Chemical Engineering and Processing 36 (1997) 291 299

An axial dispersion model for gasliquid reactors based on the

penetration theory
Jinfu Wang, Shejiao Han, Fei Wei, Zhiqing Yu, Yong Jin *
Department of Chemical Engineering, Tsinghua Uni6ersity, Beijing 100084, Peoples Republic of China
Received 25 November 1996; received in revised form 6 February 1997; accepted 10 February 1997

Abstract
An axial dispersion reactor model for gasliquid reaction systems is proposed in this paper based on the penetration theory.
The mass transfer mechanism accompanied by a chemical irreversible first-order reaction is mathematically treated in a new way
in order to use its results to develop the model conveniently. Analytical solutions can be obtained for the equation system
involving linear differential equations by using of the eigenvalues of the equation system. In addition, an iteration procedure is
given to solve the nonlinear differential equation system numerically. The influences of the important model parameters on the
concentration profile, the mass transfer and the reactant conversion are also studied. 1997 Elsevier Science S.A.
Keywords: Chemical engineering; Gasliquid reactors; Penetration theory

1. Introduction
Chemical reactions in a gas liquid system are important chemical processes in the chemical engineering. It
is significant to develop more satisfied models for the
gas liquid reaction systems. For gas liquid systems,
since materials in a separate phase must be transferred
in the other before reaction can occur, the mass balance
equations will contain both the mass transfer and
chemical rates. However, there is not enouph knowledge about the true mechanism of the mass transfer
between two adjacent phases accompanied by a chemical reaction at present yet. Hence, to the end to obtain
a more reliable mathematical model for the gas liquid
reaction system, we must select not only an appropriate
concept of the mass transfer at the interface between
the two phases, but also a practical hydrodynamic
model of the fluids in the reactor. It is well known that
the hydrodynamic behaviour of many reactor types,
e.g. tubular, loop, three-phase fluidized-bed and various
column reactors can be described by an axial dispersion
model effectively.
In the past, various concepts of mass transfer between the gas and liquid phases were proposed. They

* Corresponding author. Fax: +86 10 62562768.

0255-2701/97/$17.00 1997 Elsevier Science S.A. All rights reserved.
PII S 0 2 5 5 - 2 7 1 0 ( 9 7 ) 0 0 0 0 5 - 1

are the two-film concept [13], the penetration concept

[46], the film-penetration concept [7,8], and unsteady
two-film concept [9,10]. In all of the above, the penetration concept was widely applied in practice to describe
the mass transfer systems between the gas and liquid
phases, but all the models developed in the past only
concern the mass transfer rate at the interface and can
not ascertain the concentration profiles in the main
body of the fluids and the reactant conversion. Obviously, they have limitations for the application to design chemical gasliquid reactors.
In this paper, on the basis of the recent studies
[1117], an axial dispersion model for gasliquid reactors will be developed based on the penetration theory.
By modelling of the gasliquid reaction system we
consider that an irreversible first-order reaction occurs
only in the liquid phase and the mass transfer resistance
at the gas side will be neglected. Furthermore, an
isothermal case for the reactors is also considered. The
mass transfer mechanism accompanied by a chemical
reaction is mathematically treated in a new way in
order to obtain the average reaction velocity at an axial
location. According to the new mathematical treatment
mass balance equations can be built up for the both
bulk phases conveniently.
Because of the complexity of the mass transfer coupled with the chemical kinetics and nonlinearity of the

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

292

system it becomes usually not easy to solve the mass

balance equation system. Some times it is also difficult
to integrate the differential equation system numerically
owing to the poor convergence. Therefore, it is desirable to find out effective methods to solve the design
equation system. In this work we have obtained analytical solutions for the mass balance equations in the
linear case by means of the eigenvalues of the differential equation system. In addition, an iteration procedure
is proposed to solve the nonlinear differential equation
system numerically. Using the analytical solutions or
the iteration procedure given in this paper, we can
easily calculate the concentration profile, the mass
transfer degree, the reactant conversion, and the reactor
capacity.

2. Description of the penetration mechanism

The penetration theory was proposed by Higbie [4]
and modified by Danckwerts [5]. For convenience let us
consider a gas liquid system in which the gas phase
behaves as an ideal gas. Let A be the reactant in the gas
phase and must be transferred in the liquid phase
before it can react. The penetration mechanism can be
described by following equation
#CA
#2CA
=DA
#u
#x 2

pAb
C A = , x =0, u\ 0
H
kACA with
C A 5CAb, x =, u\ 0
C A =CAb, x \0, u= 0

C0 A =

N( Ax = 0 =

C0 A (x, S)=

&

e Su CA (x, u) du

dCA
du
dx x = 0

Se SuDA

 &
d
dx

e Su CA (x, u) du

l1 =
DA (kA + S)

(2)

(3)

The solution of the boundary value problem Eq. (2)

reads

x=0

l2 = S

'

DA
kA + S

(5)

(6)

and the average reaction velocity in the whole liquid

phase at a certain reactor location
R( A =

dC0 A (x, S)
= SA
= l1pAb/Hl2CAb
dx
x=0
where

where C0 A, the Laplace-transform of CA, is defined by



= SDA

Making use of the Laplace-transformation to the microscopic time u, the above boundary value problem
becomes

pAb
C0 A = , x =0
HS
with
CAb
C0 A 5
, x =
S

&

#2C0 A
=kAC0 A
#x 2

(4)

The above solution can be applied to describe the

mass transfer process accompanied by a chemical reaction with assumptions of: (a) the liquid surface which is
exposed to the gas phase has a certain age distribution,
for instance, say Danckwerts distribution Se Su; (b)
the depth of penetration is equal to the average depth
of the whole liquid phase. The last condition will be
satisfied by the definition in Eq. (10). Usually, this
application needs to carry out the Laplace reverse
transformation of Eq. (4) in order to obtain the reactant concentration profile in function of time CA (x, q),
from which the average mass transfer rate N( A and
reaction velocity R( A can be derived thereafter by use of
time-averaged integration according to the age distribution function. The mathematical treatment of the
Laplace reverse transformation is sometimes very
difficult and the form of the results by this way is also
complicated, so that its application will be stark limited. Due to the similarity of the Laplace transform
function e Sq in which S is an interim variable and the
age distribution function Se Sq in which S is a model
parameter, however, we can combine the two procedures of Laplace reverse transformation and time-averaged integration together to avoid the reverse
transformation. The mathematical solution from the
later has an identical accuracy with from the former,
but more simple and more practical in application.
According to the definition of the Laplace-transform of
CA, we can obtain the average mass transfer rate at the
interface

(1)

SC0 A CAb =DA

'kA + S
CAb
pAb
CAb
x
DA
+

e
kA + S
HS kA + S

1
d

& &
&
d

kAS

k S
= A
d

e Su CA (x, u) du dx

C0 A (x, S) dx=kA 8

pAb
fCAb
H

where
8=

1
d

'

DA
(1e d
kA + S/DA )
kA + S

(7)

f=

S
d(kA +S)

'

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

DA
(1 e d
kA +S/DA )
kA +S

S
kA + S

Table 1
Boundary conditions

VeL eL
=
Vai ai

z=0

(9)

and d is the average depth of penetration in the liquid

phase defined by
d=

293

(10)

The average reaction velocity in the liquid phase is a

very important parameter for modelling the mass transfer at the interface and the chemical reaction in the
liquid phase. The mass balance of the whole liquid
phase can be made by means of R( A exactly. It is
impossible if R( A is unkown. Hence, the only alternative
in the previous models based on the penetration concept is to assume that either a very slow or a very fast
reaction takes place in the system.

dcG
=0
dz
dcL
=0
dz
dcG
=0
dz

r =1

r=1

1 dcG
cG =1
PeG dz
1 dcL
cL =7
PeL dz
dcL
=0
dz
1 dcG
cG =1
PeG dz

1 dcL
cL =1
PeL dz

dispersion, flow, mass transfer across the interface, and

the chemical reaction rate. Thus the mole balances
concerning the component A for the both bulks may be
written according to Eq. (5) and Eq. (7) as:

VeDeG d2pAb LQG dpAb

p
Vai l1 Ab l2CAb =0

2
RT dy
RT dy
H
(11)

3. Bulk phase dispersion model

VLb DeL
An axial dispersion reactor model for gasliquid
reaction systems is considered as shown in Fig. 1. To
develop the mathematical dispersion model, we consider that steady state flow takes place in the reactor
and assume that the area of the interface, the gas and
liquid hold-up remain constant along the flow direction.
The mole balance for a bulk consists of terms of

z=1

d2CAb
dCAb
p
rLQL
+ Vai l1 Ab l2 CAb
2
dy
dy
H

VLb R( A = 0

(12)

where
VLb = V(1 e)

(13)

1
1

(14)

r=

for current flow

for countercurrent flow

Introducing the following dimensionless numbers and

relative variables
QGL 2
VeDeG

jli =

VaiRT
l
QGH i

QLL 2
VLbDeL

zli =

Vai
QL

PeG =
PeL =
Da=

kAVLb
QL

7=

HCAa
pAa

cG =
cL =

pAb
pAa

HCAb
pAa

z= 1

y
L

(15)

Eqs. (11) and (12) become dimensionless as

dc
d2cG
+ PeG G PeGjl1cG + PeGjl2cL = 0
dz 2
dz

(16)

d2cL
dc
+ rPeL L + PeLzl1cG + PeLzl2cL
2
dz
dz
PeLDa(8cG fcL)= 0

Fig. 1. Scheme of axial dispersion reactor model of two fluid phase

systems.

(17)

The boundary conditions are set up at the reactor

entrance and exit, i.e. the position z= 0 and z=1
respectively, as below
The differential equation system Eqs. (16) and (17)
with the boundary conditions given in Table 1 is a
two-point boundary value problem. The above mathematical model is valid for all value range of the reaction

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

294

velocity. Analytical solutions for this boundary value

problem is feasible by using of the eigenvalue method if
the system involves only linear differential equations
and boundary conditions.

4. Analytical solution of the equation system

Linear differential equation systems can be solved by
means of the eigenvalues of the equation systems analytically. The differential equation system Eqs. (16) and
(17) possesses an eigenequation according to the differential equation theory as following
(s 2 + PeGs PeGjl1)[s 2 +rPeGs PeL(zl2 fDa)]
PeGPeLjl2(zl1 8Da) =0

(18)

cG =A1 es1z + A2 es2z +A3 es3z +A4 es4z

(19)

cL =A1b1 es1z +A2b2 es2z +A3b3 es3z +A4b4 es4z

(20)

where
s 2i + PeGs PeGjl1 PeL(zl1 8Da)
,
s 2i + rPeLs PeL(zl2 fDa) PeGjl2

i=1, 2, 3, 4

(21)

and Ai are integration constants. These integration

constants can be determined by using the boundary
conditions in Table 1. To this end, a linear equation
system for the case of cocurrent flow must be solved

s
es1 1+ 1
PeG

es1b 1 1+ s1
PeL

s1
s 1b1




s2
s 2b2

 
 

s3
s 3b3

 
 

s
es2 1 + 2
PeG
s
es2b 2 1 + 2
PeL










s
es3 1 + 3
PeG
s
es3b 3 1 + 3
PeL

A 0
1

s4
A2
0
s4
e 1+
=
PeG
A3
1

s
A4
7
es4b 4 1+ 4
PeL
s4
s 4b4

es1 1+ s 1
PeG

s1

s 1b1es1

s1
b 1 1 PeL

(22)

 

es2 1+

s2
PeG

s2
s 2b2es2

 

es4 1+

To solve the above boundary value problem, we need

to find out the eigenvalues of the differential equation
system by solving the eigenequation Eq. (18), which has
four real roots s1, s2, s3 and s4, i.e. four eigenvalues in
the case of Da \0. Provided the eigenvalues of the
differential equation system are all known, then the
general solutions for the differential equation system
Eqs. (16) and (17) can be written according to the
differential equation theory as following:

bi =

and of countercurrent flow:

b 2 1

s2
PeL

 

es3 1+

s3
PeG

s3
s 3b3es3

 

b 3 1

s3
PeL

s4

PeG

A 1

A
0

2 =
A3
0

A 4 7
s
b 4 1 4
PeL
s4
s 4b4es4

(23)

So far, the analytical solution has been accomplished

and the concentration distribution, which is averaged
from the interface to the penetration depth for the
liquid phase, of the both bulk phases along the reactor
coordinate in the cases of cocurrent as well as countercurrent flow is obtainable directly using the analytical
solutions obtained above. So long as the concentrations
at the reactor exit are known, the overall mass transfer
degree hA, the reactant conversion xA, the reactor capacities Eh and Ex can be calculated by following
expressions respectively
hA = 1

pAb
= 1cGb
pAa

(24)

xA = 1

QGpAb /RT+ QLCAb

zc + jcLb
= 1 Gb
QGpAa /RT+ QLCAa
z+ j7

(25)

Eh =

QGpAah
,
RTV

Ex =

(QGpAa + RTQLCAa )x
RTV

(26)

The analytical solutions given above are only suitable

for the case that the mass balance equation system is
linear. If the change of the volumetric flow rate and the
pressure drop along the flow direction need to be taken
into account and/or a nonlinear chemical kinetics is
dealt with, the mass balance equations become nonlinear. In this case the equation system must be integrated
numerically. For this purpose the following iteration
procedure can be applied by using a numerical method
d2c iG+ 1
dc iG+ 1
=

Pe
+ PeGjl1c iG+ 1 PeGjl2c iL
G
dz 2
dz

(27)

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

295

Table 2
Model parameters and constants
Model parameter

Figure No.
2a

Da
PeG
PeL
S
z105
Constants

2b

*
*
25
25
50
50
0.5
0.5
1.2
1.2
j= 10 105

3a

3b

5
5
*
*
50
50
0.5
0.5
1.2
1.2
DA = 2109

d2c iL+ 1
dc iL+ 1
= rPeL
PeL(zl1 8Da)c iG
2
dz
dz
+PeL(zl2 fDa)c iL+ 1

(28)

with r = 1 for cocurrent flow and r = 1 for countercurrent flow. It is helpful to the computation convergence for this iteration procedure if the results of the
linear case from the analytical solution are used as first
iteration value. The analytical solutions given in this
paper are tested with the finite difference method and
both give the same results as shown in following.

4a

4b

5a

5b

6a

6b

5
25
*
1.5
1.2
eL =0.65

5
25
*
1.5
1.2

5
25
50
*
1.2
ai =150

5
25
50
*
1.2

5
25
50
0.5
*
7 =0

5
25
50
0.5
*

the mass transfer degrees of 0.59 and 0.76 by Da=1

for the cases of cocurrent and countercurrent flow
respectively, whereas almost the same mass transfer
degree is reached in the case of Da = 100 for the both
flow states. Opposed to the mass transfer degree, a
slightly better reactant conversion can be obtained by

5. Result representations and discussion

As an example of application of the axial dispersion
model for gasliquid systems, the concentration profiles of the bulks for a gas liquid system are calculated
using the model parameters and constants given in
Table 2, by use of the analytical solutions and the
numerical procedure as well. Simultaneously, the mass
transfer degree hA and the reactant conversion xA can
be obtained according to the concentrations of the both
phases at the reactor exit directly. It is worth to indicate
that the model parameter Da and kA are not independent and they have a relation of Da =dzkA. With the
identical model parameters and constants, the concentration profiles along the reactor coordinate have been
calculated for the both cases of cocurrent and countercurrent flow.
Fig. 2 shows the influence of the chemical reaction on
the concentration distribution for the cocurrent and
countercurrent flow respectively. It can be seen that the
chemical reaction enlarges the mass transfer velocity
not only as a result of the film-enhancement effect but
also as a result of the increase in the driving force for
the mass transfer. Besides, a comparison of the concentration profiles between the cases of cocurrent and
countercurrent flow can be made in Fig. 2(a) and (b). It
can be also seen that the countercurrent flow state is
more advantageous to the mass transfer between the
phases than the cocurrent flow state, especially in the
case of slow chemical reaction. For example, we have

Fig. 2. Influence of the chemical reaction on the concentration

profiles, (a) for cocurrent flow, (b) for countercurrent flow.

296

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

case of countercurrent flow. On the contrary, the influence of the gas phase dispersion on the mass transfer
degree hA is weaker in the case of cocurrent flow than
in the case of countercurrent flow.
Fig. 4(a) and (b) illustrate the influence of the liquid
phase dispersion on the concentration distribution, the
mass transfer degree, and reactant conversion for the
cocurrent and countercurrent flow respectively. The
similar influences of the liquid phase dispersion can be
found as that of gas phase dispersion except that the
liquid phase dispersion in the case of countercurrent
flow is favourable to the reactant conversion.
Fig. 5(a) and (b) show the influence of the mass
transfer at the interface on the concentration distribution, the mass transfer degree, and reactant conversion
for the cocurrent and countercurrent flow respectively.
Obviously, the mass transfer degree and the reactant
conversion will be increasing while the age distribution
parameter S also increases. For the cocurrent flow, the

Fig. 3. Influence of the gas phase dispersion on the concentration

profiles, (a) for cocurrent flow, (b) for countercurrent flow.

cocurrent flow than by countercurrent flow for the first

order reaction.
The influence of the gas phase dispersion on the
concentration distribution is presented in Fig. 3(a) and
(b) for the cocurrent and countercurrent flow respectively. The gas phase dispersion influences not only the
concentration profile of the gas phase but that of the
liquid phase as well strongly. According to the decrease
of the mass transfer degree and the reactant conversion
with increasing the back mixing (or decreasing the
Peclet number PeG), the gas phase dispersion always
decreases the mass transfer between the phases and the
reactant conversion. The gas phase behaves as plug
flow while the Peclet number of the gas phase PeG is
greater than 100. For small Peclet number PeG, e.g. 0.1,
the gas phase is mixed almost as ideally. The influence
of the gas phase dispersion on the reactant conversion
xA is starker in the case of cocurrent flow than in the

Fig. 4. Influence of the liquid phase dispersion on the concentration

profiles, (a) for current flow, (b) for countercurrent flow.

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

Fig. 5. Influence of the mass transfer at the interface on the concentration profiles, (a) for cocurrent flow, (b) for countercurrent flow.

influence of the age distribution parameter S is more

evident on the reactant conversion than on the mass
transfer degree. Contrarily for the countercurrent flow,
the influence of the age distribution parameter S is
more evident on the mass transfer degree than on the
reactant conversion.
Fig. 6(a) and (b) show the influence of the relative
feed flow rate on the concentration distribution, the
mass transfer degree, and reactant conversion for the
cocurrent and countercurrent flow respectively. For
both flow forms, the mass transfer degree and reactant
conversion will be improved by decreasing the relative
feed flow rate z/j which has a relation to the volumetric flow rates z/jQG/QL. Since the relative feed flow
rate z/j can directly influence the concentration distribution, the mass transfer degree, and reactant conversion, it becomes an important operation parameter. The
reactant concentration at the reactor exit can be controled effectively by regulating the relative feed flow

297

Fig. 6. Influence of the relative feed flow rate z/j on the concentration profiles, (a) for cocurrent flow, (b) for countercurrent flow.

rate z/j appropriately.

6. Conclusions
In this paper, an axial dispersion model for gasliquid reactors has been developed based on the penetration theory using the Danckwerts age distribution
function. The mass balance equation system consists of
two linear differential equations if a first order reaction
and constant interface area, constant volumetric flow
rates of the both phases as well as no pressure drop
along the reactor coordinate are considered, or else the
differential equations become nonlinear. Analytical solution have been accomplished for the linear case by
using of the eigenvalues of the equation system. Besides, an iteration procedure has been provided to
integrate the differential equation system for the nonlinear case.

J. Wang et al. / Chemical Engineering and Processing 36 (1997) 291299

298

The analytical solutions and the numerical procedure

with the finite difference method produce same results
for the both cases of cocurrent and countercurrent flow.
Therefore, the eigenvalue method is suitable to solve
the equation system of the axial dispersion model for
the both flow states. The mathematical model given in
this work and its solutions can be also used to describe
liquidliquid systems by substituting the concentration
of the gas phase pA /RT with the one of the first liquid
phase CA1. Obviously, they can be used to describe not
only absorption processes but also desorption processes
where the relative feed concentration 7 should be larger
than 1 for the later.
Using the analytical solutions or the iteration procedure given in this paper, the concentration profiles in
the bulks, the mass transfer degree, and reactant conversion which all are important for designing two-fluid
reactors can be easily calculated as long as the model
parameters have been known. Thus this model is useful
for designing gasliquid reactors with axial dispersion.
Besides, they can be used to determine the optimum
operating conditions of a gas liquid reactor in operation. In addition, they can also be applied to test and
verify the numerical results as well as provide initial
values for the first estimation of the iteration for many
other numerical methods.
7. Symbols used
A

ai

[m2 m3]

C
c
D

[kmol m3]

[m2 s1]

De

[m2 s1]

Da
E

[kmol (m3
s)1]
[J kmol1]
[1 s1]
[kmol (m2
s)1]
[N m2]

[m3 s1]
[J (kmol
K)1]
[kmol (m3
s)1]

[1 s1]

H
kA
N
p
Pe
Q
R
R(
s
S

and integration constant

interfacial area per
volume of reactor
concentration
relative concentration
molecular diffusion coefficient
convective diffusion
coefficient
Damkohler number
reactor capacity
Henrys law constant
reaction rate constant
mass flux
partial pressure
Peclet number
volumetric flow rate
gas constant
average reaction velocity
eigenvalues
age distribution
parameter

T
V
x

[K]
[m3]
[m]

x
y

[m]

Greek letters
b
d
e
li
h
7

[m]

[1 s1]

8, f

j, z
u

[s]
[s]

Subscripts
A
b
D
G, L
S
a, b

temperature
reactor volume
length coordinate in
direction of diffusion
reactant conversion
length coordinate in
flow direction
relative length coordinate in flow direction
coefficient
depth of the liquid
gas phase hold-up
abbreviation
mass transfer degree
relative feed concentration of the liquid
phase
dimensionless abbreviations
abbreviations
microscopic time
reactant A
bulk
dispersion
gas and liquid phase,
respectively
flow
input and output, respectively

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