Chapter 13 Chemical Kinetics

General Chemistry II

Textbook - Principles of Chemistry: A Molecular Approach by Nivaldo Tro
Rates of Reaction | 2
Chapter Outlines
Reaction Rate
How is the rate of reaction measured?
The variables/conditions that will affect the reaction rate
Quantitative Dependence of the Rate of Reaction
on Concentrations of Reactants

Quantitative Dependence of the Rate of Reaction
on Temperature
The Rate Law (Differential and Integrated)
Graphing Kinetic Data
Two Theories Collision & Transition-State
The Arrhenius Equation
Reaction Mechanism
Catalysis
Example 1: Bombardier Beetle an insect cannon

hydroquinone

p-benzoquinone
+
irritating
& hot
explosion instantaneously occurs
H2CO
HSO3

an indicator
+
~ 35 s
Fact - Chemical reactions require
varying lengths of time for completion
Example 2: the formaldehyde clock reaction with bisulfite
H
2
CO + HSO
3

C
6
H
6
O
2
+ H
2
O
2
C
6
H
4
O
2

13 | 4
What is Chemical kinetics ?
The following questions are explored in this chapter:

How is the rate of a reaction defined and measured?
What variables or conditions will affect the rate of a
reaction?
How do you express the relationship of rate to the
variables affecting the rate? (Rate Law, Arrhenius Eqn. etc.)
What happens on a molecular level during a
chemical reaction? (Reaction Mechanism)
13 | 5
Definition of Reaction Rate

Speediness/slowness of changes in concentration
the increase in molar concentration of product of
a reaction per unit time
or the decrease in molar concentration of reactant
per unit time.
The unit for reaction rate is usually mol/(Ls) or M/s.

For the reaction N
2
O
4
(aq) 2NO
2
(g) which one of the curves below
reflects the concentration change of the product

An example about change in concentration
13 | 6
!!! The quantity AX is always treated as AX=X
final
X
initial

!!! Square brackets mean molarity
) ( O ) ( NO 4 ) ( O N 2
2 2 5 2
g g g +
Notations for Reaction Rate
i) Symbolically R Rate just or
ii) Using the definition of rate
t A
A

] O N [
5 2
t A
A ] O [
2
t A
A ] NO [
2
or or
dt
d ] O N [
5 2

dt
d ] NO [
2
dt
d ] O [
2
or or
!!! The average rate vs. the instantaneous rate
For example
The average rate notation tells one how to calculate the
rate of reaction:
) ( O ) ( NO 4 ) ( O N 2
2 2 5 2
g g g +
For decomposition of N
2
O
5
2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)
It was found that during the time interval from t = 600 s to t = 1200 s,
the concentration of N
2
O
5
are
Calculate the average rate of decomposition of N
2
O
5
.
s M
6
10 5.2 : Answer

Iodide ion is oxidized by hypochlorite ion in basic solution

In 1.00 M NaOH solution at 25C, the iodide-ion concentration
(equal to the ClO

concentration) at different times was as follows

I

(aq) + ClO

(aq) Cl

(aq) + IO

(aq)
Calculate the average rate of I

over this time interval.

0.000113 M/s
Dinitrogen pentoxide, N
2
O
5
, decomposes to nitrogen dioxide and oxygen
The concentration of N
2
O
5
at the beginning of an experiment was
0.0403 M. After 4.00 min, it was 0.00930 M. The average rate of
reaction of N
2
O
5
in this time interval is qian
a. 0.00775 M/min.
b. 0.00233 M/min.
c. 0.0012 M/min.
d. 0.00101 M/min.

2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)

PracT: 1 2, 4 - 5
13 | 9
Reactants and products for any given reaction have different
rates which are related via the reaction stoichiometry:
inversely proportional to their coefficients
t A
A

] A [
t A
A

] B [
For a general chemical reaction
for any given rxn, there
are many different rates
t A
A ] E [
t A
A ] D [
or
2N
2
O
5
(g) 4NO
2
(g) + O
2
(g) For example, for
Its rate of reaction can be written as
t
] [O
2
t
] O [N
2
1
5 2
=
t
] [NO
4
1
2
=
PracT: 6 - 8
However, dividing each rate by its coefficient makes
b/c different
stoichiometry
coefficients
E D B A e d b a + +
or or
d
t
c
t
b
t
a
t A
A
=
A
A
=
A
A

=
A
A

] D [ ] C [ ] B [ ] A [
but these different rates
hold the relationship as
Note that
t
] [NO
2
=
t
] [O
2
t
] O [N
5 2
=
13 | 10
Reaction rates are determined experimentally in a variety
of ways.
For example, samples can be taken and analyzed from
the reaction at several different intervals.
How is the rate of reaction measured?
Continuously following the
reaction is more convenient.
This can be done by
measuring pressure, as
shown on the right, or by
measuring light absorbance
when a color change is part
of the reaction.
Start timing as
Solutions I and
II are combined.
Carry out paired runs simultaneously:
head to-head comparisons of reaction
rates for different concentrations.
Solutions I and II
for 1
st
run
Solutions I and II
for 2
st
run
Note time at which
each changes color.
t
] O H [
2 2
O H
2 2
A
A
= R
Lab 2. Kinetics of Dye Bleaching
Monitor concentration of dye (food coloring) using
spectrophotometry
Spectrophotometers connected to laptops
Collect data transfer to Excel
Allows continuous monitoring of dye concentration
12
A
b
s
o
r
b
a
n
c
e

Time
Blue#1 + OCl

colorless products
t
] 1 # Blue [
1 # Blue
A
A
= R
13 | 13
There are FOUR such variables:
Variables/conditions that will affect the reaction rate
#1 - The concentrations of the reactants
#4 - The concentration of the catalyst
#2 - The temperature at which the reaction occurs
#3 - The surface area of the solid reactant
Often the rate of reaction increases when the concentration of a
reactant is increased. In some reactions, however, the rate is
unaffected by the concentration of a particular reactant, as long
as it is present at some concentration.
Usually reactions speed up when the temperature increases.
empirically rate doubles for every 10 temperature rise
The greater the surface area, the faster the reaction speed
A catalyst speeds up both forward and reverse reactions
PracT: 3
D02-Th 03-
13 | 14
Each test tube contains potassium
permanganate, KMnO
4
, and oxalic acid,
H
2
C
2
O
4
, at the same concentrations.
Permanganate ion oxidizes oxalic acid to
CO
2
and H
2
O.
Top: One test tube was placed
in a beaker of warm water (40C); the
other was kept at room temperature
(20C).
Bottom: After 10 minutes, the test tube
at 40C showed a noticeable reaction,
whereas the other did not.
Chemistry here? Temperature DOES
affect rate of reaction, and the higher
the T, faster the reaction is.
13 | 15
Surface Area of a Solid Reactant or
Catalyst
If a reaction involves a solid with a gas or
liquid, then the surface area of the solid
affects the reaction rate. Because the
reaction occurs at the surface of the solid,
the rate increases with increasing surface
area. For example, a wood fire burns faster if
the logs are chopped into smaller pieces.
Similarly, the surface area of a solid catalyst
is important to the rate of reaction.

Right: The photo shows a powder igniting.
13 | 16
The reaction rate usually depends on the concentration of
one or more reactant. This relationship must be determined
by experiment.
Quantitative dependence of the rate of reaction on [rxt]
For the generic reaction
aA + bB + cC dD + eE
the rate law can always be written as
Rate = k[A]
m
[B]
n
[C]
p

This information is captured in the rate law

The rate law, a mathematical equation that relates the rate
of a reaction to the concentration of a reactant (and
catalyst) raised to various powers. The proportionality
constant, k, is the rate constant.
Familiarize with Rate Law
- (RHS)
individually the order of rxn in each reactant
[A,], [B],
the sum of m, n, p, the overall order of rxn
(LHS)
k called the rate constant
p n m
[C] [B] [A] Rate k =

many ways but one unique unit !!
exponents m, n, p, etc.
each gives the dependence of rate on the
concentration of the reactant.

p n m
Rate
k
] C [ ] B [ ] A [
=
using terms such as first order in A if m = 1
second order in B if n = 2, etc.
13 | 18
the rate law is found to be
Rate = k[NO
2
][F
2
]

In this case, the exponent for both NO
2
and F
2
is 1 (which
does not need to be written).

We say the reaction is first order in each. The reaction is
second order overall.
For example, for the reaction
Hydrogen peroxide oxidizes iodide ion in acidic solution:
H
2
O
2
(aq) + 3I

(aq) + 2H
+
(aq) I
3

(aq) + 2H
2
O(l)
The rate law for the reaction is
Rate = k[H
2
O
2
][I

]
a. What is the order of reaction with respect to each
reactant species?
b. What is the overall order?
13 | 19
a. The reaction is first order in H
2
O
2
.
The reaction is first order in I

.
The reaction is zero order in H
+
.
b. The reaction is second order overall.
13 | 20
a. The concentration of Q does not affect the rate
b/c its zeroth order in Q. The rate will depend
only on [R].

b. Rate = k[R]
2
,
i.e., drop [Q]
0
since [Q]
0
= 1.
D
13 | 21
The rate law for a reaction must be determined experimentally.
This method measures the initial rate of reaction, i.e., Rate,
using various starting concentrations [A], [B], [C], all
measured at the same temperature.
p n m
[C] [B] [A] Rate k =
By determining the rate law, it means to determine the value of
i) individual orders of reaction: m, n, p, etc, and
ii) the rate constant, k.
We will study the initial rates method of determining the
rate law
How Is the Rate Law Determined?
13 | 22
Returning to the decomposition of N
2
O
5
, we have the
following data:
2N
2
O
5
(g) 2N
2
(g) + 5O
2
(g)




Initial N
2
O
5

Concentration
Initial Rate of Disappearance
of N
2
O
5

Experiment 1 1.010
-2
M 4.810
-6
M/s
Experiment 2 2.010
-2
M 9.610
-6
M/s

In this case, when the concentration doubles and the rate
doubles, we can prove that m = 1 (see the example followed)
m
k ] O [N Rate
5 2
=
] O [N Rate
5 2
k =

Note that when the [N
2
O
5
] doubles from experiment 1 to 2,
the rate doubles.
First write the rate law symbolically as
But whats the value of m?
So its rate law really is
For the reaction 2NO(g) + O
2
(g) 2NO
2
(g)
Obtain the rate law and the rate constant using the
following data for the initial rates of disappearance of NO:
13 | 23
Exp. [NO]
0
, M [O
2
]
0
, M Initial Rate of Reaction of NO, M/s
1 0.0125 0.0253 0.0281
2 0.0250 0.0253 0.112
3 0.0125 0.0506 0.0561
Chemistry - The rate law is Rate = k[NO]
m
[O
2
]
n
.
How to find the value of m and n?
!!! To find the order for a particular reactant, you first
choose TWO runs in which the concentration of only this
reactant changes while all others not. Then, you divide the
rate laws for those two experiments. Finally, you solve the
equation to find the order in this reactant.
13 | 24
The generic rate law is Rate = k[NO]
m
[O
2
]
n
.


( ) ( )
( ) ( )
n m
n m
M M
M M
M
M
0.0253 0.0125
0.0253 0.0250

s
0.0281
s
0.112
=
m
2 4 =
We will divide the rate law for run-2 by that for run-1 because the
rate of run-2 is larger than that of run-1.


To find m, we choose two runs, 1 and 2, that [O
2
] remains constant.

For n, runs 1 and 3 were chosen b/c [NO] remains constant


n
2 2 =
2 = m
1 = n
We will divide the rate law for run-3 by that for run-1 because the
rate of run-3 is larger than that of run-1.

( ) ( )
( ) ( )
n m
n m
M M
M M
M
M
0.0253 0.0125
0.0506 0.0125

s
0.0281
s
0.0561
=
13 | 25
Alternatively, it is also possible to find the order by
examining the data qualitatively.

Again choosing experiments 1 and 2, we note that the
concentration of NO is doubled and the rate is quadrupled.
That means the reaction is second order in NO.
Exp. [NO]
0
, M [O
2
]
0
, M Initial Rate of Reaction of NO, M/s
1 0.0125 0.0253 0.0281
2 0.0250 0.0253 0.112
3 0.0125 0.0506 0.0561
Choosing experiments 1 and 3, we note that the
concentration of O
2
is doubled and the rate is doubled.
That means the reaction is first order in O
2
.
2 = m
1 = n
Rate = k[NO]
m
[O
2
]
n

13 | 26
The rate law now is Rate = k[NO]
2
[O
2
].


Using data from experiment 2: k = 7.0810
3
/M
2
s
Using data from experiment 3: k = 7.1010
3
/M
2
s
These values are the same to 2 significant figures.
( ) ( ) s
10 7.11
0.0253 0.0125
s
0.0281

1: experiment from data Using
2
3
2

= =
M
M M
M
k
| | | |
2
2
O NO
Rate
k
k

obtain we , for Solving
=
13 | 27
Summary of Initial Rates Method - Examining the effect
of doubling or tripling the initial concentration of only one
reactant gives us the order in that reactant -




halved () 1


doubles stays the same (1) 0
doubles (2) 1
quadruples (4) 2
increases eight-fold (8) 3
(or) triples stays the same (1) 0
triples (3) 1
increases nine-fold (9) 2
If the concentration and the rate the order of reaction
of a reactant, say A of reaction in A must be
increases 27-fold (27) 3
reduces by two-thirds ( ) 1
3
1
Have you seen the effect of [rxt] on the rate of reaction so far?
p n m
[C] [B] [A] Rate k =
Iron(II) is oxidized to iron(III) by chlorine in an acidic
solution:
2Fe
2+
(aq) + Cl
2
(aq) 2Fe
3+
(aq) + 2Cl

(aq)
13 | 28
Exp. [Fe
2+
], M [Cl
2
], M [H
+
], M Rate, M/s
1 0.0020 0.0020 1.0 1.010
-5
2 0.0040 0.0020 1.0 2.010
-5
3 0.0020 0.0040 1.0 2.010
-5
4 0.0040 0.0040 1.0 4.010
-5
5 0.0020 0.0020 0.5 2.010
-5
6 0.0020 0.0020 0.1 1.010
-4
The following data were collected.
Determine the rate law and the value of k.
13 | 29
The generic rate law must be
Rate = k[Fe
2+
]
m
[Cl
2
]
n
[H
+
]
p

Now can you find that n = 1 and p = 1?


Exp. [Fe
2+
], M [Cl
2
], M [H
+
], M Rate, M/s
1 0.0020 0.0020 1.0 1.010
-5
2 0.0040 0.0020 1.0 2.010
-5
3 0.0020 0.0040 1.0 2.010
-5
4 0.0040 0.0040 1.0 4.010
-5
5 0.0020 0.0020 0.5 2.010
-5
6 0.0020 0.0020 0.1 1.010
-4
To find the order in Fe
2+
, i.e., the value of m, we choose
1 and 2, or 3 and 4. In each case, [Fe
2+
] doubles and
the rate doubles,
So the rate law is Rate = k[Fe
2+
][Cl
2
][H
+
]
1

hence m = 1.
13 | 30
The same value for k is obtained using each experiment.
] [
] [ ] [
+
+

=
H
Cl Fe

2
2
k
Rate
Once a rate law was determined, one can calculate the
value of its rate constant as
] Cl [ ] Fe [
] H [
2
2

=
+
+
Rate
k
( )
( )( )
s M .
M . M .
M .
s
M
.
=

=

50 2
002 0 002 0
0 1 10 0 1
5
Using data from experiment 1:

13 | 31
Note that the units on the rate constant, k, are specific to the
overall order of the reaction.

For a zero-order reaction, the unit is M/s or mol/(L
.
s).
For a first-order reaction, the unit is 1/s or s
-1
.
For a second-order reaction, the unit is 1/(Ms) or L/(mol
.
s).

In other words, If you know the unit of a rate constant, you
can deduce the order of reaction.
PracT: 9 15
13 | 32
The rate law of kind, called the
Differential Rate Law, tells us the relationship between the
rate and the concentrations of reactants and catalysts.

To find concentrations at various times, i.e., the extent of a
reaction, we need to use the integrated rate law. The form
used depends on the order of reaction in that reactant.
p n m
[C] [B] [A] Rate k =
d03 TTh
Concentration-Time Equations (Integrated rate laws)
Summary
kt
t
=
0
] A [
] A [
ln
[A]
t
= [A]
0
kt
Order
Differential
rate law
Integrated
rate law
Units of the
rate constant k
= k
0
1
= k[A]
2
1
s M
1
s
1 1
s M
for aA products type reactions !!
or time
1
or M
1
time
1

or Mtime
1

= k[A]
0
0
1 1
[A] [A]
t
kt = +
Here [A]
t
is the concentration of reactant A at time t, and [A]
0
is
the initial concentration of A.
The ratio is the fraction of A remaining at time t.
0
] A [
] A [
t
Cyclopropane is used as an anesthetic. The
isomerization of cyclopropane to propene is a first-order
reaction with a rate constant of 9.2/s. If an initial sample
of cyclopropane has a concentration of 6.00 M, what will
the cyclopropane concentration be after 1.00 s?
13 | 34
Do translations:
Rate = k[C
3
H
6
], k = 9.2/s, [A]
0
= 6.00 M, t = 1.00 s, [A]
t
= ?
The reaction is first order,
so the integrated rate law is


Solve for [A]
t

| |
| |
1
0
A
ln (9.2 )1.00 9.2
A
t
s s

= =
| |
| |
9.2 4
0
A
1.01 10
A
t
e

= = M 10 06 . 6 ] A [
4
=
t
PracT: 16, 17, 20, 21
Half-Life of a Reaction (t
1/2
)
kt
t
=
0
] A [
] A [
ln
[A]
t
= [A]
0
kt
Order
Integrated
rate law
0
1
2
k
t
693 . 0
2 1
=
k
t
2
] A [
0
2 1
=
Half-life
a constant !!!
The half-life of a reaction, t

, is the time it takes for the

reactant concentration to decrease to one-half of its
initial value.
0
1 1
[A] [A]
t
kt = +
By substituting [A]
0
for [A]
t
, we solve the integrated
rate law for the special case of t = t

.
Ammonium nitrite is unstable because ammonium ion
reacts with nitrite ion to produce nitrogen:

NH
4
+
(aq) + NO
2

(aq) N
2
(g) + 2H
2
O(l)

In a solution that is 10.0 M in NH
4
+
, the reaction is first
order in nitrite ion (at low concentrations), and the rate
constant at 25C is 3.010
3
/s.

What is the half-life of the reaction?
13 | 36
Do translations k = 3.010
-3
/s, a 1
st
-order kinetics; t
1/2
= ?
The equation needed is kt

= 0.693
min 9 . 3 s 10 3 . 2
s 10 0 3
693 0
2
1 3
= =

= =
-
.
.
k
t
0.693
1/2
PracT: 18, 19
13 | 37
Graphs of concentration vs. time can be used to determine
the order of reaction in a reactant.
For zero-order reactions, plot of [A] versus t is linear.
For first-order reactions, plot of ln[A] versus t is linear.
For second order reactions, plot of 1/[A] versus t is linear.
PracT: 22
This is illustrated on the next slide for the decomposition of NO
2
.
y = mx + b
y = mx + b
y = mx + b
linear
y vs. x plot
[A]
t
vs. t
t
t
. vs
] A [
1
t
t
. vs ] A ln[
13 | 38
Left: The plot of ln[NO
2
] versus t is not linear, so the reaction is
not first order.
Right: The plot of 1/[NO
2
] versus t is linear, so the reaction is
second order in NO
2
.
13 | 39
t

increase with the initial

concentration, [A]
0
, for the zero-
order reactions.
t

is constant for the first-order

reactions, not depend upon [A]
0
.
t

decreases with [A]

0
for the
second-order reactions.
The reaction is second order
.

0
2 1
2 1
0
2 1
[A]
1
: Order Second
693 0
: Order First
2
[A]
: Order Zero
k
t
k
.
t
k
t
/
/
/
=
=
=
13 | 40
Rate Constant (k) and Temperature (T)
The rate constant depends strongly on temperature. How
can we explain this relationship? two theories
Quantitative dependence of the rate of reaction on T
This dependence is reflected via the rate constant, k,
rather than the rate of reaction itself
1) Collision theory assumes that reactant molecules must
collide with an energy greater than some minimum value
and with the proper orientation.

The minimum energy is called the activation energy, E
a
.
13 | 41
According to the collision theory the effect of a temperature
increase on each of the three factors for a reaction to occur.
The rate constant can be given by the equation
k = Zfp
i) The factor Z certainly, Z will increase with temperature,
as the average velocity of the molecules increases with
temperature.
However, this factor alone cannot explain the dramatic
effect of temperature changes.
where
Z = collision frequency
f = fraction of collisions with the minimum energy
p = orientation factor
13 | 42
ii) The factor f - The fraction of molecular collisions having
the minimum energy required is given by f :
RT
E
RT
E

a
a
e
e f
1
= =

iii) The factor p - The reaction rate also depends on p,
the proper orientation for the collision. This factor is
independent of temperature.
T |
Now we can explain the dramatic impact of temperature.
f increases exponentially with temperature:
PracT: 23, 24
| ) (RT
|
|
.
|

\
|

RT
E
a
| f
13 | 43
Importance of Molecular Orientation in
the Reaction of NO and Cl
2





(A) NO approaches with its N atom toward Cl
2
, and an
NOCl bond forms. Also, the angle of approach is close to
that in the product NOCl.

(B) NO approaches with its O atom toward Cl
2
. No NOCl
bond can form, so NO and Cl
2
collide and then fly apart.
13 | 44
2) Transition-state theory explains the k-T dependence in
terms of the potential energy diagram and an activated
complex (transition state), an unstable high-energy grouping
of atoms that is resulted from the collision of reacting
molecules and can break up to form products.
The potential energy diagram for a reaction visually illustrates
the changes in energy along with the structural changes in
reacting species.
The next slide shows the potential energy diagram for the
reaction
NO + Cl
2
NOCl
2

NOCl + Cl
where NOCl
2

indicates the activated complex.

http://www.youtube.com/watch?v=h5xvaP6bIZI&feature=player_detailpage#t=35s

http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/activa2.swf

13 | 45

A
!!! E
AB

> E
A
& E
B
, b/c outer-e repulsion !!!
!!! E
a
(forward) = E
AB

E
reactants
!!! E
a
(reverse) = ?
Important Quantities in A Potential Energy Diagram
A
13 | 46

The reaction of NO with Cl
2
is an endothermic reaction, i.e., AH > 0.
A
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/activa2.swf

Watch a flash video
for the reaction below as well as NO
2
+ CO NO + CO
2

Sketch a potential energy diagram for the
decomposition of nitrous oxide.
N
2
O(g) N
2
(g) + O(g)
The activation energy for the forward reaction is
251 kJ; AH
o
= +167 kJ.
Label your diagram appropriately.
What is the activation energy for the reversed
reaction?
13 | 47
13 | 48
Reactants
Products
E
a
= 251 kJ
AH = 167 kJ
E
a
(reverse)
= 84 kJ
E
n
e
r
g
y

p
e
r

m
o
l
Progress of reaction
N
2
O
N
2
+ O
PracT: 25, 26, 31, 32
13 | 49
The k T dependence for most chemical reactions closely
follows an equation in the form

This is called the Arrhenius equation. A is the frequency
factor, a constant. This equation shows that
RT
E

a
e k

= A
A more useful form of the Arrhenius equation is



|
|
.
|

\
|
=
|
|
.
|

\
|
2 1 1
2
1 1
ln
T T R
E

k
k
a
d04 TTh
Note how k and T are paired in this equation
i) When T changes, the value of k changes as well;
ii) If E
a
> 0, then increasing T, the k increases.
!!! be careful with
paired k and T !!!
iii) the greater the E
a
, the smaller k and lower the rate.
In a series of experiments on the decomposition of
dinitrogen pentoxide, N
2
O
5
, rate constants were
determined at two different temperatures:
At 35C, the rate constant was1.410
-4
/s.
At 45C, the rate constant was 5.010
-4
/s.
What is the activation energy?
What is the value of the rate constant at 55C?
13 | 50
Do translations -
T
1
= 35C = 308 K T
2
= 45C = 318 K
k
1
= 1.410
-4
/s k
2
= 5.010
-4
/s
E
a
= ? k = ? at T = 55C = 328 K




|
|
.
|

\
|
=
|
|
.
|

\
|
2 1 1
2
1 1
ln
T T R
E

k
k
a
What equation to use?



13 | 51
We calculate the both sides
|
.
|

\
|

=
|
|
.
|

\
|

K 318
1
K 308
1

K mol
J
8.315
E

/s 10 1.4
/s 10 5.0
ln
a
4
4
Set up the Arrhenius equation:
1 5 1 4
J mol 10 23 . 1 K 10 02 . 1
K mol
J
315 . 8
273 . 1

=

=
a
a
E
E
1 5
1 5
mol J 10 03 . 1
J mol 10 23 . 1
273 . 1


=

=
a
E
then solve for E
a

13 | 52
|
.
|

\
|

=
|
.
|

\
|

K 328
1
K 308
1
K mol
J
315 8
mol
J
10 04 1
10 4 1
ln
5
4
2

.
.

/s .
k
476 2
10 4 1
ln
4
2
.
/s .
k
=
|
.
|

\
|

90 11
10 4 1
476 . 2
4
2
. e
/s .
k
-
= =

/s . k
3
2
10 7 1

=
The setup for solving k at T = 55C = 328 K is




PracT: 27 - 30
13 | 53
Reaction Mechanism
A balanced chemical equation is a description of the overall
result of a chemical reaction. However, what actually
happens on a molecular level may be more involved than
what is represented by this single overall equation. For
example, the reaction may take place in several steps. That
set of steps, i.e., a collection of several sequentially
occurred molecular events, is called the reaction
mechanism.
13 | 54
Each step in the reaction mechanism is called an
elementary reaction and is a single molecular event.
Because an elementary reaction is an actual molecular
event, the rate of an elementary reaction is proportional to
the concentration of each reactant molecule.
Uni-molecular reaction
Bi-molecular reaction
Ter-molecular reaction
Molecularity the # of colliding
molecular entities involved in an
elementary reaction
!!! This means the stiochiometry coefficient of a reactant in
an elementary reaction IS the reaction order of the reactant.
!!! This means that we can write without any experiments the
rate law directly for elementary reactions.
13 | 55
Rate Law and Reaction Mechanism
A reaction mechanism cannot be directly observed.

We can, however, determine the rate law by experiment
and decide if the reaction mechanism is consistent with
that rate law.

The rate of an overall reaction is determined completely
by the slowest step, the rate-determining step.
A correct reaction mechanism must meet the following:
i) sum of all elementary steps must give the exact
overall reaction;
ii) the rate law derived from the mechanism must
be consistent with that determined experimentally.
13 | 56
For example, the reaction of NO
2
with F
2
is believed to
occur in the following elementary steps:
NO
2
+ F
2
NO
2
F + F (slow step, RDS)
F + NO
2
NO
2
F (fast step)
The overall reaction is
2NO
2
+ F
2
2NO
2
F
What is the rate law for this mechanism?
Rate = k[NO
2
][F
2
]
So this mechanism is correct. (Use the two criteria to make
this conclusion)
13 | 57
A reaction intermediate is a species produced during a
reaction that does not appear in the net equation because it
reacts in a subsequent step in the mechanism.
For example, the reaction of NO
2
with F
2
is believed to
occur in the following elementary steps:
NO
2
+ F
2
NO
2
F + F (slow step, RDS)
F + NO
2
NO
2
F (fast step)
The overall reaction is
2NO
2
+ F
2
2NO
2
F
F does not appear in the overall reaction equation. It is
produced in the first step and used in the second step.
Thus F is a reaction intermediate.
Write the rate law for the first step in the mechanism
for the decomposition of ozone.
Cl(g) + O
3
(g) ClO(g) + O
2
(g)
ClO(g) + O(g) Cl(g) + O
2
(g)

13 | 58
Rate = k[Cl][O
3
]
The mechanism of the decomposition is
Cl(g) + O
3
(g) ClO(g) + O
2
(g) (Slow step, RDS)

ClO(g) + O(g) Cl(g) + O
2
(g)

13 | 59
What is the overall reaction equation?
O
3
(g) + O(g) 2O
2
(g)
Is there a reaction intermediate? If so, what is it?
Yes. ClO.
Is there a catalyst? If so, what is it?
Yes. Cl.
What is the rate law for the overall reaction?
Rate = k[Cl][O
3
]
Consider the following reaction:
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
At 500 K, the reaction mechanism is believed to involve two
elementary reactions:
NO
2
(g) + NO
2
(g) NO
3
(g) + NO(g)
NO
3
(g) + CO(g) NO
2
(g) + CO
2
(g)
13 | 60
(Slow step, RDS)
PracT: 33 38
The overall reaction equation is (obtained by adding)
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
Note additionally that i) NO
3
is a reaction intermediate: a
species that is produced first and used up later,

The rate law then is (that for the RDS step if its the first step!!)
Rate = k[NO
2
][NO
2
] = k[NO
2
]
2
and ii)
there is no catalyst involved.

Catalysis
Catalysis is an increase in the rate of reaction that results
from the addition of a catalyst.
Enzymes are biological catalysts.
13 | 61
A catalyst is not consumed in a reaction. Rather, it is
present in the beginning, is used in one step, and is
produced again in a subsequent step. As a result, the
catalyst does not appear in the overall reaction equation.
Compare this with a reaction intermediate.
A catalyst increases the reaction rate by providing an
alternative reaction path with a lower activation energy.
When E
a
is reduced, k increases exponentially.
This relationship is illustrated on the potential energy
diagram for the decomposition of ozone.
1.
13 | 62
PracT: 39 40
The decomposition of hydrogen peroxide is catalyzed
by iodide ion. The reaction mechanism is thought to be

13 | 63
H
2
O
2
(aq) + I

(aq) H
2
O(l) + IO

(aq)
IO

(aq) + H
2
O
2
(aq) H
2
O(l) + O
2
(g) + I

(aq)
At 25C, the first step is slow relative to the second step.
What is the rate law predicted by the reaction
mechanism? Is there a reaction intermediate?
Rate = k[H
2
O
2
][I
-
]
I

is a catalyst. IO

is an intermediate.
Overall reaction equation:
2H
2
O
2
(aq) 2H
2
O(l) + O
2
(g)
Chapter Ends