(1.

44)
The energy balance in a tubular reactor is given in eq. (1.44)
by:
For an adiabatic reactor, . Usually, there is a negligible
amount of work done on or by the reacting mixture.
(1.46)
0 Q =

( ) 0 X F dT C T H dT C F W Q
0 A
T
T
p R
0
Rx
n
1 i
T
T
pi i 0 A S
R 0 i
=
(

A + A O
}

}
=

( )

} }
=
O =
(

A + A
n
1 i
T
T
pi i
T
T
p R
0
Rx
0 i R
dT C X dT C T H
The circumflex denotes that the heat capacities are evaluated
at some mean temperature value between T
R
and T.
R
T
T
p
p
T T
dT C
C

A
= A
}
(1.48)
For the case of constant or mean heat capacities:
( )
R p
T
T
p
T T C

dT C
R
A = A
}
(1.47)
In a similar fashion we can write the integral involving O
i
and
C
pi
in eq. (1.46) as
( )

}
A O = A O
0 i pi i
T
T
pi i
T T C

dT C
0 i
The circumflex denotes that the heat capacities are evaluated
at some mean temperature value between T
R
and T.
0 i
T
T
pi
pi
T T
dT C
C

0 i

A
= A
}
( ) ( ) | | ( )

=
O = A + A
n
1 i
0 i pi i R p R
0
Rx
T T C

X T T C

T H
(1.49)
For constant or mean heat capacity, eq. (1.46) becomes:
(1.50)
(1.51)
Eq. (1.51) can be solved for T
( ) ( ) | | ( )

=
O = A + A
n
1 i
0 i pi i R p R
0
Rx
T T C

X T T C

T H
( ) | | ( )

= =
O O = A + A A
n
1 i
0 i pi i
n
1 i
pi i R p p R
0
Rx
T C

T C

X T C

T X C

X T H
( ) | |
R p
n
1 i
0 i pi i R
0
Rx p
n
1 i
pi i
T C

X T C

T H X C

X C

T A + O + A =
|
.
|

\
|
A + O

= =
( ) | |
p
n
1 i
pi i
R p
n
1 i
0 i pi i R
0
Rx
C

X C

T C

X T C

T H X
T
A + O
A + O + A
=

=
=
(1.52)
This equation can be combined with the differential mole
balance derived from eq. (1.1):
(1.1)
( ) T , X r
F
dX
dV
A
0 A

=
to obtain the temperature, conversion, and concentration
profiles along the length of the reactor.
One way of accomplishing this combination is to use eq.
(1.52) to construct a table of T as a function of X.
Once we have T as a function of X, we can obtain k(T) as a
function of X and hence r
A
as a function of X alone.
The elementary reversible gas-phase reaction is carried out in
a PFR in which pressure drop is neglected and pure A enters
the reactor:
A B
Mole balance:
Rate law:
with
and
dX
r
F
dV
A
0 A

=
|
|
.
|

\
|
=
C
B
A A
K
C
C k r
(

|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
1
( )
(

|
.
|

\
|

A
=
T
1
T
1
R
H
exp T K K
1
0
Rx
1 C C
(a)
(b)
(c)
(d)
Stoichiometry: Gas, c = 0, P = P
0
( )
T
T
X 1 C C
0
0 A A
=
|
|
.
|

\
|
=
C
B
A A
K
C
C k r
T
T
X C C
0
0 A B
=
(1.46) ( )

} }
=
O =
(

A + A
n
1 i
T
T
pi i
T
T
p R
0
Rx
0 i R
dT C X dT C T H
(e)
(f)
(g)
Eqs. (a) through (g) and (1.52) can easily be solved using
either Simpson's rule or an ODE solver.
Combine:
Energy balance (eq. 1.46):
Normal butane, C
2
H
4
, is to be isomerized to isobutane in a plug-
flow reactor. The reaction is to be carried out adiabatically in the
liquid phase under high pressure using essentially trace amounts of
a liquid catalyst which gives a specific reaction rate of 3 1.1 h
1
at
360 K. Calculate the PFR volume necessary to process 100,000
gal/day (163 kg mol/h) of a mixture 90 mol % n-butane and 10 mol
% i-pentane, which is considered an inert. The feed enters at 330 K.
Additional information:
AH
Rx
= -6900 J/mol* butane
Cp
n-B
= 141 J/mol.K
Cp
i-B
= 141 J/mol.K
Cp
i-P
= 161 J/mol.K
Activation energy = 65.7 kJ/mol
K
C
= 3.03 at 60C
C
A0
= 9.3 g mol/dm
3
= 9.3 kg mol/m
3
EXAMPLE 1.2
SOLUTION
Reaction:
Mole balance:
Rate law:
with
dX
r
F
dV
A
0 A

=
|
|
.
|

\
|
=
C
B
A A
K
C
C k r
(

|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
1
(a)
(b)
(c)
(

|
.
|

\
|
=
T
1
360
1
31 . 8
700 , 65
exp 1 . 31 k
(

|
.
|

\
|
=
T
1
360
1
7906 exp 1 . 31 k
( )
(

|
.
|

\
|

A
=
T
1
T
1
R
H
exp T K K
1
0
Rx
1 C C
(d)
(

|
.
|

\
|

=
T
1
333
1
31 . 8
6900
exp 03 . 3 K
C
(

|
.
|

\
|
=
T
1
333
1
3 . 830 exp 03 . 3 K
C
Stoichiometry (liquid phase, v = v
0
):
( ) X 1 C C
0 A A
=
X C C
0 A B
=
(e)
(f)
( )
(

=
C
0 A
0 A A
K
X C
X 1 C k r
Combine:
(

|
|
.
|

\
|
+ = X
K
1
1 1 kC r
C
0 A A
(g)
(h)
(1.46) ( )

} }
=
O =
(

A + A
n
1 i
T
T
pi i 0 A 0 A
T
T
p R
0
Rx
0 i R
dT C F X F dT C T H
Energy balance (eq. 1.46):
1
F
F
0 A
0 A
A
= = O
with:
0
F
F
0 A
0 B
B
= = O
( ) 0 K . mol J 141 141 C C C
pA pB p
= = = A
1111 . 0
9 . 0
1 . 0
F
F
0 A
0 I
I
= = = O
(i)
Eq. (46) becomes:
( ) | | ( )

=
O = A
n
1 i
0 i pi i R
0
Rx
T T C X T H
( ) | |

=
O
A
+ =
n
1 i
pi i
R
0
Rx
0
C
X T H
T T
with:
( )( ) 161 111 . 0 141 C C C C
pI I pB B pA A
n
1 i
pi i
+ = O + O + O = O

=
= 158.9 J/mol . K
Eq. (i) becomes:
X 43 . 43 330 T + =
(j)
( ) mol J 900 , 6 T H
R
0
Rx
= A
At equilibrium r
A
= 0, equation (b) becomes:
|
|
.
|

\
|
= =
C
e
0 A A
K
X
1 kC 0 r
C
C
e
K 1
K
X
+
=
(k)
We will now integrate Equation (a) with Simpson's rule, but
first we have to calculate (F
A0
/-r
A
) as a function of X.
For example for X = 0.1
( ) K 34 . 334 1 . 0 43 . 43 330 T = + =
1
h 77 . 5
34 . 334
1
360
1
7906 exp 1 . 31 k

=
(

|
.
|

\
|
=
00 . 3
34 . 334
1
333
1
3 . 830 exp 03 . 3 K
C
=
(

|
.
|

\
|
=
75 . 0
0 . 3 1
0 . 3
K 1
K
X
C
C
e
=
+
=
+
=
( )
h . m
kmol
83 . 51 1 . 0
0 . 3
1
1 1
m
kmol
3 . 9
h
77 . 5
r
3 3
A
=
(

|
.
|

\
|
+
|
.
|

\
|
|
.
|

\
|
=
( ) ( )
( )
3
3
A
0 A
m 830 . 2
h . m kmol 83 . 51
h total kmol 163 total mol butane mol 9 . 0
r
F
= =

X T k K
C
Xe - r
A
F
A0
/(-r
A
)
0 330.00 4.22 3.10 0.76 39.28 3.735
0.1 334.34 5.77 3.00 0.75 51.83 2.830
0.2 338.69 7.81 2.91 0.74 67.62 2.170
0.3 343.03 10.49 2.82 0.74 87.19 1.682
0.4 347.37 14.00 2.73 0.73 111.12 1.320
0.5 351.72 18.54 2.65 0.73 139.93 1.048
0.6 356.06 24.39 2.58 0.72 174.02 0.843
0.7 360.40 31.87 2.51 0.71 213.62 0.687
0
5
10
15
20
25
30
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
F
A
0
/
(
-
r
A
)
X
1 2 3 4 5
7
6

+
|
.
|

\
|
+
+
|
.
|

\
|
+
+
|
.
|

\
|
+
+
|
.
|

\
|
+
=
2
y y
2
y y
2
y y
2
y y
1 . 0 Area
4 3 3 2 2 1 1 0
(

(
+
|
.
|

\
|
+
+
|
.
|

\
|
+
+
|
.
|

\
|
+
+
|
.
|

\
|
+
+
2
y y
2
y y
2
y y
2
y y
4 3 7 6 6 5 5 4
|
.
|

\
|
+ + + + + + + =
2
y
y y y y y y
2
y
1 . 0 Area
7
6 5 4 3 2 1
0
3
m 13 . 3 =
When the problem is to find the temperature profile along
the reactor, then the algorithm is as follows.
Mole balance:
Rate law:
Energy balance:
0 A
A
F
r
dV
dX
=
A A
C k r =
(1.1)
For no work done on the system, , and adiabatic
operation, , the energy balance is written as eq. (1.46)
0 W
S
=

0 Q =

( ) 0 X dT C T H dT C
T
T
p R
0
Rx
T
T
pi i
R 0 i
=
(

A + A O
}

}
(1.46)
Differentiating eqs. (1.46) with respect to V yields
( ) ( ) | | + A O

dV
dX
T H
dV
dT
C
R
0
Rx pi i
0
dV
dX
dT C
dV
dT
C X
T
T
p p
R
=
|
.
|

\
|
A A
}
( ) ( )
dV
dX
dT C T H
dV
dT
C X C
T
T
p R
0
Rx p pi i
R
(

A + A = A + O
}

( )
dV
dX
C X C
dT C T H
dV
dT
p pi i
T
T
p R
0
Rx
R
A + O
(

A + A
=

}
(1.53)
Combining eqs. (1.1) and (1.53) yields
( ) ( )
( )
p pi i 0 A
T
T
p R
0
Rx A
C X C F
dT C T H r
dV
dT
R
A + O
)
`

A + A
=

}
(1.54)
Here we have two equations, (1.1) and (1.54), that must be
solved simultaneously.
One method that can be used to solve the problem is Runge-
Kutta method.
( ) ( ) ( ) x z , x y , x f
dx
dy
=
( ) ( ) ( ) x z , x y , x g
dx
dz
=
( )
0 0
y x y =
( )
0 0
z x z =
( )
n n n 1
z , y , x f . h k = ( )
n n n 1
z , y , x g . h l =
|
.
|

\
|
+ + + =
2
l
z ,
2
k
y ,
2
h
x f . h k
1
n
1
n n 2
|
.
|

\
|
+ + + =
2
l
z ,
2
k
y ,
2
h
x g . h l
1
n
1
n n 2
( )
3 n 3 n n 4
l z , k y , h x f . h k + + + =
3 n n n 4
l z , k y , h x g . h l + + + =
( ) ( )
4 3 2 1
k k 2 k 2 k 6 1 k + + + = ( ) ( )
4 3 2 1
l l 2 l 2 l 6 1 l + + + =
h x x
n 1 n
+ =
+
k y y
n 1 n
+ =
+
l z z
n 1 n
+ =
+
|
.
|

\
|
+ + + =
2
l
z ,
2
k
y ,
2
h
x f . h k
2
n
2
n n 3
|
.
|

\
|
+ + + =
2
l
z ,
2
k
y ,
2
h
x g . h l
2
n
2
n n 3
One of the key steps in producing acetic anhydride is the
vapor-phase cracking of acetone to ketene and methane:
CH
3
COCH
3
CH
2
CO + CH
4
This reaction is first-order with respect to acetone and the
specific reaction rate can be expressed by:
where k is in reciprocal seconds and T is in kelvin.
In this design it is desired to feed 8000 kg of acetone per hour
to a tubular reactor. The reactor consists of a bank of 1000 1-
inch schedule 40 tubes. The reactor is operated adiabatically.
The inlet temperature and pressure are at 1035 K and 162 kPa
(1.6 atm), respectively. Plot the conversion and temperature
along the length of the reactor.
EXAMPLE 1.3
T
34222
34 . 34 k ln =
SOLUTION
Let A = CH
3
COCH
3
, B = CH
2
C0, and C = CH
4
.
Rewriting the reaction symbolically gives us:
A B + C
Mole balance:
Rate law:
0 A
A
F
r
dV
dX
=
A A
C k r =
(a)
(b)
A B C Total
Initial N
A0
0 0 N
A0
Reaction N
A0
X
Final N
A0
(1 X) N
A0
X N
A0
X N
A0
(1 + X)
0
0 A
0 A
V
N
C =
( )
V
X 1 N
V
N
C
0 A A
A

= =
If the gas mixture is assumed to behave as ideal gas:
RT N
PV
RT N
PV
t 0 0 t
0
=
( )
( )
0
0
0
0 0 A
0 A
0
0 0 t
t
V
T
T
X 1 V
T
T
N
X 1 N
V
T
T
N
N
V
|
|
.
|

\
|
+ =
|
|
.
|

\
| +
=
|
|
.
|

\
|
|
|
.
|

\
|
=
( )
( )
( )
( ) T
T
X 1
X 1 C
T
T
X 1 V
X 1 N
C
0 0 A 0
0
0 A
A
+

=
|
.
|

\
|
+

=
(c)
(d)
(e)
Combining (d) and (e) gives us:
(f)
Combining eqs. (b) and (f) yields
( )
T
T
X 1
X 1 kC
r
0 0 A
A
+

=
(g)
while combining eqs. (a) and (g) yields
( )
( ) T
T
X 1
X 1
v
k
T
T
X 1 F
X 1 kC
dV
dX
0
0
0
0 A
0 A
|
.
|

\
|
+

=
+

=
(h)
For no work done on the system, , and adiabatic
operation, , the energy balance leads to eq. (1.54)
0 W
S
=

0 Q =

( ) ( )
( )
p pi i 0 A
T
T
p R
0
Rx A
C X C F
dT C T H r
dV
dT
R
A + O
)
`

A + A
=

}
(1.54)
Calculation of mole balance parameters:
s mol 3 . 38 h kmol 9 . 137
kmol kg 58
h kg 8000
F
0 A
= = =
( )
3 3 3
0 A
0 A
m
mol
8 . 18
m
kmol
0188 . 0
K 1035
K . kmol
m . kPa
31 . 8
kPa 162
RT
P
C = =
|
|
.
|

\
|
= =
s m 037 . 2
C
F
v
3
0 A
0 A
0
= =
Calculation of energy balance parameters:
a. The standard heat of reaction :
( ) | |
R
0
Rx
T H A
( ) | | mol kJ 67 . 216 T H
acetone R
0
Rx
= A
( ) | | mol kJ 09 . 61 T H
ketene R
0
Rx
= A
( ) | | mol kJ 81 . 74 T H
methane R
0
Rx
= A
( ) | | ( ) ( ) ( ) 67 . 216 81 . 74 09 . 61 T H
R
0
Rx
+ = A
mol J 80770 mol kJ 77 . 80 = =
b. AC
p
:
K . mol J T 10 86 . 45 T 183 . 0 63 . 26 C
2 6
pA

+ =
K . mol J T 10 95 . 30 T 0945 . 0 04 . 20 C
2 6
pB

+ =
K . mol J T 10 71 . 18 T 077 . 0 39 . 13 C
2 6
pC

+ =
8 . 6 63 . 26 04 . 20 39 . 13
A B C
= + = o o + o = o A
0115 . 0 183 . 0 0945 . 0 077 . 0
A B C
= + = | | + | = | A
A B C
+ = A
6
10 8 . 3

=
2
p
T T C A + | A + o A = A
2 6
T 10 8 . 3 T 0115 . 0 8 . 6

=
c. EO
i
C
pi
:
O
A
= 1
O
B
= O
C
= 0
EO
i
C
pi
= O
A
C
pA
+ O
B
C
pB
+ O
A
C
pB
= C
pA
The two equations are solved simultaneously using 2-
dimensional Runge-Kutta method.
0.00
0.05
0.10
0.15
0.20
0.25
0 1 2 3 4
X
V (m
3
)
900
925
950
975
1000
1025
1050
0 1 2 3 4
T

(
K
)
V (m
3
)