CHEP 424: CHEMICAL REACTION ENGINEERING

LECTURE 1:
INTRODUCTION TO CHEMICAL KINETICS
Engr. Michael Allan Ramos
Department of Chemical Engineering
Technological Institute of the Philippines

Lecture Outline
Classifications of Reactions
Rate of Reaction
Rate Law Equation
Factors Affecting Rate of Reaction
Nature of Reactants
Presence of Catalyst
Concentration of Reactants
Temperature

Classifications of Reactions
Homogenous or Heterogeneous
Batch or Continuous Flow
Irreversible or Reversible
Simple or Complex
Elementary or Non-Elementary
Catalyzed or Non-catalayzed

Factors Affecting Rate of Reaction

Definition of Rate of Reaction
Consider the following reactions:
1.

A + B C

2.

2A + B 3C + D

Factors Affecting Rate of Reaction

Speed of Chemical Reactions

Magnitude of Rates of Different Reactions [moles/m3.s]

Factors Affecting Rate of Reaction

1) Nature of Reactants
based on degree of dispersion of reactants

Reactivity: Gases > Liquids > Solids

Factors Affecting Rate of Reaction

2) Presence of a Catalyst
Catalysts lowers the activation energy (Ea) needed for the reaction

to proceed by providing alternative pathway.

Ratecatalyzed > Rateuncatalyzed

Factors Affecting Rate of Reaction

The Rate Law Equation
Consider a single phase reaction:

aA

bB

cC

dD

Law of Mass Action states:

The rate of a chemical reaction is directly proportional to the active
masses of the reactants each raised to a certain power .

- rA = -rB = +rC = +rD = k CAp CBq

Where:
p = order of reaction w.r.t. A
q = order of reaction w.r.t. B
p + q = over-all order of reaction

Concentration
Dependency Term
Temperature
Dependency Term

Factors Affecting Rate of Reaction

3) Concentrations Dependency
Consider a reaction:

A + B P

The rate controlling mechanism involves collision or interaction of a

single molecule of A with a single molecule of B.

Rate of Reaction

Number of Collisions

Factors Affecting Rate of Reaction

4) Temperature Dependency
Rate of chemical reaction is observed to increase with increasing

temperature. (usually 10 deg C doubles the rate of reaction)

Arrhenius Equation:

Svante Arrhenius

k: rate constant
k0: frequency / pre-exponential factor
Ea: activation energy
R: Universal Gas Constant
T: Temperature in Kelvin

Factors Affecting Rate of Reaction

Collision Theory
Rate of reaction is governed by the number of energetic collisions between

reactants. Assumes the intermediate breaks rapidly.

k = k0 T1/2 e-E/RT
Transition-state Theory
Rate of reaction is governed by the rate of decomposition of the intermediate.

Assumes the rate of formation of the intermediate is very rapid.

k = k0 T e-E/RT

Factors Affecting Rate of Reaction

General Equation:

k = k0 T m e-E/RT

For Arrhenius Law:

Collision Theory:
Transition-state Theory:

m=0
m = 0.5
m = 1.0

Factors Affecting Rate of Reaction

Temperature Sensitivity of Reaction Rate
k = k0 T m e-E/RT

Factors Affecting Rate of Reaction

Temperature Sensitivity of Reaction Rate
Temperature Rise Needed to Double the Rate of Reaction for Activation
Energies and Average Temperatures Shown:

Factors Affecting Rate of Reaction

1. Homogeneous Reactions
rate = f ( T, P, Composition)

2. Heterogeneous Reactions
rate = f ( Heat Transfer, Mass Transfer)

Factors Affecting Rate of Reaction

Heterogeneous Reactions
More than one phase is involved
Materials may have to move from one phase to the other
Distribution of temperature results into different rates of reaction at

various points.
Examples:

Burning of coal
Exothermic reaction in a porous catalyst pellet

- END For next meeting:

Problem Solving involving Chemical Kinetics

SAMPLE PROBLEMS

PROBLEM 1
Given the reaction, what is the relation between the rates

of formation and disappearance of the three reaction

components?
2 NO2 +

O2

N2O5

PROBLEM 2
What will be the unit of the rate constant for a reaction with
the following over-all order if the rate of reaction is in moles
per cubic meter per second?
a) Zero Order
b) First Order
c) Second Order

PROBLEM 3
For a gas reaction at 400 K the rate is reported as

a. What are the units of the rate constant?

b. What is the value of the rate constant for this reaction if

the rate equation is expressed as

PROBLEM 4
The pyrolysis of ethane proceeds with an activation energy
of about 300 kJ/mol. How much faster is the decomposition
at 650C than at 500C?

PROBLEM 5
The maximum allowable temperature for a reactor is 800 K.
At present our operating set point is 780 K, the 20-K margin
of safety to account for fluctuating feed, sluggish controls,
etc. Now, with a more sophisticated control system we
would be able to raise our set point to 792 K with the same
margin of safety that we now have. By how much can the
reaction rate, hence, production rate, be raised by this
change if the reaction taking place in the reactor has an
activation energy of 175 kJ/mol?

PROBLEM 6
On doubling the concentration of reactant, the rate of
reaction triples. Find the reaction order.

PROBLEM 7
Calculate the activation energy for the decomposition of
benzene diazonium chloride to give chlorobenzene and
nitrogen. Use the following information for this first-order
reaction: