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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
- A - B
+ C + D
Rate =
or
a t
b t
c t
d t
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
2 X g Y g + Z g
Rate X or Rate = k X
2
2
10
For example:
2 N 2 O 5 g 4 NO 2 g + O 2 g
Rate = k N 2 O 5
12
13
2 NO + O 2 NO
g
2 g
Rate = k[NO] O
2 g
2 A g B g C g
Rate = k A
1.
2.
3.
4.
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
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
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.
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
nd
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
2 1
M s A B
29
Concentrations of Reactants:
The Rate-Law Expression
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
U 234Th + 4He
35
A 0
ln
akt
A
where:
[A]0= mol/L of A at time t=0.
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
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
CH2
H2C
CH2
(g)
H3C
CH
CH2
(g)
t1/2
0.693 0.693
0
.
075
s
-1
k
9 .2 s
39
40
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
41
43
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
1
1
akt
A A 0
Where:
[A]0= mol/L of A at time t=0.
t1/2
a k A 0
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
k A 0
2.0 10
1
2
hr
-1
0.10 M
5.0 10 hr
48
11
1
1
1
14 M
k t A
1
14 M
A A 0
1 A 10.071 M
1
1
1
10 M 4.0 M
A
0
.
071
mol
L
49
50
You do it!
51
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
A 0
ln
akt
A t
53
Enrichment - Derivation of
Integrated Rate Equations
d A
2
k A
adt
54
Enrichment - Derivation of
Integrated Rate Equations
d A
k
d
t
2
a A
55
Enrichment - Derivation of
Integrated Rate Equations
1
1
akt
A A 0
56
Enrichment - Derivation of
Integrated Rate Equations
d A
k
adt
57
Enrichment - Derivation of
Integrated Rate Equations
Which rearranges to:
d A a k d t
58
Enrichment - Derivation of
Integrated Rate Equations
A A 0 -a k t
or
A A 0 - a k t
59
ln A 0 ln A a k t
or
ln A a k t ln A 0
60
y mx b
Compare this equation to the rearranged first
order rate-law.
61
y mx b
ln A a k t ln A 0
62
C 2 H 5 Br g C 2 H 4 g HBr g at 700K
63
0
1.00
1
0.82
2
0.67
3
0.55
4
0.45
5
0.37
1.0
1.2
1.5
1.8
2.2
2.7
64
65
Is it linear or not?
66
67
68
Note that the only graph which is linear is the plot of ln[C 2H5Br] vs.
time.
y 2 - y1 0.80 (0.20)
slope
x 2 - x1
4 1 min
0.60
-1
slope
0.20 min
3 min
69
slope -0.20 -k
Thus the rate constant k 0.20 min .
-1
70
1
1
akt
A A 0
1
1
akt
A
A 0
71
y mx b
akt
A 0
72
2 NO 2 g 2 NO g O 2 g at 500K
73
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
1.
3.
76
77
78
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
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:
Collision Theory of
Reaction Rates
Y Y
X X
Y Y
Y
83
Collision Theory of
Reaction Rates
Y
+
84
Epot = mgh
h2
Height
Cross section
of mountain
h
h1
Epot=mgh1
86
Potential
Energy
E H
a thermodynamic
quantity
X2 + Y2
2 XY
Reaction Coordinate
87
88
89
90
Temperature:
The Arrhenius Equation
k = Ae
or
Ea
RT
Ea
ln k = ln A RT
91
Catalysts
Catalysts change reaction rates by providing an
alternative reaction pathway with a different
activation energy.
92