Chm096 Chapter 2 Chemical Kinetics Nov 2013 - Mac 2014

FOUNDATION CHEMISTRY II
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
2.1 RATE OF CHEMICAL

REACTIONS
Introduction
Rates of chemical reactions is the change in

concentration of either reactants or products as a
function of time.

REACTIONS
Rates
Different reactions have different rates
- higher rate/faster reaction the reactant
concentration decreases quickly
- lower rate/slower reaction it decreases slowly
For reactants = -ve sign (conc. decreases)
For products = +ve sign (conc. increases)
Rate = [concentration]
time
Rate = [products] = - [reactants]
time
time
5

REACTIONS
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

REACTIONS
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

REACTIONS
Reaction Rate Changes Over Time
As time goes on, the rate of a reaction generally
slows down
because the concentration of the reactants
decreases
At some time the reaction stops, either because the
reactants run out or because the system has reached
equilibrium
Average Rate
The average rate is the change in measured
concentrations in any particular time period
linear approximation of a curve
8
C4H9Cl

REACTIONS
(aq) +
H 2O
(l)
C4H9OH
(aq) +
HCl
(aq)
In this reaction, the concentration of butyl chloride,

C4H9Cl, was measured at various times.
Time, t (s)
[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

REACTIONS
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

REACTIONS
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
The average rate of the reaction over each interval:

is the change in concentration divided by the
change in time:
11

REACTIONS
A plot of [C4H9Cl] vs.
Foundations of organic chemistry time
from for
mid-1700s.
this reaction
yields a curve like
Compounds obtained from plants,this.
animals hard to
isolate, and purify.
The slope of a line
tangent
Compounds also decomposed more
easily.to the curve
at any point is the
instantaneous
Torben Bergman (1770) first to make
distinction rate at
between organic and inorganic that
chemistry.
time.
The instantaneous
It was thought that organic compounds
contain
rate atmust
the moment
some vital force because they were from living
the reactants are
sources.
mixed (t = 0s)
12

REACTIONS
All reactions
slow
Foundations of organic chemistry from
mid-1700s.
down over time.
animals
Compounds obtained from plants,
hard
tobest
Therefore,
the
indicator of the
rate of a reaction is
Compounds also decomposed morethe
easily.
instantaneous
rate near the
distinction
beginning
of the
between organic and inorganic chemistry.
reaction.
It was thought that organic compounds must contain
sources.
13

REACTIONS
Stoichiometry
C4H9Cl
(aq) +
H2O
C4H9OH
(l)
(aq) +
HCl
(aq)
In this reaction, the ratio

of C4H9Cl to C4H9OH is
1:1.
Thus, the rate of
disappearance of C4H9Cl
is the same as the rate
of appearance of
C4H9OH.
-[C4H9Cl]
Rate =
=
t
[C4H9OH]
t
14

REACTIONS
Stoichiometry
What if the ratio is not 1:1?
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
The expression for the rate of a reaction

and its numerical value depend on which
substance serves as the reference.
15
H2 (g) + I2 (g) 2 HI (g)
Using [H2], the

instantaneous rate
at 50 s is
Using [HI], the

instantaneous rate
at 50 s is

REACTIONS
Stoichiometry
To generalize, then, for the reaction
aA + bB
cC + dD
17

REACTIONS
Example 1
Write the rate expressions for the following reactions
in terms of the disappearance of the reactants and
the appearance of the products:

REACTIONS
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,
Here the coefficients are 4, 5, 4, and 6, so

REACTIONS
Example 2
For the reaction given, the [I] changes from1.000 M to
0.868 M in the first 10 s. Calculate the average rate in
the first 10 s, and [H+]/t.
H2O2
(aq)
+ 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)

REACTIONS
Answer to Example 2
solve the rate
equation for the
rate (in terms of
the change in
concentration of
the given
quantity)
solve the rate
equation (in
terms of the
change in the
concentration for
the quantity to
find) for the
unknown value

REACTIONS
Example 3
If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a
2.0 x 102 mL flask in 5.0 minutes, find the average rate
of Br2 production in M/s.
2 NOBr(g) 2 NO(g) + Br2(l)
22

REACTIONS
Answer to Example 3
Given: 240.0 g NOBr, 0.2000 L, 5.0 min.
Find: [Br2]/t, M/s
Conceptual
Plan:
Relationshi 2 mol NOBr:1 mol Br2,
ps: 1 mol = 109.91g, 1 mL=0.001 L
23

REACTIONS
Exercise 1
Because it has a nonpolluting product (water vapor),
hydrogen gas is used for fuel aboard the space shuttle
and may be used by earthbound engines in the near
future.
2H2(g) + O2(g)
2H2O(g)
(a) Express the rate in terms of changes in [H2], [O2],
and
[H2O] with time.
(b) When [O2] is decreasing at 0.23 mol/L.s, at what
rate is [H2O] increasing?
24

REACTIONS
Exercise 2
Consider the reaction
4NO2 (g) + O2 (g)
2N2O5 (g)
Suppose that, at a particular moment during the

reaction, molecular oxygen is reacting at the rate of
0.024 M/s.
(a)At what rate is N2O5 being formed?
(b)At what rate is NO2 reacting?

REACTIONS
Exercise 3
In a catalytic experiment involving the Haber process
N2 (g) + 3H2 (g)
2NH3 (g)
The rate of reaction was measured as
Rate = [NH3]/t = 2.0 x 10-4 mol/L.s.
(a)What was the rate of reaction expressed in terms
of N2 and H2?
TOPIC
FACTORS CONTROLLING
RATES OF REACTIONS
27
Origins
Organic
2.2
FACTORSof
CONTROLLING
RATES OF REACTIONS
Chemistry
Foundations of organic chemistry from mid-1700s.

1
CONCENTRATIONS OF REACTANTS
Compounds obtained from plants, animals hard to
isolate,
and purify.
2
CHEMICAL NATURE OF REACTANTS
Compounds also decomposed more easily.
3
TEMPERATURE
Torben Bergman (1770) first to make distinction
between
organic
and
inorganic
chemistry.
4
THE
USE
OF A CATALYST
sources.
28
Origins
Organic
2.2
FACTORSof
CONTROLLING
RATES OF REACTIONS
Chemistry
Concentrations
of Reactants
Foundations
of organic chemistry
from mid-1700s.
isolate,
and
purify.
As
the
concentration of reactants
increases, so does the likelihood that
Compounds
also decomposed
more
easily.
reactant
molecules will
collide.
sources.
29
2.2 FACTORS CONTROLLING

RATES OF REACTIONS
Chemical Nature of Reactants
In order to react, molecules must come
in contact with each other.
The more homogeneous the mixture of
reactants, the faster the molecules can
react.
30

RATES OF REACTIONS
Temperature
At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
31

RATES OF REACTIONS
The Use of A Catalyst
Catalysts
changing
reaction.
Catalysts
course of
speed up reactions by
the mechanism of the
are not consumed during the
the reaction.
32
TOPIC
RATE LAWS
33
2.3 RATE LAWS

Concentration and Rate
One can gain information about the rate of a reaction
by seeing how the rate changes with changes in
concentration (with the temperature held constant).
The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the
concentrations of the reactants
and homogeneous catalysts as well
The rate law must be determined experimentally!!

The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
34
2.3 RATE LAWS

Effect of Concentration and Reaction Rate
Consider, the decomposition of N2O5 to NO2 and O2.
N2O5
2NO2 + O2
[N2O5]
Rates (M.min-1)
0.17
0.00080
0.34
0.0014
0.68
0.0028
Doubling the concentration of N2O5 doubles the

reaction rate. These results showed the reaction
rate
directly
proportional
to
the
reactant
concentration
35
2.3 RATE LAWS

Effect of Concentration and Reaction Rate
In other reactions, different relationship between
reaction rate and reactant concentration
For example - reaction rate could be independent of
concentration, or it may depend on the reactant
concentration raised to some power [reactant]n
If reaction involved several reactants, the reaction
rate may depend on the concentrations of each of
them or only one of them.
If catalyst involved, its concentration may also
affect the rate of reaction.
36
2.3 RATE LAWS

Rate Equations
The relationship between reactant concentration
and reaction rate is expressed by an equation called
a rate equation or rate law.
Br2
(aq) + HCOOH
(aq)
2Br-
+
+
2H
(aq)
(aq) +
CO2
(g)
Consider, the above reaction, the rate is depend on

the concentration of Br2, but not concentration of
HCOOH.
So, the above reaction can be expressed as below.
Rate of reaction = k[Br2]
37
2.3 RATE LAWS

Rate Constant
Br2
(aq) +
HCOOH
(aq)
2Br-
(aq) +
2H+
(aq) +
CO2
(g)
38
2.3 RATE LAWS

Rate Constant
Br2
(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
2.3 RATE LAWS

General Views
For the reaction aA + bB products the
rate law would have the form given below
n and m are called the orders for each reactant
k is called the rate constant
The exponents tell the order of the reaction

with respect to each reactant
The values of m and n are not necessarily
related in any way to the coefficients a and b.
40
2.3 RATE LAWS

The Order of a Reaction
A reaction has an individual order with
respect to or in each reactant, and an
overall order, the sum of the individual orders.
Lets consider only one reactant, A
A
Products
Rate = k[A]n
Lets determine the order of a reaction, n by
using initial rate method
41
2.3 RATE LAWS

Finding the Rate Law: The Initial Rate
Method
The rate law must be determined
experimentally
The rate law shows how the rate of a reaction
depends on the concentration of the
reactants
Changing the initial concentration of a
reactant will therefore affect the initial rate
of the reaction
42
2.3 RATE LAWS

Method
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
2.3 RATE LAWS

Method
if for the
reaction
A
Products
Rate =
k[A]n
then
doubling the
initial
concentratio
n of A
doubles the
initial
reaction rate.
Thus, n = 1
(First Order)44
2.3 RATE LAWS

Method
if for the
reaction
A
Products
Rate =
k[A]n
then doubling
the initial
concentration
of A
quadruples
the initial
reaction rate.
Thus, n = 2
(Second
Order)
45
2
2.3 RATE LAWS

Method
Proposed rate law: Rate = k[A]n
If a reaction is Zero Order, the rate of the reaction
is always the same
doubling [A] will have no effect on the reaction rate
If a reaction is First Order, the rate is directly

proportional to the reactant concentration
doubling [A] will double the rate of the reaction
If a reaction is Second Order, the rate is directly

proportional to the square of the reactant
concentration
doubling [A] will quadruple the rate of the reaction
46
Plots of reactant concentration, [A], vs. time for

first-, second-, and zero-order reactions.
Plots of rate vs. reactant concentration, [A],

for first-, second-, and zero-order reactions.
2.3 RATE LAWS

Method
Determining the Rate Law when there are Multiple
Reactants
Changing each reactant will effect the overall rate
of the reaction
By changing the initial concentration of one
reactant at a time, the effect of each reactants
concentration on the rate can be determined
In examining results, we compare differences in
rate for reactions that only differ in the
concentration of one reactant
49
2.3 RATE LAWS

Individual and Overall Reaction
Orders
NH4+(aq) + NO2(aq)
N2(g) + 2 H2O(l)
If we compare Experiments 1 and 2, we see that

when [NH4+] doubles, the initial rate doubles.
50
2.3 RATE LAWS

Orders
NH4+(aq) + NO2(aq)
N2(g) + 2 H2O(l)
Likewise, when we compare Experiments 5 and 6, we

see that when [NO2] doubles, the initial rate
doubles.
51
2.3 RATE LAWS

Orders
First-order in [NH4+] and First order in [NO2-]

This means
Rate [NH4+]
Rate [NO2]
Rate [NH4+] [NO2]
which, when written as an equation, becomes
+
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
2.3 RATE LAWS

Orders
Consider the reaction between NO and O2. From the

experiment, the results showed that;2 NO
(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
2.3 RATE LAWS

Orders
The decomposition of ammonia on a platinum surface

at 856oC is a zero order reaction
NH3
(g)
1/2 N 2 + 3/2 H2 (g)

Rate = k[NH3]0 = k
The reaction rate is independent of NH3 concentration
54
2.3 RATE LAWS

The Unit of Rate Constant
Reaction rates have units of mol/L.time
concentrations are given as moles per liter.
when
The time in rate constant can be seconds, minutes,

hours, days, year or whatever time unit is
appropriate.
Rate constants must have units consistent with the
order of a reaction
First order reactions : the units of k are 1/time
Second order reactions : the units of k are L/mol.time
Zero order reactions : the units of k are mol/L.time
55
2.3 RATE LAWS

Example 4
For the following reactions, determine the reaction
order with respect to each reactant and the overall
order from the given rate law.
H2O2(aq) + 3I-(aq) + 2H+(aq)
I3-(aq) + 2H2O(l)
rate = k[H2O2][I-]
56
2.3 RATE LAWS

Answer to Example 4
PLAN:
Look at the rate law and not the coefficients of the
chemical reaction.
SOLUTION:
The reaction is 1st order in H2O2, 1st order in I- and zero
order in H+, while being 2nd order overall.
57
2.3 RATE LAWS

Example 5
The rate equation for the reaction of NO with

ozone is Rate = k[NO][O3].
If the rate is 6.60 x 105 M/sec when [NO] =
1.00 x 106 M and [O3] = 3.00 x 106 M,
calculate the rate constant k
58
2.3 RATE LAWS

Answer to Example 5
6
3
Given: [NO] = 1.00 x 10 M, [O ] = 3.00 x
106 M,
Rate = 6.60 x 106 M/s
Find:
k, M1s1
Conceptual Rate, [NO], [O3]

Plan:
Relationshi Rate = k[NO][O3]

ps:
59
2.3 RATE LAWS

Example 6
The rate law for the decomposition of

acetaldehyde, CH3CHO, is Rate = k[CH3CHO]2.
What is the rate of the reaction when the
[CH3CHO] = 1.75 x 103 M and the rate
constant is 6.73 x 106 M1s1?
60
2.3 RATE LAWS

Answer to Example 6
3
Given: [CH3CHO] = 1.75 x 10 M, k= 6.73 x
106 M1s1
Find: Rate, M/s

Conceptual
Plan: k, [acetaldehyde]
Rate
Relationshi Rate = k[acetaldehyde]2

ps:
61
2.3 RATE LAWS

Example 7
Determine the rate law and rate constant for the
reaction
NO2(g) + CO(g) NO(g) + CO2(g)
given the data below
62
2.3 RATE LAWS

Answer to Example 7
Comparing Expt #1 and Expt #2, the

[NO2] changes but the [CO] does not
63
2.3 RATE LAWS

Answer to Example 7
64
2.3 RATE LAWS

Answer to Example 7
65
2.3 RATE LAWS

Answer to Example 7
66
2.3 RATE
LAWS
Origins
of Organic
Answer
to Example 7
Chemistry
sources.
67
2.3 RATE
LAWS
Origins
of Organic
Answer
to Example 7
Chemistry
and inorganic chemistry.
n =between
2, m =organic
0
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
given the data below
sources.
70
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
sources.
71
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
sources.
72
2.3 RATE
LAWS
Origins
of Organic
Answer to Example 8
Chemistry
Rate = k[NH4+]n[NO2]m

sources.
73
2.3 RATE LAWS

Exercise 4
Ammonia decomposes to nitrogen and hydrogen
gases at ToC. The rate of decomposition is first order
with respect to ammonia.
a)Write the rate law for the decomposition of ammonia
b)The rate of the above reaction is found to be 0.0216
mol dm-3s-1 when the concentration of NH3 is 0.67 mol
dm-3. Calculate the rate constant for the
decomposition of ammonia at ToC
74
2.3 RATE LAWS

Exercise 5
The dimerization of a compound A in ethanol at 40oC
can be illustrate as a follow reaction
2A
A2
The above reaction showed a second order reaction

a)Write a rate law for the reaction
b)Calculate the initial concentration of A when k is
0.137 L.mol-1.s-1 and initial rate is found to be
3.4 x 10-4 mol L-1.s-1
75
2.3 RATE LAWS

Exercise 6
The reaction 2NO (g) + Cl2 (g) 2NOCl (g) was
studied at -10oC and the following data were
obtained.
Initial Concentration,
mol/L
Run
NO
Cl2
Initial rate of formation

of NOCl, mol/L.min
0.10
0.10
0.18
0.10
0.20
0.35
0.20
0.20
1.45
a) What is the order of reaction with respect to NO and

with respect to Cl2
b) What is the numerical value of the rate constant at
76
-10oC
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 vital force
0.080because they
0.020were from
7.7 xliving
10-3
some
sources.
3
0.080
0.010
3.8 x 10-3
77
2.3 RATE
LAWS
Origins
of Organic
Exercise 8
Chemistry
Consider the reaction X + Y
Z

These data are obtained are 360 K
Exp andInitial
Rate (M/s)
[X]
[Y]
isolate,
purify.
1
0.147
0.10
2
0.127
Compounds
also decomposed
more0.20
easily.
3
4.064
0.40
0.50
0.30
0.60
Torben4 Bergman (1770)

distinction
1.016 first to make
0.20
0.60
5
0.508
0.40
0.30

a)Determine
the
orderbecause
of the reaction
some vital
force
they were from living
sources. the initial rate of disappearance of X
b)Determine
when the concentration of X is 0.30 M and Y is 0.40 M
78
2.3 RATE LAWS

Exercise 9
The rate of reaction between bromate ions and bromide ions in acidic
aqueous solution in terms of changes in concentration of reactants and
products is given below
Rate = - [BrO-3] = -1/5 [Br-] = -1/6[H+] = 1/3[Br2] = 1/3 [H2O]
t
t
t
t
t
The data from 4 experiments are listed in table below
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
a) Write a balanced equation for the reaction

b) If the rate of the above reaction is first order with respect to BrO -3
and Br-, calculate the order of the reaction with respect to H + and
write the rate law of the reaction
79
TOPIC
INTEGRATED RATE LAWS
80
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Concentration-Time Relationships:
Chemistry
Integrated Rate Laws

The rate laws only tell us the rate or concentration at
a given instant
allowing
usplants,
to findanimals
the How
fast
Compounds
obtained
from
hard
to is
isolate,
andproceeding
purify.
the
reaction
at the moment [reactants]
are mixed.
It is important to know how long a reaction must

proceed
toorganic
reach aand
predetermined
concentration of
between
inorganic chemistry.
some reactant of product, or what the reactant and
concentrations
willcompounds
be after some
time
has
Itproduct
was thought
that organic
must
contain
elapsedtherefore
ratewere
lawsfrom
will employ
some vital
forceintegrated
because they
living
sources.
81
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
Where
[A]0 is the initial concentration of A, and
[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
Chemistry
Reactions
Foundations this
of organic
chemistry
from mid-1700s.
Manipulating
equation
produces
ln [A]t
ln [A]0 =
kt

ln [A]t = kt + ln
[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
Chemistry
Reactions
Rate = k[A]1 = k[A]

kt
+ ln[A]0
ln[A]
isolate,
purify.
t =and
Graph ln[A] vs. time gives straight line with
slope = k and yintercept = ln[A]0
Torben
Bergman
(1770) first
makeconstant
distinction
used
to determine
thetorate
sources.
84
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Reactions

ln[A]0

sl
op
Compounds
also decomposedemore easily.
ln[A]
=
distinction
k

sources.
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
to
fall to
purify.
its initial value
isolate,
and
The half-life of the reaction depends on the
order of the reaction
sources.
86
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Half Life
for First- Order
Integrated rate law : ln[A]t = kt + ln[A]0
t = [A]t = [A]0
ln [A]0 = k t + ln[A]0
Torben
Bergman (1770) first to make distinction
ln [A]0 = k t
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


sources.
88
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Rate Data for: Chemistry
C4H9Cl + H2O
C4H9OH +
HCl
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.
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.
sources.
91
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
The Half-Life of a First Order
Chemistry
Reaction is Constant

Compounds obtained from plants, animals
hard
slope
= to
2.01 x 103
k=
2.01 x 103 s-1

sources.
92
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Zero
Order Reactions
Chemistry
Using calculus to integrate the rate law for a zeroorder process
gives us
Compounds
obtained
from plants, animals hard to
[A]easily.
Where
0
[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
Rate = k[A]0 = k
from[A]
plants,
animals
hard to
Integratedobtained
rate law:
= kt
+ [A]
Compounds
initial
Graph of [A] vs. time is straight line with
Compounds
slope = k
also and
decomposed
yintercept
more easily.
= [A]initial

sources.
94
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Zero
Order Reactions
[A]
initi
Compounds
al
isolate,
and purify.
[A]
slo first to make distinction

Torben Bergman (1770)
p
e=
between organic and inorganic
chemistry.
k

sources.
time
95
1.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Half Life for
Zero Order Reactions
Integrated rate law: [A]t = kt + [A]0

t isolate,
=
[A]
[A]0
Compounds
t =purify.
and
[A]0 = -k t + [A]0

t = [A0]/2k = [A0]/2k

When
Rate = M/sec, k = M/sec
sources.
96
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Second
Order Reactions
Chemistry
Using calculus to integrate the rate law for a Secondorder process
gives us
Compounds
obtained
from plants, animals hard to
1
[A]
Where
distinction
0
[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
Graph 1/[A] vs. time gives straight line with

slope = kalso
and
yintercept
1/[A]initial
Compounds
decomposed
more =
easily.
used to determine the rate constant
sources.
98
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Second
Order Reactions
Chemistry
=
e
Compounds
also decomposed omore
easily.
p
1/[A]
l
s
1/[A]initialthat organic compounds must contain
It was thought
sources.
time
99
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Half Life for Second Order
Chemistry
Reactions
Integrated Law: 1/[A] = kt + 1/[A]0

t = [A]talso
=
[A]0
Compounds
decomposed
more easily.
[A]0organic
= k t
+ inorganic
1/[A]0 chemistry.
1/between
and
vital force
because they were from living
= 1/(k[A
tsome
0])
sources.
When Rate = M/sec, k = M s

1
100
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
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)
0
mol/L*s (or mol L-1 s-1)
1
1/s (or s-1)
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)
The rate constant is 9.2 s-1,

(a) What
is theorganic
half-life of
the inorganic
reaction? chemistry.
between
and
(b) How long does it take for the concentration of cyclopropane to
It was
thoughtofthat
compounds must contain
reach
one-quarter
the organic
initial value?

Use
the half-life equation, t1/2 0.693
sources.
=
103
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 9
0.693
k
Use the half-life equation, t1/2

Compounds
=
isolate,ofand
One-quarter
the purify.
initial value means two half-lives have passed.
SOLUTION:
(a)
t1/2 = 0.693/9.2 s-1 = 0.075 s

organic
inorganic chemistry.
(b) between
2 t = 2(0.075
s) =and
0.150
1/2

sources.
104
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
conditions.
Findpurify.
the [SO2Cl2] at 865 s when [SO2Cl2]initial
isolate, and
= 0.0225 M
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:
Relationship
sources.s:
105
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
Answer to Example 10
Compounds
Solution: obtained from plants, animals hard to
Check: the new concentration is less than the
original,
as expected
It was thought
that organic
compounds must contain
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
sources.
107
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
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:
isolate, and
k purify.
Conceptual
[Q]init, t, [Q]t
k
Plan: also decomposed more easily.
Compounds
Relationshi
between
ps: organic and inorganic chemistry.
ItSolution:
was thought that organic compounds must contain
sources.
108
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Graphical
Determination of the
Chemistry
Rate Law for A
Product

Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs.
Compounds
obtained from plants,
animals
hard tois
time allow determination
of whether
a reaction
isolate,
and
zero,
first,
or purify.
second order
Whichever plot gives a straight line determines the
order with respect to [A]
0
if linear
is [A](1770)
vs. time,
= k[A]
Torben
Bergman
firstRate
to make
distinction
inorganic
between
if linearorganic
is ln[A] and
vs. time,
Ratechemistry.
= k[A]1
if linear is 1/[A] vs. time, Rate = k[A]2
sources.
109
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
sources.
What will the rate be when the [A] = 0.010 M?
110
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
sources.
111
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
sources.
112
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
sources.
113
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
sources.
114
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Chemistry
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
sources.
115
2.4
INTEGRATED
RATE LAWS
Origins
of Organic
Relationship Between
Order and Half-Life
Chemistry
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
For a second order reaction, the half-life is

Itinversely
was thought
that organic
compounds
must contain
proportional
to the
initial concentration
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)
The following data were

obtained
a)What is the order of reaction?
b)What is the rate constant?
c)Calculate the [N2O5] at 150 s.
d)Find the half life
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
The reaction between A2 and B2 at 277oC is 2nd order overall

2A2
+chemistry
B2
2A2B mid-1700s.
Foundations of organic
from
For a mixture containing 0.5 M each of A and B at 227 oC, it
was found that doubling the concentration of B has no effect
on the rate of the reaction, and the concentration of A
decreases by 50% in 129s
a)Write the rate law for the reaction

b)Write the
integrated
rate law
reaction
Torben
Bergman
(1770)
firstfortothe
make
distinction
c)What
is theorganic
rate in A2and
B if Ainorganic
decreasingchemistry.
at 0.78Ms-1
between
d)Calculate the rate constant, k at 277oC
o
e)Calculate
the
initial
rate
at
277
C
must contain
f)How
long
will it
take for
the concentration
A to living
decrease
some
vital
force
because
they wereoffrom
bysources.
another 50%
121
TOPIC
COLLISION THEORY, TRANSITION
STATE THEORY AND ACTIVATION
THEORY
122
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
STATE THEORY AND ACTIVATION THEORY
Chemistry
The Collision Model

In a chemical reaction,
bonds are broken
and
newplants, animals hard to
Compounds
obtained
from
isolate,
and
purify.
bonds
are
formed.
Molecules can only react if

Compounds
more easily.
they collidealso
withdecomposed
each
other.
Torben
Bergman
(1770) first to make distinction
For
a
collision
to
be
effective, the reacting
molecules
mustthat
have
It was thought
organic compounds must contain
sufficient
kinetic
energy
to
some vital
force
because
they were from living
sources.the energy barrier.
overcome
123
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
The Collision Model
Furthermore, molecules must collide with the correct

Compounds
obtained
from plants,
animals
hardbond
to
orientation and
with enough
energy
to cause
breakage and formation.
sources.
124
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
The Transition State Theory

There is an energy barrier to almost all reactions
Compounds
There
exists
an intermediate stage when reactant
molecules change into products.
Compounds
The activated
complex or transition
also decomposed
more easily.state is a
chemical species with partially broken and partially
formed
bonds (1770) first to make distinction
Torben
Bergman
between
organic and
inorganic
chemistry.
an intermediate
formed
between
reactant and
product molecules
has vital
highest
energy
and extremely
some
force
because
they wereunstable
from living
sources.
125
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
The Transition State Theory

Reaction energy diagrams and possible transition
Compounds obtained from
states.
sources.
126
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
Activation Energy

In other words, there is a minimum amount of
Compounds
obtained
from plants,
hard
to
energy required
for reaction:
theanimals
activation
energy,
and purify.
Eisolate,
a.
Molecules must possess a certain minimum kinetic
Compounds
also
decomposed
easily.
energy called
the
activation more
energy
for a reaction
to occur
(1770)
makeofdistinction
Torben
energyBergman
needed to
breakfirst
theto
bonds
the reacting
molecules
ItReaction
with that
low activation
energy is easier
to take
was thought
organic compounds
must contain
place,
is force
faster because they were from living
someand
vital
sources.
127
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
Activation Energy

Just as a ball cannot get over a hill if it does not roll
Compounds
obtained
from
plants,a animals
to
up the hill with
enough
energy,
reactionhard
cannot
isolate,
and the
purify.
occur
unless
molecules possess sufficient energy
to get over the activation energy barrier.
sources.
128
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
Reaction
Coordinate
Diagram
Foundations
of organic
chemistry from
mid-1700s.
Rearrangement
of
between organic
and inorganic chemistry.
methyl isonitrile

sources.
129
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
Reaction Coordinate Diagram

The diagram shows the
energy of the
reactants
and
Compounds
obtained
from
isolate, and
products
(and,purify.
therefore,
E).
alsoon
decomposed
more easily.
Compounds
The high point
the
diagram is the transition
state. Bergman (1770) first to make distinction
Torben
The species present at the transition state is called
Itthe
was
thought complex.
that organic compounds must contain
activated
sources.
The
energy gap between the reactants and the
activated complex is the activation energy barrier.130
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry
Maxwell-Boltzmann Distributions

Temperature is
Compounds obtained from plants, defined
animalsas
hard
a to
measure of the
average kinetic
energy of the
molecules in a
sample.
It was
thought
that organic
At any
temperature
therecompounds
is a wide must contain
distribution of kinetic energies.
sources.
131
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry

As the temperature
increases, the curve
easily.and
flattens
broadens.
distinction
Thus
at higher
temperatures, a
largermust
population
containof
some vital force because theymolecules
were fromhas
living
sources.
higher energy.
132
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry

If the dotted line
represents the
Compounds also decomposed moreactivation
easily.
energy, then as
thedistinction
temperature
increases, so
does the fraction
must contain
of molecules
some vital force because they were
from living
that can
Assources.
a result, the reaction rate
overcome the
increases.
activation
133
2.5 COLLISION
TRANSITION
OriginsTHEORY,
of Organic
Chemistry

This fraction of
molecules can be
easily.
found
through the
expression
-E
a
RT
f=e

some vital force because they
were
where
R isfrom
the living
gas
sources.
constant and T is the
Kelvin temperature.
134
TOPIC
ARRHENIUS EQUATION
2.6 ARRHENIUS EQUATION

Svante Arrhenius developed a mathematical
relationship between k and Ea:
-Ea
RT
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

The Arrhenius Equation: The Exponential
Factor
The exponential factor in the Arrhenius equation is

a number between 0 and 1
The larger the activation energy, Ea, the fewer
molecules that have sufficient energy to overcome

the energy barrier, the smaller the rate constant k.
Increase in temperature, T, will gives a larger k

value
therefore increasing the temperature will increase the
reaction rate
137

Taking the natural
logarithm of both sides,
the equation becomes
ln k = - Ea
1(
R ln A T
y =
+ b
)+
Therefore, if k is determined experimentally at

several temperatures, Ea can be calculated from the
1
slope of a plotTof ln k vs. .
138

Example 13
Determine the activation energy and frequency factor
for the reaction O3(g) O2(g) + O(g) given the following
data:
139

140

slope, m = 1.12 x 104 K
yintercept, b = 26.8
141

Arrhenius Equation: Two-Point
Form
If you only have two (T,k) data points, the following
forms of the Arrhenius Equation can be used:
142

Example 14
The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a

rate constant of 2.57 M1s1 at 701 K and 567
M1s1 at 895 K. Find the activation energy in
kJ/mol
143

1
1
Given: T1 = 701 K, k1 = 2.57 M s , T2 = 895 K,
k2 = 567 M1s1
Find:
Ea, kJ/mol
Conceptual
Plan:
T1, k1, T2, k2
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)
At 550oC rate constant for the reaction is 1.1 L/mol.s

and 625oC the rate constant is 6.4 L/mol.s. Calculate
Ea
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
2.7 REACTION MECHANISMS AND

Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is
called the reaction mechanism.
Reactions may occur all at once or through
several discrete steps.
Each of these processes is known as an
elementary reaction or elementary process.
149

Multistep Mechanisms
The molecularity of a process tells how many

molecules are involved in the process.
150

In a multistep process, one of the steps will be
slower than all others.
The overall reaction cannot occur faster than this
slowest, rate-determining step.
151

Slow Initial Step
NO2 (g) + CO
CO2 (g)
(g)
NO
(g)
The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
This suggests the reaction occurs in two steps.
152

Slow Initial Step
A proposed mechanism for this reaction is
Step 1: NO2 + NO2
NO3 + NO (slow)
Step 2: NO3 + CO
NO2 + CO2 (fast)
The NO3 intermediate is consumed in the second

step.
As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.
Rate = k1[NO2][NO2] = k1[NO2]2 and Rate = k2[NO3]
[CO]
153

Slow Initial Step
NO2(g) + CO(g) NO(g) + CO2(g)
1. NO2(g) + NO2(g) NO3(g) + NO(g)
2. NO3(g) + CO(g) NO2(g) + CO2(g)
The first step is slower than the

second step because its
activation energy is larger.
The first step in this mechanism
is the rate determining step.
The rate law of the first step is
the same as the rate law of the
overall reaction.
Rateobs = k[NO2]2
Rate = k1[NO2]2 Slow
Rate = k2[NO3][CO] Fast

Validating a Mechanism
1.
2.
To validate (not prove) a mechanism, two

conditions must be met:
The elementary steps must sum to the overall
reaction
The rate law predicted by the mechanism must
be consistent with the experimentally observed
rate law

Mechanisms with a Fast Initial Step
When a mechanism contains a fast initial step, the
rate limiting step may contain intermediates
When a previous step is rapid and reaches
equilibrium, the forward and reverse reaction rates
are equal so the concentrations of reactants and
products of the step are related
and the product is an intermediate
Substituting into the rate law of the RDS will

produce a rate law in terms of just reactants

Fast Initial Step
2 NO
(g)
+ Br2
(g)
2 NOBr
(g)
The rate law for this reaction is found to be

Rate = k [NO]2 [Br2]
Because termolecular processes are rare, this rate
law suggests a two-step mechanism.
157

Fast Initial Step
A proposed mechanism is
Step 1: NO + Br2
NOBr
Step 2: NOBr2 + NO
(fast)
2 NOBr
(slow)
Step 1 includes the forward and reverse reactions.
158

Fast Initial Step
The rate of the overall reaction depends upon
the rate of the slow step.
The rate law for that step would be
Rate = k2 [NOBr2] [NO]
But how can we find [NOBr2]?
159

Fast Initial Step
NOBr2 can react two ways:
With NO to form NOBr
By decomposition to reform NO and Br2
The reactants and products of the first

step are in equilibrium with each other.
Therefore,
Ratefoward = Ratereverse
160

Fast Initial Step
Because Ratefoward = Ratereverse ,
k1 [NO] [Br2] = k1 [NOBr2]
Solving for [NOBr2] gives us
k1
[NO] [Br2] = [NOBr2]
k1
161

Fast Initial Step
Substituting this expression for [NOBr2]
in the rate law for the rate-determining
step gives
k2k1
Rate =
[NO] [Br2] [NO]
k1
= k [NO]2 [Br2]
162

Example 15
Show that the proposed mechanism for the reaction
2 O3(g) 3 O2(g) matches the observed rate law
Rate = k[O3]2[O2]1
1. O3(g) O2(g) + O(g)
Fast
2. O3(g) + O(g) 2 O2(g)
Slow
Rate = k2[O3][O]
163

1. O3(g) O2(g) + O(g)
Fast
2. O3(g) + O(g) 2 O2(g)
Slow
Rate = k2[O3][O]
164
Exercise 17
Mechanisms with a slow Initial Step
2NO2
(g)
+ F2
2NO2F
(g)
(g)
Experimental rate law is first order for NO2 and F2.

Rate = k [NO2] [F2].
Proposed mechanism
1. NO2
step)
2. NO2
(g)
+ F2
(g)
(g)
+ F
(g)
NO2F
(g)
NO2F
+ F
(g)
(g)
(slow, rate determining

(fast)
165
Exercise 18
Mechanisms with a Fast Initial Step
2NO
+ O2
(g)
2NO2
(g)
(g)
Experimental rate law is first order for NO2 and F2.

Rate = k [NO]2 [O2].
Proposed mechanism
1. NO
(g)
2. NO3
(g)
+ O2
(g)
+ NO
(g)
NO3
2NO
(g)
2 (g)
(fast, reversible)
(slow, rate determining step)
166
End of Chapter 2
Please Read Chapter 3
Thank You
Question!
167

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FOUNDATION CHEMISTRY II

2.1 RATE OF CHEMICAL

Rates of chemical reactions is the change in

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

In this reaction, the concentration of butyl chloride,

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

The average rate of the reaction over each interval:

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

In this reaction, the ratio

2.1 RATE OF CHEMICAL

The expression for the rate of a reaction

H2 (g) + I2 (g) 2 HI (g)

Using [H2], the

Using [HI], the

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

Here the coefficients are 4, 5, 4, and 6, so

2.1 RATE OF CHEMICAL

+ 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

2.1 RATE OF CHEMICAL

Suppose that, at a particular moment during the

2.1 RATE OF CHEMICAL

Foundations of organic chemistry from mid-1700s.

2.2 FACTORS CONTROLLING

2.2 FACTORS CONTROLLING

2.2 FACTORS CONTROLLING

2.3 RATE LAWS

The rate law must be determined experimentally!!

2.3 RATE LAWS

Doubling the concentration of N2O5 doubles the

2.3 RATE LAWS

2.3 RATE LAWS

Consider, the above reaction, the rate is depend on

2.3 RATE LAWS

2.3 RATE LAWS

2.3 RATE LAWS

The exponents tell the order of the reaction

2.3 RATE LAWS

2.3 RATE LAWS

2.3 RATE LAWS

2.3 RATE LAWS

2.3 RATE LAWS

2.3 RATE LAWS

If a reaction is First Order, the rate is directly

If a reaction is Second Order, the rate is directly

Plots of reactant concentration, [A], vs. time for

Plots of rate vs. reactant concentration, [A],

2.3 RATE LAWS

2.3 RATE LAWS

If we compare Experiments 1 and 2, we see that

2.3 RATE LAWS

Likewise, when we compare Experiments 5 and 6, we