VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY

UNIVERSITY OF TECHNOLOGY
FACULTY OF CHEMICAL ENGINEERING

Chemical Reaction Engineering

(Homogeneous Reactions in Ideal Reactors)

Mai Thanh Phong, Ph.D.

FCE – HCMC University of Technology Chemical Reaction Engineering

 References

1. Octave Levenspiel, “Chemical Reaction Engineering”, John Wiley&Sons, 2002.

2. H. Scot Foggler, “Elements of Chemical Reaction Engineering”,International

students edition, 1989.

3. E.B.Nauman, “Chemical Reactor Design”, John Wiley & sons, 1987.

4. Stanley M. Walas, “Reaction Kinetics for Chemical Engineers”,Int. Student

Edition, 1990.

5. Coulson & Richardsons, “Chemical Engineering – Vol 6”,Elsevier, 1979.

6. Richard M. Felder, “Elementary Principles of Chemical Processes”, John Wiley &

sons, 2000.

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 Chapter 1. Introduction

• Topic of the lecture „Chemical Reaction Engineering“ is the quantitative

assessment of chemical reactions. The selection of suitable reactor types and
their design will be discussed.

• 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.

• Thermodynamics tell us in which direction a reaction system will develop and

how far it is from its equilibrium state.

• Analyses of kinetics provide information about the rate with which the system will
approach equilibrium.

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 Chapter 1. Introduction

I. Basic Parameter

Description of the amount of a substance i:

mi
Number of moles: ni = Mi = molecular weight
Mi

ni
Molar concentration: ci = V = volume
V

ni
xi =
nj
Mole fraction:

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 Chapter 1. Introduction

Progress of chemical reactions:

ni 0 − ni
Conversion: Xi =
ni 0

ci 0 − ci
If V = const: Xi =
ci 0
ni − ni 0
Extent of reaction: =
i
Performance criteria:

produced amount of product P

Productivity: n P =
operating time

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 Chapter 1. Introduction

II. Stoichiometry of chemical reactions:

Stoichiometry is based on mass conservation and thus quantifies general laws

that must be fulfilled during each chemical reaction.

Starting point of a quantitative analysis is the following formulation of a chemical

reaction:
N

 A = 0
i =1
i i

This equation describes the change of the number of moles of N components

A1, A2, ... AN. The νi are the stoichiometric coefficients of component i. They have
to be chosen in such a way that the moles of all elements involved in the chemical
reaction remain constant.

A convention is that reactants have negative stoichiometric coefficients and products

have positive stoichiometric coefficients.

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 Chapter 1. Introduction

As an example the stoichiometric equation for the oxidation of carbon monoxide

is given by:
2CO + O2 → 2CO2
with νCO = -2, vO2 = -1, vCO2 = 2

To calculate changes in the mole number of a component i due to reaction, the

following balance has to be respected:
ni = ni 0 + i
From this equation results the important stoichiometric balance:

ni 0 − ni ni nk 0 − nk nk
= = =
i i k k
Using the conversion X of a component k, the above equation becomes:
i
ni = ni 0 − nk 0 X k
k
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 Chapter 1. Introduction

III. Chemical thermodynamics:

Chemical thermodynamics deal with equilibrium states of reaction system. This
Section will concentrate on the following two essential areas:
a) The calculation of enthalpy changes connected with chemical reactions, and
b) The calculation of equilibrium compositions of reacting systems.

3.1 Enthalpy of reaction

The change of enthalpy caused by a reaction is called reaction enthalpy ∆HR.

This quantity can be calculated according to the following equation:
N
H R =  i H Fi
i =1

∆HFi is the enthalpy of formation of component i

∆HR < 0, the reaction is exothermic

∆HR > 0, the reaction is endothermic

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 Chapter 1. Introduction

It is simple to calculate the reaction enthalpy at a certain standard state ∆HR0 from
the corresponding standard enthalpies of formation ∆HFi0. The standard enthalpies
of formation are available from databases for P = P0 = 1 bar and T = T0 = 298 K.

For pure elements like C, H2, O2,...: ∆HFi0 = 0.

The reaction enthalpy is a state variable. Thus, a change depends only on the
Initial and the end state of the reaction and does not dependent on the reaction
parthway.

3.2 Temperature and pressure dependence of reaction enthalpy

 H R   H R 
d (H R ) =   dP +   dT
 P T  T  P
The pressure dependence is usually very small. For ideal gas behaviour, the
reaction enthalpy does not depend on pressure.

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 Chapter 1. Introduction

The correlation of reaction enthalpy and temperature is related to the isobaric

heat capacities of all species involved in the considered reaction, cPi.

N T
H R (T ) = H R0 +  i  c (T )dT
Pi
i =1 T = 298K

Assuming that the reactants and the products have different but temperature
independent heat capacities, the temperarue dependence of the reaction
enthalpy can be estimated as follows:

H R (T ) = H R0 + (T − T0 )(cP,products − cP,reactants )

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 Chapter 1. Introduction

3.3 Chemical equilibrium

• Chemical reactions approach to an equilibrium, when the product and reactant
concentrations do not change anymore.
• A reacting system is in chemical equilibrium if the reaction rates of the forward
and backward reactions are equal.
• The basic quantity required to indentify the equilibrium state is the Gibbs free
enthalpy of reaction GR.
• The change of this quantity becomes zero when the equilibrium is reached (i.e.
dGR = 0)

For constant pressure and temperature, the change of free Gibbs enthalpy of
reaction can be described as follows:
N
 dGR  N
dGR =  i i d or   =  i i
i =1  d T , P i =1

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 Chapter 1. Introduction

In Figure 1-1 is shown the course of free

Gibbs enthalpy of reaction as a function
of the extent of reaction.

Free Gibbs enthalpy

The equilibrium is reached when the free
 GR   GR 
Gibbs enthalpy of reaction is minimum.    0    0
  T , P   T , P
Thus, for the chemical equilibrium:

 dGR 
  = 0
 d T , P
 GR 
  = 0
Or dGR=0 (or in an integrated form: ∆GR = 0)   T , P

Thus, the equilibrium is characterized by:


N Fig. 1-1: Changing of free Gibbs enthalpy
 
i =1
i i =0 for a chemical reaction

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 Chapter 1. Introduction

3.3.1 Reation free Gibbs enthalpy, ∆GR

N
G =  i GFi0
0
R
i =1

GFi0 free Gibbs energy of formation

Relation between ∆GR and ∆HR

(
d GR0 T )
H R0
=− 2
dT T

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 Chapter 1. Introduction

3.3.2 Equilibrium constant and temperature dependence

Relationship between the free Gibss enthalpy and the equilibrium constant:

GR0 (T ) = − RT ln K
 GR0 
K = exp  − 
 RT 
Van‘t Hoff equation describing the temperature dependence of the equilibrium
constant:

d (ln K ) H R0
=−
dT RT 2
For a small temperature range, ∆HR is constant, thus:

H R0 1 1
ln K (T2 ) = ln K (T1 ) −  − 
R  T2 T1 
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 Chapter 1. Introduction

4. Reaction rate
Based on unit volume of reacting fluid:
1 1 dni • VR is volume of the reaction mixture
r= • ni is mole number of component i
 i VR dt • t is reaction time
If VR is constant:
1 dci • ci is molar concentration of component i
r=
 i dt
Based on unit mass of solid in solid-liquid systems:
1 1 dni
r= • W is mass of solid
 i W dt
Based on unit solid surface of solid-liquid or solid-gas systems:
1 1 dni
r= • S is solid surface area
 i S dt
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 Chapter 1. Introduction

5. Standard Reactors
To carry out chemical reactions discontinuously operated reactors or
continuously operated reactors can be used.
• Discontinuously: more frequently applied to produce fine chemicals
• Continuously: more advantageous for the production of larger amounts of bulk
chemicals.
To study the different behavior of these types of reactors another important criterion
serves to distinguish two limiting cases: mixed flow and plug flow behavior
For theoretical studies and to compare the different reactors, four different ideal
reactors can be defined using the above classification:
a) Batch Reactor (BR, perfectly mixed, discontinuous operation):

Features:
• All components are in the reactor before the reaction starts
• Composition changes with time
• Composition throughout the reactor is uniform

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 Chapter 1. Introduction

Adv.:
• Simple, flexible, high conversion…

Disadv.:
• Dead times for charging, discharging, cleaning,…
• Difficult to control and automate
•…

BR are applied in particular for:

• Relatively slow reactions
• Slightly exothermic reactions

Areas of application for BR are:

• Reactions in pharmaceutical industry
• Polymerisation reactions
• Dye production
• Speciality chemicals

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 Chapter 1. Introduction

b) Semi-batch Reactor (SBR): perfectly mixed, semi continuous operation

Features:
• One reactant is introduced first and then the
second is dosed in a controlled manner.
• Composition changes with time
• Composition throughout the reactor is uniform

Adv.:
• Controlled reaction rate and heat generation
• ...

Disadv.:
• Same as BR
• More complicated than BR
•…

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 Chapter 1. Introduction

c) Continuously Stirred Tank Reactor (CSTR): perfectly mixed, continuous operation

Features:
A,B A,B,products • Reactants are continuously introduced,
products (+ unconverted reactants) are
continuously withdrawn
• Composition does not change with time
• Composition throughout the reactor is uniform

Adv.:
• Controlled heat generation
• Easy to control and automate
• No dead times
• Constant product quality,...

Disadv.:
• Complicated
• Can become unstable
• Large investmnent cost,...

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 Chapter 1. Introduction

d) Plug Flow Tubular Reactor (PFTR): no mixing, continuous operation

A, B tubular reactor A, B,
products
Features:
• Composition varies from point to point along a flow path
Adv.:
• High conversion
• Easy to automate
• No dead times
• Better to cool (compare to stirred tanks)
•…

Disadv.:
• Complicated
• Danger of “hot spot”
•…
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