Chemical Kinetics

1.
 What do we mean by kinetics?

Kinetics refers to
• the rate at which chemical reactions occur.
• The reaction mechanism or pathway through
which a reaction proceeds.

2.
Topics for study in kinetics
Reaction Rates How we measure rates.

How the reaction rate depends on

Rate Laws amounts of reactants.
Molecularity and order.
How to calculate amount left or
Integrated Rate Laws time to reach a given amount of
reactant or product.
How long it takes for 50% of
Half-life
reactants to react
How rate constant changes with
Arrhenius Equation
temperature.
How the reaction rate depends on
Mechanisms the sequence of molecular scale
processes.
3.
 Factors That Affect Reaction Rates
• The Nature of the Reactants
• Chemical compounds vary considerably in their chemical reactivities.
• Concentration of Reactants
• As the concentration of reactants increases, so does the likelihood that
reactant molecules will collide.
• Temperature
• At higher temperatures, reactant molecules have more kinetic energy,
move faster, and collide more often and with greater energy.
• Catalysts
• Change the rate of a reaction
by changing the mechanism.

4.
 Reaction Rates

The rate of a chemical reaction can be determined by monitoring the

change in concentration of either reactants or the products as a function
of time.
[A] vs t

5.
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio of C4H9Cl to C4H9OH

is 1:1.

• Thus, the rate of disappearance of C4H9Cl is

the same as the rate of appearance of
C4H9OH.
-[C4H9Cl] [C4H9OH]
Rate = =
t t
6.
Reaction Rates and Stoichiometry

N2(g) + 3 H2(g)  2 NH3(g)

7.
 In general:

aA + bB  cC + dD
Example 1: Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

[C4H9Cl]
Rate = -
t

9.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• A plot of concentration vs. time

for this reaction yields a curve
like this.

10.
Reaction Rate Determination
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• Note that the average rate decreases as

the reaction proceeds.

11.
 Concentration and Rate
Each reaction has its own equation that gives its rate as a function of
reactant concentrations.
This is called its Rate Law
The general form of the rate law is
Rate = k[A]x[B]y
Where k is the rate constant, [A] and [B] are the concentrations of the
reactants. X and y are exponents known as rate orders that must be
determined experimentally
To determine the rate law we measure the rate at different starting
concentrations.

12.
Concentration and Rate
NH4+ (aq) + NO2- (aq)  N2 (g) + 2H2O (l)

Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
13.
 Concentration and Rate
NH4+ (aq) + NO2- (aq)  N2 (g) + 2H2O (l)

Likewise, compare Experiments 5 and 6: when [NO2-

] doubles, the initial rate doubles.
14.
 Concentration and Rate
NH4+ (aq) + NO2- (aq)  N2 (g) + 2H2O (l)

This equation is called the rate law, and k is the rate

constant.
15.
Example:

2 H2(g) + 2 NO(g)  N2(g) + 2 H2O(g)

Initial rates of the reaction at 300 C

Series 1 Series 2
[H2] [NO] Initial rate [H2] [NO] Initial rate

0.10 0.10 0.10 0.10 0.10 0.10

0.20 0.10 0.20 0.10 0.20 0.40
0.30 0.10 0.30 0.10 0.30 0.90
0.40 0.10 0.40 0.10 0.40 1.30
Example:

CO(g) + NO2(g)  CO2(g) + NO(g)

The above reaction is a first order reaction in both CO and NO2. The
rate constant is 0.50 dm3 mol-1s-1. At what concentration of CO is the
rate 0.10 dm3 mol-1s-1 when [NO2] = 0.4 M?

Solution: The reaction does not depend on the concentration of CO, rate = k[NO2]

Carbon monoxide is not involve in the slowest step, ie. Rate determining step

Rate depends only on the concentration of NO2

The Rate Law
• A rate law shows the relationship between the reaction rate
and the concentrations of reactants.
• For gas-phase reactants use PA instead of [A].

• k is a constant that has a specific value for each reaction.

• The value of k is determined experimentally.

Rate = k [NH4+ ][NO2- ]
“Constant” is relative here-
the rate constant k is unique for each reaction
and the value of k changes with temperature

18.
The Rate Law
• Exponents tell the order of the reaction with respect to
each reactant.
• This reaction is
First-order in [NH4+]
First-order in [NO2−]
• The overall reaction order can be found by adding the
exponents on the reactants in the rate law.
• This reaction is second-order overall.

Rate = k [NH4+ ]1[NO2- ]1

19.
Determining the Rate constant and Order
The following data was collected for the reaction of substances A and B
to produce products C and D. Deduce the order of this reaction with
respect to A and to B. Write an expression for the rate law in this
reaction and calculate the value of the rate constant.

[NO] mol dm-3 [O2] mol dm-3 Rate mol dm-3 s-1

0.40 0.50 1.6 x 10-3

0.40 0.25 8.0 x 10-4
0.20 0.25 2.0 x 10-4

20.
The First Order Rate Equation
Consider a simple 1st order reaction: A  B
Rate = k[A]
How much reactant A is left after time t?
The rate equation as a function of time can be
written as
Where

[A]t =[A]o e-kt [A]t = the concentration of

reactant A at time t
[A]o = the concentration of
Ln [A]t - Ln[A]o = - kt reactant A at time
t=0
K = the rate
constant 21.
First-Order Processes
Consider the process in which methyl
isonitrile is converted to acetonitrile.

CH3NC CH3CN

How do we know this is a

first order reaction?

22.
First-Order Processes

CH3NC CH3CN
This data was collected for
this reaction at 198.9°C.

Does Rate = k[CH3NC]

for all time intervals?

23.
First-Order Processes

• When ln P is plotted as a function of time, a straight line

results.
• The process is first-order.
• k is the negative slope: 5.1  10-5 s-1.

24.
Half-Life of a Reaction
• Half-life is defined as the
time required for one-
half of a reactant to
react.
• Because [A] at t1/2 is one-
half of the original [A],
[A]t = 0.5 [A]0.

25.
Half-Life of a First Order Reaction
For a first-order process, set [A]t=0.5 [A]0 in integrated rate
equation:

NOTE: For a first-order

process, the half-life
does not depend on the
initial concentration, [A]0.
26.
 First Order Rate Calculation
Example 1: The decomposition of compound A is first
order. If the initial [A]0 = 0.80 mol dm-3. and the rate
constant is 0.010 s-1, what is the concentration of [A]
after 90 seconds?

27.
 First Order Rate Calculation
Example 1: The decomposition of compound A is first
order. If the initial [A]0 = 0.80 mol dm-3. and the rate
constant is 0.010 s-1, what is the concentration of [A]
after 90 seconds?

Ln[A]t – ln[A]o = -kt

Ln[A]t – Ln[0.80] = - (0.010 s-1 )(90 s)
Ln[A]t = - (0.010 s-1 )(90 s) + ln[0.80]
Ln[A]t = -0.90 - 0.2231
ln[A]t = -1.1231
[A]t = 0.325 mol dm-3

28.
 First Order Rate Calculations
Example 2: A certain first order chemical reaction required
120 seconds for the concentration of the reactant to drop from
2.00 M to 1.00 M. Find the rate constant and the concentration
of reactant [A] after 80 seconds.

29.
 First Order Rate Calculations
Example 2: A certain first order chemical reaction required
120 seconds for the concentration of the reactant to drop from
2.00 M to 1.00 M. Find the rate constant and the concentration
of reactant [A] after 80 seconds.

Solution
k =0.693/t1/2 =0.693/120s =0.005775 s-1
Ln[A] – Ln(2.00) = -0.005775 s-1 (80 s)= -0.462

ln A = - 0.462 + 0.693 = 0.231

A = 1.26 mol dm-3

30.
 First Order Rate Calculations
Example 3: Radioactive decay is also a first order process.
Strontium 90 is a radioactive isotope with a half-life of 28.8
years. If some strontium 90 were accidentally released, how
long would it take for its concentration to fall to 1% of its original
concentration?

31.
 First Order Rate Calculations
Example 3: Radioactive decay is also a first order process.
Strontium 90 is a radioactive isotope with a half-life of 28.8
years. If some strontium 90 were accidentally released, how
long would it take for its concentration to fall to 1% of its original
concentration?

Solution
k =0.693/t1/2 =0.693/28.8 yr =0.02406 yr-1
Ln[1] – ln(100) = - (0.02406 yr-1)t = - 4.60
t = - 4.60 .
- 0.0241 yr-1
t = 191 years
32.
Second-Order Processes
Similarly, integrating the rate law for a process
that is second-order in reactant A:
Rate = k[A]2
1 1
= kt +
[A]t [A]o
Where
[A]t = the concentration of reactant A at time t
[A]o = the concentration of reactant A at time
t=0
K = the rate constant

33.
Second-Order Rate Equation

So if a process is second-order in A, a graph of

1/[A] vs. t will yield a straight line with a slope of k.

34.
Determining Reaction Order
Distinguishing Between 1st and 2nd Order
The decomposition of NO2 at 300°C is described by the
equation:
NO2 (g) NO (g) + 1/2 O2 (g)

A experiment with this reaction yields this data:

Time (s) [NO2], M
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
35.
Determining Reaction Order
Distinguishing Between 1st and 2nd Order
Graphing ln [NO2] vs. t yields:
• The graph is not a straight
line, so this process cannot
be first-order in [A].

Time (s) [NO2], M ln [NO2]

0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit the first order equation:
100.0 0.00649 -5.038
200.0 0.00481 -5.337
300.0 0.00380 -5.573
36.
Second-Order Reaction Kinetics

A graph of 1/[NO2] vs. t gives

this plot.

Time (s) [NO2], M 1/[NO2]

0.0 0.01000 100 • This is a straight line.
50.0 0.00787 127 Therefore, the process
is second-order in [NO2].
100.0 0.00649 154
• The slope of the line is
200.0 0.00481 208 the rate constant, k.
300.0 0.00380 263
37.
Half-Life for 2nd Order Reactions
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.

In this case the half-life

depends on the initial
concentration of the
reactant A.

38.
Sample Problem 1: Second Order
Acetaldehyde, CH3CHO, decomposes by second-order
kinetics with a rate constant of 0.334 mol-1dm3s-1 at 500oC.
Calculate the amount of time it would take for 80 % of the
acetaldehyde to decompose in a sample that has an initial
concentration of 0.00750 M.

The final concentration will be 20% of the original 0.00750 M

or = 0.00150
1 .
= 0.334 mol-1dm3s-1 t + 1 .
.00150 .00750
666.7 = 0.334 t + 133.33
0.334 t = 533.4
t = 1600 seconds

39.
Sample Problem 2: Second Order
Acetaldehyde, CH3CHO, decomposes by second-order
kinetics with a rate constant of 0.334 mol-1dm3s-1 at 500oC. If
the initial concentration of acetaldehyde is 0.00200 M. Find
the concentration after 20 minutes (1200 seconds)

Solution
1 . = 0.334 mol-1dm3s-1 (1200s) + 1 .
[A]t 0.00200 mol dm-3
1 . = 0.334 mol-1dm3 s-1 (1200s) + 500 mol-1dm3
[A]t
= 900.8 mol-1dm3
1 _____. = 0.00111 mol dm-3
[A]t =
900.8 mol-1dm3
40.
 Summary of Kinetics Equations
First order Second order Second order
Rate
Laws

Integrat
ed Rate complicated
Laws

Half-
complicated
life

41.
Temperature and Rate
• Generally speaking, the
reaction rate increases as
the temperature
increases.
• This is because k is
temperature dependent.
• As a rule of thumb a
reaction rate increases
about 10 fold for each
10oC rise in temperature

42.
The Collision Model
• In a chemical reaction, bonds are broken and new
bonds are formed.
• Molecules can only react if they collide with each
other.
• These collisions must occur with sufficient energy
and at the appropriate orientation.

43.
The Collision Model
Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bonds to break and new bonds to form

44.
Activation Energy
• In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll up
the hill with enough energy, a reaction cannot occur
unless the molecules possess sufficient energy to get
over the activation energy barrier.

45.
Reaction Coordinate Diagrams

It is helpful to
visualize energy
changes
throughout a
process on a
reaction
coordinate
diagram like this
one for the
rearrangement
of methyl
isonitrile.

46.
 Reaction Coordinate Diagrams
• It shows the energy of the
reactants and products (and,
therefore, E).
• The high point on the diagram is
the transition state.

• The species present at the transition state is

called the activated complex.
• The energy gap between the reactants and the
activated complex is the activation energy
barrier.
47.
Maxwell–Boltzmann Distributions

• Temperature is defined
as a measure of the
average kinetic energy
of the molecules in a
sample.

• At any temperature there is a wide

distribution of kinetic energies.
48.
Maxwell–Boltzmann Distributions

• As the temperature
increases, the curve
flattens and broadens.
• Thus at higher
temperatures, a larger
population of molecules
has higher energy.

49.
Maxwell–Boltzmann Distributions
• If the dotted line represents the activation energy, as
the temperature increases, so does the fraction of
molecules that can overcome the activation energy
barrier.

• As a result, the
reaction rate
increases.

50.
Maxwell–Boltzmann Distributions
This fraction of molecules can be found through the expression:

where R is the gas constant and T is the temperature in Kelvin .

51.
Arrhenius Equation
Svante Arrhenius developed a mathematical relationship
between k and Ea:

where A is the frequency factor, a number that represents the

likelihood that collisions would occur with the proper
orientation for reaction. Ea is the activation energy. T is the
Kelvin temperature and R is the universal thermodynamics
(gas) constant.
R = 8.314 J mol-1 K-1 or 8.314 x 10-3 kJ mol-1 K-1

52.
Arrhenius Equation
Taking the natural
logarithm of both sides,
the equation becomes

1
RT
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T.
53.
Arrhenius Equation for 2 Temperatures
When measurements are taken for two different
temperatures the Arrhenius equation can be symplified
as follows:

Write the above equation twice, once for each of the two
Temperatures and then subtract the lower temperature
conditions from the higher temperature. The equation then
becomes:

54.
Arrhenius Equation Sample Problem 1
The rate constant for the decomposition of
hydrogen iodide was determined at two different
temperatures
2HI  H2 + I2.
At 650 K, k1 = 2.15 x 10-8 dm3 mol-1s-1
At 700 K, k2 = 2.39 x 10-7 dm3 mol-1s-1
Find the activation energy for this reaction.

2.39 x 10-7 Ea
Ln ---------------- = - ------------------------ x
2.15 x 10-8 (8.314 J mol-1 K-1) [ 1
700K 650K
1
------ -- ------
]
Ea = 180,000 J mol-1 = 180 kJ mol-1
55.
Overview of Kinetics Equations
First order Second order Second order

Rate
Laws

Integrated
Rate Laws complicated

Half-life complicated

Rate and
Temp (T)

56.
Reaction Mechanisms
The sequence of events that describes
the actual process by which reactants
become products is called the reaction
mechanism.

57.
 Reaction Mechanisms
• Reactions may occur all at once or through several discrete
steps.
• Each of these processes is known as an elementary reaction or
elementary process.

58.
Reaction Mechanisms

• The molecularity of a process tells how many

molecules are involved in the process.

• The rate law for an elementary step is written directly

from that step.

59.
Multistep Mechanisms
• In a multistep process, one of the steps will be
slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.

60.
 Slow Initial Step

NO2 (g) + CO (g)  NO (g) + CO2 (g)

• The rate law for this reaction is found experimentally to be

Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the rate of
the reaction does not depend on its concentration.
• This suggests the reaction occurs in two steps.

61.
 Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining step, it
does not appear in the rate law.

62.
Fast Initial Step

• The rate law for this reaction is found

(experimentally) to be

• Because termolecular (= trimolecular)

processes are rare, this rate law suggests a
two-step mechanism.

63.
 Fast Initial Step
• A proposed mechanism is

Step 1 is an equilibrium-
it includes the forward and reverse reactions.

64.
Fast Initial Step

• The rate of the overall reaction depends

upon the rate of the slow step.
• The rate law for that step would be

• But how can we find [NOBr2]?

65.
Fast Initial Step

• NOBr2 can react two ways:

• With NO to form NOBr
• By decomposition to reform NO and Br2
• The reactants and products of the first step are in
equilibrium with each other.
• Therefore,
Ratef = Rater

66.
Fast Initial Step

• Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
k−1
[NO] [Br 2 ] = [NOBr 2 ]

67.
Fast Initial Step

Substituting this expression for [NOBr2] in the

rate law for the rate-determining step gives

68.
Catalysts
• Catalysts increase the rate of a reaction by decreasing
the activation energy of the reaction.
• Catalysts change the mechanism by which the process
occurs.
• Some catalysts also make atoms line up in the correct
orientation so as to enhance the reaction rate

69.
Catalysts
Catalysts may be either
homogeneous or
heterogeneous

A homogeneous catalyst
is in the same phase as
the substances reacting.
A heterogeneous
catalyst is in a different
phase

70.
Catalysts
One way a catalyst can
speed up a reaction is
by holding the
reactants together
and helping bonds to
break.
Heterogeneous
catalysts often act in
this way

71.
Catalysts
Some catalysts help to AlCl3 + Cl2  Cl+ + AlCl4-
lower the energy for
formation for the Cl+ + C6H6  C6H5Cl + H+
activated complex or
provide a new H+ + AlCl4-  HCl + AlCl3
activated complex Overall reaction
with a lower activation
energy C6H6 + Cl2  C6H5Cl + HCl

72.
Catalysts & Stratospheric Ozone
In the stratosphere, oxygen molecules absorb ultraviolet
light and break into individual oxygen atoms known as free
radicals

The oxygen radicals can then combine with ordinary oxygen

molecules to make ozone.

Ozone can also be split up again into ordinary oxygen and

an oxygen radical by absorbing ultraviolet light.
 Catalysts & Stratospheric Ozone
The presence of chlorofluorcarbons in the stratosphere
can catalyze the destruction of ozone. UV light causes a
Chlorine free radical to be released

The chlorine free radical attacks ozone and converts it back to

oxygen. It is then regenerated to repeat the process. The result
is that each chlorine free radical can repeat this process many
times. The result is that Ozone is destroyed faster than it is
formed, causing its level to drop
Enzymes
• Enzymes are catalysts in
biological systems.
• The substrate fits into the
active site of the enzyme
much like a key fits into a
lock.