LOCUS 20

MISCELLANEOUS EXAMPLES

Example – 18

Under certain conditions the reaction between sulphate (S O 24 ) ions and hydrogen ions is first order in each of
them, i.e., rate k[SO 24 ] [H+]. A student measured the initial rate of the reaction four times using the combinations
of solutions shown in the following table. Write down the actual concentrations of both ions in each experiment and
hence determine the value of the rate in terms of k.

_____________________________________________________________________________

Experiment Solution of sulphate ions Solution of hydrogen ions

Concentration volume Concentration volume
/mol dm–3 /cm3 /mol dm–3 /cm3
_____________________________________________________________________________

A 0.5 125 0.05 125

B 0.5 250 0.05 250
C 0.5 500 0.05 500
D 0.5 500 0.05 125
_____________________________________________________________________________

Critical thinking
(1) You will have to think carefully about the difference between concentration and volume.
(2) In the rate law for a reaction, the concentration used are in terms of the number of moles of each
reacting species w.r.t. the total concentration of the solution. Here the concentrations given are
of the reactants before they have been brought together for reaction. We have been given the
volume of each of the reactants’ solution. When they are mixed, the total volume will change and
hence, the concentration of the reacting species will change too. It is these new concentrations of
the reacting species that should be put in the rate law to get the respective rate of reaction.

Solution: As pointed out the key thing to remember is that the rate will change if the concentrations of the
reagents change.
In experiment A when the two solutions are mixed, the total volume becomes 250 cm3. This is twice
the volume of each of the separate solutions, so their concentrations are halved just as they are brought
together to react.
0.5 M
Hence, the concentration of SO 24 (0.5 m in a 125 cm3 solution) becomes in a 250 cm3
2
0.05
solution. And the concentration of H+ ions (0.05 M in a 125 cm3 solution) becomes in a 250 cm3
2
solution.

Chemistry / Chemical Kinetics

LOCUS 21

So, rate of the reaction in this case will be given by,

0.5 0.05
rate k [substituting nto the given rate law]
2 2
rate = k × 6.25 × 10–3
You are requested to provide the solution for experiments B, C and D yourself. The answers are given
here:
(B) rate = k × 6.25 × 10–3
(C) rate = k × 6.25 × 10–3
(D) rate = k × 4.00 × 10–2

Example – 19

A certain compound A, was found the undergo two parallel first order rearrangements, forming B and C respectively
in the two arrangements. At 25° C, the first order rate constant for the formation of B was measured as
1.0 × 10– 5 s– 1 and for the formation of C as 2.0 × 10– 6 s– 1. What is the percentage distribution of the rearrangement
products?
Critical thinking
What the question says is that the same compound A has tendency to form two different products
by two different paths and both these different reactions can occur simultaneously:
–1
–5
× 10 s B
= 1.0
k1
A k2 = 2.
0 × 1 –6
0 s–1
C
Here, we can write the various rate laws as:
d A
– k1 A k 2 A ... (i)
dt
d B
k1 A ... (ii)
dt
d C
k2 A ... (iii)
dt
Dividing (ii) by (i), we get,
d B
dt k1 A
d A k1 A k2 A
dt
d B k1 A
d A k1 k 2 A
Hence LHS gives us the fraction of amount of B formed to amount of A reacted and this is equal to
k1
k1 k 2 . Can you see that you have all the information and analysis you need to get the answers for
this question?
Chemistry / Chemical Kinetics
LOCUS 22

B
k1
Solution: A k2

k1
percentage of B formed can be obtained by 100
k1 k 2

1.0 10 – 5
100
1.0 10 – 5 2.0 10 – 6

1 10 –5
100
1.0 10 – 5 0.2 10 – 5
= 83.33 %

k2
percentage of A formed can be obtained by 100
k1 k 2

2.0 10 – 6
100
1.0 10 – 5 2.0 10 – 6

0.2 10 – 5
100
1.0 10 – 5 0.2 10 – 5
16.67 % .

Example – 20

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 the reaction at 310 K is 30 min. 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 the reaction (ii) at 300 K.

Critical thinking
The problem is actually very simple as all you have to do is certain calculations in a logical order.
Arrange all the data in a diagram and it will be immediately clear to you so as to how you can solve
this question.
In the solution to this problem, you will be provided with the rough draft of the data and then how
it can be reorganised to see for yourself so as to how solution can be obtained.
It is expected of you that you make the rough draft and its reorganisation yourself first and then
compare it with the one given here.
It is expected then that you provide the complete solution yourself. The answer is provided for
cross-checking.

Chemistry / Chemical Kinetics

LOCUS 23

Solution: Rough Draft (data collection from Question)

2k A 300 K kA 310 K ... (i)

t 1 for (i) at 310 K 30 min

... (ii)
2

kB 310 K 2 kA 310 K ... (iii)

1
Ea ii E ... (iv)
2 a i

k B 300 K ? ... (v)

Reorganised draft

2kA (300 K) = kA (310 K)

and get value of kA at both
0.693 temperatures
30 min =
kA (310 K)

Use in two temperature get value of kB (310 K)

form of Arrhenius Equation (using (iii))
to get Ea (i) we have Ea (ii)
(using (iv))

Use both these informations in the two temperature

form of Arrhenius equation to get kB (300 K)

1 0.0462 min –1
Answer kB 300 K kB 310 K 0.0327 min –1
2 2

Chemistry / Chemical Kinetics

LOCUS 24

EXERCISE

Rate of Reaction and Rate Law

Q. 1 How will the rate of reaction 2 NO g O2 g 2NO 2 g change if the volume of the reaction
vessel is deminished to one third of its initial value? (The rate law for this reaction involves all reactants and
their respective orders are same as the stoichiometric coefficients.)
Q. 2 One mole of gas A and two moles of gas B are introduced into one vessel, and two moles of gas A and one
mole of gas B into a second vessel having the same capacity. The temperature is the same in both vessels.
Will the rate of the reaction between gases A and B in these vessels differ if it is expressed by the equation
(a) rate1 = k1[A] [B]; (b) rate2 = k2 [A]2[B]?
Q. 3 The reaction between substances A and B is expressed by the equation A + 2B C. The initial
concentrations of the reactants are [A]0 = 0.03 mol/l and [B]0 = 0.05 mol/l. The rate constant of the
reaction is 0.4. Find the initial rate of the reaction and the rate after a certain time when the concentration
of substance A diminishes by 0.01 mol/l. (rate = k[A][B]2)
Q. 4 How will the rate of the reaction 2NO(g) + O2(g) 2NO2(g) change if (a) the pressure in the system is
increased three times; (b) the volume of the system is diminished to one-third of its initial value; and (c) the
concentration of the NO is increased three times? (rate = [NO]2[O2] )
Q. 5 Rate of a reaction A + B products, is given below as a function of different initial concentrations of A
and B:
[A] (mol/l) [B](mol/l) Initial rate (mol/l/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?
Q. 6 For the given reaction, A + B products, following data were obtained.
[A] (mol/l) [B](mol/l) Initial rate (mol/l/min)
[A0] [B0] R0(mol L– 1 s– 1)
1. 0.1 0.2 0.05
2. 0.2 0.2 0.10
3. 0.1 0.1 0.05
(a) Write the rate law expression (b) Find the rate constant
Q. 7 The reaction, H2(g) + Br2(g) 2 HBr(g) has a rate given by the rate law, Rate = k [H2][Br2]1/2. (a) What
are the units of the rate constant k? (b) If the volume of the gas mixture is halved, by what factor is the rate
changed?
Q. 8 The reaction v1A + v2B products is first-order with respect to A and zero-order with respect to B. If
the reaction is started with [A]0 and [B]0, the integrated rate expression of this reaction would be
A A A 0 A
k1t (c) ln A v1k1t (d) ln
0 0
(a) ln k1t (b) ln 0 –v1k1t
A x A v1x 0
v1x A v1x
0 0 0

Chemistry / Chemical Kinetics

LOCUS 25

Q. 9 Rate of a reaction, A + B products is given as a function of different initial concentrations of A and B.

[A]/mol L– 1 [B]/mol L– 1 r0/mol L– 1 min– 1
__________________________________________________________________________________

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?
Q. 10 For a first order reaction A B, the concentration of B at two instant is given: [B] t = 10 sec = 1.0 M and
[B] t = 25 sec = 4.0 M. Using this information can you calculate the instantaneous rate of the reaction at at least
one instant in the interval from t = 10 sec to t = 25 sec.

Q. 11 If the steady-state concentration of O3 in a polluted atmosphere is 2.0 × 10– 8 mol/L, the rate of production
of O3 is 7.2 × 10–13 M/hr, and O3 is destroyed by the reaction, 2 O3 3 O2, what is the rate constant for
the reaction, assuming a rate law, Rate = – (1/2) [O3]/ t = k [O3]2?

Q. 12 In the enzymatic fermentation of sugar, the sugar concentration decreased from 0.12 M to 0.06 M in
10 hours, and to 0.03 M in 20 hours. What is the order of the reaction? What is the rate constant k?

Q. 13 The rate law for the reaction, Ce4+(aq) + Fe2+(aq) Ce3+(aq) + Fe3+(aq), is: Rate = (1.0 × 103 M–1s–1)
[Ce4+][Fe2+]. If 0.500 L of 0.0020 M Ce(SO4) 2 is rapidly mixed with 0.500 L of 0.0020 M FeSO4, how
long does it take for [Fe2+] to decrease to 1.0 × 10– 4 M?

Integrated Rate Equation

Q. 14 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
Q. 15 At constant temperature and volume, X decomposes as
2X(g) 3Y(g) 2Z(g); Px is the partial pressure of X.

Observation No. 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.

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LOCUS 26

Q. 16 While studying the decomposition of gaseous N2O5 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?

Q. 17 The rate constant for the first-order decomposition of N2O5(g) to NO2(g) and O2(g) is 7.48 × 10– 3 s– 1 at
a given temperature. (a) Determine the length of time required for the total pressure in a system containing
N2O5 at an initial pressure of 0.1 atm to rise to 0.145 atm. (b) Find the total pressure after 100 s of the
reaction.

The Arrhenius Equation.

Q. 18 The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction at 25° C are
3.0 × 10– 4s– 1, 104.4 kJ mol– 1 and 6.0 × 1014s– 1 respectively. The value of the rate constant as T
is,
(a) 2.0 × 1018 s– 1 (b) 6.0 × 1014 s– 1 (c) infinity (d) 3.6 × 1030 s– 1

Q. 19 At 380° C, the half-life period for the first order decomposition of H2O2 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.

Q. 20 The rate constant for the first order decomposition of a certain reaction is described by the equation
log(k/s– 1) = 14.34 – (1.25 × 104 K)/T
(i) What is the energy of activation of this reaction?
(ii) At what temperature will its half-life be 256 minutes?

Q. 21 The rate constant of a reaction is 1.5 × 107 s– 1 at 50° C and 4.5 × 107 s– 1 at 100° C. Evaluate the
Arrhenius parameters A and Ea.

Q. 22 A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the 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 barrier by 20 kJ mol– 1.

Q. 23 The activation energy of a certain reaction is 15 kJ/mol. The reaction is exothermic, yielding 19 kJ/mol.
What is the activation energy of the reverse reaction?

Q. 24 The activation energy of the reaction O3(g) + NO(g) O2(g) + NO2(g) is 10 kJ/mol. How many times
will the rate of the reaction change when the temperature is raised from 27 to 37° C?
Q. 25 The Ea of the reaction M + N O + P is 80 kJ/mol. At 50° C, the products are formed at the rate of 0.15
mol/L/min. What will be rate of formation of products at 100° C?

Q. 26 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.

Q. 27 A substance A was found to undergo two parallel first-order rearrangements A B and A C with rate
constants 1.26 × 10– 4 s– 1 and 3.8 × 10– 5 s– 1, respectively. What were the percentage distribution of B and
C?

Chemistry / Chemical Kinetics

LOCUS 27

TRY YOURSELF

[ ANSWERS KEY ]

TRY YOURSELF - I

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

4. (d) 5. (c) 6. (d)
7. 16 times 8. [A]0 = 0.042 mol/l
[B]0 = 0.014 mol/l

zeroth order
rate of reaction

second order

9.
first order

concentration of reactant

10. rate = k [conc.] for a first order reaction. We can see that the slope is given by the
value of k here.

TRY YOURSELF - II

1. (i) 5.0 × 10– 5 mol L– 1 s– 1 (ii) 4.175 × 10– 5 mol L– 1 s– 1

2. (c) 3. (c)

4. (i) 5.26 % (ii) 4.62 × 10 5 seconds

5. 3.44 × 10– 3 M min– 1

2.303 200
6. k = 5.21 × 10– 3 min– 1 – log
(30 min) 233.8

Chemistry / Chemical Kinetics

LOCUS 28

TRY YOURSELF - III

1. (A), (D) 2. very high temperature (or) zero activation energy

3. (c) 4. (b), (c) 5. (c)

6. False 7. False

8. False (The rate of reaction increases with increasing temperature because the no. of molecules
with Ea increases as the temperature increases. This has nothing to do with the reaction being
exothermic/endothermic)

9. 311 K 10. k27° C = 0.0231 min– 1 11. 227 kJ/mol

Ea = 43.85 kJ/mol

12. (a) Yes (b) No 13. No 14. reverse one

15. 5 times 16. 49.9 kJ/mol 17. 80.3 kJ/mol

18. (b), (d) 19. (b) 20. 283 K

Chemistry / Chemical Kinetics

LOCUS 29

EXERCISE

[ ANSWERS KEY ]

1. grow by 27 times. 2. (a) No, (b) Yes

3. 3 × 10– 5, 7.2 × 10– 6 4. (a) It will grow 27 times
(b) It will grow 27 times
(c) It will grow 9 times
5. 1, 0, 1.386 minutes 6. (a) R0 = k[A0]
(b) 0.5 sec– 1
7. (a) (mol/L)– 1/2 s– 1 8. (c)
(b) 2.8
9. (a) one, zero
(b) 1.386 minutes
10. Hint: Use mean value theorem (differential calculus).
11. 0.25 M– 1 s– 1 12. (a) first order (b) 6.9 × 10– 2 hr– 1
13. 9 seconds 14. (A), (B), (D)
15. (i) 1 16. first order related
(ii) 6.93 × 10– 3 min– 1
(iii) 200 min
(iv) 950 mmHg
17. (a) 47.7 seconds 18. (b)
(b) 0.180 atm.
19. 20.4 minutes. 20. Ea = 2.39 kJ/mol; T = 669 K
21. A = 5.45 × 1010 s– 1; Ea = 22012.7 J/mol. 22. 100 kJ/mol
23. 34 kJ/mol. 24. 1.14 times
k100 C
25. Hint: (rate)100° C = (rate)50° C
k 50 C

26. Hint
2.303 100 2.303 100 gives k 298 K Ea ? use in two temperature
log t log
k 298 K 90 k 308 K 75 k 308 K from of Arrhenius eqn to get E a

k318K = ?
Ea / RT
use k A.e
(pre exponential factor)

k 318 K 9.43 10 4 s 1

Ea 76.5 kJ / mol
Q. 27 76.83% B and 23.17% C
Chemistry / Chemical Kinetics