27

TOPIC 7 - THE RATE OF CHEMICAL REACTIONS

Examples of Solved Problems
1. The rate of formation of C in the reaction 2A + 3B C + 4D is 2.7 mol dm
-3
s
-1
. State
the rates of formation and consumption of the participants.

Answer:

1 3 1 3
1 3 1 3
1 3 1 3
1 3
8 . 10 ) 7 . 2 ( 4
] [
D, of formation of rate The
1 . 8 ) 7 . 2 ( 3
] [
4 . 5 ) 7 . 2 ( 2
] [
2
] [
A of n consumptio of rate The
] [
4
1 ] [ ] [
3
1 ] [
2
1
7 . 2
dt
d[C]
C of formation of rate The




= =
= =
= = =
= = = =
= =
s dm mol s dm mol
dt
D d
s dm mol s dm mol
dt
B d
s dm mol s dm mol
dt
C d
dt
A d
dt
D d
dt
C d
dt
B d
dt
A d
Rate
s dm mol


2. The rate law for reaction A + 2B 3C + 4D was reported as
d[C]/dt= k
r
[A][B][C]. Express the rate law in terms of the reaction rate; what is
the units for k
r
in each case?
Answer:


1 6 2
3 3
1 3
) ( ] ][ ][ [
;
] ][ ][ [
] [
4
1 ] [
3
1 ] [
2
1 ] [

= = =
= = = = =
s dm mol
dm mol
s dm mol
C B A
Rate
k
k of Unit
C B A k
dt
D d
dt
C d
dt
B d
dt
A d
Rate
r
r
r


3. At 518
o
C, the rate of decomposition of a sample of gaseous acetaldehyde,
initially at a pressure of 363 Torr, was 1.07 Torr s
-1
when 5.0 percent had reacted
and 0.76 Torr s
-1
when 20.0 per cent had reacted. Determine the order of the
reaction.
Answer:

( )
reaction order second 00 . 2 99 . 1
0746 . 0
1486 . 0
1875 . 1 log
4079 . 1 log
1875 . 1 log 4079 . 1 log 1875 . 1
80 . 0
95 . 0
4079 . 1
) 20 . 0 (
) 05 . 0 (
%) 20 (
%) 5 (
76 . 0
07 . 1
2
1
) ( ) (Pr ] [
1
1
= = =
= =
|

\
|
=

= =
=

n
n
P P k
P P k
P k
P k
s Torr
s Torr
rate
rate
x P k rate A essure A Rate
n
n
n
o o
n
o o
n
o
n
o
n
o
n n

28



4. At 518
o
C, the half-life for the decomposition of a sample of gaseous
acetaldehyde, initially at 363 Torr was 410 s. When the pressure was 169 Torr,
the half-life was 880 s. Determine the order of the reaction.

Answer:

reaction order second 00 . 2 999 . 1 999 . 0 1
999 . 0
3320 . 0
3317 . 0
1479 . 2 log
4659 . 0 log
) 1 (
1479 . 2 log ) 1 ( 4659 . 0 log
) 1479 . 2 (
) 169 (
) 363 (
4659 . 0
880
410
) 2 (
) 1 (
1
] [
1
,
1
1
1
2 / 1
2 / 1
1
1
0
1
2 / 1
= + =
=

= =
=
= = = =

n
n
n
C
C
s
s
t
t
P
P A
t life Half
n
n
n
n
o
n n
o

5. A second-order reaction of the type A + B P was carried out in a solution that
was initially 0.075 mol dm
-3
in A and 0.060 mol dm
-3
in B. After 1.0 h the
concentration of A had fallen to 0.020 mol dm
-3
. Calculate the rate constant.

1 1 3 5
10 754 . 1
66326
2231 . 0 3863 . 1
2231 . 0 66326 3863 . 1
060 . 0
075 . 0
ln ) 60 60 1 ( ) 060 . 0 075 . 0 (
055 . 0 060 . 0
020 . 0
ln
055 . 0 020 . 0 075 . 0 ] [ ] [ ] [ ] [
] [
] [
ln ] [ ] [
] [
] [
ln
] [
] [
ln : law rate d intergrate The
, : type reaction sec For

=

= + =
+ =

= = = =
+ =

=
+
s mol dm k k
s k
B B A A x
B
A
kt B A
x B
x A
B
A
P B A order ond
o o
o
o
o o
o
o

6. A reaction 2B P has a secondorder rate law with k = 4.3010
-4
dm
3
mol
-1
s
-1
.
Calculate the time required for the concentration of B to change from 0.210 mol
dm
-3
to 0.010 mol dm
-3
.
( )
s s t
t s mol dm mol dm
dm mol dm mol
k kt
B B
B B B B
dt k B d B
B
B d
B k
dt
B d
P B order ond
o t
t t
t B
B
B
B
t
o
t
o
5
1 1 3 4 1 3
3 3
1
0
1 1 2
0
1 2
0
] [
] [
2
] [
] [
2
2
10 11 . 1 110742
10 60 . 8 ) 762 . 4 100 (
210 . 0
1
010 . 0
1
0 2 2
] [
1
] [
1
1
] [
1
] [
1 2
] [
1 2
] [
2 ] [ ] [
] [
] [
] [ 2
] [
: law rate The , 2 : type reaction sec For
= =
= =
= =

=
(

+

+

= =
=


+ +

29

7. Hydrogen peroxide reacts with thiosulfate ion in slightly acidic solution as
follows: H
2
O
2
+ 2S
2
O
3
2-
+2H
+
2H
2
O + S
4
O
6
2-


This reaction is second order, independent of the hydrogen ion concentration in
the pH range 4 to 6. The rate constant, k = 9.110
-2
mol
-1
L min
-1
were obtained at
25
o
C and pH 5.0, and initial concentrations: [H
2
O
2
] = 0.036 mol L
-1
, [
3
3 2
O S ] =
0.024 mol L
-1
. How long will it take for 50% of the thiosulfate ion,
3
3 2
O S to
react?

Answer:
s t t
t
x B x bx
b a O S B O H A
B
A
kt B a A b
bx B
ax A
B A k
dt
A d
P bB aA
o
o
o
o o
o
o
06 . 117 405 . 0 10 68 . 4 9163 . 0
024 . 0
036 . 0
ln ) 10 1 . 9 ))( 024 . 0 ( 1 ) 036 . 0 ( 2 (
) 10 0 . 6 ( 2 024 . 0 (
) 10 0 . 6 036 . 0 (
ln
10 0 . 6 024 . 0 25 . 0 , ] %[ 50 2
2 ,. 1 , ] [ ], [ ] [
] [
] [
ln ) ] [ ] [ (
) ] ([
) ] ([
ln : equation rate ed interagrat The
] ][ [
] [
: law rate The , : type reaction order second For
3
2
3
3
3
2
3 2 2 2
= + =
+ =


= = = =
= = = =
+ =

= +

Exercise 7a

1. If the reaction aA Products is x
th
-order, where x = 0, x = 1, x = 2 and x = n (any
integer 1). Write the rate law, derive the integrated rate law, and also derive the
expression for half-life in terms of a, k
,
n

and [A]
o
for each order.

2. The gas-phase formation of fosgene, CO + Cl
2
COCl
2
, is order with respect to
CO. Derive the integrated rate equation for -order reaction and derive the
expression for the half-life.

3. The rate of the reaction A + 2 B 3 C + D was reported as 1.0 mol dm
3
s
1
. Which
of the following states of the rates is NOT TRUE.
A. d[A]/dt =1.0 mol dm
3
s
1
B. d[B]/dt =2.0 mol dm
3
s
1

C.-d[C]/dt=3.0 mol dm
3
s
1
D.- d[D]/dt= -1.0 mol dm
3
s
1

4. The rate law for the reaction A + 3 B C + 2 D was found to be v = k[A][B].
Which of the following state(s) is/are true.
I The unit of the rate of reaction is mol
-1
L s
-1
II The unit of k is mol
-1
L s
-1

III The reaction is second order reaction IV Rate = ] ][ [ / ] [ B A k dt C d =
A. I and III B. II and III C. I, II , and III D. IV only

5. Nitrogen pentoxide gas decomposes according to: 2N
2
O
5
(g) 4 NO
2
(g) + O
2
(g) .
At 328 K the rate of reaction v under certain conditions is 3.38 10
5
s
1
. Assuming
that none of the intermediates have appreciable concentrations. Which values is true.
A. -d[N
2
O
5
]/dt=3.38 10
5
s
1
B. d[NO
2
]/dt=3.38 10
5
s
1

C.-d[O
2
]/dt= 3.38 10
5
s
1
D. d[O
2
]/dt=3.38 10
5
s
1


30

6. In studying the decomposition of ozone: 2O
3
(g) = 3O
2
(g)
in a 2-L reaction vessel, it is found that d[O
3
]/dt = -1.510
-2
mol L
-1
s
-1
. What is the
rate of reaction in mol L
-1
s
-1
?
A.7.510
3
B.1.510
-2
C. -1.510
-2
D. - 7.510
3


7. Under certain conditions, it is found that ammonia is formed from its elements at a
rate of 0.10 mol L
-1
s
-1
. N
2
(g) + 3H
2
(g) = 2NH
3
(g) . Calculate the value of d[H
2
]/dt?

A. 0.10 mol L
-1
s
-1
B. 0.20 mol L
-1
s
-1
C. 0.30 mol L
-1
s
-1
D. -0 .30 mol L
-1
s
-1


8. The decomposition of N
2
O
5
: 2N
2
O
5
= 4NO
2
+ O
2
is studied by measuring the
concentration of O
2
as a function of time, and it is found that
d[O
2
]/dt = (1.5 10
-4
s
-1
)[N
2
O
5
] at constant temperature and pressure. Under these
conditions the reaction goes to completion to the right. Calculate the half-life of the
reaction under these conditions?
A. 4621s B. 2310 s C. 1155 s D. 577 s

9. At 400 K, the t
1/2
for the decomposition of a sample of a gaseous compound initially at
55.5 kPa was 340 s. When the P was 28.9 kPa, the t
1/2
was 178 s. The order of the
reaction is
A. n = 0 B. n =1 C. n = 2 D. n = 3

10. The composition of HI to H
2
+ I
2
at 508
o
C has a t
1/2
of 135 min when the initial
pressure of HI is 0.1 atm and 13.5 min when the pressure is 1 atm. What is the order
of the reaction?
A. n = 0 B. n =1 C. n = 2 D. n = 3

11. The rate constant for the first-order decomposition of a compound A in the reaction
2A P is k = 2.78 10
7
s
1
at 25C. Calculate the half-life of A?
A. 2.78 10
7
s
1
B. 1.25 10
6
s
1

C. s
4
10 5 . 2
D. 1.25 10
6
s
1


12. The first-order reaction 2A 2B + C is 35% complete after 325 s. How long will it
take for the reaction to be 70% complete?
A. 325 s B. 650 s C. s 908 D. 6.63 10
4
s

13. The t
1/2
of a first-order reaction A P is 12 min. What % of A remains after 50 min?
A. 5.6 % B. 6.5 % C. % 08 . 9 D. 16.63 %

14. The decomposition of ammonia at 1000
o
C was a zero-order reaction with rate constant,
k = 4.30 mol dm
-3
s
-1
.What is the t
1/2
for this reaction in which the initial concentration,
[NH
3
]
o
=0.0560 M?
A. 77 s B. 4.15 s C. 1.3010
2
s D. 1.6110
1
s

15. A solution of A is mixed with an equal volume of a solution of B containing the same
number of moles, and the reaction A + B = C occurs. At the end of 30 min. A is 75%
reacted. How much of A be left at the end of 50 min if the reaction is zero order in
both A and B?
A. 85% B. 60% C. 40% D. 15%


31

Exercise 7b

1. The rate law for the reaction 2A A
2
was found to be r = k [A]
2
. Which of the
following state(s) is / are FALSE.
A The unit of the rate of reaction is mol L
-1
s
-1
C. The unit of k is mol L
-1
s
-1

B The reaction is second order reaction D. -
2
2
] [ / ] [ A k dt A d
A
=

2. A solution of A is mixed with an equal volume of a solution of B containing the same
number of moles, and the reaction A + B = C occurs. If the reaction is first order in
both A and B, what is the rate law?
A. Rate = k[A][B] C. d[B]/dt = k([A]
o
-x)([B]
o
-x)
B. d[C]/dt = k[A]
2
= k[B]
2
D. -d[B]/dt = k([A]
o
-x)([B]
o
-x)

3. The half-life, t
1/2
of a reaction is the time required for half of the reactant to disappear.
Which of the following state(s) is / are true?
A. For a zero-order reaction, t
1/2
is dependent of the initial concentration.
B. For a first-order reaction, t
1/2
is independent of the initial concentration.
C. For a 2
rd
-order reaction, t
1/2
is inversely proportional to the initial concentration
D. All of the above are true.

4. A dimer is formed in the solution reaction 2A A
2
. The rate law is r = 2k[A]
2
,where k
= 0.015 M
-1
s
-1
. What is the half-life of A when [A]
o
= 0.05 M?
A.1333 s B.667 s C. 1.5 s D. 1.510
2
s

5. A reaction 2 A P has a rate law with k = 3.50 10
2
dm
3
mol
1
s
1
. Calculate the
time required for the concentration of A to change from 0.26 mol L
1
to 0.11 mol L
1

A. 75 s B. 150 s C. 750 s D. 1333 s

6. A gas reaction 2A B is second order in A and goes to completion in a reaction
vessel of constant volume and temperature with a half-life of 600 s. If the initial
pressure of A is 1 bar, what are the partial pressure of A at 800 s?
A. 0.328 bar B. 0.430 bar C. 0.504 bar D. 0.845 bar

7. A solution of A is mixed with an equal volume of a solution of B containing the same
number of moles, and the reaction A + B = C occurs. At the end of 30 min A is 65%
reacted. How much of A be left at the end of 50 min if the reaction is first order in
both A and B?
A. 84.8 % B. 75.6 % C. 48.8% D. 24.4%

8. Equal molar quantities of A and B are added to a liter of a suitable solvent. At the end
of 500 s one-half of A has reacted according to the reaction A + B = C. How much of
A will be reacted at the end of 800 s if the reaction is second order with respect to A
and zero order with respect to B?
A. 61.5 % B. 57.6 % C. 38.5% D. 26.0%

9. The second-order rate constant for an alkaline hydrolysis of ethyl formate in 85%
ethanol (aqueous) at 29.86
o
C is 5.43 L mol
-1
s
-1
. If the reactants are both present at
0.01 mol L
-1
, calculate the t
1/2
.
A.0.13 s B. 5.43 s C. 18.42 s D. 85 s

32

10. A second-order reaction of the type A + B P was carried out in a solution that
was initially 0.050 mol dm
3
in A and 0.080 mol dm
3
in B. After1.0 h the
concentration of A had fallen to 0.020 mol dm
3
. Calculate the rate constant?

A. 0.00413 mol
-1
Ls
-1
B.0.0 413mol
-1
Ls
-1
C. 0.248 mol
-1
Ls
-1
D. None of the above

11. A second-order reaction of the type A + 2 B P was carried out in a solution that
was initially 0.75 mol dm
3
in A and 0.80 mol dm
3
in B. After1.0 h the concentration
of A had fallen to 0.65 mol dm
3
. Calculate the rate constant.

A. 8.0310
-4
mol
-1
Ls
-1
B. 5.7410
-5
mol
-1
Ls
-1
C. 1.3410
-5
mol
-1
Ls
-1
D. None of the above

12. The second-order rate constant for the reaction 2A + B C is 0.21 dm
3
mol
1
s
1
.
What is the concentration of C after 10s when the reactants are mixed with initial
concentrations of [A] = 0.15 mol dm
3
and [B] = 0.25 mol dm
3
?
A.0.184 mol dm
3
B. 0.046 mol dm
3
C. 0.021 mol dm
3
D. 0.07 mol dm
3


13. The reaction CH
3
CH
2
NO
2
+ OH
-
H
2
O + CH
3
CHNO

2


is second order, and k at 20
o
C is 9.110
-2
mol
-1
L min
-1
. An aqueous solution is
0.006 molar in nitroethane and 0.007 molar in NaOH. How long will it take for
10% of the nitroethane to react?
A. 1.4410
-3
s B. 15.82 s C. 15.82 min D. 9.110
2
min

14. The second-order rate constant for the reaction:
CH
3
COOC
2
H
5
(aq) + OH

(aq) CH
3
CO
2

(aq) + CH
3
CH
2
OH(aq)
is 0.11 dm
3
mol
1
s
1
. What is the concentration of ester (ROOR) after 10 s when
ethyl acetate is added to NaOH so that the initial concentrations are [NaOH] = 0.050
mol dm
3
and [CH
3
COOC
2
H
5
] = 0.100 mol dm
3
?
A. 0.100 mol dm
3
B. 0.095 mol L
-1
C. 0.050 mol dm
3
D. 0.045 mol L
-1


15. The rate constant, k, for second-order decomposition of HBr at 1000 K is 6.210
-3

dm
3
mol
-1
s
-1
. In a reaction in which the initial concentration, [HBr]
o
is 0.65 mol dm
-3
,
at what time [HBr]= 0.12 mol dm
-3
?
A. 18 .27 s B. 109 s C. 182 s D. 1.110
3
s

16. The following table gives kinetic data the following reaction at 25
o
C: A+ B + C = D
[A] /molL
-1
[B] /molL
-1
[C] /molL
-1
d[D]/dt /10
-4
mol L
-1
s
-1

0.01 0.005 4.00 1.75
0.01 0.004 4.00 1.75
0.01 0.003 8.00 3.50
0.001 0.002 4.00 0.55
What is the rate law for the reaction?
A. ] [ ] [
2 / 1
C A k r = B. ] [ ] [ ] [
1 2 / 1
C B A k r

=
C. ] ][ [ C A k r = D. ] ][ ][ [ C B A k r =

17. A second-order reaction of the type A + B P , the reaction is 60 % complete in
60 seconds when [A]
o
= 0.1 M and [B]
o
= 0.5 M. What is the rate constant for this
reaction?
A. 0.0041 mol
-1
Ls
-1
B. 0.041mol
-1
s
-1
C. 0.248 mol
-1
L s
-1
D. None of the above