CHEMICAL KINETICS

Lecture 4

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Chemical Kinetics
- The study of the rates and mechanisms of chemical
reactions

Kinetics
✓ Studies the rate at which a chemical process occurs.
✓ how fast does a reaction proceed?
Reaction speed - measured by the change in concentration with time.

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

• Reactions may occur all at once or through several discrete steps.

• Each of these processes is known as an elementary reaction or
elementary process.

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 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 N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
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Chung (Peter) Chieh - University of Waterloo
 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 N2O2

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

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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.

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 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

John D. Bookstaver - St. Charles Community College 12-7

Chung (Peter) Chieh - University of Waterloo
 Collision Theory
➢In order for a reaction to occur, reactant
molecules must collide
✓with proper orientation
✓with enough energy

➢Only a small fraction of the collisions that do

occur meet these requirements.

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 Collision Theory Orientation

• Consider the following reaction that occurs in smog:

• O3(g) + NO(g) → O2(g) + NO2(g)

• Which of the following collisions has a proper orientation?

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 Collision Theory
Energy Requirements

• Inorder for reactants to convert to products, an

energy barrier called the activation energy, Ea,
must be overcome.

• Collisions that have the proper orientation and

have at least the minimum Ea can convert to
products.

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 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 12-11

 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.

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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.
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 Effect of Temperature on
the Rates of Reaction

• The average kinetic energy of the particles

increases when the temperature rises. Increase
kinetic energy causes the reaction rate to
increase by increasing the collision rate
because the particles move faster at higher
temperature.

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 Effect of temperature on fraction of
effective collisions:

Figure 12.9 (B) 12-15

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 Conditions that Affect Reaction Rates
• Increasing the concentration or surface area of
one or more reactants increases the number of
effective collisions by increasing the total
number of collisions (fraction of collisions that
are effective remains the same).

Figure 12.8

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 Conditions That Affect Reaction Rates
• Increasing the concentration (or surface area) of
reactants or the reaction temperature increases reaction
rate by increasing the number of effective collisions.

 Note that the steel wool (B) reacts faster than the iron nail (A), because more
iron atoms are exposed to the oxygen in the atmosphere.

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 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.

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 A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

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Chung (Peter) Chieh - University of Waterloo
 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
uncatalyzed reaction.
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Dan Reid - Champaign CHS
 Catalysts
One way a
catalyst can
speed up a
reaction is by
holding the
reactants
together and
helping bonds to
break.

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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)

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Dan Reid - 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.
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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 Ea for the reaction is lowered, thus the reaction rate increases.
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 Heterogeneous Catalysts

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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.

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 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.

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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
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Dan Reid - Champaign CHS
 Enzyme Catalysis

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Chung (Peter) Chieh - University of Waterloo
 The general characteristics of catalyst
may be summarized as follows:

1. A catalyst
remains unchanged in mass and
chemical composition at the end of the
reaction.

2.A small quantity of the catalyst is generally

sufficient to catalyzes almost unlimited
reactions.

3. The catalyst cannot initiate the reaction.

4.The catalyst is generally specific in nature.

5.The catalyst cannot change the position of

equilibrium.

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 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.
• Early on the rate will depend on only the amount of reactants
present. We want to measure the reactants as soon as they are
mixed.
• A general way of measuring the rate of the reaction is in terms of
change in concentration per unit time…
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Dan Reid - Champaign CHS
 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

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John D. Bookstaver, St. Charles Community College
 Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).

A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.

Chung (Peter) Chieh - University of Waterloo

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 Rate Expressions

Rate expressions describe reactions in terms of the

change in reactant or product concentrations over the
change in time. The rate of a reaction can be expressed
by any one of the reactants or products in the reaction.

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 Rate Expressions

Rules in writing rate expressions:

1) Expressions for reactants are given a negative sign. This
is because the reactant is being used up or decreasing.
2) Expressions for products are positive. This is because they
are increasing.
3) All of the rate expressions for the various reactants and
products must equal each other to be correct. (This means
that the stoichiometry of the reaction must be compensated
for in the expression)

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 Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

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Example
The gases NO2 and CO react as follows
NO2 (g) + CO (g ) ―> NO (g) + CO2 (g)

Write the rate expression.

Calculate the average rate of the reaction if pure NO 2 and
CO are mixed and after 50.0 seconds the concentration of
CO2 is found to be 0.0160 mol/L.

Ans. 3.20x 10 -4 M/s

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 Example
Consider the reaction:
CH3Cl + I- → CH3Cl + Cl-

Write the rate expression.

Suppose that the concentration of I- was 0.24 M at the start of the
reaction and after 20 minutes the concentration dropped to 0.16M, what
is the rate of the reaction ?

Ans: -0.004 M/min

Copyright McGraw-Hill Education 12-38

Exercises
1. If the rate of decomposition of ammonia NH 3, at 1150 K
is 2.10x10-6 M/s, What is the rate of production of N2?
H 2?

2. If the rate of formation of ammonia is 0.345 M/s, what

is the rate of disappearance of N2? H2?
 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

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 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.
• For reactions follow simple rate laws:
rate = k [A]m [B]n…
- [A], [B]: reactant concentrations
- The exponents m and n: reaction order (w.r.t. specific reactant)
- The constant k: rate constant
- The overall reaction order is the sum of the reaction orders:
m+n

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Dan Reid - Champaign CHS
 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)

v = k [F2][ClO2] 1

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Chung (Peter) Chieh - University of Waterloo
 Order of Reaction
The order of a chemical reaction (M) is the sum of all the
exponents to which the concentrations in the rate law
equation are raised.

❑ If the exponent m is 1, the reaction is first order with respect to A. If m is

2, the reaction is second order with respect to A.
❑ If n is 1, the reaction is first order in B. If n is 2, the reaction is second
order in B. If m or n is zero, the reaction is zero order in A or B,
respectively, and the rate of the reaction is not affected by the
concentration of that reactant.
❑ The overall reaction order is the sum of the orders with respect to each
reactant. If m = 1 and n = 1, the overall order of the reaction is second
order (m + n = 1 + 1 = 2).

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 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.

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Dan Reid - Champaign CHS