What are Chemical Kinetics?

Objectives
• Describe how various factors influence the rate of a
reaction.
• Write the mathematical relationship between the rate of a
reaction, rate constant, and concentration of the
reactants.
 Chemical Kinetics
• Study of rate of chemical reactions
• Chemical reactions occur spontaneously at a
fast rate
• Rate of reaction can be defined as the change
in the concentration of a reactant or product per
change in time
 Chemical Kinetics
Kinetics – how fast does a reaction proceed?
Thermodynamics – does a reaction take place?

Reaction speed: measured by the change in concentration with time.

Important factors which affect rates of reactions:

– reactant concentration
– temperature
– action of catalysts
– surface area
– pressure of gaseous reactants or products
 Kinetics
• Studies the rate at which a chemical process occurs.

• Besides information about the speed at which reactions occur,

kinetics also sheds light on the reaction mechanism (exactly
how the reaction occurs).
 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calculate amount left or
Integrated Rate Laws time to reach a given amount.
How long it takes to react 50% of
Half-life reactants.
How rate constant changes with
Arrhenius Equation temporature.
Link between rate and molecular
Mechanisms scale processes.
Reaction Rates
 Reaction Rates

Rates of reactions can be determined by monitoring the change in concentration of either

reactants or products as a function of time t.
Notation for Stoichiometry:
[A] = concentration of reactant A
[B] = concentration of reactant B
 Reaction Rate
• For the reaction A  B there are two ways of measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear
• Reversible reactions: as products accumulates, they can begin to turn back
into reactants.
• A general way of measuring the rate of the reaction is in terms of change in
concentration per unit time…
Instantaneous rate = ∆[A]/∆t limits to d[A]/dt
Most Common Units… Rate = M/s
Where Molarity (M) = moles/Liter
 Chemical Kinetics

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
[A] [A] = change in concentration of A over
rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t
Because [A] decreases with time, [A] is negative.
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

Factors Affecting Reaction Rate
Constants
 Factors that Affect the Reaction Rate Constant
1. Temperature: At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater energy
• Collision Theory: When two chemicals react, their molecules have to
collide with each other (in a particular orientation) with sufficient energy
for the reaction to take place.
• Kinetic Theory: Increasing temperature means the molecules move
faster.
2. Concentrations of reactants
• As the concentration of reactants increases,
so does the likelihood that reactant molecules will collide.
3. Catalysts
• Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
• More area for reactants to be in contact
5. Pressure of gaseous reactants or products
• Increased number of collisions
Reaction Rate Laws
 Concentration and Rate

Each reaction has its own equation that

expresses its rate as a function of the
concentrations of the involved species (e.g.,
reactants, products, catalysts).

This is called its Rate Law

 Rate Law
• In general, rates of reactions increase as
concentrations increase since there are
more collisions occurring between
reactants.
• The overall concentration dependence of
reaction rate is given in a rate law or rate
expression.
 Rate Law
• For reactions follow simple rate laws:
v = k [A]m [B]n…
- [A], [B]: reactant concentrations
- The exponents m and n: reaction order
(responds to variations in the concentration of
the reactant)
- The constant k: rate constant
- The overall reaction order is the sum of the
reaction orders:
m+n
 Determination of Rate Laws
• Rate laws, rate constants, and orders are
determined experimentally.

• The order of a reactant is NOT generally related

to its stoichiometric coefficient in a balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

1
v = k [F2][ClO2]
 Expression of Rate Laws

Reactions with simple rate laws:

 Elementary reactions

Always follow simple rate laws

Reactant order reflects molecularity (# of molecules

involved in reaction)
Order of Reactions
 Order of Reactions

• A reaction is zero order in a reactant if the change in

concentration of that reactant produces no effect.

• A reaction is 1st order if doubling the concentration

causes the rate to double.

• A reaction is 2nd order if doubling the concentration

causes a quadruple increase in rate.
-3rd order…doubling concentration leads to 23 (or 8 times) the rate.
- extremely rare.
Order of Reactions
 Zero-Order Processes

[A]t
t = k (constant)

So… [A]t = -kt + [A]0

action rate = -
Sample Problem 4.3
pp. 84
 First-Order Processes

For 1st order reactions: ln[A]t = −kt + ln[A]0

where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of s -1
t= time in seconds
[A]o = initial concentration of A
Example: 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?
 First-Order Processes
CH3NC CH3CN

This data was

collected for this
reaction at 198.9°C.

Does
rate=k[CH3NC]
for all time intervals?
 First-Order Processes

If a reaction is first-order:
a plot of ln [A]t versus t will yield a
straight line with a slope of -k.
 First-Order Processes

• When ln[A] is plotted as a function of time,

a straight line results.
– The process is first-order.
• John D. Bookstaver
– k is the negative slope: 5.1  10 s .
-5 -1

• St. Charles Community College

 Second-Order Processes
For 2nd order reactions: 1/[A]t = kt + 1/[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M-1s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of l/[A]t vs. t is a straight line with slope (k) and intercept of
1/[A]0.

(slope= k)
1/[A]t

Dan Reid Time (s)

Champaign CHS
Half Life
 Half-Life
• Half-life is the time taken for the concentration of a
reactant to drop to half its original value.
• Substitute into integrated rate laws: t½ is the time taken
for [A] to reach ½[A]0

NOTE: For a first-order process, the

half-life does not depend on [A]0.
Reaction Kinetics (Vallance) Dan Reid
Champaign CHS
 Half-Life - 1st order
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:

• John D. Bookstaver
• St. Charles Community College
 Half-Life - 1st order
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?

t½ = Ln 2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
-4 -1

How do you know decomposition is first order?

hint: units of k (s-1)

Chung (Peter) Chieh

University of Waterloo
 Half-Life - 1st order
First-order reaction
A product

# of
half-lives [A] = [A]0/n
1 2

2 4

3 8

4 16

NOTE: For a first-order process, the

half-life does not depend on [A]0.
Chung (Peter) Chieh
University of Waterloo
 Half-Life - 1st order

Chung (Peter) Chieh

University of Waterloo
 Half-Life - 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation:

• John D. Bookstaver
• St. Charles Community College
Equations of Reactions of
Various Orders
 Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t½ =
2k
Ln 2
1 rate = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 rate = k [A] 2 - = kt t½ =
[A] [A]0 k[A]0

Chung (Peter) Chieh

University of Waterloo
 Summary of Kinetics
Second order
First order General Second order
(1 reactant)
Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

• John D. Bookstaver
• St. Charles Community College
 Summary of Kinetics
Second order
First order General Second order
(1 reactant)
Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

k(T)

• John D. Bookstaver
• St. Charles Community College
Reaction Mechanisms
 Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is called the
reaction mechanism.

• John D. Bookstaver
• St. Charles Community College
 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.

• John D. Bookstaver
• St. Charles Community College
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product

formation is the reaction mechanism.

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

N2O2 is detected during the reaction!

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Chung (Peter) Chieh
University of Waterloo
 Rate Laws and Rate Determining Steps

Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.

The rate-determining step is the

slowest step in the sequence of
steps leading to product formation.

Chung (Peter) Chieh

University of Waterloo
 Reaction Mechanisms
• Up until now, we have only been concerned with the reactants and
products. Now we will examine what path the reactants took in
order to become the products.
• 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 & Molecularity
• Elementary step: any process that occurs in a single step.
• Molecularity: 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 uncommon to see termolecular processes…statistically improbable for an
effective collision to occur.)
Dan Reid
Champaign CHS
 Rate Laws of Elementary Steps
• Since this process occurs in one single step, the stoichiometry can
be used to determine the rate law!
• Law of Mass Action: The rate of a simple (one step) reaction is
directly proportional to the concentration of the reacting substances.

• Notice that the coefficients become the exponents.

Dan Reid
Champaign CHS
 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.

• John D. Bookstaver
• St. Charles Community College
 Reaction Intermediates

Intermediates are species that appear in a reaction

mechanism but not in the overall balanced equation.

An intermediate is always formed in an early elementary

step and consumed in a later elementary step.

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

Chung (Peter) Chieh

University of Waterloo
 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.

• John D. Bookstaver
• St. Charles Community College
Activation Energy
 Activation Energy
• There is a minimum amount of energy required for a
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.

• John D. Bookstaver
• St. Charles Community College
 Activation Energy
• Molecules must possess a minimum amount of energy to
react. Why?
– In order to form products, bonds must be broken in the
reactants. Bond breakage requires energy.
– Molecules moving too slowly, with too little kinetic energy,
don’t react when they collide.
• Activation energy, Ea, is the minimum energy required to
initiate a chemical reaction.
− Ea will vary with the reaction.

Next we will look at an example of Ea.

Dan Reid
Champaign CHS
 Activation Energy
• The change in energy ∆E for the reaction is the difference in
energy between CH3NC (reactant) and CH3CN (product).
• The activation energy Ea is the difference in energy between
reactants, CH3NC, and the transition state.
• The rate depends on Ea. If the “hill” is taller, the reaction rate is
slower. If the “hill” is shorter the rate is faster.
• Notice that if a forward reaction is exothermic… (CH3NC  CH3CN),
then the reverse reaction is endothermic… (CH3CN  CH3NC).
• The methyl isonitrile molecule needs to gain enough energy to overcome the activation energy
barrier.
• From kinetic molecular theory, we know that as temperature increases, the total kinetic energy
increases and the number of molecules with energy greater than Ea increases.
• So as long as the temperature is high enough, the reaction can make it “over the hill” and proceed.

Dan Reid
Champaign CHS
 A+B C+D

Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
Chung (Peter) Chieh
University of Waterloo
 Energy Diagrams

Exothermic Endothermic

(a) Activation energy (Ea) for the forward reaction 50 kJ/mol 300 kJ/mol
(b) Activation energy (Ea) for the reverse reaction 150 kJ/mol 100 kJ/mol
(c) Delta H -100 kJ/mol +200 kJ/mol

Chung (Peter) Chieh

University of Waterloo
Arrhenius Equation
 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.
• John D. Bookstaver
• St. Charles Community College
 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.
John D. Bookstaver
• St. Charles Community College
 Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)

k is the rate constant

Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the Kelvin temperature
A is the frequency factor

Chung (Peter) Chieh

University of Waterloo
 1/T

Dan Reid
Champaign CHS
Maxwell–Boltzmann
Distributions
 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.
• John D. Bookstaver
• St. Charles Community College
 Maxwell–Boltzmann Distributions
• As the temperature
increases, the curve
flattens and
broadens.
• Thus at higher
temperatures, a
larger population of
molecules has
higher energy.

• John D. Bookstaver
• St. Charles Community College
 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.

• John D. Bookstaver
• St. Charles Community College
 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.

• John D. Bookstaver
• St. Charles Community College
Catalysts
 A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

Chung (Peter) Chieh
University of Waterloo
 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.

• John D. Bookstaver
• St. Charles Community College
 Catalysts

One way a
catalyst can
speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.

• John D. Bookstaver
• St. Charles Community College
 Catalysts
There are two types of catalyst: Heterogeneous – one that is present in
a different phase as the reacting molecules. Homogeneous – one that is
present in the same phase as the reacting molecules.

Example: Hydrogen peroxide decomposes very slowly in the absence of a catalyst:

2H2O2(aq)  2H2O(l) + O2(g)
In the presence of bromide ions, the decomposition occurs rapidly in
an acidic environment:
2Br–(aq) + H2O2(aq) + 2H+(aq)  Br2(aq) + 2H2O(l)
Br2(aq) + H2O2(aq)  2Br–(aq) + 2H+(aq) + O2(g)

Br– is a homogeneous catalyst because it is regenerated at the end of the reaction.

The net reaction is still…2H2O2(aq)  2H2O(l) + O2(g)
Dan Reid
Champaign CHS
 Catalysts and Reaction Rates
How do catalysts increase reaction rates?
• In general, catalysts operate by lowering the overall activation
energy, Ea, for a reaction. (It lowers the “hill”.)
• However, catalysts can operate by increasing the number of
effective collisions.
• A catalyst usually provides a completely different mechanism for
the reaction.
• In the preceding peroxide decomposition example, in the absence
of a catalyst, H2O2 decomposes directly to water and oxygen.
• In the presence of Br–, Br2(aq) is generated as an intermediate.
• When a catalyst adds an intermediate, the activation energies for
both steps must be lower than the activation energy for the
Dan Reid uncatalyzed reaction.
Champaign CHS
 Heterogeneous Catalysts
• Often we encounter a situation involving a solid catalyst in contact
with gaseous reactants and gaseous products…
• Example: catalytic converters in cars.
- Many industrial catalysts are heterogeneous.
How do they do their job?
• The first step is adsorption (the binding of reactant molecules to
the catalyst surface).
• Adsorption occurs due to the high reactivity of atoms or ions on
the surface of the solid.
• Molecules are adsorbed onto active sites on the catalyst surface.
• The number of active sites on a given amount of catalyst depends
on several factors such as:
- The nature of the catalyst.
- How the catalyst was prepared.
- How the catalyst was treated prior to use.
Dan Reid
Champaign CHS
 Heterogeneous Catalysts
Example: C2H4(g) + H2(g)  C2H6(g)
• In the presence of a metal catalyst (Ni, Pt or Pd) the reaction
occurs quickly at room temperature.
Here are the steps…
- First, the ethylene and hydrogen molecules are adsorbed onto active
sites on the metal surface.
- Second, the H–H bond breaks and the H atoms migrate about the metal
surface and runs into a C2H4 molecule on the surface.
- Third, when an H atom collides with a C2H4 molecule on the surface,
the C−C π-bond breaks and a C–H σ-bond forms.
- Lastly, 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.
• The E for the reaction is lowered, thus the reaction rate increases.
Dan Reid a
Champaign CHS
 Heterogeneous Catalysts

Dan Reid
Champaign CHS
Examples of Catalysts:
Enzymes
 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.

John D. Bookstaver
St. Charles Community College
 Enzyme Catalysts
• Enzymes are biological catalysts. There may be as many
as 30,000 enzymes in the human body. (e.g., Lactase)
• Most enzymes are protein molecules with large
molecular masses (10,000 to 106 amu).
• Enzymes have very specific shapes.
• Most enzymes catalyze very specific reactions.
• The substances that undergo reaction at the active site on
enzymes are called substrates.
• A substrate locks into an enzyme and a fast reaction
occurs. The products then move away from the enzyme.
Dan Reid
Champaign CHS
 Enzyme Catalysts
• 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).
• Many poisons act by binding to the active site blocking the binding
of substrates. The binding can also lead to changes in the enzyme.
• Enzymes are extremely efficient catalysts.
• The number of individual catalytic events occurring at an active site
per unit time is called the turnover number.
• Large turnover numbers correspond to very low Ea values. For
enzymes, turnover numbers are very large ≈ 103 to 107/sec
Dan Reid
Champaign CHS
 Enzyme Catalysis

Chung (Peter) Chieh

University of Waterloo