1

UNIVERSITY OF GEZIRA
COLLEGE OF ENGINEERING &
TECHNOLOGY
Department Applied Chemistry &
Chemical Technology
Student's Lecture Notes
IN
CHEMICAL REACTOR DESIGN

Prepared by
Dr. Babiker Karama Abdalla
Associate Professor of Chemical Engineering
E-Mail Address: babiker.k.abdalla@gmail.com

2010-2011


2
Out Lines
Chemical Kinetic
Chemical Reaction Engineering
(CRE)
Mole Balances
Rate of Reaction.
Mole balance Equation
Types of Reactors
Conversion and Reactor Sizing
Rate laws & Stoichiometry
Stoichiometric Tables
Isothermal Reactor Design
Membrane Reactors
Semi-Batch & Reactive Distillation
Reactors
Collection & Analysis of Rate Data
Multiple Reactions
Steady-State Nonisothermal Reactor
Design


3
1.1Chemical Kinetic:
Chemical kinetic is concerned with the rates of chemical
reaction. Chemists use kinetics to understand fundamentals
and speeds of the reaction pathways to design new or better
ways to achieve desired product:
- Chemical Engineers use kinetics to design a reactor for
specific reaction or reactions.
- The objective of chemical kinetics is to enable us to
produce the rate of the reaction.

1.2 Chemical Reaction Engineering (CRE):
- CRE is concerned with rational design or analysis of
performance of chemical reactors.
- Chemical reactors are devises in which change in
composition of matter occurs by chemical reaction.
- CRE is to enable us to predict by rational design the
performance of a reactor.

1.3 Kinetics of CRE:
Three levels of system size can be considered for
comparing the kinetic of the CRE.
1. Microscopic or Molecular: Where
molecules react and can be characterized by (C,
T, P or )
2. Local macroscopic: Where large amounts
reactants with gradient in Ci or T with P.


4
3. Global macroscopic: Like a bed of solid
reacting with a flow fluid where gradient of Ci
and T on the bed beside the local gradient.












1.4- Mole Balances:
1.4.1 Rate of Reaction.
1.4.2 Mole balance Equation.
1.4.3 Batch Reactors.
1.4.4 Continuous flow reactors.
1- CSTR
2- FR
3- PBR



Level 2
Level 1
Level 3


5
- General Mole Balance:
In - out + generation = accumulation
FAW FA (W+W) + r
\
AW = 0
( )( )
}
= A =
= - A
A
A
F
F
A
A
A
A
r
W W r
dw
dF
mole
mass
mass
mole
W r
0
\
\
A
\
dF
&
time
A
catalyst of
catalyst of time
A
) (


Example 1:
Gas phase reaction
(1) At constant value
( )
A
A A A
r
dt
dC
dt
V N d
dt
dN
V
= = =
/ 1


(2) At constant pressure i.e. NA=CAV
( )
dt
V ln
1 1
d C
dt
dC
r
r
dt
dV
V
C
dt
dC
dt
V C d
V dt
dN
V
A A
A
A
A A A A
+ =
= + = =

Example 2:
1
st
order reaction AB in PFR v is constant. Derive the
equation relating V, CA, k and v .find the value of reactor to
reduce exiting concentration CA to 10% of entering CA0 where
min
10
3
dm
v =
And k = 0.23 min
-1

m.b. of PFR
A
A
r dV
dF
=

1
st
order reaction -rA = kCA


6
v is constant there v0 = v
( )
A
A
V
V
C
C
A
A
A
A
A
A
A A A
C
C
Ln
k
v
V
dv
C
dC
k
dV
C
dC
k
v
kC
dN
dC
v
rA
dN
dC
v
dv
v C d
dV
dF
o
A
A
0
0
0
o
0
0
0
0
v
-

=
=
=
|
|
.
|

\
|
=
= = =
} }
}

m 0.1 , L 100 i.e 100 10 ln
23 . 0
10
1 . 0
ln
min 23 . 0
10
3
3
0
0
min * 3
dm
dm
C
C
dm
V
A
A
= = =
2. Conversion and Reactor Sizing:
- Conversion (X):
XA X
=
+ +
+ +
fed A of moles
reacted A of moles
X
D
a
d
C
a
c
B
a
b
A
dD cC bB aA
A


2.1 Design Equations:
| |
| |
| | | | | | ] [
reacted A of
0 at t reaactor to fed
initially A of
at t reactor in the
A of
. (consumed) reacted A of
fed A of moles
reactor A of
*
fed
A of
consumed
A of
0 0
0
X N N N N
moles
moles moles
X N moles
moles
moles moles
A A A
A
=

=
=
(

=
(

=
(

7
Moles of A in the reactor after X conversion
( )
( )
AB
A
A A A A
kC rA
V rA
dt
D
a
d
C
a
c
B
a
b
A
V r
dt
X N X N N N
o
=
=
+ +
=
= =
A
A
dN
-
then component key the is A ,
dN
system both in the balance mole
1
0 0

In both systems we are looking for (t) then
A
A A A
A
A
A
A
A A A
dt
dC
dt
V N d
dt
dN
V
V r
dt
dX
V r
dt
dX
combing
dt
dX
N
dt
dN
X N N N
= = =
=
=
=
=
/ ( 1
] [N
reactor batch of equation design
N -
0
0
0 0
A
A

The design equation can be expressed as
} }

=

=
X(t)
0
) (
0
A
0
dX
int
N dt or
A
A
t X
A
A A
A
A
r
dX
C
V r
egratig
V r
dX
r
dX
N Vdt



8
-Flow systems:
| || |
| |
| |
0
3
0
3
A
A
0
0
0 0
0 0
0 0 0 0
* C
] ( F ], [ ] [ ] [
system the leaving
A of flow molar
consumed A
of rate feed
fed A rate feed olar
time
reacted A of moles
.
fed A of moles
reacted A of
.
time
fed A of moles
.
v C F
s
dm
v
cm
moles
s
mol
F
X F F F X F F
molar
m
X F
moles
X F
A A
A
A A A A A
A
A
=
|
|
.
|

\
|
|
.
|

\
|
=
= =
(

=
(

=
=

for gas systems CA0 can be calculated form ideal gas equation
0
0
0
0
0
0
RT
p y
RT
p
C
A
A
A
A
= =

-CSTR:-
assuming
( )exit
X F
then
V X F
then
X F F F
V F F
D
a
d
C
a
c
B
a
b
A
A
A
A A
A A A
A A A

=
=
=
=
+ +
0
0
0 0
0
CSTR
V
is CSTR for equation design




9
-PFR:-
Using the mole balance equation of the PFR and multiply by (-
1) then
| |
(

=
= =
+ =
= =
=
}
X
A
A PFR
A A A
A A A A
A A A A
A
A
r
dX
F V
r
dV
dX
dX F dF
dX F XdF dF dF
X F F F F
r
dV
dF
0
A
0
0 0
0 0 0
0 0 0
F then
0


-PBR:
using the same analyses as for PFR now
(

=
=
}
x
A
A PFR
A A
r
dX
F V
r
dW
dX
F
A
0
\
\
0


Use of the design equation:
the rate of reactant A, -rA is function of the concentration, CA
which is function of the conversion CA (1-x)
( )
|
|
.
|

\
|

=
x kC r
x kC r
A A
A A
1
1 1 1
) 1 (
0
0




10
mol
dm
A
3
1

Reactor sizing:
- Consider the gas phase decomposion reaction
A B + C
The reaction was 422.2 k press at 10 atm initially A was
charged with equal molar ratio with an inert


1/-rA as X 1
if A B + C
1/ - rA as X Xe

sizing a CSTR

A
A
r
X F
V

=
0

X
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.85
s dm
mol
r
A
.
3

0.0053 0.0052 0.005 0.0045 0.004 0.0033 0.0025 0.0018 0.00125 0.001
mol
dm
r
A
3
1

189 192 200 222 250 303 400 556 800 1000
1000
300

600

400

200
0.2 0.4 0.6 0.8 1
conversion (x)


11


Sizing a PFR }

=
X
A
A PFR
r
dx
F V
0
0



Using five point equation formula x=0.2
(
(
(

A
=
8 . 0 6 . 0 4 . 0 2 . 0 0
1 4 2 4 1
3
0
A A A A
x
A
A
r r r r r
x
F V
Also using Simpsons rules
800


600


400

200
0.2 0.4 0.6 0.8
800

600

400

200
0.2 0.4 0.6 0.8


12

comparing CSTR and PFR






600


400


200
0.2 0.4 0.6
PFR
1
V
PFR
dm
3
250
X


13

Reactor in Series

FA1 = FA0 FA0X1
FA2 = FA0 FA0X2
FA3 = FA0 FA0X3
Now Reactor value are given as
( )
}
}

=
3
0
2
0
2
2 1
1
0
3
1 2
2
0
1
V

A
A
A
A
A
A A
X
A
r
dx
F
r
x x F
r
F F
V
rA
dx
F V


-2CSTRs in series


V
2
V
3
V
1

F
A2
X
2
F
3
X
3
F
A1
X
1
X=0
F
A0
V
2
V
1

X
2
= 0.8
X
1
=0.4
F
A0


14
( )
2
0
1
0
1 2
2
1
1
V ,
A
A
A
A
r
X X
F
r
X
F V

=



-2PFRs:



V
2
V
1

X
2
= 0.8
X
1
=0.4
800


600


400

200
0.2 0.4 0.6 0.8
0.2 0.4 0.6 0.8
800

600

400

200


15
Order of Sequencing reactors:
(A)


(B)



800


600


400

200
0.2 0.4 0.6 0.8
(A)
X
1

V
2

X
2
= 0.8
F
A0
X
1



X
2
= 0.8
F
A0


16

-Relative Rate of reaction:
A+b/aB c/aC+d/aD
The rate of formation of C=c/a (rate of disappearance of A)
rC=c/a(-rA)= -c/a rA
From the Stoichiometry of the reaction
-rA/a = -rB/b = rC/c = rD/d
Space time: ( )

}

=

X
A
A
r
dx
C
v
V
0
0
0
t
t


800


600


400

200
0.2 0.4 0.6 0.8
(B)


17
space velocity:

}
}
}

=
= =
= =

=
=

=
=

=
=
=

0
0
0
0
0
0
0 0
0
0
0 0
0
A
A
0
0
0
0 A
0
0
0
C x X
C 0 X when
:
F ,
:
1
) (
A
A
A
A
C
C
A
A
C
C
A
A
A
A
A
A
A
A A
A
A A A A
A
A A
A
x
A
r
dC
r
dC
v V
C
dC
dX
c
C
C
C C
v C
v C v C
F
F F
X
v v when
F
F F
X
C v
r
dx
V
v v when
SV
V
v
SV
t
t










C
A
C
A0


18
3. Rate laws & Stoichiometry:
- Homogeneous reaction
- Heterogeneous reaction
- Irreversible reaction
A+B C +D
- Reversible reaction
A+B C+D

3.1 Reaction rate constant ( K)
-rA = [ KA(T)] [fn(CA , CB, ..)]
the Arrhenius equation
kA(T) = Ae
-E/RT

A : pre exponential factor or frequency factor
E : activation energy J/mol , cal/mol
R : gas constant = 8.314 J/mol.k = 1.987 cal/mol.k
T : absolute temperature k
ln kA = lnA E/R(1/T)
Straight line equation with slope (E/R)
Also can be determined by

1 2
1
2
1 2 1
2
2
2
1
1
1 1
ln
1 1
ln
)
1
( ln ln
)
1
( ln ln
T T
K
K
R
E
T T R
E
K
K
T R
E
A k
T R
E
A k

=
|
|
.
|

\
|
=
=
=



19

3.2 Reaction order & Rate Law
-rA= kAC

A C

n = +

Example : gas phase reaction
2NO + O2 2NO2
-rNO = kNO C
2
NO CO2
CO + Cl2 COCl2
-rCO = k Cco CCl2
3/2

2
2 2
\
2
2 2 2
1

2 2
O
O N O N
Pt
C K
C k
O rN
O N O N
+
=
+

Rate constants correspond to :
Zeroorder (-rA)= kA
{k} = mol /dm
3
.s

1
st
order
-rA= kACA
{k} = S
-1


2
nd
order
-rA= kAC
2
A
{k} = dm
3
/mol .S

3
rd
order
-rA= kAC
3
A
{k}= (dm
3
/mol)
2
1/s


20

n
th
order
-rA= kAC
n
A
{k}= (dm
3
/mol)
n-1
1/s

-3.3 Elementary rate laws & Molecularity
elementary rate law if the reaction order is identical with the
stoichiometric coefficient
H2+ I2 2HI
-rH2= kCH2CI2

Reversible Reactions :
aA + bB cC + dD
at equilibrium

C C
C C
b
Bc
a
Ae
d
De
C
Ce
C
K =


units of Kc is (mol/dm
3
)
d+c-b-a

2C6H6 C12H10+H2
2B D+ H2
6 6 2 10 12
2
B
2 10 12 6 6
2
k forward
2
H C H H C
r
H H C H C
B
B
k
B
B
k
C
+
=
+

rB reverse = k-B CD CH2
rB rB Net = rB forward + rB reverse
rB = - kB C
2
B + k-BCDCH2



21
multiplying by ( 1)
C
C
C C
e
e
B
H D
C
C
B
B
C
H D
B
B B
H D
B
B
B
B H D B
B
B B
C C
K
K
k
k
K
C C
k r
C C
k
k
k C C k k r
2
2
2 2
2
2
2 2
=
=
|
|
.
|

\
|
=
|
|
.
|

\
|
= =

-3.4 Non elementary rate laws & reactions
H2 + Br2 2HBr
Reaction rate law :

2
2 / 1
2
/
1
Br HBr
Br H
HBr
C C k
C C k
r
+
=

Also
CH3CHO CH4+CO
C
CHO CH
CHO CH
k r
2 / 3
3
3
=

Catalytic gas phase decomposing of cumene
C6H5CH (CH3)2 C6H6 + C3H6 + C3H6
C B + P
Langmuir Hinshellwood kinetics:
( )
B B C C
P P B C
c
P K P K
K P P P k
r
+ +

=
1
/
\

KP press equilibrium constant (atm,bar,kPa).


22
KC,KB adsorption constant (atm
-1
,bar
-1
,kP
-1
a).
K rate constant (mole cumene /kg cat.s.atm).
At equilibrium


C
C C
C C
C C C
C
P B
P
B C C
P P B C
P
P P
K
K P K
K p P P
r
=
+ +

= =
1
/
0


-3.5 Stiochiometric Tables:
aA + bB cC + dD
taking A as basis and assuming irreversible reaction
A + b/a B c/a C + d/a D
3.5.1 Batch Systems





t= t
N
A

N
B

N
C

N
D

N
I

t=0
N
A0
N
B0
N
C0
N
D0
N
I0
Batch Systems

N
A
=N
A0
N
A0
X
= N
A0
(1-X)


23
Species Initial mol Change mol Remaining mol
A NA0 -(NA0X) NA=NA0-NA0X
B NB0 -b/a (NA0X) NB =NB0-b/a(NA0X)
C NC0 c/a (NA0X) NC = NC0 +c/a(NA0X)
D ND0 d/a (NA0X) ND = ND0 + d/a(NA0X)
I NI0 --------- NI = NI0
Total NT0 NT = NT0+(d/a+c/a-b/a-1)NA0X

Moles of B reacted = (moles B reacted/moles A reacted).moles
A reacted = b/a(NA0X) = NB = NB0 b/a NAoX
= d/a + c/a b/a -1 increase or decrease of on total No of mole
NT0 = NT0 + NA0X
Known CA = NA/V if V is a constant
( ) ( )
( ) ( )
( )
( )
|
.
|

\
|
+ =
|
.
|

\
|
+ =
|
.
|

\
|

=
=

=
=
|
.
|

\
|
+
=
|
.
|

\
|
+
=
|
.
|

\
|

=
= = = =
+
= =
+
= =

= =

= =
X
a
d
C C
X
a
c
C C
V
X
a
b
N
C
X C
V
X N
C
V
X
a
d
N
C
V
X
a
c
N
V
X
a
b
N
C
N
N
N
N
N N
N
V
X N a d N
V
N
V
X N a c N
V
N
C
V
X N a b N
V
N
V
X N
V
N
C
D A D
C A C
B A
B
A
A
A
D A
D
C A B A
B
A
I
A
D
C
A A
B
B
A D
D
A C
C
C
A B
B
A
A
A
u
u
u
u
u u
u u u u
0
0
0
0
0
0
0 0
0
0
0
0
0
0
0
0
0 0 0 0
0 0 0
0
0
0
C
I D
C
D
B
1
1
V V valume consatant for
C ,
, ,
N
,
/
C ,
/
/
C ,
1



24
3.5.2 Flow system
For flow system CA can be expressed as
CA = FA/v = [moles/time]/[dm
3
/time] = moles/dm
3

( )
v
F
a
d
F
v
F
v
X F
a
c
F
v
F
C
v
F
a
b
F
v
F
X
v
F
v
F
C
X A D
D
A C
C
C
A B
B
A
A
A
0 0 0 0
0 0
0
D
B
C ,
C , 1
+
= =
+
= =

= = = =




I D C
0
0
, ,
0
0
0
0
0
0
0
0
u u u
u
similarly
y
y
C
C
v C
v C
F
F
A
B
A
B
A
B
A
B
B
= = = =


A+b/a Bc/a C+d/aD
F
A
F
B
F
C
F
D
FI
F
A0
F
B0
F
C0
F
D0
F
I0
entering


25

Species Initial molar
feed
Change
mol/t
Remaining mol
A FA0 -FA0X NA=FA0(1-X)
B FB0=BFA0 -b/a FA0X NB =(B-b/a*X)
C FC0= CFA0 c/a FA0X FC= FA0(co + c/a*x)
D FD0= DFA0 d/a FA0X FD = FA0 (D+d/a*X)
I FI0= IFA0 --------- FI = IFA0
Total FT0 FT = FT0+(d/a+c/a-b/a-1)FA0X
FT=FT0+FA0

For liquid without phase charge v = v0
CA=FA0/V0(1-X)=CA0(1-X)
CB=CA0(B-b/c*X)
Volume charge with reaction
N2 + 3N2 2NH3
For gas system using equation of state
PV = Z0NTRT
at t = 0
P0V0 = Z0NT0RT0
Dividing
V = V0(P0/P)T/T0(Z/Z0) NT/NT0
Volume V as function of X
NT = NT0+NA0X
Dividing by NT0
NT/NT0= 1+ (NA0/NT0)X = 1+ yA0X
= yA0=(d/a+ c/a b/a -1)NA0/NT0
V= V0 ( P0/P) T/T0(Z/Z0)(1+ X)


26
Assuming no change on Z I.e. Z0 =Z
V = V0 (P0/P) (1+ X) T/T0
Also for variable volume
CT = FT/V = P/ZT
CT0 = FT0/V0 = P0 /Z0RT0
Combining assuming no change on Z
V = V0 (FT/ FT0) P0/P (T/T0)
FT = FT0+ FA0X substitute
V = V0(FT0+FA0X)/FT0(P0/P)(T/T0)

( )
( )
( )
( )
( ) T
T
P
P
X
X
C Cj
C y
F
F
T
T
P
P
X
F
F
X
F
F
C C
T
T
P
P
X F F
X F
C C
T
T
P
P
F
F
C Cj
T
T
P
P
F
F
v
F
T
T
P
P
F
F
v
F
v
T
T
P
P
X V V
T
T
P
P
X y V
T
T
P
P
X
F
F
V V
j j
A
T A
T
A
T
A
j j
T
A
T j
A T
j j A
T j
T
j
T
T
j T
T
T
j
A
T
A
0
0
A A
0
0
T
0
0
0
0
0
0 0
0 0
0
j
0
0
0
0
0
0
0
0
0
1
C & y Recalling
1
`
leveles both F by dividing
F
Cj
j species any for
1
1 1
0
0 0 0
0
0
0
0
0 0
0
0
0
0 0
0
0
0
0
0
0
0
0
|
|
.
|

\
|
+
+
=
= =
|
.
|

\
|
|
|
.
|

\
|
|
.
|

\
|
+
+
|
|
.
|

\
|
=
|
.
|

\
|
|
|
.
|

\
|
+
+
=
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
=
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
=
|
.
|

\
|
|
.
|

\
|
|
|
.
|

\
|
= =
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =
|
|
.
|

\
|
|
|
.
|

\
|
+ =

o u
o
o u
o
o u
,
o o





27
Assuming j is stoichiometric number, then
( ) ( )
( )
( )
( )
( )
( )
( )
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
) 1 ( 1
) 1 ( 1
) 1 ( 1
) 1 ( 1
) 1 (
1
1
1 1
0 0 0
0
0 0
0
0 0
0
0 0
0
0 0
P
P
T
T
X
C
P
P
T
T
X v
F
v
F
v
F
C
P
P
T
T
X
X
a
d
C
P
P
T
T
X v
X
a
d
F
v
X
a
d
F
v
F
C
P
P
T
T
X
X
a
c
C
P
P
T
T
X v
X
a
c
F
v
X
a
c
F
v
F
C
P
P
T
T
X
X
a
b
C
P
P
T
T
X v
X
a
b
F
v
X
a
b
F
v
F
C
P
P
T
T
X
X
C
P
P
T
T
X v
X F
v
X F
v
F
C
I A I A A
I
I
D
A
D A D A
D
D
C
A
C A C A
C
C
B
A
B A B A
B
B
A
A A
A
A
|
.
|

\
|
+
=
+
= = =
|
.
|

\
|
+
|
.
|

\
|

=
+
|
.
|

\
|

=
|
.
|

\
|

= =
|
.
|

\
|
+
|
.
|

\
|

=
+
|
.
|

\
|

=
|
.
|

\
|

= =
|
.
|

\
|
+
|
.
|

\
|

=
+
|
.
|

\
|

=
|
.
|

\
|

= =
|
.
|

\
|
+

=
+

= =

u u

u

u u

u u

u u





4.Isothermal Reactor Design

4.1 Procedure:
1- Mole Balance (M.B)

dt
dN
dv r F F
A
V
A A A
= +
} 0

2- Design equations:
Batch
}

= =
X
A
A A
V
dX
V r
dt
dX
N
0
A
0 0
N t &

CSTR
A
A
r
X F
V

=
0



28
PFR }

= =
X
A
A A
r
dX
r
dV
dX
F
0
A
0 0
F V &

(3)
No

given
yes ) (
+
= x f r
A



1- Rate law: -rA = k(CACB- CCC0/Kc)

2- Stoichiometry:
liquid phase or
constant value
Gas phase Isothermal
isobaric
CA= CA(1-X)
CB = CA0(B b/a
*X)
B = yB0/yA0

( )
|
|
.
|

\
|
+

=
0
0
1
1
0
P
P
T
T
X
X
C C
A A
c


( )
o c
c
0
0
1
) 1 (
A
A A
y
X
X
C C
=
+

=




6 Combine gas law and Stoichiometry to find r then
proceed to (7 ).
7 Evaluate the above equations to find tbatch, VCSTR or VPFR




29
4.2 French Menu Analogy






0
A
A
F
r
dv
dx
=
C
A
=F
A
/V
C
A
=N
A
/V
-r
A
=kC
A
V= F
A0
X
-r
A
0
A
A
N
V r
dt
dx
=

(

=
e
e B
A
k
C C
C k r
A A
A
C k
kC
r
+
=
1

2-Rate law
3-Stoichiometry
flow
F
A
=F
A0
(1-X)
N
A
=N
A
(1-k)
Bate
CSTR
Batch 1-M.B
PFR


30

Liquid
constant
flow rate
Ideal gas variable
flow rate
Ideal gas variable
volume
Liquid or gas
constant
volume
v= v0
( )
0
0
0
1
T
T
P
P
X v v c + = ( )
0
0
0
1
T
T
P
P
X v v c + =
v =v0
( ) X C C
A A
= 1
0
( )
( ) T
T
P
P
X
X C
C
A
A
0
0
1
1
0
c +

=
( )
T
T
P
P
X C C
A A
0
0
1
0
=
( ) X C C
A A
= 1
0



4-Combining 1
st
order G.P. in PFR
From M.B From R.L from Stoichiometry

( )
( )
|
|
.
|

\
|
+

= =

=
T
T
p
P
X
X
C
F F
r
dv
dX
A
A A
A 0
0 A
A
1
1
F
k

kC

0
0 0 0
c



T
T
P
P
X
X
v
k
dV
dX
0
0 0
1
1
|
.
|

\
|
+

=
c


Integrating for const Temp & press.

( )
(

+ = X
X k
v
V c c
1
1
ln 1
0

Batch system:
- No in or out flow
- Well mixed.
- For liquids density change is negligible.
- For gases volume remains constant.


31
M.B
A
A
r
dt
dN
V
=
|
.
|

\
| 1

In forms of concentration:
A
A
A
A
A
A A
r
dt
dC
r
dt
dC
dt
V
N
d
dt
dN
v dt
dN
v
=
= =
|
|
.
|

\
|
= =
0
0
1 1

consider A B
2
nd
order in A
R.L -rA= kC
2
A
Combining M.B with R.L
-dCA/dt = kC
2
A
-dCA/kC
2
A= dt
CA= CA0 at t = 0 and reaction was isothermal
t
C C k
dt
dC
k
A A
t C
C
A
A
A
A
C
=
|
|
.
|

\
|

} }
0
0
1 1 1
1
0
2


Reaction times for batch systems:
M.B
V
N dt
dx
A
A
0

=
R.L 1
st
order
-rA = kCA
2
nd
order
-rA=kC
2
A
Stoichiometry
2
nd
order isothermal
liquid phase batch
reaction


32
( ) X C
V
N
C
A
A
A
= = 1
0
0

Combining
( ) X k
dt
dx
= 1
( )
2
1
0
X kC
dt
dx
A
=

Integrate
X k
t

=
1
1
ln
1

( ) X kC
X
t
A

=
1
0


- CSTR:
( )
exit A
A
CSTR
r
X F
V

=
0

where v =v0

A
A A
A
st
A
A A
A
A A
kC
C C
kC r
r
C C
v
V
r
C C
v V

=
=

= =
|
|
.
|

\
|

=
t
t
A
0
0
- order 1
0
0


Solving for CA then
k
C
C
A
A
t
=
1
0

No volume change
( ) X C C
A A
= 1
0

Combining
k
k
X
t
t

=
1



33
k is Damkoher Number (Da)
Da is the ratio of the rate reaction of A to the rate of
convective transport of A at the entrance of the reactor.
1
st
order
k
C v
V kC
F
V
Da
A
A
A
A
t

= =

=
0
0
0
0
0

2
nd
order
0
0
0
0
2
A
A
A
kC
C v
V
C
k
Da t = =

90% X 10 Da
10% X 1 . 0
> >
< s Da

Assuming 2 reactors in series
( )
C
k
C C v
r
F F
B M
k
C
C
A
A A
A
A A
A
A
2
2
0
2
1 1
2 1
2
2 1
0
1
V
2 rector for .
1

=
+
=
t


Solving for CA2
( )( )
2 2 1 1 2 2
1 1 1
0 1
2
k k
C
k
C
C
A A
A
t t t + +
=
+
=

Suppose we have n reactor in series
( )
( )
n
n
A
n
A
A
for
Da
C
k
C
C
n
Da 1
1
- 1 X
conversion the
) 1 ( 1
0 0
+
=
+
=
+
=
t



34
Rate consumption of A in the n
th
reactors:

n
A
A A
k
C
k kC r
n n
) 1 (
0
t
= =

CSTR in parallel:
Reactors are of the same size then
|
|
.
|

\
|

=
i
i
A
i
A i
r
X
F V
0
X1 = X2 = . = Xn=X
Rate will be the same
A A A A
r r r r
n
= = = = ....
2 1

volume of reactor in compared to total number of reactors
Vi = V/n
Total moles flow will be related as

n
F
F
A
A
i
0
0
=

Now

i i
A
i
A
i
A
r
X
r
X
n
F
n
V

=
|
|
.
|

\
|

=
0 0
A
F
V ,

2
nd
order in CSTR
Combining M.B with R.L then

c
A
i A
r
X F
V
2
0

=

For constant density



35
( )
( ) ( ) ( )
( )
( )
Da
Da Da
X
kC
kC kC
X
kC
kC kC kC
X
kC X kC X
X kC
X
then
k
C C
v
V
A
A A
A
A A A
A A
A
A
A A
c
2
4 1 2 1
2
4 1 2 1
2
2 2 1 2 1
0 2 1 kC

) 1 (

0
0 0
0
0 0 0
0 0 0
0
0
2 2
2
A
2
2
0
+ +
=
+ +
=
+ +
=
= + +

=

= =
t
t t
t
t t t
t t t
t
t


Tubular reactors:
- Gas phase.
- Turbulent
- No Radial dispersion.
- No Radial Gradient of temp, velocity & conc.
1- D.E
FA0dx/dv = -rA
if no press drop & heat exchange with surrounding

}

=
x
A
A
r
dx
F V
0
0

assuming 2
nd
order reaction & combing

}
=
x
C
A
A
k
dx
F V
0
2
0

for constant temp press gas phase


36
( )
( )
( )
( )
( )
( )
( )
( )
( )
}
}

+
=

=
+

=
+

=
=
= =
dx
X
X
k
F
V
dx
X k
X
F V
X
X
C
X v
X F
X v
F
v
F
C
C
C
A
A
X
A
A PFR
A
A
A A
A
2
2
2
0
2
2
2
0 0
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
c
c
c c c

integrating we obtain
( ) ( )
( )
(

+
+ + + =
x
X
X
kC
v
V
A
1
1
1 ln 1 2
2
2
0
0
c
c c c c

since no change on the tube radius the X-section area AC is
constant and
( ) ( )
( )
(

+
+ + + =
x
X
X
A kC
v
L
C A
C
1
1
1 ln 1 2
2
2 0
0
c
c c c c

Pressure Drop In Reactors
For ideal gas

( )
( )
0
i
0
0
0
1
C
operation isothermal for Design
1
0
0
P
P
X
X
C
T
T
P
P
X v
X F
v
F
C
i i
A
i i A
i
i
|
.
|

\
|
+
+
=
|
|
.
|

\
|
|
.
|

\
|
+
+
= =
c
o u
c
o u

Now we must determine the ratio P/P0 as function of volume.
Using the differential form of mole balance.
Consider the 2
nd
order isomerization
A B
Carried in a packed bed


37
M.B FA0 dx/dw = -r
\
A
R.L -r
\
A = kC
2
A
Stoichiometry for gas phase
( )
( ) T
T
P
P
X
X C
C
A
A
0
0
1
1
0
c +

=

R.L can be written as
( )
( )
2
0
0
\
1
1
0
(

+

=
T
T
P
P
X
X C
k r
A
A
c

combing and using isothermal design case
( )
( ) P X F
P
P
X
X
v
kC
dw
dx
P
P
X
X C
k
dw
dx
F
A
A
A
1 1
2
0
2
0
2
0
2
1
1
1
1
0
0
0
=
(

|
.
|

\
|
+

=
(

+

=
c
c


- Flow through a packed bed using the Ergun equation
( )
(

|
|
.
|

\
|
= G
D D Pg
G
dz
dp
P P C
75 . 1
1 150 1
3
|
|
|

where
G: PU: superficial mass velocity [ g/cm
2
.s]
g: conversion factor for gravitational acceleration
Dp: partial diameter
p: pressure
u: superficial velocity (cm/s)
z: length along the packed bed
: porosity : void volume /Total bed volume
: viscosity of gases passing through the bed g/cm.s
p: gas density g/cm
3



38
Using the Ergun equation the only variable is the gas density P
at S.S mass flow rate m (kg/s) is the same all through the bed

( ) ( )
( ) ( )
0
0
0
0
0
0
3
0
0
0
0
3
0
0 0
0
0
0
0
0 0
0
0 0
0
dz
dP

75 . 1
1 150 1

75 . 1
1 150 1
T
T
P P C
T
T
P P C
T
T
T
T
F
F
T
T
P
P
then
G
D D g P
G
let
F
F
T
T
P
P
G
D D g P
G
dz
dp
Combining
F
F
T
T
P
P
P
v
v
P P
F
F
T
T
P
P
v v
Pv v P
m m
|
|
.
|

\
|
=
(

+

=
|
|
.
|

\
|
(

+

=
|
.
|

\
|
= =
|
|
.
|

\
|
=
=
=
|
|
|
|
|
|
|
|

The catalyst weight W can be related to z by
W =(1-)Ac z*Pc
Pb =(1-)Pc bulk density
dW =Pb Ac dz
( )
0
0
0 0
0
0
1
2
/ 2
0
P P A
F
F
T
T
P P
P
dw
dp
C C
T
T
|
|
o
o

=
|
|
.
|

\
|
=

For single reaction Ergun equation can be expressed in terms
of X


39
( )
( ) X
P P
P
T
T
dW
dP
now
y
F
X
F
F
X
F
F
F X F F
F
F
A
T T
T
T
A
T A T
T
T
c
o
o o c o
o o
+ =
= = + =
|
|
.
|

\
|
+ = + =
1
/ 2
F
WHREE 1
1
0
0
0
A
0
0
0
0
0
0
0 0 0
0

Note when =0 P will be independent of conversion
= +ve pressure will damp
= -ve pressure will increase.
Now dP/dW=F2(X,P)
Solution isothermal system with = 0
( )
( )
( )
o
o
o
=
=
=
dW
P P d
dW
P P d
P
P
ing rearr
P P
P
dW
dP
2
0
0
0
0
0
/
/ 2
arg
/ 2

Integrating with P = P0 at W=0
(P/P0)2 = 1-W
(P/P0) = (1-W)
1/2

Also
2 / 1
0 0
2
1
|
|
.
|

\
|
=
P
z
P
P |


Membrane Reactor
There are two main types of catalytic membrane reactors


40
Inert membrane reactor with catalyst pellets on the feed side
[MRCF]

Catalytic Membrane Reactor [CMR



e .g C6H12 C6H6 + 3H2
symbolically A B + C
M.B
For A FBv - FAv+v-RBv+Bv = 0
As before dFB/dv = rB - RB
-R.L
feed
H
2
H
2
H
2
Catalytic
membrane
product
CMR
H
2
H
2
Feed
H
2
H
2
H
2
catalyst
C
6
H
6
Inert membrane
IMRCF


41
A C
A B
C
C B
A A
r r
r r
k
C C
C k r
=
=
|
|
.
|

\
|
=

- Transport Theory membrane:
RB = kCCB
- Stoichiometry:
C B
C B A
T
C
T
T
B
T
T
A
T A
r r r
F F F
F
F
C
F
F
C
F
F
C C
= =
+ + =
= = =
T
C B
F
C , C ,
0 0 0

- Combining & Summarizing:

C F F F F
F
F
F
F
K
C
F
F
C K r
r
dW
dF
F
F
C K r
dV
dF
r
dV
dF
B A T
T
C
T
B
C
T
T
A
T C A
A
C
T
B
T C A
B
A
A
+ + =
(

|
|
.
|

\
|
|
|
.
|

\
|

|
|
.
|

\
|
=
=
|
|
.
|

\
|
=
=

0
0
0



42
Unsteady State Operation









A,B Heat
Reactive distillation
C
A0
C
A
A
B
Heat
Semi Batch


43
Steady State Operation of CSTR
Startup of a CSTR :
Assuming semi-batch condition with reaction
A + B C +D
B is fed gradually to A
- M.B FA0 FA + rAV = dNA/dt
to liquid phase v =v0 & V = V0 using = V0/v0
then CA0 CA + rA = dCA/dt
1
st
order (-rA = kCA)
( )
(

+
+
=
=
+
+
t
t
t
t t
t
t
K
K
C
C
C
C
K
dt
dC
A
A
A
A
A
1 1 exp 1
1
1
0
0

Suppose t
s
is time for 99% conversion of CAs
CAs = CA0 /1+k
Using CA = 0.99 CAs
ts = 4.6 /1+k
slow reactions ts = 4.6
for fast reactions ts = 4.6/k

Semi batch Reactor:
Elementary liquid phase reaction
A+B C





B
A


44
M.B for A
0 +0 + rA V(t) = dNA/dt
inters of concentration

( )
dt
dV
C
dt
dC
V
dt
V C d
V r
A
A A
A
+ = =
over all mass balance
P0v0- 0+0 = d(Pv)/dt
Constant density P0=P & dV/dt = 0
V=V0 at t = 0 integrating
V = V0 + v0t
Substitute in the M. B
dt
dC
V Vr C v
A
A A
= +
0
M.B for A can be rewritten as
A A
A
C
V
v
r
dt
dC
0
=


M.B for B with feed rate of FB0
( )
( )
V
C C v
r
dt
ng substituti
F V r
dt
dC
V C
dt
dV
dt
VC d
F V r
dt
dN
B B
B
B B
B
B
B
B B
B

+ =
+ = + =
+ =
0
0
0
0
B
dC
g integratin & V for

Interims of conversion:
A+ B C+ D
For A


45
NA= NA0- NA0X
For B
}
+ =
t
A B B B
X N dt F N N
i
0
0 0

Constant molar feed rate
NB= NBi+FB0t NA0X
M.B on A rAV =dNAdt
Assuming 2
nd
order
( )
( )( )
( )
( )( )
( ) ) ( 1
/ -
D C B A for
1
N by dividing k
C

1
0 0 0
0 0
0
0 0
0
0
0
0 0
0
A
0 0
2
A
0 0
0 0
0 0
B
0 0
e A B e A
e A e A
C
B A
D C
B A
D C
B A
D C
C
C D C B A
e
C
A
A B B
A
D
A
C
A B B
A
A
A
A
D C
B A A
X N t F X N
X N X N
K
N N
N N
V
N
V
N
V
N
V
N
C C
C C
K
k C C C C k r
X
t v V
k
X N
X N t F N X k
dt
dX
combining
t v V
X N
C
t v V
X N
C
t v V
X N t F N
V
N
t v V
X N
V
N
C
dt
C C
C C k V r
e e
e e
e e
e e
e e
e e
i
i

=
= = =
=
+ +
+
|
|
.
|

\
|
+
=
+
=
+
=
+
+
= =
+

= =
|
.
|

\
|
=



46
Rearranging
( )
( ) 1 2
1 4 1 ) 1 (
1
0
0
0
0
0
0
0
0
2
2

(
(

|
|
.
|

\
|
+
=
|
|
.
|

\
|

+ =
C
A
B
C
A
B
C
A
B
C
e
e
e
e C
B C
A
K
N
t F
K
N
t F
K
N
t F
K
X
or
X
X
X K
F K
N
t

Reactive Distillation
( )
( )
V r
dty
dX
X N X
a
b
N N
X N N
dt
dN
V r
volume
D C B A
O H COOH CH OH CH COOH CH
A
A B A B
A A
A
A
k
k
=
=
|
.
|

\
|
=
=
= + +
+ +
+ +
0
0 0
0
2
1
A
2 3 3 3 3
N
B & A fead molar equal 1
1
0 0
A on
u

Balance on D with FD rate of evaporation
0+FD+rDV = dND


47
Integrating
( )
( )
( )
V
dt F
N
X
K
X
X kN
V r
V
dt F X N
V
N
C
V
X N
V
N
C
V
X N
V
N
C
V
X N
C
K
C C
C C k r
dt F X N N
t
D
A C
A
A
t
D A
D
D
A
C
C
A
B
B
A
A
C
D C
B A
t
D A D
(
(

|
|
.
|

\
|

=

= =
= =

= =

=
|
|
.
|

\
|
=
=
}
}
}
0
2
2
0
A
0
0
0
0
0
0
0
0
1
1
1
1
- R.L

Find volume as f(X or t)

( )
( )
D
WD D
WD D
F
P
M F
dt
dV
dt
PV d
M F
o = =
= + 0 0

specify the rate of evaporation of D

Case 1:
Immediate evaporation

dt
dx
N V r V r F
A A D D
0
= = =



48
Integration
V= V0-NA0X
V = V(1+LX)
Where L = -CA0 = MwDCA0/
Combining with CD = 0
(

+
=
(

=
x x
x
x
x
kC
dt
dx
L
L
L
A
1
1
ln
1
) 1 (
kC
1
t
g integratin by for t solving
1
) 1 (
0
0
A
2
c
c
c


Case 2: Inert gas is bubbled through reactor
Assuming Raoults law
( ) ( )
D
D C B A D
D
D C B A
I
D
D
D
D
I
T
T D I D I F
T D D
V
D C B D
D V
D D
F
V
N N N N
k
dt
dN
F
V
N N N N
k
dt
Coupling
F
y
y
F
y
F
F
F y F F F F
F y F
P
D P
N N N N
N
P
D P
l x g y

=
|
|
.
|

\
|

=
+ = + =
=
+ + +
= =
) (
) ( dN
M.R with
1
1
A
0 0



49
5. Collection & Analysis of Rate Data
Objective of this chapter is to obtain and analysis reaction
rate data to obtain the rate law of specific reaction.
Two type of reactor are discussed:
1- batch reactor Homogeneous
2- Differential reactor Solid fluid.
Two techniques of data acquisition are presented:
1- Concentration time batch.
2- concentration only differential reactor
Six method of data analysis are used
1- Differential method.
2- Integral method.
3- Half-live method.
4- Initial rates method.
5- Linear regression method.
6- Non linear (least-sequences analysis)

5.1 Batch Reactor Data:
5.1.1 Differential Method:
Assuming the decomposition reaction.
A product
-rA = kC

A
or for A + B product
-rA = kC

AC

B
the reaction can be run in excess of B and CB will remain
constant then
-rA = k
1
C

A
where K
1
= kC

B kC

B0


50
then will be determined and the reaction will be run again
in excess of A and
-rA = k
\\
C

A
where K
\\
= kC

A kC

A0
the will be determined now k are determined. Then kA
can obtained
S
mol
dm r
k
C C
B A
A
A
/
1
3
+
|
|
.
|

\
|
=

=
| o
| o
Also using the differential method
A A
A
A
A
A
C k
dt
dC
k
dt
dC
C
ln ln ln o
o
+ =
|
.
|

\
|

=



Ln(-dC
A
/dt
lnC
A


51



( )
o
P
A
P
A
A
C
dt
dC
k
|
.
|

\
|

=

-dCA/dt can be obtained by
1- Graphical differentiation
2- Numerical differentiation
3- Polynomial differentiation

1. Graphical Method
- plotting CA/t as function of t
Equal Area Differentiation
1-Tabulate xi&yi
2- Calculate xn= xn- xn-1 & y= yn-yn-1
3- Calculate yn/xn as estimate of average slope in interval xn-
1 to xn
4- plot these values versus xi e.g
-dC
A
/dt
C
AP
( )
o
P
A
P
A
A
C
dt dC
k

=



52
|
|
.
|

\
|

2 3
2 3
3 2
y
is x &
x x
y
x

5-Draw smooth curve
Dy/dx y/x y x yi

xi

(dy/dx)1

- - - y1

x1

(dy/dx)2 (y/x)2 y2-y1 x2-x1

y2

x2
(dy/dx)3

(y/x)3

y3-y2

x3-x2

y3

x3

(dy/dx)4

(y/x)4

y4-y3

x4-x3

y4

x4


(y/x)5

y5-y4

x5-x4

y5

x5


2- Numerical Method
if data is equally spaced i.e.
t1-t0 = t2 - t1= t
t0 t1 t2 t3 t4 t5

time (min)
CA0 CA1 CA2 CA3 CA4 CA5

Conc. mol/dm
3


Using 3-point formula
Initial point
( ) ( )
| |
| |
| | 3 4
1 dC
point last
1 dC
e.g
1 dC
points inter
4 3
5 4 3
5
2 4
3
2 1 0
0
A
A
1 1
A
A A A
t
A A
t
i A i A
t
A A A
t
A
C C C
t Z dt
C C
t Z dt
C C
t Z dt
t Z
C C C
dt
dC
i
+
A
=
|
.
|

\
|

A
=
|
.
|

\
|

A
=
|
.
|

\
|
A
+
=
|
.
|

\
|
+



53
3- Polynomial Fit:
Fit the concentration time data to an n
th
order polynomial:
CA = a0 +a1t +a2t
2
+ .+ant
n

Then dCA/ dt = a1 + 2a2t + 3a3t
2
+.+nant
n-1

Now knowing dCA/dt at different t we can do the following
t3 t2

t1

t0

time
CA3

CA2 CA1 CA0

Conc.
3
dt
dC
A

2
dt
dC
A

1
dt
dC
A

0
dt
dC
A

Derivative

Now plotting ln(-dCA/dt) versus ln CA then the reaction order
is obtained and the intercept will give lnkA since
A A
A
C k
dt
dC
ln ln ln o + =
|
.
|

\
|

5.2 Integral Method
Is used when reaction order known and rate constant or
activation energy is to be obtained for the reaction
A product
dCA/dt=rA
for zero- order
dCA/dt = -k
integrating with CA=CA0 at t=0
then
CA= CA0-kt


54


1
st
order
-dCA/dt = kCA
Integrating with CA = CA0 at t=0
lnCA0/CA = kt

if reaction is 2
nd
order then
C
A
A
k
dt
dC
2
=

integrating with same initial conditions
kt
C C
A A
=
0
1 1



lnC
A0
/C
A
t
C
A0


C
A
Zero order
t


55


5.3- Initial rates:
When it is difficult to run experiments of concentration at
different times, then the initial rate method is used. In which,
different runs at different initial concentrations are done. The
initial rate (-rA0) are calculated. Since rate law is [-rA0=kC

A0]
Plotting (ln(-rA0)) versus (lnCA0) will give

5.4- Method of halfLive:
Half lives (t1/2) of a reaction is the time required for a reactant
to drop to half of its initial concentration. If two reactants are
used.
Assume
A products
C
A
A
A
k r
dt
dC
o
= =

integrating with CA = CA0 at t = 0

A
C
1



0
1
A
C

t


56
( )
( )
(
(

|
|
.
|

\
|

=
|
|
.
|

\
|

1
1
1
1 1
1
1
1
1
1 1
0
0
0
o
o
o o
o
o
A
A
A
A A
C
C
k
t
k
t
C
C C


solving for CA = 1/2CA0 at t = t1/2
then

( )
( )
|
|
.
|

\
|

CA
k
t
1
1
2 / 1
0
1
1
1
2
o
o
o

the concentration can fit to any 1/n value of its initial
concentrations. Then
( )
( )
( )
0
0
ln 1
1
1
ln ln
1
1
1
2
1
2 / 1
1
1
/ 1
A
A
n
C
k
t
k
t
C
n
o
o
o
o
o
o
+

=
|
|
.
|

\
|

plotting lnCA0 versus lnt1/2 with give slope equal to (1-) & then
=1- slope


57


5.5 Differential Reactor:
There are similar to using batch reactor with small initial
concentration. The reactor is concentrated to be gradient less
with low conversion










S.S M-B. on A
1-

lnt
1/2

lnC
A0
Catalyst
inert
F
A0
inert

F
Ae
L L

F
A0


C
A0
F
Ae


F
P

C
P


58

( )
W
F F
W F
catalyst
rate
F F
e
e
e
A A
A
A
A
A A

=
=
=
|
|
.
|

\
|
+
0
0
0
\
\
A
0 F
0 mass
mass catalyst
reaction of
`

In terms of concentrations

W
vC C v
r
e
A A
A

=
0
0
\

Interims of conversion product
( )
W
C v
W
C C v
r
W
F
W
X F
r
P
A A
A
P
A
A
e 0
0 \
0
0
0
- v constant for =

=
= =

-r
\
A can be determined by the concentration of the partial CP
Assuming CAb in the concentration in the bed then
r
\
A = - r
\
A (CAb)
let CAb=(CA0- CAe)/2
since very small reaction is taking place then
CAb CA0
-r
\
A= -r
\
A(CA0)

5- least squares Analysis
- linearization of the rate law
if rate law depend one concentration of more than one
species also if it is to determine other parameter like ( ,A& E)
mole balance on a constant volume batch


59
2 2 1 1 0
2 1 0
2 A 1
0
A
0
A
a & a , ln
ln x , lnC x ,
dC -
ln y
ln ln ln
dC -
ln
rates initial of method using
0 0
0 0
x a x a a y
k a
C
dt
let
C C k
dt
k r
dt
dC
B
B A
B A
A
A
C C
+ + =
= = =
= =
|
.
|

\
|
=
+ + =
|
.
|

\
|
= =

| o
| o
| o


if N experiments are carried out then
yj=a0+a1x1j+a2x2j
The values of the parameters a0, a1 and a2 are found by



= = = =
= = = =
= = =
+ + =
+ + =
+ + =
N
j
j
j
N
j
j
N
j
j j
N
j
j
N
j
j
j
N
j
j
N
j
j j
N
j
j
N
j
j
N
j
j
N
j
j
X a X X a X a y X
X X a X a X a y X
X a X a Na y
1
2
2
2 2
1
1
1
1 2 0
1
2
1
2
2
2
2
1
1
2
1
1 1 0
1
1
1
2
1
2 1 1 0
1

6- Nonlinear least squares
For the nonlinear least square method we want to minimize
the sum of the estimate differ
i.e. if we have rm: measured rate and
rC: calculated rates then we want to minimize
( )

=
N
i
i i
K N
c r m r
k N
s
1
2
2
2
o
Where


60
s
2
= (r1M-riC )
2

N= Numbers of runs
K= number of parameters to be determined
riM= measured rate for run i
riC = calculated rate for run i

6. Multiple Reactions
There are 3types of basic multiple reactions
1- Series
2- Parallel
3- Independent

1\ Parallel (competing)

e.g. oxidation of ethylene to ethylene oxide avoiding complete
combustion to CO2 & H2O



2- series (consecutive ) reactions
K
1
B




C
A
K
2
O
CH
2
=CH
2
+O
2
CH
2
-CH
2
2CO
2
+2H
2
O


61

C B A
k k

2 1

e.g. reaction of ethylene oxide with NH3 to form mono-, di-
and tri-ethanolamine

it is desired to produce di-ethanolamine and tri
* Multiple reaction combining both is
A+B C+D
A+C E
e.g. formation of butadiene from ethanol
C2H5OH C2H4+H2O
C2H5OH CH3CHO+H2
C2H4+CH3CHO C4H6+H2O

3- independent reactions
A B
C D+E
- in the parallel reaction
( )
( ) product undesierd
product desired
u A
D A
u
D
k
k




CH
2
- CH
2
+NH
3
HOCH
2
CH
2
NH
2
(HOCH
2
CH
2
)
2
NH(HOCH
2
CH
2
)
3
N
O


62

Maximizing Desired product in parallel Reaction:
( )
( )
C
C
A
u u
A
D D
k
k
k r
k r
u A
D A
u
D
2
1
undesired
desired
o
o
=
=



Rate of consumption of A is

C
C C
A
u
D
u
D
A
u
A
D u D A
k
k
r
r
k k r r r
2 1
2 1
Du
S
is (S) parameter seletivity rate
o o
o o

= =
+ = + =

Case 1:- 1>2 i.e. 1-2=a
Reactor

Separator
D
u
Total
cost
cost
Separator cost
Reactor cost


63
C
a
A
u
D
u
D
Du
k
k
r
r
S = =

To maximize D:-
1-use high CA e.g. for gas phase use pure A at high pressure
Possible for liquid phase use minimum diluents possible.
Use batch or PFR reactors . CSTR is not used because of CA
exit.

Case 2:- 2>1 i.e. 2-1=a
C C C
C
a
A
u
D
A
u
D
A
u
A
D
u
D
Du
k
k
k
k
k
k
r
r
S = = = =

1 2 2
1
o o o
o

to maximize D use low CA by diluting or use inert. CSTR is the
best if the activation energy is known then
| |
e
RT E E
u
D
u
D u D
A
A
k
k
/
=


Case 3: ED>ED
To maximize D run the reactor at high possible temp.

Case 4: Eu>ED
To maximize D run at low possible temp.
Reaction with reactants
C C
C C
C C
B A
u
D
u
D
Du
B A
u
k
B A
D
k
k
k
r
r
S
k r u B A
k r D B A
u
D
2 1 2 1
2 2
u
D


| | o o
| o
| o

= =
= +
= +




64
Case1: 1>2 , 1>2
1-2=a , 1-2=b
C C
b
B
a
A
u
D
u
D
Du
k
k
r
r
S = =

to maximize D use high CA & CB possible
* PFR or batch and high pressure for gas phase

Case 2: 1>2 , 1<2 a=1-2 & b= 2-1
C
C
b
B
u
a
A
D
u
D
Du
k
k
r
r
S = =

to maximize SDu use high possible CA and low CB
* use semi batch reactor containing large A &B is fed slowly

* PFR with side stream of B


* series of small CSTR with A fed to 1
st
reactor and small
amount of B fed to each
A
B
B
Pure A


65


Case 3: 1<2 & 1<2 a=2-1 & b=2-1
C C
b
B
a
A
u
D
u
D
Du
k
k
r
r
S = =

to maximize SDu lower possible conc. Of A&B
* use CSTR
* PFR with large recycle
* feed diluted with inert
* low possible pressure if gas phase

Case 4: 1<2 , 1>2 , a= 2-1 & b=1-2
C
C
a
A
u
b
B
D
u
D
Du
k
k
r
r
S = =

to maximize SDu use high possible CB and low possible CA
* semi batch will B and A feed slowly
* PFR with side streams of A
A
A

A

B
B

B



66
* semis of small CSTR with B and A fed at small amounts to
each reactor

Series reactions:
In case of consecutive reactive reactions it is important to
control the time of reaction or the space time

C B A
CO CHO CH OH CH CH
k k
k k


2 1
2 1
2 3 2 3
2

desired product is acetaldehyde (B) reaction is 1
st
order one
(A) &(B)
e
k
A
A
b b
A
A
A
A
A
A
C
C egrating
P v v P v w
C k
dw
dC
Combining
v C try stoichiome
C k r Rate
r
dw
\
1
0
0
A
A
0 0
\
1 0
0 A
1
\
\
A
C
0 at w C using int
/ / /
v
F
- law
dF
balance mole 1
t
t t

=
= =
= = =
=
=
=
=

e
k
A B
B
B A
B
B
B A
B B B
B
C k C
d
dC
g u
C C
dw
dC
combining
C v try stoichiome
C C
r r r Rate
r
dw
\
1
0
1 2
\
A
2 1 0
0 B
2 1
2
\
1
\ \
\
B
k
above from C sin
k k v
F
k k
- law
dF
balance mole 2
t
t

= +
=
=
=
=
=



67
using the integration factor
( )
( )
|
|
.
|

\
|

=
= = =
=

1 2
1 B
B
0
\
1
\
\
2
\
1
0
\
1 2
0
\
2
C
interance at the 0 C and 0 w sin
k k
C k
v
w
g u
C k
d
C d
e e
e
e
k k
A
k k
A
k
B
t t
t
t
t
t



differentiating equation CB to find maximum concentration
( )
2
1
2 1
0
2
1
2 1
\
1 1
1 2
1
\
ln
ln
1
0
\
2
\
1 0
k
k
k k
v
W
k
k
k k
k k
k k
C k
d
dC
opt
opt
k k A
B
e e

=
+

= =

t
t
t t

Optimum conversion of A

\
1

\
2

\
3
\
4

\
C
i
A
B C


68
( )
( )
2 1
1
2 1
1
\
1
0
0
2
1
2
1
1
ln exp
1
k k
k
opt
k k
k
opt
k
A
A A
opt
k
k
X
k
k
X
C
C C
X
e

|
|
.
|

\
|
=
(
(
(

|
|
.
|

\
|
=
=

=
t

Multiple Reactions:
Consider the gas phase reactions
NO+2/3NH3 5/6N2+H2O ..(1)
2NO N2+O2 .(2)
O2+1/2N2 --> NO2 ..(3)
For gas phase concentration with no pres drop and isothermal
Cj=cT0Fi/FT
FT = FNO+FNH3+FN2+FH2O+FO2+FNO2
Mole balances for each component


69
|
|
.
|

\
|
|
|
.
|

\
|

|
|
.
|

\
|
+
|
|
.
|

\
|
|
|
.
|

\
|
=
+ = =
|
|
.
|

\
|
|
|
.
|

\
|
=
= =
|
|
.
|

\
|
|
|
.
|

\
|
=
= = =
|
|
.
|

\
|

|
|
.
|

\
|
|
|
.
|

\
|
=
= =
T
O
T
N
T
T
NO
T
T
NO
T
NH
T
NH
N
O C N NO
NO
NH
N
T
NO
T
NH
T
o H
NO
NH
o H
T
NO
T
NH
T
NH
NO
NH
NH
T
NO
T
T
NO
T
NH
T
NO
NO O N
NH
NO
F
F
F
F
k
F
F
k
F
F
F
F
C C k
dv
dF
C k k C C k
dv
dF
N
F
F
F
F
C k
dv
dF
C C k O rH
dv
dF
O
F
F
F
F
C k
dv
dF
C C k r rNH
dv
dF
F
F
C k
F
F
F
F
C k
dv
dF
C k C kC rNO
dv
dF
C C
C
2 2
0 0
3
0
3
2
2
2
2
3
2
3
0
2
3
2
3
0
3
3
3
0
3
0
2
3
3
3
2
2
2
5 . 1
5 . 1
1
3
2
2
5 . 1
1 2 2
5 . 1
5 . 2
1
5 . 1
1 2 2
5 . 1
5 . 2
1
5 . 1
1 1 3 3
2
2
2
5 . 1
5 . 2
1
2
2
5 . 1
2
1
6
5

2
1
6
5
rN 4

H 3
3
2

3 / 2
3
2
NH 2
2
2 NO 1


2
3
3
O N
3
O N
2
2
3
3
2
NO
2
T 2
O
3 2
O
2
2 2
0
2
2
2
2 2
0
0
2
2
2
dF

dF
6
F
C k
dF

dF
O 5
|
|
.
|

\
|
|
|
.
|

\
|
=
= =
|
|
.
|

\
|
|
|
.
|

\
|

|
|
.
|

\
|
=
= =
T
O
T
N
T
NO
T
O
T
N
T
T
O
F
F
F
F
C k
dv
r r
dv
NO
F
F
F
F
C k
F dv
r r r
dv




70
7. Steady-State Non-isothermal Reactor Design
The Energy Balance:
Consider a flow system at steady state with the following
energy balance equation

= =
= +
n
i
n
i
i i i i S
H F H F W Q
1 1
0 0
0

Suppose the following reaction is taking place
A+(b/a)B (c/a)C+(d/a)D
HioFio = HA0FA0 +HB0FB0 +HC0FC0+HD0FD0+HI0FI0
HiFi = HAFA+HBFB+HCFC+HDFD+HIFI
also
FA=FA0(1-X) , FB =FA0(B-bx/a)
FC =FA0(C-cx/a) , FD =FA0(D-dx/a) , FI = QIFA0
Substitute these values in the two equation & subtract
( ) ( ) ( )
( ) ( )
( ) ( ) ( ) ( ) ( )
( ) ( ) # X
now reaction of Heat
0 0 0
0 0
0 0 0
0
1 1 1
1 1
A RX
n
i
I I I A
n
i
i i
n
i
iO iO
A B C D RX
A B C D
I I I D D D
C C C B B B A A
A
n
i
i i
n
i
iO iO
F T H H H F F H F H
T H T H
a
b
T H
a
c
T H
a
d
T H
H H
a
b
H
a
c
H
a
d
H H H H
H H H H H H
F F H F H
A =
+ = A
|
.
|

\
|
+

(
(

+ +
+ +
=


= = =
= =
u
u u
u u

More stable form
( ) ( )

= A + 0
0 0 0
X F T H H H F W Q
A RX i I i A S
u

The enthalpies Hi of species i are expressed


71
( )
}
+ =
T
T
p R
i
i
dt C T H H
i
1
0

CPi = i+iT+iT
2
[J/mol of i.k]
The change on enthalpy (Hi-Hi0) with change on phase

( ) | | ( ) | |
}
} }
=
+ + + =
T
Pi
T
T
Pi R i
T
T
Pli R i i i
i
T
i
R R
dT C
dT C T dT C T H H
H H
0
0
0

0 0

Substituting in E.B
( )

}
=
= A
n
i
T
T
A RX p i A S
i
i
X F T H dT C F W Q
1
0
0 0
0 u


The heat of reaction at T is given by
( ) ( ) ( ) ( ) ( )
( )
}
+ =
+ + = A
T
T
P R
i
i
A B C D RX
R
i
dt C T H
T H T H
a
b
T H
a
C
T H
a
d
T H
H
0

Substituting we will have
( ) ( ) ( ) ( ) ( )
}
(

+
+
(

+ = A
A B C D
p p p p
A
R
B
R
C
R
D
RX
C C
a
b
C
a
C
C
a
d
T T
a
b
T
a
c
T
a
d
T H
H H H H
0 0 0 0

Combing these equations
( ) ( )
}
A + A = A
T
T
P R
RX
RX
R
dT C T T H
H
0

this will gave the heat of reaction of any temp. in terms of heat
of reaction & reference temp TR(298k)



72
Mean Heat Capacity
HRX(T) = H
0
RX(TR) + C
\
P(T-TR)
where
( )
0
0
0
0
|
|
i i
|

i
T
Ti
P
P
i
i P
T
Ti
P
R
T
T
P
P
T T
dT C
C
where
T T C dT C
Similary
T T
dT C
C
i
i
R

=
=

A
= A
}

}
}
u u

Substitution in S.S. E.B
( ) ( ) ( ) | | 0
\
0
\
0 0 0
= A + A
R
P
R
RX
A i
P
i
A S
T T C T X F T T C F W Q
H
i
u

Variable Heat Capacities:
( ) ( ) ( )
}
A + A + A + A = A
+ + =
dt T T T T H
T T C
HRX
RX
i i i P
i
2
0
2
v | o
v | o


Integrating gives
( ) ( ) ( ) ( ) ( )
A B C D
A B C D
A B C D
R R
R
RX
RX
a
b
a
c
a
d
a
b
a
c
a
d
a
b
a
c
a
d
where
T T T T T T T H T H
v v v v v
| | | | |
o o o o o
v |
o
+ = A
+ = A
+ = A

A
+
A
+ A + A = A

3 2
3 3 2 2 0

Similarly the heat capacity of the heat input can be evaluated



73
( )
( )
( ) ( )
3 2
0
3 3
0
2 2
0
1
2
1
0
0 0
T T T T
T T dt C
dt T T dt C
i i i i
i i
n
i
T
T
P i
T
T
i i i i i i
n
i
T
T
P i
i
i

+ =
+ + =


}
}

}
=
=
u v u |
u o u
u v u | u o u

Substituting these integration in the S.S.EB equation we get

Application to continuous Reactors (CSTR)
A B
1- CSTR design eqn.
V= FA0X/-rA
2- Rate law
-rA = kCA
With k= Aexp[-E/RT]
3- Stoichiometry
CA = CA0(1-x )
4- Combining
V=(v0/Aexp[-E/RT])(x/1-x)

Case 1 x , v0 , CA0 , Fi0 are known and V will be calculated

5.1.1 solve for T using the E.B equation

5.1.2 calculate k

5.1.3 then calculate V

Case 2 v0 , CA0 , V and Fi0 are known X and T will be
calculated

5.2.1 solve the E.B equation for XEB as function of T

5.2.2 solve the combined equation for XMB as for of
( )
( ) ( )
( ) ( )
( ) ( )
0
3 2
3 2
0
3 3
0
2 2
0
0
0
3 3
0
2 2
0
0
0
=
(

A
+
A
= A + A

(
(

T T T T
T T T H X F
T T T T
T T F W Q
R
RX
A
i i i i
i i A S
v |
o
u v u |
u o


74

5.2.3 find values of X and T that satisfy the two
equations



PFR & PBR
AB

1- Mole balance dx/dv = -rA/FA0


2- Rate law -rA = k(CA- CR/kC)

( )
(

|
|
.
|

\
|

A
=
(

|
|
.
|

\
|
=
1 2
0
2
1
1
1 1
exp
1 1
exp
T T R
H
T k k
T T R
E
k k
RX
C

3- Stoichiometry

( )
T
T
X C C
T
T
X C C
A B
A A
0
0
0
0
1
=
=


4- Combining
X

X
X
EB
X
MB
T T


75

( )
T
T
k
X
X kC r
C
A A
0
1
0
(

=


5- solve the E.B equation to find X & T as before then solve the
M.B of PFR or PBR

REFERNCES:

1. H. Scott Fogler, Elements of Chemical Reaction
Engineering 3
rd
Edition, Prentice Hall
International Inc., 1999.

2. Octave Levenspiel, Chemical Reaction
Engineering, 3
rd
Edition, John Wiley and Sons
Inc., New York, 1998.

3. Ronald W. Missen, Charles A. Mims and Bradley
A. Saville, Introduction to Chemical Reaction
Engineering and Kinetics, John Wiley and Sons
Inc., New York, 1999.

4. Froment, G. F. and Bischoff, K. B., "Chemical
Reactor Analysis and Design", 2
nd
Edition, Wiley
Series in Chem. Eng. 1990.