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Unit 6 Chemical Kinetics

Zumdahl Chapter 12, pages 555-595


Upon completion of this unit you should be able to:
Identify factors which affect reaction rates
Calculate the rate of production of product or consumption of a reactant using mole
ratios and given rate
Determine the rate law for a reaction from given data, overall order and value of the
rate constant, inclusive of units
Determine the instantaneous rate of reaction
Use integrated rate laws to determine concentrations at a certain time and create
graphs to determine the order of a reaction.
Determine half-life of a reaction
Write the rate law from a given mechanism given th e speeds of each elementary step
Write the overall reaction for a mechanism and identify catalysts and intermediates
present
Determine the activation energy for the reaction using the Arrhenius equation
Graphically determine the activation energy using the Arrhenius equation
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Reaction Rates
The reaction rate of a chemical reaction is defined

as the change in concentration of a reactant or


product per unit time.
Rate =
=

Reaction Rates
Consider the decomposition of nitrogen dioxide:
2NO2(g) 2NO(g) + O2 (g)
We start with a flask of nitrogen dioxide at 300 oC and
measure the concentrations of nitrogen dioxide, nitric
oxide and oxygen as the nitrogen dioxide decomposes.
Concentration (mol/L)

Time (1 sec)

NO2

NO

O2

0.0100

50

0.0079

0.0021

0.0011

100

0.0065

0.0035

0.0018

150

0.0055

0.0045

0.0023

200

0.0048

0.0052

0.0026

250

0.0043

0.0057

0.0029

300

0.0038

0.0062

0.0031

350

0.0034

0.0066

0.0033

400

0.0031

0.0069

0.0035

Rate Laws

50 10 15 20
0 Time
0 (s)
0

25
0

30
0

35
0

Reaction Rates
Note from these results that the concentration of

the reactant decreases with time and the


concentrations of the products increase with time.
Chemical kinetics deals with the speed, or rate, at
which these changes occur.
The average rate at which the concentration of NO 2
changes over the first 50 seconds of the reaction is
=

= -4.2 x 10-5 mol/Ls


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Reaction Rates
Since the concentration of NO 2 decreases with time, any
rate expression involving a reactant will include a
negative sign.
It is customary to work with positive reaction rates, so we
define the rate of this particular reaction as
Rate = The average rate of this reaction from 0 to 50 seconds
then is 4.2 x 10-5 mol/Ls
The rate is not constant but decreases with time. This is
because the concentration changes with time.
The instantaneous rate can be determined by calculating
the slope of a line tangent to the curve at that point.
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Reaction Rates
The reaction rate can also be defined in terms of products.
When looking at reaction rates for products, stoichiometry
must be considered. For our example, the coefficients for
NO2 and NO are both 2 so NO is produced at the same rate
that NO2 is consumed. O2 has a coefficient of 1 so it is
produced half as fast as NO2 is consumed.
Because the reaction rate changes with time and because
the rate is different depending on which reactant or product
is being studied, we must be very specific when we
describe a rate for a chemical reaction.

Rate Laws
Chemical reactions are reversible. So far, we have only considered
the forward reaction. However, the reverse reaction can also occur.
As the concentration of products builds, it will reach a point where
the reverse reaction can start to occur.
For the reaction studied, the change in concentration of NO 2 depends
on the difference in the rates of the forward and reverse reactions.
This complication can be avoided if we study the rate of reaction
under conditions where the reverse reaction makes only a negligible
contribution. Typically, this means we study the reaction at a point
soon after the reactants are mixed, before the product has had time
to build to significant levels.
If we choose conditions where the reverse reaction can be
neglected, the reaction rate will depend only on the concentrations
of the reactants.
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Rate Laws
For the decomposition of nitrogen dioxide, we can write
Rate = k[NO2]n
This expression shows how the rate depends on the
concentration of the reactants and is called a rate law. The
proportionality constant, k, called the rate constant and n, called
the order of the reactant, are determined experimentally.
The order of a reactant can be an integer or a fraction. For our
relatively simple reactions, the orders will be positive integers.
We could define the rate in terms of the reactant or either of the
two products, each of which would give different values of the
rate constant.
We must be careful to specify which species we are discussing in
a given case.
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Rate Laws
A rate law that expresses how the rate depends on
concentration is technically called the differential rate law,
but is often simply called the rate law.
A rate law that expresses how the concentrations depend
on time is called the integrated rate law.

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Rate Laws
There are two types of rate laws.
The differential rate law shows how the rate of a reaction depends on
concentration.
The integrated rate law shows how the rate of a reaction depends on
time.
Our rate laws will only involve concentrations of reactants. The reverse
reaction is unimportant.
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.
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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Determining the Form of the Rate Law


The first step in understanding how a reaction occurs is to
determine the form of the rate law.
Consider the decomposition reaction of dinitrogen
pentoxide in carbon tetrachloride solution:
2N2O5(soln) 4NO2(soln) + O2 (g)
Data for this reaction are listed on the next slide.
In this reaction, the oxygen gas escapes from the solution
and thus does not react with the nitrogen dioxide, so we do
not have to be concerned about the effects of the reverse
reaction.
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Determining the Form of the Rate Law


[N2O5] (mol/L)

Time (s)

1.00

0.88

200

0.78

400

0.69

600

0.61

800

0.54

1000

0.48

1200

0.43

1400

0.38

1600

0.34

1800

0.30

2000

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Determining the Form of the Rate Law


Evaluation of the reaction rates at concentrations of N2O5 of 0.90 M and 0.45
M yields the following:
[N2O5
]
0.90
M
0.45
O ]Mis

Rate (mol/Ls)
5.4 x 10

-4

2.7 x 10-4

Note that when [N2 5


halved, the reaction rate is also halved. This means
that the rate of this reaction depends on the concentration of N2O5 to the first
power. The rate law for this reaction is:
Rate = k [N2O5] 1 = k [N2O5]
The reaction is first order in N2O5. The order is not the same as the coefficient
of N2O5 in the balanced equation. The order must be obtained by observing
how the reaction rate depends on the concentration of that reactant.
In general terms, rate = k [A]
Doubling the concentration of A doubles the reaction rate.
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Determining the Form of the Rate Law


Method of Initial Rates
The initial rate of a reaction is the instantaneous rate
determined just after the reaction begins (just after t=0).
Several experiments are carried out using different initial
concentrations 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. This allows the
form of the rate law to be determined.

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Determining the Form of the Rate Law


Method of Initial Rates
Consider the reaction
NH4+ (aq)+ NO2- (aq) N2(g) + 2H2O(l)
With initial rates shown below
Experime
nt

Initial Concentration of
NH4+

Initial Concentration of
NO2-

Initial Rate
(Mol/Ls)

0.100 M

0.0050 M

1.35 x 10-7

0.100 M

0.010 M

2.70 x 10

-7

0.200 M

0.010 M

5.40 x 10

-7

The general form of the rate law is


Rate = k[NH4+]n[NO2-]m

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Determining the Form of the Rate Law


Method of Initial Rates
For experiment 1:
Rate = 1.35 x 10 -7 mol/Ls = k(0.100 mol/L)n (0.0050 mol/L)m
For experiment 2:
Rate = 2.70 x 10 -7 mol/Ls = k(0.100 mol/L)n (0.010 mol/L)m
The ratio of these rates is:
=
= 2.00 = (2.0) which means m is 1 and the rate law for this
reaction is first order in NO217

Determining the Form of the Rate Law


Method of Initial Rates
A similar analysis yields
=
= 2.00 = (2.0) n which means m is 1 and the rate law for
this reaction is first order in NH4+
The rate law is
Rate = k[NH4+] [NO2-]
The rate law is first order in both NO2- and NH4+. It is merely
a coincidence that the coefficients of NO2- and NH4+ are the
same.
The overall rate order is n + m = 2. The reaction is second
order overall.
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Determining the Form of the Rate Law


Method of Initial Rates
The value of the rate constant k can be calculated using the results of
any of the three experiments. Rate = k[NH 4+][NO2-]
Experiment 1
1.35 x 10 -7 mol/Ls = k (0.100 mol/L)(0.0050 mol/L)
k= 2.7 x 10 -4 L/mol s
Experiment 2
2.70 x 10 -7 mol/Ls = k (0.100 mol/L)(0.010 mol/L)
k= 2.7 x 10 -4 L/mol s
Experiment 3
5.40 x 10 -7 mol/Ls = k (0.200 mol/L)(0.010 mol/L)
k= 2.7 x 10 -4 L/mol s

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Determining the Form of the Rate Law


Sample Exercise 12.1 page 566
Consider the reaction
BrO3- (aq) + 5Br- (aq) + 6 H+ (aq) 3Br2(l) + 3H2O(l)
Using the data from the table below, determine the orders
for all three reactants, the overall reaction order and the
Experime
Initial
Initial
Initial
Initial Rate
value
of
the
rate
constant.
nt
Concentration of Concentration of Concentration of
(Mol/Ls)
BrO3- (Mol/L)

Br- (Mol/L)

H+ (Mol/L)

0.10

0.10

0.10

8.0 x 10

-4

0.20

0.10

0.10

1.6 x 10

-3

0.20

0.20

0.10

3.2 x 10

-3

0.10

0.10

0.20

3.2 x 10

-3

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First Order Rate Laws


The differential rate laws consider rate as a function of
reactant concentrations. It is also useful to express the
reactant concentrations as a function of time.
For the reaction
2N2O5(soln) 4NO2(soln) + O2 (g)
We found that the rate law is
Rate = k [N2O5] =
It is a first order reaction, which means if the concentration of
N2O5 is doubled, the reaction rate is doubled. Integration of
this expression yields the form
ln[N2O5] = -kt + ln[N2O5]0
Note that this equation expresses reactant concentration as a
function of time
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Integrated Rate Law First Order


Consider the reaction aA products
Where the kinetics are first order in [A], the rate law is
rate = =k[A]
And the integrated first order rate law is
ln[A] = -kt + ln[A]0
The equation shows how the concentration of A depends on time.
If the initial concentration of A and the rate constant are known,
the concentration of A at any time can be calculated.
The equation is of the form y=mx+b, so if a reaction is first order,
a plot of ln[a] versus time will be linear. If this plot is not a
straight line, the reaction will not be first order.
The equation can be rewritten as ln( ) = kt.
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Integrated Rate Law First Order


Sample exercise 12.2 page 569
The decomposition of N2O5 in the gas phase was studied at constant
temperature.
2N2O5(g) 4NO2(g) + O2 (g)
The following results were collected:
[N2O5]
(mol/L)

Time (s)

0.1000

0.0707

50

0.0500

100

0.0250

200

0.0125

300

0.00625

400

Using these data, verify that the rate law is first order in [N2O5], and
calculate the value of the rate constant, where the rate = -[N2O5]/t.
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Integrated Rate Law First Order


The time required for a reaction to reach half its original

concentration is called the half-life of a reactant and is designated


by the symbol t1/2.
The half life for the decomposition reaction in Sample Exercise
12.2 is 100 seconds. It always takes 100 seconds for [N2O5] to be
halved.
In general terms of aA products, for a first order reaction
ln( ) = kt
and
when t = t 1/2, [A] =
For t = t1/2 ln( ) = kt1/2
Substituting for ln(2) and solving for t1/2 gives
t1/2 =
This is the general equation for the half-life of a first order
reaction. For a first order reaction, half-life does not depend on
concentration.
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Integrated Rate Law Second Order


Consider the reaction aA products
Where the kinetics are second order in [A], the rate law is
rate = =k[A]2
And the integrated second order rate law is
= kt +
A plot of versus time will be linear with a slope equal to k.
The expression for the half-life of a second order reaction is
t1/2 =
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Integrated Rate Law Zero Order


Consider the reaction aA products
Where the kinetics are zero order in [A], the rate law is
rate = =k[A]0
And the integrated zero order rate law is
[A] = -kt +[A]0
A plot of k versus time will be linear with a slope equal to
-k.
The expression for the half-life of a zero order reaction is
t1/2 =
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Integrated Rate Law


Consider the reaction
BrO3- (aq) + 5Br- (aq) + 6 H+ (aq) 3Br2(l) + 3H2O(l)
where [BrO3-]0 = 1.0 x 10 -3 M, [Br-]0 = 1.0 M and [H+]0 = 1.0 M.
As the reaction proceeds, [BrO3-] decreases significantly, but the Br- and
H+ ion concentrations are so large initially, relative little of these two
reactants is consumed. Thus Br - and H+ remain relatively constant. We
can assume [Br-]0 = [Br-] and [H+ ]0 = [H+ ]. This means the rate law can
be written
Rate = k [Br-]0 [H+ ]0 2 [BrO3-] = k [BrO3-].
Where k = k [Br-]0 [H+ ]0 2
Since this law was obtained by simplifying an more complicated
arrangement, it is called a pseudo-first-order rate law.

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Reaction Mechanisms
Most chemical reactions occur by series of steps called the
reaction mechanism.
Consider the reaction
NO2(g) + CO(g) NO(g) + CO2 (g)
The rate law for this reaction is known from experiment to be
Rate = k [NO2]2
This reaction is more complicated than it appears from the
balanced equation. This is quite typical; the balanced equation
fro a reaction tells us the reactants, the products and the
stoichiometry but gives no direct information about the reaction
mechanism.
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Reaction Mechanisms
For the reaction between nitrogen dioxide and carbon
monoxide, the mechanism is thought to involve the following
steps:
k
1

NO2(g) + NO2(g) NO3(g) + NO


k (g)
2

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


where k1 and k2 are rate constants of the individual
reactions. In this mechanism, gaseous NO3 is an
intermediate, a species that is neither a reactant or a
product but is formed and consumed during the reaction
sequence.

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Reaction Mechanisms
Each of these two reactions is called an elementary step, a reaction
whose rate law can be written from its molecularity.
Molecularity is the number of species
that must collide to produce
k1
the reaction indicated by that step.
A reaction involving one molecule is called a unimolecular step.
k2
Bimolecular and termolecular reactions involve the collisions of two
and three species, respectively.
A reaction mechanism is a series of elementary steps that must
1. Give the overall balanced equation for the reaction
2. Agree with the experimentally determined rate law
Multistep reactions often have one step that is much slower than all
the others. Reactants can becomes products only as fast as they
can get through the slowest step. This slowest step is called the rate
determining step.
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Reaction Mechanisms
For the reaction between nitrogen dioxide and carbon
monoxide, the sum of the two steps results in the overall
balanced equation, so the first requirement for a correct
mechanism is met.
NO2(g) + NO2(g) NO3(g) + NO (g)
NO3(g) + CO(g) NO2(g) + CO2 (g)
NO2(g) + CO(g) NO(g) + CO2 (g)

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Reaction Mechanisms
Assume that the first step is rate determining and the second step is
relatively fast.
NO2(g) + NO2(g) NO3(g) + NO (g) (slow)
NO3(g) + CO(g) NO2(g) + CO2 (g) (fast)
This assumes that the formation of NO3 occurs much more slowly than is
reaction with CO. The rate of CO2 production is then controlled by the rate
of formation of NO3 in the first step. Since this is an elementary step, we
can write the rate law from the molecularity.
Rate of formation of NO3= k [NO2]2
Since the overall rate can be no faster than the slowest step,
Overall rate = k [NO2]2
This agrees with the experimentally determined rate law given earlier.
The mechanism we assumed satisfies both requirements and may be the
correct mechanism.
A mechanism can never be proved absolutely.
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Reaction Mechanisms
Sample Exercise 12.6 page 581
The balanced equation for the reaction of the gases
nitrogen dioxide and fluorine is
NO2(g) + F2 (g) NO2F (g)
The experimentally determined rate law is
rate = k [NO2] [F2]
A suggested mechanism for this reaction is
NO2(g) + F2 (g) NO2F (g) + F (g)
(slow)
F (g) + NO2(g) NO2F (g)
(fast)
Is this an acceptable mechanism?

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A Model for Chemical Kinetics


The collision model is built around the central idea that molecules
must collide to react.
The kinetic molecular theory of gases predicts that an increase in
temperature raises molecular velocities and increases the frequency of
collisions between molecules. This idea agrees with the observation
that reaction rates are greater at higher temperatures.
So there is a qualitative agreement between the collision model and
experimental observations.
However, it is found that the rate of reaction is much smaller than the
calculated collision frequency in a collection of gas particles. That
means that only a small fraction of the collisions produces a reaction.
Arrhenius proposed that there is a threshold energy, called the
activation energy, that must be overcome to produce a chemical
reaction.
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A Model for Chemical Kinetics


Consider the reaction
2BrNO(g) 2NO (g) + Br2 (g)
In this reaction two Br-N bonds must be broken and one Br-Br bond
must be formed. Breaking a Br-N bond requires considerable energy
(243 kJ/mol).
The collision model postulates that the energy comes from the kinetic
energy possessed by the reacting molecules before the collision. This
kinetic energy is changed into potential energy as the molecules are
distorted during a collision to break bonds and rearrange into product
molecules.
The arrangement of atoms found at the top of the potential energy
barrier is called the activated complex, or transition state.
The conversion of BrNO to NO and Br2 is exothermic as indicated by the
fact that the products have lower potential energy than the reactant.
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A Model for Chemical Kinetics

Potential Energy

ON---Br
ON---Br

(transition state)

E
a

(reactant)

2NO + Br2

Reaction progress

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A Model for Chemical Kinetics


A minimum energy is required for two BrNO molecules to
react so that products can form.
This energy comes from the energy of the collision.
A collision between two BrNO molecules with small kinetic
energies will not have enough energy to get over the barrier.
At a given temperature only a certain fraction of the
collisions possess enough energy to result in product
formation.

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A Model for Chemical Kinetics


The fraction of effective collisions increase exponentially with
temperature. Arrhenisu postulated that the number of collisions
having an energy greater than or equal to the activation energy is
given by the expression
Number of collisions with the activation energy =
(total number of collisions) e Ea/RT
where Ea is the activation energy, R is the universal gas constant and
T is the Kelvin temperature.
Taking into account some other factors, this can written in the form
K = A e Ea/RT
which is called the Arrhenius equation.
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Catalysis
A catalyst is a substance that speeds up a reaction without being
consumed itself.
A catalysts works by providing a new pathway for the reaction with
lower activation energy.
Uncatalyzed
pathway
Catalyzed
pathway
Product
s
E
Reactan
ts

A homogeneous catalyst is present in the same phase as the reacting


molecules. A heterogeneous catalyst exists in a different phase.
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Kinetics
Practice pages 599-605
Problems 21, 23, 25, 27, 31, 35, 39, 41, 43, 45, 47, 49. 51,
53 and 71

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