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Chemical Kinetics

Part I
Describing the Rate of a Reaction
What is Kinetics?
What Is It Good For?
Kinetics is the study of reaction rates.
Information about reaction rates
allows us to predict how long it will take for a reaction
to reach completion
tells us how the reaction proceeds at the molecular level
(mechanism)
Understanding reaction mechanisms provides chemists with
important insight into how reactions work, and also provides a
basis for designing new reactions and processes.
Measuring Reaction Rates
Image from http://www.cstl.nist.gov/div838/crds_web/gas_app.htm
An apparatus designed to measurement very fast reaction rates in gases
(NIST Experimental Chemical Kinetics Thermodynamics Division)
Factors Affecting Rate of a Reaction
Reaction conditions
Concentration (solutions)
Surface area (solids)
Temperature
Chemical effects
Nature of reactants (reaction mechanism)
Catalysts
Describing the Rate of a Reaction
Reaction rate and rate law
Order of a reaction
Dependence on concentration and Time
Half life
Defining Rate
2NO
2
(g) 2NO(g) + O
2
(g)


Rate is expressed as a positive number!
Rate of appearance of product NO

Rate of disappearance of reactant NO
2
unit time per ion concentrat in change = =
dt
dC
Rate
| |
dt
NO d
Rate=
dt
NO d
Rate
] [
2
=
Measuring Rate
Instantaneous Rate
For disappearance of NO
2
Rate = -(slope of tangent)

2NO
2
(g) 2NO(g) + O
2
(g)
Average rate
( )
1 1 5
10 1 . 2
) 0 300 (
/ 0100 . 0 0038 . 0
=
=

=
s L mol
s
L mol
Rate
| |
1 1 5
2
10 4 . 2
110
) / 0026 . 0 (

=

=
A
A
=
s L mol
s
L mol
t
NO
Rate
At t = 100 s
For average rate from 0 and 300 s, use
actual values of [NO
2
] at these times.
100 s
0.0038
Relating Rates for Reactants and Products
Relative rate depends on
stoichiometry
Reaction rate must be reported
with respect to a specific
reactant or product!
2NO
2
(g) 2NO(g) + O
2
(g)
| | | | | |
t
O
t
NO
t
NO
A
A
=
A
A
=
A
A

2 2
2
For NO
2
reaction
1 1 6
1 1 6
10 3 . 4
10 6 . 8
2
2


=
= =
s L mol R
s L mol R R
O
NO NO
At 250 s, the rates are
250 s
Rate and Concentration
Rate Law and Reaction Order
Method of Initial Rates
Rate Law and Reaction Order
For the reaction
aA + bB products
The rate law is
| | | |
n m
B A k Rate =
k = rate constant
m = order w.r.t. A
n = order w.r.t. B
Overall order = m + n
Determine by
experiment
Determining the Rate Law
Goal
Determine rate constant k and orders m and n.
Two approaches
Method of initial rates
Plots of concentration vs time
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
| | | |
n m
CO NO k Rate
2
=
Reaction Order by Method of Initial
Rates
Goal: Determine rate constant k and orders m and n.
To determine m, observe effect of [NO
2
] on rate while holding
[CO] constant.
To determine n, observe effect of [CO] on rate while holding
[NO
2
] constant.
Once m and n are known, calculate k directly from rate equation
and experimental data.
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
| | | |
n m
CO NO k Rate
2
=
Method of Initial Rates - Example
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
| | | |
n m
CO NO k Rate
2
=
Trial [CO] [NO
2
] Rate
mol/L s
1 0.10 0.10 0.005
2 0.10 0.20 0.010
3 0.20 0.10 0.010
| | | |
| | | |
1
2
1
2
1
20 . 0
10 . 0
010 . 0
005 . 0
2 and 1 For trials
2 2 2
1 1 2
2
1
=
|
.
|

\
|
=
|
.
|

\
|
=
=
m
CO NO k
CO NO k
R
R
m
m
n m
n m
To determine m
observe effect of [NO
2
] on
rate while holding [CO]
constant.
Method of Initial Rates - Example
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
| | | |
n m
CO NO k Rate
2
=
Trial [CO] [NO
2
] Rate
mol/L s
1 0.10 0.10 0.005
2 0.10 0.20 0.010
3 0.20 0.10 0.010
| | | |
| | | |
1
2
1
2
1
20 . 0
10 . 0
010 . 0
005 . 0
2 and 1 For trials
2 2 2
1 1 2
2
1
=
|
.
|

\
|
=
|
.
|

\
|
=
=
n
CO NO k
CO NO k
R
R
n
n
n m
n m
To determine n
observe effect of [CO]
on rate while holding
[NO
2
] constant.
( ) ( )
( )
( )
( )
1
5 . 0 log
5 . 0 log
5 . 0 log
5 . 0 log 5 . 0 log
= =
=
=
n
n
n
For more difficult
cases, take logarithm
of both sides
Method of Initial Rates - Example
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
| | | |
n m
CO NO k Rate
2
=
Trial [CO] [NO
2
] Rate
mol/L s
1 0.10 0.10 0.005
2 0.10 0.20 0.010
3 0.20 0.10 0.010
We have determined that m = 1
and n = 1. Using data from trial 1,
we can calculate k.






| | | |
( ) ( )
s mol L
L mol L mol
s L mol
CO NO
Rate
k
n m
/ 50 . 0
/ 10 . 0 / 10 . 0
/ 005 . 0
1 1
2
=
=
=
Summary results
the reaction is 1
st
order wrt NO
2
the reaction is 1
st
order wrt CO
the rate constant k = 0.50 L/mol s
the rate law is


| || | CO NO k Rate
2
=
Relations Between Concentration
and Time
Integrated form of the rate law
Graphical method for determination of the
order of a reaction
Half-life and rate constant
Derivation of the Integrated Rate Law
A Products
Two equations for rate:
| |
dt
A d
Rate =
Equate the right-hand sides:
(Differential form of rate law)
| |
| |
n
A k
dt
A d
=
Integrate from [A]
0
to [A] and t = 0 to t,
where A
0
is initial [A] at t =0:
(I ntegral form of rate law)
Rearranging,
| |
| |
} }
=
t A
A
n
dt k
A
A d
0
0
| |
| |
kdt
A
A d
n
=
| |
n
A k Rate =
Relations Between Concentration and Time
Expressions for the Integrated Rate Law
| |
| |
} }
=
t A
A
n
dt k
A
A d
0
0
Zero order
Rate = k
(n = 0)
| | | |
| | | | kt A A
or
kt A A
=
=
0
0
[A]
t
-k
First order
Rate = k[A]
(n = 1)
| |
| |
| | | | kt A A
or
kt
A
A
=
=
0
0
ln ln
ln
ln[A]
t
-k
Second order
Rate = k[A]
2
(n = 2)
| | | | ( )
| | | |
kt
A A
or
kt A A
+ =
=

0
1
0
1
1 1
1/[A]
t
k
A products
Relations between concentration and time
Expressions for the Integrated Rate Law
Zero order:

First order:

Second order:

To determine reaction order w.r.t. A, generate plots.
If [A] vs t is linear, reaction is 0
st
order.
If ln[A] vs t is linear, reaction is 1
st
order.
If 1/[A] vs t is linear, reaction is 2
nd
order.
| | | | kt A A =
0
| | | | kt A A =
0
ln ln
| | | |
kt
A A
+ =
0
1 1
Graphical Determination of Reaction Order
A products

If zero order, plot of [A] vs t should be linear.
Zero Order Plot
0.000
0.020
0.040
0.060
0.080
0.100
0.120
0 10 20 30 40 50
time, s
[
A
]
time, s [A] ln[A] 1/[A]
0 0.100 -2.303 10.0
10 0.067 -2.703 14.9
20 0.045 -3.103 22.3
30 0.030 -3.503 33.2
40 0.020 -3.903 49.5
| | | | kt A A =
0
Not zero order
Graphical Determination of Reaction Order
A products

If first order, plot of ln[A] vs t should be linear.
First Order Plot
-4.000
-3.800
-3.600
-3.400
-3.200
-3.000
-2.800
-2.600
-2.400
-2.200
-2.000
0 10 20 30 40 50
time, s
l
n
[
A
]
time, s [A] ln[A] 1/[A]
0 0.100 -2.303 10.0
10 0.067 -2.703 14.9
20 0.045 -3.103 22.3
30 0.030 -3.503 33.2
40 0.020 -3.903 49.5
| | | | kt A A =
0
ln ln
Reaction is first order!
Graphical Determination of Reaction Order
A products

If second order, plot of 1/[A] vs t should be linear.
Second Order Plot
0.0
10.0
20.0
30.0
40.0
50.0
60.0
0 10 20 30 40 50
time, s
1
/
[
A
]
time, s [A] ln[A] 1/[A]
0 0.100 -2.303 10.0
10 0.067 -2.703 14.9
20 0.045 -3.103 22.3
30 0.030 -3.503 33.2
40 0.020 -3.903 49.5
| | | |
kt
A A
+ =
0
1 1
Not second order!
Graphical Determination of Rate Law
2H
2
O
2
2H
2
O + O
2
Data
Time (s) [H2O2] (mol/L)
0 1.00
120 0.91
300 0.78
600 0.59
1200 0.37
1800 0.22
2400 0.13
3000 0.082
3600 0.050
Generate the following plots in Excel
[H
2
O
2
] vs t
ln[H
2
O
2
] vs t
1/[H
2
O
2
] vs t

see Excel spreadsheet

The plot of ln[H
2
O
2
] vs t yields a
straight line. Reaction is first order!
What is
the rate law for the reaction
the integrated rate law
the value of the rate constant
[H
2
O
2
] at 4000 s
Half-Life
Half-life is the time required for the concentration
of a reactant to decrease by a factor of 2.
t
1/2
= half-life
Many reactions, including radioactive processes,
are first order. Lets examine the quantitative
aspects of half-life for a first-order reaction.
A products
Rate = k[A]
Half-Life for a 1st Order Reaction
A products
t
1/2
= time for [A] to decrease by factor of 2.
0.000
0.020
0.040
0.060
0.080
0.100
0.120
0 10 20 30 40 50
time, s
[
A
]
t
1/2
=10 s
time, s [A] n 2^n
0 0.100 0 1.0
10 0.050 1 2.0
20 0.025 2 4.0
30 0.013 3 8.0
40 0.006 4 16.0
Data for a reaction with a 10-s half-life
After n half-lives,
[A] = [A]
0
/2
n

Relating t
1/2
and k
For the 1st order reaction A products
Rate = k[A]
Noting that [A] = [A]
0
/2 when t = t
1/2

| | | |
| |
| | A
A
A A kt
kt A A
0
0
0
ln ] ln[ ] ln[
ln ln
= =
=
k k
t
kt
693 . 0 2 ln
2 ln
2 / 1
2 / 1
= =
=
Calculations Involving Half-Life for a
First-Order Reaction
The radioactive isotope
32
P decays by first-order kinetics, t
1/2
= 14.3 days. How
long does it take for 95.0% of a given sample of
32
P to decay?
32
P products
Rate = k[
32
P]
| | | | kt A A =
0
ln ln
k k
t
693 . 0 2 ln
2 / 1
= =
For a 1
st
order-reaction, expressions for the integrated rate law and t
1/2
are
1
2 / 1
0485 . 0 3 . 14 693 . 0 2 ln

= = = d d t k
The rate constant is calculated from t
1/2


| | | | ( ) | | | | ( )
days
d k
A A
k
A A
t 8 . 61
0484 . 0
20 ln 050 . 0 ln ln
1
0 0 0
= = = =

At 95.0% decay, [A] = 0.050[A]
0
. Solving the integrated rate law for t


Summary of Kinetics I
Describing the Rate of Reaction
Kinetics tells us
how fast reaction
proceeds
mechanism of reaction
Factors affecting rate
Describing rate
Rate = -dC/t

aA + bB products
Summary of Kinetics I
Describing the Rate of Reaction
Kinetics tells us
how fast reaction proceeds
mechanism of reaction
Factors affecting rate
Reaction conditions
C, T, surface area
Nature of reactants
Catalysts
Describing rate
Rate = -A[A]/At
Instantaneous rate, average rate
Rate and Concentration
Rate Law
Rate = k[A]
m
[B]
n

Method of initial rates
to determine k, m, n
Concentration and time
Integrated rate laws
zero order
[A] = [A]
0
- kt
first order
ln[A] = ln[A]0 - kt
second order
1/[A] = 1/[A]
0
+ kt
Graphical determination of
order and rate constant
Half-life and rate constant
t
1/2
= ln2/k
aA + bB products