• The rate of reaction is defined in various forms:

Based on unit volume of

reacting fluid

Based on unit mass of solid in

fluid-solid system

Based on unit interfacial

surface in two-fluid system

Based on unit volume of solid in

gas-solid systems

Based on unit volume of

reactor
2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 4
 Factors that Affect Reaction Rate

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 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
• Bread and Butter theory: more area for reactants to be in
contact
5. Pressure of gaseous reactants or products
• Increased number of collisions

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 6

• Each reaction has its own equation that gives its
rate as a function of reactant concentrations. this is
called its Rate Law
• To determine the rate law we measure the rate at
different starting concentrations.
 Chemical Kinetics

The study of reaction rates, the changes in concentrations of

reactants (or products) as a function of time

Quantitative relationships through the derivation of a rate law

Kinetics can reveal much about the mechanism of a reaction.

Reaction rate: the central focus of chemical kinetics
 The wide range of reaction rates

Figure 16.2
 Factors Influencing Reaction Rates

Reactant Concentration: molecular collisions are required for

reactions to occur

reaction rate a collision frequency a concentration

Physical State: molecules must mix to collide

When reactants are in different phases, the more finely divided

a solid or liquid reactant, the greater the surface area per unit
volume, the more contact it makes with other reactants,
and the faster the reaction.

Temperature: molecules must collide with sufficient energy to react

Higher T translates into more collisions per unit time and

into higher-energy collisions
reaction rate a collision energy a temperature
 The effect of surface area on reaction rate
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

steel nail in O2 steel wool in O2

 Collision energy
and reaction rate

Other factor: reaction

trajectory (not all collisions
with sufficient energy
are productive)
 Molecule
A

Molecule
B

k
A  B C
Hana El-Samad
UCSB
 Collision Model

• Most reactions speed up as temperature increases.

- Example: food spoils when not refrigerated.
• Since the rate law equation has no temperature term in it, the rate constant, k,
must depend on temperature.
• The collision model assumes that in order for molecules to react
they must collide.
- The greater the number of collisions the faster the rate.
- The more molecules present, the greater the probability of collisions and
the faster the rate.
- The higher the temperature, the more energy available to the molecules
and the faster the rate.
- Complication: not all collisions lead to products. In fact, only a
small fraction of collisions lead to product.

2-Dec-18
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.

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 16

 A+B C+D

Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 17
 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

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 18

aA  bB  cC  dD
b c d
A B  C  D
a a a
rA rB rC rD
  
a b c d
 Chapter 3

2A  B  3C
Given mol
 rA  10
dm  s
3

Then rA rB rC
 
 2 1 3
 rA mol
 rB  5
2 dm  s
3

3 mol
rC  rA  15
2 dm  s
3
 a A  bB  c C  d D
Choose limiting reactant A as basis of calculatio n

b c d
A  B
 C  D
a a a

moles A reacted
X
moles A fed

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 21

Power Law Model:

a  α order in A
 rA  kCA CB
β order in B
Overall Rection Order  α  β
 Chapter 3

2A  B  3C

A reactor follows an elementary rate law if the

reaction orders just happens to agree with the
stoichiometric coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate
law
 rA  k AC ACB
2

2nd order in A, 1st order in B, overall third order

• Rate Laws are found from Experiments

2A+B3C
• Rate Laws could be non-elementary. For
example, reaction could be:
› Second Order in A
› Zero Order in B
› Overall Second Order
rA  k AC 2
A

rB  k B C A2
rC  kC C A2
 Chapter 3

kA
A+2B 3C
k-A

 C 3

 rA  k AC AC B  k  ACC  k A C A C B 
2 3 2 C

 k A k A 
 2 CC3 
 k A C A C B  
 K e 
 Chapter 3

kA
A+2B 3C Reaction is: First Order in A
k-A Second Order in B
Overall third Order

moles
 rA   3
moles
CA 
dm s dm 3

  rA  mole dm3 s dm6

k    2   
 A B
C C mole dm 3

mole dm 3

2
mole 2 s
• To explain the kinetics of nonelementary reactions
we assume that a sequence of elementary
reactions is actually occurring but that we cannot
measure or observe the intermediates formed
because they are only present in very minute
quantities.
• we observe only the initial reactants and final
products, or what appears to be a single reaction.
For example, if the kinetics of the reaction
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.

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 28

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

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 29

• Conventional stoichiometric equations show the
reactants that take part and the products formed in
a chemical reaction.

• There is no indication about what takes place

during this change.

• A detailed description of a chemical reaction

outlining each separate stage is referred to as the
mechanism.

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 30

 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
 • 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
 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.

2-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 33

 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.)

2-Dec-18
 Correlating the Mechanism with the Rate Law

Chemical mechanisms can never be proven

unequivocally! But potential chemical mechanisms
can be eliminated based on experimental data.

Three Key Criteria for Elementary Steps

1. The elementary steps must add up to the overall equation.

2. The elementary steps must be physically reasonable.

3. The mechanism must correlate with the rate law.

1. Prediction and validation of reaction mechanism
2. Comparison of Theories with Arrhenius' Law for
temperature dependence