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# Chemical Kinetics

Chemical Kinetics

## It is not enough to understand the stoichiometry

and thermodynamics of a reaction; we also must
understand the factors that govern the rate of the
reaction.

Chapter 12

## We can use thermodynamics to tell if a

reaction is product or reactant favored.
But this gives us no info on HOW FAST reaction
goes from reactants to products.
H2O2 decomposition in
an insect

## KINETICS the study of REACTION RATES

H2O2 decomposition
catalyzed by MnO2

## and their relation to the way the reaction proceeds,

i.e., its MECHANISM.
The reaction mechanism is our goal!

Reaction Rates

## Determining a Reaction Rate

Blue dye is oxidized
with bleach.
Its concentration
decreases with time.
The rate the
change in dye conc
with time can be
determined from the
plot.

## So, if chemical kinetics is the study of

reaction rates, it might be a good idea to
understand what reactions rates are.
We define the reaction rate as the change
in concentration of a reactant or product
per unit time.
concentration of A at time t 2 concnetration of A at time t 1 [A]
=
t 2 t1
t

Dye Conc

Rate =

considered.

Example

Time

## We have the follow set of data. What method of

visualizing data might be useful to use here?

## Using the following reaction we will

explorer the world of reaction rates.
2NO2(g) 2NO(g) + O2(g)

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## A graph can help

you visualize
what is going on
a lot easier than
looking at a table
of data.

## You know the definition of a rate is as

follows.
Therefore to determine the average
rate at which the concentration of NO2
changes over the first 50 seconds you
would?

Using a
combination of
the graph and the
table we can start
determining
some rates.

Rate =

Instantaneous Rate

Rate =

[A]
t

=
= 4.2 M/sec
t
50 sec 0 sec

## We can see that the rate of the reaction is not

constant, but changes with time.

## Sometimes it is important to know what the

rate of a reaction is at a certain time.
This is known as an instantaneous rate.
Instantaneous rates can be determined by the
slope of a tangent line at a certain point on the
curvature.
For example: if we wanted to know the
instantaneous rate at t = 100 sec. of NO2.

10

- 0.0026 M

110 sec.

2.410-5 M/sec

negative sign?

## Draw a tangent line at the point on the curve.

Determine the slope of that tangent line

change in y
Slope =
change in x

## 2NO2(g) 2NO(g) + O2(g)

Average Rate

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It is customary to
work with positive
reaction rates.

see?

## Fact: All chemical reactions are reversible.

So let us examine the decomposition of NO2
2NO2(g) 2NO(g) + O2(g)
{Forward Reaction}
If all reactions are reversible at some point in time the
reverse reaction will be come important. (Think of a
closed container.)

## If you look at the

balanced chemical
reaction and the graph
you should be able to
notice that the rate at
which NO2 is used up is
equal to the rate that
NO is produced.

{Reverse Reaction}
2NO(g) + O2(g) 2NO2(g)
As you can probably already see this makes life a little
more complicated. So, we avoid this by studying the
reaction when the reverse reaction makes only a
negligible contribution.
What is it called when the forward and reverse reaction
rates are equal? (CH13)

## Looking at O2 you can

notice that the reaction
rate is half of that of
NO2 or NO.

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## We defined a rate as a change in concentration per unit

time.
However, which reactant or product concentration do we
choose in defining the rate?

## Therefore the reaction rate will only depend on the

concentration of the reactants.
Rate = k[NO2]n

## 2NO2(g) 2NO(g) + O2(g)

[ NO2 ]
Rate =
= k[ NO2 ]n
T
[O2 ]
Rate ' =
= k '[ NO2 ]n
T
Rate = 2 Rate '

k = rate constant
n = rate order (can be an integer including zero or a fraction)
Important Points
1. The concentration of the products do no appear in the rate law.
Why?

## 2. The value of the exponent n must be determined by experiment; it

CANNOT be written from the balanced equation.

## Rate Laws: Types

{Forward Reaction}

Because 2 NO2
molecules are
consumed for every O2
molecule produced.

k = 2 k'

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(What is n?)

## There are two types of rate laws.

1. The differential rate law (often called simply the rate law) shows
how the rate of a reaction depends on concentrations.
2. The integrated rate law shows how the concentrations of species in
the reaction depend on time.

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## We need to be able to determine more than just the rate

equation.
We need to be able to determine the value of n and also the
value of k.
The method we use is called the Method of Initial Rates
Let us consider the following reaction.

## Because we typically consider reactions only under

conditions where the reverse reaction is unimportant, out
rate laws will involve only concentrations of reactants.
Because the differential and integrated rate laws for a
given reaction are related in a well-defined way, the
experimental determination of either of the rates laws is
sufficient.
Experimental convenience usually dictates which type of
rate law is determined experimentally.
Knowing the rate law for a reaction is important mainly
because we can usually infer the individual steps involved
in the reaction from the specific form of the rate law.

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Order
Determination

## Rate 1 = 1.35 10-7 M s = k(0.100 M)n (0.0050 M)m

[ NH 4 ]
+

Rate =
= k[ NH 4 ]n [ NO2 ]m
t

## 1. Look at the data and determine the differences

You doubled the concentration of NO2- from experiment
1 to 2, but kept the concentration of NH4+ the same.
This leads to a doubling of the initial rate.
You doubled the concentration of NH4+ from experiment
2 to 3, but kept the concentration of NO2- the same.
This leads to a doubling of the initial rate.

## Rate 2 2.70 10 -7 M s k(0.100 M)n (0.010 M)m

=
= 2.00
=
Rate 1 1.35 10 -7 M s k(0.100 M)n (0.0050 M)m
m = 1

## Rate 3 5.40 10 -7 M s (0.200 M)n

=
=
= 2.00
Rate 2 2.70 10 -7 M s (0.100 M)n
n = 1

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## Rate Orders and Ratios

How the initial rate
Rate Order
changes when the
concentration is doubled

## Therefore we know the rate law is first order

in terms on NH4+ and NO2-.

Rate = k[NH4+][NO2-]

No change

Rate Doubles

+

## Rate = k[NH4 ][NO 2 ]

1.35 10-7 M sec = k(0.100 M)(0.0050 M)
k = 2.7 10-4 M sec

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## Overall Reaction Order

Sum of the order of each component in the rate
law.
rate = k[H2SeO3][H+]2[I]3
The overall reaction order is 1 + 2 + 3 = 6.
Determine the rate law and rate constant for the following data

Get it?

Rate = k[BrO3-][Br-][H+]2

OVER-ALLS

k = 8.0 M 3 sec

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## From the differential format we

can rewrite the equation as follows

## Up until now we have been talking about differential rate

laws.
It is also useful to be able to express the reactant
concentrations as a function of time.

Rate = -

## To start we will look at reactions involving a single

reactant

aA products

d[A]
= k[A] (first order)
dt

d[A]
= k(dt)
[A]
[A]

[A]
Rate =
= k[A]n
t
where n = 0, 1, 2 (zero, first, and second order)

d[A]
= k(dt)
[A] t =0
[A]0

or
[A] = [A]0 e -kt

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## First Order Integrated Rate Law

ln[A] = -kt + ln[A]0

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Example
2N2O5(g) 4NO2(g) + O2(g)

depends on time.

[N2O5] (M)
0.1000
0.0707
0.0500
0.0250
0.0125
0.00625

## If the initial concentration of A and the rate constant k are known,

the concentration of A at any time can be calculated.

y=ln[A]
x=t
m=-k
b=ln[A]

## 1. Verify that the rate

law is first order.
2. Calculate the rate
constant.

## If it is first order we need to be able to plot ln [N2O5] vs.

time
So, we construct a new table and plot the data.

ln [N2O5]
-2.303
-2.649
-2.996
-3.689
-4.382
-5.075

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Example
Time (sec)
0
50
100
200
300
400

Time (sec)
0
50
100
200
300
400

## Well, we have no information on the initial rates; so, we

start thinking about the integrated rate laws

## So, we have discovered a way to test if the

reaction is first order. If we plot ln[A] vs time and
get a straight line we know the reaction is first
order.

ln [N2O5]
-2.303
-2.649
-2.996
-3.689
-4.382
-5.075

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Time (sec)
0
50
100
200
300
400

Example

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## 2N2O5(g) 4NO2(g) + O2(g)

Since it is a first order reaction,
we know that in the first order
integrated rate law that k is
equal to the -slope of the line.
Y (ln[N 2O 5 ])
=
X
t
- 5.075 - (-2.303) 2.772
Slope =
=
= 6.93 10 3 s 1
400 0
400
k = (slope) = 6.93 10 3 s 1
Slope =

## The plot proves it

is a straight line
and so it is a first
order reaction.

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## Half-life is defined as the time required for a reactant

to reach half of its original concentration.

t1/2 =

30

## A certain first-order reaction has a half-life of

20.0 minutes.
1. Calculate k for the reaction
2. How much time is required for this reaction to be 75 %
complete?

0.693
k

## t1/2 = half-life of the reaction

k = rate constant
For a first-order reaction, the half-life does not
depend on concentration.

k=

0.693
t 1/2

k=

0.693
= 3.47 10 2 min 1
20.0min

## If the reaction is 75% complete

that means there is 25% of the
reactant left.
ln[A] = - kt + ln[A]0
If we assume that the orignal
concentration is 1 then the concentration
at 75% completion is 0.25.
ln 0.25 = -kt + ln 1
ln 0.25 - ln 1 = (3.47 10- 2 min -1 )t
- 1.3863 = -(3.47 10- 2 min -1 )t
t = 39.95 min 40 min

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## We will skip the calculus lesson and just give

you the second-order integrated rate law.
For aA products in a second-order reaction,

Rate =

t1/2 =

A
=k A 2
t

## t1/2 = half-life of the reaction

k = rate constant
Ao = initial concentration of A

1
1
= kt +
A
Ao

## The half-life is dependent upon the

initial concentration.

Therefore

1
kA

## A plot of 1/[A] vs. time with produce a straight line

with the slope equal to k

Example

t(s)
0
1000
1800
2800
3600
4400
5200
6200

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2 C4H6(g) C8H12(g)
With the following data determine:
1. Is the reaction first of second order?
2. What is the value of the rate constant for the
reaction?
3. What is the half-life for the reaction under the
conditions of this experiment
[C4H6] (M)
0.01000
0.00625
0.00476
0.00370
0.00313
0.00270
0.00241
0.00208

Time (sec)
0
1000
1800
2800
3600
4400
5200
6200

Time (sec)
0
1000
1800
2800
3600
4400
5200
6200

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Example
From the previous data you
can do some calculations and
obtain the following table.

## From the graphs we will

be able to ascertain what
order the reaction is.
So, what order is the
reaction?

Example

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We can do the same thing to calculate the half life or use the secondorder half life equation.

Since we know that the reaction is second order we can use the
second order integrated rate-law to determine k.

[C4H6] (M)
0.01000
0.00625
0.00476
0.00370
0.00313
0.00270
0.00241
0.00208

ln[C4H4]
-4.605
-5.075
-5.348
-5.599
-5.767
-5.915
-6.028
-6.175

## If we plot this data we will

obtain the following two
graphs.

## Since we know that first order

reactions create a straight line
when you plot ln [A] vs. time
and second order reactions
create a straight line when you
plot 1/[A] vs. time. We can
create a new table and graphs.

Example

1/[C4H6]
100
160
210
270
320
370
415
481

1
1
= kt +
[A]0
[A]

1
1
= kt +
[A]
[A]0

1
1
= k(6200) +
0.00208
0.01000

1
1
= (6.14 10 2 M1 sec)(t 1/2 ) +
0.00500
0.01000

## 100 = (6.14 10 2 M1 sec)(t 1/2 )

381
= k = 6.14 10 2 M1 sec
6200

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Example

## However, there can be zero-order reactions.

We can do the same thing to calculate the half life or use the secondorder half life equation.

t 1/2 =

1
k[A]0

t 1/2 =

1
(6.14 10 2 M1 sec)(0.010 00 M)

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## Most reactions involving a single reactant show either first or

second order kinetics.
The rate is constant.
It does not change with concentration.

Example:

[A] = kt + [A]0
t 1/2 =

## The following reaction takes

place on a hot platinum
surface.

[A]0
2k

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A Summary

40

## Simplification: Conditions are set such that only

forward reaction is important.
Two types:
differential rate law
integrated rate law
Which type? Depends on the type of data collected differential and integrated forms can be interconverted.
Most common: method of initial rates.

molecules.

## Concentration v. time: used to determine integrated rate

law, often graphically.

## For several reactants: choose conditions under which

only one reactant varies significantly (pseudo first-order
conditions).

## Since only those N2O molecules on the surface can react.

An Example of a zero-order reaction.

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Reaction Mechanisms

42

## The sequence of events at the molecular level that

control the speed and outcome of a reaction.
A chemical equation does not tell us how reactants
become products - it is a summary of the overall
process.

## Br from biomass burning destroys

stratospheric ozone.
(See R.J. Cicerone, Science, volume 263, page 1243, 1994.)

Page 7

Step 1:

Br + O3 ---> BrO + O2

Step 2:

Cl + O3 ---> ClO + O2

Step 3:

NET:

2 O3 ---> 3 O2

## The reaction has many steps in

the reaction mechanism.

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## Often Used Terms

Intermediate: formed in one step and used up in a
subsequent step and so is never seen as a product.

## Molecularity: the number of species that must collide

to produce the reaction indicated by that step.

## Elementary Step: A reaction whose rate law can be

written from its molecularity.

Example

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## The sum of the elementary steps must give

the overall balanced equation for the reaction.

## NO2(g) + CO(g) NO(g) + CO2(g)

Here is a basic reaction.
Rate = k[NO2]2
But the mechanism is thought to involve the
following steps.

k1

k2

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## The mechanism must agree with the

experimentally determined rate law.

Rate-Determining Step
In a multistep reaction, it is the
slowest step. It therefore
determines the rate of reaction.

slow

fast

[NO3 ]
= k 1[NO2 ]2
t

## Which agrees with the experimentally

determined rate law.

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Concentration

Collision Model

## What is an easy way to increase the number

of collisions?
Increase the concentration
If we have a higher concentration, then we
will have more molecules, which in turn
gives us more collisions per unit time.
If we have more collisions, then the reaction
rate must increase.

## We will discuss a model that accounts

for the observed characteristics of
reaction rates, the collision model.
The basic idea of the model is that in
order for molecules to react, they must
collide.

## Concentration can affect the

rate of a chemical reaction

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Concentrations

Temperature

## Another way to change the

number of collisions is to
change the temperature.
Let us consider temperature of a
gas:

52

## If we increase the temperature:

1. We increase the molecular velocity
2. Which would increase the frequency
of collisions between molecules
3. Which increases the reaction rate

## Temperature can affect the

rate of a chemical reaction

53

## Example of Change in Temperature

and Concentration

Temperature

Bleach at 54 C

54

## As the "temperature" increases, the spheres hit

the edges more frequently.
When more spheres are added, the interparticle
collisions are more frequent.
Bleach at 22 C

http://chemed.chem.purdue.edu/demos/main_pages/4.4.html

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## It has been shown that the reaction

rate is much smaller than the
calculated collision frequency.
In other words, only a small fraction of
all collisions produces a reaction.

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Svante Arrhenius

## Example of Activation Energy

Let us look at an example of activation
energy.
We will use the decomposition of BrNO(g) as
an example:

## In the 1880s, this problem was first

He proposed that there is a threshold
energy which must be overcome in
order for the chemical reaction to
take place.
This threshold energy is called the
activation energy.

(contd)

## In this reaction, two Br-N bonds need to be

broken and one Br-Br bond needs to form.
The energy required to break a Br-N bond is
considerable (243 kJ/mol).
This energy must be supplied from
somewhere, but from where?

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60

Svante Arrhenius

## Based upon the collision model, the energy comes from

the kinetic energy of the molecules.
Once the molecules collide, the kinetic energy is changed
into potential energy which breaks the bonds and
rearranges the atoms.

## Number of collisions with the activation energy =

(total number of collisions) e -Ea/RT

Transition
State
Where do you think
Activation
the
products would
be Energy
if the reaction
was endothermic?
Reactants

## Arrhenius postulated that the number

of collisions having the activation
energy is a fraction of the total number
of collisions.

## Because the products

are lower in energy
than the reactants,
this chemical reaction
Products (it
is exothermic
produces heat).

## Ea is the activation energy

R is the universal gas constant
T is the temperature in Kelvin
e Ea/RT is the fraction of collisions with
energy Ea or greater at temperature T

Page 10

Molecular Orientation

61

More Details

## It has to do with molecular orientation.

When molecules collide, they must be lined up a
certain way for the reaction to proceed.

## Experiments have shown that the

observed reaction rate is considerably
smaller than the rate of collisions with
enough energy to surmount the barrier.
In other words, there are enough collisions
with enough energy to cause the reaction,
but the reaction does not occur.
Why (does chemistry have to be so
difficult)?

two Br atoms can
react with each
other and NO(g)
can be ejected.

## 2BrNO(g) 2NO(g) + Br2(g)

Remember this is the
decomposition reaction

Main Points

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## Concentration (the more molecules, the more collisions).

Temperature (if we speed up the movement of the molecules, this will
help the reaction to occur and speed it up).
Molecular orientation (molecules must be properly orientated in order
to react)
Activation energy (must provide enough energy to get over the hill)

## If we consider the Arrhenius Equation, we can easily see

how temperature affects the rate of a chemical reaction.
What other factors could there be?

k = A e -Ea/RT
Can we change the
activation energy?

## A is the frequency factor that is made up of the collision

frequency and the steric factor (molecular orientation).

Potential Energy

Temperature
can change

## Figure 12.18: The exhaust gases from

an automobile engine are passed
through a catalytic converter to
minimize environmental damage.

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## We have seen and reviewed different factors that affect

the rate of a chemical reaction.

k = A e -Ea/RT

## This is done through

the use of a catalyst.
A catalyst is a
substance that speeds
up a reaction without
being consumed.
It does this by
providing a new
reaction pathway that
has a lower activation
energy.
Two different
classifications of
catalysts:

## The Br atoms are

not lined up to
allow for the
reaction to
efficiently occur.

## Factors So Far that Affect the Rate

of a Chemical Reaction

## For a reaction to occur:

The collision must involve enough energy to
produce the reaction or the collision energy
must be equal or greater than the activation
energy.
The relative orientation of the reactants must
allow efficient formation of any new bonds
necessary to produce the products.
We can represent these factors as a rate
constant (k) with one equation called the
Arrhenius Equation.

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Reaction Progress

Homogenous
Heterogeneous

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Heterogeneous Catalyst

## Factors Affecting Rates

68

(hydrogenation of ethylene)
H

## Catalysts: catalyzed decomp of H2O2

2 H2O2 --> 2 H2O + O2

H
C

(g) + H2(g)

C
H

H C
H

H
C H (g)
H

## A heterogeneous catalyst is one that exists

in a different phase relative to the
reactants, usually a solid.
Heterogeneous catalytic reactions typically
involves four steps:
2. Migration of the adsorbed reactants on
the surface
3. Reaction of the adsorbed substances
4. Escape, or desorption, of the products

Homogeneous Catalyst

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21

## A homogeneous catalyst is one that exists in

the same phase as the reacting molecules.
An example of this is the breakdown of ozone
(O3).

## There are five major factors that

influence a chemical reaction.
1.
2.
3.
4.
5.

## Chlorine atoms are released from CCl2F2 (Freon-12)

when it reacts with light.
These chlorine atoms then go on to break down
ozone.

## Cl(g) + O3(g) ClO(g) + O2(g)

O(g) + ClO(g) Cl(g) + O2(g)
O(g) + O3(g) 2O2(g)

## Therefore, the chlorine gas is the homogeneous catalyst.

Page 12

Concentration of Reactants
Temperature
Activation Energy
Molecular Orientation
Use of Catalyst

## The Arrhenius equation (k = A e Ea/RT)

describes how some of these factors
affect the reaction rate (k).
A catalyst lowers the activation energy
and is not consumed.

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