Chemical Kinetics

Chapter 5

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Chapter 14

Factors that Affect Reaction

Rates
Kinetics

is the study of how fast

chemical reactions occur.
There are 4 important factors which
affect rates of reactions:
reactant concentration,
temperature,
action of catalysts, and
surface area.
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Chapter 14

Reaction Rates
Speed

of a reaction is measured by
the change in concentration with
time.
For a reaction A B
change in concentration (molarity) of B
Average rate
change in time
[ B ]

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Chapter 14

Reaction Rates
the reaction A B there are two
ways of measuring rate:

For

the speed at which the products appear

the speed at which the reactants

disappear

[ A]
Average rate with respect to A
t

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Chapter 14

Reaction Rates
Change of Rate with Time
Most useful units for rates are to look
at molarity. Since volume is
constant, molarity and moles are
directly proportional.
Consider:
C4H9Cl(aq) + H2O(l) C4H9OH(aq) +
HCl(aq)
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Chapter 14

Reaction Rates
Change of Rate with Time
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
We

can calculate the average rate in terms of the

disappearance of C4H9Cl.
The units for average rate are mol/Ls or M/s.
The average rate decreases with time.
We plot [C4H9Cl] versus time.
The rate at any instant in time (instantaneous rate)
is the slope of the tangent to the curve.
Instantaneous rate is different from average rate.
We usually call the instantaneous rate the rate.
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Chapter 14

Reaction Rates
Reaction Rate and Stoichiometry
For the reaction
C4H9Cl(aq) + H2O(l) C4H9OH(aq) +
HCl(aq)
C4H9Cl C4H9OH
Rate

we know
t
t
In

general for
aA1 + AbB

B +1 dD
C
1 cC

1 D
Rate

a t
b t
c t
d t

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Chapter 14

Concentration and Rate

In

general rates increase as concentrations

increase.
NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

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Chapter 14

Concentration and Rate

For

the reaction
NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)
we note
as [NH4+] doubles with [NO2-] constant the rate

doubles,
as [NO2-] doubles with [NH4+] constant, the rate
doubles,
We conclude rate [NH4+][NO2-].

Rate

k
[
NH
][
NO
Rate law:
4
2]
The

constant k is the rate constant.

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Chapter 14

Concentration and Rate

Exponents in the Rate Law
For a general reaction with rate law
m

Rate k[reactant 1] [reactant 2]n

we say the reaction is mth order in reactant 1 and

nth order in reactant 2.
The overall order of reaction is m + n + .
A reaction can be zeroth order if m, n, are
zero.
Note the values of the exponents (orders) have
to be determined experimentally. They are not
simply related to stoichiometry.
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Chapter 14

Concentration and Rate

Using Initial Rates to Determines Rate
Laws
A reaction is zero order in a reactant if the
change in concentration of that reactant
produces no effect.
A reaction is first order if doubling the
concentration causes the rate to double.
A reacting is nth order if doubling the
concentration causes an 2n increase in rate.
Note that the rate constant does not depend
on concentration.
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Chapter 14

The Change of Concentration

with Time
First Order Reactions
Goal: convert rate law into a convenient equation
to give concentrations as a function of time.
For a first order reaction, the rate doubles as the
concentration of a reactant doubles.

[A]
Rate
k[A]
t
ln A t ln A 0 kt
At
kt
ln
A 0
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Chapter 14

The Change of Concentration

with Time
First Order Reactions
A plot of ln[A]t versus t is a straight
line with slope -k and intercept
ln[A]0.
In the above we use the natural
logarithm, ln, which is log to the
base e.

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Chapter 14

The Change of Concentration

with Time
First Order Reactions

ln A t kt ln A 0

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Chapter 14

The Change of Concentration

with Time
Second Order Reactions
For a second order reaction with just
one reactant
1
1

At

kt

A 0

plot of 1/[A]t versus t is a straight

line with slope k and intercept 1/[A]0
For a second order reaction, a plot of
ln[A]t vs. t is not linear.
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Chapter 14

The Change of Concentration

with Time
Second Order Reactions
1
1
kt
At
A 0

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Chapter 14

The Change of Concentration

with Time
Half-Life
Half-life is the time taken for the
concentration of a reactant to drop
to half its original value.
For a first order process, half life, t
is the time taken for [A]0 to reach
[A]0.
Mathematically, ln 1
0.693
t1
2

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Chapter 14

The Change of Concentration

with Time
Half-Life
For a second order reaction, half-life
depends in the initial concentration:
t1

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Chapter 14

k A 0

Temperature and Rate

The Collision Model
Most reactions speed up as temperature
increases. (E.g. food spoils when not
refrigerated.)
When two light sticks are placed in water: one at
room temperature and one in ice, the one at
room temperature is brighter than the one in
ice.
The chemical reaction responsible for
chemiluminescence is dependent on
temperature: the higher the temperature, the
faster the reaction and the brighter the light.
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Chapter 14

Temperature and Rate

The
Collision
Model
As
temperatur
e
increases,
the rate
increases.

Temperature and Rate

The Collision Model
Since the rate law has no temperature term in it,
the rate constant must depend on temperature.
Consider the first order reaction CH3NC
CH3CN.
As temperature increases from 190 C to 250 C the

rate constant increases from 2.52 10-5 s-1 to 3.16

10-3 s-1.

The

temperature effect is quite dramatic. Why?

Observations: rates of reactions are affected by
concentration and temperature.
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Chapter 14

Temperature and Rate

The Collision Model
The collision model: in order for
molecules to react they must collide.
The greater the number of collisions
the faster the rate.
The more molecules present, the
greater the probability of collision
and the faster the rate.
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Chapter 14

Temperature and Rate

The Collision Model
The higher the temperature, the more energy
available to the molecules and the faster the
rate.
Complication: not all collisions lead to products.
In fact, only a small fraction of collisions lead to
product.
The Orientation Factor
In order for reaction to occur the reactant
molecules must collide in the correct orientation
and with enough energy to form products.
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Chapter 14

Temperature and Rate

The Orientation Factor
Consider:
Cl + NOCl NO + Cl2
There are two possible ways that Cl
atoms and NOCl molecules can
collide; one is effective and one is
not.

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Chapter 14

Temperature and Rate

The Orientation Factor

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Chapter 14

Temperature and Rate

Activation Energy
Arrhenius: molecules must posses a
minimum amount of energy to react.
In order to form products, bonds must be

broken in the reactants.

Bond breakage requires energy.
Activation

energy, Ea, is the

minimum energy required to initiate
a chemical reaction.

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Chapter 14

Temperature and Rate

Activation Energy
Consider the rearrangement of methyl isonitrile:

H3C N C

H3C

N
C

H3C C N

In H3C-NC, the C-NC bond bends until the C-N bond

breaks and the NC portion is perpendicular to the H3C

portion. This structure is called the activated complex or
transition state.
The energy required for the above twist and break is the
activation energy, Ea.
Once the C-N bond is broken, the NC portion can continue
to rotate forming a C-CN bond.
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Chapter 14

Temperature and Rate

Activation Energy
The change in energy for the reaction is the
difference in energy between CH3NC and CH3CN.
The activation energy is the difference in energy
between reactants, CH3NC and transition state.
The rate depends on Ea.
Notice that if a forward reaction is exothermic
(CH3NC CH3CN), then the reverse reaction is
endothermic (CH3CN CH3NC).

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Chapter 14

Temperature and Rate

Activation Energy
How does a methyl isonitrile molecule gain
enough energy to overcome the activation
energy barrier?
From kinetic molecular theory, we know that as
temperature increases, the total kinetic energy
increases.
We can show the fraction of molecules, f, with
energy equal to or greater than Ea is
E
a
RT
f e
where R is the gas constant (8.314 J/molK).
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Chapter 14

Temperature and Rate

Activation Energy

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Chapter 14

Temperature and Rate

The Arrhenius Equation
Arrhenius discovered most reaction-rate data
obeyed the Arrhenius equation:
Ea
RT
k Ae
k is the rate constant, Ea is the activation energy, R

is the gas constant (8.314 J/K-mol) and T is the

temperature in K.
A is called the frequency factor.
A is a measure of the probability of a favorable
collision.
Both A and Ea are specific to a given reaction.
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Chapter 14

Temperature and Rate

Determining the Activation
Energy
If we have a lot of data, we can
determine Ea and A graphically by
Ea
rearranging ln
the
Arrhenius
equation:
k
ln A
RT

From

the above equation, a plot of ln

k versus 1/T will have slope of Ea/R
and intercept of ln A.

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Chapter 14

Temperature and Rate

Temperature and Rate

Determining the Activation
Energy
If we do not have a lot of data, then
Ea
Ea
we recognize
ln k
ln A and ln k
ln A
1

RT1

RT2

Ea
Ea
ln k1 ln k2
ln A
ln A
RT1
RT2

k1 Ea 1 1
ln

k2 R T2 T1
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Chapter 14

Reaction Mechanisms
The

balanced chemical equation provides

information about the beginning and end of
reaction.
The reaction mechanism gives the path of
the reaction.
Mechanisms provide a very detailed picture
of which bonds are broken and formed
during the course of a reaction.
Elementary Steps
Elementary step: any process that occurs in
a single step.
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Chapter 14

Reaction Mechanisms
Elementary Steps
Molecularity: the number of molecules
present in an elementary step.
Unimolecular: one molecule in the elementary

step,
Bimolecular: two molecules in the elementary
step, and
Termolecular: three molecules in the elementary
step.
It

is not common to see termolecular

processes (statistically improbable).

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Chapter 14

Reaction Mechanisms
Multistep Mechanisms
Some reaction proceed through more
than one step:
NO2(g) + NO2(g) NO3(g) + NO(g)

NO3(g) + CO(g) NO2(g) + CO2(g)

Notice that if we add the above
steps, we get the overall reaction:
NO2(g) + CO(g) NO(g) + CO2(g)
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Chapter 14

Reaction Mechanisms
Multistep Mechanisms
If a reaction proceeds via several
elementary steps, then the
elementary steps must add to give
the balanced chemical equation.
Intermediate: a species which
appears in an elementary step which
is not a reactant or product.
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Chapter 14

Reaction Mechanisms
Rate Laws for Elementary Steps
The rate law of an elementary step is
determined by its molecularity:
Unimolecular processes are first order,
Bimolecular processes are second order,

and
Termolecular processes are third order.

Rate Laws for Multistep

Mechanisms
Rate-determining step: is the slowest

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Chapter 14

Reaction Mechanisms
Rate Laws for Elementary Steps

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Chapter 14

Reaction Mechanisms
Rate Laws for Multistep
Mechanisms
Therefore, the rate-determining step
governs the overall rate law for the
reaction.
Mechanisms with an Initial Fast
Step
It is possible for an intermediate to
be a reactant.
Consider

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Chapter 14

Reaction Mechanisms
Mechanisms with an Initial Fast
Step
2NO(g) + Br2(g) 2NOBr(g)
The experimentally determined rate
law is
Rate = k[NO]2[Br2] k1
NOBr2(g)
Step 1: NO(g) + Br2(g)
(fast)
Consider the following
k-1 mechanism
Step 2: NOBr2(g) + NO(g)
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Chapter 14

k2

2NOBr(g) (slow)

Reaction Mechanisms
Mechanisms with an Initial Fast Step
The rate law is (based on Step 2):
Rate = k2[NOBr2][NO]
The rate law should not depend on the
concentration of an intermediate (intermediates
are usually unstable).
Assume NOBr2 is unstable, so we express the
concentration of NOBr2 in terms of NO and Br2
assuming there is an equilibrium in step 1 we have

k1
[ NOBr2 ]
[ NO][Br2 ]
k1
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Chapter 14

Reaction Mechanisms
Mechanisms with an Initial Fast
Step
By definition
k1[ NO][Br
] k1[ NOBr2 ]
of 2equilibrium:
k1
Therefore,
Rate k2

k1
becomes

k1 law 2
the
overall
rate
[ NO][Br2 ][ NO] k2
[ NO] [Br2 ]
k1

Note the final rate law is consistent

with the experimentally observed

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Chapter 14

Catalysis
A

catalyst changes the rate of a

chemical reaction.
There are two types of catalyst:
homogeneous, and
heterogeneous.

Chlorine

atoms are catalysts for the

destruction of ozone.

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Chapter 14

Catalysis
Homogeneous Catalysis
The catalyst and reaction is in one
phase.
Generally, catalysts operate by
lowering the activation energy for a
reaction.

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Chapter 14

Catalysis

Catalysis
Homogeneous Catalysis
Catalysts can operate by increasing the
number of effective collisions.
That is, from the Arrhenius equation:
catalysts increase k by increasing A or
decreasing Ea.
A catalyst may add intermediates to the
reaction.
Example: In the presence of Br-, Br 2(aq) is
generated as an intermediate in the
decomposition of H2O2.
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Chapter 14

Catalysis
Homogeneous Catalysis
When a catalyst adds an intermediate, the
activation energies for both steps must be lower
than the activation energy for the uncatalyzed
reaction.
Heterogeneous Catalysis
The catalyst is in a different phase than the
reactants and products.
Typical example: solid catalyst, gaseous
reactants and products (catalytic converters in
cars).
Most industrial catalysts are heterogeneous.
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Chapter 14

Catalysis
Heterogeneous Catalysis
First step is adsorption (the binding of reactant
molecules to the catalyst surface).
Adsorbed species (atoms or ions) are very reactive.
Molecules are adsorbed onto active sites on the
catalyst surface.

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Chapter 14

Catalysis

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Chapter 14

Catalysis
Heterogeneous Catalysis
When an H atom collides with an ethylene molecule
on the surface, the C-C bond breaks and a C-H
bond forms.
When C2H6 forms it desorbs from the surface.
When ethylene and hydrogen are adsorbed onto a
surface, less energy is required to break the bonds
and the activation energy for the reaction is lowered.
Enzymes
Enzymes are biological catalysts.
Most enzymes are protein molecules with large
molecular masses (10,000 to 106 amu).
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Chapter 14

Catalysis
Enzymes
Enzymes have very specific shapes.
Most enzymes catalyze very specific
reactions.
Substrates undergo reaction at the
active site of an enzyme.
A substrate locks into an enzyme
and a fast reaction occurs.
The products then move away from
the enzyme.

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Chapter 14

Catalysis
Enzymes
Only substrates that fit into the enzyme
lock can be involved in the reaction.
If a molecule binds tightly to an enzyme
so that another substrate cannot displace
it, then the active site is blocked and the
catalyst is inhibited (enzyme inhibitors).
The number of events (turnover number)
catalyzed is large for enzymes (103 - 107
per second).
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Chapter 14

Catalysis
Enzymes

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Chapter 14