Chemical Reaction Engineering

(CRE)
(203103303)
Course Synopsis:
• This subject covers the knowledge of reaction kinetics,
reactor design and separation which distinguishes
chemical engineer from other engineers.
• The course introduces the basic reactor design calculation
and design of commercial chemical reactors, emphasizing
synthesis of chemical kinetics and transport phenomena.
• The topics cover in this subject are kinetic rate theory,
homogeneous reaction in batch and flow systems,
heterogeneous reaction and catalysis, temperature effect,
effect of heat transfer and catalytic reactor also reactor
design, sizing and modeling of performance
Course Objectives:
• Apply basic fundamentals of chemical reaction
engineering such as reaction progress variables,
conversion, rate laws, order of reaction and molecularity,
reversible reactions and stoichiometry.
• Acquire the analytical and modeling skills required for the
design and operation of industrial reactors for the
chemical processes.
 Typical Chemical Process:

Typical chemical process consist of these steps:

Raw Material Product

Separator Reactor Separator

(Physical Process) (Physical Process)

Undesired Product
What’s involved in reactor design?
What is Chemical Reaction Engineering?
• CRE deals with chemically reactive systems of engineering
significance.
• Chemical reaction engineering is the discipline that quantifies the
interactions of transport phenomena and reaction kinetics in relating
reactor performance to operating conditions and feed variables.
• CRE is needed in the development of new and the improvement of
existing technologies.
 search for alternative processes to replace old ones
 find routes to make a product from different feedstock
novel processes for synthesis-gas production
Hydrocarbon production from syn gas
Biodiesel production
 reduce/eliminate unwanted byproducts
fuel-cells for automobiles
NOx reduction
 CRE: Introduction
 Every industrial chemical process is designed to produce economically a
desired product from a variety of starting materials through a succession
of treatment steps.
 The subject of chemical reaction engineering initiated and evolved
primarily to accomplish the task of describing how to choose, size, and
determine the optimal operating conditions for a reactor whose purpose is
to produce a given set of chemicals in a petrochemical application.
 The principles of chemical reaction engineering are presented in such
accuracy to make possible a comprehensive understanding of the subject.
Mastery of these concepts will allow for generalizations to reacting
systems independent of their origin and will furnish strategies for attacking
different problems.
 So, Reactor design uses information, knowledge, and experience from a
variety of areas-thermodynamics, chemical kinetics, fluid mechanics, heat
transfer, mass transfer, and economics. Chemical reaction engineering is
the synthesis of all these factors with the aim of properly designing a
chemical reactor.
 CRE: Introduction
• To find what a reactor is able to do we need to know the kinetics, the
contacting pattern and the performance equation.
• The expression to relate input to output for various kinetics and various
contacting patterns, or
• output = f [input, kinetics, contacting]
• This is called the performance equation.
• Why is this important?
Because with this expression we can compare different designs and conditions,
find which is best, and then scale up to larger units.
CRE: Introduction
• Chemical reaction engineering is that engineering activity concerned
with the utilization of chemical reactions on a commercial scale. Its
goal is the successful design and operation of chemical reactors, and
probably more than any other activity, it sets chemical engineering
apart as a distinct branch of the engineering profession.
• The ingredients of CRE are (i) thermodynamics, (ii) kinetics, (iii)
transport processes, (iv) types of reactors, (v) mode of operation and
contacting, (vi) modelling and optimization, and (vii) control.
• Chemical kinetics is a study of rates at which chemical reaction occur
and the effect of parameters such as temperature, pressure and
reactant concentration
Classification of Chemical reaction
 Classification based on state of reactant and products
1.Homogeneous reactions
2.Heterogeneous reactions

 Classification based on presence of catalyst

1.Catalytic reaction
2.Non-catalytic reaction

 Classification based upon the directions

1.Reversible reaction
2.Irreversible reaction
Classification of Chemical reaction
 Classification based on molecularity of a reaction
1.Unimolecular reactions
2.Bimolecular reactions
3. Tri molecular reactions

 Classification based upon the heat effect

1.Exothermic reaction
2.Endothermic reaction

 Classification based upon the order of reaction

1.First order reaction
2.Second order reaction etc.
Parameters Affecting Rate of Reaction: The Rate
Law
• Rate of reaction depends on a number of parameters, the most
important of which are usually
1.The nature of the species involved in the reaction; Many
examples of types of very fast reactions involve ions in solution, such
as the neutralization of a strong acid by a strong base, and explosions.
In the former case, the rate of change may be dictated by the rate at
which the reactants can be brought into intimate contact. At the other
extreme, very slow reactions may involve heterogeneous reactions,
such as the oxidation of carbon at room temperature. The reaction
between hydrogen and oxygen to form water can be used to illustrate
both extremes. Subjected to a spark, a mixture of hydrogen and
oxygen can produce an explosion, but in the absence of this, or of a
catalyst such as finely divided platinum, the reaction is extremely slow.
In such a case, it may be wrongly supposed that the system is at
equilibrium, since there may be no detectable change even after a very
long time.
Parameters Affecting Rate of Reaction: The Rate
Law
2.Concentrations of species; Rate of reaction usually depends on
concentration of reactants (and sometimes of products), and usually
increases as concentration of reactants increases. Thus, many
combustion reactions occur faster in pure oxygen than in air at the
same total pressure.
3.Temperature; Rate of reaction depends on temperature and usually
increases nearly exponentially as temperature increases. An important
exception is the oxidation of nitric oxide, which is involved in the
manufacture of nitric acid; in this case, the rate decreases as T
increases.
4.Catalytic activity; Many reactions proceed much faster in the
presence of a substance which is itself not a product of the reaction.
This is the phenomenon of catalysis, and many life processes and
industrial processes depend on it. Thus, the oxidation of SO, to SO3 is
greatly accelerated in the presence of V2O5 as a catalyst, and the
commercial manufacture of sulfuric acid depends on this fact.
Parameters Affecting Rate of Reaction: The Rate
Law
5.Nature of contact of reactants; The nature or intimacy of contact of
reactants can greatly affect the rate of reaction. Thus, finely divided
coal burns much faster than lump coal. The titration of an acid with a
base occurs much faster if the acid and base are stirred together than if
the base is simply allowed to “dribble” into the acid solution. For a
heterogeneous, catalytic reaction, the effect may show up in a more
subtle way as the dependence of rate on the size of catalyst particle
used.
6.Wave-length of incident radiation: Some reactions occur much
faster if the reacting system is exposed to incident radiation of an
appropriate frequency. thus, mixture of hydrogen and chlorine can be
kept in the dark, and the reaction to form hydrogen chloride is very
slow; however, if the mixture is exposed to ordinary light, reaction
occurs with explosive rapidity. Such reactions are generally called
photochemical reactions.
Rate Equations:
Kinetics of homogeneous reaction:
Single and Multiple Reaction:
Elementary and Nonelementary Reaction:
 Elementary and Nonelementary Reaction:

Non-elementary is reaction is not single step reaction and it is a series of

elementary reaction and there if formation of intermediates.

Different types of intermediates are as follows. Free radical, ions, polar

substances, molecules and transition complex.

Transition complex is divided into chain and non-chain reaction. Chain

reaction involves three steps. Initiation, propagation and termination.

Chain reactions are divided into three types. Free radicals chain reaction
mechanism, molecular intermediates non chain mechanism and transition
complex non chain mechanism.
Reaction mechanism of Nonelementary
reactions:
Reaction mechanism of Nonelementary
reactions:
Molecularity and Order of Reaction
Molecularity and Order of Reaction
Concentration can be represented in another form using a term called
‘conversion’ .

And it is denoted by Xi where NA0 initial amount of moles and NA is

amount of moles after some time ‘t1’.
XA = NA0 – NA/ NA0 = 1- (NA/V) / (NA0/V) = 1-CA/CA0

dXA = -dCA/CA0

Where, CA0 concentration at t=0

V = volume of the reactor
CA = Concentration at t = t1
Rate Constant
Temperature Dependency from Arrhenius’ Law
Rate of reaction = f(concentration). g(temperature)

= f(concentration).k

Rate constant is experimentally found value and it is well represented

by Arrhenius’ law
k = k0 exp (-E/RT)
Where, k = rate constant
k0 = frequency/pre-exponential factor
E = Activation energy
R = Universal ideal gas constant, T = Temperature
 Temperature Dependency from Arrhenius’ Law

If we write full rate equation, we obtain,

Rate of reaction = f(concentration). g(temperature)

= f(concentration). K

= f(concentration). k0 exp (-E/RT)

At same composition, but at two temperatures, Arrhenius’ law gives

Temperature Dependency from Arrhenius’ Law
Rate of reaction is directly proportional to rate constant so we can
equate the ratio of rate constant to the ratio of rate terms.

 Rate equation term is related with time.

 Rate of reaction is inversely proportional to time because as time

increases rate of reaction decreases and vice versa.

By relating time and rate of reaction the following equation is obtained
Temperature Dependency from Arrhenius’ Law
Comparison of theories with Arrhenius’ law

General equation for rate constant is represented by

k = k0 Tm exp (-E/RT)
where ‘m’ is a constant varies from 0 to 1.

If m = 0, k = k0 exp (-E/RT) , Arrhenius’ equation

If m = 1/2, k = k0 T1/2 exp (-E/RT), collision theory equation

If m = 1, k = k0 T exp (-E/RT), transition theory equation

Temperature Dependency from Arrhenius’ Law

ln
Activation Energy and Temperature Dependency

 From Arrhenius' law a plot of In k vs. 1/T gives a straight line, with large
slope for large E and small slope for small E.

 Reactions with high activation energies are very temperature-sensitive;

reactions with low activation energies are relatively temperature-
insensitive.

 Frequency factor does not influence the temperature sensitivity.

 It is observed that activation energy is very dependent on temperature.

Activation Energy and Temperature Dependency

• Example: Milk is pasteurized if it is heated to 336 K for 30 min, but if it is

heated to 347 K it only need 15 s for the same result. Find the activation
energy of this sterilization process.

Solution: T1 = 336 K in 30 min (t1)

T2 = 347 K in 15 sec (t2)
•As it discussed rate is proportional to rate constant and inversely proportional
to time.
•Following equation can be used to find the activation energy.

R = 8.314 J/mole. K
So, E= 422 kJ/mole
Examples:
1. On doubling the concentration of reactant the rate of
reaction triples. Find the reaction order.
Solution:
Assume rate of reaction is, -rA = k CAn
At CA1 rate is, -rA1 = k CA1n
And At CA2 rate is, -rA2 = k CA2n
If CA2= 2 CA1
Than, -rA2 = 3(-rA1)
2. The pyrolysis of ethane proceeds with an activation energy
of about 75000cal. How much faster is the decomposition at
650°C than at 500°C.
Solution:
C2H6 Product
E =75000 cal/mol
Let k1 be the rate constant at T1 and k2 be the rate constant at T2
T1 = 500°C = 773 K, T2 = 650°C= 923 K
3. Phosphine decomposes when heated according to following
reaction:
4PH3(g) → P4(g) + 6H2(g)
At a given instant , the rate at which phosphine decomposes is
2.4 Χ 10-3 (mol/l.s).
a. Express the rate in three different ways using differential notation
and shows the relation between them.
b. What is the rate of formation of 1) P4 and 2) H2
Solution:
4PH3(g) → P4(g) + 6H2(g)
From stoichiometry the rate of decomposition of PH3, formation
of P4 and H2 are related as follows:
b.
4. For a gas reaction at 400 k the rate is reported as
-rpA = -dpA/dt = 3.66 pA2, (atm/h)
a. What are the units of rate constant
b. What is the value of the rate constant for the this
reaction if the rate equation is written as
I. - rA = (-1/V)x(dNA/dt) = kCA2, (mol/l.h)
II. - rA = kCA2, (mol/m3.s)
Solution,
5. A rocket engine, burns a stoichiometric mixture of fuel (liquid
hydrogen) in oxidant (liquid oxygen). The combustion chamber is
cylindrical, 75 cm long and 60 cm in diameter, and the
combustion process produces 108 kg/s of exhaust gases. If
combustion is complete, find the rate of reaction of hydrogen and
of oxygen.
6. A human being (75 kg) consumes about 6000 kJ of food per
day. Assume that the food is all glucose, and that the overall
reaction is

Find man's metabolic rate (the rate of living, loving, and

laughing) in terms of moles of oxygen used per m3 of person per
second.