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Kultur Dokumente
CHM096
CHAPTER
2
CHEMICAL
KINETICS
PREPARED BY
SYED ABDUL ILLAH ALYAHYA BIN SYED ABD KADIR
TOPICS
2.1 Rate of Chemical Reactions
2.2 Factors Controlling Rates of
Reactions
2.3 Rate Laws
2.4 Integrated Rate Laws
2.5 Collision Theory, Transition State
Theory,
and Activation
Energy
2.6 Arrhenius
Equation
2.7 Reaction Mechanisms and Rate
Determining Step
2
TOPIC
RATE OF CHEMICAL REACTIONS
Rate = [concentration]
time
Rate = [products] = - [reactants]
time
time
5
at t = 0
[A] = 8
[B] = 8
[C] = 0
at t = 16
[A] = 4
[B] = 4
[C] = 4
at t
[X]
[Y]
[Z]
=
=
=
=
0
8
8
0
at t = 16
[X] = 7
[Y] = 7
[Z] = 1
A 2 A 1
A
Rate
t 2 t1
t
X
X 2 X1
Rate
t 2 t1
t
Rate
Rate
4 8
16 0
0.25
7 8
16 0
0.0625
C C 2 C1
Rate
t 2 t1
t
Z Z 2 Z1
Rate
t 2 t1
t
Rate
Rate
4 0
16 0
0.25
1 0
16 0
0.0625
Average Rate
The average rate is the change in measured
concentrations in any particular time period
linear approximation of a curve
8
C4H9Cl
(aq) +
H 2O
(l)
C4H9OH
(aq) +
HCl
(aq)
[C4H9Cl] (M)
0.0
0.100
50.0
0.0905
100.0
0.0820
150.0
0.0741
200.0
0.0671
300.0
0.0549
400.0
0.0448
500.0
0.0368
800.0
0.0200
10,000
0
9
Time, t (s)
[C4H9Cl] (M)
Average Rate
(M/s)
0.0
0.100
50.0
0.0905
1.9 x 10-4
100.0
0.0820
1.7 x 10-4
150.0
0.0741
1. 6x 10-4
200.0
0.0671
1.4x 10-4
300.0
0.0549
1.22 x 10-4
400.0
0.0448
1.01x 10-4
500.0
0.0368
0.8x 10-4
800.0
0.0200
0.560 x 10-4
0
Note that10,000
the average rate decreases as the reaction
proceeds.
This is because as the reaction goes forward, there
are fewer collisions between reactant molecules. 10
Time, t (s)
[C4H9Cl] (M)
Average Rate
(M/s)
0.0
0.100
50.0
0.0905
1.9 x 10-4
100.0
0.0820
1.7 x 10-4
150.0
0.0741
1. 6x 10-4
200.0
0.0671
1.4x 10-4
300.0
0.0549
1.22 x 10-4
400.0
0.0448
1.01x 10-4
500.0
0.0368
0.8x 10-4
800.0
0.0200
0.560 x 10-4
10,000
1 x 10-5
(aq) +
H2O
C4H9OH
(l)
(aq) +
HCl
(aq)
[C4H9OH]
t
14
H2(g) + I2(g)
2HI
(g)
[HI] increases twice as fast as
[H2] decreases.
Rate = -
Rate =
[H2]
t
[HI]
t
=-
= -2
[I2]
t
[H2]
t
[HI]
1
=
t
2
= -2
[I2]
t
15
aA + bB
cC + dD
17
Answer to Example 1
Strategy To express the rate of the reaction in terms
of the change in concentration of a reactant or product
with time, we need to use the proper sign (minus or
plus) and the reciprocal of the stoichiometric
coefficient.
Solution
Because each of the stoichiometric coefficients equals
1,
(aq)
22
23
2N2O5 (g)
TOPIC
FACTORS CONTROLLING
RATES OF REACTIONS
27
Origins
Organic
2.2
FACTORSof
CONTROLLING
RATES OF REACTIONS
Chemistry
Origins
Organic
2.2
FACTORSof
CONTROLLING
RATES OF REACTIONS
Chemistry
Concentrations
of Reactants
Foundations
of organic chemistry
from mid-1700s.
Compounds obtained from plants, animals hard to
isolate,
and
purify.
As
the
concentration of reactants
increases, so does the likelihood that
Compounds
also decomposed
more
easily.
reactant
molecules will
collide.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
29
30
31
speed up reactions by
the mechanism of the
are not consumed during the
the reaction.
32
TOPIC
RATE LAWS
33
34
2NO2 + O2
[N2O5]
Rates (M.min-1)
0.17
0.00080
0.34
0.0014
0.68
0.0028
(aq) + HCOOH
(aq)
2Br-
+
+
2H
(aq)
(aq) +
CO2
(g)
(aq) +
HCOOH
(aq)
2Br-
(aq) +
2H+
(aq) +
CO2
(g)
38
(aq) + HCOOH
(aq)
2Br-
+
+
2H
(aq)
(aq) +
CO2
(g)
rate [Br2]
rate = k [Br2]
rate
k=
[Br2]
k = rate
constant
= 3.50 x 10-3 s-1
Knowing the k allow you to calculate the rate at a particular
concentration. The units of k depends on the rate law or order of
reaction for a particular reaction- next slide will discussed further.
39
42
if for the
reaction
A
Products
Rate =
k[A]n
then
doubling the
initial
concentratio
n of A does
not change
the initial
reaction rate.
Thus, n = 0
(Zero Order)
43
Rate =
k[A]n
then
doubling the
initial
concentratio
n of A
doubles the
initial
reaction rate.
Thus, n = 1
(First Order)44
Rate =
k[A]n
then doubling
the initial
concentration
of A
quadruples
the initial
reaction rate.
Thus, n = 2
(Second
Order)
45
2
49
NH4+(aq) + NO2(aq)
N2(g) + 2 H2O(l)
50
NH4+(aq) + NO2(aq)
N2(g) + 2 H2O(l)
51
+
Rate
=
k
[NH
]
[NO
The overall reaction order can
4
2 ]
be found
by adding the
exponents on the reactants in the rate law.
This reaction is second-order overall.
52
(g)
+ O2 (g)
2 NO 2 (g)
Rate = k[NO]2[O2]
The reaction is:
second order with respect to [NO],
first order with respect to [O2],
and third order overall.
53
(g)
54
when
I3-(aq) + 2H2O(l)
rate = k[H2O2][I-]
56
57
58
59
60
Rate
61
62
63
64
65
66
2.3 RATE
LAWS
Origins
of Organic
Answer
to Example 7
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
67
2.3 RATE
LAWS
Origins
of Organic
Answer
to Example 7
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
and inorganic chemistry.
n =between
2, m =organic
0
It was thought that organic compounds must contain
some vital force because they were from living
sources.
68
2.3 RATE
LAWS
Origins
of Organic
Answer
to Example 7
Chemistry
Substitute
the of organic
Foundations
from
mid-1700s.
Expt. chemistry
Initial
Initial Rate
Initial
concentrations
Number [NO2], (M) [CO], (M)
(M/s)
and
rate for
Compounds
obtained from plants, animals hard to
1.
0.10
0.10
0.0021
any isolate,
experiment
and purify.
into the rate
2.
0.20
0.10
0.0082
law
and solve also decomposed more easily.
Compounds
3.
0.20
0.20
0.0083
for k
4.
0.40
0.033
Torben Bergman (1770)
first
to make0.10
distinction
Ratebetween
k[NO2 ]2organic and inorganic chemistry.
for expt 1
It was thought that
organic compounds must contain
2
M k 0.10 M
0.0021
some
vital force because they were from living
s
sources.
0.0021 Ms
1
1
k
0.21
M
s
0.01 M2
69
2.3 RATE
LAWS
Origins
of Organic
Example 8
Chemistry
Foundations
organic
chemistry
fromfor
mid-1700s.
Determine theofrate
law and
rate constant
the reaction
NH4+ + NO2
N 2 + 2 H2O
Compounds obtained from plants, animals hard to
given the data below
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
70
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
71
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
72
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
Rate = k[NH4+]n[NO2]m
74
A2
NO
Cl2
0.10
0.10
0.18
0.10
0.20
0.35
0.20
0.20
1.45
2.3 RATE
LAWS
Origins
of Organic
Exercise 7
Chemistry
When
methylof
bromide
with from
hydroxide
ion in
Foundations
organicreacts
chemistry
mid-1700s.
solution, methyl alcohol and bromide ion form.
Compounds obtained
from plants, animals hard
to
CHisolate,
Br
+
OH
CH
OH
+
Br
3
3
and purify.
Determine
the
rate
law and evaluate
the rate
Compounds
also
decomposed
more easily.
constant from the experimental data.
Torben
Bergman
firstInitial
to make
Experime
Initial(1770)
[CH3Br]
[OH-]distinction
Initial Rate
between
organic
and inorganic
nt
(M)chemistry.(M/s)
(M)
1
0.050
0.010
2.4 x 10-3
2.3 RATE
LAWS
Origins
of Organic
Exercise 8
Chemistry
Consider the reaction X + Y
Z
0.147
0.10
2
0.127
Compounds
also decomposed
more0.20
easily.
3
4.064
0.40
0.50
0.30
0.60
0.508
0.40
0.30
Exp
[BrO3-]
[Br-]
[H+]
Rate
(L/mol.s
)
0.1
0.1
0.1
8.0 x 10-4
0.2
0.1
0.1
1.6 x 10-3
0.2
0.2
0.1
3.2 x 10-3
0.1
0.1
0.2
3.2 x 10-3
79
TOPIC
INTEGRATED RATE LAWS
80
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Concentration-Time Relationships:
Chemistry
Integrated Rate Laws
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Integrated Rate Laws : First-Order
Chemistry
Reactions
Foundations
of organic
chemistry
from
mid-1700s.
Using calculus
to integrate
the rate
law
for a firstorder process gives us
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Where
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
[A]0 is the initial concentration of A, and
It was thought that organic compounds must contain
[A]t some
is the vital
concentration
of A atthey
some
time,
t, during
force because
were
from
living the
sources.
course
of the reaction.
82
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Integrated Rate Laws : First-Order
Chemistry
Reactions
Foundations this
of organic
chemistry
from mid-1700s.
Manipulating
equation
produces
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
ln [A]t
ln [A]0 =
kt
ln [A]t = kt + ln
It was thought that organic compounds must contain
[A]
which
in the
form
0 because they were from living
some is
vital
force
sources.
mx
+ b
83
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Integrated Rate Laws : First-Order
Chemistry
Reactions
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Integrated Rate Laws : First-Order
Chemistry
Reactions
sl
op
Compounds
also decomposedemore easily.
ln[A]
=
distinction
Torben Bergman (1770) first to make
k
between organic and inorganic chemistry.
time
85
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Half-Life
Chemistry
of organic
from mid-1700s.
The half-life,
t1/2, chemistry
of a reaction
is the time
Foundations
it takes for the concentration of the reactant
Compounds obtained from plants, animals hard to
to
fall to
purify.
its initial value
isolate,
and
The half-life of the reaction depends on the
Compounds also decomposed more easily.
order of the reaction
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
86
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Half Life
for First- Order
Foundations of organic chemistry from mid-1700s.
Integrated rate law : ln[A]t = kt + ln[A]0
Compounds obtained from plants, animals hard to
isolate, and purify.
t = [A]t = [A]0
Compounds also decomposed more easily.
ln [A]0 = k t + ln[A]0
Torben
Bergman (1770) first to make distinction
between organic and inorganic chemistry.
ln [A]0 = k t
It was thought that organic compounds must contain
some[A]
vital
force because they were from living
0
sources.
t = 0.693/k. The half-life of a first order reaction is
87
constant
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
The Half-LifeChemistry
of a First Order Reaction
is Constant
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Rate Data for: Chemistry
C4H9Cl + H2O
C4H9OH +
Foundations of organic chemistry from mid-1700s.
HCl
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
89
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
The Half-Life
of a First Order
Reaction
is Constant
Foundations of
organic chemistry
from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
90
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
The Half-Life
of a First Order
Reaction
is Constant
Foundations of
organic chemistry
from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
91
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
The Half-Life of a First Order
Chemistry
Reaction is Constant
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Zero
Order Reactions
Chemistry
Foundations of organic chemistry from mid-1700s.
Using calculus to integrate the rate law for a zeroorder process
gives us
Compounds
obtained
from plants, animals hard to
isolate, and purify.
[A]easily.
Compounds also decomposed more
Where
0
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
[A]0 is the initial concentration of A, and
It was thought that organic compounds must contain
[A]t some
is the vital
concentration
of A atthey
some
time,
t, during
force because
were
from
living the
sources.
course
of the reaction.
93
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Zero
Order Reactions
Chemistry
Foundations of organic chemistry from mid-1700s.
Rate = k[A]0 = k
from[A]
plants,
animals
hard to
Integratedobtained
rate law:
= kt
+ [A]
Compounds
initial
isolate, and purify.
Graph of [A] vs. time is straight line with
Compounds
slope = k
also and
decomposed
yintercept
more easily.
= [A]initial
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Zero
Order Reactions
Foundations of organic chemistry from mid-1700s.
[A]
initi
Compounds
obtained from plants, animals hard to
al
isolate,
and purify.
[A]
time
95
1.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Half Life for
Zero Order Reactions
Foundations of organic chemistry from mid-1700s.
t =purify.
and
Compounds also decomposed more easily.
[A]0 = -k t + [A]0
t = [A0]/2k = [A0]/2k
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Second
Order Reactions
Chemistry
Foundations of organic chemistry from mid-1700s.
Using calculus to integrate the rate law for a Secondorder process
gives us
Compounds
obtained
from plants, animals hard to
isolate, and purify.
1
Compounds also decomposed more easily.
[A]
Where
Torben Bergman (1770) first to make
distinction
0
between organic and inorganic chemistry.
[A]0 is the initial concentration of A, and
It was thought that organic compounds must contain
[A]t some
is the vital
concentration
of A atthey
some
time,
t, during
force because
were
from
living the
sources.
course
of the reaction.
97
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Second
Order Reactions
Chemistry
of2organic chemistry from mid-1700s.
Foundations
Rate = k[A]
1/[A]t = ktobtained
+ 1/[A]from
Compounds
plants, animals hard to
0
isolate, and purify.
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Second
Order Reactions
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
=
e
Compounds
also decomposed omore
easily.
p
1/[A]
l
s
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
1/[A]initialthat organic compounds must contain
It was thought
some vital force because they were from living
sources.
time
99
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Half Life for Second Order
Chemistry
Reactions
t = [A]talso
=
[A]0
Compounds
decomposed
more easily.
Torben Bergman (1770) first to make distinction
[A]0organic
= k t
+ inorganic
1/[A]0 chemistry.
1/between
and
It was thought that organic compounds must contain
vital force
because they were from living
= 1/(k[A
tsome
0])
sources.
100
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
101
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Table 1
Units of the Rate
Chemistry
Constant
k from mid-1700s.
Foundations of organic
chemistry
Overall Reaction Order
Units of k (t in
seconds)
Compounds obtained from plants, animals hard to
isolate, and purify.
0
mol/L*s (or mol L-1 s-1)
Compounds also decomposed more easily.
1
1/s (or s-1)
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
2
L/mol*s (or L mol -1 sIt was thought that organic1)compounds must contain
some
vital force because
2 they2 were from
2 living
-2 3
L
/
mol
*s
(or
L
mol
s
sources.
1
)
102
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Example 9
Chemistry
Determining
Half-Life
of a First-Order
Reaction
Foundations
of the
organic
chemistry
from mid-1700s.
Cyclopropane is the smallest cyclic hydrocarbon. It is thermally
o
unstable
and rearranges
to from
propene
at 1000
C via the
following
Compounds
obtained
plants,
animals
hard
to
isolate,
and purify.
first-order
reaction:
CH2
H
CH2 (g)
3C CHeasily.
Compounds also
more
H2C decomposed
CH2 (g)
103
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 9
Foundations of organic chemistry from mid-1700s.
0.693
k
(a)
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Example 10
Chemistry
Foundations
of organic
chemistry
from
mid-1700s.
The
reaction SO
Cl
SO
+
Cl
is
first order with
2
2(g)
2(g)
2(g)
a rate constant of 2.90 x 104 s1 at a given set of
Compounds obtained from plants, animals hard to
conditions.
Findpurify.
the [SO2Cl2] at 865 s when [SO2Cl2]initial
isolate, and
= 0.0225 M
Compounds also decomposed more easily.
Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4
s1
Torben
Bergman (1770) first to make distinction
Find:
between organic] and inorganic chemistry.
Conceptual[SO2Cl2[SO
[SO2Cl2]
2Cl2]init, t, k
Plan:
It was thought that organic compounds must contain
some vital force because they were from living
Relationship
sources.s:
105
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 10
Foundations of organic chemistry from mid-1700s.
Compounds
Solution: obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
Check: the new concentration is less than the
original,
as expected
It was thought
that organic
compounds must contain
some vital force because they were from living
sources.
106
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Example 11
Chemistry
The
reaction Qoforganic
2 R is second
order
in mid-1700s.
Q. If the initial
Foundations
chemistry
from
[Q] = 0.010 M and after 5.0 x 102 seconds the [Q] =
0.0010
M, find
the
rate constant
Compounds
obtained
from
plants,
animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
107
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 11
2
Foundations
of organic
chemistry from mid-1700s.
Given: [Q]
init = 0.010 M, t = 5.0 x 10 s, [Q]t =
0.0010 M
Find:
Compounds obtained from plants, animals hard to
isolate, and
k purify.
Conceptual
[Q]init, t, [Q]t
k
Plan: also decomposed more easily.
Compounds
Relationshi
Torben Bergman (1770) first to make distinction
between
ps: organic and inorganic chemistry.
ItSolution:
was thought that organic compounds must contain
some vital force because they were from living
sources.
108
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Graphical
Determination of the
Chemistry
Rate Law for A
Product
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Example 12
Chemistry
Complete
the Table
and Determine
the
Foundations
of organic
chemistry
from mid-1700s.
Rate Equation for the Reaction A
2 Product
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
110
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
111
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
112
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
113
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
114
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 12
Foundations of organic chemistry from mid-1700s.
Conclusion for the determination of the
rate equation
for thefrom
reaction
A animals2hard
Product
Compounds
obtained
plants,
to
isolate,
and
purify.
Because
the
graph 1/[A] vs. time is linear,
the reaction is second order,
Compounds also
decomposed more easily.
2
Rate k[A]
Torben
Bergman
(1770)
toMmake
distinction
1
k slope
of the
line first
0.10
s 1
between organic and inorganic chemistry.
It was thought that organic compounds must contain
some vital force because they were from living
sources.
115
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Relationship Between
Order and Half-Life
Chemistry
Foundations of organic chemistry from mid-1700s.
For a zero order reaction, the half-life is directly
proportional
to the initial
Compounds
obtained
from concentration.
plants, animalsThe
hardlower
to
the
initialand
concentration
of the reactants, the shorter
isolate,
purify.
the half-life
t1/2 = [A]init/2k
Compounds
also decomposed more easily.
For a first order reaction, the half-life is
independent
of (1770)
the concentration.
Torben
Bergman
first to make(tdistinction
1/2 = constant)
organic and inorganic chemistry.
t1/2 = ln(2)/k
between
some vital
force
they were
from living
increasing
the
initialbecause
concentration
shortens
the
sources.
half-life
t1/2 = 1/(k[A]init)
116
Exercise 10
The reaction of decomposition
as follow
N2O5
(g)
4NO 2
(g) + O2
(g)
Ex
p
[N2O5]
(M)
Time
(s)
0.1000
0.0707
50
0.0500
100
0.0250
200
0.0125
300
0.00625
400
117
Exercise 11
The pesticide fenvalerate, C25H22ClO3N, is insect
repellent to combat the mosquitoes that spread West
Nile virus. It degrades in the environment with first
order at a rate constant 3.9 x 10-7 s-1. An accidental
discharge of 100kg fenvalerate into a holding pond
results in a fenvalerate concentration of 1.3 x 10-5 M.
Calculate the concentration after 1 month (2.6 x 106
s) after the spill.
118
Exercise 12
Substance A reacts according to a first order rate law
with k = 5.0 x 10-5 s-1
a)If the initial concentration of A is 1.00M what is the
initial rate?
b)What is the rate after 1.00 hr?
119
Exercise 13
The age of Otzi, the Ice Man was determined by
carbon-14. Carbon-14 is a radioisotope with a half life
of 5730 years. A sample of carbon containing material
was found to have 52.7% of its original amount of
carbon -14. Calculate how long ago Otzi lived.
120
Origins
Organic
Try
this- Testof
1 Nov-Mac
2012
Chemistry
TOPIC
COLLISION THEORY, TRANSITION
STATE THEORY AND ACTIVATION
THEORY
122
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Activation Energy
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Activation Energy
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Reaction
Coordinate
Diagram
Foundations
of organic
chemistry from
mid-1700s.
Compounds obtained from plants, animals hard to
isolate, and purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction
Rearrangement
of
between organic
and inorganic chemistry.
methyl isonitrile
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Maxwell-Boltzmann Distributions
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Maxwell-Boltzmann Distributions
Thus
at higher
between organic and inorganic chemistry.
temperatures, a
largermust
population
It was thought that organic compounds
containof
some vital force because theymolecules
were fromhas
living
sources.
higher energy.
132
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Maxwell-Boltzmann Distributions
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
Maxwell-Boltzmann Distributions
RT
f=e
Kelvin temperature.
134
TOPIC
ARRHENIUS EQUATION
k=Ae
where A is the frequency factor, a number that
represents the likelihood that collisions would occur
with the proper orientation for reaction.
where T is the temperature in kelvins
R is the gas constant in energy units, 8.314 J/(molK)
Ea is the activation energy, the minimum
energy needed for the molecules to react
136
y =
+ b
)+
139
140
141
142
143
Ea, kJ/mol
Conceptual
Plan:
Ea
Relationshi
ps:
Solution:
144
Exercise 14
a) Define the activation energy
Determine the Activation Energy (Ea ) and (A) in the hydrolysis of
an ester if one set of data points given to you as follow:
Exp
T (K)
K
(L/mol.
s)
288
0.0521
298
0.101
308
0.142
318
0.332
145
Exercise 15
Determine the Activation Energy (Ea ) in the reaction
between:
CH4
(g)
+ 2S2
(g)
CS2
(g)
+ 2H2S
(g)
146
Exercise 16
Biochemists often define Q10 for a reaction as the
ratio of the rate constant at 37oC to the rate constant
at 27oC. Determine the activation energy for a
reaction that has a Q10 of 2.5
147
TOPIC
REACTION MECHANISMS AND
RATE DETERMINING STEP
148
149
151
(g)
NO
(g)
NO3 + NO (slow)
Step 2: NO3 + CO
153
Rateobs = k[NO2]2
Rate = k1[NO2]2 Slow
Rate = k2[NO3][CO] Fast
1.
2.
2 NO
(g)
+ Br2
(g)
2 NOBr
(g)
157
NOBr
Step 2: NOBr2 + NO
(fast)
2 NOBr
(slow)
158
159
Fast
Slow
Rate = k2[O3][O]
163
Fast
Slow
Rate = k2[O3][O]
164
Exercise 17
Mechanisms with a slow Initial Step
2NO2
(g)
+ F2
2NO2F
(g)
(g)
(g)
+ F2
(g)
(g)
+ F
(g)
NO2F
(g)
NO2F
+ F
(g)
(g)
165
Exercise 18
Mechanisms with a Fast Initial Step
2NO
+ O2
(g)
2NO2
(g)
(g)
(g)
2. NO3
(g)
+ O2
(g)
+ NO
(g)
NO3
2NO
(g)
2 (g)
(fast, reversible)
166
End of Chapter 2
Please Read Chapter 3
Thank You
Question!
167