1.

Introduction to the chemical process

The conversion process of any raw materials to
products could pass through a number of steps.

Wanted
products

Raw
materials 1 2 3 4

Unwanted
products
Step 1. Preparation of raw materials
(Purification, Grinding etc.).

Step 2. Chemical process with partial conversion

Step 3. Separation of non-converted raw

material(obtained from step 2)

Step 4. Separation of unwanted and wanted

products
In the above processes,

 the steps 1, 3 and 4 are physical

treatments and are mainly carried out
in unit operations (Crushing,
distillation, extraction)

 Step 2 is the chemical treatment

process / Chemical reaction / which
is carried out in the reactor /
The steps of a chemical process can be
simple or complex,
 depending upon the purity of the raw
material,
 the desired quality of the products etc
 Chemical Reaction /Process /
There are three levels of understanding about the
chemical process /Reaction/.
1.If a certain condition fulfills a certain output
can be erected with the so called
thermodynamic phenomena.
Subject of kinetics

2. The various reactions follow a certain well

defined equation.
These constitute a mathematical model which can
be used by a chemical engineer to design a
reactor or to control the performance of a reactor.
Eg. rate equation

3. Mechanism, why a certain reaction path are favored?

The main objective of the chemical engineer is

 to design appropriate reactor and or

 analysis of performance of chemical reactors

to secure quality of the wanted products
with a minimum cost of production

using the tools of chemical reaction

engineering
Chemical Reaction Engineering (CRE)
The subject
 is concerned with the rational design and/o
analysis of performance of chemical reactors.

 In another word it is a means to determine

something about the reactor: size, flow and
thermal configuration, product distribution,.

• CRE does not provide all the information

required for the reactor design, and other rate
processes are involved in designating a
reactor. Among them are included : fluid
mechanics and mixing, heat transfer, and
diffusion and mass transfer
Reactor design concept
 A complete reactor design involves two
types of design, namely,
process design and
 mechanical design.
The process design, which is done by chemical
engineer, engages with
 the size of the reactor;
 methods of operation and
 condition for the required output.
The mechanical design involves with specific matters
relating to
 the equipment design,
 including structural, mixing equipment.
In process design, a chemical engineer is involved
in making decisions on:
•Type of processing :- batch, semi-batch, continuous, etc

•Nature of the reacting system:-

reactant and product; single and multiple reactions; desired

and undesired products; stoichiometry relationship;
homogeneous and heterogeneous; catalytic and non
catalytic; endothermic and exothermic; reversible and
irreversible; possibilities of equilibrium limitation, etc

•Type of reactors:-

batch reactor; continuous stirred tank reactor (CSTR); or

plug flow reactor (PFR); fixed bed reactor (FBR); fluidized
reactor, etc
•Mode of operation:-
single stage; multistage; thermal like adiabatic, isothermal,
non isothermal etc

•Process condition:-
Temperature profile, Pressure profile, feed composition
and rate, product composition and rate, etc

•Optimum condition:-
process condition; size; product distribution;
conversion; cost, etc

•Control and stability of operation

•Socioeconomic; cost, environment, safety etc

•Startup and shutdown procedure

Reactors performance
• is measured by
Fraction of unreacted

conversion

Yield

Selectivity
•is described mainly by
material balance equation and

rate equation
A chemical reactor
• Is the “heart” of an overall chemical or biochemical
process
• is a device in which change in composition of matter
occurs by chemical reaction
• is used as a tool for determining something about
the reacting system: rate of reaction, and
dependence of rate on various factors, such as
concentration of species j(cj) and temperature (T)
• is a device also involved in energy production, as in
engines (internal-combustion, jet, rocket, etc.) and in
certain electrochemical cells (lead-acid, fuel), in
animate objects (e.g., the human body),etc.. The
rational design of this last is rather beyond our capabilities
To ensure good designing of a reactor in the
chemical process one has to describe the stand
point of thermodynamics and kinetics
The thermodynamic treatment based on the study of
 the energetic properties of a system
These properties allows us to determine
 the possibilities of reactions and
 achievable equilibrium

On the other hand, A chemical kinetics may be defined as that

 which deals with the velocity of a chemical reaction

(i.e., reaction rate) between the species involved
in the reaction.
 In other words, chemical kinetics is the phenomena
to study the rate and mechanism of how one
chemical species is converted to another.
Hence, to ensure good designing of a reactor in the
chemical process / reaction / it needs:
• To answer the following two questions:
 What changes can we expect to occur?

Thermodynamics
 How quickly will they take place?

Rate of the process

Rates of processes include
 Chemical kinetics
 Heat transfer and
 Mass transfer.
• Information, knowledge and experience from
the different sciences such as fluid mechanics,
heat transfer, mass transfer, economics etc.
Thermodynamics Fluid Flow Mathematics

Mass transfer
Kinetics

Chemical
Reactor
Heat transfer Env.
friendly
Materials
Chemical
Economics Products
$P
1. 1 Thermodynamics in chemical process
Generally
A chemical reaction cannot be made to produce a product
beyond that of chemical equilibrium due to the application of
the Second law of thermodynamics,

∆GR = 0

where ∆GR, Gibs free energy of the reaction

Thermodynamics in chemical process is concerned with two

main aspects:

 the heat liberated (or absorbed) during reaction (heat of

reaction)

 the maximum attainable conversion

 Heat of reaction
Chemical reactions are invariably accompanied by the liberation
or absorption of heat; such type of reaction is demonstrated as
aA  bB  cC  dD  HR (1.1.1)
where ∆HR heat of reaction; ( + ) for endothermic and ( - ) for
exothermic
Handling of this heat is a major concern in a chemical process
and therefore, the magnitude of ∆HR must be known for
proper design of chemical process
Maximum conversion
Thermodynamics also allows calculation of the equilibrium
constant, K from the well known standard free energies ∆G0R
equation of the reacting material.

G0R  H 0R - T S0R  - RT ln K (1.1.1)

 With the equilibrium constant known, the expected
maximum conversion of the reactant and or the yield of the
product of reaction can be estimated as we show for the following
reaction,
A B
C A,eq  C A,0 - C A,0 X (1.1.2)
A, eq

C B,eq  C A,0 X (1.1.3)

A, eq

where C A,eq and C B,eq are equilibrium concentrations of A and B ;

X A,eq equilibrium conversion of A
The equilibrium constant for the above reaction can be written

C B,eq
K (1.1.4)
C A,eq
Substitution the magnitude, we get equilibrium conversion

K (1.1.5)
X A,eq 
1 K
Recalling

G0R  H 0R - T S0R  - RT ln K

we need to specify ∆HR , ∆SR and ∆GR from

thermodynamics relation for every reaction in
order of proper design of a chemical process
1.2 Kinetics in the chemical process
Chemical kinetics
•is the study of the rate and mechanism in the reactor
Regarding to the rate
chemical kinetics
• gives us a quantitative description of how fast
chemical reactions occur, and the factors
affecting these rate

• is to enable us to predict beforehand the rate at

which given chemical substances react, and to
control the rate in some desirable fashion;
• is to enable us to “tailor” chemical reactions so as
to produce substances with desirable chemical
characteristics in a controllable manner, including
choice of an appropriate catalyst
The term Kinetics
is relevant to many branches of science and
has different understanding of it.

As illustration

The chemist
uses kinetics as a tool to understand
fundamental aspects of reaction pathways
(mechanism), a subject that continues to evolve
with ongoing research.
The applied chemist

uses this understanding to devise new and/or better

ways of achieving desired chemical reactions.
This may involve improving the yield of desired
products or developing a better catalyst
The chemical engineer
uses kinetics for reactor design
under the subject of chemical
reaction engineering or process
engineering
Classification of Reactions
• According to the number of phases involved in the
reactions
• According to the type of reaction(Single, Multiple)
• According to the process nature of the reaction
Irreversible, Reversible)
• According to the conditions of the process of
reactions 12’
1.3 The General Mole Balance
The Mole Balance is the tool to

calculate the size of a reactor

 performance of the reactor

 calculate and assess the quantity

of a particular molecular species
(reactant or product) in a given
system volume of reaction.
(Stoichiometry)
In the process of balance, it takes a small volume of
the reactor to observe what happens there in the
small interval of time.

A material balance on any reactant species can be

drawn up the application of the principle of
conservation of mass :

Flow in Flow out

Fj,o Fj
Mole entering = Mole leaving + Mole reacting + Change of Moles

Input = Output + Disappearance + Accumulation

General Mole Balance
Input - Output + Reacting/Generating = Accumulation
dn j
F j ,0  F j  G j  (1.3.1)
dt
Rate of generation of species by reaction

( 1.4.1)
Where G j  rj .V
0 - denote in the text as initial
Fj,0 - represents initial molar flow rates of species j, mol /
time
Fj - represents final molar flow rates of species j, mol /
time
rj - the rate of formation of species j
V - the reaction volume
Suppose that the rate of formation of species j for the system
volume varies with the position in the system,

where it has a value r , r

j ,1 j ,2 at location 1 and 2
respectively which is surrounded by a small volume V1 and V2

then the the rate of generation becomes

G j ,1  rj ,1V1
G j , 2  rj , 2 V2
The total rate of generation within the system would be the
sum total all of rate of generation

G  r V  r V  r V  .......... .
j j,1 1 j,2 2 j,3 3
By taking the appropriate limits and following the
definition of integrals ,
the rate of generation of species j becomes

v
G j   r j .dV
v dn j
F j,0  F j   r j dV  (1.8)
dt
Batch Reactor
In a batch reactor, no material is supplied to or withdrawn
from the reactor during the reaction. The amounts of
individual components may change due to reaction, but
not due to flow in or out of the system.

dn V
j   r dV
(1.5)
dt j
The rate of formation of species j is uniform and is equal to
the system average rate, every where in the reaction, and
therefore, we can take the rate of formation out of the integral
V V
 r dV  r  dV  r V
j j j
and can rewrite the equation of the mole balance
for a batch reactor in the form of :

dn j
 r jV (1.5.1)
dt
Continuous Flow Reactors
 In this type of reactors, the chemical reactions occur while
the reacting stream is flowing through the reactor.
 The reaction is operated at steady-state and this means that
the variables such as concentration, temperature etc. at
each point with in the system do not vary with time
 V
F  F   r dV (1.6)
j,0 j j
a) Continuous Stirred Tank Reactor (CSTR)
In this type of reactors, due to continuous stirring,
vigorous agitation takes place. As a result, the
contents are thoroughly mixed and the conditions
through out the reactor are the same and equal to
the conditions at the outlet
For the same reason, the rate of formation is
constant throughout the reactor. Therefore, the rate
of formation can be taken out of integral and the
equation can be simplified as
 V rj dV  rj V dV  rjV
F j ,0  F j  r jV (1.6.1)
F j ,0  F j
V 
 rj (1.6.2)

b) Plug Flow Reactor

 In this reactor type, the content of the reactor is perfectly
mixed in the radial direction.
 No mixing takes place in axial direction. This condition
provides the concentration, temperature, rate of
formation etc to vary continuously in the axial direction.
 Hence the material balance has to be applied to a differential
element of volume
 F j ,in Fj F j  dFj F j ,out
V

Figure: Plug flow reactor

The differential element of volume can be expressed in equation
form as under:

 
F   F  dF   r V  0
j  j j j
and taking the limit as ∆V  0, we obtain
V  dV
dF  r dV
j j
dF j
r  (1.7.1)
j dV
 1.4 The General Energy Balance
In principle, all forms of energy must be taken into
consideration, like:
 heat,

 kinetic energy,

 potential energy,

 electrical and

 magnetic field

 Thermal

 work done
But, in most reactor calculations, the terms

 with thermal energy and

 work done on the surroundings are of the

main importance.

Energy balance
A similar word statement as of material balance can be
used for energy balance,
i.e the application of the principle of conservation of
energy leads to an energy balance which is in general states
that:
Rate of Rate of Rate of
Rate of
Accumulation = Energy - Energy + Energy
of Energy In Out Production
 HF dH HE
dt
Q

Figure 1.2 Energy balance on an open system

Where
HF – inflow of enthalpy;
HE – outflow of enthalpy;
Q – rate of heat supply from the
surrounding or withdrawn from the
system
dH - Change of enthalpy
Using the above diagram the General Energy Balance for the
for batch and continuous processes is

dH ( 1.10.1)
HF  HE  Q 
dt

or
dH (1.10.2)
H F  H E  KA(TS  T ) 
dt

where
K - Overall heat transfer coefficient
TS - Surrounding (cooling, heating) temperature
A - Effective area for heat transfer
T - The temperature of the reaction mixture
In a batch process

The enthalpy change should be expressed into two elements:

i)The enthalpy change with time due to the change in
composition. In another word, the energy change due
to the heat of the reaction.
H R (rV )dt

ii)The enthalpy change due to the change of

temperature mT C P dT
hence
dH  mT CP dT  H R (rV )dt
Where : mT is the total mass of the reaction mixture; CP is
the specific heat for the composition of the mixture
In a batch process where there is no in- and out-flow, then
the energy balance equation (1.10.2 ) yields to
 mT CP
dT
 H R (rV )  KA(TS  T ) (1.11)
dt
In a continuous process where accumulation is not existing,
the energy balance equation then becomes
H E  H F  dH  KA(TS  T )
The enthalpy change should be expressed
H E - E F  dH  FRCP dT  H R (rV ) (1.12)
Then, the energy balance for continuous process is

(1.13)
FT CP dT  H R (rV )  KA(TS  T )
Where :
r - rate of disappearance low rate
FT is the total molal feed flow rate; CP is the molal heat capacity
of the reaction mixture
1.5 Stoichiometry relationship in reaction
 A chemical species is said to have reacted when it has
lost its chemical identity 19’
 identity of a chemical species is
determined by the kind, number, atoms,
etc
 This lost of chemical identity /change of elements/ can
occur in a reactor in two types.

• Advective change due to material brought into the

system or removed from it and expressed in the
material balance equation appropriate to the reactor.

• The internal change due to chemical reactions and are

common to all types of reactor
Our interest is here to study the composition change
/Change of elements/ which occurs during reaction.
Stoichiometry
is defined as the measurements of the
change of elements (composition
change)

The composition change, which occurs during the

reaction obeys certain laws.
 All chemical change obeys the law of
conservation of mass,

 including the conservation of the chemical

elements making up the species involved.
For each element in the closed reacting system, there
is a conservation equation stating that the amounts
of that element are fixed Stoichiometrically , no
matter how combined or recombined.
To understand this phenomena, let us take a well
known reaction,
2H2 + O2 = 2H2O
Reaction such as this can have two
meanings:

Kinetic description
Two molecules of hydrogen combine directly with
one of oxygen to form two molecules of water
Stoichiometric description
The numbers of hydrogen and oxygen molecules
combining to form water in the ratio 2:1
i.e. the amounts of that element are fixed
The proportions 2:1 in the Stoichiometric
description are absolutely definite
an equation such as 3H2 + O2 ≠ 3H2O is
nonsence
Hence, it follows that the change in composition will
be definite, for every time a given number of
molecules of water are formed, the same number
of hydrogen and half the number of oxygen
molecules will disappear
In conclusion

 All chemical change obeys the law of conservation of mass,

including the conservation of the chemical elements
making up the species involved.

 For each element in the closed reacting system, there is a

conservation equation / Stoichiometric equation /

 stating that the amounts of that element

are fixed, no matter how combined or
recombined
2H2 + O2 = 2H2O (a)
The reaction (a) can be expressed in one side
and set equal zero as:
2H2O - 2H2 - O2 =0
If we identify A1 with H2O; A2 with H2 and A3 with
O2, then the reaction (a) can be expressed in one
side and set equal zero as: 2A -2A -A = 0
1 2 3

Generally , this is represented by

s
  jAj 0 (1.8)
j 1
Where-  j The Stoichiometric Coefficient of Aj
S- Reaction species in the process
j=1,2,3,..S
1 =2,  2 =-2, 3= -1 is called the Stoichiometric
Coefficient of Aj in the reaction.

 The species with positive stoichiometic

coefficients are the product of the reaction and
those with negative Stoichiometric coefficients are
the reactants.

 The important thing to observe at this point is that

the meaning of the reaction equation is
unchanged if it is multiplied by non-zero
constant.
 The reaction -2 H2O + 2 H2 + O2 =0 is multiplied
by (-1), the same reaction with the decomposition
of H2O, can be viewed from the other side.
1.5.1 Measurement of the quantity of changes
with single reaction in a batch system
Considering the following single reaction

 A A   B B  C C   D D
  A A   B B  C C   D D  0
As per stoichiometric law, it is true that the
change in number of moles are directly related to the
stoichiometric number, and it is fixed thus
n n n n
A  B  C  D
(1.9)
  C D
A B
where n j  n j  n j ,0
nj number of moles j present at any time
nj,0 number of moles j originally present
and can be represented with the common value of
n A n B nC n D
    (1.9.1)
 A  B C D
Where 
is called molar extent of reaction or
reaction coordinate or degree of
advancement of the reaction.
n j  n j ,0

 (1.9.2)
j
The change in mole
n j  n j ,0  
j
 (1.9.3.1)
where
j : (+) for products; (-) for reactants
The total mole is expressed
s s s
 n   n
j j ,0
   j (1.9.3.2)
j 1 j 1 j 1
nT  nT ,0   (1.9.3.3)
s
 
j
   
pr
 
re
j 1 
where  pr and rea are the sum of Stoichiometry

coefficient of products and reactants

Equation (1.9.3.1) expresses the variation of the amount of
species j present during the course of reaction. If j is limiting
reactant (i.e. species present in least amount), the maximum
extent of reaction is found when all j is consumed, i.e. equation
(1.9.3.1) becomes,
0  n j ,0   j  max
Progress Test 1.1 For the system in which the
following reaction occurs
3H 2  CO  CH 4  H 2O
Assume there are initially 2 moles of CH4, 1 mole of H20,
1 mole of CO and 4 moles of H2. Write mole of each
species in terms of extent of reaction 26
Conversion
In a chemical reaction, the composition of the
reaction mixture can be expressed in terms of
one variable, the extent or conversion of the
reaction. The conversion of XA is the number of
moles of A that have reacted per mole of A fed to
the system, or in other word
 Moles of A reacted
A  (1.10.1)
Moles of A fed
For batch system n A,0  n j n A
A   (1.10.2)
n A,0 n A,0
For continuous process 27
FA, 0  FA
XA  (1.10.3)
FA, 0
Since conversion is unitless, it can be used for many variables
like moles, concentrations, etc. As for example, we can see:
For constant density, batch and continuous process
C A, 0  C A
XA  (1.10.4)
C A, 0
Note
• For Irreversible reactions

The maximum value of conversion, XA, is that for

complete conversion, i.e., XA = 1.0

• For Reversible reactions

The maximum value of conversion, XA, is the

equilibrium conversion, i.e., XA = XA,equ.

Progress Test 1.1 For the reaction

aA  bB  cC  dD
Write equilibrium constant in terms of conversion
1.5.1.1 Mole change with conversion

The change in moles can also be obtained using

stoichiometry relationship equation (1)
n j n A

j 
A

n j  j
n A

A

n j  n j ,0  j
( n A  n A, 0 )

A
 
n j  n j ,0  j
n A, 0  A (1.11)

A

S S 1 S
 n   n    jn 
j 1 j j 1 j ,0  j 1 A,0 A
A

1
n n   n 
T T ,0
A A, 0 A

14B
1.5.1.2 Concentration change with conversion
nj
Cj  (1.12)
Vf
j
n n  n 
j j ,0
A A, 0 A
Cj  (1.12.1)
Vf
For constant Volume Reaction System, the change of
concentration at any time V0  V f

j
C j  C j ,0  C A,0  A (1.13)
A
16B
the total concentration
1
C C   C 
T T ,0
A A, 0 A (1.13.1)

Variable Volume Reaction System

V0  V f ;   0
The volume change during reaction can be determined
using equation of state (Ideal gas law)
At time t = 0
Equation of state becomes
P0V 0  nT ,0 RT0 (1.14)
At any given time t, (1.15)
PV f  nT RT
Dividing the two equations, and rearranging, we
obtain
 P0  T  nT
V f  V0    (1.16.1)
 P  T0  nT ,0
The ratio of total moles can be calculated for  A 1
nT n A, 0
 1   A (1.17.1)
nT ,0 nT ,0
and the mole fraction is defined by
nj n j ,0
yj  ; y j ,0 
nT nT ,0
Substituting to equation (1.17.1), we get
nT
 1   y A,0  A (1.17.2)
nT ,0
and then equation (1.16.1) becomes,

 P0  T 
V f  V0   (1   y A,0  A ) (1.16.2)
 P  T0 
If we put a new concept

 
Change in total number of moles when the reaction is completed

Total number of moles fed to the reaction

In symbols
d c b n
    1 A,0  y
 
  (1.19)
 a a a  T ,0
n A,0

For variable of volume at constant temperature

and pressure equation (1.16.2), becomes

V f V0 (1    ) (1.16.3)
A
concentration as a function of conversion in a variable
volume batch system under constant temperature and pressure

j
C j ,0  C A, 0  A
A (1.20)
Cj 
1  
A 19B
1.5.1.3 Mole Fraction as a function of Conversion
nj
y j (1.22.1)
nT
s
nT   nj
j 1
  n A,0  A
1
nT  nT , 0 
 A
j
y j ,0  y A, 0  A
A
yj  (1.22.3)
1
1  y A, 0  A
A
20B
1.5.1.4 Extent of Reaction as a function of Conversion
n j  n j ,0

j
The same way it can be defined for reactant A as

n A  n A, 0


 n A  n A, 0  n  nA
 
A, 0
   A (1.23.1)
A A
Recalling
n  n  n A  n A,0  A
A, 0 A
Substituting this equation into the above equation we get
n A, 0  A
 24B
A
when  A = 1, the extent of reaction as a function of conversion
can be represented as,
  n A, 0  A
1.5.2 Measurement of the quantity of changes
with single reaction in a flow system
 A A  B B  C C  D D
FB,0 FB

FA,0 FA

Input Output

FC,0 FC

FD,0 FD
FIn,0 FIn,0 = FIn
The flow system used to describe stoichiometric relationships for
the reaction

FA FB FC FD

  
     
A B C D

Recalling conversion for the flow system

Fj ,0  Fj
Xj 
Fj ,0
The change in molar flow rate as a function of conversion can also
be obtained following the same method as that of a batch
 j
F j  F j ,0  F A, 0  A
A
The total molar flow rate can be expressed as
S S 1 S
 F   F   F 
j 1 j j 1 j , 0 A j 1 j A, 0 A
27B
F  F  F X
T T ,0 A, 0 A
1.5.2.1 Concentration as a function of
conversion
F j moles / time moles
Cj   
FV , f litre / time litre
i) Constant Volume Reaction System
Fj Fj
Cj  
FV , f FV ,0
j
F j ,0  F A, 0  A
Fj A
Cj  
FV , 0 FV , 0

C C  j C  28B
j j,0  A,0 A
A
 ii) Variable Volume Reaction System

Fj
Cj 
FV , f
j
F j ,0  F A,0  A
A
Cj 
FV , f

At time t = 0 equation of state becomes

P0V 0  nT ,0 RT0
n P0
T ,0

V0 RT0
 n P0
T ,0
CT ,0  
V0 RT0

In flow system Fj
Cj 
FV , f
FT ,0 F
CT ,0  C  T
FV ,0 T F
V ,0
or FT ,0 P
C T ,0   0
FV ,0 RT0

RT0
FV ,0  FT ,0
P0
Similarly
RT
F F
V, f T P
Hence
FV , f FT  P0  T 
   
FV ,0 FT ,0  P  T0 

or
FT  P0  T 
FV , f  FV ,0   
F  P  T 
T ,0   0 
The ratio of total moles can be calculated for  A 1
Then Concentration for variable volume reaction system

j
F j ,0  F 
Fj A A, 0 A
Cj  
FV , f F
V , 0 (1 A )


C  jC 
j,0  A,0 A
C  A
j 1 30B
A
31B
1.6 Measurement of the quantity of
changes with multiple reactions
Consider the following reactions
aA  bB  cC  dD 1 ( 1 ) X1, A
gA  fC  eE  2 ( 2 ) X 2, A
We defined XA,1 as the conversion of A to form C and D in reaction
1
moles of A consumed by reaction 1
X 
1, A moles of A initially
and we define XA,2 as the conversion of A to form E in reaction 2
moles of A consumed by reaction 2
X 
2, A moles of A initially
1.6.1.1 Mole changes with conversion in batch
system
Following the same pattern that was derive in the
single reaction as:

n j  n j ,0  j
n A, 0  A (1.11)

A

S S 1 S
 n   n    jn 
j 1 j j 1 j , 0  j 1 A, 0 A
A
1
n n   n 
T T ,0
A A, 0 A
Mole changes for multiple reactions

R
 i, j
n n n i 1 
j j ,0 A,0 i, A
 i, A

where,  i, j is the Stoichiometric coefficients in ith –

reaction for species j

R
  i
n n n i 1 
T T ,0 A,0 i, A
 i, A
 i  i, pr  i, re


are the sum of stoichiometry coefficient of products and reactants

in ith reaction

35B
Mole fraction can be computed using the
relation

R
  i, j
n j ,0  n A,0 i 1  i, A
nj  i, A
yj  
nT R
 i
nT ,0  n A,0 i 1  i, A
 i, A
1.6.1.2 Concentration change with conversion
R
 i, j
n n i 1 
j ,0 A,0 i, A
n
j  i, A
C  
j V V
f f

a) Constant volume Vf = Vo

R
nj nj  i, j
C   C C i 1 
j j ,0 A,0 i, A
V
f
V
0  i, A
 1 R
CT  CT ,0  C A,0    i, j
 i, A i 1 i
38B
a) Variable volume

The volume change for multiple reactions in a batch

process can be defined

 P0  T  n
 T
V V  
f 0 P  T n
  0  T ,0
 R
nT n A,0  i
 1 i 1  i, A
nT , 0 nT , 0 
i, A
R
 
nT i 1 i
 1  y A,0  i, A
nT , 0  i, A
 R
 

 i 1 i  P0  T 
V f  V0 1  y A,0  i , A  
  P   T 
 i, A   0
 
For constant temp. and pressure

R
 
i  1 i, j
n j ,0  n A,0  i, A
nj  i, A
Cj  
Vf  R
 

 i 1 i 
V0 1  y A,0  i, A 
  i, A 
 
 R
 i, A
C j ,0  C A,0 i  1  i, A
 i, A
Cj 
R
 i 39B
1  y A,0 i 1  A,i
 i, A
1.6.2 Measurement of the quantity of
changes with multiple reactions in flow
system
1.6.2.1 Molar flow changes with conversion
in flow system
In a similar way for batch system we have
R
  i, j
F F F i r 
j j ,0 A,0
 i, A i, A

R
  i

F F F i 1 
T T ,0 A,0
 i, A i, A

The volumetric flow rate change for multiple reactions in

a continuous process can be defined similarly
 R  T  P 
y A,0  i  i, A   0 
1
FV , f  FV ,0 1 
 A i 1   T  P 
 0 
 R
 i, j
F j ,0  F A,0 i  1  i, A
Fj  i, A
Cj  
FV , f  R 
  i 
FV ,0 1  y A,0 i 1  i, A 
R   
 i, j  i, A 
C j ,0  C A,0 i  1  i, A 
 i, A
Cj 
R
 i
1  y A,0 i 1  i, A
 i, A
1.7 modified conversion as a function of
conversion 
 n i (1.30)
i, j T ,0

  i
i, j V (1.31.2)
0

 m i (1.31.3)
i, j T ,0

Taking the relationship   n A, 0  A

We have n
  n j,0   y 
i, j T ,0 j j,0 j (1.32)
Mole change as a function of modified
conversion for a single reaction
Taking mole change equation for single reactio

n j  n j ,0  j
n A, 0  A

A

n n y  j n y 
j T ,0 j,0  T ,0 A,0 A
A
 
 



 



n n

y 
 j y 


 
j T ,0 j,0
 



 A,0 A 


 

 A 

Hence mole change equation fpr single
becomes

 
 
 

n n y  j
 


(1.33)

j T ,0 j,0  A





 A 


Mole change as a function of modified

conversion for multiple reactions
Taking mole change equation for multipl
R
reactions
 i, j
n n n i 1 
j j ,0 A,0 i, A
 i, A
 R

n  n y  n y i 1 i, j 
j T ,0 j,0 T ,0 A,0  i,A
i,A  
 R 


 
 
 

i 1 i, j
 
 
n n y  
 y  

j T ,0 j,0 

A,0 i, A





 


   
 i, A 

r i, j
 
   
 

n n y 



 


j T ,0 j,0 i1
 i,A 





r i
   
   
i,A
n  n 1  
   
   
 
T T ,0 i1


i,A 

 


i,A 

Hence, modified conversion for multiple reaction
 


 
 
 
r i, j (1.34)
n n y 



 


j T ,0 j,0 i1


i,A 
 
  r


i,A y   i, j 


j,0 i1 i, A
y  i,A (1.36)
j r i
1  
i1 i, A
r i, A
P (y    )
RT j,0 i1 i, j
C  
j r i A,i
1  (1.38)
i1
i,A
1.8. Selectivity and Yield B Desired Product
1.8.1. Selectivity
Reactant A
U Undesired Product
1-Selectivity is the ratio between the amounts
of a desired product, B obtained with respect of
the key reactant converted is called selectivity
/ total selectivity

A nB
SB 
 B n A, 0  n A
For a flow system

A FB
SB 
 B F A, 0  F A

If the system is also at constant density, this can also be written

 C
S  A B
B B C C
A,0 A
2-Selectivity Similar definition also given as selectivity
ratio, which is defined as the ratio formation of the desired
product, B divided by the formation of all products

amount of desired product B formed

SB 
amount of all products formed
For pure reactant, the following relations exist

C A, 0  C B  C U  C A

C
SB  B
51B
C  C
B U
3-Selectivity selectivity is also defined on the basis of
reaction rate. This is the ratio of the reaction rate of the
desired product to the unwanted product

r
SB  B
r
D
Differential selectivity
For computational purposes it is often used the differential
selectivity. If there is a single reactant A on which we can base
the conversion and selectivity, then the differential selectivity
can be written as
dC dC
s  B
 - B
B dC  dC dC
B U A
This quantity indicates the direction of the desired product
of species B at a certain reactant concentration of A. This
is sometimes known as local selectivity, while it serve as tools
for choosing local condition of the reaction.

The selectivity / total selectivity

Can be computed using

CA
dC  -  s dC
B B A
CA,0
integration gives

CA
C  -  s dC
B B A
CA,0

Calling the definition of Selectivity

CB -1 CA
S    s dC
B CA,0 - CA CA,0 - CA C B A
A,0
1.8.2Yield

It refers to the amount of a specific product formed in a given

reaction process per mole of entering reactant and is defined as

desired product j formed

 
j reac tan t fed
Throughput (capacity) Feed Rate
This is the volumetric or mass flow rate through the reactor system

m
C C
t

Where mj is the mass flow rate of species j
Load (Intensity)
This is the volumetric or mass flow rate per unit reactor
volume or catalyst mass.

m m
I C  C 1  C 1
V t V t W