The energy balance in a tubular reactor is given in eq. (1.

44)
by:

n T  T

  0
 
Q  WS  FA 0   iCpidT   HRx TR   Cp dT FA 0 X  0 (1.44)
i 1 T
i0  T R 

For an adiabatic reactor, Q  0 . Usually, there is a negligible

amount of work done on or by the reacting mixture.

 0 T
 n T
  HRx TR    Cp dT  X     iCpidT (1.46)
 T
R  i 1 T
i0
For the case of constant or mean heat capacities:
T

 Cp dT  Ĉp T  TR  (1.47)

TR

The circumflex denotes that the heat capacities are evaluated

at some mean temperature value between TR and T.
T

 Cp dT
Ĉp 
TR
(1.48)
T  TR
In a similar fashion we can write the integral involving i and
Cpi in eq. (1.46) as
T
 i  CpidT   i Ĉpi T  Ti0  (1.49)
Ti 0

The circumflex denotes that the heat capacities are evaluated

at some mean temperature value between TR and T.
T

 CpidT
Ĉpi 
Ti 0
(1.50)
T  Ti 0

For constant or mean heat capacity, eq. (1.46) becomes:

 H TR   Ĉp T  TR  X   iĈpi T  Ti0 

n
0
Rx (1.51)
i 1
Eq. (1.51) can be solved for T

 H TR   Ĉp T  TR  X   iĈpi T  Ti0 

n
0
Rx
i 1

 H TR  X  ĈpX T  Ĉp TRX   iĈpi T   iĈpi Ti0

n n
0
Rx
i 1 i 1

T   iĈpi  XĈp   X H TR    iĈpi Ti0  XĈp TR

n n
0

 i 1  Rx
i 1

X H TR    iĈpi Ti0  XĈp TR

n
0
Rx
T n
i 1
(1.52)
  iĈpi  XĈp
i 1
This equation can be combined with the differential mole
balance derived from eq. (1.1):

dV FA 0
 (1.1)
dX  rA X , T 

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 – rA 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
FA 0
Mole balance: dV  dX (a)
 rA
 CB  (b)
Rate law:  rA  k  C A  
 KC 
 E  1 1 
with k  k 1 exp      (c)
R  T1 T  
 HRx
0
 1 1 
and K C  K C T1 exp     (d)
 R  T1 T  
Stoichiometry: Gas,  = 0, P = P0
T0
C A  C A 0 1  X  (e)
T
T0
CB  C A 0 X
T (f)
 CB 
Combine:  rA  k  C A  
 KC  (g)
Energy balance (eq. 1.46):
 0 T
 n T
  HRx TR    Cp dT  X     iCpidT (1.46)
 RT  i 1 T
i0

Eqs. (a) through (g) and (1.52) can easily be solved using
either Simpson's rule or an ODE solver.
EXAMPLE 1.2
Normal butane, C2H4, 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:
HRx = -6900 J/mol* butane
Cpn-B = 141 J/mol.K
Cpi-B= 141 J/mol.K
Cpi-P = 161 J/mol.K
Activation energy = 65.7 kJ/mol
KC = 3.03 at 60°C
CA0 = 9.3 g mol/dm3 = 9.3 kg mol/m3
SOLUTION
Reaction:

Mole balance: FA 0
dV  dX (a)
 rA
 CB 
Rate law:  rA  k  C A   (b)
 KC 
 E  1 1 
with k  k 1 exp     
R  T1 T  

 65,700  1 1  
k  31.1 exp    
 8.31  360 T  
  1 1 
k  31.1 exp 7906    (c)
  360 T  
  HRx
0
 1 1 
K C  K C T1 exp    
 R  T1 T  

  6900  1 1  
K C  3.03 exp    
 8.31  333 T  

  1 1 
K C  3.03 exp   830.3    (d)
  333 T  

Stoichiometry (liquid phase, v = v0):

C A  C A 0 1  X  (e)

CB  C A 0 X (f)
Combine:

 C A0X 
 rA  k C A 0 1  X    (g)
 K C 

  1 
 rA  kC A 0 1   1   X  (h)
  KC  

Energy balance (eq. 1.46):

 0 T
 n T
  HRx TR    Cp dT FA 0 X  FA 0    iCpidT (1.46)
 T R  i 1 Ti0

with:
FA 0 FB 0
A  1 B  0
FA 0 FA 0
 FI0 0.1
I    0.1111
FA 0 0.9

Cp  CpB  CpA  141  141 J mol.K  0

Eq. (46) becomes:

 H T X    C T  T 
n
0
Rx R i pi i0
i 1

T  T0 
 H T X 0
Rx R
n
  iCpi (i)
i 1
n
with:   C   C   C   C  141  0.111161
i pi A pA B pB I pI
i 1

= 158.9 J/mol . K
  HRx
0
TR   6,900 J mol
Eq. (i) becomes:

T  330  43.43 X (j)

At equilibrium – rA = 0, equation (b) becomes:

 Xe 
 rA  0  kC A 0  1  
 KC 
KC
Xe 
1  KC (k)

We will now integrate Equation (a) with Simpson's rule, but

first we have to calculate (FA0/-rA) as a function of X.
For example for X = 0.1

T  330  43.43 0.1  334.34 K

  1 1 
k  31.1 exp 7906      5.77 h
1

  360 334.34  
  1 1 
K C  3.03 exp   830.3      3.00
  333 334.34  
KC 3.0
Xe    0.75
1  K C 1  3.0

 5.77   kmol    1   kmol

 rA     9.3 3  1   1   0.1  51.83 3
 h  m    3.0   m .h
FA 0 0.9 mol butane mol total163 kmol total h
  2.830 m3

 rA 51.83 kmol m3 .h

X T k KC Xe - rA FA0/(-rA)

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
 30

25

20
FA0/(-rA)

15

10

5
7
1 2 3 4 5 6
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
X
  y 0  y 1   y 1  y 2   y 2  y 3   y 3  y 4 
Area  0.1     
 2   2   2   2 

 y 4  y5   y5  y6   y6  y7   y3  y 4  
     
 2   2   2   2  

 y0 y7 
Area  0.1   y 1  y 2  y 3  y 4  y 5  y 6  
2 2

 3.13 m3
When the problem is to find the temperature profile along
the reactor, then the algorithm is as follows.

Mole balance: dX  rA
 (1.1)
dV FA 0

Rate law:  rA  k C A

Energy balance:
For no work done on the system, W  S  0 , and adiabatic
operation, Q  0 , the energy balance is written as eq. (1.46)

T
 0 T

    iCpidT   HRx TR    Cp dT  X  0 (1.46)
T i0  T
R 
Differentiating eqs. (1.46) with respect to V yields

  iCpi   HRx TR  

dT 0 dX
dV dV

dT  T  dX
 X C p    Cp dT   0
dV  T
R  dV

 0  dX
 iCpi  X Cp    HRx TR    CpdT
dT T

dV  T R  dV

 0 T

  HRx TR    Cp dT 
dT
  RT  dX (1.53)
dV   iCpi  X Cp dV
Combining eqs. (1.1) and (1.53) yields

  0 T

 rA  HRx TR    CpdT  
dT
   T  (1.54)
FA 0   iCpi  X Cp 
R

dV

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.
 dy
 f  x , y x , z x  y x 0   y 0
dx

dz
 g  x , y x , z x  zx 0   z0
dx

k 1  h . f  x n , y n , zn  l1  h . gx n , y n , zn 

 h k1 l1 
k 2  h . f  x n  , y n  , zn    h k1 l1 
l2  h . g  x n  , y n  , z n  
 2 2 2  2 2 2
  h k2 l2 
k 3  h . f  x n  , y n  , zn    h k2 l2 
l3  h . g  x n  , y n  , z n  
 2 2 2  2 2 2

k 4  h . f x n  h, y n  k 3 , zn  l3  l4  h . gx n  h, y n  k , zn  l3 

k  1 6  k1  2k 2  2k 3  k 4  l  1 6  l1  2l2  2l3  l4 

x n1  x n  h

y n1  y n  k

zn1  zn  l
 EXAMPLE 1.3
One of the key steps in producing acetic anhydride is the
vapor-phase cracking of acetone to ketene and methane:
CH3COCH3  CH2CO + CH4
This reaction is first-order with respect to acetone and the
specific reaction rate can be expressed by:
34222
ln k  34.34 
T
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.
SOLUTION
Let A = CH3COCH3, B = CH2C0, and C = CH4.
Rewriting the reaction symbolically gives us:
AB+C
Mole balance: dX  rA
 (a)
dV FA 0

Rate law:  rA  k C A (b)

A B C Total
Initial NA0 0 0 NA0
Reaction NA0 X
Final NA0 (1 – X) NA0 X NA0 X NA0 (1 + X)
 NA 0
CA0  (c)
V0
NA NA 0 1  X 
CA   (d)
V V
If the gas mixture is assumed to behave as ideal gas:
PV0 PV

Nt 0RT0 NtRT

 Nt   T  NA 0 1  X   T  T
V      V0    V0  1  X    V0 (e)
 Nt 0   T0  NA 0  T0   T0 
Combining (d) and (e) gives us:

NA 0 1  X   T0  C A 0 1  X  T0
CA    (f)
V0 1  X   T  1  X  T
Combining eqs. (b) and (f) yields

kC A 0 1  X  T0
 rA  (g)
1 X T
while combining eqs. (a) and (g) yields

dX kC A 0 1  X  T0 k  1  X  T0
    (h)
 
dV FA 0 1  X T v 0  1  X  T

For no work done on the system, W  S  0, and adiabatic

operation, Q  0 , the energy balance leads to eq. (1.54)
  0 T

 rA  HRx TR    CpdT  
dT
   T  (1.54)
FA 0   iCpi  X Cp 
R

dV
Calculation of mole balance parameters:

8000 kg h
FA 0   137.9 kmol h  38.3 mol s
58 kg kmol

PA 0 162 kPa kmol mol

CA0    0.0188 3  18.8 3
RT  kPa.m 
3
m m
 8.31  1035 K 
 kmol .K 

FA 0
v0   2.037 m3 s
CA0
Calculation of energy balance parameters:
a. The standard heat of reaction HRx
0
TR  :

H T 
0
Rx R acetone
  216.67 kJ mol

H T 
0
Rx R ketene
  61.09 kJ mol

H T 
0
Rx R methane
  74.81 kJ mol

H T    61.09   74.81   216.67

0
Rx R

 80.77 kJ mol  80770 J mol

b. Cp :
CpA  26.63  0.183T  45.86  10 6 T 2 J mol.K

CpB  20.04  0.0945T  30.95  10 6 T 2 J mol.K

CpC  13.39  0.077T  18.71  10 6 T 2 J mol.K

  C  B   A  13.39  20.04  26.63  6.8

   C  B   A  0.077  0.0945  0.183   0.0115

   C   B   A   3.8  10 6

Cp     T   T 2
 6.8  0.0115 T  3.8  10 6 T 2
c. i Cpi :

A = 1

B = C = 0

i Cpi = A CpA + B CpB + A CpB = CpA

The two equations are solved simultaneously using 2-

dimensional Runge-Kutta method.
 0.25

0.20

0.15
X

0.10

0.05

0.00
0 1 2 3 4
V (m3)
 1050

1025

1000
T (K)

975

950

925

900
0 1 2 3 4
V (m3)