CHE411 Fall 2010-Chemical Reaction Engineeirng-Ahmed A Abdala

Chemical Reaction Engineering
CHEG 411
Fall 2010
Ahmed Abdala
Chemical Engineering program
The Petroleum Institute
Abu Dhabi, UAE
CHEG411: Chemical Reaction Engineering
Introduction
Chemical Plants: The Refinery EXAample

A
refinery converts crude oil into valuable petroleum

products such as gasoline, kerosene, diesel, aviation
fuel, .etc
Catalyst/
H2
Crude
Oil
Cracking,
reforming,
Distillation
LPG
Blending
Petrochemical
Feedstock,
Coke, Sulfur
Gasoline
Kerosine
Diesel
$$$
Processes in Chemical Plants
The aim of any chemical plant is to produce valuable

products form available raw materials
A Chemical plant involves chemical and physical processes
A chemical process is a process that involves chemical

reactions
A physical process includes separation, miXAing, or

blending of different materials
Reactants
Catalyst
Raw
Materials
Physical
Processes
Chemical
Processes
Products
products
Physical
Processes
products
$$$
Course Overview
This
course focuses in the chemical processes part

where chemical reactions take place
It
focuses mainly on the design of the vessels where

these reactions occur, i.e. the chemical reactors
We
do not, however, focus on the mechanical design of

the reactor
Course Objectives
The aim of the course is to answer the following

questions:
1. Will a certain reaction take place under certain conditions
(temperature, pressure and catalyst)?
2. If the answer for question 1 is yes, how fast will the reaction
proceed?
3. What type of reactor(s) should we use?
4. What is the size of the reactor(s) and, if more than one reactor
is to be used, how those reactors should be arranged?
Approach
1.
To answer the first question we need information

about thermodynamic functions for the products and
reactants at the reaction conditions
2.
To answer the second question we need to have the

necessary information to determine the reaction rate
equation
3.
Chemical reaction equilibria [thermodynamics]
Kinetics
To answer the third and fourth questions we need

information about the reaction rate and
reactants/products flow rates
Kinetics, transport (fluid, heat and mass)
Chemical Reaction Equilibria
Consider the gas phase reaction:

aA
cC + d D
bB
From the Law of Mass Action:
C +
aC a D a
K =
a A aB a
a
(1)
ai is activity of species i
fi
=
ai
=
i Pi
0
fi
The true (dimensionless) equilibrium constant K is:

c
fi is the fugacity of species i

fi0 is the fugacity of species i at the standard state
For gases, standard state is 1 atm
i is the activity coefficient
(2)
Chemical Reaction Equilibria
The true equilibrium constant, K

aC a a D a
=
=
K
a A aB a
c
C a Da
A Ba
c
PC a PD a
=
b
PA PB a
activity
pressure
equilibrium constant equilibrium const ant
d c b
+ 1
atm s a a
The pressure equilibrium constant, KP

KP
PC a PD a
=
b
PA PB a
(4 )
Pi is the partial pressure of species i, Pi=Ci RT
The concentration equilibrium constant, KC

c
KC
d c b
+ 1
atm s a a
KP
K=1 for ideal gas

c
C C a C Da
=
b
C A C Ba
(5)
For ideal gases:

K P = K C ( RT
; =
(6 )
(3)
Equilibrium Constant versus Temperature

KP is
a function of temperature only

d ln K P H Rx ,T
=
dT
RT 2
van' t Hoff ' s equation
d ln K P H Rx ,T R + C P (T T R )
=
dT
RT 2
(8)
Integrating
ln P ,T
=
K P ,T1
(7 )
H Rx
1
,T R C P (T T R ) 1
R
T R T
C P
R
T
ln
TR
If CP is assumed to be constant (CP=0), then

K P ,T
H Rx ,T R
K P ,T R exp
R
1
1
T R T
( 10 )
(9)
Equilibrium Constant versus Temperature

For
eXAothermic Reactions:
As T increases, the equilibrium

shifts to the left. i.e. both K and
XAe decreases
exothermic reactions
For
endothermic Reactions:
As T increases, the equilibrium

shifts to the right. i.e. both K
and XAe increases
endothermic reactions
Equilibrium Constant and Free Energy

The
equilibrium constant at temperature T can be

calculated from the change in the Gibbs free energy as
follow:
0
RT ln K ( T ) =
G Rx
(11)
(T )
where
GRx0 = cGC0 + dGD0 - aGA0 - bGB0
(12)
is related to the reaction enthalpy and entropy as

follow:
G =H T S
(13)
Example: Calculation of Equilibrium Constant
Acetic acid is esterified in the liquid phase with ethanol

at 100 C and atmospheric pressure to produce ethyl
acetate and water according to the reaction:
CH 3 COOH + C 2 H 5 OH CH 3 COOC 2 H 5 + H 2 O
For this reaction G0298 = -4.65 kJ/mol and H0298 =

3.64 kJ/mol
Estimate:
1.
The equilibrium constant for the reaction at 100 C. For this

reaction G0298 =-4.65 kJ and H0298 = 3.64 kJ
2.
The mole fraction of the reaction components at equilibrium,

if initially there is one mole of each of acetic acid and ethanol.
Solution: Equilibrium Constant

Calculation
K298
of the equilibrium constant:
K ( 298 )
ln =
0
G Rx
( 298 )
4650
=
= 1.876
Rx 298
8.314 x 298.5
=
K ( 298 ) exp
=
( 1.876 ) 6.527
K373
Assume constant Cp between 298 and 373 K

K P (T
H Rx (T R ) 1 1
K P (T 1 ) exp

R
T 1 T
0
K ( 373 ) H 298
1 3640 1
1
1
ln
0.295
=
=
=
R 298 373 8.314 298 373

K ( 298 )
=
K ( 373 ) K=
( 298 ) exp (0.295 ) 8.77
Solution: Equilibrium Composition

CH 3 COOH + C 2 H 5 OH CH 3 COOC 2 H 5 + H 2 O
aCH 3COOC 2 H 5 aH 2O
K =
aCH 3COOH aC 2 H 5 OH
The
activity coefficient () is assumed to be 1

K=
K=
C
Calculation
C CH 3COOH C C 2 H 5 OH
of equilibrium composition
C CH 3COOC 2 H 5 C H 2O
=
KC
=
C CH 3COOH C C 2 H 5 OH
X
=
8.77
(1 X
C CH 3COOC 2 H 5 C H 2O
X2
=
2
(1 X )
(1 X
=
X 0.75
CH3COOH
C2H5OH
CH3COOC2H5
Initial, Ni0
Change, dNi
-XA
-XA
XA
XA
Equilibrium,
Nie
1-XA
1-XA
XA
XA
(1-XA)/2
(1-XA)/2
(XA)/2
(XA)/2
(1-0.75)/2
= 12.5%
(0.75)/2
= 37.5%
(0.75)/2 =
37.5%
Mole fraction
H 2O
(1-0.75)/2
= 12.5%
EXample 2: Gas phase
The water-gas shift reaction:
CO 2 +H 2
CO + H 2 O
is carried out under different conditions. Calculate the equilibrium

conversion of steam following cases:
a)
b)
c)
d)
e)
The reactants consist of 1 mol of H2O vapors and 1 mol of CO. the
temperature is 1100 K and the pressure is 1 bar
Same as in a but the total pressure is 10 bar
The reactants consist of 1 mol of H2O vapors, 1 mol of CO, and 1
mol of CO2. the temperature is 1100 K and the pressure is 1 bar
The equilibrium constant (K) for this reaction at 1100 K is 1.

Assume ideal gas.
Chapter 2:
Conversion and Reactor Sizing
Batch Reactor Design Equation
The reaction
Can be rewritten as:
aA + bB cC + dD
c
d
A+b B C + D
a
a
a
Conversion, Xi, is used to quantify how far the reaction

proceeds in the right direction
Conversion, XA, is the number of moles of A that have reacted
per mole of A fed to the system
XA =
Moles of A reacted
Moles of A fed
The maximum conversion
For irreversible reaction is 1

For reversible reaction is the equilibrium conversion, Xe
Assume number of moles of A initially fed to the reactor is NA0
Number of moles of A reacted after a time t

Mole of A
reacted = Mole of A Mole of A reacted

fed Moles of A Fed
( consumed )
=N A0 X
Number of moles of A that remain in the

reactor after a time t (NA):
Mole of A
in reactor
=
at time t
Mole of A
initially fed Mole of Athat
have been consumed
to reactor at
by chemical reaction
=
t
0
N A0 N A0 X
N A =
NA =
N A0 ( 1 X

For
ideal batch reactor
No spatial variations in concentration nor reaction rate
The
mole Balance for species A:

dN A
= r AV
dt
Since
N A =
N A0 ( 1 X
dN A
= r AV
dt
N A0
dX
= r A V
dt
t = N A0
dX
r A V
dN A
dX
0 N A0
=
dt
dt
dX
N A0 = r AV
dt
Design equation
Design equation
( differential form )
( Integral )
Constant Volume Batch Reactor

For
constant volume batch reactor V=V0

dN A
=
r AV =
r AV 0
dt
d ( N A / V0 )
dt
=
rA
dC A
= rA
dt
The
Design Equation becomes:
The differential form

N A0
dX
=
rA V
dt
C A0
dX
=
rA
dt
The integral form

=
t N A0
X dX
dX
=
t C A0
0 r
rA V
A
Conversion for Flow Reactors

For
flow reactors
Mole of A reacted
Moles of A fed
Moles of A fed Mole of A reacted Mole of A reacted
X
=
tim e
Moles of A fed
time
X =
FA0
Molar rate at
Molar Flow rate
Molar flow rate
at which A is which A is consumed =
at which A
fed to the system within the system leaves the system
FA0
FA0 X
=
FA FA0 ( 1 X
FA
Molar Flow Rate for Ideal Gas System

FA = C A0 0
For
ideal gas system

C
=
A0
PA0
=
RT0
FA0 C=
=
A0 0
y A0 P0
RT0
PA0
y P
=
0 0 A0 0
RT0
RT0
ideal gas system
ideal gas system
Design Equation for CSTR
For the reaction:
c
d
A+b B C + D
a
a
a
The volume of batch reactor, V
With
The reactor volume becomes
=
FA FA0 ( 1 X
V =
FA0
( FA0 FA0 X )
r A
V =
FA0 X
( r A )exit
V =
FA0
FA
r A
Tubular Flow Reactor PFR
The differential Equation for PFR:

-dF
r A = A
dV
FA =
FA0 ( 1 X
FA0 dX
dFA =
But
Hence, the differential Equation becomes

FA0
r A =
dX
dV
The integral Equation for PFR:

Fj
dFj
Fj 0
rj
V =
X dx
-FA0 dx
=
V = FA0
0
0 r
rA
A
X
Volume of Plug Flow Reactor

The
volume of PFR can be obtained by plotting The

parameter FA0/(-rA) versus conversion X
The
volume correspond to the area under curve
Dashed Area
The
area of equivalent CSTR

reactor is the area under
curve plus the dotted area
CSTR volume= the area of
the rectangle
PFR volume = area under curve (dashed area)
Packed-bed Reactor (PBR)
The differential form of the design Equation for PBR:

FA =
FA0 ( 1 X
-dF
r A' = A
dW
But
Hence, the differential Equation becomes
dFA =
FA0 dX
r A' =
FA0
dX
dW
The integral Equation for PBR:

W =
=
W
Fj
dFj
Fj 0
r A'
X -F dx
X dx
A0
=
F
A0 0
0 rA'
rA'
CSTRs in Series
Consider two CSTRs connected in series:
For the first reactor

V1 =
Mole Balance around the second

reactor
In
FA1
FA0 ( 1 X
Out
FA 2
+
+
Generation
V 2 rA 2
FA0 ( 1 X 2 ) +V 2 r A 2
V2 =
FA0 X 1
( r A )1
FA0 ( X 2 X 1 )
( r A ) 2
The volume of 2 CSTRs

connected in series is smaller
than the volume of one CSTR
to achieve the same conversion
=
0
=
0
=
0
CSTRs in Series
For n CSTRs connected in

series we have:
=
Vn
As the number of CSTRs

increases:
FA0
(X X )
( r A )1 n n 1
The volume of the CSTRs

becomes equivalent to that of
PFR to achieve the same
conversion
PFR can be modeled with a

large number of CSTRs
connected in series
PFRs in Series
For two PFRs in series we have:
The volume of the first reactor

V1 = FA0
X1
The volume of the second reactor

V2 = FA0
X2
X1
dx
rA
The total volume of the two reactors

=
V
FA0
1 + V2
X1
dx
rA
X 2 dx
X 2 dx
dx
+ FA0 = FA0
X1 r
0
rA
rA
A
The volume of n PFRs in

series is the same as the
volume of one PFR to achieve
the same conversion
Combination of CSTRs and PFRs in Series

CSTRs
and PFRs can be connected in series
The
arrangement of the reactors in this case is of high

importance
For
the case of two CSTRs and one PFR:
Option 1: CSTR-CSTR-PFR
FA0, X=0
FA1, X1
FA2, X2
Option 2: CSTR-PFR-CSTR
FA2, X2
FA0, X=0
FA1, X1
Option 3: PFR-CSTR-C,STR
FA0, X=0
FA1, X1
FA3, X3
FA2, X2
FA3, X3
V1
FA0, X=0
V3
V2
X1
FA0/(-rA)
FA0/(-rA)
Combination of CSTRs and PFRs in Series
X1
V1
X1
X1
FA1, X1
FA2, X2
FA0, X=0
X1
X
FA1, X1
FA3, X3
V3
V2
X1
FA2, X2
FA3, X3
Space Time and Space Velocity
Space time is the time necessary to

process one reactor volume of fluid based
on the entrance conditions
V
v0
The space time is equal to the mean

residence time, tm
Space Velocity (SV) is the reciprocal of
the space time
v0 1
SV
Reactor
Mean Residence
Time
Batch
1 5 min - 20 h
CSTR
1 0 min- 4 h
Tubular
0. 5 s - 1 h
Space Velocity
Space velocity commonly reported as either:
Liquid Hourly Space Velocity, LHSV

LHSV
v0
liquid @ 60F
Gas Hourly Space Velocity, GHSV
LHSV
v0
Gas @ STP

CHEG 411
Fall 2010
Chapter 3: Rate Laws and Stoichiometry
Ahmed Abdala
Abu Dhabi, UAE
Rate Laws and Stoichiometry
Chapter 3
Types of Reactions
Reaction can be classified according to:

Phases
Homogeneous
Involves one
phase
Heterogeneous
Involves more
than one phase
Interfacial
Occurs on the
interface of two
or more phases
Direction
Irreversible
Reversible
Molecularity
Unimolecular
Bimolecular
Termolecular
The Rate of Reaction and the Rate Law

The
rate of reaction is usually reported as the rate of

disappearance of the limiting species A, -rA
-rA
is function of temperature and concentration

k (T ) fn (C A ,C B , ..... )
r A =
k(T) is the rate constant and is a function of temperature
The
rate equation is an algebraic equation that relates rA

to the species concentration
For
the reaction:
aA + bB cC + dD
The rate constant for different species are related as follow:

rA rb rC rD ri
=
= = =
a
b
c
d i
k A k b kC k D
= = = =
a
b
c
d
ki
vi
Reaction Rate Equation: Power Law Models

Zero
Order
mole
=
rA k ; =
[k ]
volume time
1
rA k C A=
; [k ]
First =
Time
Order
Volume
Second =
rA k C =
; [k ]
Mole Time
Order
2
A
1 n
n-th
Order
Mole
; [k ]
=
rA k C =
V
olume
n
A
Time
Reaction Rate Constant: k

k
is the specific reaction rate (constant) and is given by the

Arrhenius Equation: k = A e
E
RT
E is the activation energy, kcal/mol
R is the gas constant
T is the Absolute temperature
Products
Reaction coordinates
Ln(k)
Low E
Hr
Reactants
A is the frequency factor (same units as k)
Potential Energy
Slope=-E/R
High E
1/T
Reaction Rate Constant: In Class Exercise

The
rule of thumb that the rate of reaction doubles for a

10 C increase in temperature occurs only at a specific
temperature for a given activation energy.
Develop a relationship between the temperature and activation

energy for which the rule of thumb holds.
Determine the activation energy and the frequency factor from the
following data:
k (min-1)
T ( C)
0.001
0.050
0.500
2.00
100
200
300
Power Law Model and Elementary Laws

The
dependence of reaction rate on concentration is

usually determined by experimental observation
It can also be postulated from theory
The rate law is the product of concentration of the
individual reacting species each of which is raised to a
power :
r =
k C C
A
Where
is the reaction order with respect to species A
is the reaction order with respect to species A
n= + is the overall reaction order
The
dimension of the rate constant k will vary depending on

the reaction order
(Concentration )
{k }
1 n
Time
Elementary Reactions
Elementary
reaction are reactions that involves a single step
The
stoichiometric coefficients in elementary reaction are

identical to the powers of the Rate Law
The
equation can be written based on the stoichiometric

equation
aA + bB cC + dD
For the reaction:
The rate equation is:

r A =
k AC AaC Bb
Pseudo Elementary Reactions

The
powers of the rate law for some reactions are identical

to the stoichiometric coefficients but it involves more than
one step
These reactions are nonelementary but follow elementary rate

law
Example is the oxidation of nitric oxide:

2 NO + O 2 2 NO
which has the rate equation

2
r NO =
k NO C NO
C O2
but the mechanism involves more than one step
Nonelementary Reactions
Many reactions does not follow simple rate laws:
Reactions with non-integer reaction order

CO + Cl 2 COCl 2 ;
rCO =
kCO CCO CCl2 2
Reaction with rate equation that cannot be separated into temperature

dependent term and concentration dependent term:
2 N 2 O 2 N 2 + O2 ;
k N 2O C N 2O
rN 2O =
1 + k' CO2
The overall reaction order cannot be stated

At the beginning of the reaction:
low concentration of O2,

the reaction is apparent first order
1st order w.r.t. N2O and zero order w.r.t. O2
At the end of reaction:
high concentration of O2 and low concentration of N2O

The reaction has an apparent order of 0
1st order w.r.t. N2O and order of -1 w.r.t. O2
Heterogeneous Reaction Rate

For
catalyzed reactions the reaction rate is expressed as

the rate of disappearance of species A per unit mass of
moles
the catalyst:
r
'
A
catalyst mass time
For
gas catalyzed reaction the rate law is usually written in

terms of partial pressure
Catalyst
C 6 H 5 CH 3 + H 2
C 6 H 6 + CH 4 ;
rC' 6 H 5 CH 3 =
Where
kPH 2 PT
1 + K B PB + K T PT
k is the rate constant, [mole/(kg cat.s.kPa2)]

KB, KT are the adsorption constant, [kPa-1]
-rA and
-rA are related through the bulk density b

r = ( r )
A
'
A
Reversible Reactions
For
the reversible reaction:

kf
cC + dD
aA + bB
kr
The equilibrium constant, KC

c
d
C Ce
C De
kA
=
=
KC
a
b
C Ae
C Be
k A
Assuming
elementary reaction
k AC AaC Bb
The rate of disappearance of A: r A ,forward =
The rate of formation of A: r A ,reverse = k AC Cc C Dd
The overall rate of formation of A,
=
r A r A ,reverse r A ,forward
= k AC Cc C Dd k AC AaC Bb
The overall rate of disappearance of A:

=
r A k AC AaC Bb k AC Cc C Dd
a b k A c d
c
d
C
k
C CC D
=
r A k AC AaC Bb k AC =
C
D
A C AC B
k
A
a b C Cc C Dd
= k A C AC B
KC
Similarly
a b C Cc C Dd
=
r B k B C AC B
KC
a b C Cc C Dd
=
rC k C C AC B
KC
a b C Cc C Dd
r D = k D C AC B
KC
Remember:
r A
=
a
kA
=
a
r B rC r D
= =
b
c
d
k B k C k D k A k B k C k D
= =
; = = =
b
c
d
a
b
c
d
In Class Exercise:
Write
the rate law for the following reactions

assuming each reaction follows an elementary
rate law:
C2 H6
C2 H4 + H2
C2 H4 + 12 O2
( CH )
3 3
CH2 CH2
O
C H + 2CH COCH
COOC ( CH3 ) 3
2 6
3
3
n C4 H10
i C4 H10
CH COOC H + C H OH
C4 H9 OH + CH3 COOC2 H5
3
4 9
2 5
Stoichiometry
cC + dD
aA + bB
For the reaction
The relative rates of reaction are related through the

stoichiometric coefficients as follow
r A r B rC r D
=
= =
a
b
c
d
We can rewrite the reaction as follow:

A+
b
c
d
B
C
+
D
a
a
a
Everything is put on a basis of per mole of A
We can now setup a stoichiometric table for different reaction

systems
Stoichiometric Table: Batch System
For the reaction
Which can be written As

A+
NA0
cC + dD
aA + bB
NB0
NC0
b
c C + d D
B
a
a
a
ND0
NIO
The Stoichiometric is as follow:

Species
Initial Moles
Ni0
Change
Ni
NA0
- (NA0X)
NB0
- b/a (NA0X)
NC0
c/a (NA0X)
ND0
d/a (NA0X)
I, inert
NI0
Totals
NT0
Remaining moles
Ni
NA
=
N A N A0 N A0 X
b
=
N B N B 0 N A0 X
a
c
=
N C N C 0 + N A0 X
a
d
=
N D N D 0 + N A0 X
a
t=t
NC
NI
N i = N i0
NB
ND
NA0X(d/a+ c/a- b/a- 1 ) N T= N T 0 + + 1 N A0 X

a a a
t=0
Stoichiometric Table
For
the reaction
cC + dD
aA + bB
Moles reacted of A
NA = NA0X
Moles reacted of species i

Ni= (i/A)NA0X
Total number of moles, NT
Where ,
=
N T N T 0 + N A0 X
d c b
+ 1
a a a
Concentration Equations for Batch System

Ci =
N A N A0 N A0 X
C
=
=
A
V
V
NB
=
=
C
B
V
N B0
b
N X
a A0
V
NA
V
=
C
C
NC
=
V
c
N X
a A0
V
NC 0 +
=
C
D
ND
=
V
N D0 +
d
N X
a A0
V
N i0
C i0
y i0
Let =
i
= =
N A0
C A0
y A0
N A0 B i X
A
Ci =
V
N A N A0 N A0 X
C
=
=
A
V
V
N A0 B X
NB
a
C
=
=
B
V
V
N A0 C + X
NC
a
C
=
=
C
V
V
N A0 D + X
ND
a
C
=
=
D
V
V
Concentration Equations for Constant Volume Batch

System
For constant volume system, V=V0
Liquid phase reaction

Gas phase reaction with =0
The concentration of species i becomes, Ci=Ni/V0

C
=
A
N A N A0 ( 1 X )
=
= C A0 ( 1 X
V0
V
N A0 B X
NB
a
C
=
=
= C A0
B
V0
V0
B a X
N A0 C + X
NC
a
C
=
=
= C A0
C
V0
V0
C + a X
N A0 D + X
ND
a
C
=
=
= C A0
D
V0
V0
D + a X
Now the rate equation can be reported in terms of CA0

and X
Stoichiometric Table: Flow Systems
For the reaction:

A+
Species
FA0
FB0
FC0
FD0
FI0
b
c C + d D
B
a
a
a
Feed rate to reactor
Leaving
Entering
A +
Change within reactor
a
c
d
B C + D
b
a
a
FA
FB
FC
FD
FI
Effluent rate from reactor
FA0
FA0 X
FB0 = FA0 B
FC0 = FA0 C
FD0 = FA0 D
b
FA0 X
a
c
+ FA0 X
a
d
+ FA0 X
a
FI0 = FA0 I
FI = FA0 I
FT=
FA0 (1 + B + C + D + I )
0
d c b
FA0 X + 1 =
FA0 X
a a a
d c b
FT = FT 0 + FA0 X + 1 = FT 0 + FA0 X
a a a
Total
=
FA FA0 (1 X )
b
=
FB FA0 B X
a
c
FC FA0 C + X
=
a
d
FD FA0 D + X
=
a
Stoichiometric Table: Flow Systems
For the reaction:
A+
( ( ) )
b
c
d
B
C
D
+
a
a
a
i
Fi FA0 i a X
C=
=
i
C ( ( i ) X ) ;
( ( a) X ) =
a
FA0
Ci =
i i
Species
Feed rate to
reactor
FA0
FB0 = FA0 B
FC0 = FA0 C
FD0 = FA0 D
FI0 = FA0 I
Total
A0
Change
FA0 X
constant
=
0 =
Effluent
Concentration
Effluent rate
from reactor
=
FA FA0 (1 X )
CA =
b
b
FB FA0 B X C=
FA0 X=
a B
a
c
c
FC FA0 C + X C=
FA0 X =
a C
a
d
d
FD FA0 D + X C=
FA0 X =
a D
a
FT 0 FA0 1 + i FA0 X
=
i
FI = FA0 I
F=
FT 0 + FA0 X
T
C=
I
FA FA0 (1 x )
FB
=
FC
=
FD
=
FI
=
Effluent
Conc, v=constant
C A C A0 (1 x )
=
FA0 B ( b a ) X
CB C A0 B ( b a ) X
=
FA0 C + ( c a ) X
=
CC C A0 C + ( c a ) X
FA0 D + ( d a ) X
=
CD C A0 D + ( d a ) X
FA0 I
CI = C A0 I
In Class Exercise
For the following liquid-phase elementary reaction:
2 A + B
2C
Write the rate law in terms of conversion, XA
Species
Feed rate to
reactor
Change
A
B
C
I
Total
Effluent rate
from reactor
Effluent
Concentration
Effluent
Conc, v=constant
Variable Volume Batch Reactor

For
gas- phase reaction in a batch reactor where

the volume of reactor is not constant
The concentration of individual component can be
determined by expressing the volume at any time
t as follow:
PV = ZN RT
At
time t=0 this equation becomes

P0V0 = Z 0NT 0RT0
The
reaction volume at time t, V, as function of

the initial volume, V0, becomes
P0
V = V0
P
T Z NT

T0 Z 0 NT 0
Variable Volume Batch Reactor

But
N
=
NT 0 + N A0 X
T
Then
NT
N
1 + A0 X =
1 + y A0 X =
1+ X
=
NT 0
NT 0
=
y=
A0
Where
NT 0 X
At X=1, NT=NTf and becomes

=
=
N T NT 0
N Tf NT 0
NT 0
Chnage in total numbers of Moles at complete conversion
total moles fed
And the volume at time t becomes (assuming Z Z0)

P0
T
=
V V0 (1 + X )
T0
P
Variable Volumetric Flow Rate Flow Reactors

The
total concentration at any point of the

reactor, CT is given by
FT
=
C=
T
The
P
ZRT
concentration at the entrance of the

reactor, CT0
F
P
C=
T0
T0
=
Z 0 RT0
The
volumetric flow rate at some point along the

reactor, v as function of the volumetric flow
rate at the entrance, v0
FT P0 T

F
T 0 P T0
= 0
Concentrations in Terms Other Than Conversion

The
concentration of species j at any point of

the reactor, Cj is given by
Fj
C=
=
j
Fj
FT P0 T
F
P
T
0
T0
The
concentration at the entrance of the

reactor, CT0
FT 0 Fj
0 FT
P T0

P T
0
Fj
C j = CT 0
F
T
P T0

P T
0
Cj =
Variable Volumetric Flow Rate Reactors
To express the concentration as function of conversion for

variable v reactors
We have
Then
FT
= 0
FT 0
P0
FT 0 + FA0 X P0
FT 0
P
T

T0
F=
FT 0 + FA0 X
T
and
T
P0
=
+
1
y
X
(
)
0
A0
T
P
0
T

T0
P0 T
== 0 (1 + X )
P T0
The concentration of species j, Cj becomes

Fj
C=
=
j
C A0 j + j X P
=
P0
1
+
X
P0 T
(
)
0 (1 + X )
P T0
FA0 j + j X
T0
Summary
In-Class Exercise (Fogler P3-13)
The gas-phase reaction
1
2
N2 + 23 H2
NH3
is to be carried out isothermally. The molar feed is 50% H2,

and 5O% N2, at a pressure of 16.4 atm and 227 K.
a) Construct a complete stoichiometric table.
b) What are CA0, , and ?. Calculate the concentrations of
ammonia and hydrogen when the conversion of H2 is 60%.
c) Suppose by chance the reaction is elementary with kN2 =
40 dm3/mol/s. Write the rate of reaction solely as a
function of conversion for:
i. A flow system
ii. A constant volume batch system
Chapter 3 Review
Rate Laws and Stoichiometry
Reaction Rate Equation

-rA
is function of temperature and concentration

k (T ) fn (C A ,C B , ..... )
r A =
The
rate constant for different species are related as

aA + bB cC + dD
follow:
Rate
constant
E
k = A exp
RT
Units
k A k b kC k D
= = = =
a
b
c
d
E 1
ln
k
ln
A
;
=
RT
1 n
mole
[ k ] =
volume
ki
vi
Low E
Ln(k)
rA rb rC rD ri
=
= = =
a
b
c
d i
Slope=-E/R
time
High E
1/T
Rate Law
For
the reaction:
The
power-law rate equation:
aA + bB cC + dD
r A =
k AC AC B
If
the reaction is elementary or pseudo-elementary

r A =
k AC AaC Bb
Non-power-law
forms
2 N 2 O 2 N 2 + O2 ;
k N 2O C N 2O
rN 2O =
1 + k' CO2
Heterogeneous Reaction Rate

moles
catalyst mass time
r A'
Gas
catalyzed reaction the rate law is usually written in

terms of partial pressure
Catalyst
C 6 H 5 CH 3 + H 2
C 6 H 6 + CH 4 ;
Where
rC' 6 H 5 CH 3 =
kPH 2 PT
1 + K B PB + K T PT
k is the rate constant

KB, KT are the adsorption constant, [kPa-1]
-rA and
-rA are related through the bulk density b

(
r A = b r A'
k A = b k 'A
For
the reversible reaction:

kf
cC + dD
aA + bB
kr
The equilibrium constant, KC

c
d
C Ce
C De
kA
=
=
KC
a
b
C Ae
C Be
k A
Assuming
elementary reaction
k AC AaC Bb
The rate of disappearance of A: r A ,forward =
The rate of formation of A: r A ,reverse = k AC Cc C Dd
The overall rate of formation of A,
=
r A r A ,reverse r A ,forward
= k AC Cc C Dd k AC AaC Bb
The overall rate of disappearance of A:

=
r A k AC AaC Bb k AC Cc C Dd
Stoichiometry
cC + dD
aA + bB
For the reaction
We can rewrite the reaction as follow:

A+
b
c
d
B
C
+
D
a
a
a
Everything is put on a basis of per mole of A
Stoichiometric
i
N i N A0 i + X
=
a
C i C A0 + X
=
a
liquid phase
Gas Phase
Fi FA0 i + X
=
a
F
V =V 0 T
FT 0
P0
T Z
T Z
0 0
F P
C i C A0 + X T 0
=
a FT P0
FT
FT 0
= 0
P0
T0 Z 0

T Z
T Z
T Z
0 0
Stoichiometric Table
cC + dD
aA + bB
d c b
= + 1
a a a
F=
FT 0 + FA0 X
T
N
=
NT 0 + N A0 X
T
F
FT
1 + A0 X =
1 + y A0 X =
1+ X
=
FT 0
FT 0
N
NT
1 + A0 X =
1 + y A0 X =
1+ X
=
NT 0
NT 0

CHEG 411
Fall 2010
Chapter 4
Ahmed Abdala
Abu Dhabi, UAE
Isothermal Reactor Design
Chapter 4
End
Start
General mole balance equation
V
dN
FA0 FA + rA dV = A
dt
Chapter 1
Mole Balance to specific

reactor design equations
in terms of conversion
is
rA=f(X)
given?
Evaluate the design equations

numerically or analytically to
Estimate the reactor volume
the reaction time, or conversion
Chapter 2
Yes
Chapter 2
Obtain rA=f(X)
No
Using stoichiometry, express

concentration as function of X
Chapter 3
Chapter 3
Elementary reaction
Yes
Determine the rate law in

terms of concentration
Chapter 4
Liquid phase
or gas phase
with P=P0
Combine mole balance, rate law

and stoichiometry and transport
law, and P terms in an ODE solver
No
Chapter 4
Algorithm for Reaction Design

The
1.
solution of reactor design involve the following steps:

Mole balance
2.
Based on the limiting species
Rate law
Based on reaction type, mechanism, or experimental data
3.
Stoichiometry
4.
Combine the mole balance, the rate equation, and the

Stoichiometry relations
5.
Evaluate to get reactor volume, reaction time, or

conversion
Analytical, numerically, graphically, or using

software
Evaluate
Combine
Stoichiometry
Rate Law
Mole Balance
French Menu
French Menu
Scale UP of Liquid Phase Batch Reactor Data to the

Design of a CSTR
To design of a full-scale plant:

1.
Microplant, laboratory-bench-scale unit is used to collect data about

the process
2.
A pilot-plant maybe designed based on the laboratory data
3.
The full-plant is designed by scaling up the pilot plant data
Step 2 can be surpassed and a full scale plant may be

designed based on laboratory data. However, this
requires thorough understanding and careful analysis of
the laboratory data
Liquid Phase-Batch Operation

For
a batch system, the mole balance equation is:

1 dN A
V dt
For
= rA
a liquid phase reaction, the volume is constant and the

mole balance equation can be written in terms of
concentration as follow:
1 dN A
=
V dt
1 dN A
=
V0 dt
d ( N A V0 )
=
dt
dC A
dt
dC A
= rA
dt
This
form will be used to analyze the reaction rate data
Batch Operation
For
batch system, the time calculated to achieve

certain conversion is the reaction time
The
total time required to process one batch, total

cycle time, tt
Total Cycle time = Filling time + Heat time + Reaction time + Cleaning time
tc
=
tf
+
te
+
tR
+
tc
The
reaction time is usually optimized with the

processing time to produce the maximum number of
batches per day
Design of CSTR
The
volume of CSTR reactor to achieve conversion X

=
V
And
FA0 X
0 C A0 X
=
rA
( rA )exit
the space time,

=
For
V C A0 X
=
0
rA
a first order liquid phase reaction:

-rA = k CA=k CA0(1-X)
X
=
k (1 X )
CA =
C A0
1 +k
k
X=
1 +k
Design of CSTR
Damkohler number, Da, is the ratio of the rate of

reaction at entrance to the entering flow rate of A
=
Da
rA0 V
Reatcion rate
=
FA0
Convection rate
rA0 V kC A0 V
= = k
FA0
C A0 0
For a first order reaction:

The conversion is related to Da as follow
=
Da
X
=
1
0.9
At high Da, Da 10, X is greater

than 90%
At low Da, Da 0.1, X is less
than 10%
For a second order reaction:

rA0 V kC V
=
Da = = kC A0
FA0
C A0 0
2
A0
0.8
0.7
first order reaction
0.6
X
k
Da
=
1 + k 1 + Da
0.5
0.4
0.3
0.2
0.1
0
10
20
Da
30
CSTR in Series: First Order Reactions
For two CSTRs in series:

C A1
C A0
C A1
=
and C A 2
1 + 1 k1
1 + 2 k2
C A1
=
1 + 2 k2
C A0
=
+
k
1
1
( 1 1 )( + 2 k 2 )
CA2
X2
-rA1
V1
-rA2
V2
C A0
(1 + k )
For n reactors connected in series

=
C An
CA1
X1
If both reactors are of equal size

( 1 =1 = ) and operates at same
temperature (k1 =k2=k)
=
CA2
CA0
C A0
C A0
=
( 1 + k )n ( 1 + Da )n
If the final conversion based on reactor n is X

C An= C A0 (1 X=
)
C A0
(1 + Da )
1
1
X=
1
=
1
n
n
(1 + Da )
(1 + k )
CSTR in Series: First Order Reactions
For n CSTRs connected in series

1
1
X=
1
=
1
n
n
(1 + Da )
(1 + k )
The rate of disappearance of species A the nth reactor

is
r=
= k
kC An
A
C A0
(1 + k )
Da = 1
Da = 0.5
0.9
0.8
0.7
Da = 0.1
0.6
0.5
0.4
0.3
0.2
0.1
0
0
7
n
9 10 11 12 13 14
CSTR in Parallel
For n equal size CSTRs connected in

parallel, operates at the same
temperature and the feed is distributed
equally among them
FA01
-rA1
V1
X=
X=
................
= X=
X
1
2
n
FA02
The rate in each reactor is

rA1 =
rA 2 =
................ =
rAn =
rA
The volume of each reactor

And the total volume V,
=
V
X1
FA0
V FA0 X i
=
V=
i
n
n rAi
FA0n
FA0 X i FA0 X
=
rAi
rA
Xn
Design of PFR
Recall the assumption for PFR:
No radial variation in velocity, temperature, concentration, nor

reaction rate
Plug flow assumption is valid when Re > 2300
The design equations of PFR
Differential:
FA0
dX
= r A
dV
Integral:
V = FA0
dX
r A
Reactants
Products
Second Order Liquid Phase Reaction in PFR
Products
For the second order reaction A
r =
kC
The rate law is
The differential form of the design equation becomes
2
A
kC A2
dX
=
dV
FA0
1.
liquid phase isothermal reaction

=
C A C A0 ( 1 X
From stoichiometry
Combine the design equation with the stoichiometry
w hy
2
2
kC A0
(1 X )
dX kC A0 ( 1 X )
= =
dV
FA0
C A0 0
V
X
FA0 X
0
dx
dx
=
=
V =
dV
2
2 0
0
kC A0
( 1 X ) kC A0 0 ( 1 X
2
Evaluate
kC=
=
Da
A0
2
X =
kC=
A0
Da 2
1 + Da 2
dx
(1 X )
X
Second Order Gas Phase Reaction in PFR
Products
For the second order reaction A
r =
kC
The rate law is
The differential form of the design equation becomes
2
A
kC A2
dX
=
dV
FA0
2.
Gas phase isothermal reaction with no pressure drop

(P=P0)
FA0 ( 1 X ) FA0 ( 1 X )
(1 X )
=
= C A0
0 ( 1 + X ) 0 ( 1 + X )
(1 + X )
From stoichiometry
Combine the design equation with the stoichiometry
Evaluate
C A ==
FA0
=
V =
dV
2
0
kC A0
V
V
=
0
kC A0
FA
( 1 + X ) dx
0 (1 X ) 2
2
1
X
+
(
)
2
2 ( 1 + ) ln ( 1 X ) + X +
1X
Gas Phase reactions in PFR
For gas phase reaction, the volume of the PFR reactor

depends not only on X but also with
Therefore, the conversion depends on both the reactor
volume and
V
=
0
kC A0
1
X
+
(
)
2
2 ( 1 + ) ln ( 1 X ) + X +
1X
1.0
=-0.5
0.9
=0
0.8
=1
0.7
=2
X
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
6
V, m3
10
12
Pressure Drop in Reactors
The effect of pressure on the concentration of

reactants in liquid phase reaction is insignificant
In gas phase reactions, the concentration of reacting

species is proportional to the total pressure
Effect of pressure drop can be ignored
Proper accounting for pressure drop is crucial

This is very important in packed bed system, in particular
microreactors and reaction in membranes
Recall that the concentration of Species i for variable

density, variable pressure system is
expressed as:
C = C A0
( i + i X )
P T0

(1 + X ) P0 T
Pressure Drop in Packed Bed Reactors
The gas phase second order reaction:

is to be carried in a packed bed reactor (PBR)
The mole balance for Packed Bed Reactor is:
2 A
B +C
r '
dX
= A
dW FA0
The rate equation is :
From Stoichiometry for gas phase reactions:
r A' =
kC A2
C = C A0
(1 X ) P T0
kC A0
rA' =
(1 + X ) P0 T
And the rate equation becomes
Combining the rate equation and the mole balance:

dX
= kC 2A0
FA0
dW
(1 X ) P

(1 + X ) P0
(1 X ) P T0

(1 + X ) P0 T
dX kC A0 (1 X ) P
F1 ( X ,P )
= =

0 (1 + X ) P0
dW
To solve this equation, the relation between the pressure drop and the
catalyst weight must be known
Flow Through a Packed Bed
Many gas phase reactions are carried in a

tubular reactor packed with catalyst,
Packed Bed reactor
The pressure drop for flow through a
packed porous bed is given by Ergun
Equation: dP
G 1 150 (1 )
dZ
g c Dp 3
DP
The only parameter that

varies with pressure in the
right hand side is density,
.
P = pressure
porosity
=
=
volume of void
= void fraction
total bed volume
volume of solid
1 =
total bed volume
= vis cos ity of gas

z = length down the packed bed
P T F
= 0 0 T
P0 T FT 0
+ 1.75G
DP = Particle diameter
= 0 0 = 0 0
g c = conversion factor (32.174 lbm .ft / s 2 .lbf or1kg m .m / s 2 .kg f )
.
.
m0
m
;
and m m0
=
=
=
0
P0 T
G (1 ) 150 (1 )
dP
1.75G
=
.dZ
0 g c Dp 3
DP
P T0
G = superficial mass velocity ,kg / m2 .s
FT
FT 0
P T
dP
= 0 0
dZ
P T0
FT
FT 0
Flow Through a Packed Bed
To relate the pressure drop to the

catalyst weight rather than z
W=
(1 )
Ac
CrossSection Area
W = Ac z
density of catalyst
bulk density
P T
dP
= 0 0
dZ
P T0
FT
FT 0
0
P0 T FT
dP
=

dW
Ac (1 ) c P T0 FT 0
2
P0
dP
=
(1 + X )
dW
2 P
By solving the two differential

equation we can get the relation
between W and X
dP
= F2 ( X ,P )
dW
dX
dX
== FF11 ( X
X ,P
,P)
dW
dW
Analytical Solution for Reaction with Pressure Drop
for a second order reaction

we had:
dX
dW
=-0.5
kC A0 (1 X ) P
F1 ( X ,P )
=

0 (1 + X ) P0
=0
=2
PP2
dP
dP
0 (1 + X ) =
=
FF2 (( X
,P
))
1
X
X
,P
=
+
=
(
)
2
dW
dW
22 PP0
For =0 we get
dX kC A0
2 P
F1 ( X ,P )
= (1 X ) =
0
dW
P
0
2
dP
P0
=
=
F2 ( P )
dW
2 P
W 2
2
kC A0 1
=
0 1 X
W, kg
=
P P0 (1 W ) 2
1
dX kC A0
=
(1 X ) 2 (1 W )
dW
0
X
0
=1
kC A0
1
1
W
dW
dX
=
(
)
0
0 0 (1 X ) 2
W 2
W=
kC A0 1
kC A0 X
1
=
0 1 X
0 1 X
In-Class Exercise
Ethyl acetate is an extensively used solvent and can be

formed by the vapor- phase esterification of acetic acid
and ethanol. The reaction was studied using a
microporous resin as a catalyst in a packed bed reactor
[Ind. Eng. Chem. Res. , 26(2), 1 98 (1 987)]. The reaction
is first- order in ethanol and pseudo first- order in acetic
acid. For an equal molar feed rate of acetic acid and
ethanol, the specific reaction rate is 1 . 2 dm3/g cat/min.
The total molar feed rate is 1 0 mol/min, the initial
pressure is 1 0 atm, the temperature is 1 1 8 C, and the
pressure drop parameter, , equals 0. 01 g- 1 .
Calculate the maximum weight of catalyst that one could use and
maintain an exit pressure above 1 atm. (Ans: W = 99 g)
Determine the catalyst weight necessary to achieve 90%
conversion. What is the ratio of catalyst needed to achieve the
last 5% (85 to 90%) conversion to the weight necessary to
achieve the first 5% (0 to 5%) conversion in the reactor? Vary
and write a few sentences describing and explaining your findings.
What generalizations can you make?
Solution
Acetic Acid + Ethanol Ethyl Acetate + Water
A+B C+D
Mole Balance PBR
1.
FA0 dX/dW=-rA
Rate equation
2.
-rA=k CA=k CA
Stoichiometry
3.
Combine 2 and 3
1.
5.
(why?)
CA=CA0(1-X)/(1+X) (P/P0)(T0/T)=CA0(1-X)(P/P0)
=0 and isothermal conditions

CB=CA0 (FB0/FA0-X) (1+X) (P/P0)(T0/T)=CA
4.
P0=10 atm
T=118 C
F0=2FA0=10 mol/min
-rA=kCA0(1-X)(P/P0)
Combine 4 and 1
FA0 dX/dW=kCA0 (1-X) (P/P0)

dX/dW=kCA0/FA0 (1-X) (P/P0) =F1(X,P)
Solution, continue
1.
X versus W
dX kC A0
2 P
F1 ( X ,P )
= (1 X ) =
0
dW
P0
6.
Pressure drop function

P02
P02
dP
=
=
F2 ( X ,P )
(1 + X ) =
dW
2 P
2 P
Separating the variables and integrating:

P
2PdP =
P0
P02 W
2
=
W
2
0
P02
P P =
dW
P02 P 2
=W
P02
100 1
= 99 g
0.01x100
Solution, Part B
P
dX kC
=
We have
(1 X )
dW
F
P
And from the pressure drop equation
A0
A0
P02 P 2
=W
P02
1
P
=(1 W ) 2
P0
Substitute (1 - W) for (P/P0)2

dX kC A0
=
(1 X ) (1 W )
dW
FA0
Separating the variables

F
A0
dX
(1 W )0.5 dW =
kC A0 (1 X )
Integrating
W
FA0
1
1 W dW =
dX
kC A0 0 (1 X )
3
FA0
2
(1 w ) 2=
( ln(1 X ) )
kC A0
3
3
FA0
2
X
ln(1 X ) 0
(w w )2 =
kC A0
3
0
2kC A0
X=
1 exp
3 FA0
(1 W ) 32 1
Analytical Solution for Reaction with Pressure

Drop
=0
W, kg
=0
W, kg
Production of Ethylene Glycol

Ethylene
Glycol is produced by the first order reaction

of ethylene oxide and water in presence of catalyst
(H2SO4)
It is required to design a CSTR reactor to produce 200
million pounds of EG per year
The reaction will be carried at 55 C to avoid formation
of by-products
A laboratory experiment is carried to estimate the
reaction rate equation and use that equation to design
the CSTR reactor (find the reactor volume)
The laboratory data was obtained using 500 ml batch
reactor using 2 mol/liter of ethylene oxide in water
which is mixed with mixed with 2 obtained
Chapter 4: Sizing of Isothermal reactor

Reaction
Liquid
System
Constant
Density
Constant
density, no
pressure
drop
effect
Variable
Density,
Constant
Pressure
Gas
System
Evaluate
Combine
Stoichiometry
Variable
Density,
Constant
Pressure
Rate Law
Mole Balance
Variable
Density,
Variable
Pressure
Chapter 4: Sizing of Isothermal reactor
Reaction Types
Liquid phase, V=V0 or = 0, and no pressure effect
Gas phase [V=V0 (1+X) (P0/P) or v=v0 (1+X) (P0/P)]

1.
n = 0, no pressure drop (same as liquid phase)
2.
n = 0, pressure drop (V=V0(P0/P) or v= v0 (P0/P)
3.
n 0, no pressure drop (V=V0 (1+X) or v=v0 (1+X))
4.
n 0, pressure drop (V=V0 (1+X) (P0/P) or

v=v0 (1+X) (P0/P))
Evaluate
Combine
Stoichiometry
Rate Law
Mole Balance

CHEG 411
Fall 2008
Chapter 4
Sections 4.6 4.10
Ahmed Abdala
Abu Dhabi, UAE
Overview
Design
of Chemical Plant
Microreactors
Membrane
Unsteady
Reactors
State Operation of CSTR
Production of Ethylene Glycol

Most chemical Plants involve number of reaction and
separation steps
For example, production of polyethylene glycol requires the
following reaction and separation steps
H3C
H2C
CH3
CH2
+
O
H2C
CH2
+ 1/2
O2
O
H2C
CH2
Ag
H2SO 4
H2O
H2
H2C
CH2
CH2 CH2
HO HO
Some of the reactors shown

will include multiple reactors
connected in series or in parallel
For production of 200 tons/year
of polyethylene glycol requires the
following flow rates and reactor
sizes
Ethylene Glycol Plant

Ethylene
is produced in 100 parallel PFR reactors
Ethylene
oxide is produced in 1000 parallel tubes

packed with catalyst coated with silver
Ethylene
Profit
glycol is produced in 197 ft3 CSTR reactor
value of products cost of reactants operating cost Separation costs
Profit
can be increased by
optimizing separation and conversion and using
recycles
Microreactor
Microreactors
are characterized by their high surface

area-to-volume ratios in their microstructured regions
that contain tubes or channels.
A typical channel width might be100 m with a length

of 20000 m
The resulting high surface area-to volume ratio (ca.
10000 m2/m3 reduces or even eliminates heat and mass
transfer resistance
Microreactors
are also used for the production of

special chemicals, combinatorial chemical screening,
lab-on-a-chip, and chemical sensors
Design of Microreactors
The
gas-phase reaction
2 NOCl
2 NO + Cl 2
is carried out at 425C and 1641 kPa (16.7 atm). Pure

NOCl is to be fed and the reaction follows an
elementary rate. It is desired to produce 20 tons of NO
per year in a microreactor system using a bank of ten
microrractors in parallel. Each microreactor has 100
channels with each channel 0.2 mm square and 250
mm length.
Assume 85% conversion, plot the molar flow rates as a
function of volume down the length of the reactor.
The reaction rate constant, k, is 0.29 dm3/mol/s at 500
K and the activation energy, E, is 24 kcal/mole
Membrane Reactors
Membrane
reactors are used to:
Increase conversion of thermodynamically limited

reactions
Increase selectivity for multiple reactions
The
membrane can either provide a barrier to certain

components, preventing certain components such as
particulates from contacting the catalyst or contacting
reactive sites and being catalyst in itself
Membrane Reactors
Like reactive distillation, the membrane reactor is another

technique for driving reversible reactions the right toward
completion in order to achieve high conversions.
These high conversion can he achieved having one of the

reaction products diffuse out of a semipermeable
membrane surrounding the reacting mixture.
As a result, the reverse reaction will not be able to take place

and the reaction will continue to proceed to the right toward
completion.
Types f catalytic membrane reactors
Inert membrane reactor with catalyst pellets on the feed side

(IMRCF)
Catalytic membrane reactor (CMR)
Types of Catalytic Membrane Reactors
Design of Membrane Reactor

The
following reaction
C H + 3H
C6H12
6 6
2
is to be carried out isothermally in a membrane reactor

with no pressure drop. The membrane is permeable to
Product C, but it is impermeable to all other species.
The total initial concentration is 0.2 mol/dm3 and the
molar flow of A is 10 mol/s. The reaction rate constant,
kA is 10 dm3/kg-cat/s. the equilibrium constant, KC, is
200 mol3/dm9 and the mass transfer coefficient for H2,
0.5 dm3/kg.cat/s.
Plot the concentration of the reacting species as
function of catalyst mass.
Unsteady State Operation

Example
of Unsteady state Operations
Batch Reactor
Startup of CSTR
Semibatch reactor
Startup of CSTR: Steady State time

Estimate
the time required to reach steady state after

the startup of CSTR reactor for a first-order liquidphase reaction
Solution:
Mole balance
dN
FA 0 FA + rAV = A
dt
FA 0 FA
dC
+ rA = A
V
V
dt
Rate Equation
rA =
kC A
( unsteady state )
CA0
CA
dC
+ rA = A
dt
Semibatch Reactor
The
production of methyl bromide is an irreversible

liquid-phase reaction that follows laws an elementary
rate Paw. The reaction is carried out isothermally in a
semibatch reactor. An aqueous solution of methyl
amine (B)at a concentration of 0.025 mol/dm3 is to be
fed at a rate of 0.05 dm3/s to an aqueous solution of
bromine cyanide (A) contained in a glass-lined reactor
The initial Volume of fluid in the vessel is to be 5 dm3
with a bromine cyanide concentration of 0.05 mol/dm3.
The specific reaction rate constant is k = 2.2 dm3/mol/s
Solve for the concentrations of bromine cyanide and
methyl bromide and the rate reaction as a function of
time.

CHEG 411
Fall 2010
Chapter 5
Ahmed Abdala
Abu Dhabi, UAE
Collection and Analysis of Rate Data
Chapter 5
Lecture 1: Differential Method
The Rate Expression
The rate law is an algebraic equation that relates the reaction rate of
reaction to the concentration of reacting species
=
r A
E
A0 exp
=
C AC B
k C AC B
RT
Concentation
Dependent
Temperature Dependent
Term
term
The temperature dependent term can be evaluated by knowing the

equilibrium constant k at different temperatures
E
k = A0 exp
RT
=
ln ( k ) ln ( A0 )
E 1
RT
Collecting and Analyzing of Experimental

Data
Experimental
data obtained from Batch reactor or

flow reactor system
Data
obtained are:
Concentration-time measurement (Batch Reactor)
Concentration measurements (flow reactor)
Data
Analysis
Differential Method
Integral Method
Method of half-lives
Method of initial rates
Linear and nonlinear regression
Batch Reactor Data
Batch reactor is preferred for collecting data for estimating of

the rate equation parameters
A + B Product
For the irreversible reaction
Which is carried at constant volume batch reactor
Assume that the rate law takes a power-law form:
r A=
dC A
= k AC A
dt
For Batch reactor and constant density reaction we know that:

dC A
r A =
dt
k AC C B
Rate equation of the form r A =
can also be converted to the previous form
1. Using excess concentration of component B
2. Using equimolar concentration of A and B
Combining with the rate expression
dC A
=
kC A
dt
( how ?)
Analysis of Batch Reactor Data: Integral Method

Using the integral method the reaction order and rate constant
can be determined:
1.
Guess the reaction order
2.
Substitute the rate expression into the mole balance equation
3.
Integrate the differential design equation
4.
Linearize the time concentration relation
5.
Plot the appropriate concentration function versus time
6.
Linear relation?
Yes, find k
No, repeat steps 2-4

Mole
balance
Guess
rA =
kC A2
dC A
=
kC A2
dt
Integrate
CA
Linearize
t
1
1
dC A
=
kt
2 =
k dt
C
C
A
A
0
CA C A
0
Plot
Check
Analyzing Batch Reactor Data: 1. Differential

Method
For constant volume batch reactor:
dC A
=
kC A
dt
The concentration of a reactant species is measured as function of time

Taking the natural logarithm for both sides of the equation
dC
ln
= ln ( k ) + ln (C )
dt
A
Plotting ln(-dCA/dt) versus ln(CA) gives straight line
= the slope
k can be calculated = the intercept
-dCA/dt is obtained from the CA versus

t data using one of the following methods:
Graphical method
Numerical method
For equally spaced data point
Polynomial fit
CA= a0 + a1t + a2t2 + a3t3 ++ antn
-dCA/dt = -[ a1+ 2a2t + 3a3t2++ nantn-1]
Ln(-dCA/dt)
Ln(CA)
Numerical Estimation of dCA/dt
For equally spaced data points
ti = constant i.e. (t1-t0)=t2-t1=t3-t2=..ti+1-ti

t, min
t0
t1
t2
t3
tn
CA, mol/liter
CA0
CA1
CA2
CA3
CAn
-dCA/dt
first
First Point
Interior points:
Interior points
3C A0 + 4C A1 C A 2
dC A
dt =
2 t
t 0
C A( i +1 ) C A( i 1 )
dC A
dt =
2 t
t i
t, min
10
15
20
25
C A,
mol/liter
1.0
0.92
0.85
0.78
0.74
0.68
-dCA/dt
Last Point:
last
C A( n 2 ) 4C A( n 1 ) + 3C An
dC A
dt =
2 t
t n
Determination of Reaction order and Rate Constant
The following reaction

A B +C
was carried out in a constant volume batch reactor and

the following concentration measurement was estimated
t, min
10
15
20
25
CA, mole/liter
1.6
1.35
1.1
0.87
0.7
Determine the reaction order and the rate constant using

the differential Method
Solution: Differential Method

A B +C
t, min
10
15
20
30
40
60
CA,
mole/lit
er
1.6
1.35
1.1
0.87
0.7
0.53
0.35
1.
Let:
dC A
r A =
=
kC A
dt
2.
Hence:
dC A
ln
dt
3.
Estimation of dCA/dt graphically:
= ln ( k ) + ln C A
( )
t, min
1.
Calculate
CA, mole/liter 2.0
C A
t
C A
t
CA/t=
C i C i 1
-(Ci-Ci-1)/(ti-ti-1)
t i t i 1
t i 1 ,t i
1.6 2.0
0.12
=
=
0.08
5
0
t 1 , t 2
10
15
20
30
40
60
1.6
1.35
1.1
0.87
0.7
0.53
0.35
0.08
0.063
0.042
0.033
0.021
0.017
0.009
0.1
Plot
versus time
0.08
-DCA/Dt
2.
C A
t
0.06
0.04
0.02
10
20
30
40
t, min
50
60
70
Solution, Continued
Using equal-area differentiation,
t, min
C mole/liter
the value of dCA/dt can
C /t=
be estimated
-(C -C )/(t -t )
3.
A,
10
15
22
20
30
40
60
2.0
1.6
1.35
1.1
0.87
0.7
0.53
0.35
0.08
0.063
0.042
0.033
0.021
0.017
0.009
0.07
0.053
0.035
0.0024 0.016
0.006
i-1
-dCA/dt
0.12
0.1
-DCA/Dt .
0.08
0.06
0.04
0.02
0
0
10
20
30
40
t, m in
50
60
70
i i-1
0.092
Solution, continued
Plot ln(-dCA/dt) versus ln(CA)
Fit to a straight line
Slope = =1.58
-1
ln(k)=-3.45
k = 0.032
(what units?)
0.1
y = 1.58x - 3.45
R2 = 1.00
-2
ln(-dCA/dt)
-3
-4
y = 0.032x1.580
R2 = 0.996
-dCA/dt
-5
-6
-1
-0.8
-0.6
-0.4
-0.2
ln(CA), mole/liter
0.01
0.1
1
CA, mole/liter
10
0.2
0.4
0.6
0.8
Collection and Analysis of Rate Data
Chapter 5
Lecture 2: Integral Method
Integral Method: Zero Order Reactions
For zero order reaction:
Substitute the rate expression into the design equation for

batch reactor
dC
r A= kC A0= k
dt
Separate variables and integrate
CA
C A0
=
k
dC A =
k dt
0
The concentration time relation
Plot CA versus t
Straight line?
C
=
C A0 kt
A
k = -slope
Assume different order and repeat
CA
slope=-k
time
Integral Method: First Order Reactions
For first order reaction:
Substitute the rate expression into the design equation for batch
reactor
rA =
kC A
CA
C A0
dC A
=
k dt
CA
0

C
ln A0
CA
Plot ln(CA0/CA) versus t

Straight line?
= kt
k = Slope
Ln(CA0/CA)
dC A
=
kC A
dt
slope=k
time
Integral Method: Second Order Reactions
For second order reaction:
Substitute the rate expression into the design equation for batch
reactor
dC A
2
kC A2
rA =
CA
C A0
=
kC A
dC A
=
k dt
C A2
0
Plot 1/CA versus t
Straight line?
1
1
=
+ kt
C A C A0
k = Slope
1/CA
dt
slope=k
time
Integral Method: Example

The
irreversible isomerization
A B
was carried out in a batch reactor and the following

concentration-time data were obtained:
t, min
10
CA, mol/dm3
4.0
2.89 2.25 1.45 1.0
12
15
17.5
0.65 0.25 0.07
Determine the reaction order and the reaction rate

constant.
Solution
A B
1.
Assume zero order reaction:
CA=CA0-kt
Plot CA versus time
The data does not follow

a zero order relation
t, min
CA, mol/dm3
4.0
2.89 2.25 1.45 1.0
10
12
15
17.5
0.65 0.25 0.07
Solution, continued
A B
Assume first order reaction:
ln(CA0/CA)= k t
Plot ln(CA0/CA) versus time
The relation is not linear
4.5
y = 0.214x - 0.3673
R = 0.9226
4
3.5
3
The reaction does not follow

a first order kinetics
Ln(CA,/CA)
2.
2.5
2
1.5
1
0.5
0
10
time, min
t, min
CA, mol/dm3 4.0

ln(CA0/CA)
10
2.89 2.25 1.45 1.0
12
15
17.5
0.65 0.25 0.07
0.00 0.33 0.58 1.01 1.39 1.82 2.77 4.05
15
20
Solution, continued
A B
3. Assume
second order reaction:
1/CA0 = 1/CA0+ k t
Plot 1/CA0 versus time
The relation is not linear
second order kinetics

zero, first, or second order
reaction
Try differential method or
nonlinear regression method
t, min
10
12
15
17.5
CA, mol/dm3
4.0
2.89
2.25
1.45
1.0
0.65
0.25
0.07
1/CA
0.25
0.35
0.44
0.69
1.00
1.54
4.00
14.29
Integral Method: n-order Reaction

For
reaction of n order
kC nA
rA =
Substitute
in the mole balance equation
Integrate
CA
C A0
dC A
=
kC nA
dt
t
dC A
=
k t
n
CA
0
1 n
1 n
1 C A0 C A
t=
k 1 n
Because
n is not know, this expression cannot be
plotted
Using regression method, least squares, the reaction
order, n, and the rate constant (k) can be estimated
Nonlinear Regression Analysis

kC nA
rA =
Assuming the rate expression is:
The integral methods yield the following relation:

C A10 n C A1 n =
( 1 n ) kt
Using regression analysis we can search for values for n and k

that minimize the sum of the square of the error (S2):
1
2
1 n
1
n
S
C
C
C
C
1
n
kt
=
(
)
A ,c
i
A0
A ,m
A ,m
i 1=
i 1
=
This can be done numerically using one of software packages

such as Matlab, Polymath, etc.

CHEG 411
Fall 2008
Chapter 6
Ahmed Abdala
Abu Dhabi, UAE
Multiple Reaction
Chapter 6
Lecture 1: Parallel Reactions
Multiple Reactions
Parallel Reactions
A B
A C
Series Reaction
A B C
Complex Reactions
A + B
C +D
A + C
Independent Reactions
A B +C
D E +F
Multiple Reactions
Parallel Reactions
CH2=CH2 + 3 O2
2 CO2 + 2 H2O
CH2=CH2 + 0.5 O2 Ethylene Oxide
Series Reaction
-H2
-H2
Paraffins Naphthenes Aromatics
Complex Reactions
Ethylene Oxide + NH3 HOCH2CH2NH2
Ethylene Oxide + HOCH2CH2NH2 (HOCH2CH2)2NH
Independent Reactions
C15H32 C12H26 + C3H6
C8H18
C6H14 + C2H4
Selectivity
For the following Parallel Reaction:

A D (Desired )
A U
(Undesired)
Minimization of undesired compound U relative to

desired product D is always desirable
Selectivity is used to quantify formation of desired

product D with respect to undesired
Instantaneous Selectivity, SD/U:

~
S=
D
U
SD :
Overall selectivity,=
U S
~
D
U
rate of formation ofD

rD
=
rU Rate of formation of U
ND
=
NU
BatchReactor
FD
FU
Flow Reactor
Reaction Yield
Instantaneous Yield, YD:

=
YD
Overall Yield, Y D :
U=
Y
D
rate of formationof D
rD
=
rA Rate of reactionof key reactant
ND
FD
=
NA 0 NA FA 0 FA
Batchreactor
Flow Reactor
For CSTR reactor:
The instantaneous yield is equivalent to the overall yield
The instantaneous selectivity is equivalent to the overall

yield
Parallel Reactions:
For the following Parallel Reactions

kD
A
D
rD = kDC A1
kU
A
U
rU = kU C A1
Rate of disappearance of reactant A, -rA

rA = rD + rU = kDC A1 + kU C A1
The instantaneous selectivity

rD kDC A1 kD 1 2
S=
CA
=
=
D
2
rU kU C A
kU
U
Parallel Reactions: Maximizing Selectivity
For the parallel reactions:
rD = kDC A1
A
D
rU = kU C A 2
A
U
kD 1 2
SD = C A
U
kU
We can maximize the selectivity by choosing the right

reactor system (reactor type, arrangement, feed)
Case 1: 1 > 2
(1 - 2 = + ve)
To make SD/U large , CA must be maintained as high as

possible
Inert
A
or diluents should be kept minimum
Batch or plug-flow reactor should be used
Parallel Reactions: Maximizing Selectivity
Case 2: 1 < 2
(1 - 2 = -ve)
To make SD/U large , CA must be maintained as low as

possible
Use
Inert or diluents and/or use recycle to dilute reactant

with products
Low
pressure for gas phase
Use
CSTR
Case
3: 1 = 2
Case 3-1: ED >EU

Operate
S=
D
U
kD AD
=
e
kU AU
( ED EU )
RT
at highest possible T
Case 3-2: ED < EU

Operate
at low T (high enough to have significant rate)
Parallel Reactions: Example Trambouze

Reaction (P6-6)
Consider the following system of gas-phase reactions:

The reactions are to be carried at 27 C
and 4 atm. Pure A enters the system at
volumetric flow rate of 10 dm3/min.
a.
b.
c.
d.
e.
f.
g.
k1
X (Undesired)
A
rX = 0.004 C A 2
k2
B (Desired)
A
rB = 0.3 C A
k2
R (Undesired)
A
rR = 0.35 C A2
mol
dm3 .min
mol
dm3 .min
mol
dm3 .min
Sketch the instantaneous selectivity SB/X, SB/R, SB/XR as function of CA

Consider a series of reactors. What should be the volume of the first
reactor?
What is the conversion of A in the first reactor?
What are the effluent concentration of A, B, X, and R from the first
reactor.
If 99% conversion of A is desired, what reaction scheme and reactor sizes
should we use to maximize SB/XR.
Suppose that E1=20 kcal/mol, E2=10 kcal/mol, E3=30 kcal/mol. What
temperature would you recommend for a single CSTR with a space time
of 10 min and entering concentration of A of 0.1 mol/dm3?
If you could vary the pressure between 1 and 100 atm, what pressure
would you choose?
Solution: Part a
B
k1
0.3 10.5
75C A0.5
CA
=
0.004
k2 2 3
0.3 1 2
0.86C A1
S
C
CA
=
=
=
B
A
R
0.35
k3
r
rX + rR
B
=
=
S
B
k2
B (Desired)
A
rB = 0.3 C A
k2
R (Undesired)
A
rR = 0.35 C A2
35
180
160
120
100
CA*=0.032 mol/dm3
25
20
SB/R
80
15
60
10
40
20
0
-5.55E-170.02
SB/XR
0.04
0.06
0.08
CA
0.1
dSB
XR
CA
=
0.3 0.004C A0.5 + 0.35C A2 + 0.3C A 0.5 * 0.004C A0.5 + 2 * .35=
0
dC A
30
SB/X
140
We can find CA* by setting

dSB/XS/dCA=0
mol
dm3 .min
mol
dm3 .min
mol
dm3 .min
200
note that SB/XR curve have

a maxima at CA*
rX = 0.004 C A 2
SB/R
XR
0.3C A
0.004C A0.5 + 0.35C A2
k1
X (Undesired)
A
SB/X or SB/XR
k2
=
S
CA
=
0.12
0.14
0
0.16
Solution: Part b, c
To maximize the selectivity SB/XR, we need to operate at the

maximum selectivity
Use the first reactor as CSTR operates at final CA=CA*
PA0
1* 4
3
C
0.16
mol
/
dm
=
=
=
A0
RT 0.082* ( 27 + 273 )
V CSTR
=
Reaction Direction
FA0 X
FA0 X
=
r A*
k 1C A0.5 + k 2C A + k 3C A2
C A0 C *A 0.16 0.032
X
=
=
= 0.8
C A0
0.16
10
VCSTR =
0.004* 0.032
= 119 dm 3
0.5
1.6 * 0.8
+ 0.3* 0.032 + 0.35* 0.032 2
SB/XR
=
FA0 =
10*=
0.16 1.6mol / min
0 C A0
CSTR
PFR
0
0.16
CA0
0.14
0.12
0.1
0.08
CA, mol/liter
0.06
0.04
0.02
Solution: Part d
CA=0.032 mol/dm3
CB, CR, CX?

FR FR0
FX FX 0
FA0 FA FB FB0
=
VCSTR =
=
=
rA
rR
rX
rB
VCSTR
=
CB
=
0C B
0C R
0C X
=
=
0.3C A 0.35C A2 0.004c 0.5
A
0.3C AV 0.3* 0.032* 119
=
= 0.114 mol / dm 3
0
10
0.004C 0.5
V 0.004* 0.032 0.5 * 119
A
CX =
=
= 0.0085 mol / dm 3
10
0
0.35C A2V 0.35* 0.032 2 * 119
CR =
=
= 0.004 mol / dm 3
0
10
Check : C A + C B + C X + X R must equal toC A0
Part e
For
99% conversion:
The first reactor is CSTR (X=0 to X=0.8, V=119 dm3)
The second reactor is PFR:

FA 2
dFA
=
=
V PFR
rA
FA
1
( 1 0.8 )C A0
( 1 0.99 )C A0
k 1C A0.5
FA 2
( 10.99 )C A
v 0 dC A
+ k 2C A + k 3C A2
0
dFA
dC A
3
VPFR = 10
9.1dm
=
=
0.5
2
rA
FA
( 10.8 )C A 0.004C A + 0.3C A + 0.35C A
Solution Part f
For
For
single CSTR:
k2C Af
rB
=
=
SB
XR
rX + rR k1C Af0.5 + k3C Af2
max selectivity
dS
= k ( k C + k C ) k C ( 0.5 * k C
dC
B
XR
0.5
A
2
A
0.5
A
k1C A0.5 + k3C A2 0.5 * k1C A0.5 2 * k3C 2A =

0
0.5k1C A0.5 k3C A2 =
0
2
3
0.5k1
=
C Af =
k
3
A01 exp ( E1 / RT )
A exp ( E / RT )
3
03
2
3
+ 2 * k3C A= 0
Solution Part f
For
max selectivity
2
3
0.5k1
=
C Af =
k
3
2
3
0.5 A01 exp ( E1 / RT )

=
A exp ( E / RT )
3
03
0.5 A01
E3 E1
exp

A
RT
03
2/3
2
3
k
0.1 1
C A0 C A
C A0 C A
2 k3
=
=
=
=
10
1/ 3
2/3
4/3
rA
k1C A0.5 + k2C A + k3C A2
k
k
k
k1 1 + k2 1 + k3 1
2 k3
2 k3
2 k3
2/3
2/3
( 0.2k ) k
substitute expressions for k1 , k2 , and k3 as function of T and solve for T
10 = 4 /3 1/3 3 2 /3 1 4 /3
k1 k3 + k2 k1 + k1 k3
dm3 / mol
0.5
20 x10
12
k=
E
RT
exp
/
.
exp
0
004
=
(
)
1.49x10
1
1
min
1.987 x 300
10 x103
6
1
A02 k=
exp ( E2 / RT ) 0.3 exp=
5.79x10 min
2
1.987 x 300
30 x103
21
3
1
1
A03 k=
exp ( E3 / RT ) 0.35 exp=
2.52x10 dm mol min

3
1.987 x 300
Solving for T using Polymath givesT = 315 K
3
A01
Solution part f and g

The
optimum pressure should be selected such that the

initial concentration of A, CA0=0.1 mol/dm3
This will ensure that the exit condition of the CSTR

reactor will correspond to maximum selectivity
=
P0 C=
RT 0.1x 0.08205=
x 315 2.6 atm
A0
Parallel Reactions: Reactor Selection
For the following parallel reactions

k1
A + B
D
rD = k1C A1 C B1
k2
A + B
U
rU = k2C A 2 C B2
The instantaneous Selectivity

SD =
/U
rD k1 1 2 1 2
=
C
CB
rU k 2 A
Depending on the values of 1, 2, 1, and 2 we have

the following cases
Case 1: 1 > 2 and 1 > 2
Case 2: 1 > 2 and 1 < 2
Case 3: 1 < 2 and 1 < 2
Case 4: 1 < 2 and 1 > 2
Case 1: 1 > 2, 1 > 2

k1
A + B
D rD = k1C A1C B1
rU = k2C A 2 C B2
k2
A + B
U
SD =
/U
High CA and High CB is preferred
Use PFR or Batch Reactor
Use high Pressure (gas reaction)
Do not use inert or diluents
rD k1 1 2 1 2
=
C A CB
rU k 2
A
B
AB
Case 2: 1 > 2, 1 < 2

k1
A + B
D rD = k1C A1C B1
k2
A + B
U
rU = k2C A 2 C B2
SD =
/U
rD k1 1 2 1 2
=
C A CB
rU k 2
High CA and Low CB is preferred

Semibatch reactor
A present initially and B is continuously fed to the reactor
PFR with side streams or membrane

A
B
Series of Small CSTR with A fed to the first reactor and B is divided
between the reactors
B
A
Case 3: 1 < 2, 1 < 2

k1
A + B
D rD = k1C A1C B1
k2
A + B
U
Low CA and Low CB is preferred
CSTR
PFR with large recycle
Diluted feed or inert
Low pressure
Recycle
rU = k2C A 2 C B2
rD k1 1 2 1 2
=
C A CB
rU k 2
SD =
/U
B
A
Recycle
Case 4: 1 < 2, 1 > 2

k1
A + B
D rD = k1C A1C B1
rU = k2C A 2 C B2
k2
A + B
U
SD =
/U
rD k1 1 2 1 2
=
C A CB
rU k 2
Low CA and High CB is preferred

Semibatch reactor
B present initially
A is continuously fed to the reactor
PFR with side streams or membrane
B
A
Series of Small CSTR with B fed to the first reactor and A is divided
between the reactors
A
B
Series Reactions: Batch System
For the series reactions:

k1
k2
B(Desired )
C (undesired )
A
rC k2CB
=
rA k1C A=
=
rB k1C A k2C B
The exact reaction time to maximize B is very

important
C
C
For Batch System:

dC
A =
k1C A C A =
C A 0 exp( k1t )
rA =
dt
dCB
rB =k1C A k2C B =k1C A 0 exp( k1t ) k2C B
=
dt
CB = k1C A 0
e k1t e k2 t
k2 k1
CA
k1/k2=2
CB
dCC
e k1t e k2 t
= rC= k2C B= k2 k1C A 0
k2 k1
dt
CC
=
C A0
k2 (1 e k1t ) k1 (1 e k2 t )
k2 k1
remember C C = C A 0 C A C B
Series Reactions: Maximum Yield of B
The maximum CB is at dCB/dt=0

CB = k1C A 0
e k1t e k2 t
k2 k1
kC
dCB
=
0 =1 A 0 ( k1e k1t + k2 e k2 t )
dt
k1 k2
topt =
k
1
ln 1
k1 k2 k2
CC
CA
k1/k2=2
CB
topt
Series Reaction: Example
For the following liquid-phase series reaction

rC = 0.01C B
rA =
0.4 C A
B
C (undesired )
A
is carried in a 500-dm3 batch reactor. The initial

concentration of A is 1.6 mol/dm3. The desired product is
B, and separation of the undesired product C is very
difficult and costly. The given rate constants are in h-1 and
are at 100C.
Plot the CA, CB, CC as function of time for batch system.
What is the optimum reaction time?
Assuming the reaction is carried in CSTR of a space time 0.5

h. What temperature would you recommend to maximize B?
(E1=10 kcal/mol, E2=20 kcal/mol)
Solution: Batch System

rA =
0.4C A
rC = 0.01C B
rC = 0.01C B
0.4 C A
rA =
A
B
C (undesired )
Mole
Balance for Batch Reactor
dC A
=rA =.
0 4C A
dt
dC B
= rB= 0.01C B 0.4C A
dt
dC C
= rC= 0.01C B
dt
Ci
C=
C A 0 exp( k1=
t ) 1.6 exp( 0.4t )
A
( )
e k1t e k2t
CB k1C A 0=
2=
k2 k1
( 3)
1.64 e 0.01t e 0.4 t
) (
C A0
k2 1 e k1t k1 1 e k2t
k2 k1
1.6
0.01 1 e 0.4 t 0.4 1 e 0.01t
=
0.01 0.4
CB
1.5
(1)
=
rC 0.01C B 0.4C A
=
CC
0.5
0
CC
CA
20
40
time, min
=
topt
60
k
0.4
1
1
ln 1
ln
=
=
9.46 min
k1 k2 k2 0.4 0.01 0.01
Solution Batch System Using PolyMath
Solution: CSTR
Mole
Balance for CSTR
FA 0 X FA 0 FA 0 ( C A 0 C A )
=
V =
=
rA
rA
rA
1.6 C A
1.6
CA =
1 + k1
k1C A
CB0 CB
C B
=
= 5
1.6
rB
k2C B k1
1 + k1
5k2C B
8k1
8k1
=
C B C B =
1 + 5k1
(1 + 5k1 )(1 + 5k2 )
E1 1 1
E2 1 1
=
k1 k1,T1 exp ; =
k2 k2 ,T1 exp
R T T
R T T
1
2
Toptimum = 388 K = 115 C

k1
k2
CB
200
3.4E-06
7.3E-13
2.7E-05
225
5.6E-05
2.0E-10
4.5E-04
250
5.2E-04
1.7E-08
4.2E-03
275
3.3E-03
6.7E-07
2.6E-02
300
1.5E-02
1.4E-05
1.1E-01
325
5.5E-02
1.9E-04
3.4E-01
350
1.6E-01
1.7E-03
7.2E-01
375
4.3E-01
1.2E-02
1.0E+00
388
6.7E-01
2.8E-02
1.1E+00
400
9.9E-01
6.2E-02
1.0E+00
425
2.1E+00
2.7E-01
6.2E-01
450
4.0E+00
1.0E+00
2.5E-01
475
7.3E+00
3.3E+00
8.9E-02
500
1.2E+01
9.5E+00
3.3E-02
525
2.0E+01
2.5E+01
1.3E-02
550
3.1E+01
5.9E+01
5.4E-03
1.200
1.000
0.800
CB 0.600
0.400
0.200
0.000
200
300
T, K
400
500
In Class Exercise
A large fully automated municipal incinerator is being designed. A survey
estimates the garbage load to be 1440 tons/day. This will be harvested by a
fleet of compaction trucks which will disgorge their loads into an
underground storage bin. A conveyor will then feed the garbage to the
Incinerator. The proposed daily collection route is such that at the beginning
of the working day (6 A.M. sharp!) relatively large quantities of garbage
(average of 6 tons/min) are returned from nearby commercial areas.
Subsequently, the supply will diminish as more remote suburban areas are
serviced. It is assumed that the collection rate is proportional to the amount
of garbage still to be collected, the initial rate being one truck load/min. The
conveyor, on the other hand, will transport garbage at a uniform 1 ton/min to
the incinerator. At the beginning of the working day, the trucks will work
faster than the conveyor; later in the day, slower. Thus, each day the bin will
accumulate material, then lose material. To evaluate this operation, we need
information. Please help us with this.
a)
b)
c)
d)
At what time of day will the trucks have collected 95% of the day's garbage?
How much garbage should the storage bin be designed for?
At what time of day will the bin be fullest?
At what time of day will the bin be empty?

CHEG 411
Fall 2010
Chapter 8
Ahmed Abdala
Abu Dhabi, UAE
Non-Isothermal Reaction
Chapter 8
Non-Isothermal Reactions
Consider the following liquid-phase exothermic

reaction:
A
B
The reaction takes place in a PFR under adiabatic,

non-isothermal conditions
We need to calculate the volume of flow reactor to

achieve conversion X
The mole balance:

kCA0 (1 X )
dX
=
=
dV
FA0
rA
dX
=
dV
FA0
E 1 1
1
k1exp CA0 (1 X
FA0
R T1 T
Energy Balance for Flow Reactors
Since the reaction is non-isothermal, the temperature will

vary along the reaction length
The temperature is related to conversion through energy

^
balance equation:
d=
E Q W
For a flow reactor:

rate of
Rate of flow Rate of work
Accumulation = of heat to done by

of energy the system the system
Rate of energy Rate of energy

+ added to the system leaving the system

by mass flowin by mass flowout
Q
dE sys
dt
= Q W + Fin Ein Fout Eout
Fi0
Fi
Hi0
Hi
Energy Balance for Flow Reactors

dE sys
dt
=
Fin Ein
=
Fi Ei ; Fout Eout
Where:
FE
i 1
=i 1 =
in
i 1
=i 1 =
in
But
i
out
dE sys
dt
Fi
Hi0
Hi
out
Fi0
+ Ws
n
n
= Q Fi PVi + Fi PVi
i1 =
dt =
i 1
in
dE sys
Therefore:
Remember
W=
Fi PVi + Fi PVi
Rearranging
= Q W + Fin Ein Fout Eout
=Q Ws + Fi Ei + PVi
n
n
+ Ws + Fi Ei Fout Eout
i 1
out=i 1 =
in
) F ( E + PV )
n
in
=i 1 =i 1
negligible
out
u i2
Ei = U i + + gzi + others = U i
2
H i =U i + PVi =Ei + PVi
dE sys
dt
=Q Ws + Fi H i in Fi Fi
=i 1 =i 1
out
=Q Ws + Fi 0 H i 0 Fi H i
=i 1 =i 1
out
The Energy Balance equation
For the following reactions:

n
H =F H
+F H
+F H
+F H
A+
=F
b
c
d
B C+ D
a
a
a
i0 i0
A0
A0
B0
B0
C0 C0
D0
D0
A0
i 1 =i 1
and
FH
= F H +F H +F H +F H = F
then F H F=
H
n
i0 i0
=i 1 =i 1
n
i0
H (
i
+ i X )
c
b
d
H i ) i FA0 H D + H C H B H A X
a
a
a
H =
Fi H i FA0 ( H i 0 H i )i ( H Rx )T FAo X
i0 i0
=i 1 =i 1
(H
i
i
A0
=i 1
i0
i
i
A
A
B
B
C
C
D
D
A0
i 1 =i 1
=i 1
For steady state conditions, the energy balance

dE sys
dt
= Q W + FA0 ( H i 0 H i ) i ( H Rx )T FAo X = 0
i =1
1. Adiabatic Reactions with constant CP
Q W + FA0 ( H i 0 H i ) i ( H Rx )T FAo X =0
i =1
For Adiabatic reactor

with
negligible shaft work:
=
Q 0=
and W S 0
The energy balance equation becomes

n
FA0 ( H i 0 H i ) i ( H Rx )T FAo X =0
i =1
But
Hi0 Hi =
C Pi dT =
C Pi (T T 0 )
No phase Change and constant C Pi
Ti 0
Then
And the temperature is now related to conversion
C (T T ) ( H )
i =1
Pi
T= T0 +
Rx T
( H Rx )T X
n
C
i =1
X =0
Pi
1. Adiabatic Reactions with constant CP
From energy balance find T at different X

X
H rx ) X
(
T=
T0 +
1
0
C
i Pi
0.1
Find the rate equation at each X
0.2
rA kCA0 (1 X
=
=
)
E 1 1
k1exp CA0 (1 X
R T1 T
Estimate FA0/-rA
Plot FA0/-rA versus X
Find the reactor volume from the

corresponding area
T
T0
-rA
-rA/FA0
Example: F P-8-6
The elementary irreversible organic liquid phase reaction

A + B C
is carried out adiabatically in a flow reactor. An equimolar feed in A and
B enters at 27 C, and the volumetric flow rate is 2 dm3/s and CA0=0.1
kmol/m3.
a)
Calculate the PFR and CSTR volume necessary to achieve 85%

conversion.
b)
What is the maximum inlet temperature one could have so that the
boiling point of the liquid (550 K) would not be exceeded even for
complete conversion?
c)
Plot the conversion and temperature as function of PFR volume.
d)
Calculate the concentration achieved in one 500 dm3 and in two 250-dm3
CSTRs in series.
HA(273)= -20 kcal/mol, HB(273)= -15 kcal/mol, HC(273)= -41 kcal/mol

CP,A=CPB=15 cal/mol.K, CP,C=30 cal/mol.K
k = 0.01 dm3/mol.s at 300 K, E =10000 cal/mol
Solution Part a:
A + B C
CP=CPC-CPA-CPB=0 HRX = constant

T1
H A + H B H C )
(
H rx ) X
(
T +
300 +
=
=
0
i C P
T1 =
300 +
C PA + C PB
6000X
=
300 + 200X
30
E
k 1 exp
R
1 1
10000 1
1
=
0.01exp
1.987 300 T
T1 T
=
-rA kC A20 (1 X ) 2
CA
-rA
FA0/-rA
300
0.01
0.1
1.00E-04
2000
0.1
320
0.03
0.09
2.31E-04
865
0.2
340
0.07
0.08
4.61E-04
434
0.3
360
0.16
0.07
8.03E-04
249
0.4
380
0.34
0.06
1.23E-03
163
0.5
400
0.66
0.05
1.66E-03
121
0.6
420
1.21
0.04
1.93E-03
104
0.7
440
2.08
0.03
1.87E-03
107
0.8
460
3.42
0.02
1.37E-03
146
0.9
480
5.40
0.01
5.40E-04
371
0.91
482
5.64
0.009
4.57E-04
438
0.92
484
5.88
0.008
3.77E-04
531
0.93
486
6.14
0.007
3.01E-04
665
0.94
488
6.41
0.006
2.31E-04
867
0.95
490
6.68
0.005
1.67E-04
1197
0.96
492
6.97
0.004
1.12E-04
1794
0.97
494
7.26
0.003
6.54E-05
3059
0.98
496
7.57
0.002
3.03E-05
6607
0.99
498
7.88
0.001
7.88E-06
25372
Solution: Part a
Volume
VCSTR = 0.85 x 206

= 175 dm3
Volume
of CSTR equals the area of rectangle
of PFR equals the entire Area under the curve
VPFR ~ 305 dm3
3000
2500
FA0/-rA
2000
1500
1000
VPFR
VCST
500
0
0
0.1
0.2
0.3
0.4
0.5
X
0.6
0.7
0.8
0.9
Solution: Part a Using Excel
Volume of CSTR at X
FA0 X FA0
V
=
=
X
CSTR
r A
r A
Volume of PFR at X
dV PFR =
FA0 dX
r A
FA0 X FA0
V PFR =
X
=
r A
r A
X has to be small
X
V PFR = V PFR
0
CA
-rA
FA0/-rA
VCSTR
VPFR
VPFR
300
0.01
0.1
1.00E-04
2000
0.05
310
0.02
0.095
1.55E-04
1290
64
82.25
82
0.1
320
0.03
0.09
2.31E-04
865
87
53.88
136
0.15
330
0.05
0.085
3.32E-04
602
90
36.69
173
0.2
340
0.07
0.08
4.61E-04
434
87
25.92
199
0.25
350
0.11
0.075
6.18E-04
324
81
18.95
218
0.3
360
0.16
0.07
8.03E-04
249
75
14.32
232
0.35
370
0.24
0.065
1.01E-03
198
69
11.18
243
0.4
380
0.34
0.06
1.23E-03
163
65
9.02
252
0.45
390
0.48
0.055
1.45E-03
138
62
7.51
260
0.5
400
0.66
0.05
1.66E-03
121
60
6.46
266
0.55
410
0.90
0.045
1.82E-03
110
60
5.76
272
0.6
420
1.21
0.04
1.93E-03
104
62
5.33
277
0.65
430
1.59
0.035
1.95E-03
102
67
5.15
282
0.7
440
2.08
0.03
1.87E-03
107
75
5.23
288
0.75
450
2.68
0.025
1.68E-03
119
89
5.65
293
0.8
460
3.42
0.02
1.37E-03
146
117
6.64
300
0.85
470
4.32
0.015
9.71E-04
206
175
8.80
309
0.9
480
5.40
0.01
5.40E-04
371
334
14.41
323
0.95
490
6.68
0.005
1.67E-04
1197
1137
39.19
362
Reactor Volume versus Conversion

500
3000
450
2500
400
350
2000
VPFR
250
1500
200
1000
150
100
VCSTR
50
500
FA0/-rA
0
0
0.1
0.2
0.3
0.4
0.5
X
0.6
0.7
0.8
0.9
Volume
FA0/-rA
300
Solution : Part b
What is the maximum inlet temperature one could have so that the
boiling point of the liquid (550 K) would not be exceeded even for
complete conversion?
( H rx ) X =
T=
T0 +
T 0 + 200X
C
i Pi
T0,max =
550 200* X max =
550 200*1 =
350 K
Part c:
Plot the conversion and temperature as function of PFR volume.
600
0.9
500
0.8
0.7
400
0.5
300
0.4
200
0.3
0.2
100
0.1
0
0
0
50
100
150
200
VPFR
250
300
350
400
0.6
Part d
Calculate the concentration achieved in one 500 dm3 and in two
250-dm3 CSTRs in series.
V
=
CSTR
For 1 CSTR
V
=
CSTR
FA0 X
FA0
=
=
X
2
r A
kC A0 ( 1 x )
=
VCSTR
,2
E
k 1 exp
R
1
1 2
C A0
(1 x )
T1 T
FA0
E 1
1
k 1 exp
R T 1 .300 + 200 X
2
C A0 ( 1 x )
0.2
10000
0.01 exp
1.987
For 2 CSTRs
V CSTR=
,1
FA0
FA0 X 1
=
r A
=
X 500 ,
1
1
2
300 300 + 200 X 0.1 ( 1 x )
=
X 0.92
0.2
10000
0.01 exp
1.987
FA0 ( X 2 X 1 )
=
rA
1
1
300 300 + 200 X 1
0.2
2
0.1 ( 1 X 1 )
X=
250
1
=
X 2 250
10000 1
2
1
0.01exp
0.1 ( 1 X 2 )
1.987 300 300 + 200 X 2
0.881
X=
1
=
X 2 0.97
Steady State Reactors with Heat Exchange
We have studied the operation of reactor under adiabatic

condition
In many cases we need to introduce heat or remove heat from

the reactor
.
UA (T T a )
Q
Let Q be the heat added to the reactor=
The energy Balance around differential volume V:

Coolant
Q + Fi H i
Fi H i
V +V
=
0
FA0
T0
=
Q U A ( Ta =
T ) U a V ( Ta T )
where a is heat exchange area per unit volume of the reactor,a =
U a V (Ta T ) + Fi H i
Fi H i
V +V
=
0
Ta
A
V
d Fi H i
=
U a (Ta T )
0
dV
FA
T
Expanding the energy balance equation:

d ( F H )
=
0
U a (T T )
i
FA0
T0
V
T
dV
We get:
The PFR mole Balance equation:

dFi
= r=
i ( r A )
i
U a (Ta T )
Ta
Coolant
dFi
dH
0
H i i Fi =
dV
dV
dV
Differentiating the enthalpy equation with respect to V:
dH i d C pi dT
dT
= = CPi
dV
dV
dV
Substituting into the
expanded energy balance equation:
H Rx
U a (Ta T ) ( i H i ) ( rA )
dT
F
C
0
i Pi d=
V
dT rA H Rx U a (T Ta )
=
dV
FiCPi
FA
T
The design equation for PFR with heat exchange:

rA H Rx U a (T T a )
dT
=
dV
Note:
=
FC
F (
i
Pi
A0
Heat Removal
Heat Generation
Coolant
( F C )
i
+=
FA 0 i C Pi + =
FA 0
i X )C Pi
i C Pi X
( C
i
+ C Pi X
And the friendly form of the design equation becomes:

r H Rx U a (T T a )
dT
= A
dV
FA 0 i C Pi + C Pi X
Pi
For PBR, W=V b and the design equation becomes

rA' H Rx
dT
=
dW
FA 0
( C
i
Pi
a (T T a )
+ C Pi X
FA
T
FA0
T0
Pi
Ta
Solving CRE Problem for Reactors with Heat Exchange

The
Differential Equation describes the change in T

along the reactor
rA H Rx U a (T T a )
dT
=
dV
FA 0
Must
If
( C
i
Pi
+ C Pi X
or
rA' H Rx
dT
=
dW
FA 0
( C
i
Pi
a (T T a )
+ C Pi X
be coupled with mole balance equation:

r
dX
= A
dV
FA 0
or
rA'
dX
=
dW
FA 0
the coolant temperature varies down the reactor we

must add coolant balance:
dT a U a (T T a )
=
.
dV
m c C Pc
This
dT a
= B
dw
a (T T a )
.
m c C Pc
set of equation must be solved simultaneously
Non-Isothermal Reactor Design: Example
The elementary irreversible organic liquid phase reaction

A + B C
is carried out in a flow reactor. An equimolar feed of A and B
enters at 27 C. The volumetric flow rate is 2 dm3/s and CA0 =
0.1 kmol/m3.
a)
Plot the conversion and temperature as function of PFR volume

when a heat exchange is added, Ua = 20 cal/m3.s.K, and the coolant
temperature is constant at Ta= 450 K
b)
Repeat for a coolant flow rate of 50 g/s and CPc = 1 cal/g.K and inlet
cooling temperature of Ta0 = 450 K
c)
Vary the cooling rate between 1-1000 g/s
HA(273)=-20 kcal/mol, HB(273) = -15 kcal/mol, HC(273) =-41 kcal/mol

CP,A= CP,B =15 cal/mol.K, CP,C= 30 cal/mol.K
k = 0.01 dm3/mol.s at 300 K, E =10000 cal/mol
Solution: Part A
Reaction Kinetic Data:
Ta
Coolant
mol/dm3
mol/dm3
(Hrx)273=
CP =
Heat Exchange Data
Ua =
Ta =
FA
T
FA0
T0
; T1=
Thermal Data
-rA =
CA0 =
CB0 =
v0 =
T0 =
k1 =
E=
A + B C
XA
?
VPFR
Solution Cont.:
Mole Balance:
Energy Balance:
Stoichiometry:
FA0 =
rA =
kT
CA =
CB =
E 1 1
k1 exp
R T1 T
( H rx )T =
C
i
dX
=
dV
dT
=
dV
Pi
Solve the two differential equations using Polymath
Polymath Solution:
Polymath Solution:
Solution: Part A
Reaction Kinetic Data:
-rA = k CA CB
CA0 = 0.1 mol/dm3
CB0 = 0.1
mol/dm3
v0 = 2 dm3/s
T0 = 300 K
k1 = 0.01 dm3/mol. S ; T1= 27+273 = 300 K
E = 1x104 cal/mol. K
FA0
T0
(Hrx)273= -41 + 15 + 20 = - 6 kcal/mol. K

XA
CP = 30 - 15 -15 = 0
Heat Exchange Data
Ta
Coolant
Thermal Data
A + B C
Ua = 20 cal/m3.s. K
Ta = 400 K
FA
T
?
VPFR
Solution Cont.:
Mole Balance:
Energy Balance:
Stoichiometry:
dX rA
=
dV FA0
dT rA ( H Rx )T U a (T Ta )
=
dV
FA0 i CPi + CPi X
C A C A0 (1 X )
=
CB= C A0 (1 X )= C A
=
FA0 C=
0.1
=
x 2 0.2 mol / s
A 0 v0
E 1 1 2
2
rA= f ( X , T )= kC A= k1 exp C A 0 (1 X )
R T1 T
6000 cal / mol. K
( H rx )T =
( H rx )273 =
Pi
CP ,i =
= A CPA + BCPB + C=
CPC 30 cal / mol. K
C
i
P,i
= C P ,C C P , A C P , B = 0
Research
RESEARCH
COLORADO SCHOOL OF MINES
Projects
CSM faculty
PI faculty
Integrated Carbonate Reservoirs

Characterization and Simulation of Abu Dhabi Fractured
Carbonate Reservoirs
H. Kazemi (CSM),
S. Ghedan (PI)
Fluid Sensitivity of Seismic Properties in Carbonate

Reservoirs
M. Batzle (CSM)
M. Prasad (CSM)
S. Vega (PI)
Selection and Optimization of Miscible and Immiscible

Displacement to Improve Production from Fractured,
Carbonate Reservoirs of Abu Dhabi
H. Kazemi (CSM)
S. Ghedan (PI)
Integrated Carbonate Reservoir Characterization
J. Sarg (CSM),
S. Lokier (PI)
T. Steuber (PI)
Imaging Two-Phase Flow and Hydrofracturing in Carbonate

Rocks by Looking at the Joint Inversion of Passive Seismic
and Electrical Signals
Revil (CSM)
S. Vega (PI)
RESEARCH
Projects
CSM faculty
Upstream Materials and Equipment Engineering

Minimizing Corrosion of Petroleum Production Equipment by
B. Mishra
Hydrogen Sulfide and Carbon Dioxide
Damage Diagnosis and Structural Integrity Evaluation of
R. Zhang
Pipelines and Infrastructural Systems
Corrosion Behavior of Expanded Tubes in Harsh
B. Mishra
Environments
Chemical Processing
C. Koh
Desalination by Hydrate Nucleation and Growth
A. Sum
B. E. D. Sloan
Pyrolysis Reactions of Butene Isomers at Low Temperatures
A Direct Internal Reforming Protonic-Ceramic Fuel Cell
A. Dean
R. O'Hayre
N. Sullivan
PI faculty
A. Al-Shoabi
A. Seibi
A. Seibi
C. Peters
I. Economou
H. Carstensen
A. Al-Shoabi
A. Almansoori
RESEARCH
Projects
CSM faculty
PI faculty
Power Distribution
Development of a PV Grid Connected Inverter for
Smart Grids
M. Simoes
A. Al Durra
Engineering Education
Establishing and Supporting a Center of Teaching
Excellence at the PI in Abu Dhabi
R. Miller
Preparing Global Engineers: Developing Engineering

Design Education Across Cultures
S. Scott
R. Knecht
B. Bielenberg
RESEARCH
UNIVERSITY OF MINNESOTA
Projects
UMN Faculty
PI Faculty
Hydrocarbon processing
Catalytic Removal of Sulfur from Process Gas Streams
without Addition of Hydrogen: Effect of Zeolite Topology,
Composition and Mesoporosity
Selective Catalytic Synthesis of Branched C4-C7
Hydrocarbons from CH3OH
or CH3OCH3
Coatings for Catalytic Processes
Aditya Bhan
Michael Tsapatsis
Saleh Al Hashimi
Radu Vladea
Aditya Bhan
Matteo Cococcioni
Saleh Al Hashimi
Radu Vladea
Michael Tsapatsis
Lorraine Francis
Saleh Al Hashimi
Radu Vladea
Simulation and optimization

Simulation, Optimization and Control of Solid Oxide Fuel
Cell Systems
Molecular Modelling of Fluid Phase Equilibria
P. Daoutidis
Jeffrey J. Derby
A. Almansoori
I. Siepmann
I. Economou
C. Peters
RESEARCH
UNIVERSITY OF MINNESOTA
Projects
UMN Faculty
PI Faculty
Polymer processing
Polymeric Membranes for Advanced Process Engineering
Graphene/Polymer Composites
Synthesis and Processing of Functionalized Polyolefins
F. Bates
E. Cussler
M. Hillmyer
T. Lodge
C. Macosko
F. Bates
M. Hillmyer
C. Macosko
A. Abdala
I. Economou
C. Peters
A. Abdala
A. Abdala
Materials Science and Engineering (SEED)

Processing Improved Microstructures for the Energy Industry
Conversion of CO2 into polymers and chemicals
William W. Gerberich
K. Andre Mkhoyan
Jeffrey J. Derby
Friedrich Srienc
Ahmed Abdala
RESEARCH
UNIVERSITY OF MARYLAND
Projects
UM Faculty
Energy Recovery and Conversion

Sulfur Recovery from Gas Stream using Flameless and Flame
A.K. Gupta
Combustion Reactor
PI Faculty
A. Al Shoaibi
Separate Sensible and Latent Cooling with Solar Energy
R. Radermacher
Y. Hwang
I. Kubo
Waste Heat Utilization in the Petroleum Industry
R. Radermacher
Y. Hwang
S. Al Hashimi
P. Rogers
Energy-Efficient Transport Processes

Multidisciplinary Design and Characterization of Polymer
Composite Seawater Heat Exchanger Module
A. Bar-Cohen
S.K. Gupta
D. Bigio
P. Rogers
Study on Microchannel-Based Absorber/Stripper for CO2

Separation from Flue Gas
M. Ohadi
S. Dessiatoun
M. Al Shehhi
Enhancement of Polymerization Processes Using Microchannel

Reactor
M. Ohadi
S. Dessiatoun
E. Al Hajri
RESEARCH
UNIVERSITY OF MARYLAND
Projects
UM Faculty
PI Faculty
S. Azarm
P.K. Kannan
A. Almansoori
S. Al Hashimi
Dynamics and Control of Drill Strings
B. Balachandran
Y. Abdelmagid
H. Karki
Studies on Mobile Sensor Platforms
B. Balachandran
N. Chopra
H. Karki
M. Modarres
A. Seibi
M. Chookah
Energy System Management

Integration of Engineering and Business Decisions for Robust
Optimization of Petrochemical Systems
Development of a Probabilistic Model for Degradation Effects of

Corrosion-Fatigue Cracking in Oil and Gas Pipelines
William Marsh RICE University
RESEARCH
RICE UNIVERSITY
Projects
Modeling Asphaltene behaviour and deposition in Crude Oil

Systems
Mobility Control for CO2 EOR in heterogeneous high temp, high
salinity carbonate reservoirs
Rice Faculty
PI Faculty
Walter Chapman
Francisco Vargas
George Hirasaki, Lisa

Biswal, Keith
Johnston, Quoc
Nguyen
RESEARCH
STANFORD UNIVERSITY
Stanford
Faculty
PI Faculty
S. Azarm
P.K. Kannan
A. Almansoori
S. Al Hashimi
Dynamics and Control of Drill Strings
B. Balachandran
Y. Abdelmagid
H. Karki
Studies on Mobile Sensor Platforms
B. Balachandran
N. Chopra
H. Karki
M. Modarres
A. Seibi
M. Chookah
Projects
Integration of Engineering and Business Decisions for Robust
Optimization of Petrochemical Systems
Development of a Probabilistic Model for Degradation Effects of

Corrosion-Fatigue Cracking in Oil and Gas Pipelines
RESEARCH
UNIVERSITY OF TEXAS AT AUSTIN
Projects
UT Faculty

Kamy Sepehrnoori,
Director
Enhanced Oil Recovery by CO2 Injection
Russell T. Johns
Larry W. Lake
Kishore K. Mohanty
Quoc P. Nguyen
PI Faculty
A. Almansoori
S. Al Hashimi

CHE411 Fall 2010-Chemical Reaction Engineeirng-Ahmed A Abdala

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHE411 Fall 2010-Chemical Reaction Engineeirng-Ahmed A Abdala

Uploaded by

Copyright:

Available Formats

Chemical Reaction Engineering

CHEG411: Chemical Reaction Engineering

Chemical Plants: The Refinery EXAample

refinery converts crude oil into valuable petroleum

CHEG411: Chemical Reaction Engineering

Processes in Chemical Plants

The aim of any chemical plant is to produce valuable

A Chemical plant involves chemical and physical processes

A chemical process is a process that involves chemical

A physical process includes separation, miXAing, or

CHEG411: Chemical Reaction Engineering

course focuses in the chemical processes part

focuses mainly on the design of the vessels where

do not, however, focus on the mechanical design of

CHEG411: Chemical Reaction Engineering

The aim of the course is to answer the following

CHEG411: Chemical Reaction Engineering

To answer the first question we need information

To answer the second question we need to have the

Chemical reaction equilibria [thermodynamics]

To answer the third and fourth questions we need

Kinetics, transport (fluid, heat and mass)

CHEG411: Chemical Reaction Engineering

Chemical Reaction Equilibria

Consider the gas phase reaction:

From the Law of Mass Action:

The true (dimensionless) equilibrium constant K is:

fi is the fugacity of species i

CHEG411: Chemical Reaction Engineering

Chemical Reaction Equilibria

The true equilibrium constant, K

The pressure equilibrium constant, KP

Pi is the partial pressure of species i, Pi=Ci RT

The concentration equilibrium constant, KC

K=1 for ideal gas

For ideal gases:

CHEG411: Chemical Reaction Engineering

Equilibrium Constant versus Temperature

a function of temperature only

van' t Hoff ' s equation

If CP is assumed to be constant (CP=0), then

CHEG411: Chemical Reaction Engineering

Equilibrium Constant versus Temperature

As T increases, the equilibrium

As T increases, the equilibrium

CHEG411: Chemical Reaction Engineering

Equilibrium Constant and Free Energy

equilibrium constant at temperature T can be

GRx0 = cGC0 + dGD0 - aGA0 - bGB0

is related to the reaction enthalpy and entropy as

CHEG411: Chemical Reaction Engineering

Example: Calculation of Equilibrium Constant

Acetic acid is esterified in the liquid phase with ethanol

For this reaction G0298 = -4.65 kJ/mol and H0298 =

The equilibrium constant for the reaction at 100 C. For this

The mole fraction of the reaction components at equilibrium,

CHEG411: Chemical Reaction Engineering

Solution: Equilibrium Constant

of the equilibrium constant:

Assume constant Cp between 298 and 373 K

R 298 373 8.314 298 373

Solution: Equilibrium Composition

activity coefficient () is assumed to be 1