Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

Mass Transfer from Single Spherical Bubble with the Presence of

Chemical Reaction: the Effect of Interface Contamination at Low
Reynolds Number
A. Dani, A. Cockx and P. Guiraud*
UMR5504, UMR792 Ingnierie des Systmes Biologiques et des Procds, CNRS, INRA, INSA,
135 av. de Rangueil, F-31077 Toulouse cedex 4, France
*Corresponding author: INSA-GPE 135 av. de Rangueil, F-31077 Toulouse cedex 4, France,
pascal.guiraud@insa-toulouse.fr

Abstract: The objective of this work is to

compute mass transfer with chemical reaction
(first order) from a single spherical bubble at low
Reynolds number by Direct Numerical
Simulation. Firstly, the contamination of bubble
surface by the surfactants is considered, since
they can reduce the slip velocity at the interface.
The stagnant cap model is used to represent these
phenomena and to simulate the influence on
hydrodynamics and on mass transfer.
Corresponding transports equations are solved
with COMSOL and characterized by the
Reynolds numbers and the Schmidt numbers.
Secondly, the reaction rate is considered for
three chemical reaction types (slow, intermediate
and rapid) which can be characterized by the
Damkhler number. The rate of the mass transfer
from the bubble to the liquid can be
characterized by the Sherwood number and
enhancement factor. The numerical simulation
results show that the Sherwood number increases
with the Peclet number, the contamination angle
and the Damkhler number. For the clean
spherical bubbles, the results are agreed with the
film theory.
Keywords: bubble, mass transfer, Sherwood
number, chemical reaction, surfactant.

1. Introduction
Mass transfer across gas-liquid and liquidliquid interfaces is a limiting step in many
chemical engineering processes like extraction,
distillation and chemical or biological reactions
like oxidations and fermentations. In each case,
an accurate prediction of the reactor mass
transfer performance is important to propose the
better design and operating conditions that would
increase productivity. In the case of mass
transfer from bubbles to a liquid phase, overall
mass transfer performance in a reactor results

from several phenomena at various scales. At the

molecular level, mass transfer is always
performed by a diffusion process that tries to
reduce non-equilibrium of the chemical activities
on both sides of the interface. The mass transfer
rate at this level is related to the diffusion
coefficients in each phase of the chemical
species that are being transferred. In the case of
mass transfer from bubbles to a continuous liquid
phase, as diffusion processes, the mass transfer
in the gas phase is much faster than in the liquid
phase. The main resistance is located in the
liquid phase, so the mass transfer rate is
governed, at this level, by the diffusion in the
liquid. At this molecular level, the mass transfer
can be affected by the presence of surfactants on
the interface that can either change the
equilibrium between the phases or modify the
diffusion within the few molecular adsorbed
layers. At the level of the bubble, transfer of the
molecules crossing the interface results from the
combination of the diffusion which is always
present with the advection induced by the flow
around the inclusion. Advection directly relates
to the flow field generated around the bubble,
itself a function of its shape, of the bubble
Reynolds number Re, and also of the
hydrodynamic condition offered to the liquid
flow at the bubble interface. The presence of
adsorbed constituents at this interface
immobilizes the interface and as a consequence
changes drastically the flow field around the
bubble. The mass transfer between dispersed
bubbles and the liquid phase can be enhanced by
the presence of chemical reaction.
Ruchenstein et al. (1971) and Dang and
Steinberg (1976) have analytically analyzed the
effects of first order chemical reaction on mass
transfer in a spherical system for both low and
high Reynolds numbers. Ishii and Johnson
(1970) and Klinzing et al. (1980) have studied
similar situations from a numerical point of view

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

with the presence of surfactant. In recent years,

several studies have been reported on numerical
analysis of mass transfer from a single bubble
with the presence of chemical reaction (Gerlinger
et al., 2000; Khinast, 2001; Juncu, 2002; Khinast
et al., 2003; Koynov and Khinast, 2004).
The aim of this paper is to investigate by
Direct Numerical Simulation the effect of
chemical reaction on mass transfer from bubbles
with the presence of adsorbed molecules at the
interface. Numerical simulations are performed
with COMSOL Software and are limited in this
paper to two-dimensional situations for spherical
bubbles. After a brief presentation of the related
equations and numerical conditions, the rate of
chemical reaction is quantitatively describe. The
last part shows the effect of the chemical reaction
on mass transfer for fully contaminated, partially
contaminated and clean spherical bubbles.
Hydrodynamics results represented in other
works (see Dani et al., 2006) are validated by
comparing the drag coefficients with those of the
other literatures

2. Governing equations and simulation

conditions
2.1 Governing equations
The situation under consideration consists of
an inclusion (a fully contaminated spherical
bubble behaving as a solid sphere, a clean
spherical bubble and a partially contaminated
spherical bubble) of diameter di moving at a
steady velocity U in a liquid at rest and of
infinite extent. The dynamic viscosity of the
liquid is and its density . The dynamic of the
inclusion can be characterized by the particle
Reynolds number Re defined as:
Re =

di U

The Peclet number Pe plays a similar role in the

mass transfer of the solute in the liquid phase
around the inclusion as the Reynolds number
plays in momentum transport:
d U
Pe = Re . Sc = i
DL

where Sc= / DL is the Schmidt number and DL

is the diffusion coefficient.

Pe<<1 relates to mass transfer situations

governed by diffusion and Pe>>1 to mass
transfer dominated by convection.
The chemical reaction is characterized by the
Damkhler number which is defined as follows:

Da =

k di
DL

U, di and U2 are used as characteristic velocity,

length and pressure respectively. c=(c'-c'0)/(c'sc'0) is the dimensionless concentration where c'
is the concentration of the solute that is
transferred from inclusion to the bulk liquid
phase, c'0 is the concentration in the liquid phase
at an infinite distance from the inclusion, and c's
is the concentration at the interface.
Mass transfer around the inclusion can be
described by solving the Navier-Stokes equation
and the diffusion-convection equations for
uncompressible liquid. This paper is limited to
axisymmetrical flows and for low Reynolds
number (Re=0.01).
At steady state, the axisymmetic forms of the
Navier-Stokes
and
diffusion-convection
equations can be written in dimensionless
primitive variables in cylindrical coordinates as
follows:
u

u
u
p 1 2u 1 u u 2u (1)

+v
= +
+
+
r
z
r Re r 2 r r r 2 z 2

v
v
p 1 2 v 1 v 2 v

+v
=
+
+
+
r
z
z Re r 2 r r z 2
1 ru v
+
=0
r r z

(2)
(3)

c 2 c 1 c 2 c
c ' (4)
c
+ 2 Da c Da ' 0 '
Pe u + v = 2 +
z r
r r z
cs c0
r

Equations (1)-(4) are solved numerically by a

finite element method (COMSOL 3.2) over the
computational domain and under the boundary
conditions presented below.
2.2 Flow domain
The axisymmetrical computational domain is
represented on Figure 1. The inclusion is located
at the center of this semi circular domain. In this
work, the radius of the computational domain R
is: R=60 di.

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

Inlet

bubble surface contamination is characterized via

the angle cap delimiting contaminated and clean
areas (Figure 1). The surfactant free bubble
surface (<cap) can move with the liquid (mobile
surface) meanwhile the contaminated zone
(>cap) behaves as "stagnant cap" (immobile
surface). In the studies of the mass transfer from
bubbles, the Stagnant Cap Model has been used
for creeping flow (Dani et al., 2006) and
intermediate Reynolds number (Takemura and
Yabe, 1999; Liao and McLaughlin, 2000; Ponoth
and McLaughlin, 2000). Their studies on mass
transfer without chemical reaction show an
important effect of interface contamination on
mass transfer.

Outlet

cap

Bubble
Symmetry axis

Figure 1. Computational domain R=60 di

2.3 Boundary conditions
Boundary conditions have to be imposed at
the inlet and at the outlet of the computational
domain as well as on the bubble surface and on
the symmetry axis. The inlet is located at the left
boundary of the flow domain (Figure 1) where a
uniform velocity U and a zero concentration are
imposed. The dimensionless boundary conditions
are as follows:

u = 0, v = 1, c = 0

(5)

Outlet boundary conditions are imposed at

the right of the flow domain (Figure 1): the
normal stress contribution vanishes and the flux
of the transferring specie is equal to its
convective flux. These conditions write as
follows:

p = 0, n = 0, J n = c u n

(6)

Where is the dimensionless shear stress, J is the

dimensionless mass flux vector and n is the
normal vector.
Whatever the level of the bubble surface
contamination, the concentration of the
transferring specie on the interface is determined
by the thermodynamics of absorption (Henry's
law). As the gas phase inside the bubble can be
supposed to be perfectly mixed, this results in a
constant concentration at the interface where the
dimensionless concentration of the transferring
specie is fixed to unity.
The hydrodynamic boundary conditions
depend upon the level of the bubble surface
contamination.
This
adsorption-desorption
process results in a stationary situation that have
been described by the Stagnant Cap Model
(Savic, 1956). In the Stagnant Cap Model, the

Finally, at the bubble interface, the

dimensionless boundary conditions are as
follows:
- Fully contaminated spherical bubbles (cap
= 0) :

u = 0, v = 0, c = 1

(7)

Fully contaminated bubbles behave as solid

spheres.
- Clean spherical bubbles ( cap =180 ) : the
normal component of the velocity is zero as well
as the shear, and the dimensionless concentration
equals to unity:

u n = 0, t n = 0, c = 1

(8)

- Partially contaminated bubbles (0 < cap

<180): following Stagnant Cap Model, the
boundary conditions at the contaminated
spherical bubble interface are:
1. The boundary condition of the solid sphere
(Equation 7), if > cap;
2. The boundary condition of the spherical
bubble (Equation 8), if < cap.

3. Quantities of interest
In all cases analyzed in this work, the
chemical reaction takes place only in continuous
phase (liquid phase). The rate of a chemical
reaction can be quantitatively described in two
ways:

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

using a Sherwood number Sh that

includes the effect of the chemical
reaction,
based on the enhancement factor E.

The Sherwood number is defined as follows:

1
c
(9)
Sh =
ds
di2 r r =1 / 2
The enhancement factor E is roughly defined
as follows:

E=

Sh( Da 0)
Sh( Da = 0)

(10)

For spherical clean bubble, the values of the

enhancement factor computed in this work are
compared to those provided by film theory. In
the film theory, the enhancement factor for a
first-order irreversible chemical reaction is given
by the relation (Juncu, 2002):

E=

Ha ,
Da
Ha =
Sh ( Da = 0)
tanh Ha

4. Results
The numerical simulation results of this
study can be represented by showing the effect
of interface contamination and that of chemical
reaction on Sherwood number and enhancement
factor for spherical bubbles.
4.1 Field concentration
As examples, Figure 2 presents the
concentration distributions around a clean
spherical bubble, at Da=0, Da=1, Da=10,
Da=100, Da=500 and Da=1000. The Reynolds
number is 0.01 and the Schmidt number is
10000. The bubble is supposed to rise in a liquid
at rest. This figure clearly shows the effect of
chemical reaction on concentration distribution
around the bubble which increases with Da
number. At low Da (Figure 2b and 2c), for this
high value of Schmidt number, mass transfer is
controlled by advection which leads to a
decrease of the concentration boundary layer
thickness in the front of the bubbles. The solute
is convected to the wake of the bubbles and the
concentration decreases from the interface to the
bulk. The scalar distribution becomes quite foreand-aft symmetric around the bubble for high

Damkhler numbers (Figures 2e and 2f). In this

case, the chemical reaction becomes the

predominant mechanism for mass transfer and
leads to a decrease of the concentration boundary
layer thickness around bubbles. Then, for rapid
reaction (Da500), the reaction occurs closing to
the interface of the bubble, while for slow
reaction (Da10), the reaction is located both in
the vicinity and in the wake of the bubble.

4.2 Average Sherwood number

The average mass transfer from bubble to
liquid can be characterized by the average
Sherwood numbers deduced from field
concentration (Equation 9). Figures (3a) and (3b)
show the Sherwood number Sh as a function of
Damkhler number Da for Sc=10 and
Sc=100000, respectively. At a low Peclet
number (Pe=0.1), the mass transfer with (Da0)
and without (Da=0) chemical reaction is
independent to interface contamination level
(Figure 3a). It should be noted that the Sherwood
number increases with Damkhler numbers. At a
high Peclet number (Pe=1000), the Sherwood
number depends to interface contamination level
and chemical reaction rate (Figure 3b). The
dependence is very important for slow chemical
reaction and becomes less important for rapid
reaction.

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

Figure 2. Field concentration around clean spherical bubbles for different Damkhler number (with Re=0.01,
Sc=10000). a) Da=0, b) Da=1, c) Da=10, d) Da=100, e) Da=500 and f) Da=1000

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

a)

a)

b)

b)

Figure 3. Sherwood number vs. Damkhler number

at Re=0.01. First order chemical reaction with
interface contamination effects. (a) Sc=10 and (b)
Sc=100000

Figure 4. Enhancement factor vs. Damkhler number

at Re=0.01. First order chemical reaction with
interface contamination effects. (a) Sc=10 and (b)
Sc=100000

4.3 Enhancement factor

noted that the film theory is not valid for low

Peclet number (Pe=0.1).

Enhancement factor E is defined as the ratio

between the Sherwood number with chemical
reaction and that without reaction (Equation 10).
Figures (4a) and (4b) present the enhancement
factor vs. Damkler number for Sc=10 and
Sc=100000, respectively. Enhancement factor
increases as a function of Damkhler number. For
rapid chemical reaction (Da=1000) and Sc=10,
the enhancement factor is in the order of 16.
Whatever the bubble surface contamination level
is, the enhancement factor E keeps constant. For
a clean spherical bubble, E converges to unity for
high Peclet number (Pe=1000) at rapid chemical
reaction regime (Figure 4b). Our numerical
simulation results are agreed with the film theory
with the differences less than 4%. It should be

5. Conclusions
Numerical simulations with COMSOL show
the influence of the hydrodynamics, of the
interface contamination, of the diffusion and of
the chemical reaction on the Sherwood number.
The Sherwood number increases with the
contamination angle, the Peclet number and the
Damkhler number. For clean spherical bubbles,
at high Peclet number, the numerical simulation
results agree with the film theory. For low Peclet
number,
whatever
the
bubble
surface
contamination level is, the enhancement factor E
keeps constant.

Excerpt from the Proceedings of the COMSOL Users Conference 2007 Grenoble

6. References
1. Dang, V. D. and Steinberg, M., Mass transfer
from swarms of bubbles or drops with chemical
reactions in continuous phase, AICHE J., 22, 925
(1976).
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numerical simulation of mass transfer from
spherical bubbles: the effect of interface
contamination at low Reynolds numbers,
International Journal of Chemical Reactor
Engineering, 4, A2 (2006).
3. Gerlinger, W., Schneider, K., Falk, L. and
Bockhorn, H., Numerical simulation of the
mixing of passive and reactive scalars in twodimensional flows dominated by coherent
vortices, Chemical Engineering Science, 55,
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4. Ishii, T. and Johnson, A. I., Can. J. Chem.
Engng., 48, 56 (1970).
5. Juncu, Gh., The influence of Henry number on
the conjugate mass transfer from a sphere: IImass transfer accompanied by a first-order
chemical reaction, Heat and Mass Transfer, 38,
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6. Khinast, J. G., Impact of 2-D bubble dynamics
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7. Khinast, J. G., Koynov, A. A. and Leib, T. M.,
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selectivity
of
liquid-phase
cyclohexane
oxidation, Chemical Engineering Science, 58,
3961-3971 (2003).
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9. Koynov, A. A. and Khinast, J. G., Effects of
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drops falling through a viscous medium, Tech.
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7. Acknowledgements
The Authors gratefully acknowledge
Huang Zhujun (INSA, Toulouse, France) for
her helps.