.5 × 106 kJ
 Chemistry : Chemical Kinetics and Nuclear Chemistry

17. At radioactive equilibrium the ratio between two atoms of radioactive elements A and B are 3×109 :
1. If t1/2 of A is 1010 years. What is t1/2 of B
(a) 30 years (b) 0.3 years
(c) 3.3 years (d) none
18. In the sequence of following nuclear reactions
238     n
92 X  Y   Z   L  84 M 218 the value of n is
(a) 3 (b) 4
(c) 5 (d) 6
1 4
19. The mass of 1H is 1.0076 amu and that of 2He is 4.0015 amu the energy released in the reaction
41 H1 2 He4  20 e1 is nearly
(a) 9 meV (b) 27 meV
(c) 36 meV (d) 54 meV
20. Co–60 has t1/2 = 5.3 years the time taken for 7/8 of the original sample of disintegrate will be
(a) 4.6 years (b) 9.2 years
(c) 10.6 years (d) 15.9 years
Chemistry : Chemical Kinetics and Nuclear Chemistry

SECTION - III
MULTIPLE CHOICE QUESTIONS
1. Molecularity of a reaction can’t be
(a) zero (b) (–) ve
(c) fractional (d) greater than 3 (genrally
2. For a 1st order reaction
(a) dx/dt = k(a–x)

2.302 a
(b) K  log
t ax

2.302 a  x1
(c) t 2  t1  k
log
a  x2

(d) Plot between t and log(a–x) will be straight line

3. For a 1st order reaction
(a) t 3/ 4  2t1/ 2 (b) t 7 /8  3t1/ 2

10
(c) t 99%  2t 90% (d) t 90%  t 50%
3
4. Conditions when K =a
(a) Ea = 0 (b) T = 0
(c) T   (d) all
5. Which are temperature independent?
(a) A (b) Ea
(c) R (d) K
6. Which is true statement
(a) lightest radioactive isotope is tritium
(b) nuclides having at no. > 82 are radioactive
(c) highest degree of radioactive is shown by uranium
(d) all of these are true
7. Primary emission is
(a)  –emission (b)  –emission
(c)  –emission (d) all
8. A radioactive element present in VIII group of the periodic table. If it emits one  –particle, the
new position of the nuclide will be
(a) VI B (b) VIII
(c) VII B (d) IB
 Chemistry : Chemical Kinetics and Nuclear Chemistry

9. Which is true about  emission

(a)  rays are the most penetrating
(b) emission of  rays leads to the formation of a new element
(c)  –emission is known as secondary emission
(d) all of these
10. Which is true about decay constant (  )
(a) unit of  is time –1
(b) value of  is always less than 1
(c)  is independent of temperature
(d)  is defined as the ratio of no. of atoms disintegrating per unit time to the total no. of atom
present at that time
Chemistry : Chemical Kinetics and Nuclear Chemistry

MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS

Write-up I
In a parallel reaction reactant cobalt which is a transition metal decays by parallel pathways to form
2 products B and C.

B
 - emission (k1 )

58
27 Co
  emission (k2 ) .

The ratio of concentration of [B] : [C] are 2 : 98 and the half life of Co is 22 years.

1. The decay constant for (B) should be

(a) 63  10–5 y–1 (b) 126  10–5 y–1
(c) 863  10–3 y–1 (d) None of these
2. The product B will be
(a) Copper (b) Manganese
(c) Nickel (d) Zinc
3. The product C will be
(a) Copper (b) Manganese
(c) Nickel (d) Iron

Write-up II
Ozone is prepared in laboratory by passing silent electric discharge through pure and dry oxygen in
an apparatus known as ozoniser. This conversion from oxygen to ozone is a reversible and endothermic
reaction. When oxygen is subjected to an ordinary electric discharge, most of the O3 produced will
get decomposed. When any insulating material such as glass, is inserted in the space between the
two electrodes and high current density is applied, silent electric discharge passes on between the
two electrodes. By this process no spark is produced and much less heat is generated, and as a
result the decomposition of the produced ozone is much retarded.
The decomposition of ozone is believed to occur by the following mechanism:
Kf
O3 O2  O (fast step)
Kb

K1
O3  O   2O 2 (slow)
 Chemistry : Chemical Kinetics and Nuclear Chemistry

4. Molecularity of reaction is defined by

(a) slow step (b) reversible step
(c) from overall reaction (d) fast step
5. When the concentration of O2 is increased, for the same concentration of ozone, its rate
(a) increases (b) decreases
(c) remains the same (d) cannot be answered
6. When the concentration of O3 is increased, for the same concentration of oxygen, its rate
(a) increases (b) decreases
(c) remains the same (d) cannot be answered

MULTIPLE MATCHING TYPE QUESTIONS

Match the following

7. Column – I Column – II
(a) Decomposition of H2O2 (p) 10t1/2

k 308 K
(b) k 298 K (q) 1st order

(c) Arrhenius equation (r) Temperature coefficient

k2 E a  T2  T1 
(d) t99.9% (s) log k  2.303 R  T T 
1  1 2 

8. Column – I Column – II
(a) Rate of reaction (p) Can be fractional
(b) rate constant (q) Will be a whole number
(c) Order of reaction (r) Decreases with increase in concentration
(d) Molecularity (s) Increases with increase in temperature
Chemistry : Chemical Kinetics and Nuclear Chemistry

ASSERTION-REASON TYPE QUESTIONS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.

9. Assertion : In zero order reaction, the conc. vs time graph is a straight line.
Reason : The rate of change of conc. per unit time in zero order reaction remains constant.
10. Assertion : Photochemical reactions always occur in the presence of light.
Reason : Photochemical reactions do not require activation energy.
11. Assertion : Many of photochemical changes have positive sign of , yet they are spontaneous.
Reason : The activation energy in photochemical reactions is provided by light energy.
12. Assertion : The order of a reaction can have a fractional value.
Reason : The molecularity of a reaction can have a fractional value.
13. Assertion : For a zero order reaction, rate of reaction is independent of conc. of reactants.
Reason : For a zero order reaction, reaction proceeds at a constant rate which is equal to rate
constant of the reaction.
14. Assertion : To separate U-235 from the more abundant, all the uranium converted into UF6
Reason : UF6 is one of the few compounds that exist in gaseous state under ordinary conditions
which helps in separation of U-235 from U-238.
30 40
15. Assertion : Nucleide 13 Al
is less stable than 20 Ca

Reason : Nucleide having odd number of protons and neutrons are generally unstable.
 Chemistry : Chemical Kinetics and Nuclear Chemistry

SECTION - V

A. Only one option is correct (Objective Questions)

23
1. A positron is emited from 11 Na
. The ratio of the atomic mass and atomic number of the resulting
nuclide is
(a) 22/10 (b) 22/11
(c) 23/10 (d) 23/12
2. Consider a reaction aG + bH  Products. When concentration of both the reactants G and H is
doubled, the rate increases by eight times. However, when concentration of G is doubled keeping the
concentration of H fixed, the rate is doubled. The overall order of the reaction is
(a) 0 (b) 1
(c) 2 (d) 3
23 24
3. 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
139 94
4. The number of neutrons accompanying the formation of 54 Xe
and 38 Sr
from the absorption of a slow
235
neutron by 92 U
, followed by nuclear fission is :
(a) 0 (b) 2
(c) 1 (d) 3
5. The rate constant for the reaction, 2N 2 O5  4NO 2  O2 is 3.0 × 10 –5 sec –1 . If the rate is
2.40 ×10–5 mol/L/sec., then the concentration of N2O5 (in mol/L) is :
(a) 1.4 (b) 1.2
(c) 0.04 (d) 0.8
6. If l 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
(c) I 2 (d) C.I
7. Consider the chemical reaction,
N 2  g   3H 2  g   2NH3  g 
The rate of this reaction can be expressed in terms of time derivatives of concentration of N2 (g), H2
(g) or NH3 (g). Identify the correct relationship amongst the rate expressions:
d  N2  1 d  H 2  1 d  NH 3  dN2  d H 2  d  NH3 
(a) Rate     (b) Rate    3 2
dt 3 dt 2 dt dt dt dt

d  N2  1 d  H 2  1 d  NH3  dN2  d H 2  d  NH 3 
(c) Rate     (d) Rate    
dt 3 dt 2 dt dt dt dt
Chemistry : Chemical Kinetics and Nuclear Chemistry

8. In a first order reaction the concentration of reactant decreases from 800 mol/dm3 in 2×104 sec. The
rate constant of reaction in sec–1 is :
(a) 2 × 104 (b) 3.45 × 10–5
(c) 1.386 × 10à (d) 2 × 10–4
9. (A) follows first order reaction. (A)  product
Concentration of A, changes from 0.1 M to 0.025 M in 40 minutes. Find the rate of reaction of A when
concentration of A is 0.01 M:
(a) 3.47 × 10–4 M min –1 (b) 3.47 × 10–5 M min –1
(c) 1.73 × 10–4 M min –1 (d) 1.73 × 10–5 M min –1
10. Which 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 power of concentration terms in differential rate law
(c) It is not affected with stoichiometric coefficient of the reactants
(d) Order can not be fractional

B. More than one options are correct (Objective Question)

1. The nuclear reactions accompanied with emission of neutron (s) are
17 4 30 12 1
(a) 13 Al  2 He 15 P (b) 6 C 1 H 14
7 N
30 30
(c) 14
15 P Si  e10 (d) 241
96 Am  24 He 97
244
Bk  e10
2. Decrease in atomic number is observed during :
(a) alpha emission (b) beta emission
(c) positron emission (d) electron capture

SUBJECTIVE
1. 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 the 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.

2. The rate constant of a reaction is 1.5  107 sec –1 at 50°C and 4.5  107 sec –1 at 100°C. Evaluate the
Arrhenius parameters A and E a .
3. A first order reaction A   B requires activation energy of 70 kJ mol –1 . When a 20% solution of
A was kept at 25°C for 20 minute, 25% decomposition took place. What will be the per cent decomposition
in the same time in a 30% solution maintained at 40°C ? Assume that activiation energy remains
constant in this range of temperature.
4. A 1st order reaction is 50% complete in 30 minute at 27°C and in 10 minute at 47°C. Calculate the :
(a) Rate constant for reaction at 27°C and 47°C
(b) Energy of activation for the reaction.
(c) Energy of activation for the reverse reaction if heat of reaction is –50 kJ mol –1 .
 Chemistry : Chemical Kinetics and Nuclear Chemistry

5. At 380°C, the half life period for the first order decomposition of H 2 O 2 is 360 min. The energy of
activation of the reaction is 200 kJ mol –1 . Calculate the time required for 75% decomposition at
450°C.
6. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the
reaction if the catalyst lowers the activation energy barrier by 20 kJ mol –1 .
The rate constant for the first order decomposition of a certain reaction is given by the equation,
1.25  104
ln K(sec –1 )  14.34 –
T
Calculate :
(a) The energy of activation
(b) The rate constant at 500 K.
(c) At what temperature will its half life period be256 minute?
8. Two reactions (I) A   Products (II) B   Products follow first kinetics. The rate of the
reaction (I) is doubled when temperature is raised from 300 K to 310 K. The half life for this
reaction at 310 K is 30 minute. At the same temperature B decomposes twice as fast as A. If the
energy of activation for the reaction (II) is half that of reaction (I), calculate the rate constant of
reaction (II) at 300 K.
9. From the following data from the reaction between A and B,

–1 –1
Initial rate mol litre–1 Sec–1
[A] mol litre [B] mol litre
300 K 320 K
2.5  10 –4 3.0  10 –5 5.0  10 –4 2.0  10 –3

5.0  10 –4 6.0  10 –5 4.0  10 –3 —

1.0  10 –3 6.0  10 –5 1.6  10 –2 —

Calculate :
(i) The order of reaction with respect to A and with respect to B.
(ii) The rate constant at 300 K.
(iii) The energy of activation.
(iv) The pre-exponential factor.
10. In the Arrhenius equation for a certain reaction, the values of A and E a (energy of activation) are
4  1013 sec –1 and 98.6 kJ mol –1 respectively. If the reaction is of first order, at what temperature will
its half life period be 10 minute?
Chemistry : Chemical Kinetics and Nuclear Chemistry

ANSWERS
EXERCISE - 1
4 d[O2 ] d[NO] 4 d[H 2 O]
1.   
5 dt dt 6 dt
2. 1.2 × 10–2 atm min–1
3. (a) 5 × 10–4 mol litre–1sec–1 (b) 1.25 × 10–4 mol litre–1 sec–1
(c) 2.5 × 10–4 mol litre–1sec–1

EXERCISE - 2
1. (a) K[A]1 [B]2 [C]0 (b) r2 = 8r1
1 2
2. rate = K [NO] [Br2 ]
3. (a) 2O3(g)  3O2(g);
(b) intermediate is O(g);
(c) first step is unimolecular second is bimolecular.

EXERCISE - 3
Do your self

EXERCISE - 4
1. (i) Greater the temperature dependence for reaction with larger value of Ea.
(ii) A = 6.73  1011 sec–1 K = 5.10  105sec–1 Ea = 92.011 Kj /mol
2. (a) 1.386 × 10–4s–1
(b) 2000s
(c) 124.46kJ mol
3. T = 282 K

EXERCISE - 5
1. 0.537
2. (a) 132 sec (b) 0.58 mol dm–3
(c) [A] = 0, [B] = 0.12 mol dm–3, [C] = 0.88 mol dm–3

EXERCISE - 6
1. 14,000 years
2. Specific activity = 30.69 dis.g–1s–1
239 240
3. Pu = 45.1%, Pu = 54.9%
 Chemistry : Chemical Kinetics and Nuclear Chemistry

SECTION - I
(Subjective Questions)
LEVEL - I

1. 127.7 s 2. 0.069 min–1

3. 40 sec 4. 4.37 × 108 yr–1
5. 327°C 6. 1.15 × 10–3 sec–1
7. 500 yrs and 1.386 × 10–3 yrs–1 8. 60 sec
9. 84.7% 10. 236.48 min

LEVEL - II

1. 3.38  10–9 mol L–1 sec–1 2. 1.25  10–3

3. 13.51 hours 4. 0.7488 atm
5. 311.35K 7. K1 = 5.2 × 10–3 min–1
8. 10kJ/mol 9. 21.5 hours
–1
10. First; 0.138 minute .

LEVEL - III

1. 7.5937 2. 2.07 × 10–2 min–1

3. rate = k[NO]2 [H2] 4. k = 0.0119, t = 105.4 min
5. 0.022 hr–1 6. K [Sugar]1 [H+]0
7. 0.768, 0.232
8. K comes constant and thus, it is I order reaction
2.303 1
K log
t a

(2P 0  P) 2
9. PT  2P 0 
P0
10. Pt = 268.11 mm Hg, t7/8 = 43.76 min
Chemistry : Chemical Kinetics and Nuclear Chemistry

SECTION - II
(Single Choice Questions)

1. (d) 2. (b)
3. (b) 4. (c)
5. (c) 6. (a)
7. (c) 8. (d)
9. (b) 10. (b)
11. (d) 12. (c)
13. (b) 14. (b)
15. (c) 16. (c)
17. (c) 18. (b)
19. (b) 20. (d)

SECTION - III
(Multiple Choice Questions)

1. (a, b, c, d) 2. (a, b, c, d)
3. (a, b, c, d) 4. (a, c)
5. (a, b, c) 6. (a, b)
7. (a, b) 8. (a, b, c)
9. (a, c) 10. (a, b, c, d)

SECTION - IV
(Comprehension Type Questions)

1. (a) 2. (c)
3. (d) 4. (a)
5. (b) 6. (a)

(Multiple Matching Type Questions)

7. (a) (q) (b) (r)

(c) (s) (d) (p)
8. (a) (r, s) (b) (s)
(c) (p, q) (d) (q)
 Chemistry : Chemical Kinetics and Nuclear Chemistry

(Assertion Reason Type Questions)

9. (a) 10. (c)

11. (b) 12. (c)
13. (b) 14. (a)
15. (a)

SECTION - V

A. Only one option is correct (Objective Questions)

1. (c) 2. (d)
3. (a) 4. (d)
5. (d) 6. (d)
7. (a) 8. (c)
9. (a) 10. (d)

B. More than one option are correct (Objective Questions)

1. (a, d) 2. (a, c, d)

SUBJECTIVE
1. K318 = 9.22 × 10–4 sec–1
Ea = 18.3 kcal mol–1
2. Ea = 2.2 × 104 J mol–1
A = 5.42 × 1010
3. 67.21%
4. (a) K1 at 27°C = 2.31 × 10 –2 min–1
K2 at 47°C = 6.93 × 10 –2 min–1
(b) Ea = 43.85 kJ mol–1
(c) 93.85 kJ mol–1
5. 20.39 min 6. 100 kJ mol–1
7. 24.83 k cal mol–1 , 2.35 × 10–5 sec–1 ; T = 513 K
8. 0.0327 min–1
9. (i) 2 and 1
(ii) 2.66 × 108 litre2 mol–2 sec–1
(iii) 55.33 kJ
(iv) 1.140 × 1018
10. 311.35 K