ADDIS ABABA SCIENCE AND

TECHNOLOGY UNIVERSITY

CHEMICAL ENGINEERING DEPARTMENT

Chemical Reaction Engineering
Lecture 3
Lecturer Assefa A.(M.Sc.)
Date 04-11-19
Chemical Kinetics
Chemical kinetics is the study of the rates of chemical reactions, the
factors that affect these rates, and the reaction mechanisms by which
reactions occur.
 Reaction rates vary greatly
Fast reaction: a reaction which completes in less than (10-12 s) time
eg. Burning, organic substitution reaction, ionic reaction etc
Slow reaction: a reactions which completes in a long time from some
minutes to some years.
eg. disintegration of a plastic bottle in sunlight, rusting of iron etc.
Moderately slow reaction: reactions which are intermediate between
slow and fast reactions are called moderately slow reactions.
Cont…
1. Rate of Reaction/speed of reaction
• Reaction rate tells how quickly reactants will transform in to products.
• Reaction rate is independent of the type of reaction system (batch, plug flow, etc.)
Mathematically

Where = extent of reaction

= rate of reaction
= volume

• The rate of reaction has the units of moles per (units of) volume per (unit of) time.
eg. mol L-1 s-1 or Ms-1.
Cont…
Relative Rates
 Relative Rates tell us how fast one species is disappearing or appearing relative to
the other species in the given reaction
 The general definition of rate of reaction, r, is given by

 After substituting and differentiating

𝑟𝑗 1 𝑑𝑁 𝑗
𝑟 = where 𝑟 𝑗 =
 This tell us relationship between rateνof
𝑗 reaction and𝑉 𝑑𝑡 rates
relative
Where is Relative rates of reaction
Consider a reaction
 The relationship between rate of reaction and relative rates and among relatives each
other are:

 The relative rates of reaction of the various species involved in a reaction can be
obtained from the ratio of the stoichiometric coefficients.
For example: The relationship between the rates of formation of C and D is

The relationship between the rate of formation of C and disappearance

of A is
Example1: Consider the decomposition reaction
2N2O5 → 2N2O4 + O2
what is relationship b/n rate of reaction, rate of disappearance of N2O5, rate of
formation of N2O4 and O2?

Example2: The rate of change of molar concentration of CH3 radicals in the

reaction 2CH3(g) CH3CH3(g) was reported as - under particular conditions.
What is a) the rate of reaction and b) the rate of formation of CH3CH3.
 In homogeneous systems, the volume of fluid(V) in the reactor is often
identical to the volume of reactor(Vr).
In such a case V and Vr are identical and are used interchangeably
 Based on unit volume of reacting fluid

 Basedon unit volume of reactor, if different from the rate based on unit
volume of fluid.
Cont...
Rate law/Power law /Kinetic expression
Consider a takes place in the reactor
In terms of pressure: Total pressure or partial pressures

P = the sum of partial pressures of all species (PA,PB,PC,PD)

In terms of concentration: Total concentration or concentrations of individual species

l
Cont...

 The overall order of reaction is the sum of all orders with respect to each
species

 Values of order of reaction must be determined experimentally (can not

be predicted from chemical equation).
 Order of reaction can be any real number
 Order of reaction can be integer (…-2,-1,0,1,2…) or fraction (1/2)
e.g 2HI H2 + I 2
CH3CHO CH4 + CO
CO + O2 CO2
Cont…

Law of Mass Action of kinetics

 Law mass action states that rate of reaction is only the dependant of reactant concentrations, it does not
depend on the product concentrations
 Or the rate of reaction increases with increasing concentration of reactants owing the corresponding
increase in the number of molecular collisions.
Consider a reaction

Example: CO + 2H2 CH3OH

A B C
Cont...

 A reaction follows an elementary rate law if the reaction orders just happens to
agree with the stoichiometric coefficients for the reaction as written.
Exapmle: If the reaction below follows an elementary, rate law

2 A  B  3C

 rA  k AC A2 C B

 It is 2nd order wrt A, 1st order B, overall 3rd order

Cont...
2. Variables affecting the rate of reaction
For homogeneous reaction, rate of reaction is dependent of
 Concentrations of reactants: As the concentrations of the reactants increase,
reaction rate generally increases
 Pressure : For gas phase reaction, rate of reaction increases as pressure increases
 Temperature: Reaction rates generally increase rapidly as the temperature is
increased. .
 Catalyst: Catalysts speed up reactions and inhibitors slow them down.
Homogenous catalysts
For heterogeneous reaction, beside reaction rate, mass and heat transfer rates are
considered.
In addition to above variables, other variables has effect on overall rate
Surface area: For reactions that occur on a surface rather than in solution like solid-gas,
solid-liquid reactions, the rate increases as the surface area is increased
Catalyst: Heterogeneous catalysts
Cont….
i. Concentration dependence of the rate of a reaction
Rate law is an equation that expresses the rate of a reaction as a function of the concentrations of all
species present in the overall chemical equation at some time.

rjα f([A],[B],….)

rj = f(T) * f([A],[B],….)

rj = k[A]α[B]β…… or

rj = kCAαCBβ…..
ii. Pressure dependence of the rate of a reaction
 For homogenous gas-phase reactions, pressure is often used:
rjα f(PA, PB, ….)
rj = f(T) * f(PA, PB, ….)

rj = k(PA/RT)α(PB/RT)β….= kpPAαPBβ
kp=k/[(RT)α(RT)β]=k/[(RT)α+β]
Cont...
iii. Temperature dependence of the rate of a reaction
 Rate(constant)s increase when temperature increases.

 Arrhenius equation:

 A and Ea are called Arrhenius parameters.

 For a homogeneous chemical reaction, the dimensions(units) of the rate constant k for the
nth- order reaction are (Time-1)(concentration)1-n
Determination of Arrhenius parameters
 Plot ln k vs 1/T
 A plot of lnk against 1/T is a straight line
 The slope gives –Ea/R and the intercept at 1/T = 0 gives lnA
Cont…

Example1: Milk is pasteurized if it is heated to 63°C for 30 min, but if it is heated to

74°C it only needs 15 s for the same result. Find the activation energy of this
sterilization process.
Answer: See your text book Octave Levenspiel page 29
Example2: The rate constants of a reaction at 500K and 700K are 0.02s-1 and 0.07s-
1
respeetively. Calculate the activation energy? Take gas constant R = 8.314J/mol.K
Answer: 28,312J = 28.312kJ
Cont…

Example3: How much does a reaction rate with an activation energy of 15,000
Cal/mol vary when the temperature is increased from 300 to 310 K? From 300
to 400 K? Take gas constant R = 1.986 cal/mol.K

Solutions

 This shows that for this activation energy an increase of temperature by 10K
approximately doubles the rate and an increase of 100K increases it by more
than a factor of 500.
 This example shows why the temperature is so important in chemical
reactions.
Cont…
Collision Theory of chemical reaction
 In a chemical reaction, molecules, atoms or ions can only react if
they collide with each other.
 During collision, old bonds are broken and new bonds are formed.
 Molecular collusion produce kinetic energy
 Further collision - kinetic energy can be transferred into vibrational
energy
 A reaction cannot occur unless the molecules possess sufficient
energy to get over the activation energy barrier.
 The minimum energy that must be supplied by collisions for a
reaction to occur is called the activation energy, Ea.
Cont…

Why is there an Activation Energy?

 For the reaction to occur, the reactants must overcome an energy

barrier or activation energy EA.
 The energy to overcome their barrier comes from the transfer of the
kinetic energy from molecular collisions to internal energy (e.g.
Vibrational Energy).
1. The molecules need energy to disort or stretch their bonds in order to
break them and thus form new bonds
2. As the reacting molecules come close together they must overcome
both stearic and electron repulsion forces in order to react.
Cont…

Activation energy:
 Activation energy is the minimum kinetic energy that the
reactants must have in order to react.
Pre-exponential factor
 The exponential factor in the equation corresponds to the
fraction of all occurring collisions that have enough
kinetic energy to lead to reaction.
 A: rate of successful collisions.
Cont…

CO(g) + NO2(g) CO2(g) + NO(g)

Cont…

Consider a decomposition reaction

2HBr H2 Br2
A B + C
Cont.
3. Reaction Mechanism
A reaction mechanism: is the step by step sequence of elementary reactions
involved in a reaction leading to the overall chemical reaction

Example: H2 + Br2  2HBr

 Experimental rate

 This equation represents the specific process occurring to individual

molecules.
Cont…
Non elementary Reactions
None-elementary reactions is one whose stoichiometry does not match with its
kinetics (stoichiometric coefficient does not match with order of reaction)

Two types of non elementary reaction

• Non-chain Reactions.

• Chain Reactions.

 Intermediates - Free Radicals, Ions and Polar Substances, Transition

Cont…

Kinetic Models for Non elementary Reactions

• Multistep reaction model to explain the kinetics.

Example: The irreversible reaction A+B AB has been studied kinetically, and
the rate of formation of product has been found to be well correlated experimentally
by the following rate equation:

• What reaction mechanism is suggested by this rate expression if the chemistry

of the reaction suggests that the intermediate consists of an association of
reactant molecules and that a chain reaction does not occur?

Model1: Four elementary reactions

Cont…

• Because the concentration of A2* is always extremely small we may assume

that its rate is zero

• If k3 is very small, rAB reduces to

• If k2 is very small, this expression reduces to

Cont…

Model 2

• Just interchange A and B in Model 1, put k2= 0 and we will get rAB= k[B]2 =
kCA2

Home work!!!
Cont…

Molecularity: the number of free atoms, ions, or molecules that

involved in the elementary reaction.

 The number of reacting species taking part in an elementary

reaction which must collide simultaneously in order to bring about
a chemical reaction is called molecularity of reaction.

Unimolecular reaction: an elementary reaction that involves one

reactant molecule
Bimolecular reaction: an elementary reaction that involves two
reactant molecules
Ter-molecular reaction: an elementary reaction that involves three
reactant molecules.
Cont…

Unimolecular:

 A P with

Bimolecular:

 2 A  P with

or
 A + B  P with
Cont…

Molecularity vs. reaction order

 Reaction order: is an empirical quantity, and obtained from the

experiment.
 Molecularity: refers to an elementary reaction proposed as an
individual step in a reaction mechanism.
 In an elementary reaction, the order of reaction is equal to the
molecularity.