Kinetics Practice Problems

Ex. 1: Consider the following reaction, NH

4
+
(aq) + NO
2

(aq) N
2
(g) + H
2
O(l), at 25C.

[NH
4
+
] (in M) [NO
2

] (in M) Initial Rate (in M/s)

a. Determine the rate law for
the reaction.

rate = k [NH
4
+
]
x
[NO
2

]
y

0.24
0.12
0.12
0.10
0.10
0.15
7.210
-6

3.610
-6

5.410
-6


M/s 10 3.6
M/s 10 7.2
[0.10M] [0.12M] k
[0.10M] [0.24M] k
] [NO ] [NH k
] [NO ] [NH k
rate
rate
6 -
6 -
y x
2
y x
y
2
2
x
2 4
y
1
2
x
1 4
2
1

= = =
+
+
(2.0)
x
= 2.0 x=1

M/s 10 3.6
M/s 10 5
[0.10M] [0.12M] k
[0.15M] [0.12M] k
] [NO ] [NH k
] [NO ] [NH k
rate
rate
6 -
6 -
y x
2
y x
y
2
2
x
2 4
y
3
2
x
3 4
2
3

= = =
+
+
4 .
(1.5)
y
= 1.5 y=1

rate = k [NH
4
+
] [NO
2

]

b. Determine the rate constant for the reaction.

=

= =
+
(0.10M) (0.24M)
M/s 10 7.2
] [NO ] [NH
rate
k
-6
`
2
1 4
1
3.010
-4
M
-1
s
-1


Ex. 2: At 600C acetone (CH
3
COCH
3
) decomposes to form several compounds.

Experiment [CH
3
COCH
3
] (in M) Initial Rate (in M/s)
a. Determine the rate law for the
reaction.

rate = k [CH
3
COCH
3
]
x

1
2
6.010
-3

9.010
-3

5.210
-5

7.810
-5


M/s 10 5
M/s 10
[0.0060M] k
[0.0090M] k
] H CO H [ k
] H CO H [ k
rate
rate
5 -
5 -
x
x
x
1
3 3
x
2
3 3
1
2

= = =
2
8 7
.
.
C C
C C
(1.5)
x
= 1.5 x=1
rate = k [CH
3
COCH
3
]

b. Calculate the rate constant for the reaction.

=

= =
.0060M
M/s 10
] H CO H [
rate
k
-5
1
3 3
1
0
2 5.
C C
8.710
-3
s
-1


c. What is the reaction order for this reaction at 600C? 1
st
-order

d. Calculate the concentration of acetone after 45 minutes if the initial concentration of
acetone is 0.0100M at 600C.

kt
[A]
[A]
ln
0
t
= [A]
t
= [A]
0
e
-kt

[A]
t
=(0.0100M)
min) (45
min 1
s 60 1 -
s (0.008666
kt
e (0.0100M) e

=
)


[A]
t
=(0.0100M) e
-23.4
=6.910
-13
M
(or essentially 0 since 0 dec. pl. 0 s.f.)

e. What is the half-life for this reaction at 600C?

= = =
1 -
s 0.008666
0.693
k
0.693
t
2
1 80. s

Ex. 3: At 500C cyclopropane (C
3
H
6
) rearranges to propene (CH
3
CHCH
2
). The reaction is first-order
with a rate constant of 6.710
-4
s
-1
.

a. Calculate the molarity of cyclopropane after 25 minutes if the initial concentration is 0.25M.

[A]
t
= [A]
0
e
-kt
=(0.25M)
min) (25
min 1
s 60 1 -
s 10 (6.7
kt
4 -
e (0.25M) e

=
)


[A]
t
=(0.25M) e
-1.005
=0.09M (1 dec. pl. = 1 s.f.)

b. How many minutes does it take for the concentration of cyclopropane to drop from 0.150M
to 0.050M at 500C?
kt
[A]
[A]
ln
0
t
=
s 10 6.7 -

k -

1 - 4 -
=

= =
s 60
min. 1 (0.150M)
(0.050M)
ln
[A]
[A]
ln
t
0
t
27 min.

c. What is the half-life for the reaction at 500C?

=

= =
s 60
min. 1
s 10 6.7
0.693
k
0.693
t
1 - 4 -
2
1 17 min.

d. How long does it take for the concentration to drop to 25% of the original concentration at
500C?
kt
[A]
[A]
ln
0
t
=
s 10 6.7 -

k -

1 - 4 -
=

= =
s 60
min. 1 [A]
(0.25)[A]
ln
[A]
[A]
ln
t
0
0
0
t
34 min.



Ex 4. Consider the following reaction energy diagram:


a. Indicate the activation energy (E
a
) and the transition state on the diagram.

b. Check all of the following statements that are true:
i. NO---O
3
in the diagram above is the transition state. NO!
ii. NO---O
3
in the diagram above is the activated complex.
iii. The activated complex and transition state are two terms that mean the same thing. NO!
iv. Given H for this reaction, the reaction is exothermic. E
products
< E
reactants

v. Given H for this reaction, the reaction is endothermic.
vi. Given the relative activation energies for the forward and reverse reactions, the rate
for the forward reaction should be greater than the rate for the reverse reaction.

A lower E
a
for the forward reaction compared to the reverse reaction means
more of the collisions occur with the required energy, so more of the collisions
lead to successful conversion of reactants to products and a higher reaction rate.

















transition state
E
a

Ex. 5. Atmospheric chemistry involves highly reactive odd-numbered electron molecules, such as the
hydroperoxyl radical, HO
2
, which decomposes to form oxygen,
2 HO
2
(g) H
2
O
2
(g) + O
2
(g). Consider the following experimental data at 25C:

Time (s) [HO
2
] (M) a. Show work supporting that the reaction is first-order
with respect to HO
2
.

zero-order reaction

slope 1 = =
s 0 - 0.6
M 8.5 - 5.1

-0.5666 M/s
0
0.6
1.0
1.4
1.8
2.4
8.5
5.1
3.6
2.6
1.8
1.1
too different not zero order!
slope 2 = =
s 1.8 - 2.4
M 1.8 - 1.1

-.1666 M/s

1
st
-order reaction
slope 1 = =
s 0 - 0.6
ln(8.5) - ln(5.1)

-0.8513 s
-1

about the same probably 1
st
-order!
slope 2 = =
s 1.8 - 2.4
ln(1.8) - ln(1.1)

-0.8207 s
-1


2
nd
-order reaction
slope 1 = =
s 0 - 0.6
8.5
-
5.1

M M
1 1

0.1307 M
-1
s
-1

slope 2 = =
s 1.8 - 2.4
1.8
-
1.1

M M
1 1

-0.5892 s
-1




too different not 2
nd
-order!

Thus, this is a 1
st
-order reaction.

b. Calculate the rate constant and the half-life for the reaction.

k = - slope = - =
+

2
1

s (-0.8207) [-0.8513 ]
0.8 s
-1


= = =
s .836
0.693
k
0.693
t
1 -
2
1
0
0.8 s


rate constant = 0.8 s
-1
and the half-life = 0.8 s .