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Chapter 12

Chemical Kinetics

Section 12.1
Reaction Rates
Reaction Rate
Change in concentration of a reactant or
product per unit time.
concentration of A at time t2 concentration of A at time t1
Rate =
t2 t1
A
=
t

[A] means concentration of A in mol/L; A is


the
reactant or product being considered.
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Section 12.1
Reaction Rates
The Decomposition of Nitrogen Dioxide

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Section 12.1
Reaction Rates
The Decomposition of Nitrogen Dioxide

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Section 12.1
Reaction Rates
Instantaneous Rate
Value of the rate at a particular time.
Can be obtained by computing the slope of
a line tangent to the curve at that point.

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Section 12.2
Rate Laws: An Introduction
Rate Law
Shows how the rate depends on the
concentrations of reactants.
For the decomposition of nitrogen dioxide:
2NO2(g) 2NO(g) + O2(g)
Rate = k[NO2]n:
k = rate constant
n = order of the reactant
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Section 12.2
Rate Laws: An Introduction
Rate Law
Rate = k[NO2]n
The concentrations of the products do not
appear in the rate law because the reaction
rate is being studied under conditions where
the reverse reaction does not contribute to
the overall rate.

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Section 12.2
Rate Laws: An Introduction
Rate Law
Rate = k[NO2]n
The value of the exponent n must be
determined by experiment; it cannot be
written from the balanced equation.

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Section 12.2
Rate Laws: An Introduction
Types of Rate Laws
Differential Rate Law (rate law) shows how
the rate of a reaction depends on
concentrations.
Integrated Rate Law shows how the
concentrations of species in the reaction
depend on time.

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Section 12.2
Rate Laws: An Introduction
Rate Laws: A Summary
Because we typically consider reactions only
under conditions where the reverse reaction
is unimportant, our 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 rate laws is sufficient.

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Section 12.2
Rate Laws: An Introduction
Rate Laws: A Summary
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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Section 12.3
Determining the Form of the Rate
Law
Determine experimentally the power to which
each reactant concentration must be raised
in the rate law.

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Section 12.3
Determining the Form of the Rate
Law
Method of Initial Rates
The value of the initial rate is determined for
each experiment at the same value of t as
close to t = 0 as possible.
Several experiments are carried out using
different initial concentrations of each of the
reactants, and the initial rate is determined
for each run.
The results are then compared to see how the
initial rate depends on the initial
concentrations of each of the reactants.
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Section 12.3
Determining the Form of the Rate
Law
Overall Reaction Order
The sum of the exponents in the reaction rate
equation.
Rate = k[A]n[B]m
Overall reaction order = n + m
k = rate constant
[A] = concentration of reactant A
[B] = concentration of reactant B
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Section 12.3
Determining the Form of the Rate
Law
CONCEPT CHECK!

How do exponents (orders) in rate laws


compare to coefficients in balanced
equations?
Why?

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Section 12.4
The Integrated Rate Law
First-Order
Rate = k[A]
Integrated:
ln[A] = kt + ln[A]o
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
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Section 12.4
The Integrated Rate Law
Plot of ln[N2O5] vs Time

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Section 12.4
The Integrated Rate Law
First-Order
Time required for a reactant to reach half its
original concentration
HalfLife:
t1

0.693
=
k

k = rate constant
Halflife does not depend on the
concentration of reactants.
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Section 12.4
The Integrated Rate Law

A first order reaction is 35% complete at


the end of 55 minutes. What is the value of
k?

k = 7.8 103 min1

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Section 12.4
The Integrated Rate Law
Second-Order
Rate = k[A]2
Integrated:

1
1
= kt +
A
A 0
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
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Section 12.4
The Integrated Rate Law
Plot of ln[C4H6] vs Time and Plot of 1/[C4H6]
vs Time

Section 12.4
The Integrated Rate Law
Second-Order
HalfLife:

t1

1
=
k A 0

k = rate constant
[A]o = initial concentration of A
Halflife gets longer as the reaction progresses and
the concentration of reactants decrease.
Each successive halflife is double the preceding
one.
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Section 12.4
The Integrated Rate Law
EXERCISE!

For a reaction aA Products,


[A]0 = 5.0 M, and the first two half-lives are
25 and 50 minutes, respectively.
a) Write the rate law for this reaction.
rate = k[A]2
b) Calculate k.
k = 8.0 10-3 M1min1
c) Calculate [A] at t = 525 minutes.
[A] = 0.23 M
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Section 12.4
The Integrated Rate Law
Zero-Order
Rate = k[A]0 = k
Integrated:
[A] = kt + [A]o
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
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Section 12.4
The Integrated Rate Law
Plot of [A] vs Time

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Section 12.4
The Integrated Rate Law
Zero-Order
HalfLife:

t1 =
2

A 0
2k

k = rate constant
[A]o = initial concentration of A
Halflife gets shorter as the reaction progresses
and the concentration of reactants decrease.
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Section 12.4
The Integrated Rate Law
CONCEPT CHECK!

How can you tell the difference among 0th, 1st,


and 2nd order rate laws from their graphs?

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Section 12.4
The Integrated Rate Law
Rate Laws

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Section 12.4
The Integrated Rate Law
Summary of the Rate Laws

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Section 12.4
The Integrated Rate Law
EXERCISE!
Consider the reaction aA Products.
[A]0 = 5.0 M and k = 1.0 102 (assume the units are
appropriate for each case). Calculate [A] after 30.0
seconds have passed, assuming the reaction is:

4.7 M
a) Zero order
3.7 M
b) First order
c) Second order 2.0 M

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Section 12.5
Reaction Mechanisms
Reaction Mechanism
Most chemical reactions occur by a series of
elementary steps.
An intermediate is formed in one step and
used up in a subsequent step and thus is
never seen as a product in the overall
balanced reaction.

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Section 12.5
Reaction Mechanisms
A Molecular Representation of the Elementary Steps in
the Reaction of NO2 and CO

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

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Section 12.5
Reaction Mechanisms
Elementary Steps (Molecularity)
Unimolecular reaction involving one
molecule; first order.
Bimolecular reaction involving the collision
of two species; second order.
Termolecular reaction involving the collision
of three species; third order. Very rare.

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Section 12.5
Reaction Mechanisms
Rate-Determining Step
A reaction is only as fast as its slowest step.
The rate-determining step (slowest step)
determines the rate law and the molecularity
of the overall reaction.

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Section 12.5
Reaction Mechanisms
Reaction Mechanism Requirements
The sum of the elementary steps must give
the overall balanced equation for the
reaction.
The mechanism must agree with the
experimentally determined rate law.

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Section 12.5
Reaction Mechanisms
Decomposition of N2O5

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Section 12.5
Reaction Mechanisms
Decomposition of N2O5
2N2O5(g) 4NO2(g) + O2(g)

)
Step 1: 2(N2O5
NO2 + NO3
(fast)
Step 2: NO2 + NO3 NO + O2 + NO2
(slow)
Step 3: NO3 + NO 2NO2
(fast)
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Section 12.5
Reaction Mechanisms
CONCEPT CHECK!

The reaction A + 2B C has the following


proposed mechanism:
A+B
D
(fast equilibrium)
D+BC
(slow)
Write the rate law for this mechanism.
rate = k[A][B]2
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Section 12.6
A Model for Chemical Kinetics
Collision Model
Molecules must collide to react.
Main Factors:
Activation energy, Ea
Temperature
Molecular orientations

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Section 12.6
A Model for Chemical Kinetics
Activation Energy, Ea
Energy that must be overcome to produce a
chemical reaction.

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Section 12.6
A Model for Chemical Kinetics
Transition States and Activation Energy

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Section 12.6
A Model for Chemical Kinetics
Change in Potential Energy

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Section 12.6
A Model for Chemical Kinetics
For Reactants to Form Products
Collision must involve enough energy to
produce the reaction (must equal or exceed
the activation energy).
Relative orientation of the reactants must
allow formation of any new bonds necessary
to produce products.

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Section 12.6
A Model for Chemical Kinetics
The Gas Phase Reaction of NO and Cl2

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Section 12.6
A Model for Chemical Kinetics
Arrhenius Equation

k = Ae

Ea / RT

A
Ea

=
=

frequency factor
activation energy

R
T

=
=

gas constant (8.3145 J/Kmol)


temperature (in K)

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Section 12.6
A Model for Chemical Kinetics
Linear Form of Arrhenius Equation

Ea
ln(k ) =
R

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1
+ ln A
T

46

Section 12.6
A Model for Chemical Kinetics
Linear Form of Arrhenius Equation

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Section 12.6
A Model for Chemical Kinetics
EXERCISE!

Chemists commonly use a rule of thumb that


an increase of 10 K in temperature doubles
the rate of a reaction. What must the
activation energy be for this statement to be
true for a temperature increase from 25C to
35C?
Ea = 53 kJ
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Section 12.7
Catalysis
Catalyst
A substance that speeds up a reaction
without being consumed itself.
Provides a new pathway for the reaction with
a lower activation energy.

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Section 12.7
Catalysis
Energy Plots for a Catalyzed and an Uncatalyzed
Pathway for a Given Reaction

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Section 12.7
Catalysis
Effect of a Catalyst on the Number of ReactionProducing Collisions

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Section 12.7
Catalysis
Heterogeneous Catalyst
Most often involves gaseous reactants being
adsorbed on the surface of a solid catalyst.
Adsorption collection of one substance on
the surface of another substance.

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Section 12.7
Catalysis
Heterogeneous Catalysis

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Section 12.7
Catalysis
Heterogeneous Catalyst
1. Adsorption and activation of the reactants.
2. Migration of the adsorbed reactants on the
surface.
3. Reaction of the adsorbed substances.
4. Escape, or desorption, of the products.

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Section 12.7
Catalysis
Homogeneous Catalyst
Exists in the same phase as the reacting
molecules.
Enzymes are natures catalysts.

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Section 12.7
Catalysis
Homogeneous Catalysis

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