Chemical Kinetics

The area of chemistry concerned

with the rates, or speeds, of
chemical reactions.
The Rate of a Chemical
Reaction
Reaction rate -
Units of M/s.
1
What is happening to the concentration of A as time
goes by?
A+B C
What is the sign of the change of
concentration of A: A[A]?
Remember, A is final initial.
1. Positive
2. Negative
A+ B C
As the reaction proceeds, the concentration
of A decreases
The rate of change can be defined in terms
of A decreasing:
What is happening to the concentration of C as time
goes by?
A+B C
If rate is defined by C
you have:
A+B C
Which reaction has the faster
rate?
1. A + B C
2. D + E F
A+B C
D+E F
Is the rate of the
reaction constant during
the course of the
reaction?
AB
Therefore, calculations of rate using the change
in concentration formula will give different
results depending on what time interval you
choose.
Making the interval of time smaller and smaller
we can calculate the rate of the reaction at a
specific instance in time.
Rates can be defined in
terms of changes of
pressure as well as
changes of
concentration.
Comparing Rate of Change
of Reactants and Products
Not all substances in a chemical reaction appear
or disappear at the same rate.
Lets look at a simple demonstration to
understand the relationships.
2
Paper Demo
Two pieces of paper make one booklet.
2A B
The process was recorded for 30 s.
Initial Final
Paper
Booklets
How does the rate of disappearance of
A (the paper) relate to
B (the booklets)?
Paper Demo. 2A B
| | | |
t
B
t A
A
=
A
A
=
A
2
1
rate
1. B appears at twice the rate that A is
disappearing.
2. A disappears at twice the rate that B is
appearing.
3. A disappears at the same rate that B appears.
| | | |
t
B
t A
A
=
A
A
=
A
2
1
rate
So, for the reaction:
aA + bB cC + dD
When a question asks you to write the
rate expression for a reaction in terms of
the disappearance of the reactants and the
appearance of the products, this (above)
is what they want you to do.
For the reaction
BrO
3
-
+ 5Br
-
+ 6H
+
3Br
2
+ 3H
2
O
the value of A[BrO
3
-
]/At = 1.5 10
-2
M/s at a particular
time. What is the value of the A[Br
-
]/At at the same
instant?
For the reaction
BrO
3

+ 5Br

+ 6H
+
3Br
2
+ 3H
2
O
Br

disappears at a rate of 7.5 10

-2
M/s at a particular
time. What is the value of the appearance of Br
2
at the same
instant?
The Rate Law
Rate Law -
For the reaction:
aA + bB cC + dD
The rate law is:
rate = .

We will learn how to determine

x and y later, for now, lets look at some
examples of reactions and rate laws.
3
A(aq) + B(aq) C(aq) + D(aq)
k is called the rate constant.
k has units and is obtained by solving the
equation for k.

Every time this reaction takes place, at a constant

temperature, the same value for k will be
obtained
Rate = k[A]
For the reaction:
2NO(g) + 2H
2
N
2
(g) + 2H
2
O(g)
The rate law was determined to be:
rate = k[NO]
2
[H
2
]
The reaction is said to be

Orders can be zero (when

concentration does not affect the rate.)
Orders can be fractions
Rate = k[NO]
2
[H
2
]
Lets look at what this rate law tells us about
the connection between concentrations and
rate. What happens to the rate if [H
2
] is
doubled (while [NO] remains constant?)
1. Rate stays the same
2. Rate doubles
3. Rate is cut in half
4. Rate quadruples
Rate = k[NO]
2
[H
2
]
Lets look at what this rate law tells us about
the connection between concentrations and
rate. What happens to the rate if [NO] is
doubled (while [H
2
]remains constant?)
1. Rate stays the same
2. Rate doubles
3. Rate is cut in half
4. Rate quadruples
Determination of a Rate Law
As stated earlier, the orders of the rate law must
be determined experimentally.
The best way to learn how to take experimental
data and obtain a rate law is through
demonstration. Lets work through a couple of
examples.
4
Nitric oxide gas, NO, reacts with chlorine gas
according to the equation: NO + 1/2 Cl
2
NOCl.
The following initial rates of reaction have been
measured for the given reagent concentration.
Rate (M/hr) NO (M) Cl
2
(M)
1.19 0.25 1.5
4.79 0.50 1.5
9.59 0.50 3.0
Hydroxide ion is involved in but not consumed by the
reaction:
OCl
-
+ I
-
OI
-
+ Cl
-
(a) From the data in the table, determine the order of the
reaction with respect to OCl
-
, I
-
, and OH
-
OH
-
[OCl
-
],M [I
-
], M [OH
-
], M Rate, M/s
0.0080 0.0040 2.00 4.8 10
-4
0.0040 0.0080 2.00 5.0 10
-4
0.0040 0.0040 2.00 2.4 10
-4
0.0040 0.0040 1.00 4.6 10
-4
0.0040 0.0040 0.50 9.4 10
-4
(b) Write the
rate law, and
determine a
value of the
rate constant, k
[OCl
-
],M [I
-
], M [OH
-
], M Rate, M/s
0.0080 0.0040 2.00 4.8 10
-4
0.0040 0.0080 2.00 5.0 10
-4
0.0040 0.0040 2.00 2.4 10
-4
0.0040 0.0040 1.00 4.6 10
-4
0.0040 0.0040 0.50 9.4 10
-4
Now that we know the order, what
is the rate law and the value of k?
1. Rate = k[OCl
-
][I
-
][OH
-
] k = 60 M/s
2. Rate = k[OCl
-
][I
-
]/[OH
-
] k = 30 1/Ms
3. Rate = k[OCl
-
][I
-
][OH
-
]
-1
k = 30 1/s
The Integrated Rate Law
Rate laws can be used to determine the
concentration of reactants at any time during the
course of a reaction.
We will look at the most simple cases:
1
st
order overall
2
nd
order overall
0
th
order
5
First-Order Kinetics
For the reaction:
Aproducts

because the coefficient is one

This can give us:
ln = kt
[A]
[A]
o
The previous equation forms this equation using calculus.
1
st
Order Kinetics
2N
2
O
5
4NO
2
+ O
2
Because concentration is proportional to
pressure in a gas, partial pressures can be used
in place of the concentrations.
ln P = -kt + ln P
o
A(g) B(s) + C(s)
Half-life - (t
1/2
) -
at t
1/2
,
For a first order reaction we have:
ln = kt
[A]
[A]
o
Gives:
First-Order Kinetics and
the Half-Life
6
t
1/2
=
0.693
k
This is the half-life equation for a first order
reaction.
Notice that it is independent of the [A].
If a 1
st
order reaction started with 8 M of
substance A, and the half-life was 1 minute,
what concentration would remain after 3
minutes?
1. 5 M
2. 4 M
3. 2 M
4. 1 M
5. 0.5 M
A first-order reaction has a rate constant of 3.0 10
-3
s
-1
.
The time required for the reaction to be 75% complete
is?
What if the question were:
A first-order reaction has a rate constant of 3.0 10
-3
s
-1
.
The time required for the reaction to be 30% complete
is?
Second-Order Reactions
A products
Setting each equation equal to each other and using
calculus gives:
7
kt + =
o
A] [
1
A] [
1
o
A] [
1
A] [
1
+ = kt
What will the slope
equal?
y = mx + b
o
A] [
1
A] [
1
+ = kt
1. kt
2. k
3. -k
4. 1/[A]
o
1
[A]
1
[A]
o
+ kt
=
For the half-life equation, [A] = [A]
o
/2 when
t = t
1/2
.
Substitute this into the above equation gives:
What about zero-order reactions?
Rate = k[A]
0
or

A plot of [A] versus t is a straight line.

What would a plot of rate versus time look like?
Using Plots to Determine Order
Collision Theory
What is the difference between baking a cake at
250
o
versus 350
o
F?

8
Dependence of Rate Constant
on Temperature
The Collision Theory of Chemical
Kinetics
What is occurring on the molecular level that
causes rate to increase with concentration and
temperature?

Rate increases with the number of collisions per

second.
What happens to the number of
collisions as the concentration
increases?
Concentration and Number of
Collisions
We must have a collision in order to have a
reaction.
If every collision resulted in a reaction, all reactions
would occur virtually instantaneously.
So, why do some reactions take minutes, hours,
even days to happen?

Activation Energy -
Potential Energy Diagrams
Based on what we have learned, why does the
reaction rate increase with temperature?
The Arrhenius Equation
k = Ae
-E
a
/RT
What unit would
temperature be in?
9
k = Ae
-E
a
/RT
If we take the natural log of both sides we get:
RT
A ln ln
Ea
= k
A plot of lnk
vs 1/T gives a
straight line
with slope = ?
As E
a
goes l,
As T goes l ,
ln k vs. 1/T
Take the Arrhenius equation:
and derive a two point equation for two different
temperatures (T
1
and T
2
) and two different rate
constants (k
1
and k
2
)
A ln
T
1
R
E
ln
a
+
|
.
|

\
|
|
.
|

\
|
= k
The activation energy for the following first-order reaction
is 102 kJ/mol.
N
2
O
5
(g) 2NO
2
(g) + 1/2O
2
(g)
The value of the rate constant (k) is 1.35 10
-4
s
-1
at 35
o
C.
What is the value of k at 0
o
C?
The quantity A is the
frequency factor.
This takes into account
two factors:
1.
2.
Reaction Mechanisms
A chemical equation does not give us a good
picture of how the atoms rearrange themselves to
form products. It is a sum of several
Elementary steps -
Reaction mechanism-
10
Lets consider the reaction:
2NO + O
2
2NO
2
Fact: While monitoring the reaction, it was found that
N
2
O
2
existed for a brief time.
What does this mean?
Instead this is what is proposed:
NO + NO N
2
O
2
N
2
O
2
+ O
2
2NO
2
Elementary step
Elementary step
N
2
O
2
is an intermediate -
They are canceled as you add the
elementary steps
unimolecular reaction - an elementary step in
which only one reacting molecule participates
bimolecular reaction -
termolecular reaction - an elementary step
involving three molecules
In thes mechanism for the formation
of NO
2
, what type or types of
elementary step does it have?
1. Unimolecular
2. Bimolecular
3. termolecular
NO + NO N
2
O
2
N
2
O
2
+ O
2
2NO
2
2NO + O
2
2NO
2
Rate Laws and Elementary Steps
The rate law of an elementary step can be
determined by using the coefficients as the order.
Aproducts
A + B products
A + A products
NOTE: this is not true for the overall equation!
only for the elementary step!
Remember: How do you determine the
orders of an overall reaction?

Rate-determining step -
.
The rate of this step gives the rate of the overall
reaction.
Lets look at a specific example:
The rate law for the reaction:
H
2
O
2
+ 2H
+
+ 2I
-
I
2
+ 2H
2
O
is rate = k[H
2
O
2
][I
-
]. The following mechanism has
been suggested.
H
2
O
2
+ I
-
HOI + OH
-
OH
-
+ H
+
H
2
O
HOI + H
+
+ I
-
I
2
+ H
2
O
Which step would be the rate-determining step?
slow
fast
fast
What is(are) the intermediate(s)
in the mechanism?
1. HOI
2. OH
-
3. H
+
4. HOI and OH
-
5. I
-
and H
2
O
H
2
O
2
+ I
-
HOI + OH
-
OH
-
+ H
+
H
2
O
HOI + H
+
+ I
-
I
2
+ H
2
O
slow
fast
fast
Catalysis
Catalyst -
The substance reacts within an elementary step of
the mechanism but is regenerated in a subsequent
step.

11
Uncatalyzed vs. Catalyzed
There are three general types of catalysts.
Heterogeneous Catalyst
Homogeneous Catalyst
Enzyme Catalyst
Heterogeneous and
Homogeneous Catalysts
These are simply defined by the state of the catalyst.

Often a solid catalyst that a gas is passed through

Catalytic converter on a car is an example

All aqueous or all gases, for example.

Enzymes

Often made up of very large and complex

molecules with molar masses in the thousands.
All aspects of a catalyst apply to enzymes.
Enzyme
Ubiquitin
Activated
Enzyme
End of Kinetics Unit