Reaction with phase change, conducted in a PFR

e.g. 3.10 (slightly modified)

Consider a gas phase reaction, where one of the products can also condense at the operating
conditions. This is done in a PFR, with negligible pressure drop and at isothermal conditions.

A g   2B g   C g   D g ,l 

The vapor pressure of D is given by PV= 16 kPa. The operating pressure is 101.3 kPa.

Let us say the reaction is a first order reaction with k = 0.1 s -1. The inlet conditions are FA0 = 10
mol/s, FB0 = 20 mol/s, Q = 1 m3/s.

(i) Find the conversion (x) when condensation begins

(ii) Write CA, CB, etc in terms of conversion.
(iii) What is the volume of reactor needed to get 80% conversion?

Ans:

Let us first write the stoichiometric table. Here X c denotes the conversion at the point of
condensation.

Species Initial At any x ≤ Xc At any x ≥ Xc

A FA0 FA0 (1-x) FA0 (1-x)
B 2 FA0 2 FA0 (1-x) 2 FA0 (1-x)
C 0 FA0 x FA0 x
D (gas) 0 FA0 x YD FT,g
D (liquid) 0 0 FA0 x- YD FT,g
D (Total) 0 FA0 x FA0 x
Total (gas) 3 FA0 FA0 (3-x) YD FT,g + 3 FA0 -2 FA0 x
Total (liquid) 0 0 FT – FT,g
Total 3 FA0 FA0 (3-x) FA0 (3-x)

Note that the mole fraction of D in the gas phase is given by

FD , g
yD 
FT , g

Before condensation, all the species are in the gas phase. After condensation, part of D is in the
liquid phase.

At condensation, the partial pressure of D PD  PV  16 kPa

16 FA0 x FA0 x  yD FT , g
yD   
101.3 FA0  3  x  yD FT , g  3FA0  2FA0 x
Implying Xc = 0.41
At that point, FD,l = FT,l =0. After that, it will increase.
F  3  2 xc 
i.e. At the point of condensation FA0  3  xc   A0  0 . We can re-arrange this also and
1  yD
get Xc.

Before condensation
F F 1  x  C A0 1  x 
C A  A  A0 
Q Q0 1   x  1  0.33x 

FT RT FT Q0
Here, Q    Q0 1   x  Please note that this is before condensation. Here
P FT 0
23
  0.33
3

After condensation:
FT , g RT
Q . Note that the liquid phase flow rate will be negligible because the liquid density is
P
typically much more than the gas density.

We have to calculate the total molar flow rate in gas phase. This is obtained by rearranging the
equation
FT , g  yD FT , g  3FA0  2FA0 x
FA0  3  2 x 
FT , g 
1  yD

Therefore,

FT , g RT FA0  3  2 x  RT
Q 
P 1  yD P
Q0 RT
We can use the initial conditions to get 
FT 0 P

Therefore,

FA0  3  2 x  Q0 FA0  3  2 x  Q0 Q 3  2x 
Q   0
1  yD FT 0 1  yD 3FA0 3 1  yD 

FA FA0 1  x  3 1  yD  3C A0 1  x 1  yD 
The concentration can be written as CA   
Q 1 Q0  3  2 x  3  2x 
 dFA
To find the PFR volume, we need to use the design equation  rA . Since the expression for
dV
C A and hence rA change during condensation, we need to write this in two parts.
dFA F dx
 rA becomes A0 A  kCA
dV dV

Re arranging
FA0 dxA
 dV
kC A

0.8 V 0.41 0.8

FA0 dxA FA0 dxA F dx

0
kC A
  dV  V 
0

0
kC A
  A0 A
0.41
kC A

First part:
0.41
FA0 dxA F 1  0.33x  dxA
0.41
10
0.41
 0.67  0.33  0.33x  dxA
0 kC A
 A0
kC A0 0 1  x  
0.110 
0 1  x 
10 
0.41
 0.67  dxA  3.3 0.41
dxA  6.7 ln 1  x  0  3.3  0.41  4.88 m3
0
0.41

0 1  x 
Second part

0.8
FA0 dxA FA0  3  2 x  dxA 
0.8
10  3  2 x  dx 0.8

0.41 kC A
 
3kC A0 1  yD  0.41 1  x  
3  0.110  1  0.16  0.41 1  x 
 1 
0.8

     3.97  3.21  1.35

0.8
 3.97    1  x 
0.41 
 2 dx  3.97   ln 1  x  2 x
0.41

 7.4 m3

Total volume needed is roughly 12.28 m3.