1

Chemical Kinetics
2
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
3
Chapter Goals
6. Transition State Theory
7. Reaction Mechanisms and the Rate-Law
Expression
8. Temperature: The Arrhenius Equation
9. Catalysts
4
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.
3
5
The Rate of a Reaction
• Thermodynamics (Chapter 15) determines if a reaction
can occur.
• Kinetics (Chapter 16) determines how quickly a reaction
occurs.
– Some reactions that are thermodynamically
feasible are kinetically so slow as to be
imperceptible.
, ) , )
, ) , ) , )
OUS INSTANTANE
kJ -79 = G O H OH + H
SLOW VERY
kJ 396 G CO O C
o
298 2
-
aq
+
aq
o
298 g 2 g 2 diamond
A ÷
÷ = A ÷ +
l
6
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:
4
7
0
0.2
0.4
0.6
0.8
1
1.2
0
5
0
1
0
0
1
5
0
2
0
0
2
5
0
3
0
0
3
5
0
Time
C
o
n
c
e
n
t
r
a
t
i
o
n
s

o
f
R
e
a
c
t
a
n
t
s

&

P
r
o
d
u
c
t
s
[A] & [B]
[C] & [D]
• [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.
8
The Rate of Reaction
• Reaction rates are the rates at which reactants
disappear or products appear.
• This movie is an illustration of a reaction rate.
5
9
The Rate of Reaction
• Mathematically, the rate of a reaction can
be written as:
j ¦ j ¦ j ¦ j ¦
t d
D +
t c
C +
or
t b
B -
t a
A -
= Rate
A
A
=
A
A
A
A
=
A
A
10
The Rate of Reaction
• The rate of a simple one-step reaction is directly
proportional to the concentration of the reacting
substance.
• [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.
j ¦ j ¦ A k = Rate or A Rate
C + B A
(g) (g) (g)
·
÷
6
11
The Rate of Reaction
• For a simple expression like Rate = k[A]
– 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.
12
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.
, ) , ) , )
j ¦ j ¦
2 2
g g g
X k = Rate or X Rate
Z + Y X 2
·
÷
7
13
The Rate of Reaction
• 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
14
The Rate of Reaction
• 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:
, ) , ) , )
j ¦
overall. order first and
O N in order first is reaction This
O N k = Rate
O + NO 4 O N 2
5 2
5 2
g 2 g 2 g 5 2
÷
8
15
The Rate of Reaction
• A second example is:
, )
, ) , )
, )
, ) , )
, )
, )
overall. order first and , OH in order zero
CBr, CH in order first is reaction This
] CBr CH k[ = Rate
Br COH CH OH CBr CH
-
3 3
3 3
-
aq aq 3 3
-
aq aq 3 3
+ ÷ +
16
The Rate of Reaction
• A final example of the order of a reaction is:
, ) , ) , )
j ¦
ALLY EXPERIMENT DETERMINED
ARE S EXPRESSION RATE ALL REMEMBER,
overall order third and , O in order first
NO, in order second is reaction This
O k[NO] = Rate
NO 2 O + NO 2
2
2
2
g 2 g 2 g
÷
9
17
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.
• 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. 2
2
= 4
– If the [A] is halved the rate of the reaction will
decrease by a factor of 4. (1/2)
2
= 1/4
, ) , ) , )
j ¦
2
g g g
A k = Rate
C B A 2 + ÷
18
Factors That Affect Reaction
Rates
• There are several factors that can
influence the rate of a reaction:
1. The nature of the reactants.
2. The concentration of the reactants.
3. The temperature of the reaction.
4. The presence of a catalyst.
• We will look at each factor individually.
10
19
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.
, ) , ) , ) , )
burns. and ignites H The
reaction. rapid and violent a is This
H NaOH 2 O H 2 Na 2
2
g 2 aq 2 s
+ ÷ +

20
Nature of Reactants
• Calcium reacts with water only slowly at
room temperature to liberate hydrogen
and form calcium hydroxide.
, ) , )
, )
, )
, )
reaction. slow rather a is This
H OH Ca O H 2 Ca
g 2
aq 2 2 s
+ ÷ +

11
21
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.
, ) , )
reaction No O H Mg
2 s
÷ +

22
Nature of Reactants
• However, Mg reacts with steam rapidly to
liberate H
2
and form magnesium oxide.
• The differences in the rate of these three
reactions can be attributed to the changing
“nature of the reactants”.
, ) , ) , ) g 2 s
C 100
) g ( 2 s
H MgO O H Mg + ÷ ÷ ÷ ÷ +
o
12
23
Concentrations of Reactants:
The Rate-Law Expression
• This movie illustrates how changing the
concentration of reactants affects the rate.
24
Concentrations of Reactants:
The Rate-Law Expression
• This is a simplified representation of the
effect of different numbers of molecules in
the same volume.
– The increase in the molecule numbers is
indicative of an increase in concentration.
A
(g)
+ B
(g)
Products
A B
A B
A B
B
A B
A B
A B
A B
4 different possible
A-B collisions
6 different possible
A-B collisions
9 different possible
A-B collisions
13
25
Concentrations of Reactants:
The Rate-Law Expression
• Example 16-1: The following rate data were obtained at
25
o
C 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
Initial [A]
(M)
Initial [B]
(M)
Initial rate of
formation of
C (M/s)
1 0.10 0.10 2.0 x 10
-4
2 0.20 0.30 4.0 x 10
-4
3 0.10 0.20 2.0 x 10
-4
26
Concentrations of Reactants:
The Rate-Law Expression
j ¦ j ¦
, )
j ¦ j ¦
j ¦. B ignore can can we Thus,
k[A] = Rate or B A k = Rate
0 1 2
constant. remains rate initial that the Notice
2. by increases [B] that the and constant is [A] the
that see we 3 and 1 s experiment compare we If
B A k = Rate
: form the of be must law rate The
0
x
x
y
y x
y = =
14
27
Concentrations of Reactants:
The Rate-Law Expression
, )
You do it!
x
x
reaction? for this
k of units and value the is What
overall. order 1 and A to
respect order with 1 is reaction This
k[A] = Rate or k[A] = Rate
1 2 2
2. by increases rate the and
2 by increases [A] that the Notice
2. and 1 s experiment compare Next,
st
st
1
= =
28
Concentrations of Reactants:
The Rate-Law Expression
j ¦
[A] 10 x 2.0 = Rate
as written be can law rate the Thus
10 x 2.0
10 . 0
10 x 2.0
= k
1 experiment from [A] and Rate of values the Using
A
Rate
= k
law. rate the from k of value the find can We
s
1
3 -
s
1
3 - s
4 -
=
÷
M
M
15
29
Concentrations of Reactants:
The Rate-Law Expression
• Example 16-2: The following data were obtained
for the following reaction at 25
o
C. What are the
rate-law expression and the specific rate constant
for the reaction?
2 A
(g)
+ B
(g)
+ 2 C
(g)
÷ 3 D
(g)
+ 2 E
(g)
Experimen
t
Initial [A]
(M)
Initial [B]
(M)
Initial
[C]
(M)
Initial rate
of
formation
of D (M/s)
1 0.20 0.10 0.10 2.0 x 10
-4
2 0.20 0.30 0.20 6.0 x 10
-4
3 0.20 0.10 0.30 2.0 x 10
-4
4 0.60 0.30 0.40 1.8 x 10
-3
30
Concentrations of Reactants:
The Rate-Law Expression
j ¦ j ¦
j ¦
, )
j ¦ j ¦ j ¦ j ¦ j ¦
y x z y x
z
z
B A k = Rate or C B A k = Rate
0 1 3
constant. remains rate but the 3 by increases C The
constant. remain B and A that Notice
3. and 1 s experiment Compare
= =
16
31
Concentrations of Reactants:
The Rate-Law Expression
j ¦
j ¦
, )
j ¦ j ¦ j ¦ j ¦ B A k = Rate or B A k = Rate
1 3 3
3. by increases rate the and 3 by increases B The
constant. remains A The
2. and 1 s experiment compare Next,
1 x x
y
y = =
32
Concentrations of Reactants:
The Rate-Law Expression
j ¦
j ¦
, )
j ¦ j ¦ j ¦j ¦
overall. order 2 and B, respect to order with 1
A, respect to order with 1 is reaction This
B A k = Rate or B A k = Rate
1 3 3
3. by increases rate the and 3 by increases A The
constant. remains B The
4. and 2 s experiment compare Next,
nd st
st
1 1
= = x
x
17
33
Concentrations of Reactants:
The Rate-Law Expression
j ¦j ¦ j ¦j ¦
j ¦j ¦ B A 10 0 . 1 = Rate
as written be can law - rate the Thus,
10 0 . 1
0.10 0.20
10 0 . 2
B A
Rate
= k
4. or 3, 2, 1, experiment from data the use Can
k. of units and value the determine Finally,
s
1
2
s
1
2
s
4
M
M
M
M M
÷
÷
÷
×
× =
×
=
34
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
given below, fill in the blanks.
You do it!
Experiment
Initial Rate
(M/s)
Initial [A]
(M)
Initial [B]
(M)
1 4.0 x 10
-3
0.20 0.050
2 1.6 x 10
-2
? 0.050
3 3.2 x 10
-2
0.40 ?
18
35
Concentrations of Reactants:
The Rate-Law Expression
j ¦j ¦
j ¦j ¦ j ¦j ¦
j ¦j ¦ B A 40 . 0 Rate the Thus
40 . 0
0.050 0.20
10 0 . 4
B A
Rate
= k
k. of value the determine can we 1 experiment From
B A k = Rate
s
1
s
1
s
3
M
M
M
M M
=
=
×
=
÷
36
Concentrations of Reactants:
The Rate-Law Expression
, ), )
M
M M
M
80 . 0 ] A [
050 . 0 s 0.40
s 10 6 . 1
] A [
k[B]
Rate
[A]
2 experiment from data and k of value the Use
1 - 1
1 - 2
=
×
=
=
÷
÷
19
37
Concentrations of Reactants:
The Rate-Law Expression
, ), )
M
M M
M
20 . 0 [B]
40 . 0 s 0.40
s 10 2 . 3
[B]
k[A]
R
[B]
determine can we 3 experiment from Similarly,
1 - 1
1 - 2
=
×
=
=
÷
÷
38
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 1
st
order in the reactant
and 1
st
order overall.
20
39
Concentration vs. Time: The
Integrated Rate Equation
• An example of a reaction that is 1
st
order
in the reactant and 1
st
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 N
2
O
5(g)
÷2 N
2
O
4(g)
+ O
2(g)
238
U ÷
234
Th +
4
He
40
Concentration vs. Time: The
Integrated Rate Equation
where:
[A]
0
= mol/L of A at time t=0. [A] = mol/L of A at time t.
k = specific rate constant. t = time elapsed since
beginning of reaction.
a = stoichiometric coefficient of A in balanced overall
equation.
• The integrated rate equation for first order reactions
is:
j ¦
j ¦
k t a
A
A
ln
0
=
21
41
Concentration vs. Time: The
Integrated Rate Equation
• Solve the first order integrated rate equation for t.
• Define the half-life, t
1/2
, 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
.
j ¦
j ¦
|
|
.
|

\
|
=
A
A
ln
k a
1
t
0
42
Concentration vs. Time: The
Integrated Rate Equation
• At time t = t
1/2
, the expression becomes:
j ¦
j ¦
, )
k a
693 . 0
t
2 ln
k a
1
t
A 1/2
A
ln
k a
1
t
1/2
1/2
0
0
1/2
=
=
|
|
.
|

\
|
=
22
43
Concentration vs. Time: The
Integrated Rate Equation
• Example 16-4: Cyclopropane, an
anesthetic, decomposes to propene
according to the following equation.
The reaction is first order in cyclopropane
with k = 9.2 s
-1
at 1000
0
C. Calculate the half
life of cyclopropane at 1000
0
C.
C H
2
CH
2
CH
2
CH
2
C H
3
CH
(g)
(g)
s 075 . 0
s 2 . 9
693 . 0
k
693 . 0
t
1 -
1/2
= = =
44
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.
23
45
Concentration vs. Time: The
Integrated Rate Equation
, ), )
, )
remains 1% or g 03 . 0 e A
5 . 3 10 . 1 6 . 4 A ln
6 . 4 A ln 10 . 1
s 50 . 0 s 2 . 9 A ln - 3.0 ln
k t A ln A ln
. logarithms of laws the use must We
reaction for this k t k t a
A
A
ln
3.5 -
1 -
0
0
~ = =
÷ = ÷ ÷ =
= ÷
=
= ÷
= =
|
.
|

\
|
46
Concentration vs. Time: The
Integrated Rate Equation
• Example 16-6: The half-life for the
following first order reaction is 688 hours
at 1000
0
C. Calculate the specific rate
constant, k, at 1000
0
C and the amount of
a 3.0 g sample of CS
2
that remains after
48 hours.
CS
2(g)
÷ CS
(g)
+ S
(g)
You do it!
24
47
Concentration vs. Time: The
Integrated Rate Equation
1 -
1/2
1/2
hr 00101 . 0
hr 688
0.693
k
t
0.693
k
k
693 . 0
t
1. a reaction For this
= =
=
=
=
48
Concentration vs. Time: The
Integrated Rate Equation
j ¦
j ¦
j ¦ j ¦
j ¦ hr) 48 )( hr 00101 . 0 ( A ln - ln(3.0)
k t A ln A ln k t
A
A
ln
1 -
0
0
=
= ÷ =
j ¦
j ¦
j ¦ j ¦
j ¦
j ¦
j ¦
j ¦ unreacted 97% or g 9 . 2 g 86 . 2 e A
1.052 1.10) - -(0.048 A ln
0.048 A ln - 1.10
hr) 48 )( hr 00101 . 0 ( A ln - ln(3.0)
k t A ln A ln k t
A
A
ln
1.052
1 -
0
0
~ = =
= =
=
=
= ÷ =
25
49
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:
• Where:
[A]
0
= mol/L of A at time t=0. [A] = mol/L of A at time t.
k = specific rate constant. t = time elapsed since
beginning of reaction.
a = stoichiometric coefficient of A in balanced overall equation.
j ¦ j ¦
k t a
A
1
A
1
0
= ÷
50
Concentration vs. Time: The
Integrated Rate Equation
• Second order reactions also have a half-life.
– Using the second order integrated rate-law as a
starting point.
• At the half-life, t
1/2
[A] = 1/2[A]
0
.
j ¦ j ¦
j ¦
0
1/2
0 0
A of r denominato common a has which
k t a
A
1
A 2 / 1
1
= ÷
j ¦ j ¦
j ¦
1/2
0
1/2
0 0
k t a
A
1
or k t a
A
1
A
2
=
= ÷
26
51
Concentration vs. Time: The
Integrated Rate Equation
• If we solve for t
1/2
:
• Note that the half-life of a second order
reaction depends on the initial
concentration of A.
j ¦
0
1/2
A k a
1
t =
52
Concentration vs. Time: The
Integrated Rate Equation
• Example 16-7: Acetaldehyde, CH
3
CHO, undergoes
gas phase thermal decomposition to methane and
carbon monoxide.
The rate-law expression is Rate = k[CH
3
CHO]
2
,
and k = 2.0 x 10
-2
L/(mol
.
hr) at 527
o
C. (a) What
is the half-life of CH
3
CHO if 0.10 mole is
injected into a 1.0 L vessel at 527
o
C?
, ) , ) , )
CH CHO CH + CO
3 g 4 g g
A
÷ ÷ ÷
27
53
Concentration vs. Time: The
Integrated Rate Equation
j ¦
, )
, )
t
k A
hr
hr
1/2
-1
=
=
×
= ×
÷ ÷
1
1
2 0 10 010
50 10
0
2 1
2
. .
.
M M
54
Concentration vs. Time: The
Integrated Rate Equation
• (b) How many moles of CH
3
CHO remain after
200 hours?
j ¦ j ¦
j ¦
, )
, )
j ¦
1 1
1 1
010
2 0 10 200
1
10 4 0
0
2 1
1 1
A A
k t
A
hr hr
A
-1
÷ =
÷ = ×
÷ =
÷ ÷
÷ ÷
.
.
.
M
M
M M
j ¦
j ¦
j ¦
1
14
1
14
0 071
0 071 mol
1
1
A
A
A
mol =1.0 L x 0.071
mol
L
= =
=
=
÷
÷
M
M
M .
? .
28
55
Concentration vs. Time: The
Integrated Rate Equation
• (c) What percent of the CH
3
CHO remains
after 200 hours?
reacted 29% and unreacted % 71
% 100
mol 0.10
mol 0.071
= unreacted %
=
×
56
Concentration vs. Time: The
Integrated Rate Equation
• Example 16-8: Refer to Example 16-7. (a)
What is the half-life of CH
3
CHO if 0.10
mole is injected into a 10.0 L vessel at
527
o
C?
– Note that the vessel size is increased by a
factor of 10 which decreases the
concentration by a factor of 10!
You do it!
29
57
Concentration vs. Time: The
Integrated Rate Equation
j ¦
, )
, )
t
k A
hr
hr
note the time has increased by 10
over Example 16- 7:
1/2
-1
=
=
×
= ×
÷ ÷
1
1
2 0 10 0 010
50 10
0
2 1
3
. .
.
M M
58
Concentration vs. Time: The
Integrated Rate Equation
• (b) How many moles of CH
3
CHO remain
after 200 hours?
You do it!
30
59
Concentration vs. Time: The
Integrated Rate Equation
j ¦ j ¦
j ¦
, )
, )
j ¦
1 1
1 1
0 010
2 0 10 200
1
100 4 0
0
2 1
1 1
A A
k t
A
hr hr
A
-1
÷ =
÷ = ×
÷ =
÷ ÷
÷ ÷
.
.
.
M
M
M M
j ¦
j ¦
j ¦
1
104
1
104
0 0096
0 096 mol
1
1
A
A
A
mol =10.0 L x 0.0096
mol
L
= =
=
=
÷
÷
M
M
M .
? .
60
Concentration vs. Time: The
Integrated Rate Equation
• (c) What percent of the CH
3
CHO remains
after 200 hours?
You do it!
31
61
Concentration vs. Time: The
Integrated Rate Equation
% unreacted =
0.096 mol
0.100 mol
unreacted & 4% reacted
×
=
100%
96%
62
Concentration vs. Time: The
Integrated Rate Equation
• Let us now summarize the results from the last
two examples.
Initial
Moles
CH
3
CHO
[CH
3
CHO]
0
(M)
[CH
3
CHO
]
(M)
Moles of
CH
3
CH
O at 200
hr.
%
CH
3
CHO
remainin
g
Ex. 16-
7
0.10 0.10 0.071 0.071 71%
Ex. 16-
8
0.010 0.010 0.0096 0.096 96%
32
63
Enrichment - Derivation of
Integrated Rate Equations
• For the first order reaction
a A ÷products
the rate can be written as:
j ¦
|
.
|

\
|
A
A
t
A
a
1
- = Rate
64
Enrichment - Derivation of
Integrated Rate Equations
• For a first-order reaction, the rate is proportional
to the first power of [A].
j ¦
j ¦
-
1
a
A
t
k A
A
A
|
\

|
.
|
=
33
65
Enrichment - Derivation of
Integrated Rate Equations
• In calculus, the rate is defined as the
infinitesimal change of concentration d[A] in an
infinitesimally short time dt as the derivative of
[A] with respect to time.
j ¦
j ¦
-
1
a
A
t
k A
d
d
|
\

|
.
|
=
66
Enrichment - Derivation of
Integrated Rate Equations
• Rearrange the equation so that all of the [A]
terms are on the left and all of the t terms are on
the right.
j ¦
j ¦
, )
-
A
A
a k t
d
d =
34
67
Enrichment - Derivation of
Integrated Rate Equations
• Express the equation in integral form.
j ¦
j ¦
j ¦
j ¦
, )
-
A
A
a k t
A
A
t
d
d
0
0
}
=
}
68
Enrichment - Derivation of
Integrated Rate Equations
• This equation can be evaluated as:
j ¦
j ¦ j ¦ , ) , )
j ¦ j ¦
-ln A a k t or
-ln A A a k t - a k 0
which becomes
-ln A A a k t
t
0
t
t
t
0
0
0
=
+ =
+ =
ln
ln
35
69
Enrichment - Derivation of
Integrated Rate Equations
• Which rearranges to the integrated first order
rate equation.
j ¦
j ¦
k t a
A
A
ln
t
0
=
70
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:
j ¦
j ¦
2
A k
t a
A
= ÷
d
d
36
71
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.
j ¦
j ¦
t k
A a
A
2
d
d
= ÷
72
Enrichment - Derivation of
Integrated Rate Equations
• Then integrate the equation over the limits as for
the first order reaction.
j ¦
j ¦
j ¦
j ¦
} }
= ÷
t
0
A
A
2
t k a
A
A
0
d
d
37
73
Enrichment - Derivation of
Integrated Rate Equations
• Which integrates the second order integrated
rate equation.
j ¦ j ¦
k t a
A
1
A
1
0
= ÷
74
Enrichment - Derivation of
Integrated Rate Equations
• For a zero order reaction the rate expression is:
j ¦
k
t a
A
= ÷
d
d
38
75
Enrichment - Derivation of
Integrated Rate Equations
• Which rearranges to:
j ¦ t k a A d d = ÷
76
Enrichment - Derivation of
Integrated Rate Equations
• Then we integrate as for the other two cases:
j ¦
j ¦
j ¦
} }
= ÷
t
0
A
A
t k a A
0
d d
39
77
Enrichment - Derivation of
Integrated Rate Equations
• Which gives the zeroeth order integrated rate
equation.
j ¦ j ¦
j ¦ j ¦ k t a - A A
or
k t -a A A
0
0
=
= ÷
78
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.
j ¦ j ¦
j ¦ j ¦
0
0
A ln k t a A ln
or
k t a A ln A ln
+ ÷ =
= ÷
40
79
Enrichment - Rate Equations to
Determine Reaction Order
• The equation for a straight line is:
• Compare this equation to the rearranged first
order rate-law.
b m y + = x
80
Enrichment - Rate Equations
to Determine Reaction Order
b m y + = x
• Now we can interpret the parts of the equation
as follows:
– 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.
j ¦ j ¦
0
A ln k t a A ln + ÷ =
41
81
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.
, ) , ) , )
700K at HBr H C Br H C
g g 4 2 g 5 2
+ ÷÷ ÷
A
82
Enrichment - Rate Equations to
Determine Reaction Order
Time
(min) 0 1 2 3 4 5
[C
2
H
5
Br] 1.00 0.82 0.67 0.55 0.45 0.37
ln [C
2
H
5
Br] 0.00 -0.20 -0.40 -0.60 -0.80 -0.99
1/[C
2
H
5
Br] 1.0 1.2 1.5 1.8 2.2 2.7
42
83
Enrichment - Rate Equations
to Determine Reaction Order
• We will make three different graphs of the
data.
1 Plot the [C
2
H
5
Br] (y-axis) vs. time (x-axis)
– If the plot is linear then the reaction is zero
order with respect to [C
2
H
5
Br].
2 Plot the ln [C
2
H
5
Br] (y-axis) vs. time (x-axis)
– If the plot is linear then the reaction is first order
with respect to [C
2
H
5
Br].
3 Plot 1/ [C
2
H
5
Br] (y-axis) vs. time (x-axis)
– If the plot is linear then the reaction is second
order with respect to [C
2
H
5
Br].
84
Enrichment - Rate Equations
to Determine Reaction Order
• Plot of [C
2
H
5
Br] versus time.
– Is it linear or not?
[C
2
H
5
Br] vs. time
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5
Time (min)
[
C
2
H
5
B
r
]
43
85
Enrichment - Rate Equations
to Determine Reaction Order
• Plot of ln [C
2
H
5
Br] versus time.
– Is it linear or not?
ln [C2H5Br] vs. time
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1 2 3 4 5
Time (min)
l
n

[
C
2
H
5
B
r
]
86
Enrichment - Rate Equations
to Determine Reaction Order
• Plot of 1/[C
2
H
5
Br] versus time.
– Is it linear or not?
1/[C
2
H
5
Br] vs. time
0
1
2
3
0 1 2 3 4 5
Time (min)
1
/
[
C
2
H
5
B
r
]
44
87
Enrichment - Rate Equations
to Determine Reaction Order
• Note that the only graph which is linear is the plot of
ln[C
2
H
5
Br] vs. time.
– Thus this is a first order reaction with respect
to [C
2
H
5
Br].
• Next, we will determine the value of the rate constant
from the slope of the line on the graph of ln[C
2
H
5
Br] vs.
time.
– Remember slope = y
2
-y
1
/x
2
-x
1
.
1 -
1 2
1 2
min 20 . 0
min 3
60 . 0
slope
min 1 4
) 20 . 0 ( 80 . 0
x - x
y - y
slope
÷ =
÷
=
÷
÷ ÷ ÷
= =
88
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.
. min 0.20 k constant rate the Thus
-k -0.20 slope
1 -
=
= =
45
89
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.
• This equation can be rearranged to:
j ¦ j ¦
k t a
A
1
A
1
0
= ÷
j ¦ j ¦
0
A
1
k t a
A
1
+ =
90
Enrichment - Rate Equations
to Determine Reaction Order
• Compare the equation for a straight line and the
second order rate-law expression.
• Now we can interpret the parts of the equation
as follows:
– 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.
b m y + = x
j ¦ j ¦
0
A
1
k t a
A
1
+ =
46
91
Enrichment - Rate Equations
to Determine Reaction Order
• Example 16-10: Concentration-versus-
time 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
, ) , ) , )
500K at O NO 2 NO 2
g 2 g g 2
+ ÷÷ ÷
A
92
Enrichment - Rate Equations
to Determine Reaction Order
Time
(min) 0 1 2 3 4 5
[NO
2
] 1.0 0.53 0.36 0.27 0.22 0.18
ln [NO
2
] 0.0 -0.63 -1.0 -1.3 -1.5 -1.7
1/[NO
2
] 1.0 1.9 2.8 3.7 4.6 5.5
47
93
Enrichment - Rate Equations
to Determine Reaction Order
• Once again, we will make three different graphs
of the data.
1. Plot [NO
2
] (y-axis) vs. time (x-axis).
• If the plot is linear then the reaction is zero order with
respect to NO
2
.
2. Plot ln [NO
2
] (y-axis) vs. time (x-axis).
• If the plot is linear then the reaction is first order with
respect to NO
2
.
3. Plot 1/ [NO
2
] (y-axis) vs. time (x-axis).
• If the plot is linear then the reaction is second order
with respect to NO
2
.
94
Enrichment - Rate Equations
to Determine Reaction Order
• Plot of [NO
2
] versus time.
– Is it linear or not?
[NO2] vs. time
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5
Time (min)
[
N
O
2
]
48
95
Enrichment -Rate Equations
to Determine Reaction Order
• Plot of ln [NO
2
] versus time.
– Is it linear or not?
ln [NO
2
] vs. time
-2
-1.5
-1
-0.5
0
0 1 2 3 4 5
Time (min)
l
n

[
N
O
2
]
96
Enrichment - Rate Equations
to Determine Reaction Order
• Plot of 1/[NO
2
] versus time.
– Is it linear or not?
1/[NO
2
] vs.time
0
1
2
3
4
5
6
0 1 2 3 4 5
Time (min)
1
/
[
N
O
2
]
49
97
Enrichment - Rate Equations
to Determine Reaction Order
• Note that the only graph which is linear is
the plot of 1/[NO
2
] vs. time.
• Thus this is a second order reaction with
respect to [NO
2
].
• Next, we will determine the value of the
rate constant from the slope of the line on
the graph of 1/[NO
2
] vs. time.
98
Enrichment - Rate Equations
to Determine Reaction Order
• From the equation for a second order reaction
we know that the slope = a k
– In this reaction a = 2.
1 - 1
min 0.45 k constant rate the Thus
k 2 0.90 slope
÷
=
= =
M
min
1
1
1
1 2
1 2
90 . 0
min 4
60 . 3
slope
min 1 5
) 90 . 1 ( 50 . 5
x - x
y - y
slope
M
M
M
= =
÷
÷
= =
50
99
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.
100
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:
• 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.
kJ 891 O H CO O CH
(g) 2 2(g) 2(g) 4(g)
+ + ÷ +
51
101
Collision Theory of
Reaction Rates
• Illustrate the proper orientation of
molecules that is necessary for this
reaction.
X
2(g)
+ Y
2(g)
÷2 XY
(g)
• Some possible ineffective collisions are :
X
X
Y Y
Y
Y
X X
X X Y Y
102
Collision Theory of
Reaction Rates
• An example of an effective collision is:
X Y
X Y
X Y
X Y
X Y
+
X Y
52
103
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 E
a
.
• Look at a mechanical analog for activation
energy
104
Transition State Theory
E
pot
= mg h
Cross section
of mountain
Boulder
E
activation
h
h
2
h
1
E
pot
=mgh
2
E
pot
=mgh
1
Height
53
105
Transition State Theory
Potential
Energy
Reaction Coordinate
X
2
+ Y
2
2 XY
E
activation
- a kinetic quantity
E ~AH
a thermodynamic
quantity
Representation of a chemical reaction.
106
Transition State Theory
54
107
Transition State Theory
• The relationship between the activation
energy for forward and reverse reactions
is
– Forward reaction = E
a
– Reverse reaction = E
a
+ E
– difference = E
108
Transition State Theory
• The distribution of molecules possessing
different energies at a given temperature is
represented in this figure.
55
109
Reaction Mechanisms and the
Rate-Law Expression
• Use the experimental rate-law to postulate a
molecular mechanism.
• The slowest step in a reaction mechanism is the
rate determining step.
110
Reaction Mechanisms and the
Rate-Law Expression
• Use the experimental rate-law to
postulate a mechanism.
• The slowest step in a reaction mechanism
is the rate determining step.
• Consider the iodide ion catalyzed
decomposition of hydrogen peroxide to
water and oxygen.
, ) , ) , ) g 2 2
I
2 2
O + O H 2 O H 2
-
 
÷÷ ÷
56
111
Reaction Mechanisms and the
Rate-Law Expression
• This reaction is known to be first order in H
2
O
2
,
first order in I
-
, and second order overall.
• The mechanism for this reaction is thought to be:
j ¦j ¦
-
2 2
2 2 2 2
-
2 2 2 2
-
2
- -
2 2
I O H k = R law rate al Experiment
O + O H 2 O H 2 reaction Overall
I + O + O H O H + IO step Fast
O H + IO I + O H step Slow
÷
÷
÷
112
Reaction Mechanisms and the
Rate-Law Expression
• Important notes about this reaction:
1. One hydrogen peroxide molecule and one
iodide ion are involved in the rate determining
step.
2. The iodide ion catalyst is consumed in step 1
and produced in step 2 in equal amounts.
3. Hypoiodite ion has been detected in the
reaction mixture as a short-lived reaction
intermediate.
57
113
Reaction Mechanisms and the
Rate-Law Expression
• Ozone, O
3
, reacts very rapidly with nitrogen
oxide, NO, in a reaction that is first order in each
reactant and second order overall.
, ) , ) , ) , )
j ¦j ¦ NO O k = Rate is law - rate al Experiment
O + NO NO + O
3
g 2 g 2 g g 3
÷
114
Reaction Mechanisms and the
Rate-Law Expression
• One possible mechanism is:
2 2 3
2 2 3
3 3
O + NO NO + O reaction Overall
O + NO NO + O step Fast
O + NO NO + O step Slow
÷
÷
÷
58
115
Reaction Mechanisms and the
Rate-Law Expression
• A mechanism that is inconsistent with the
rate-law expression is:
j ¦
correct. be cannot mechanism this proves which
O k = Rate is mechanism this from law - rate The
O NO NO + O reaction Overall
NO NO + O step Fast
O + O O step Slow
3
2 2 3
2
2 3
+ ÷
÷
÷
116
Reaction Mechanisms and the
Rate-Law Expression
• Experimentally determined reaction
orders indicate the number of molecules
involved in:
1. the slow step only or
2. the slow step and the equilibrium steps
preceding the slow step.
59
117
Temperature:
The Arrhenius Equation
• Svante Arrhenius developed this
relationship among (1) the temperature
(T), (2) the activation energy (E
a
), and (3)
the specific rate constant (k).
k = Ae
or
ln k = ln A-
E
RT
-
E
RT
a
a
118
Temperature:
The Arrhenius Equation
• This movie illustrates the effect of temperature
on a reaction.
60
119
Temperature:
The Arrhenius Equation
• If the Arrhenius equation is written for two
temperatures, T
2
and T
1
with T
2
>T
1
.
ln k ln A-
E
RT
and
ln k ln A-
E
RT
1
a
1
2
a
2
=
=
120
Temperature:
The Arrhenius Equation
1. Subtract one equation from the other.
ln k k A- ln A-
E
RT
E
RT
ln k k
E
RT
-
E
RT
2 1
a
2
a
1
2 1
a
1
a
2
÷ = ÷ ÷
|
\

|
.
|
÷ =
ln ln
ln
61
121
Temperature:
The Arrhenius Equation
2. Rearrange and solve for ln k
2
/k
1
.
ln
k
k
E
R T T
or
ln
k
k
E
R
T - T
T T
2
1
a
1 2
2
1
a 2 1
2 1
= ÷
|
\

|
.
|
=
|
\

|
.
|
1 1
122
Temperature:
The Arrhenius Equation
• Consider the rate of a reaction for which E
a
=50
kJ/mol, at 20
o
C (293 K) and at 30
o
C (303 K).
– How much do the two rates differ?
, ), )
ln
k
k
E
R
T - T
T T
ln
k
k 8.314
K
ln
k
k
k
k
e
2
1
a 2 1
2 1
2
1
J
mol
J
K mol
2
1
2
1
0.677
=
|
\

|
.
|
=
÷ |
\

|
.
|
=
= = ~
50 000 303 293
303 293
0 677
197 2
,
.
.
62
123
Temperature:
The Arrhenius Equation
• For reactions that have an E
a
~50 kJ/mol, the
rate approximately doubles for a 10
0
C rise in
temperature, near room temperature.
• Consider:
2 ICl
(g)
+ H
2(g)
÷ I
2(g)
+ 2 HCl
(g)
• The rate-law expression is known to be
R=k[ICl][H
2
].
At 230 C, k = 0.163 s
At 240 C, k = 0.348 s
k approximately doubles
0 -1 -1
0 -1 -1
M
M
124
Catalysts
• Catalysts change reaction rates by providing an
alternative reaction pathway with a different
activation energy.
63
125
Catalysts
• Homogeneous catalysts exist in same phase as
the reactants.
• Heterogeneous catalysts exist in different
phases than the reactants.
– Catalysts are often solids.
126
Catalysts
• Examples of commercial catalyst systems
include:
, ) , ) , ) , )
, ) , ) , )
, ) , ) , )
system converter catalytic Automobile
O N NO 2
CO 2 O + CO 2
O H 18 CO 16 O 25 + H C
g 2 g 2
Pt and NiO
g
g 2
Pt and NiO
g 2 g
g 2 g 2
Pt and NiO
g 2 g 18 8
+ ÷ ÷ ÷ ÷ ÷
÷ ÷ ÷ ÷ ÷
+ ÷ ÷ ÷ ÷ ÷
64
127
Catalysts
• This movie shows catalytic converter
chemistry on the Molecular Scale
128
Catalysts
• A second example of a catalytic system is:
, ) , ) , )
n preparatio acid Sulfuric
SO 2 O SO 2
g 3
NiO/Pt or O V
g 2 g 2
5 2
÷ ÷ ÷ ÷ ÷ ÷ +
65
129
Catalysts
• A third examples of a catalytic system is:
, ) , ) , )
Process Haber
NH 2 H 3 N
g 3
O Fe or Fe
g 2 g 2
3 2
÷ ÷ ÷ ÷ ÷ +
130
Catalysts
• Look at the catalytic oxidation of CO to CO
2
• Overall reaction
2 CO
(g)
+ O
2(g)
÷ 2CO
2(g)
• Absorption
CO
(g)
÷ CO
(surface)
+ O
2(g)
O
2(g)
÷ O
2(surface)
• Activation
O
2(surface)
÷ 2 O
(surface)
• Reaction
CO
(surface)
+O
(surface)
÷CO
2(surface)
• Desorption
CO
2(surface)
÷CO
2(g)
66
131
Synthesis Question
• The Chernobyl nuclear reactor accident
occurred in 1986. At the time that the
reactor exploded some 2.4 MCi of
radioactive
137
Cs was released into the
atmosphere. The half-life of
137
Cs is 30.1
years. In what year will the amount of
137
Cs released from Chernobyl finally
decrease to 100 Ci? A Ci is a unit of
radioactivity called the Curie.
132
Synthesis Question
Ci 100 reaches Chernobyl at emitted Cs from
ity radioactiv the when 2426 440 1986
years 440 years 439
y 0230 . 0
10.1
t
t y 0230 . 0 10.1
t y 0230 . 0
Ci 100
Ci 10 2.4
ln
decay e radioactiv for this 1 a and k t a
A
A
ln
Ci 10 2.4 MCi 2.4
y 0230 . 0
y 1 . 30
693 . 0
t
693 . 0
k
k
693 . 0
t
137
1 -
1 -
1 -
6
0
6
1 -
2
1
2
1
= +
~ = =
- =
- =
|
|
.
|

\
| ×
= =
|
.
|

\
|
× =
= = = =
67
133
Group Question

99m
Tc has a half-life of 6.02 hours and is
often used in nuclear medical diagnostic
tests. Patients are injected with
approximately 10 mCi of
99m
Tc that is then
directed to specific sites in the patient’s
body to detect gallstones, brain tumors
and function, and other medical
conditions. How long will the patient have
a higher than normal radioactivity level
after they have been injected with 10 mCi
of
99m
Tc?
16
Chemical Kinetics

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