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# Chemical Kinetics

Chapter Goals
1. The Rate of a Reaction
Factors That Affect Reaction Rates
2. Nature of the Reactants
3. Concentrations of the Reactants: The
Rate-Law Expression
4. Concentration Versus Time: The
Integrated Rate Equation
5. Collision Theory of Reaction Rates
2

Chapter Goals
6. Transition State Theory
7. Reaction Mechanisms and the Rate-Law
Expression
8. Temperature: The Arrhenius Equation
9. Catalysts

## The Rate of a Reaction

Kinetics is the study of rates of chemical
reactions and the mechanisms by which
they occur.
The reaction rate is the increase in
concentration of a product per unit time or
decrease in concentration of a reactant per
unit time.
A reaction mechanism is the series of
molecular steps by which a reaction occurs.
4

## The Rate of Reaction

Consider the hypothetical reaction,
aA(g) + bB(g) cC(g) + dD(g)
equimolar amounts of reactants, A and B,
will be consumed while products, C and D,
will be formed as indicated in this graph:

## [A] is the symbol for the concentration of A in M ( mol/L).

Note that the reaction does not go entirely to completion.
The [A] and [B] > 0 plus the [C] and [D] < 1.

## The Rate of Reaction

Mathematically, the rate of a reaction can
be written as:

- A - B
+ C + D
Rate =

or

a t
b t
c t
d t

## The Rate of Reaction

The rate of a simple one-step reaction is directly
proportional to the concentration of the reacting substance.

## A (g) B(g) + C (g)

Rate A or Rate = k A
[A] is the concentration of A in molarity or moles/L.
k is the specific rate constant.
k is an important quantity in this chapter.
8

## If the initial concentration of A is doubled, the initial

rate of reaction is doubled.

## If the reaction is proceeding twice as fast, the amount of

time required for the reaction to reach equilibrium would
be:
A. The same as the initial time.
B. Twice the initial time.
C. Half the initial time.

## If the initial concentration of A is halved the

initial rate of reaction is cut in half.
9

## The Rate of Reaction

If more than one reactant molecule appears
in the equation for a one-step reaction, we
can experimentally determine that the
reaction rate is proportional to the molar
concentration of the reactant raised to the
power of the number of molecules involved in
the reaction.

2 X g Y g + Z g

Rate X or Rate = k X
2

2
10

## Rate Law Expressions must be determined

experimentally.
The rate law cannot be determined from the
balanced chemical equation.
This is a trap for new students of kinetics.

## The balanced reactions will not work because most

chemical reactions are not one-step reactions.

## Other names for rate law expressions are:

1. rate laws
2. rate equations
3. rate expressions
11

## Important terminology for kinetics.

The order of a reaction can be expressed in
terms of either:
1 each reactant in the reaction or
2 the overall reaction.
Order for the overall reaction is the sum of the orders
for each reactant in the reaction.

For example:
2 N 2 O 5 g 4 NO 2 g + O 2 g
Rate = k N 2 O 5

## This reaction is first order in N 2 O 5

and first order overall.

12

## The Rate of Reaction

A second example is:

## CH 3 3 CBr aq OH -aq CH 3 3 COH aq Br-aq

Rate = k[ CH 3 3 CBr ]
This reaction is first order in CH 3 3 CBr,
zero order in OH - , and first order overall.

13

## The Rate of Reaction

A final example of the order of a reaction is:

2 NO + O 2 NO
g

2 g

Rate = k[NO] O

2 g

## This reaction is second order in NO,

first order in O , and third order overall
2

## REMEMBER, ALL RATE EXPRESSIONS ARE

DETERMINED EXPERIMENTALLY
14

## The Rate of Reaction

Given the following one step reaction and its rate-law expression.
Remember, the rate expression would have to be experimentally
determined.

2 A g B g C g
Rate = k A

## Because it is a second order rate-law expression:

If the [A] is doubled the rate of the reaction will increase
by a factor of 4. 22 = 4
If the [A] is halved the rate of the reaction will decrease
by a factor of 4. (1/2)2 = 1/4
15

Rates

1.
2.
3.
4.

## There are several factors that can

influence the rate of a reaction:
The nature of the reactants.
The concentration of the reactants.
The temperature of the reaction.
The presence of a catalyst.
We will look at each factor individually.
16

Nature of Reactants
This is a very broad category that encompasses the
different reacting properties of substances.
For example sodium reacts with water explosively at
room temperature to liberate hydrogen and form
sodium hydroxide.

2 Na s 2 H 2 O 2 NaOH aq H 2 g
This is a violent and rapid reaction.
The H 2 ignites and burns.
17

Nature of Reactants
Calcium reacts with water only slowly at
room temperature to liberate hydrogen
and form calcium hydroxide.

Ca s 2 H 2 O Ca OH 2 aq H 2 g
This is a rather slow reaction.

18

Nature of Reactants
The reaction of magnesium with water at
room temperature is so slow that that the
evolution of hydrogen is not perceptible to
the human eye.

Mg s H 2 O No reaction

19

Nature of Reactants
However, Mg reacts with steam rapidly to
liberate H2 and form magnesium oxide.
100 o C

Mg s H 2 O ( g ) MgO s H 2 g
The differences in the rate of these three
reactions can be attributed to the changing
nature of the reactants.
20

Concentrations of Reactants:
The
Rate-Law
Expression
Example 16-1: The following rate data were obtained at
25oC for the following reaction. What are the rate-law
expression and the specific rate-constant for this reaction?
2 A(g) + B(g) 3 C(g)

Experiment
Number
1
2
3

Initial [A]
(M)
0.10
0.20
0.10

Initial [B]
(M)
0.10
0.30
0.20

Initial rate of
formation of
C (M/s)
2.0 x 10-4
4.0 x 10-4
2.0 x 10-421

Concentrations of Reactants:
The Rate-Law Expression
The rate law must be of the form :
Rate = k A B
x

## If we compare experiments 1 and 3 we see that

the [A] is constant and that the [B] increases by 2.
Notice that the initial rate remains constant.

2 1 y 0
x
0
x
Rate = k A B or Rate = k[A]
Thus, we can can ignore B.
y

22

Concentrations of Reactants:
TheNext,
Rate-Law
Expression
compare experiment
s 1 and 2.
Notice that the [A] increases by 2
and the rate increases by 2.

2 x 1

## Rate = k[A] 1 or Rate = k[A]

This reaction is 1st order with respect
to A and 1st order overall.
What is the value and units of k
for this reaction?
You do it!

23

Concentrations of Reactants:
The Rate-Law Expression
We can find the value of k from the rate law.
Rate
k=
A
Using the values of Rate and [A] from experiment 1
-4 M

2.0 x 10 s
-3 1
k=
2.0 x 10 s
0.10 M
Thus the rate law can be written as
Rate = 2.0 x 10

-3 1

[A]

24

Concentrations of Reactants:
The Rate-Law Expression
Example 16-2: The following data were obtained
Initial rate
for the following reaction at 25oC.Initial
What are the
of
[A] Initial
[B]specific
[C] rateformation
rate-law Initial
expression
and the
constant
Experimen
for
t the reaction?
(M)
(M)
(M)
of D (M/s)
2 A(g) + B(g) + 2 C(g) 3 D(g) + 2 E(g)
1
0.20
0.10
0.10
2.0 x 10-4
2

0.20

0.30

0.20

6.0 x 10-4

0.20

0.10

0.30

2.0 x 10-4

0.60

0.30

0.40

1.8 x 10-3
25

Concentrations of Reactants:
The Rate-Law Expression
Compare experiments 1 and 3.

## The C increases by 3 but the rate remains constant.

3 1 z 0
x
y
z
x
y
Rate = k A B C or Rate = k A B
z

26

Concentrations of Reactants:
The Rate-Law Expression
Next, compare experiments 1 and 2.
The A remains constant.
The B increases by 3 and the rate increases by 3.

3 3 y 1
x
1
x
Rate = k A B or Rate = k A B
y

27

Concentrations of Reactants:
The Rate-Law Expression
Next, compare experiments 2 and 4.
The B remains constant.
The A increases by 3 and the rate increases by 3.

3 3 x 1
1
1
Rate = k A B or Rate = k A B
x

st

st

nd

## 1 order with respect to B, and 2 order overall.

28

Concentrations of Reactants:
The Rate-Law Expression
Finally, determine the value and units of k.
Can use the data from experiment 1, 2, 3, or 4.
4 M

Rate
2.0 10 s
k=

A B 0.20 M 0.10 M
1.0 10

2 1

Ms

## Thus, the rate - law can be written as

Rate = 1.0 10

2 1

M s A B

29

Concentrations of Reactants:
The Rate-Law Expression

## Example 16-3: consider a chemical reaction

between compounds A and B that is first order
with respect to A, first order with respect to B,
and second order overall. From the information
Initial Rate
Initial [A]
Initial [B]
given below, fill in the blanks.
Experiment
(M/s)
(M)
(M)
You
do it!
-3
1
4.0 x 10
0.20
0.050
2

1.6 x 10-2

0.050

3.2 x 10-2

0.40

?
30

Concentrations of Reactants:
The Rate-Law Expression

Rate = k A B
From experiment 1 we can determine the value of k.
3 M

Rate
4.0 10 s
k=

A B 0.20 M 0.050 M
0.40 1 M s
Thus the Rate 0.40 1 M s A B
31

Concentrations of Reactants:
The Rate-Law Expression
Use the value of k and data from experiment 2
Rate
[A]
k[B]
2

1.6 10 Ms
[A]
1 -1
0.40 M s 0.050 M
[A] 0.80 M

-1

32

Concentrations of Reactants:
The Rate-Law Expression
Similarly, from experiment 3 we can determine
R
[B]
k[A]
2

3.2 10 Ms
[B]
1 -1
0.40 M s 0.40 M
[B] 0.20 M

-1

33

## Concentration vs. Time: The

Integrated Rate Equation

## The integrated rate equation relates time and

concentration for chemical and nuclear
reactions.
From the integrated rate equation we can predict the
amount of product that is produced in a given
amount of time.

## Initially we will look at the integrated rate

equation for first order reactions.
These reactions are 1st order in the reactant and 1st
order overall.
34

## Concentration vs. Time: The

Integrated Rate Equation

## An example of a reaction that is 1st order in the

reactant and 1st order overall is:
a A products
This is a common reaction type for many
chemical reactions and all simple radioactive
decays.
Two examples of this type are:
2 N2O5(g) 2 N2O4(g) + O2(g)
238

U 234Th + 4He
35

## Concentration vs. Time: The

Integrated Rate Equation
The integrated rate equation for first order reactions is:

A 0
ln
akt
A
where:
[A]0= mol/L of A at time t=0.

## k = specific rate constant.

t = time elapsed since beginning of
reaction.
a = stoichiometric coefficient of A in balanced overall equation.
36

## Concentration vs. Time: The

Integrated Rate Equation
Solve the first order integrated rate equation for t.

1 A 0
t
ln

a k A
Define the half-life, t1/2, of a reactant as the time
required for half of the reactant to be consumed,
or the time at which [A]=1/2[A]0.
37

## Concentration vs. Time: The

Integrated Rate Equation
At time t = t1/2, the expression becomes:

t 1/2
t 1/2
t 1/2

A 0

ln
ak
1/2 A 0
1
ln 2

ak
0.693

ak

38

## Concentration vs. Time: The

Integrated Rate Equation
Example 16-4: Cyclopropane, an
anesthetic, decomposes to propene
according to the following equation.

CH2

H2C

CH2

(g)

H3C

CH

CH2

(g)

## The reaction is first order in cyclopropane with

k = 9.2 s-1 at 10000C. Calculate the half life of
cyclopropane at 10000C.

t1/2

0.693 0.693

0
.
075
s
-1
k
9 .2 s

39

## Concentration vs. Time: The

Integrated Rate Equation

## Example 16-5: Refer to Example 16-4.

How much of a 3.0 g sample of
cyclopropane remains after 0.50 seconds?
The integrated rate laws can be used for any
unit that represents moles or concentration.
In this example we will use grams rather than
mol/L.

40

## Concentration vs. Time: The

Integrated Rate Equation
A
ln
a k t k t for this reaction
A
We must use the laws of logarithms.
0

ln A ln A k t
0

ln 3.0 - ln A 9.2 s

-1

0.50 s

1.10 ln A 4.6

## ln A 4.6 1.10 3.5

A e 0.03 g or 1% remains
-3.5

41

## Concentration vs. Time: The

Integrated Rate Equation

## Example 16-6: The half-life for the

following first order reaction is 688 hours
at 10000C. Calculate the specific rate
constant, k, at 10000C and the amount of
a 3.0 g sample of CS2 that remains after
48 hours.
CS2(g) CS(g) + S(g)
You do it!
42

## Concentration vs. Time: The

Integrated Rate Equation
For this reaction a 1.
0.693
t1/2
k
0.693
k
t1/2
0.693
-1
k
0.00101 hr
688 hr

43

## Concentration vs. Time: The

Integrated Rate Equation

A ln A 0 k t ln A ln A k t
ln
k t ln A ln0 A k t
A A
-1
ln(3.0) - ln A (0.00101
ln(3.0)
00101hr
hr )(
)(48
48 hr)
hr)
1.10 - ln A 0.048
ln A -(0.048 - 1.10) 1.052
0

-1

A e

1.052

44

## Concentration vs. Time: The

Integrated Rate Equation

## For reactions that are second order with respect

to a particular reactant and second order
overall, the rate equation is:

1
1

akt
A A 0

Where:
[A]0= mol/L of A at time t=0.

## t = time elapsed since

beginning of reaction.
a = stoichiometric coefficient of A in balanced overall equation.
45

## Concentration vs. Time: The

Integrated Rate Equation
If we solve for t1/2:

t1/2

a k A 0

## Note that the half-life of a second order

reaction depends on the initial
concentration of A.
46

## Concentration vs. Time: The

Integrated Rate Equation
Example 16-7: Acetaldehyde, CH3CHO, undergoes gas
phase thermal decomposition to methane and carbon
monoxide.

CH 3CHO g CH 4 g + CO g
The rate-law expression is Rate = k[CH3CHO]2,
and k = 2.0 x 10-2 L/(mol.hr) at 527oC. (a) What
is the half-life of CH3CHO if 0.10 mole is
injected into a 1.0 L vessel at 527oC?
47

## Concentration vs. Time: The

Integrated Rate Equation
t1/2

k A 0

2.0 10

1
2

hr

-1

0.10 M

5.0 10 hr
48

## Concentration vs. Time: The

Integrated Rate Equation
(b) How many moles of CH3CHO remain after
200 hours?

11
1
1
1
14 M
k t A
1
14 M
A A 0

1 A 10.071 M

. M
A 010
mol

1
1
1
10 M 4.0 M
A

0
.
071
mol
L
49

## Concentration vs. Time: The

Integrated Rate Equation
(c) What percent of the CH3CHO remains
after 200 hours?
0.071 mol
% unreacted =
100%
0.10 mol
71% unreacted and 29% reacted

50

## Concentration vs. Time: The

Integrated Rate Equation

## Example 16-8: Refer to Example 16-7. (a)

What is the half-life of CH3CHO if 0.10
mole is injected into a 10.0 L vessel at
527oC?
Note that the vessel size is increased by a
factor of 10 which decreases the
concentration by a factor of 10!

You do it!
51

## Concentration vs. Time: The

Integrated Rate Equation
t1/2

k A 0

2.0 10

1
1
-1
M hr 0.010 M

5.0 10 hr
note the time has increased by 10
over Example 16 - 7:

52

Enrichment - Derivation of
Integrated Rate Equations

## Which rearranges to the integrated first order

rate equation.

A 0
ln
akt
A t
53

Enrichment - Derivation of
Integrated Rate Equations

## Derive the rate equation for a reaction that is

second order in reactant A and second order
overall.
The rate equation is:

d A
2

k A

54

Enrichment - Derivation of
Integrated Rate Equations

## Separate the variables so that the A terms are

on the left and the t terms on the right.

d A

k
d
t
2
a A
55

Enrichment - Derivation of
Integrated Rate Equations

## Which integrates the second order integrated

rate equation.

1
1

akt
A A 0
56

Enrichment - Derivation of
Integrated Rate Equations

## For a zero order reaction the rate expression is:

d A

k
57

Enrichment - Derivation of
Integrated Rate Equations
Which rearranges to:

d A a k d t
58

Enrichment - Derivation of
Integrated Rate Equations

equation.

A A 0 -a k t
or

A A 0 - a k t
59

## Enrichment - Rate Equations to

Determine Reaction Order
Plots of the integrated rate equations can help us
determine the order of a reaction.
If the first-order integrated rate equation is
rearranged.
This law of logarithms, ln (x/y) = ln x - ln y, was applied
to the first-order integrated rate-equation.

ln A 0 ln A a k t
or

ln A a k t ln A 0

60

## Enrichment - Rate Equations to

Determine Reaction Order
The equation for a straight line is:

y mx b
Compare this equation to the rearranged first
order rate-law.

61

## Enrichment - Rate Equations

to Determine Reaction Order

y mx b
ln A a k t ln A 0

## y can be identified with ln[A] and plotted on the y-axis.

m can be identified with ak and is the slope of the line.
x can be identified with t and plotted on the x-axis.
b can be identified with ln[A]0 and is the y-intercept.

62

## Enrichment - Rate Equations to

Determine Reaction Order

## Example 16-9: Concentration-versus-time data for

the thermal decomposition of ethyl bromide are
given in the table below. Use the following graphs
of the data to determine the rate of the reaction
and the value of the rate constant.

C 2 H 5 Br g C 2 H 4 g HBr g at 700K

63

## Enrichment - Rate Equations to

Determine Reaction Order
Time
(min)
[C2H5Br]

0
1.00

1
0.82

2
0.67

3
0.55

4
0.45

5
0.37

1/[C2H5Br]

1.0

1.2

1.5

1.8

2.2

2.7
64

## Enrichment - Rate Equations

to
Determine
Reaction
Order
We will make three different graphs of the
data.
1 Plot the [C2H5Br] (y-axis) vs. time (x-axis)

## If the plot is linear then the reaction is zero order

with respect to [C2H5Br].

## 2 Plot the ln [C2H5Br] (y-axis) vs. time (x-axis)

If the plot is linear then the reaction is first order
with respect to [C2H5Br].

## 3 Plot 1/ [C2H5Br] (y-axis) vs. time (x-axis)

If the plot is linear then the reaction is second
order with respect to [C2H5Br].

65

## Enrichment - Rate Equations

to
Determine
Reaction
Order
Plot of [C H Br] versus time.
2

Is it linear or not?

66

## Enrichment - Rate Equations

to Determine Reaction Order
Plot of ln [C2H5Br] versus time.
Is it linear or not?

67

## Enrichment - Rate Equations

to Determine Reaction Order
Plot of 1/[C2H5Br] versus time.
Is it linear or not?

68

## Enrichment - Rate Equations

to Determine Reaction Order

Note that the only graph which is linear is the plot of ln[C 2H5Br] vs.
time.

## Thus this is a first order reaction with respect to [C2H5Br].

Next, we will determine the value of the rate constant from the slope
of the line on the graph of ln[C 2H5Br] vs. time.

## Remember slope = y2-y1/x2-x1.

y 2 - y1 0.80 (0.20)
slope

x 2 - x1
4 1 min
0.60
-1
slope
0.20 min
3 min

69

## Enrichment - Rate Equations to

Determine Reaction Order
From the equation for a first order reaction we
know that the slope = -a k.
In this reaction a = 1.

slope -0.20 -k
Thus the rate constant k 0.20 min .
-1

70

## Enrichment - Rate Equations

to Determine Reaction Order
The integrated rate equation for a reaction that is
second order in reactant A and second order
overall.

1
1

akt
A A 0

1
1
akt
A
A 0

71

## Enrichment - Rate Equations

to Determine Reaction Order

y mx b

## Compare the equation for a straight line and the

second order1rate-law expression.
1

akt

A 0

## y can be identified with 1/[A] and plotted on the y-axis.

m can be identified with a k and is the slope of the line.
x can be identified with t and plotted on the x-axis
b can be identified with 1/[A]0 and is the y-intercept.

72

## Enrichment - Rate Equations

to Determine Reaction Order

## Example 16-10: Concentration-versustime data for the decomposition of

nitrogen dioxide are given in the table
below. Use the graphs to determine the
rate of the reaction and the value of the
rate constant

2 NO 2 g 2 NO g O 2 g at 500K

73

## Enrichment - Rate Equations

to Determine Reaction Order
Time
(min)
[NO2]

0
1.0

1
0.53

2
0.36

3
0.27

4
0.22

5
0.18

ln [NO2]

0.0

-0.63

-1.0

-1.3

-1.5

-1.7

1/[NO2]

1.0

1.9

2.8

3.7

4.6

5.5
74

## Enrichment - Rate Equations

to Determine Reaction Order

1.

## Once again, we will make three different graphs

of the data.
Plot [NO2] (y-axis) vs. time (x-axis).

respect to NO2.
2.

3.

respect to NO2.

## If the plot is linear then the reaction is second order

with respect to NO2.
75

## Enrichment - Rate Equations

to Determine Reaction Order
Plot of [NO2] versus time.
Is it linear or not?

76

## Enrichment -Rate Equations

to Determine Reaction Order
Plot of ln [NO2] versus time.
Is it linear or not?

77

## Enrichment - Rate Equations

to Determine Reaction Order
Plot of 1/[NO2] versus time.
Is it linear or not?

78

## Enrichment - Rate Equations

to Determine Reaction Order

## Note that the only graph which is linear is

the plot of 1/[NO2] vs. time.
Thus this is a second order reaction with
respect to [NO2].
Next, we will determine the value of the
rate constant from the slope of the line on
the graph of 1/[NO2] vs. time.
79

## Enrichment - Rate Equations

to Determine Reaction Order
1
y 2 - y1 5.50 (1.90)
slope

x 2 - x1
5 1 min

3.60 1 M
slope
0.90 1 M min
4 min
From the equation for a second order reaction we
know that the slope = a k
In this reaction a = 2.

slope 0.90 2 k
Thus the rate constant k 0.45 M

min

-1
80

Collision Theory of
Reaction Rates

## Three basic events must occur for a

reaction to occur the atoms, molecules
or ions must:
1. Collide.
2. Collide with enough energy to break and
form bonds.
3. Collide with the proper orientation for a
reaction to occur.
81

Collision Theory of
Reaction Rates
One method to increase the number of collisions and
the energy necessary to break and reform bonds is to
heat the molecules.
As an example, look at the reaction of methane and
oxygen:

## CH 4(g) O 2(g) CO 2(g) H 2 O (g) 891 kJ

We must start the reaction with a match.
This provides the initial energy necessary to break the
first few bonds.
Afterwards the reaction is self-sustaining.
82

Collision Theory of
Reaction Rates

## Illustrate the proper orientation of molecules

that is necessary for this reaction.
X2(g) + Y2(g) 2 XY(g)

## Some possible ineffective collisions are :

X
X

Y Y

X X

Y Y

Y
83

Collision Theory of
Reaction Rates

Y
+

84

## Transition State Theory

Transition state theory postulates that reactants
form a high energy intermediate, the transition
state, which then falls apart into the products.
For a reaction to occur, the reactants must
acquire sufficient energy to form the transition
state.
This energy is called the activation energy or Ea.

energy
85

Boulder
Eactivation
Epot=mgh2

Epot = mgh

h2

Height
Cross section
of mountain

h
h1
Epot=mgh1

86

## Transition State Theory

Representation of a chemical reaction.
Eactivation - a kinetic quantity

Potential
Energy

E H
a thermodynamic
quantity

X2 + Y2

2 XY
Reaction Coordinate

87

88

## Transition State Theory

The relationship between the activation
energy for forward and reverse reactions
is
Forward reaction = Ea
Reverse reaction = Ea + E
difference = E

89

## Transition State Theory

The distribution of molecules possessing
different energies at a given temperature is
represented in this figure.

90

Temperature:
The Arrhenius Equation

## Svante Arrhenius developed this

relationship among (1) the temperature
(T), (2) the activation energy (Ea), and (3)
the specific rate constant (k).

k = Ae
or

Ea

RT

Ea
ln k = ln A RT

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Catalysts
Catalysts change reaction rates by providing an
alternative reaction pathway with a different
activation energy.

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