Chemical Kinetics - Students

Copyright2000 by Houghton
Mifflin Company. All rights reserved.

1
Chemistry
FIFTH EDITION
Chapter 12
Chemical Kinetics
2
Chemical Kinetics
The area of chemistry that
concerns reaction rates.
3
Reaction Rate
Change in concentration (conc) of a reactant or
product per unit time.
Rate =
conc of A at time conc of A at time
2 1
2 1
t t
t t
=
A
A
A
t
Concentration of reactants and products as a function of time
for the reaction at 300C
2NO
2
(g) 2NO (g) + O
2
(g)
Time (+ 1 s) Concentration (mol/L)
NO
2
NO O
2

0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035
4
5
Figure 12.1
Definition of Rate
Starting with a flask of
nitrogen dioxide at 300 C,
the concentration of
nitrogen dioxide, nitric
oxide, and oxygen are
plotted vs. time.
Rate of consumption of
NO
2
= Rate of
consumption of NO = 2
times the rate of
consumption of O
2

6
Figure 12.2
Representation of the Reaction of 2NO
2
(g) 2NO(g) + O
2
(g)
The figure shows the initial concentration, and the concentration as time passes.
NO
2
is converted to NO and O
2

7
Rate Laws
Rate = k[NO
2
]
n

k = rate constant
n = rate order
8
Types of Rate Laws
Differential Rate Law: expresses how rate
depends on concentration.
Integrated Rate Law: expresses how
concentration depends on time.
9
Figure 12.3
A Plot of the Concentration
of N
2
O
5
as a Function of
Time for the Reaction
Note that the reaction
rate at [N
2
O
5
]=0.90 M
is twice the rate at
[N
2
O
5
]=0.45 M
Rate Laws
10
] O N [ ] O N [
] O [N
- Rate
5 2
1
5 2
5 2
k k
t
= =
A
A
=
The reaction is first order
Note that the order is not the same as the coefficient
from the reaction
11
Method of Initial Rates
Initial Rate: the instantaneous rate just
after the reaction begins.
The initial rate is determined in several
experiments using different initial
concentrations.
12
Overall Reaction Order
Sum of the order of each component in the
rate law.
rate = k[H
2
SeO
3
][H
+
]
2
[I
]
3

The overall reaction order is 1 + 2 + 3 = 6.
Example 12.1
The reaction between bromate ions and bromide
ions in acidic aqueous solution is given by the
equation
BrO
3
-
(aq) + 5Br
-
(aq) + 6H
+
(aq) 3Br
2
(l) +3H
2
O(l)
The following table gives the results from four
experiments. Using this data, determine the
orders for all three reactions, the overall reaction
order, and the value of the rate constant.
13
Example 12.1
Experiment Initial
Concentration of
BrO
3
-
(mol/L)
Initial
Concentration
of Br
-
(mol/L)
Initial
Concentration
of H
+
(mol/L)
Measured
Initial Rate
(mol/L s)
1 0.10 0.10 0.10 8.0x10
-4

2 0.20 0.10 0.10 1.6x10
-3

3 0.20 0.20 0.10 3.2x10
-3

4 0.10 0.10 0.20 3.2x10
-3

14
The results from four experiments to study the reaction
BrO
3
-
(aq) + 5Br
-
(aq) + 6H
+
(aq) 3Br
2
(l) +3H
2
O(l)

Example 12.1
Rate = k[BrO
3
-
]
n
[Br
-
]
m
[H
+
]
p

Determine the values of n, m, and p by
comparing rates from the various experiments.

Compare exp 1 to exp 2 where only [BrO
3
-
]
changes.
n = 1

15
Example 12.1
Compare exp 3 to exp 2 where only [Br
-
]
changes.
m = 1

Compare exp 4 to exp 1 where only [H
+
]
changes.
p = 2
16
Problem 12.23
The reaction
2NO (g) + Cl
2
(g) 2NOCl (g)
Was studied at -10C. The following results were obtained
where

a. What is the rate law?
b. What is the value of the rate constant?

17
t
Cl
A
A
=
] [
- Rate
2
[NO]
0
(mol/L) [Cl
2
]
0
(mol/L) Initial Rate (mol/L min)
0.10 0.10 0.18
0.10 0.20 0.36
0.20 0.20 1.45
18
First-Order Rate Law
Integrated first-order rate law is
ln[A] = kt + ln[A]
o

The reaction is first order in A if a plot of
ln[A] versus t is a straight line.
Rate =
A
A
=
A
At
k
For aA Products in a 1st-order reaction,
Example 12.2
The decomposition of N
2
O
5
in the gas phase was
studied at constant temperature.
2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)
The following results were collected:
Using this data verify that
The reaction is first order in
[N
2
O
5
], and calculate the
Value of the rate constant,
Where the rate = -[N
2
O
5
]/t

19
[N
2
O
5
] (mol/L) Time (s)
0.1000 0
0.0707 50
0.0500 100
0.0250 200
0.0125 300
0.00625 400
Example 12.3
Using the data given in example 12.2, calculate
[N
2
O
5
] at 150 s after the start of the reaction.

From example 12.2, [N
2
O
5
] = 0.0500 mol/L at
100 s, and [N
2
O
5
] = 0.0250 mol/L at 200 s.

ln[N
2
O
5
] = -kt + ln[N
2
O
5
]
0

Where t = 150 s, k = 6.93x10
-3
s
-1
,
[N
2
O
5
]
0
=0.10000 mol/L
20
Problem 12.29
The decomposition of hydrogen
peroxide was studied, and the
following data was obtained at a
particular temperature.
Assuming that

Determine the rate law, the
integrated rate law. What is the
value of the rate constant.
Calculate [H
2
O
2
] exactly 4000 s
after the start of the reaction.
Time (s) [H
2
O
2
] (mol/L)
0 1.00
120 1 0.91
300 1 0.78
600 1 0.59
1200 1 0.37
1800 1 0.22
2400 1 0.13
3000 1 0.082
3600 1 0.050
21
t
O H
Rate
A
A
=
] [
2 2
22
Half-Life of a First-Order
Reaction
The time required for a reactant to reach half
its original concentration is called the half-life.

Calculate the half-life of the reaction in
example 12.2
23
Figure 12.5
A Plot of (N
2
O
5
) Versus Time for the Decomposition Reaction of N
2
O
5

Consider the following numbers
[N
2
O
5
] (mol/L) t(s)
0.100 0
t=100 s [N
2
O
5
]
t=100 =
0.050
=
1
0.0500 100 [N
2
O
5
]
t=0
0.100 2
t=100 s [N
2
O
5
]
t=200 =
0.025
=
1
0.0250 200 [N
2
O
5
]
t=100
0.050 2
t=100 s [N
2
O
5
]
t=300 =
0.0125
=
1
0.0125 300 [N
2
O
5
]
t=200
0.0250 2
24
Note that it always takes 100 seconds for [N
2
O
5
] to decrease by 1/2
25
Reaction
If the reaction is first order in [A],
ln([A]
0
/[A]) = kt
By definition, when t = t
1/2

[A] = [A]
0
/2
26
Reaction
t
1/2
= half-life of the reaction
k = rate constant
For a first-order reaction, the half-life does
not depend on concentration.
t
k
1/ 2
=
0 693 .
Example 12.4
A certain first-order reaction was a half-life of
20.0 minutes.
a. Calculate the rate constant for this reaction.
b. How much time is required for this reaction
to be 75% complete?
27
Problem 12.37
A certain first order reaction is 45.0% complete
in 65 s. What is the rate constant for this
process? What is the half-life for this process?
28
Problem 12.39
A first order reaction is 38.5% complete in 480 s.
a. Calculate the rate constant.
b. What is the value of the half-life.
c. How long will it take for the reaction to go to 25%
completion?
d. How long will it take for the reaction to go to 75%
completion?
e. How long will it take for the reaction to go to 95%
completion?

29
30
Second-Order Rate Law
For aA products in a second-order
reaction,

Integrated rate law is
Rate =
A
A
=
A
At
k
2
1
A
+
1
A
o
= kt
31
Half-Life of a Second-Order
Reaction
t
1/2
k = rate constant
A
o
= initial concentration of A
The half-life is dependent upon the initial
concentration.

t
k
1/ 2
o
A
=
1
Example 12.5
Butadiene reacts to form
its dimer according to the
equation
2C
4
H
6
(g) C
8
H
12
(g)
The following data were
collected for this reaction
at a given temperature:
[C
4
H
6
] (mol/L) Time (+ 1 s)
0.08000 0
0.00625 1000
0.00476 1800
0.00370 2800
0.00313 3600
0.00270 4400
0.00241 5200
0.00209 6200
32
a. Is this reaction first or second order?
b. What is the value of the rate constant for the reaction?
c. What is the half-life for the reaction under the conditions
of this experiment?
Problem 12.31
The rate of the reaction
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
depends only on the concentration of
nitrogen dioxide below 225C. At a
temperature below 225C, the
following data were collected
Time (s) [NO
2
] (mol/L)
0 0.500
1.20 x 10
3
0.444
3.00 x 10
3
0.381
4.50 x 10
3
0.340
9.00 x 10
3
0.250
1.80 x 10
4
0.174
33
Determine the rate law and the integrated rate law. What is the
value of the rate constant? Calculate the [NO
2
] at 2.70 x 10
4
s
after the start of the reaction.
Problem 12.33
The decomposition of ethanol (C
2
H
5
OH) on an alumina
(Al
2
O
3
) surface
C
2
H
5
OH (g) C
2
H
4
(g) + H
2
O (g)
Was studied at 600K. Concentration versus time data were
collected for this reaction, and a plot of [A] versus time
resulted in a straight line with a slope of -4.00x10
-5
mol/L s.
a. Determine the rate law and the integrated rate law. What
is the value of the rate constant for this reaction?
b. If the initial concentration of C
2
H
5
OH was 1.25 x 10
-2
M,
calculate the half life for this reaction.
c. How much time is required for all the 1.25 x 10
-2
M
C
2
H
5
OH to decompose?

34
35
Zero-Order Rate Law
For aA products in a zero-order reaction,

Rate = k[A]
0
= k(1) = k

Integrated rate law is
[A] = -kt + [A]
0

36
Half-Life of a Zero-Order Reaction
t
1/2
k = rate constant
A
o
= initial concentration of A
The half-life is dependent upon the initial
concentration.

k
A
t
2
] [
0
2
1
=
37
Figure 12.7
A Plot of (A) Versus t for a Zero-Order
Reaction
A first order reaction
has a constant rate.
38
A Summary
1. Simplification: Conditions are set such
that only forward reaction is important.
2. Two types: differential rate law
integrated rate law
3. Which type? Depends on the type of
data collected - differential and
integrated forms can be interconverted.
39
A Summary
(continued)
4. Most common: method of initial rates.
5. Concentration v. time: used to
determine integrated rate law, often
graphically.
6. For several reactants: choose
conditions under which only one
reactant varies significantly (pseudo
first-order conditions).
40
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Order Rate Law
Concentration-Time
Equation Half-Life
0
1
2
rate = k
rate = k [A]
rate = k [A]
2

ln[A] = ln[A]
0
- kt
1
[A]
=
1
[A]
0

+ kt
[A] = [A]
0
- kt
t

ln 2
k
=
t
=
[A]
0

2k
t
=
1
k[A]
0

Order Units
zero
first
second
third
molV
-1
s
-1
s
-1

Vmol
-1
s
-1
(Vmol
-1
)
2
s
-1
42
Arrhenius Equation
Collisions must have enough energy to
produce the reaction (must equal or exceed
the activation energy).
Orientation of reactants must allow
formation of new bonds.
43
Arrhenius Equation
(continued)
k = rate constant
A = frequency factor
E
a
= activation energy
T = temperature
R = gas constant
k Ae
E RT
=

a
/
Example 12.7
The reaction
2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)
Was studied at several
temperatures, and the following
values of k were obtained:
k (s
-
) T (C)
2.0 x 10
-5
20
7.3 x 10
-5
30
2.7 x 10
-4
40
9.1 x 10
-4
50
2.9 x 10
-3
60
44
Calculate the value of E
a
for this reaction.
Problem 12.53
Experimental values for
the temperature
dependence of the rate
constant for the gas phase
reaction
NO + O
3
NO
2
+ O
2

Are as follows:
T (K) k (L/mol s)
195 1.08 x 10
9

230 2.95 x 10
9

260 5.42 x 10
9

298 12.0 x 10
9

369 35.5 x 10
9

45
Make the appropriate graph using this data and
determine the activation energy for this reaction.
46
Alternate Form of the Arrhenius Equation
At two temperatures, T
1
and T
2
or

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