Você está na página 1de 29

Available online at www.sciencedirect.

com

Applied Mathematical Modelling 32 (2008) 901929


www.elsevier.com/locate/apm

Gas absorption with rst order chemical reaction in a


laminar falling lm over a reacting solid wall
M. Danish *, R.K. Sharma, S. Ali
Department of Chemical Engineering, Aligarh Muslim University, Aligarh, UP, India
Received 1 December 2005; received in revised form 1 November 2006; accepted 16 February 2007
Available online 12 March 2007

Abstract
In the present work, a general case of gas absorption with rst order irreversible chemical reaction in a liquid lm, for
laminar ow over a solid wall, has been analyzed theoretically. First order chemical reaction between the diused solute
and the wall is also considered. Laplace transform followed by power series method has been applied to solve the governing equations. Thereafter, the obtained analytical solution of the developed general model has been successfully veried by
an explicit numerical scheme. The general model has also been reduced to six simplied cases, tackled by previous workers
and an excellent agreement in the solutions is observed. Moreover, the results are validated by the experimental data available in the literature. The obtained concentration proles in both the phases have been used to nd the absorption rates
and enhancement factor.
Further, the eect of various parameters on concentration prole of solute, enhancement factor and eigen-values have been
analyzed. Existence of positive eigen-values for the counter-current absorption is also described which was not pointed out by
any of the previous researchers. It is concluded that in a co-current system, for Hatta number greater than 7 approximately, the
variation in enhancement factor follows a linear trend on a loglog plot and that there is no eect of rate constants for higher
values of Hatta number. It is further shown that the reaction at solid wall has appreciable eect on the absorption rate.
 2007 Published by Elsevier Inc.
Keywords: Absorption; Falling lm; Chemical reaction; Mass transfer; Enhancement factor; Laplace transform

1. Introduction
Physical and chemical gas absorption is one of the most important separation processes and is widely
employed in chemical and allied industries either for separating undesirable components from a gas or for
the manufacturing purposes of some important chemicals. Generally, the former one is due to the stringent
environment norms, set nowadays and the latter one is the requirement of industry either for quality or design
purposes. Because of these vital reasons, a vast amount of theoretical as well as experimental research material
is available and still increasing.

Corresponding author. Tel.: +91 5712721152; fax: +91 5712700042.


E-mail address: mdanish77@redimail.com (M. Danish).

0307-904X/$ - see front matter  2007 Published by Elsevier Inc.


doi:10.1016/j.apm.2007.02.019

902

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

Nomenclature
Ai
an
B
Bi
Ca
CA
CA
c0
C0
C a0
C A0
Cg
C g0
CG
CG
DAB
DAG
E
Fi
f
kG
k1
k2
K1
K2
log
m
p
M0
p
M 00
R
R01
s
Vg
Vy
Vz
Vz
V max
y
Y
z
Z

series coecients for the solution of dimensionless concentration in the liquid lm


nth coecient of the series solution
dimensionless gas phase or surface resistance parameter equivalent to Biot number for mass
transfer
series coecients for the solution of dimensionless concentration in the gas phase
concentration of the solute A in the liquid phase, g/cm3
dimensionless concentration of the solute A in the liquid phase
Laplace transform of CA
1st term in series solution of CA corresponding to k0 0
dimensionless solute concentration in the entering liquid
solute concentration at gas liquid interface, g/cm3
dimensionless solute concentration at gasliquid interface
concentration of the solute A in the gas phase, g/cm3
initial gas phase concentration of the solute A, g/cm3
dimensionless gas phase concentration of the solute A
Laplace transform of C G
diusion coecient of solute A in the liquid phase, cm2/s
diusion coecient of
A in the gas phase, cm2/s
 solute

enhancement factor RR0
1
series coecients for the solution of absorption rate
series function of g
mass transfer coecient for innitesimally small gas liquid interface, cm/s
rate constant for 1st order chemical reaction in liquid lm, 1/s
rate constant for 1st order chemical reaction at solid wall, cm/s
 2
d
dimensionless rate constant for rst order chemical reaction in the liquid lm kD1AB
dimensionless
rate constant for rst order chemical reaction between solute and dissolving solid
 
wall Dk 2ABd
logarithm of a quantity on base10
the amount of gas absorbed
unit area after a contact time s, g/m2

qper
p
a form of Hatta number
4 K 1Z
q
 p 
a form of Hatta number independent from rate constant
4 Z
total mass rate of absorption, g/s
total mass rate of absorption without reaction in an innitely deep, stagnant liquid, g/s
Laplace transform variable
gas phase constant velocity, cm/s
velocity in y-direction, cm/s V y 0
average linear velocity of the liquid lm in the direction of ow, cm/s
linear velocity of the falling lm in the direction of ow, cm/s
maximum linear velocity of the liquid lm in the direction of ow, cm/s
coordinate along the thickness of the liquid lm from interface, cm
dimensionless coordinate along the thickness of the liquid lm from wall
coordinate along the direction of ow of the liquid lm, cm
dimensionless coordinate along direction of ow of the liquid lm

Greek symbols
d
thickness of the liquid lm, cm
d1
width of the gas ow channel, cm

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

g
ki
q
x
s
/m

903

dimensionless distance along the thickness of the liquid lm


ith eigen-value for the solution of dimensionless liquid phase concentration
density of the owing liquid, g/cm3
ratio of liquid to gas volumetric ow rates
contact time (z=V max , s
absorption rate, g/cm2 s.

Subscripts
i; j
index variables
n
nth value of a parameter

The process of isothermal gas absorption with and without chemical reaction in the liquid lm for laminar
ow over a solid surface has been analyzed by many researchers. Higbie in 1935 [1] carried out the analysis of
gas absorption process by assuming penetration theory model for short time of contact and Pigford in 1941 [2]
attempted the same by using parabolic velocity prole for long contact time. Later on, Pigford extended this
work for various other situations [38]. Nysing and Kramers [9] carried out an experimental study of CO2
absorption in solutions of Na2CO3/NaHCO3 and K2CO3/KHCO3 accompanied by 1st order chemical reaction in a wetted wall column, to verify the penetration theory for short contact time. Olbrich and Wild [10]
and Walker and Davis [11] extended the work of physical gas absorption for several simple geometries.
Absorption with nite gas phase resistance was further demonstrated by Tamir and Taitel [12] and Gupta
et al. [13]. The same problem was studied by Tamir and Taitel [14], Stepanek and Achwal [15] and Best
and Horner [16], but with the addition of rst order chemical reaction in the liquid lm. Continuing with
the above problem, Datta and Rinker [17] provided solution of gas absorption for short time of contact, taking into account the nite gas phase resistance and axial decrease of the solute concentration in gas phase with
rst order chemical reaction in the liquid lm. Later, Riazi and Faghri [18] and Riazi [19] stretched the above
work for zero order chemical reaction in the liquid lm. Elperin and Fominykh [20] in 2003, derived the coefcients of mass transfer during chemical absorption from a single Taylor bubble in the approximation of the
thin concentration boundary layer in liquid phase and veried the results with those of Nysing and Kramer [9].
Recently, a comprehensive model of gas absorption with chemical reaction has been developed by Sharma [21]
in 2004 in which most of the above cases have been included.Sharma, Danish and Ali [22] in 2006, solved the
original penetration theory model of Higbie [1] by using Similarity transform, Laplace transform and Sine
transform methods. Various parameters considered by dierent authors for the isothermal gas absorption
problem along with chemical reaction are listed in Table 1.
The case of reaction at the solid wall has not been considered so far. In the present work, an attempt has
been made to obtain an analytical solution for a more general case of absorption with nite resistance and
axial decrease of the solute concentration in gas phase and irreversible rst order chemical reaction in liquid
lm in laminar ow over a reacting plane wall. A combined method of Laplace transform and power series has
been applied to arrive at the concentration proles of both the phases, which are eventually used to evaluate
absorption rate and enhancement factor. Moreover, the eects of gas ow rate, gas phase resistance and reaction rate constants on concentration proles and enhancement factor have been shown and discussed in detail.
Subsequently, various simplied models, studied by dierent workers have been derived. To get more condence over the derived general analytical solution, a comparison with the results obtained by an explicit
numerical scheme has been carried out. By reducing the general analytical solution for a simplied case of
CO2 absorption in Na-buer solution accompanied by 1st order chemical reaction, the expression for absorption rate has been derived. Thereafter, the absorption rate is compared successfully with the available experimental data of Nysing and Kramer [9] and Elperin and Fominykh [20]. This substantiates the developed
model and its analytical solution.
The rest of the paper is organized as follows: In Section 2, the partial dierential equations are formulated
for the general gas absorption model. Section 3 describes the solution for general case using Laplace transform
and power series methods; this section also illustrates the derivation of the expression for enhancement factor

904

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

Table 1
Various parameters considered by dierent workers
No.

Authors

Years

d1

df

K1

K2

1
2
3
4
5
6
7
8
9
10
11
12
13

Higbie
Pigford
Nysing and Kramers
Olbrich and Wild
Tamir and Taitel
Tamir and Taitel
Stepnek and Achwal
Best and Horner
Riazi and Fagri
Datta and Rinker
Gupta et al.
Elperin and Fominykh
Present analysis

1935
1941
1958
1969
1971
1975
1976
1979
1985
1984
1986
2003
2006

X
NA
X
NA
NA
NA
NA
NA
NA
X
NA
X
NA

NA
X
NA
X
X
X
X
X
X
NA
X
NA
X

X
X
X
X
X

X
X

X
X

1
1
1
0
1
1
0, 1
1

X
X
X

X
X

and reduction of the general model and its solution to various simplied cases. In the same section, a comparison between the analytical and numerical solutions has been included and the results obtained from analytical
solution are veried with the available experimental data. Section 4 presents a detailed discussion on the
obtained results and is followed by Section 5, which concludes the whole study.
2. Physical model and model equations
A thin liquid lm, in fully developed laminar ow, is falling down over a dissolving solid wall and is
exposed to a gas, which ows either co-currently or counter-currently with respect to the lm; the schematic
view is shown in Fig. 1. Mass transfer of solute takes place from gas to liquid phase. Time of contact between
solute and liquid is long enough to presume a parabolic velocity prole. Steady state conditions are assumed to
prevail. A constant gas phase resistance is present and the concentration of solute in gas phase varies axially
due to the absorption by liquid. Irreversible rst order chemical reaction takes place between the solute and
liquid. It is further assumed that the diused solute in liquid phase also reacts with the wall with the same
order of reaction; physical properties of both the uids remain constant.
The law of conservation of mass is applied on an innitesimally small element in the liquid lm as well as in
the gas phase, as shown in Fig. 1, and the governing relations [23,24] are obtained as below.
2.1. Steady state modeling equations for liquid phase
The steady state modeling equation for liquid phase is obtained by applying the species balance over an
innitesimally small element in liquid phase as shown in Fig. 1. In doing so, it is assumed that there is no
velocity component in y-direction and the axial diusive transport is negligible in comparison to convective
transport. The ow is fully developed and the density of the liquid and diusivity of the solute are constant.
Incorporating these assumptions and putting the well-known parabolic velocity prole in the thus obtained
mass balance equation, we get the following linear partial dierential equation along with the relevant boundary conditions:


y 2 oC a
o2 C a
V max 1  2
DAB 2  k 1 C a  C 0 :
oz
oy
d
B.C.1: C a C 0 at z 0.
a
B.C.2: DAB oC
k G C g  C a at y 0.
oy
oC a
B.C.3: DAB oy k 2 C a  C 0 at y d.

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


Gas

Liquid

Cgo

Co

905

Y,

z, Z

Vg = constant, Plug Flow

Wall
Vz (y)

Cg (z) = constant

Cg (z)

P2

P1

P3
Vg C g DAG
z

Ca (z,0)
Ca (z,y)

dC g
dz

P4

Reaction at
wall =
k2.(Ca - Co)

kG (Cg Ca )

z
Vg C g

z +z

DAG

dC g
dz

z +z

Interface

At P1 : C g = C g At P
2
At P3 : kG (C g Ca ) = DAB
At P4 : DAB

Ca
y

Ca
= k 2 (Ca Co )
y

Vy Ca DAB
y

Ca
y

Vz ( y)Ca z DAB
y

dC
Vz ( y)Ca z DAB a
dz

dCa
dz

k1(Ca Co)
VyCa

y +y

DAB

Ca
y

y +y

z +z

Fig. 1. Schematic diagram of gas absorption process over a dissolving solid wall with axial variation of gas phase concentration.

2.2. Steady state modeling equations for gas phase


The species balance over an innitesimally small element in gas phase, shown in Fig. 1, yields Eq. (2), with
the assumptions that gas ows with uniform velocity and the contribution of axial diusion is insignicant in
comparison to convective transport. After some simple mathematical manipulations one easily arrives at the
following 1st order linear ordinary dierential equation:
dC g
kG

C g  C a :
2
dz
d1 V g
The associated B.C. is:
B.C.1: C g C g0 at z 0.
The preceding equations and the respective B.Cs are non-dimensionalized, using the following denitions
for dimensionless variables:
d  y
Ca  C0
C g  C g0
DAB
; CA
g
; CG
; Z
z;
d
C g0  C 0
C g0  C 0
V max d2
2
kGd
k2d
k1d
V max d
; K2
; K1
and x
:
B
DAB
DAB
V g d1
DAB

906

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

The governing equations thus take the following form:


For liquid phase:
g2  g

oC A o2 C A

 K 1CA:
oZ
og2

B.C.1: C A 0 at Z 0 8g.
A
B.C.2: oC
B1 C G  C A at g 1 8Z.
og
oC A
B.C.3: og K 2 C A at g 0 8Z.
For gas phase:
oC G
xBC G  C A 1jg1 at g 1 8Z:
oZ
Using B.C.2 for liquid phase, the above equation can be rewritten as:


oC G
oC A
x
at g 1 8Z:
oZ
og g1

B.C.1: C G 0 at Z 0.
Eqs. (3) and (4) including all the B.Cs constitute the general model. The parameter x can be regarded as the
ratio of the maximum possible absorption capacity to the rate at which gas enters into the channel [13]. It may
be noted that the gas phase concentration C g0 , at the top of the column, is the inlet gas concentration for cocurrent ow and the exit concentration when the gas ows counter-currently. The positive sign in Eq. (4) refers
to the counter-current ow, while the negative sign refers to the co-current ow. C 0 is the initial concentration
in the liquid lm i.e. concentration of solute in the liquid lm before absorption starts.
3. Solution by Laplace transform with power series method
After taking the Laplace transform of model Eqs. (3) and (4) along with their B.Cs, using the following
denition [25,26]
Z 1
CA
C A esZ dZ
5
0

one obtains the equations, in transformed form as:


For liquid phase:
d2 C A
 K 1CA:
dg2


B 1s C G  C A at g 1 8Z.

g2  gsC A
B.C.2:
B.C.3:

dC A
dg
dC A
dg

K 2 C A at g 0 8Z.

For gas phase:




dC A
sC G x
:
dg g1

3.1. Evaluation of liquid phase concentration prole


The transformed ordinary dierential equation (6) is solved by using a power series solution of the form:
1
X
CA
an  gn :
8
n0

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

Substituting the above in Eq. (6) leads to the following recurrence relation:
s
K 1  an2
2an3  an4 
;
an
nn  1
nn  1


where, a1 K 2 a0 , a2 K21 a0 and a3 3s K 16K 2 a0 .
Hence, one nds an independent series solution of C A as:


C A a0 1 K 2 :g K21 g2 3s K 16K 2 g3    or
C A a0 f ;

907

10

where; f is a function of s and g:

The coecient a0 is obtained from B.C.2 as:



B
sB
of
f
a0
s  Bx
s  Bx
og g1
and the solution in transformed form becomes:
,


s  Bx of
CA 1
sf
 f:
B
og g1

11

After applying the residue theorem [26,27], the following expression for inverse Laplace transform of C A is
obtained:



1
X
s  Bx of
sf
lim s  ki
f  esz ;
12
CA
s!ki
B
og
g1
i0
where, ki denote the eigen-values which are the zeros of the following relation:


s  Bx of
s:f
0:
B
og
g1

13

Applying LHospital rule to evaluate the limit in Eq. (12), the required solution for concentration prole in the
liquid lm is found to be:



1
X
1 of
s  Bx o2 f
of
ki Z
f
s
Ai  f  e ; where; Ai 1
:
14
CA
B og
B osog
os g1
i0
ski

Fig. 2 demonstrates the liquid phase concentration proles C A for x 1:0, K 1 0:1, K 2 0:1 and B 106 at
dierent Z.
3.2. Evaluation of gas phase concentration prole
To nd the gas phase concentration prole, the above expression for liquid phase concentration i.e. Eq.
(14), is substituted in Eq. (4) to get
 
1
X
oC G
of
x
Ai 
 ek i Z
15
og g1
oZ
i0
and is integrated. Alternatively, one can substitute Eq. (11) in Eq. (7) and obtain the gas phase concentration
by taking its inverse Laplace transform.
The subsequent steps are not as straight forward as were in the case of liquid phase and depend upon the
magnitude of rst eigen-value. The two cases, covering all the intricacies that arise in such conditions, are
described below:
3.2.1. Case (a): k0 6 0
These types of cases arise, when velocities of both phases have non-zero but nite values (i.e. x 6 0) and
none of the two reaction rates are zero (K 1 6 0; K 2 6 0).

908

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


3.5
z=0.05

z=.1

z=.2

z=.3

z=.4

z=.5

z=.6

z=.7

z=1

B = 10 , = 1.0
K 1 = 0.1, K 2 = 0.1

CONCENTRATION, CA

DIMENSIONLESS LIQUID PHASE

z=0.01
6

2.5

1.5

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DISTANCE FROM SOLID WALL,


Fig. 2. Development of concentration prole in the liquid lm, for nite gas phase resistance and axial variation of gas phase
concentration for counter-current system over a dissolving wall under rst order chemical reaction.

On integration with respect to Z, with limits from 0 to Z, Eq. (15) leads to:
"
 
  #
1
1
X
X
Ai of
Ai
of
ki Z
C G x
e 

:
og
og g1
k
k
i
i
g1
i0
i0
This may be rearranged as:
 
1
X
x  Ai of
Bi 1  eki :z ; where; Bi 
;
CG
og g1
ki
i0

i 0; 1; 2 . . .

16

Eq. (16) represents the concentration prole for solute in gas phase for those cases where magnitude of rst
eigen-value is non-zero. Fig. 3 portrays the concentration prole of solute in gas phase for x 1:0,
K 1 0:1; K 2 0:1 and B 106 . Table 2 presents the eigen-values and series coecients of the same, for different values of x with K 1 0:1; K 2 0:1 and B 106 .
3.2.2. Case (b): k0 0
Following two sub-cases generate zero as their rst eigen-value:
(i) All the absorption models with stationary liquid lm and/or very high gas velocity (i.e. x 0), with/
without any of the two reactions and for any value of gas phase resistance.
(ii) All the absorption models with no reactions (K 1 K 2 0) and with any values of x and gas phase
resistance.
Here, only the second sub-case is described and the same approach can be adopted for the rst one.
3.2.2.1. Sub-case: k0 0.
For such systems, the liquid phase concentration prole C A may be expressed as:
1
X
Ai  f  eki Z ; where; c0 A0 f eki Z jsk0 0 :
C A c0

17

i1

h
i
o2 f
Also, A0 is the series coecient evaluated for the rst eigen-value k0 0 at g 1 or c0 1= 1  x osog

g1;s0

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

909

2.5

DIMENSIONLESS GAS PHASE


CONCENTRATION, CG

K1 = 0.1
K2 = 0.1
B = 10

= 1.0

1.5

= 0.4

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS AXIAL DISTANCE, Z


Fig. 3. Gas phase concentration prole for counter-current ow.

Table 2
Eigen-values and series coecients for counter-current gas absorption system at various range of axial variation parameter x, with
K 1 0:1, K 2 0:1 and B 106
n

0
1
2
3
4
5
6
7
8
9
10

x 0:0

x 0:4

x 1:0

ki

Ai

Bi

ki

Ai

Bi xF i

ki

Ai

Bi xF i

0.0000
5.6465
40.311
106.97
205.64
336.31
498.97
693.64
920.30
1178.9
1469.4

0.8679
1.1944
0.5297
0.3528
0.2687
0.2189
0.1857
0.1619
0.1439
0.1298
0.1178

0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000

0.0937
4.5732
39.285
105.95
204.62
335.29
497.95
692.62
919.28
1177.9
1468.3

1.1048
1.4408
0.5414
0.3557
0.2698
0.2195
0.1860
0.1621
0.1440
0.1299
0.1187

1.3005
0.24415
0.0262
0.0096
0.0049
0.0030
0.0020
0.0014
0.0011
0.0008
0.0006

0.4090
2.8532
37.739
104.42
203.09
333.76
496.42
691.09
917.76
1176.4
1466.7

1.6913
2.0393
0.5558
0.3590
0.2711
0.2201
0.1864
0.1623
0.1442
0.1300
0.1187

2.1365
0.9924
0.0681
0.0244
0.0125
0.0076
0.0051
0.0036
0.0027
0.0021
0.0017

Consequently, the required liquid phase concentration prole is expressed as:


1
X
1
i

Ai  f  eki z
CA h
o2 f
1  x osog
i1

18

g1;s0

and from Eq. (4), the gas phase concentration prole is obtained as:
 
1
X
x  Ai of
ki :z
Bi 1  e ; where; Bi 
; i 1; 2; 3 . . .
CG
og g1
ki
i1

19

The above mentioned Eq. (19) represents the concentration prole of solute in gas phase for those cases where
magnitude of rst eigen-value is zero and the gas possesses an axial variation in the solute concentration.
Fig. 4 shows the concentration prole of solute in gas phase for x 1:0, K 1 K 2 0 and B 106 .

910

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


2

DIMENSIONLESS GAS PHASE


CONCENTRATION, CG

1.8
1.6
1.4

= 1.0

1.2
1
0.8
0.6
0.4
0.2
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS AXIAL DISTANCE, Z


Fig. 4. Development of gas phase concentration prole for counter-current ow for x 1:0, K 1 0:0, K 2 0:0 and B 106 at Z 1:0.

3.3. Enhancement factor


The inuence of chemical reaction and nite lm thickness on the absorption is best summarized by comparing the actual absorption rate R, with that of an innitely deep stagnant liquid with no chemical reaction
R01 , as used in [16]. The ratio R=R01 is equal to the well-known enhancement factor E. The absorption rate
from penetration model, for physical absorption in an innitely deep stagnant liquid exposed to a gas for a
time period z=V max , is given by:
r
4Z
0
:
20
R1 C g0  C 0 dV max W
p
In the present condition, the total amount of gas absorbed per unit elapsed time is evaluated from the diusive
ux at interface and is given as:

Z z

oC a
R DAB W
dz:
21
oY Y d
0
Yet again, to determine the derivative term in the above expression, we consider two dierent cases depending
upon the magnitude of rst eigen-value.
3.3.1. Case (a): k0 6 0
As explained earlier, these types of cases arise when both the uids have non-zero but nite velocities
(x 6 0) and none of the reaction rates are zero (K 1 6 0; K 2 6 0). For such conditions, we directly use Eq.
(14) for liquid phase concentration prole and substitute it in Eq. (21) to get the following expression for
absorption rate:
1
X
R

F i 1  eki Z ;
22
C a0  C 0 dV max W
i0
 
where, F i  Akii of
Bxi ; i 0; 1; 2 . . .
og
g1

A little use of mathematics leads to the following expression for enhancement factor E
P1
R
F i 1  eki Z
:
E 0 i0 r
R1
4Z
p

23

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

911

10000

1000

= 1.0

ENHANCEMENT FACTOR, E

= 0.4
100

= 0.0

10

0.01

0.1

10

100

= -0.4
0.1

= -2.0

0.01

= -1.0

0.001

''
Fig. 5. Loglog graph showing eect of x on variation of E with
K 2 0:1 and B 106 .

M 00 for cocurrent and counter-current ow systems at K 1 0:1,

p
In Fig. 5, the enhancement factor E has been plotted on a loglog graph as a function of the modulus M 00
(a form of Hatta number independent of rate constant), for various values of x with K 1 K 2 0:1 and
B 106 . The modulus is dened as:

r
p
p
00
M
Z:
24
4
3.3.2. Case (b): k0 0
As argued earlier, two situations yield zero as their rst eigen-values i.e.
(i) x 0,
(ii) K 1 K 2 0.
We now proceed to nd the expression for enhancement factor E for the rst case only, since for the second
situation, it does not have any meaning. By rearranging the liquid phase concentration prole, as given in Eq.
(17) and following the same procedure, as adopted in Section 3.2.2.1 the expression for c0 is found to be:
p
p
K 2 sinh K 1 g
p
cosh K 1 g
K1
p
p :
c0 p
p K 2 cosh K 1
p K 2 sinh K 1
K1
p
sinh K 1
cosh K 1
B
B
K1
Finally, one obtains the required concentration prole for liquid phase as:
p
p
K 2 sinh K 1 g
p
cosh K 1 g
1
X
K1
p
p
C A p
A  f  eki Z :
25
p K 2 cosh K 1
p K 2 sinh K 1 i1 i
K1
p
sinh K 1
cosh K 1
B
B
K1
With the substitution of C A from the above equation, we can evaluate the gas absorption rate as:
p
p
R
K 1 sinh K 1 K 2 cosh K 1
Z p
p
p
p
p
p
K 1 p
C a0  C 0 dV max W
K 1 sinh K 1 K 2 cosh K 1 K 1 cosh K 1 K 2 sinh K 1
B
 
1
X
Ai of
ki Z
F i 1  e where; F i 
; i 1; 2; 3 . . .
26

ki og g1
i1

912

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

From Eqs. (20) and (26) we can nd the enhancement factor E as:
8
9,
p
p
1
= p
X
R <
K 1 sinh K 1 K 2 cosh K 1
ki Z
i
E 0 Z hp p
F i 1  e
4Z=p:
p

p
p

K1
;
R1 :
K 1 sinh K 1 K 2 cosh K 1 K 1 cosh K 1 K 2 sinh K 1
1
B

27
3.3.2.1. Sub-case for x 0 with K 1 0 and K 2 6 0.
Here too, the rst eigen-value comes out to be zero. The enhancement factor E given by Eq. (27) is no
longer valid because on substituting K 1 0, it results in an indeterminate form. For such cases, one needs
to start again from Eqs. (6) and (7) keeping K 1 0. Following the same steps, as adopted previously, c0 is
found to be:
c0

1 gK 2
:
1 K 2 KB2

Hence, the concentration prole C A , may be written as:


CA

1
X
1 gK 2
Ai  f  eki Z :
K2
1 K2 B
i1

28

Now using this concentration prole, the enhancement factor E is expressed as:
X1
K2
F i 1  eki Z
K2 Z
i1
1 K2 B
R
r
E 0
:
R1
4Z
p

29

The enhancement factor E has been plotted on a loglog graph as a function of Hatta number in Fig. 10 for
x 0 and dierent values of K1 and K2.
3.4. Reduction of general model into simplied cases
To show the general nature of the developed model and its solution, we reduce it to some simple cases,
which were earlier studied by various researchers. Many more linear model equations can also be deduced.
The results obtained from the reduced models and their solutions match exceptionally well with those available in literature. Only the concentration proles of both phases have been discussed; the enhancement factor
and other related quantities can be obtained in a similar way.
3.4.1. Reduced model 1 (x 0, K 1 K 2 0 and B 1)
This is the simplest case of physical gas absorption which takes into account the parabolic velocity prole in
the liquid lm without any gas phase resistance. The velocity of gas phase is considered to be very high. This
case was rst considered by [2,4] and later on by [10]. The respective model equations for both phases along
with B.Cs are found by keeping x 0, K 1 K 2 0 and B 1 in Eqs. (3) and (4) and are presented
below:
For liquid phase:
g2  g

oC A o2 C A

:
oZ
og2

B.C.1: C A 0 at Z 0 8g.
B.C.2: C A 1 at g 1 8Z.
A
B.C.3: oC
0 at g 0 8Z.
og

30

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

913

For gas phase:


oC G
0 at g 1 8Z:
oZ

31

B.C.1: C G 0 at Z 0.
The solution methodology for the above equations is as follows:
For liquid phase:
Taking Laplace transform of Eq. (30) and using B.C.1, one gets:
d2 C A
:
dg2

g2  gsC A

32

The other two boundary conditions now become:


A
B.C.2: C A 1s and B.C.3: dC
0.
dg
P1
n
Substituting, C A n0 an g in Eq. (32), and using B.C.3, the following recurrence relation is
obtained:
s
s
2an3  an4 ; where a1 0; and a2 0 and a3
an
a0 :
nn  1
3

Thus, the transformed concentration prole turns out to be:




s
s
s4
C A a0 1 g3  g4 g6    a0 f s; g:
3
12
45
1
f s; g
and C A
. After taking its inverse Laplace transform one nds:
B.C.2 gives a0
sf jg1
sf jg1
1
X
s  ki
CA
lim
f s; gesZ ; where; ki are roots of sf jg1 0:
s!ki sf j
g1
0

33

Using LHospital rule for evaluating the limits in the above equation, the following expression for C A is
obtained:
CA

1
X
0

1
X
1
 f s; gesZ
lim 
Ai f ki ; geki Z ;
s!ki
df 
0
f s
ds g1

where Ai lim 
s!ki

C A A0

1
X
1

1

df 
f s
ds g1

Ai f ki ; geki Z 1

or
34
1
X

Ai f ki ; geki Z ;

1
 1:
where; A0 lim 
s!k0 0
df 
f s
ds g1
For gas phase:
Now, the gas phase Eq. (31) is integrated which gives the gas phase concentration C G 0 throughout.

914

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

3.4.2. Reduced model 2 (x 0, K 1 K 2 0 and B 6 1)


Tamir and Taitel [12] studied a similar case of physical gas absorption with x 0 along with nite gas
phase resistance, by considering parabolic liquid phase velocity prole. By putting the values of parameters
given above, the following desired model equations are obtained:
For liquid phase:
g2  g

oC A o2 C A

:
oZ
og2

35

B.C.1: C A 0 at Z 0 8g.
A
B1  C A at g 1 8Z.
B.C.2: oC
og
A
B.C.3: oC
0 at g 0 8Z.
og

For gas phase:


oC G
0
oZ

at g 1 8Z:

36

B.C.1: C G 0 at Z 0.
The above governing system of equations is solved by applying Laplace transform followed by
power series method as done previously and the obtained liquid phase concentration prole is given
below:
1
1
X
X
Ai f ki ; geki Z 1
Ai f ki ; geki Z ;
37
C A A0
1

where,
A0 lim 
s!k0 0

1 of
B og

f s

and ki are the roots of s

1
B

1
2
1 o f
B osog



of
f 
og

of
os

g1





1
g1

0.

Proceeding in a similar manner like the previous case, for gas phase we have concentration C G 0
throughout.
3.4.3. Reduced model 3 (x 0, K 1 6 0; K 2 0 and B 1)
This case refers to the situation where gas absorption takes place with rst order chemical reaction and
without gas phase resistance with no gas ow. Best and Horner [16] have described such a case. Appropriate
values of parameters give the following model equations.
For liquid phase:
g2  g

oC A o2 C A

 K 1CA:
oZ
og2

38

B.C.1: C A 0 at Z 0 8g.
B.C.2: C A 1 at g 1 8Z.
A
B.C.3: oC
0 at g 0 8Z.
og
For gas phase:
oC G
0
oZ

at g 1 8Z:

B.C.1: C G 0 at Z 0.

39

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

915

Following the earlier solution methodology one nds the liquid phase concentration as:
C A A0

1
X

Ai f ki ; geki Z

where, A0 lims!k0 0

p
1
cosh K 1 g X
p
Ai f ki ; geki Z ;
cosh K 1
1

40

p
1g
pK
cosh
and ki are the roots of sf jg1 0.
cosh K 1

1
of
f s os

jg1
Again for gas phase, we have concentration C G 0 throughout.

3.4.4. Reduced model 4 (x 0, K 1 6 0; K 2 0 and B 6 1)


The process of gas absorption with rst order chemical reaction and with nite gas phase resistance and no
gas ow was worked out by [14,15]. For this situation the general model Eqs. (3) and (4) reduce to:
For liquid phase:
g2  g

oC A o2 C A

 K 1CA :
oZ
og2

41

B.C.1: C A 0 at Z 0 8g.
A
B.C.2: oC
B1  C A at g 1 8Z.
og
oC A
B.C.3: og 0 at g 0 8Z.
For gas phase:
oC G
0 at g 1 8Z:
oZ

42

B.C.1: C G 0 at Z 0.
For this case we get the following expression for liquid phase concentration:
C A A0

1
X

Ai f ki ; geki Z

1
X
1

Ai f ki ; geki Z ;
p p
p

cosh K 1 BK 1 sinh K 1
1

43

where,
A0 lim 
s!k0 0

1 df
B dg

f s

and ki are the roots of s

1
B

1
2
1 o f
B osog



df

f

dg




g1

of
os

g1

1
p p
p
cosh K 1 BK 1 sinh K 1

0.

Similarly, for gas phase we have concentration C G 0 throughout.


3.4.5. Reduced model 5 (x 6 0, K 1 0; K 2 0 and B 6 1)
Physical gas absorption with nite gas phase resistance and gas ow was theoretically analyzed by [13]. The
presence of non-zero x couples equations of both phases. The gas phase equation is solved after the liquid
phase concentration prole is found. For this case, we have a non-zero gas phase dimensionless concentration
unlike all the previous cases derived. The governing equations become:
For liquid phase:
g2  g

oC A o2 C A

:
oZ
og2

44

916

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

B.C.1: C A 0 at Z 0 8g.
A
B.C.2: oC
B1 C G  C A at g 1 8Z.
og
oC A
B.C.3: og 0 at g 0 8Z.
For gas phase:


oC G
oC A 
x
oZ
og g1

at g 1 8Z:

45

B.C.1: C G 0 at Z = 0.
Again, going through the same steps, we have the liquid phase concentration prole as given below:
1
1
X
X
1

Ai f ki ; geki Z 
Ai f ki ; geki Z ;
46
C A A0
2
o f 
1  x osog
1
1

g1
 



1
sxB
where, A0 lims!k0 0  o2 f  and ki are the roots of of

sf
 0.
B
og
1xosog

g1

g1

After putting this in Eq. (45), we get the gas phase concentration C G as:
!
!



1
1
X
oC G
oC A 
o X
of
k
;
g

i
ki Z
ki Z 
e
x

x
A
f
k
;
ge

x
A


i
i
i


og
og
oZ
og g1
0
0
g1

Integration of the above expression and using B.C.1 for gas phase gives:
!

1
1
X
X



Ai of ki ; g 
1  eki Z
Bi 1  eki Z ;
C G x


og
k
i
g1
0
0


where, Bi x Akii of kogi ;g .

:
g1

47

g1

3.4.6. Reduced model 6 (x 0, K 1 0; K 2 0, B 1 and dy  1)


This is the simplest case rst considered by [1], while founding the penetration theory for gas absorption for
short time of contact. Recently, Sharma et al. [22] have obtained the solution for this case by three dierent
techniques i.e. Laplace transform, Similarity transform and Sine transform. We describe below the solution by
Laplace transform only. The governing equations are as follows:
For liquid phase:
V max

oC a
o2 C a
DAB
:
oz
oy 2

48

B.C.1: C a C 0 at z 0.
B.C.2: C a C g0 at y 0.
B.C.3: C a C 0 at y d.
This system is made non-dimensionalized by using the same denitions except g dy (used for this case
only). Hence, the following parabolic partial dierential equation is obtained:
oC A o2 C A

:
oZ
og2
B.C.1: C A 0 at Z 0.
B.C.2: C A 1 at g 0.
B.C.3: C A 0 at g 1.

49

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

917

Taking the Laplace transform with respect to Z on both sides of diusion equation (49) and incorporating
the boundary condition at Z 0 gives:
sC A

d2 C A
:
dg2

50

The solution of the ordinary dierential Eq. (50) is given [57] as:
p
p
C A Aeg s Beg s ;

51

where, C A is a function of s and g. The constants A and B are found with the help of the boundary conditions 2
and 3, and the solution in transformed form becomes:
p
eg s
:
52
CA
s
The inverse transform of this expression is obtained by using FourierMellin inversion theorem [26] as:
Z cib
1
C A g; Z
lim
C A esZ ds:
53
2pi b!1 cib
This is approximated by the contour integral [26,28] which is given by:
I
 esZ C A ds:

54

Putting C A from Eq. (52) in Eq. (54) and after doing some mathematical manipulations, the following liquid
phase concentration prole of the absorbed solute, for short contact time, is obtained
g
C A erfc p :
55
4Z
3.5. Numerical solution of the general model
The developed analytical solution has been veried using a simple explicit numerical scheme for many sets
of parameter values. The scheme utilizes nite dierence approach and the discretized model domain is demonstrated in Fig. 13. The adopted nite dierence method has been programmed in MATLAB 6 for ease and
the results are saved as an EXCEL data le. Only the liquid and gas phase concentration proles are shown in
Figs. 14 and 15 respectively, for one set of parameter values pertaining to the general case. From the two plots,
it is clear that the results show a good agreement with the analytical solutions presented in Figs. 2 and 3.
3.5.1. Numerical scheme
The whole problem domain of interest was divided into two parts: one for the liquid lm and the other for
gas phase, as depicted in Fig. 13. The liquid part was discretized along two directions; while gas phase was discretized along axial coordinate only. Subsequently, at their respective border points, B.Cs have been specied.
Discretization in liquid phases
The dimensionless liquid lm thickness g and the dimensionless axial distance Z are divided into N and M
equal parts, respectively. The general model equation in liquid lm at a point i; j 1 is expressed as:




oC A 
o2 C A 

g2  g


K
C
; or
1 A

oZ i;j1
og2 i;j1
i;j1

56



oC A 
o2 C A 

g2  g

 K 1CA

oZ i;j1
og2 i;j
i;j

and the associated B.Cs are:

918

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

B:C:1 : C A i; 0 0; 8i 2 0; N 

oC A 
B1 C G  C A jN ;j1 ; 8j 2 0; M
B:C:2 :
og N ;j1

oC A 
K 2 C A j0;j1 ; 8j 2 0; M:
B:C:3 :
og 

57
58
59

0;j1

Discretization in gas phase


Only axial discretization is needed in gas phase and is given below:


oC G 
oC A 

x
; 8j 2 0; M:
oZ j1
og N ;j1

60

The B.C. for gas phase is introduced as:


B:C:1 C G 0 0:

61

Solution algorithm:
1. Concentrations C A and C G of liquid and gas phases at the starting of the boundary are specied using Eqs.
(57) and (61).
2. Using the discretized form of Eq. (56), the liquid phase concentrations C A i; j 1 at the next axial position
are calculated for all i 2 1; N  1.
3. Thereafter, from Eq. (59), the liquid phase concentration at wall is obtained.
4. Next, C A N ; j 1 and C G j 1 are evaluated from Eqs. (58) and (60) simultaneously.
5. The procedure is repeated for the next axial step.
3.6. Verication of the mathematical model with the experimental results
Though the problem of gas absorption with and without chemical reaction has been tackled by many workers and a vast amount of material, both theoretical and experimental, is available. Mostly, the experimental
studies have been carried out to nd the related unknown parameters such as rate constant, diusivity and
saturation concentration of solute in liquid etc. or the derived quantities like average or total absorption rate,
rather than to nd the concentration proles of both the phases. For the purpose of verication, the experimental data are chosen from [9], in which an experimental study of CO2 absorption in the Na buer solutions
of various strengths was carried out for short time of contact. The whole process of absorption was accompanied by 1st order homogeneous chemical reaction and the rate of absorption of CO2 was measured in a wetted wall column.
The equations used in [9] for concentration prole, mass transfer rate per unit area and the total amount of
gas absorbed per unit area, in a certain time interval, have been reproduced below in terms of the symbols used
in the present paper:
0
0
s1
s1
 r
 r
Ca
1
k1
k1z C 1
k1
k1z C
B y
B y
exp y
62
erfc@ q 
erfc@ q
A exp y
A:
V max
2
V max
C g0 2
DAB
DAB
2 zDAB
2 zDAB
V max

V max

The rate of mass transfer through a unit area of the gas liquid interface is given [9] as:
0 s
1
k1 z


pB
oC a 
k1z
e V max C
C g0 DAB k 1 @erf
qA:
/m DAB

V max
oy y0
1z
p Vkmax

63

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

919

z
The total amount of gas absorbed per unit area, after a contact time s V max
is given [9] as:
20s
1 s
3
k1 z
r
Z s
V max
z 6B k 1 z
1 C
k1z
e
7
/m dt C g0 DAB
qAerf
p 5:
ms
4@
V max
V max 2 k1 z
V max
p
0
V max

64

In order to compare our results with the experimental data [9], the above quantities are now evaluated from
the present model equations for the case when x 0, K 1 6 0; K 2 0 and B 1.
The rate of mass transfer through a unit area of the gas liquid interface is given by:



oC a 
oC a 
DAB C g0 oC A 
/m DAB

:
65
AB
oy y0
oY Y d
d
og g1
0

The total amount of gas absorbed per unit area after a contact time s zDz
d
V max
height of end eects [9]) as:

Z z
Z Z
Z s
1
oC A 
/m dt
/ dz C g0 d
dZ;
ms
V max 0 m
og g1
0
0

ZDZ 0
DAB

is given (Dz0 is the

66

where

 
1
p
p X
oC A 
of
K 1 tanh K 1
Ai
eki Z
og g1
og g1
i1

67

or
!
1
p
p X
ki Z
F i 1  e ;
ms C g0 d Z K 1 tanh K 1

and

Fi 

i1

!
1
D s
p X
DAB s p
ki AB
2
C g0 d
F i 1  e d :
K 1 tanh K 1
d2
i1

 
Ai of
ki og g1
68

The values of chosen parameters are same as those used for the runs 5 and 6 of [9] and are listed below:
Run No. 5 of [9]: C g0 2:31 104 g cm3 ; k 1 0:56 s1 ; d 0:04 cm;
DAB 1:17 105 cm2 s1 ; V max 32 cm s1 ; Dz 2 cm.
Table 3
Eigen-values and series coecients for experimental data of gas absorption with rst order chemical reaction, x 0, K 1 76:5812 and
144.957265, K 2 0 and B 1
No. of eigen-values

0
1
2
3
4
5
6
7
8
9
10

For K 1 76:5812

For K 1 144:957265

ki

Ai

Fi

ki

Ai

Fi

0.000000
107.6611314
166.3823198
247.9379144
354.9497511
489.75184370
654.1933116
849.4538967
1076.1708969
1334.5388988
1625.5418988

0.0003165843
0.0099496611
0.0348871199
0.0656352839
0.0911870510
0.1068187151
0.1134069768
0.1139208620
0.1110551986
0.1062974349
0.0011747340

0.000000
185.8518694
257.1461211
350.5565811
468.4541818
612.5116393
784.0615829
984.2776336
1214.1646337
1474.1656341
1726.177

0.0000118087
0.0015920387
0.0074742510
0.0183812004
0.0324252865
0.0468084563
0.0592897557
0.0687116330
0.0748928678
0.0330288412
1.358284e-05

0.00757368037899
0.00762832934056
0.00637605737965
0.00508712756082
0.00403212778099
0.00321390217994
0.00259132581195
0.00198260994417
0.00842749504505
0.00518678921917

0.00369423528606
0.00419537415163
0.00391993865534
0.00341452963397
0.00289332452554
0.00243452255674
0.00197917740811
0.00262807504592
0.01797114826218
0.00013246396498

920

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

Run No. 6 of [9]: C g0 2:25 104 g cm3 ; k 1 1:06 s1 ; d 0:04 cm;
DAB 1:17 105 cm2 s1 ; V max 32 cm s1 ; Dz 2 cm.
The obtained results have been shown in Fig. 16 and an excellent agreement is found between the analytical
solution and the experimental data. A detailed discussion of the results can be found in the next section. Eigenvalues and other coecients for these runs have been shown in Table 3.
4. Results and discussion
The concentration proles of solute, in both phases depend upon four parameters namely x, K1, K2 and B.
The liquid phase concentration shows variation in both y- and z-directions while, the gas phase concentration
varies with z only. The parameters also aect absorption rate in the liquid phase. An assessment of the plots of
various quantities for a range of parameter values reveals these variations.
4.1. Parameter x
Figs. 3 and 6 show that as gas phase velocity increases, both the liquid and gas phase concentrations
increase in counter-current systems. This is also true for co-current systems. When x is small, the axial variation in gas phase concentration is negligible and the error introduced by assuming a constant axial concentration is also small. However, as x increases, the variation in gas phase concentration becomes large.
x depends on the relative liquid to gas volumetric ow rates. For the gases of larger solubility, large axial
variation in the gas composition can be expected.
In the light of the above discussion, Figs. 3 and 15 may cause some confusion in the sense that the concentration of solute in gas phase is large for lower gas velocity (i.e. x 1:0) as compared to the one for higher gas
velocity (i.e. x 0:4) for counter-current ow, for all values of Z. This is in sharp contrast with the above
discussion. This issue is resolved below.
G
A close look on Eq. (2) or (4) reveals that the slope oC
decreases with increase in gas phase velocity. This
oZ
means that for higher gas phase velocities, the outlet and inlet concentrations are nearly same. Whereas, for
lower gas velocities the slope is positive which indicates that inlet concentration is greater than the outlet concentration C g0 . Since the outlet concentration C g0 has been used in all our calculations, and because the slope
3.5
= 0.0
= 0.4

DIMENSIONLES LIQUID PHASE


CONCENTRATION, CA

= 1.0

2.5

1.5

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS DISTANCE FROM SOLID WALL,


Fig. 6. Development of liquid phase concentration prole for counter-current ow, x varies from 0.0 to 1.0 for, K 1 0:1, K 2 0:1 and
B 106 at Z 1:0.

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

921

tends to zero for higher gas velocities, this C g0 will be available through out the axial direction for x 0.
However, for non-zero slopes, a concentration greater than C g0 , but lesser than inlet concentration is observed
for all axial positions and hence, a higher gas phase concentration at a particular Z is seen for lower gas velocities and vice-versa. To understand these arguments clearly, one can also study the plots by shifting the concentration proles such that the inlet concentrations become same for all gas velocities, which accordingly
makes the outlet concentrations C g0 dierent.
Fig. 5 shows the variation of enhancement factor with Hatta number on a loglog plot for various values of
x. As is evident from the plot, the absorption rate for co-current system is much lower than that of constant gas
phase concentration. This is due to the gradual decline of gas phase concentration in a cocurrent ow resulting in a nite amount of solute absorption. In counter-current or co-current systems, increase
in gas phase velocity leads to an increase in enhancement factor E. In co-current systems, it is also observed,
that enhancement factor E decreases linearly on a loglog plot for Hatta number greater than 7.
4.2. Parameter K1
As liquid lm reaction rate constant K1 increases, the exit liquid phase concentration decreases which is
portrayed in Fig. 7. This is due to the enhanced rate of reaction which increases the absorption rate; it can
also be seen from the increasing slope of liquid phase concentration proles at interface. Higher the absorption
rate, higher is the axial variation in gaspphase
concentration as shown in Fig. 8.
Fig. 9 shows the variation of E with M 00 (Hatta number) and K1 for co-current as well as counter-current
systems. Initially, for any of the systems, the eect of K1 is negligible since the rate of reaction is small enough
(due to very low concentration in the liquid lm) to impress any change in enhancement factor E. In co-current systems, for Hatta number greater than 10, the absorption rate overcomes the reaction rate and saturation starts. This behavior is shown by a single line with constant negative slope in spite of dierent values of
K1, while, in the
case
p
of counter-current system no such relation is found. The enhancement factor E increases
steadily with M 00 as the value of parameter K1 increases. The rate of absorption for counter-current ow is
higher than for co-current ow for xed values of all process parameters. The reaction parameter K1, indicates
the ratio of the rate of reaction to the rate of diusion in relation to the thickness of the lm. Thus, a small
value of K1 may be due to a very slow reaction, a very thin lm or a high rate of diusion. The eect of lm
thickness on the rate of absorption is seen only when K1 is less than 5. At higher values of K1, the rate of

K1 = 0.0

DIMENSIONLESS LIQUID PHASE


CONCENTRATION, CA

K1 = 0.1
K1 = 0.4

1.5

K1 = 2.0

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS DISTANCE FROM SOLID WALL,


Fig. 7. Development of liquid phase concentration prole for counter-current ow over a dissolving solid wall, K1 varies from 0 to 2 for
x 0:4, K 2 0:1 and B 106 at Z 1:0.

922

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


1.2
K1 = 0.0
K1 = 0.1

DIMENSIONLESS GAS PHASE


CONCENTRATION, CG

K1 = 0.4

0.8

K1 = 2.0

0.6

0.4

0.2

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS AXIAL DISTANCE, Z


Fig. 8. Gas phase concentration prole for counter-current ow over a dissolving solid wall, K1 varies from 0 to 2 for x 0:4, K 2 0:1
and B 106 .

100

ENHANCEMENT FACTOR, E

K1 =2.0

0.4

10

COUNTER-CURRENT
0.1
0.0

1
2.0

0.4
0.1

0.0

0.1

0.01
0.01

CO-CURRENT

0.1

10

100

''
Fig. 9. Loglog graph showing eect of K1 on variation of E with
K 2 0:1 and B 106 .

M 00 for co-current and for counter-current ows in gas phase at

reaction is suciently high to prevent the absorbed gas molecules from reaching the solid wall for a particular
Z.
4.3. Parameter K2
The eect of K2 on concentrations of both the phases and on enhancement factor E follows approximately
the same pattern as that of K1, while keeping other parameters constant. But these eects are slightly less due

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

923

ENHANCEMENT FACTOR, E

100

10

0.1 &
0.0
K1 = 0.0 &
K2 = 0.1

K1 = 0.2 &
K2 = 0.0
0.1 &
0.1

0.1
0.1

10

100

''
Fig. 10. Loglog graph showing eect of K1 and K2 on variation of E with

M 00 .

to the more pronounced eect of liquid phase reaction as compared to the reaction at the wall. With the help
of Fig. 10, the combined as well as independent eects of parameters K1 and K2 on the enhancement factor E
can be easily appreciated.
4.4. Parameter B
Figs. 11 and 12 show liquid and gas phase concentration proles for a counter-current system at steady
state. It can easily be noticed that as the surface resistance increases i.e. parameter B decreases, the exit liquid
1.6
K1 = 0.1
K2 = 0.1
w = 0.4

DIMENSIONLESS LIQUID PHASE


CONCENTRATION, CA

1.4

at Z = 1.0

1.2

0.8

0.6
B = 106

0.4

0.2

at Z = 0.01

B = 10

0
0

0.2

0.4

0.6

0.8

DISTANCE FROM SOLID WALL,


Fig. 11. Development of liquid phase concentration prole for counter-current ow, B varies from 10 to 106 for x 0:4 at Z 1:0 and
Z 0:01.

924

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


0.45
K 1 = 0.1
K 2 = 0.1
= 0.4

DIMENSIONLESS GAS PHASE


CONCENTRATION CG

0.4

B = 106

0.35
B = 10

0.3
0.25
0.2
0.15
0.1
0.05
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS AXIAL DISTANCE, Z


Fig. 12. Gas phase concentration prole for counter-current ow.

phase concentration decreases and a similar pattern is observed in the gas phase concentration at the interface.
It is also worth mentioning that in a counter-current system, the liquid phase concentration at interface may
be greater than the outlet gas phase concentration C g0 after some Z. This is because, the gas phase boundary
condition at Z 0, for the two systems i.e. co-current as well as counter-current, uses C g0 which is the inlet
concentration for co-current ow and the outlet concentration for counter-current ow. In case of co-current
ow, the inlet concentration C g0 is the highest concentration at interface among all axial positions whereas, for
counter-current ow it is the lowest. Therefore, in counter-current system the liquid lm after some Z, encounters a gas phase concentration which is greater than C g0 . While, in co-current gas ow, the dimensionless liquid
phase concentration C A will be less than 1 for all values of Z.
4.5. Reduction of general model into simple cases
In Section 3.5, six simple cases have been successfully derived by reducing the general model for dierent
situations. All these cases were earlier researched by [1,2,4,10,1216,22].
4.6. Numerical scheme
The numerical technique chosen is of explicit type, thus it is simple to implement. But, while discretizing the
problem, care should be taken in selecting a proper step size. At times, larger increments may destabilize the
method or may even give poor results. Though, smaller steps do give accurate results but the computational
time increases manifolds due to increase in the number of machine calculations.
For the selected parameters, we have taken N 2050 and M 106 105 . More powerful numerical
approaches will not only yield good results but also in a reasonable time. The employed scheme is pictorially
depicted in Fig. 13.
4.7. Validation by experimental data
The present general model and its solutions are compared with the available simplied experimental case of
gas absorption accompanied by 1st order chemical reaction in lm only, with no gas phase resistance and no

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

Gas

Liquid

Cgo

Co

N, 0

N-1, 0

i+1, 0

i, 0

i-1, 0

3, 0

2, 0

1, 0

925

,i
Z, j

N, 1

0, 1

N, 2

0, 2

0, 3

N, 3

Wall
N, 4

0, 4

N, 5

0, 5

N, 6

0, 6

N, j-1

0, j-1

N, j

i+1, j

i, j

0, j+1

0, M-1

N, M

Interface

0, j

i, j+1

N, j+1

N, M-1

i-1, j

0, M

Fig. 13. Grid points in numerical scheme.

gas side ow. A close look on this model reveals that it can be considered as a practical example of reduced
model 3, described in Section 3. The amount of gas absorbed per unit area after a contact time s, calculated
presently and the one found by the other two groups [9,20], has been shown in Fig. 16 on a loglog scale. It is
easily understood that the outcome from our model and that of Nysing and Kramers [9] match outstandingly
and is even better than those discussed by Elperin and Fomynikh [20]. In initial stages or for short contact
time, our model deviates slightly from those of [9,20]. This is due to the limited terms considered in Eq.
(40), which makes the solution incompatible with B.C.1
p
1
cosh K 1 g X
p
C A jZ!0 0
Ai f ki ; g:
69
cosh K 1
1
Finite terms in the above equation do not satisfy it for small Z, while for larger Z, only few terms are sucient.
That is why the present results deviate to a small extent only for initial values of Z and this point can also be
veried by varying the number of terms in Eq. (69).
4.8. Miscellaneous
Laplace transform technique is found to be superior to separation of variables method as it does not require
homogeneous boundary conditions and can easily be applied to systems of linear dierential equations. Eigenvalues are found by the hybrid scheme of bisection and NewtonRaphson methods. Accuracy in eigen-values

926

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929


3.5
Z=0.01

Z=0.05

Z=0.1

Z=0.2

0.3

Z=0.4

0.5

Z=0.6

0.7

Z=1.0

B = 10 , = 1.0
K1 = 0.1, K2 = 0.1

DIMENSIONLESS CONCENTRATION, CA

2.5

1.5

0.5

0
0

0.1

0.2
0.3
0.4
0.5
0.6
0.7
DIMENSIONLESS DISTANCE FROM SOLID WALL,

0.8

0.9

Fig. 14. Liquid phase concentration prole evaluated from numerical scheme.

2.5
K1 = 0.1

DIMENSIONLESS GAS PHASE


CONCENTRATION, CG

K2 = 0.1
B = 106

= 1.0

1.5

= 0.4

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

DIMENSIONLESS AXIAL DISTANCE, Z


Fig. 15. Gas phase concentration prole evaluated from numerical scheme.

decreases with their numbers and therefore, only eleven eigen-values are presented. However, 11th eigen-value
was determined with some error. Higher eigen-values could not be found due to the divergence of the series in
Eq. (13). It is also observed that the 11th eigen-value cannot be found if we express Eq. (3) in terms of dimensionless variable g dy (where, y coordinate starts from the interface). The nth eigen-value can be found from a
quadratic polynomial of n, which helped in predicting the initial guess for all the cases. This point was also
mentioned by [10]. It is also observed that the magnitude of eigen-values increases with an increase in any
of the rate constants while in case of increased surface resistance, it decreases. Further, the magnitudes of
eigen-values for co-current ow are greater than the corresponding eigen-values for counter-current ow
for the same absolute values of the parameters.

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

927

3.50
Run 5

Run 6

log (m()/) + 7.0

3.00

Ref. [20]

2.50

Ref. [20]

Ref. [9] &


Present work

2.00
Ref. [9] &
Present work

1.50

1.00

0.50

0.00
-1

-0.5

0.5

1.5

2.5

log
Fig. 16. Comparison with experimental data.

An important point regarding eigen-values is also discovered, that the rst eigen-value becomes positive for
counter-current ow with axial variation in the gas phase concentration which was not mentioned by any of
the previous authors. The magnitude of this value increases with the increase in gas ow rate. Moreover, for
the two situations i.e. (i) x 0 and (ii) K 1 K 2 0, we get zero as the rst eigen-value. Table 4 shows the rst
eigen-value for dierent values of parameters.
For special cases, our results show excellent agreement with those obtained by [1] for simple physical
absorption for small contact time; [4,10] for simple physical absorption for large time of contact; [9,16,20]
for gas absorption with 1st order chemical reaction; [12] for gas absorption with surface resistance; [14] for
gas absorption accompanying 1st order chemical reaction with nite gas phase resistance and [13] for gas
absorption with surface resistance and with gas side ow.

Table 4
First eigen-value for various sets of parameters values
S. no.

K1

K2

k0

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

0.0
0.4
1.0
0.0
0.4
1.0
0.4
0.4
0.4
0.4
0.0
0.0
0.0
0.0
0.4
0.4

0.1
0.1
0.1
0.0
0.0
0.0
0.0
2.0
0.1
0.1
0.0
0.0
0.1
0.1
0.0
0.0

0.1
0.1
0.1
0.0
0.0
0.0
0.1
0.1
0.0
2.0
0.0
0.0
0.0
0.0
0.0
0.0

106
106
106
106
106
106
106
106
106
106
1
104
1
104
106
10

0.0000
0.0937
0.4090
0.0000
0.0000
0.0000
0.0483
0.5836
0.0517
0.3356
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000

928

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

5. Conclusions
A more general situation of gas absorption with nite gas phase resistance, axial variation in the gas phase
concentration and irreversible 1st order chemical reaction in the liquid lm and at the wall is analyzed.
Eigen-values and series coecients for various cases are also calculated and some of them are shown in
the Tables 2 and 3.
Eects of various parameters on the liquid and gas phase concentrations as well as on the enhancement factor E are shown and it is found that a strong surface resistance leads to a negligible rate of gas absorption,
while a higher reaction rate increases the absorption rate for both the co-current and counter-current systems. Though, for counter-current system, the eect of K1 (or K2) on enhancement factor E may be observed
over the whole axial distance but for co-current system there is a limited region where this eect is visible,
beyond which K1 (or K2) does not have any eect and hence absorption rate for simple physical absorption
can be used. Changes due to reaction at wall follow a similar pattern as those exhibited by the reaction in
liquid lm but these are less pronounced. For both the systems, the increase in gas phase velocity increases
the enhancement factor E. The total mass absorbed by a co-current system is constant and does not vary
with Z after attaining the steady state, while in case of counter-current system, it increases with thepaxial
distance Z, which can be veried by evaluating the enhancement factor in terms of Hatta number M 00 .
It is also concluded that the exit liquid phase concentration for B 1000 is nearly equal to the value for
B 1. It implies that for B 1000 and above, the gas lm resistance is almost negligible. These results
are expected to be useful in measuring diusivities, mass transfer coecients, solubilities and reaction rate
constants for the experiments of gaseous mixtures. The present analysis is a step forward, as it is useful
when gas is not necessarily pure and it is applicable for the condition of low as well as high gas ow rates.
The reaction parameter K1, indicates the ratio of the rate of reaction to the rate of diusion in relation to
the thickness of the lm. Thus, a small value of K1 could be due to a very slow reaction or a very thin lm or
a high rate of diusion. For K1 greater than 5, the lm thickness does not have any eect on the rate of
absorption. The higher values of K1 prevent the penetration of the absorbed gas molecules towards the solid
wall. This is the reason that the results predicted from our analysis match very well with the experimentally
reported results of [9], where K 1
5 and the parabolic velocity prole was not taken into account and thus,
the lm thickness did not come into picture.
When x is small, the axial variation in the gas phase is negligible and hence the error introduced by assuming a constant axial concentration is small. However, as x increases, the error becomes large.
The present general model has been successfully reduced to some of the previously studied simple models.
Results obtained from an explicit numerical technique, programmed in MATLAB 6, have been presented
and compared with those of analytical solutions and an excellent agreement between the two has been
found.
Absorption rates found from the analytical solution, for a simplied case, are veried with the experimental
data of [9]. The conformity between the two substantiates the present work.
Acknowledgements
The authors are gratefully indebted to Dr. Surendra Kumar, Professor, Department of Chemical Engineering, I.I.T. Roorkee, (Roorkee-247667, U.A., India.) for his invaluable guidance in the preparation of manuscript. We are also thankful to Professor S. M. Yusuf, (Retd.), Department of Mechanical Engineering,
A.M.U., (Aligarh-202002, U.P., India.) for his helpful suggestions and to Ms. Arees Qamareen, Lecturer,
Department of Mechanical Engineering, A.M.U., (Aligarh-202002, U.P., India.) for her support in formatting
the document.
References
[1] R. Higbie, The rate of absorption of pure gas in to a still liquid during short periods of exposure, Trans. Am. Inst. Chem. Engr. 31
(1935) 365389.
[2] R.L. Pigford, Ph. D. Thesis, Univ. Illinois, 1941.

M. Danish et al. / Applied Mathematical Modelling 32 (2008) 901929

929

[3] R.H. Perry, R.L. Pigford, Kinetics of gasliquid reactions: simultaneous absorption and chemical reaction, I. & E.C. 45 (6) (1953)
12471253.
[4] R.E. Emmert, R.L. Pigford, A study of gas absorption in falling liquid lms, Chem. Eng. Prog. 50 (1954) 8793.
[5] G.H. Roper, T.F. Hatch Jr., R.L. Pigford, Theory of absorption and reaction of two gases in a liquid, I. & E.C. Fundam. 1 (2) (1962)
144152.
[6] T.F. Hatch Jr., R.L. Pigford, Simultaneous absorption of carbon dioxide and ammonia in water, I. & E.C. Fundam. 1 (3) (1962)
209214.
[7] Y. Kameoka, R.L. Pigford, Absorption of nitrogen dioxide into water, sulfuric acid, sodium hydroxide, and alkaline sodium sulte
aqueous solutions, I. & E.C. Fundam. 16 (1) (1977) 163169.
[8] G. Carta, R.L. Pigford, Absorption of nitric oxide in nitric acid and water, I. & E.C. Fundam. 22 (3) (1983) 329335.
[9] R.A.T.O. Nysing, H. Kramers, Absorption of CO2 in carbonate bicarbonate buer solutions in a wetted wall column, Chem. Eng. Sci.
8 (1958) 8189.
[10] W.E. Olbrich, J.D. Wild, Diusion from the free surface into a liquid lm in laminar ow over dened shape, Chem. Eng. Sci.
24 (1969) 2532.
[11] G. Walker, T. Davis, Mass transfer in laminar ow between parallel permeable plates, AIChE J. 20 (5) (1974) 881889.
[12] A. Tamir, Y. Taitel, Diusion to ow down an incline with surface resistance, Chem. Eng. Sci. 26 (1971) 799808.
[13] S.K. Gupta, H. Singh, P.N. Sahgal, Gas absorption in laminar falling lm with a nite gas phase resistances, Ind. Chem. Eng. 29 (2)
(1986) 38.
[14] A. Tamir, Y. Taitel, The eect of the gas side resistance on absorption with chemical reaction from binary mixtures, Chem. Eng. Sci.
30 (1975) 14771482.
[15] J.B. Stepanek, S.K. Achwal, Absorption with rst order chemical reaction into a liquid lm in laminar ow, Canad. J. Chem. Eng.
54 (1976) 545550.
[16] R.J. Best, B. Horner, Gas absorption with rst order chemical reaction in laminar falling lms, calculation of rates and enhancement
factors, Chem. Eng. Sci. 34 (1979) 759762.
[17] R. Datta, R.G. Rinker, Penetration theory for gas absorption and chemical reaction in concurrent and counter-current ow wetted
wall columns, Canad. J. Chem. Eng. 62 (1984) 7884.
[18] M.R. Riazi, Estimation of rates and enhancement factors in gas absorption with zero order chemical reaction and gas phase masstransfer resistances, Chem. Eng. Sci. 41 (1986) 29252929.
[19] M. Riazi, A. Faghri, Gas absorption with zero order chemical reaction, AIChE J. 31 (12) (1985) 19671972.
[20] T. Elperin, A. Fominykh, Model for gas absorption in gas liquid plug ow with rst-order and zero-order chemical reaction, Heat
Mass Transfer. 39 (2003) 195199.
[21] R.K. Sharma, An analytical solution to falling lm absorption with surface resistance, M.Tech. dissertation, A.M.U., Aligarh, 2004.
[22] R.K. Sharma, M. Danish, S. Ali, Solution of physical gas absorption in falling liquid lm by alternate analytical methods, Indian
Chem. Engnr. 48 (3) (2006) 190193.
[23] R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, Wiley, New York, 1960.
[24] T.K. Sherwood, R.L. Pigford, C.R. Wilke, Mass Transfer, McGraw-Hill, New York, 1975.
[25] E. Kreyszig, Advanced Engineering Mathematics, eighth ed., John Wiley & Sons, Inc., 2000.
[26] H.S. Carslaw, J.C. Jaeger, Operational Methods in Applied Mathematics, Dover Publications, Inc., New York, 1948.
[27] T. Shibata, M. Kogo, Generalization and application of Laplace transformation formulas for diusion, Int. J. Heat Mass Transfer 26
(7) (1983) 10171027.
[28] R.V. Churchill, Operational Mathematics, McGraw-Hill Book Company, New York, 1958.

Você também pode gostar