B. Subramaniam, C&PE Dept.

, University of Kansas
Notes on Chemical Reaction Engineering


5.1
5. Semi-Batch Reactor

5.1 Mathematical Model
Consider the liquid-phase reaction A + B ---> C in which reactant A is continuously
added to a stirred vessel containing reactant B (Figure 5.1). It is assumed that the reactor
is operated isothermally at a temperature T. It is required to determine how the
concentrations of the reactants (C
A
, C
B
) change in the reactor with time (see also
example 4.10 of Fogler's text).
F , v ,C
Ao
Ao
V , C , C
o
Bi
o
Ai
at t = 0
V, C , C
B A
at any t

Figure 5.1. Semi-Batch Reactor Schematic
The definitions of the variables in Fig. 5.1 are as follows:
v
o
volumetric flow rate of feed stream containing species A, vol/time
C
Ao
concentration of species A in feed stream, mol/vol
C
Ai
concentration of species A in reactor initially (t = 0), mol/vol
C
A
concentration of species A in reactor at any time t, mol/vol
C
Bi
concentration of species B in reactor initially (t = 0), mol/vol
C
B
concentration of species B in reactor at any time t, mol/vol
V
o
volume of reaction mixture initially (t = 0), vol
V volume of reaction mixture at any time t, vol
N
j
Moles of species j in reactor at any time t, mol


B. Subramaniam, C&PE Dept., University of Kansas
Notes on Chemical Reaction Engineering


5.2
A material balance for species A around the reactor yields,
F
Ao
! F
A
+ r
A
V =
dN
A
dt
=
d
(
V C
A
)
dt
(
5. 1
)
v
o
C
Ao
+ r
A
V = V
dC
A
dt
+ C
A

dV
dt
(
5. 2
)

0

The reaction volume changes with time as reactant A is added. An expression for the
volume change with time is obtained by writing an overall mass balance as follows:
! V = !
o
V
o
+
"
t
0
!
f
v
o
dt (5. 3)
If ! # !
o
# !
f
(constant$density reactions), eq. (5. 3) becomes
V = V
o
+ v
o
t (5. 4)
%
dV
dt
= v
o
(5. 5)
Substituting eqs. (5. 4$5) in eq. (5. 2) yields
v
o
C
Ao
+ r
A
(V
o
+ v
o
t) = (V
o
+ v
o
t)
dC
A
dt
+ v
o
C
A
(5. 6)
%
dC
A
dt
=
v
o
(C
Ao
$ C
A
)
(V
o
+ v
o
t)
+ r
A
= f (C
j
' s, t) (5. 7)
Initial Condition: t = 0, C
A
= C
Ai

For first-order rate expression (i.e., if B is in excess), - r
A
= k C
A
. In such a case, eq.
(5.7) may be solved analytically to yield C
A
(t), as given by eq. (4.61) of Fogler's text.
If the reaction is second-order, eq. (5.7) must be solved numerically.
If - r
A
= k C
A
C
B
, eq. (5.7) becomes
dC
A
dt
=
v
o

(
C
Ao
! C
A
)
(
V
o
+ v
o
t
)
! k C
A
C
B
= f
1

(
C
A
, C
B
, t
) (
5. 8
)

Eq. (5.8) involves two variables, C
A
and C
B
. Hence, the material balance for species
'B' is needed to solve for C
A
and C
B
. A material balance for species B yields:
B. Subramaniam, C&PE Dept., University of Kansas
Notes on Chemical Reaction Engineering


5.3
F
Bo
! F
B
+ r
B
V =
dN
B
dt
=
d
(
V C
B
)
dt
(
5. 9
)
+ r
B
V = V
dC
B
dt
+ C
B

dV
dt
(
5. 10
)
0 0

Recognizing that - r
B
= k C
A
C
B
, and substituting eqs. (5.4-5) into eq. (5.10) yields:
(! k C
A
C
B
) (V
o
+ v
o
t) = (V
o
+ v
o
t)
dC
B
dt
+ v
o
C
B
(5. 11)
"
dC
B
dt
= ! k C
A
C
B
!
v
o
C
B
(V
o
+ v
o
t)
= f
2
(C
A
, C
B
, t) (5. 12)
Initial Condition: t = 0, C
A
= C
Ai
, C
B
= C
Bi

Eqs. (5.11 and 5.12) may be solved simultaneously using a numerical scheme such as
fourth-order Runge-Kutta or Mathcad software.
Alternate Approach: C
B
can be expressed in terms of C
A
as follows:
C
B
(t) =
N
B
V
=
Moles of B in reactor at time t
Volume of reaction mixture at time t
=
(Moles of B initially) ! (Moles of B reacted)
V
=
(Moles of B initially) ! (Moles of A reacted)
V
=
(V
o
C
Bi
) ! {(V
o
C
Ai
+ v
o
C
Ao
t) ! V C
A
}
V
(5. 13)
" C
B
= C
A
!
{V
o
(C
Ai
! C
Bi
) + v
o
C
Ao
t}
V
(5. 14)

Substituting eq. (5.14) in eq. (5.8) makes the RHS of eq. (5.8) a function of only C
A
.
In other words, only one ODE needs to be solved. In general, it is possible to reduce the
number of ODEs to one in the case of an isothermal semi-batch reactor in which a single
reaction occurs. However, the resulting equation would still require a numerical solution.