Mass Transfer Models:

Efficient Numerical Solutions

Using Boundary Elements
P. A. Ramachandran
Washington University, St Louis, MO

Paper Presented at
International Symposium In honor of
Prof. V. G. Pangarkar

UICT, Mumbai, India
Dec 12
th
2005
Chemical Reaction Engineering Laboratory
ST. LOUIS ARCH
The Gate Way of the West
Center for Environmentally Beneficial
Catalysis (CEBC)
NSF EEC-0310689
Outline
Mass Transfer Models: Governing Equations,
Problem Complexities
Boundary Element Concepts
Solution Algorithm Steady State Model
Examples and Illustrative Results
Solution Algorithm Transient Problem: MOLBEM
Concluding Remarks
Steady State Diffusion Model
Film Model: Gas Absorption
Gas-Absorption with Heat Effects
Liquid-Liquid Reactions
Phase Transfer Catalysts

Other studies:
Porous Catalytic Particle
Membranes with Carriers
Membranes with Fixed Charges
Theories for Analysis of Transport
Effects in Gas-Liquid Reactions
Two-film theory
1. W.G. Whitman, Chem. & Met. Eng., 29 147 (1923).
2. W. K. Lewis & W. G. Whitman, Ind. Eng. Chem., 16, 215 (1924).
Penetration theory
P. V. Danckwerts, Trans. Faraday Soc., 46 300 (1950).
P. V. Danckwerts, Trans. Faraday Soc., 47 300 (1951).
P. V. Danckwerts, Gas-Liquid Reactions, McGraw-Hill, NY (1970).
R. Higbie, Trans. Am. Inst. Chem. Engrs., 31 365 (1935).

Surface renewal theory
P. V. Danckwerts, Ind. Eng. Chem., 43 1460 (1951).

Rigorous multicomponent diffusion theory
R. Taylor and R. Krishna, Multicomponent Mass Transfer,
Wiley, New York, 1993.
Two-film Theory Assumptions
1. A stagnant layer exists in both the gas and the
liquid phases.

2. The stagnant layers or films have negligible
capacitance and hence a local steady-state exists.

3. Concentration gradients in the film are one-
dimensional.

4. Local equilibrium exists between the the gas and
liquid phases as the gas-liquid interface

5. Local concentration gradients beyond the films are
absent due to turbulence.
Types of Heat Generation
1. Heat of solution (H
s
), which is generated at the gas-liquid
interface due to the physical process of gas dissolution

2 Heat of vaporization (H
v
), of volatile reactants due to
evaporative cooling in oxidation reaction

3. Heat of reaction (H
r
), which is generated in the film near the
gas-liquid interface (for fast reactions), or in the bulk liquid
(for slow reactions).
Uncontrolled heat generation can lead to:
1. Undesired production of by-products
2. Thermally-induced product decomposition
3. Increased rate of catalyst deactivation
4. Local hot spots and excess vapor generation
5. Reactor runaway and unsafe operation

Modeling of simultaneous mass and heat transport effects in
the film is necessary for accurate predictions
How Heat Generation Can Affect Mass
Transfer Rates in Gas-Liquid Reactions
1. Physical, transport, and thermodynamic
properties of the reaction medium exhibit
various degrees of temperature dependence

2. Kinetic parameters exhibit exponential
dependence on the local temperature

3. Instabilities at the gas-liquid reaction
interface that are driven by surface tension effects
(Marangoni effect) and density effects
) J ( T ), j ( C
g g
i
1 1
Gas Film
Liquid Bulk
) J ( T ), j ( C
g g
i
) J ( T ), j ( C
L L
i
) J ( T ), j ( C
L L
i
1 1
Gas Bulk

=
A =
NR
j
R
f
j
f
H R
dx
T d
1
2
2
) ( k

=
=
NR
j
f
j ji
f
i
i
R
dx
C d
D
1
2
2
u
Liquid Film
Cell J
th

0 = X
f
) j ( , i
N
1 = X
f
) j ( , i
N
1 = X
f
) j ( , i
q
0
) ( ,
= X
f
j i
q
m
o
h
o
Two-Film Theory: Mass and Heat Transfer
Heat
Film
Gas-Liquid Film Model: Mass Transfer
j
NR
j
ji
f
i
i
R
dZ
C d
D

=
=
1
2
2
u
) (
0 ,
0 , g
z i
g
i g
f
z i
i
C C k
dZ
dC
D
=
=
=
B.C.1
f
z i
f
i
g
z i
C H C
0 , 0 , = =
=
m
Z Z Z o = =0








Gas Film
f
Z i
N
0 , =
Liquid Film
f
Z i
m
N
o = ,
i g
p
,
g
Z
i g
p
0
,
=
f
Z i
C
0 , =
b
i
f
Z i
C C
m
=
=o ,
Bulk Liquid
( )
f
ref
ref
f
Z
Si ref
i
f
i
h H
T T R
H
H H
0
0
)
1 1
( exp
=
=
=
(
(

A
=

u
Solubility or Violability
( ) | |
0
0
0
*
, ,
=
=
=
=

u
d
dc
h c c Bi
f
i
f
i
f
i i g i m
i
i ref g m
i m
D
H k
Bi
,
,
o
=
i ref i ref
i g
i g
C H
p
c
, ,
, *
,
=
B.C.2: Dirichlet conditions

=
A =
|
|
.
|

\
|
NR
j
j j r
f
L
R H
dZ
T d
1
,
2
2
) )( (
B.C.1
B.C.2
( )
0
1
, 0
0
) ( ) (
=
=
=
=
A + =

Z
f
i
i
NS
i
i s
f
z
g
out g
Z
f
L
dZ
dC
D H T T h
dZ
dT

( )
m h
f
Z
L
L
Z
f
L
m
h
T T
dZ
dT
o o

o
o

=
=
=
) (






g
T
f
T
g
A
C
g
B
C
f
B
C
f
A
C
h
o
b
A
C
b
B
C
Z
Gas Film Liquid Film
Liquid Bulk
Heat Transfer Film
Mass Transfer Film
b
T
m
o
Gas-Liquid film
Gas-Liquid Film Model: Heat Transfer
Mixing Cell Model
- Cells arranged in different modes to simulate the averaged flow patterns
- These averaged flow patterns can be obtained from the CFD simulations
Cells in series:
G and L mixed flow
Cells in
series-parallel
combination

Exchange
between
Upward and
downward
moving liquid
Liquid
Gas
Liquid
Gas
Cell 1
Cell N
Cell j
Cells in series:
G plug flow, L mixed flow
Prototype cell
Compartment Models: Multiphase
Reactors
i,j,k
i,j,k+1
i,j,k-1
i-1,j,k i+1,j,k
i,j-1,k
i,j+1,k
u
u
u
u
u
r
u
r
u
z
u
z
Solve macroscopic
equations for all
compartments
simultaneously
Solve flow equations
using CFD to
generate the flow
field in the tank
Calculate flows in and out
of the compartments;
Estimate the exchanges
due to fluctuations
Macroscopic equation consists of convection due to main flow, dispersion due to
turbulence and the reaction terms
i,j,k
i,j,k+1
i,j,k-1
i-1,j,k i+1,j,k
i,j-1,k
i,j+1,k
u
u
u
u
u
r
u
r
u
z
u
z
Solve macroscopic
equations for all
compartments
simultaneously
Solve flow equations
using CFD to
generate the flow
field in the tank
Calculate flows in and out
of the compartments;
Estimate the exchanges
due to fluctuations
Macroscopic equation consists of convection due to main flow, dispersion due to
turbulence and the reaction terms
i,j,k
i,j,k+1
i,j,k-1
i-1,j,k i+1,j,k
i,j-1,k
i,j+1,k
u
u
u
u
u
r
u
r
u
z
u
z
i,j,k
i,j,k+1
i,j,k-1
i-1,j,k i+1,j,k
i,j-1,k
i,j+1,k
u
u
u
u
u
r
u
r
u
z
u
z
i,j,k
i,j,k+1
i,j,k-1
i-1,j,k i+1,j,k
i,j-1,k
i,j+1,k
u
u
u
u
u
r
u
r
u
z
u
z
Solve macroscopic
equations for all
compartments
simultaneously
Solve flow equations
using CFD to
generate the flow
field in the tank
Calculate flows in and out
of the compartments;
Estimate the exchanges
due to fluctuations
Macroscopic equation consists of convection due to main flow, dispersion due to
turbulence and the reaction terms
Guha, D., Ramachandran, P.A., Dudukovic, M.P., AIChE J., In press
Mixing Cell Model for gas-liquid systems
Novel features
Non-isothermal effects in the gas-liquid film and
in the bulk liquid
Effect of volatility of the liquid phase reactant on
the interfacial properties
Interfacial region modeled using film theory and
solved using integral formulation of the Boundary
Element Method (BEM)
Model validity over a wide range of dimensionless
numbers like Hatta, Arrhenius, solubility parameter,
Biot, Damkohler.
Application to oxidation reactions like
cyclohexane, p-xylene, etc. in stirred tank and
stirred tank in series
Film model: (Kongto et al., Comp.&Chem.Eng.,
2005)
Reactor model: (Ruthiya et al. under progress)
Prototype Gas Cell
Prototype Liquid Cell
Non-Dimensionalized parameters
Variables
Reaction based
ref i
f
i f
i
g
ref i
g
i g
i
C
C
c and
C
C
c
, ,
= =
ref i
g
ref i ref i
H C C
, , ,
/ =
r
L
ref
L cell
gL
A u
k aV
= o
ref ref , i i
C C = e
ref
j
ref
L
m L cell
j
R
C Q
a V
M
) ( o c
=
ref
aj
j
RT
E
=
ref
L
p L L
D C Le =
ref
L
p L
ref j , r
j
T C
C H
B

A
=
ref ref
2
m
ref
j 2
j
C D
R
Ha
o
=
i
g ref i m
i M
D
k H
Bi
,
,
o
=
Mass transfer based
ref L
ref ref
j
r
j
T
C D H

|
) (
,
A
=
L
m g
H
h
Bi

o
=
ref L
ref i i i S
i S
T
C D H

|
, ,
,
) ( A
=
ref i
g
ref
L
ref
fi
H u
u
,
=
ref
i
i
D
D
s =
g p m g
L cell gl g
C m
V a
S
,
o

=
m L p L
L cell gl L
C m
V a
S
o

,
=
Heat transfer based
Gas-Liquid Reactor Model
m
Z
o
=
g
ref
g
g
Q
Q
f =
ref
L
L
T
T
= u
ref
g
g
T
T
= u
Heat of reaction
parameter
Bulk reaction number
Hatta number
Arrhenius
number
Heat of reaction
parameter
Damkohler number Biot number
Biot number
Heat of solution
parameter
Liquid heat
transfer number
Gas heat
transfer number
Lewis number
Diffusivities
ratio
Effective G/L ratio
( ) ( )
f
i i
g
in i i M
f
i
c h c Bi
d
dc
0 , ,
*
,
0
=
=
=

i M i fi gl
i M
i M
Bi s
Bi
Bi
,
, *
,
1 o +
=
where
( )

=
=
=
-
=
|
|
.
|

\
|
+
=
NS
i
f
i
Si
H
g
f in
g H
f
d
dc
Bi S
Bi
d
d
1
0
0
0
1
1

| u u

u
( )
g
H
H
H
S Bi 1
Bi
Bi
+
=
-
Coupling with the reactor model
-Reactor model is incorporated in the BEM solution by changing the film model
boundary conditions
Gas-Liquid Reactor Model
Mass Transfer
Heat Transfer
non-linear Robin condition
(

|
.
|

\
|
=

=
L
j
b
j j
NR
j
ji
i i
f
i
r Ha
s d
c d
u
u
e
1
1 exp
1
2
1
2
2
B.C.1
B.C.1
(

|
.
|

\
|
=

=
L
j
NR
j
b
j j j
f
r Ha
d
d
u
|

u 1
1 exp
1
2
2
2
(

=
|
|
.
|

\
|

=
=
)
1
1 ( exp
1
1
1
L
j
b
j j
NR
j
ji
i
out
L
i
in
L
i
f
i
gL i
r M c c
d
dc
s
u
u
e
o

+ =

=
=
)
1
1 ( exp
1
1
1
L j
b
j ji
NR
j
j j
i
out
L
in
L
L
L
r B M
d
d
S
u
u
e
u u

B.C.2
where
B.C.2
non-linear Robin condition
Computational Methods for
Diffusion Reaction Problems
Collocation methods using various basis functions
(U. Ascher, R. M. Mattheij & R. D. Russell, SIAM Press, 1995).

Boundary element methods
(P. A. Ramachandran, Boundary Element Methods in Transport
Phenomena, Elsevier, London, 1994).
Robust software available
Approximate solutions not necessary
Can readily solve complex problems
- Vas Bhat R.D., van Swaaij W.P.M., Kuipers, J.A.M., Versteeg,G.F., Mass transfer with
complex chemical reaction in gas-liquid , Chem. Eng. Sci., 54, 121-136, (1999)

- Vas Bhat R.D., van Swaaij W.P.M., Kuipers, J.A.M., Versteeg,G.F., Mass transfer with
complex chemical reaction in gas-liquid , Chem. Eng. Sci., 54, 137-147, (1999)

- Al-Ubaidi B.H. and Selim M.H. (1992), Role of Liquid Reactant Volatility in Gas
Absorption with an Exothermic Reaction, AIChE J., 38, 363-375, (1992)

- Bhattacharya, A., Gholap, R.V., Chaudhari, R.V., Gas absorption with exothermic
bimolecular (1,1 order) reaction, AIChE J., 33(9), 1507-1513, (1987)

- Pangarkar V.G., Sharma, M.M., Consecutive reactions: Role of Mass Transfer
factors, Chem. Eng. Sci., 29, 561-569, (1974)

- Pangarkar V.G., Sharma, M.M., Simultaneous absorption and reaction of two
gases, Chem. Eng. Sci., 29, 2297-2306, (1974)

- Ramachandran P.A. and Sharma, M.M., Simultaneous absorption of two gases,
Trans. Inst. Chem. Engr., 49, 253, (1971)
Studies for Complex Gas-Liquid Reactions
Original
Formulation
Finite Difference
Collocation
Original Galerkin
Weak Formulation
(Integrating once)
Finite Elements
Galerkin Methods
Inverse Formulation
(Integrating twice)
Boundary Elements
Integral Methods
Weighted Residuals: Solution Approaches
BEM Introduction
Greens function method (George Green, 1793-1841)
Integral formulation
The solution to the homogeneous part of the
differential equation is used as the weighting function
Applied over elements here
No need to approx. the first and second derivatives

0 a 1 b

c
ai
c

bi
c

ai
p slope =
bi
p slope =
Element level representation of the film
model definition of local variables for
any particular element
BEM Methodology
BEM Element Level equations
Element Level Osculation:
Four unknowns per element
2 gradients and 2 concentrations
(p
a
, c
a
and p
b
, c
b
)
Cubic Osculating Polynomial for concentration
Quadratic polynomial for gradient
Set of non-linear algebraic-integral equations
Newton-Raphson solution procedure
Dimensionless Film Thickness
D
i
m
e
n
s
i
o
n
l
e
s
s

C
o
n
c
e
n
t
r
a
t
i
o
n

A
c
B
c
P
c
0
.
0
0
.
2
0
.
4
0
.
6
0
.
8
1
.
0
0 0
.
2 0
.
4 0
.
6 0
.
8 1
1
.
035
1
.
040
1
.
045
1
.
050
1
.
055
D
i
m
e
n
s
i
o
n
l
e
s
s

T
e
m
p
e
r
a
t
u
r
e

Non-volatility (Bi
m
=0)
Volatility (Bi
m
=1.5)

(Bim=1.5)
(Bim=0)
Temp.
Conc.
Case 1: Single non-isothermal reaction
Reaction Scheme:
A + vB C
Ha = 10, q = 0.05, = 22,
s = -7.5, vap = 2, |s=0.001,
|
vap
= -0.005, B
iHg
= 1
No vaporization
Vaporization of B
6.7 13.0 Enhancement
0.31 0.42 Product (C)
0.33 0.58 Reactant (B)
0.76 0.70 Gas (A)
Volatile Non-
volatile
6.7 13.0 Enhancement
0.31 0.42 Product (C)
0.33 0.58 Reactant (B)
0.76 0.70 Gas (A)
Volatile Non-
volatile

Bi
Hg
= 0.75
Bi
Hg
= 1.5
Bi
Hg
= 10
Ha
D
i
m
e
n
s
i
o
n
l
e
s
s


T
e
m
p
e
r
a
t
u
r
e

1
.
00
1
.
02
1
.
04
1
.
06
1
.
08
1
.
10
1
.
12
1
.
14
1
.
16
0 5 10 15 20 25 30 35
m g
Hg
h
Bi
o
k
=
Bi
Hg
Temp
A
b
B m ref
D
C k
Ha
2
2
o
=
Ha

Rxn Temp.
Case 1: Single non-isothermal reaction
Case 2: Local Supersaturation in the film
No C reaction here
Shah, Y.T., Pangarkar, V.G. and Sharma, M.M., Criterion for supersaturation in gas-liquid reactions
involving a volatile product, Chem. Eng. Sci., 29, 1601-1612, (1974)
Reaction Scheme:
A + B C
A + C D
Dimensionless Groups:
Hatta Number
Rate constant Ratio
Concentration Ratio
Non-Volatile B and C
No gas side Resistance for Species A.


Example : Chlorination of p-cresol
V. G. Pangarkar and M. M. Sharma, Consecutive reactions: Role of Mass
Transfer factors, Chem. Eng. Sci., 1974, Vol. 29, 561-569.
Case 3: Consecutive Reaction
Case 3: Consecutive Reaction
Case 3: Consecutive Reaction
Ha = 100
q = 1
k
2
/k
1
= 0.001
Case 3: Consecutive Reaction
Effect of k
l
on Selectivity
Agrees with the experimental results presented in
Pangarkar V.G. and Sharma M.M., Chem. Eng. Sci., 29, 561-569, (1974)
Case 4: Phase Transfer Catalysis (PTC)
Liquid-Liquid Reactions
Reactant A in Aqueous phase
Reactant B in Organic phase
Rate of reaction slow due to solubility limitations
Practical applications need faster rate
Phase transfer agent enhances the reaction
PTC Principle
Phase transfer agent, M
has large solubility in both
phases and acts as an
intermediary
Case 4: PTC Example
NaCN + QCl QCN + NaCl
(A1) + (A2) (A3) + (A4)
RCN + QCl QCN + RCl
(A5) + (A2) (A3) + (A6)
Aqueous Reaction:
Organic Reaction:
Case 4: PTC Application Areas
1. Ether Synthesis
Replacement for Williamson reaction

2. Ester Hydrolysis
Transport of OH
-
group

3. Oxidation Reactions
Transport of permanganate, periodate, etc.

4. Phenol Recovery
Transport of phenolate ion

5. O-alkylation of p-tert-butylphenol with benzyl chloride

6. 3-methyl-4-nitro-diphenyl ether (solid-liquid system)
Case 4: PTC Two-Film Model
Model Reaction Scheme
Aqueous phase: A1 + A2 A3 + A4
Organic phase: A5 + A2 A3 + A6
Case 4: PTC Model Results
Concentration profiles: PTC in Organic phase, Fast reactions
Case 4: PTC Model Results
Concentration profiles: PTC in Organic phase, Instantaneous reaction
Case 4: PTC Model Results
PTC in Aqueous, Effect of
rate constant
Finite difference approximation in time
P.A.Ramachandran, Boundary Element Methods in Transport
Phenomena, 1994

MOL concepts for time integration with LSODI routine.
P. A. Ramachandran, J Partial differential equations, in press.

Time dependent weighting functions (Gaussian or error
function type)
P.A.Ramachandran, Boundary Element Methods in Transport
Phenomena, 1994
TRANSIENT PROBLEMS
Transient Problems: MOL
MOL: Method of Lines
) , , ( ) ( p y x f y
t
y
x g =
c
c

0 =
|
.
|

\
|
c
c
c
c
x
G
x
t
o
dx p y x f x G x y x
dx
dG
x
y
Gx dx
t
y
x G x g x
b
a
b
a
b
a
b
a
) , , ( ) ( ) ( ) (
} }

(

c
c
=
c
c
o o o o
Integration by parts twice; choosing the function G such that
Using this weighting function
where
|
.
|

\
|
c
c
c
c
=
x
y
x
x x
y
o
o
1

Pore diffusion equation

x
y
Pe
x
y
y
c
c

c
c
=
2

Convection-diffusion
| |
} }
=
c
c
b
a
b
a
dx p y x f y x G x dx
t
y
x G x g x ) , , ( ) ( ) ( ) (
o o
Transient Problems: MOL contd..
dx p y x f x G x y x
dx
dG
x
y
Gx dx
t
y
x G x g x
b
a
b
a
b
a
b
a
) , , ( ) ( ) ( ) (
} }

(

c
c
=
c
c
o o o o
A cubic osculation is defined for y:
( ) ( )
b b a a
y p a b y p a b y
4 3 2 1
| | | | + + + = where
b k b k a k a k
b
k
b
k
a
k
a
k
y H p H y H p H
dt
dy
L
dt
dp
L
dt
dy
L
dt
dp
L
4 3 2 1 4 3 2 1
+ + + = + + +
a b
a x

= q
Substituting y in original eq. leads to an implicit set of ODEs in terms
of element level variables y
a
, p
a
, y
b
, and p
b
.
where L
k
s and H
k
s are element level integrals
K = 1, K = 2
Transient Problems: TDWF
TDWF: Time Dependent Weighting Functions
} } } }
c
c
=
c
c
tf
ti
b
a
tf
ti
b
a
dx dt
c
t x G dx dt
t
c
t x G
2
2
) , ( ) , (

) ( ) (
2
2
f
t t x
t
G
x
G
=
c
c
+
c
c
o o
| | | | dx dt x p c f t x G dx ti x c ti x G dt
x
G
c dt
x
c
t x G t c
tf
ti
i
b
a
b
a
tf
ti
b
a
tf
ti
b
a
f
} } } } }
=
(

c
c
+
(

c
c
) , , ( ) , ( ) , ( ) , ( ) , ( ) , (
Integration by parts for both the LHS (with time) and the RHS (with distance)
Choosing the function G as
Where G is a Gaussian function
Interfacial Flux vs Initial Time Physical Absorption
Transient Problems
Evolution Of Concentration Profiles: Second Order Reaction
Transient Problems
Transient Profiles for Flux Second Order Reaction
Transient Problems
Flux at Initial Time
Transient Problems
BEM concepts applied at element level leads to integral
formulation of the diffusion-reaction problems.
The solutions, in general, are accomplished by using a piece-
wise cubic polynomial for each element for integration of
the rate terms.
Method is mass conserving, robust, and has a wider range of
convergence.
Can be coupled with arc length continuation to track the
effect of a dimensional group (paper in preparation).
A number of mass transfer problems (consecutive reactions,
supersaturation, PTC, etc.) were presented as case studies.
Concluding Remarks
Effect of mass transfer on selectivity, supersaturation,
etc forms the earlier work of V.G. Pangarkar and
remain a landmark contribution in this area