Chemical Engineering Science 62 (2007) 2698 – 2711

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Conceptual design of a novel hydrodynamic cavitation reactor

K. Sampath Kumar, Vijayanand S. Moholkar ∗
Department of Chemical Engineering, Indian Institute of Technology Guwahati, North Guwahati, Guwahati – 781039, Assam, India

Received 25 June 2006; received in revised form 31 December 2006; accepted 9 February 2007
Available online 4 March 2007

Abstract
Hydrodynamic cavitation has been increasingly used as a substitute to conventional acoustic (or ultrasonic) cavitation for process intensification
owing to its easy and efficient operation. In this paper, we have put forth conceptual design of a new kind of hydrodynamic cavitation reactor
that uses a converging–diverging nozzle for generating pressure variation required for driving radial motion of cavitation bubbles. Moreover,
the reactor uses externally introduced bubbles of a suitable gas (argon or air) for cavitation nucleation. This design differs from earlier designs
used by researchers where an orifice plate is used for creating cavitating flow. The new design offers a good control over two crucial parameters
that affect the cavitation intensity produced, viz. rate of nucleation and nature of pressure variation driving bubble motion. Using numerical
simulations of bubble dynamics and associated heat and mass transfer, trends in cavitation intensity produced in the reactor are assessed with
varying design parameters. The results of simulation show that the externally introduced bubbles undergo transient motion in the flow through
the nozzle generating moderate cavitation intensity. On the basis of results of simulation, some recommendations have been made for the
effective design and scale up of the new kind of hydrodynamic cavitation reactors using concept introduced in this paper.
䉷 2007 Elsevier Ltd. All rights reserved.

Keywords: Cavitation; Bubble dynamics; Sonochemistry; Physical acoustics

1. Introduction
Use of cavitation for the intensification of chemical pro-
cesses is well known. This effect is attributed to production of
highly reactive radical species as a result of transient bubble
motion driven by pressure variation in the bulk liquid medium.
Under the influence of pressure variation in bulk medium, gas
bubbles or nuclei in the medium undergo high amplitude, non-
linear volume oscillations. In the expansion phase, liquid va-
por diffuses into the bubble due to evaporation at gas–liquid
interface, when the pressure in the bubble falls below vapor
pressure of liquid at operating temperature. During the subse-
quent compression phase, pressure inside the bubble increases
and vapor starts to condense. However, depending on the na-
ture of the pressure variation, the collapse can be so rapid that
the bubble wall velocity reaches or even exceeds the velocity
of sound in the medium. At this time, the vapor present in the
central core of the bubble has insufficient time to escape. This
“trapped” vapor is then subjected to extremes of temperature
and pressure reached during adiabatic collapse of the bubble.
These conditions of temperature and pressure are adequate to
cause cleavage of vapor molecules to yield radicals. In most
of the applications, water is used as the liquid medium due to
its low viscosity and low vapor pressure, which assist the oc-
currence of cavitation. Chemical reactions are induced in the
bulk medium when the bubble contents mix with the surround-
ing liquid. The process of mixing can occur by two means: (1)
with the fragmentation of bubble at point of maximum com-
pression (or minimum radius), and (2) by diffusion of various
chemical species across bubble wall during pulsations of the
bubble (Yasui et al., 2005). However, the contribution to the
overall mixing process by fragmentation is much higher, as
the diffusion is a slow process.
1.1. Acoustic and hydrodynamic cavitation

∗ Corresponding author. Fax: +91 361 269 0762.
E-mail addresses: vmoholkar@iitg.ac.in, vmoholkar@iitg.ernet.in
(V.S. Moholkar).
0009-2509/$ - see front matter 䉷 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.02.010
The word cavitation basically refers to the formation, growth
and collapse of gas or vapor bubbles under influence of a pres-
sure variation in the bulk liquid medium. The word formation
 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711
also refers to the excitation of the nuclei or small microbub-
bles, which are already present in the medium, under the in-
fluence of pressure variation. Various kinds of cavitation can
be distinguished on the basis of cause of pressure variation.
Acoustic cavitation is a result of pressure variation in liquid due
to passage of an ultrasound wave. Ultrasound passes through
the medium in the form of compression/rarefaction cycles. The
bubbles expand in the rarefaction half cycle and subsequently
compress or even collapse in the compression half cycle, if the
amplitude of the ultrasound wave is sufficiently high. Ultra-
sound has been the most popular means of generating cavitation
in laboratory scale studies. Hydrodynamic cavitation is caused
by the pressure variation in the flow of a liquid due to variation
in the velocity of the flow as a result of a change in the geometry
of the conduit. For example, hydrodynamic cavitation can be
generated by throttling discharge of a pump through an orifice.
When the pressure downstream of the orifice plate falls close to
vapor pressure of the liquid with rise in velocity, a number of
bubbles are generated—as a result of release of dissolved gas in
the liquid or partial vaporization of liquid, which subsequently
oscillate and collapse with recovery of pressure. The nature
of bulk pressure variation in acoustic cavitation is sinusoidal
around the mean or ambient pressure, while the pressure vari-
ation in hydrodynamic cavitation is more-or-less linear. Since
both types of cavitation have their origin in the characteristic
radial motion of the bubble, theory of bubble dynamics can be
applied for the analysis by proper choice of the mathematical
term describing the time variation of bulk pressure in the liquid
medium, which drives the radial bubble motion.
1.2. Purpose of the present study
Several papers have appeared in literature in last one decade,
which report successful application of hydrodynamic cavita-
tion to physical and chemical processing. These include hydro-
lysis of fatty oils (Joshi and Pandit, 1993), polymerization
and depolymerization of aqueous polymeric solutions (Chivate
and Pandit, 1993), microbial cell disruption (Save et al., 1994,
1997; Balasundaram and Pandit, 2001a,b), wastewater treat-
ment (Kalumuck and Chahine, 2000; Sivakumar and Pandit,
2002; Gogate, 2002), oxidation of arylalkanes (Ambulgekar
et al., 2004, 2005), water disinfection (Botha and Buckley,
1995; Jyoti and Pandit, 2003, 2004a,b), synthesis of nanos-
tructured catalysts (Moser et al., 1995; Find et al., 2001). A
state-of-the-art review of literature published in the area of hy-
drodynamic cavitation reactors is given by Shah et al. (1999)
and Gogate and Pandit (2001).
In most of the studies mentioned above, an orifice plate
has been used for generating cavitation. In an orifice flow the
cavitation nuclei are provided by the gas released due to re-
duction in pressure or by the partial vaporization of liquid. It
was shown in our earlier papers (Moholkar and Pandit, 1997,
2001; Krishnan et al., 2006) that the turbulent pressure fluctua-
tions in the flow field downstream of an orifice are responsible
for transient behavior of bubbles. These pressure fluctuations
are completely random in nature. An exact modeling of these
fluctuations would require direct numerical simulations (DNS)
2699
of Navier–Stokes equations, which is an enormously inten-
sive procedure. However, in the above-mentioned papers, the
turbulent pressure fluctuations were approximated by a sinu-
soidal function. Due to randomness of the turbulent pressure
fluctuations driving the bubble motion, the cavitation effect (or
cavitation intensity) produced in the hydrodynamic cavitation
reactors employing an orifice plate also fluctuates significantly.
The rate of cavitation nucleation (in terms of number of bubble
generated and their size) in an orifice flow is also random, as
it is difficult to control both the rate of release of dissolved gas
and vaporization of liquid precisely. Moreover, orifice plates
create huge pressure head losses due to flow separation down-
stream of the plate, which could be a deterrent in scale up.
In this work, we put forth conceptual design of a novel hy-
drodynamic cavitation reactor that uses a converging–diverging
nozzle for creating pressure variation in the flow necessary for
driving bubble motion. The cavitation bubbles or nuclei are in-
troduced in the water flow externally, in the upstream flow prior
to nozzle using a sparger. Different gases can be used for in-
troduction of the bubbles. In the simplest case, air can be used.
However, in special cases monatomic gases like argon can also
be used, as these gases have higher specific heat capacity ratio,
which gives higher temperatures at bubble collapse. With nu-
merical simulations we show that this design is able to produce
cavitation effect of moderate intensities sufficient for processes
such as hydrolysis of fatty oils, microbial cell disruption, water
disinfections, etc. The major advantage of such a design is that
it gives a well-defined and consistent pressure variation in the
flow for radial bubble motion, which can be calculated using
simple fluid mechanics equations. Due to this, the cavitation
intensity produced in a single bubble can be reliably predicted
with simulations of bubble dynamics equation. Moreover, the
total cavitation intensity in the reactor can be controlled by
controlling the amount of gas introduced through the sparger
upstream of the nozzle that forms cavitation nuclei.
2. The mechanism of cavitation chemistry
It is well known that the liquid vapor trapped in the bubble
during instance of minimum compression undergoes cleavage
to yield radicals due to high temperature and pressure reached
in the bubble. However, the current status of instrumentation
does not permit a direct quantitative measurement of this phe-
nomenon. These quantities need to be obtained indirectly, i.e.,
using a bubble dynamics model. This matter has been addressed
by numerous researchers earlier. In the following paragraphs,
we present a review of the literature published in this area, and
also highlight the important facets of this phenomenon.
The first attempt (known to the present authors) to model
production of OHQ radicals during cavitation was made by
Kamath et al. (1993) by modeling radial bubble motion, but
with decoupling of the chemical kinetics. Prasad Naidu et al.
(1994) modeled equilibrium production of various radicals us-
ing Rayleigh–Plesset equation for radial motion of the bub-
ble, coupled with Flynn’s assumption (1964) that the bubble
becomes a closed system during collapse, when the partial
pressure of gas equals vapor pressure of liquid. The growth
2700 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711
phase of the bubble was assumed to be isothermal, while the
collapse phase (after bubble becoming a closed system) was
assumed to be adiabatic. Similar approach was taken by other
authors, viz. Sochard et al. (1997) and Gong and Hart (1998).
Moss et al. (1999) performed numerical simulations of the bub-
ble motion, keeping the amount of water vapor in the bubble
constant, and without taking into account the chemical reac-
tions. In a remarkable work published in 1997, Yasui (1997a,b)
modeled the non-equilibrium phase change and chemical re-
actions in a collapsing air bubble. He used a Rayleigh–Plesset
type equation for the bubble radius, with the water vapor trans-
port by condensation–evaporation. In addition, 25 chemical re-
actions of radicals formed out of water vapor dissociation were
taken into account. The transport of water vapor in the bub-
ble in the bubble was assumed to be condensation limited; i.e.,
mass diffusion was considered to be instantaneous, and not ex-
plicitly modeled. The principal result of Yasui’s papers was that
some water vapor remains in the bubble even at collapse. Quite
obviously, with intense heating of the bubble during transient
collapse, this water vapor undergoes endothermic dissociation,
generating radicals. The endothermicity of the dissociation re-
actions, however, works towards reduction in the temperature
peak reached in the bubble.
The most general treatment of this problem, relaxing several
assumptions made in earlier studies, was presented by Storey
and Szeri (2000). The salient features of the approach of Storey
and Szeri were as follows:
1. The Navier–Stokes equations for the gas mixture in the bub-
ble were coupled to a reaction mechanism.
2. The transport properties such as thermal and mass diffusion
coefficient were determined from the equations based on
Chapman–Enskog theory. The equation of state used for the
bubble contents was of Redlich–Kwong–Soave type.
3. The transport rate of water molecules was proportional to
the difference between partial pressure of water vapor in the
bubble and saturation pressure at the interface.
An important aspect of the condensation of water vapor
at bubble interface is that not all the water molecules that
approach the surface stick to it; thus giving non-equilibrium
phase change. Another mechanism, which contributes to non-
equilibrium phase change, is the difference between time scales
of bubble dynamics and vapor condensation, as discussed later.
The physical parameter that characterizes this phenomenon is
the accommodation coefficient (a ), which is the fraction of
water molecules that stick or condense at the surface. In other
words, accommodation coefficient represents the resistance to
condensation at the bubble interface during collapse. Lower val-
ues of a give higher resistance to condensation, and hence, re-
sult in higher amount of water vapor entrapment (Colussi et al.,
1998; Colussi and Hoffmann, 1999). Storey and Szeri (2000)
have used in their model, a value of 0.4 for a , following Yasui
(1997a,b) and Eames et al. (1997). The principal result of the
work of Storey and Szeri (2000) was that water vapor trans-
port in the bubble is a two-step process: (1) the diffusion of
water molecules to the bubble wall, and (2) condensation at
the bubble wall. Thus, the process of water vapor transport
is influenced by two time scales, viz. the time scale of dif-
fusion (tdif ) and time scale of condensation (tcond ), and their
magnitude relative to the bubble dynamics (or oscillations)
time scale (tosc ). During the growth and early phases of col-
lapse, the condensation and diffusion time scales are much
shorter than the bubble dynamics time scale (tosc ?tdif , tcond ),
and thus, the composition of the bubble is uniform. How-
ever, during the final moments of bubble collapse, the bubble
wall velocity becomes very high, which reverses the above
inequality, i.e., tdif , tcond ?tosc . At this condition, the water
vapor has insufficient time to diffuse to the bubble wall, which
results in nearly fixed distribution of water vapor in the bubble,
or the water vapor is “trapped” in the bubble.
Non-equilibrium phase change at the bubble wall is yet an-
other mechanism that results in water vapor entrapment. Qual-
itatively, when tosc ? tcond , the phase change or condensation
at the bubble wall is in equilibrium with the bubble motion.
During the final moments of collapse, the time scale of bubble
dynamics becomes much smaller than the time scale of vapor
condensation (i.e., tosc >tcond ). At this point, the phase change
turns out to be non-equilibrium, and the bubble contents reach
super saturation.
The exact mechanism that contributes to water vapor entrap-
ment in the bubble is determined by the relative magnitudes
of tosc , tcond and tdif . The condition necessary for water vapor
entrapment is tosc >tcond , tdif . However, both mechanisms viz.
slow diffusion and slow condensation can contribute. Storey and
Szeri (2000) showed that the condition tdif < tosc is reached well
before tosc < tcond , and hence, water vapor trapping is diffusion
limited. Based on this result, a simpler diffusion limited model
using boundary layer approximation was later developed by
Toegel et al. (2000). This model forms the basis of the present
study. The existence of boundary layer near bubble wall even
at the moments of rapid bubble collapse has been confirmed
from studies of Kwak and co-workers (Kwak and Yang, 1995;
Kwak and Na, 1996, 1997). These studies have shown that the
spatial variation of temperature in the bubble was negligible,
except at the bubble wall. This result has also been justified by
other authors (Fujikawa and Akamatsu, 1980; Kamath et al.,
1993). Toegel et al. (2000) have validated their model with full
numerical simulations of Storey and Szeri (2000), finding an
excellent qualitative and quantitative agreement. This agree-
ment is yet another confirmation that the water vapor transport
in the bubble is indeed diffusion limited.
3. Mathematical formulation
The present study aims at modeling of a hydrodynamic cav-
itation reactor from bubble dynamics point-of-view, in which
a converging–diverging nozzle is used for generating pressure
variation in the flow that drives the radial bubble motion. The
liquid medium in the present study is water, with gas bub-
bles (of either argon or air) introduced in it externally using
a small sparger, which does not cause any significant flow
disturbance. The exact flow configuration is shown in Fig. 1.
A detailed modeling of the flow field in a nozzle requires
 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711
Cross-Sectional Area, A (x)
Flow
x determined by the excluded volume of gas molecules. Since the
L hard core radii of the species considered in the present work
Gas Sparger
Bubble Radius, R(x,t)
Fig. 1. A converging–diverging nozzle for generating hydrodynamic cavitation.
The bubbles of desired gas (air or argon) can be introduced in the flow using a
sparger upstream. The sparger comprises of a small tube, connected at one end
to the gas source (a cylinder). The gas is distributed in the flow using a glass
frit having opening of suitable size connected at the other end of the tube.
simulation of Navier–Stokes equation coupled with bubble
dynamics equation. This is a highly complicated model. Major
disadvantage of such a model is that it does not allow easy
scanning of all parameter space; moreover, these are numeri-
cally intensive. Therefore, we take an approximate approach,
yet representing the physical picture, for modeling the pressure
variation in the stream and the radial bubble motion driven by
this variation. We would like to emphasize that our approach
addresses the basic physics of the problem. A more rigorous
approach relaxing the approximations in our model would
modify only the final quantitative answers.
One-dimensional bubbly flow in ducts and nozzles is an ex-
ample of simplest confined gas–liquid flows. Modeling such a
flow is an important aspect of fluids engineering in many prac-
tical applications; however, very few studies have addressed
this problem in the context of cavitation and bubble dynam-
ics. In a simplified approach for treating this problem, which
assumes that fluid pressure is a function of density only, a
barotropic relation P = f () can be established. This means
that all effects for the compressibility and for the bubbly mix-
ture can be regarded as single-phase compressible fluid. Such
a barotropic criterion is not met in many practical applica-
tions. In the present context, the hydrodynamic effects of the
flow acceleration (in the converging section of the nozzle) are
manifested in terms of the expansion of bubble introduced in
the flow, and the flow deceleration in the diverging section of
the nozzle makes these bubbles collapse.
3.1. Bubble dynamics model
The bubble motion is described by Keller–Miksis equation
(Prosperetti and Lezzi, 1986; Brennen, 1995) as
     present case) in the bubble. Diffusion of vapor into the bubble,
dR/dt d2 R 3 dR/dt dR 2
1− R 2 + 1−
c dt 2 c dt
 
1 dR/dt R dPi
= 1+ (Pi − Pt ) +
 c c dt
dR/dt 2
− 4 − , (1)
R R
2701
where Pt is the time variant pressure in the bulk liquid driv-
ing bubble motion. Algorithm for the calculation of Pt is ex-
plained in the next section. The pressure inside the bubble, Pi is
written as
Ntot (t)kT
Pi =    , (2)
4 3 (t) − h3
3 R
where h ∼ R0 /8.86 is the van der Waals hard core radius
viz. nitrogen, oxygen, water and argon differ only by a small
magnitude, we take a common value for the hard core radius.
 is the effective polytropic exponent of the bubble contents.
Plesset and Prosperetti (1977) calculated as how it depends
on the thermal Peclet number (P e = R02 /), which gives the
√ of bubble length (R0 ) and the thermal diffusion length
ratio
( /). However, Hilgenfeldt et al. (1996) later argued that
the frequency  should be replaced by the bubble dynamics
time scale, i.e., R|dR/dt|. With this substitution, the thermal
Peclet number becomes as high as 104 at the moments of rapid
bubble collapse, implying that  should take value of ratio of
specific heats. However, condition for which P e?1 holds lasts
only for a very short duration (∼ 1 ns or so). Hence, the global
dynamics is not affected by setting  = 1 uniformly in time.
Another consequence of this approximation is that we assume
isothermal conditions at the bubble wall, which is supported
by large heat capacity of water. This condition is further used
in the model for mass transfer across the bubble, described in
the next subsection. Eq. (1) can be easily transformed into two
simultaneous ODEs by following substitution:
dR
= s, (3)
dt
ds (1 + s/c) 1 dPi
= (Pi − P ) +
dt R(1 − s/c) c(1 − s/c) dt
4s 2 3s 2 (1−s/3c)
− − − . (4)
R 2 (1−s/c) R 2 (1−s/c) 2R(1−s/c)
3.2. Heat and mass transfer across bubble
Both gas and water vapor diffuse across bubble wall during
radial bubble motion. The time scale of gas diffusion can be
given as ∼ R02 /D where R0 is the initial radius of the bubble
(∼ 100 m) and D is the diffusion coefficient (∼ 10−9 m2 /s).
Thus, the time scale of gas diffusion becomes ∼ 100 ms, which
is much higher than the time scale of pressure variation (trec )
driving bubble motion (refer to Table 2A). With this condition,
we have neglected the diffusion of gas (argon and air, in the
as a result of evaporation occurring at the bubble interface needs
to be taken into account, nonetheless.
The temperature inside the bubble exceeds the surface tem-
perature of the bubble (which is same as bulk liquid tempera-
ture) only for a very brief moment during collapse. We use this
condition for dividing the bubble into two parts: (1) a “cold”
2702 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711

Table 1
Thermodynamic properties of various species

Species Degree of freedom (f) Molecular specific heat (Cp ) Molecular specific heat (CV )
( N2 /T )2 exp( N2 /T )
N2 5 7
2k k( 25 + )
(exp( N2 /T )−1)2
( O2 /T )2 exp( O2 /T )
O2 5 7
2k k( 25 + )
(exp( O2 /T )−1)2
3 ( i,H2 O /T )2 exp( i,H2 O /T )
H2 O 6 4k k(3 + i )
(exp( i,H2 O /T )−1)2
5 3
Ar 3 2k 2k

Note: i ’s are the vibrational temperatures of various species: N2 = 3350 K , O2 = 2273 K , 1,H2 O = 2295 K , 2,H2 O = 5255 K , 3,H2 O = 5400 K .

boundary layer in thermal equilibrium with the liquid, and (2) with boundary conditions: (1) at r = 0, jCw /jr = 0 for t 0;
a hot homogeneous core. An underlying assumption in this (2) at r =R, Cw =CwR for t 0; and (3) Cw =Cw0 =0 for t =0
hypothesis is that the condensation of water molecules at and 0 r R. The analytical solution to the above equation is
the bubble wall is fast enough to maintain equilibrium phase (Crank, 1975):
change. By dimensional analysis, the instantaneous
√ diffusive
penetration depth is given by ldiff = Dt osc , where tosc is ∞
Cw − Cw0 2R
(−1)n
the time scale of bubble oscillations, R/|dR/dt|. The rate of =1+
CwR − Cw0 r n
change of water molecules in the bubble by diffusion is given by n=1
   
  nr −Dtn2
dNw jCw CwR − Cw × sin exp . (8)
= 4R 2 D = 4R 2
D , (5) R/ (R/)2
dt jr r=R ldiff

where CwR is the equilibrium concentration of water molecules
at the bubble wall, and it is calculated from the equilibrium
vapor pressure at the bubble wall corresponding to bulk liquid
temperature. Cw is the actual concentration of water molecules
in the bubble core.
From the inspection of above solution, the characteristic length
for the diffusion is R/. We choose this as the upper limit for
the thermal and mass diffusion length. Thus, the expressions
for the thermal and mass diffusion length are given as


With complete analogy with mass transfer, the heat transfer RD R
across bubble wall is given by ldiff = min , , (9)
|dR/dt| 
 
dQ T0 − T 

= 4R 2
, (6)
dt lth R R
lth = min , . (10)
|dR/dt| 
where
is the thermal conductivity of the bubble contents
√ and
lth is the thermal diffusion length written as lth = tosc . The
3.4. Overall energy balance
thermal diffusivity,  of the gas–vapor mixture in thebubble is
calculated as  =
/mix Cp,mix , where mix Cp,mix = i i Cpi ,
During radial motion, both heat and mass transfer occurs
i ’s are the densities of the species present in the bubble (in
across the bubble wall, and thus the overall energy balance for
molecule/m3 ) and Cpi ’s are the molecular specific heats of
the bubble contents is written as
these species. Values of Cpi are listed in Table 1.
dE dQ dW dNw
3.3. Limits on the diffusion length = − + hw . (11)
dt dt dt dt

In the expressions for the thermal and mass diffusion length, The total energy E of the bubble is a function of temperature and
the term dR/dt (the bubble wall velocity) appears in the de- volume of the bubble and the number of molecules of various
nominator. At the instances of maximum and minimum radius, species in it. Thus, the rate of change of total energy is written
the bubble wall velocity becomes zero. Thus, an alternate ex- for the bubbles of air and argon as follows:
pression for the diffusion length is needed. One can easily per- (1) Argon bubble:
ceive that for dR/dt = 0, the transport of water molecules in
   
the bubble (with spherical symmetry) is described by a pure dE jE dNAr jE dNw
diffusion equation = +
dt jNAr Nw ,V ,T dt jNw NAr ,V ,T dt
     
jCw j 2 Cw 2 jCw jE dT jE dV
=D + (7) + + . (12)
jt jr 2 r jr jT Nw ,NAr ,V dt jV Nw ,NAr ,T dt
 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711 2703

(2) Air bubble: 1954; Reid et al., 1987) can be used for determination of dif-
    fusion coefficient (D) and the thermal conductivity (
). Since
dE jE dNN2 jE dNO2 we assume a cold boundary layer in which the effective heat
= +
dt jNN2 Nw ,NO ,V ,T dt jNO2 NN ,Nw ,V ,T dt and mass transport occurs, both D and
are evaluated at the
2 2
    bulk liquid temperature, T = T0 .
jE dNw jE dT
+ +
jNw NN ,NO ,V ,T dt jT Nw ,NN ,NO ,V dt 3.5.1. Diffusion coefficient
2 2 2 2
  Diffusion coefficient of species 1 (water vapor) in the mixture
jE dV
+ , (13) of two species, viz. water vapor and argon (species 2), to a first
jV Nw ,NN ,NO ,T dt approximation is written as
2 2

where dNN2 /dt, dNO2 /dt and dNAr /dt are the rate of change 3 kT /12
of molecules of nitrogen, oxygen and argon, respectively, in D= . (17)
the bubble. As we neglect the change in the gas content of the
bubble for the reasons stated earlier, dNN2 /dt = dNO2 /dt =
dNAr /dt = 0. The term dNw /dt is the rate of change of water
vapor content of the bubble and is evaluated according to Eq.
(5). Various other terms in the energy balance are evaluated as
follows:
8 n12 2 (1,1)
12 12
m1 and m2 are the molecular masses of water and argon,
respectively, and 12 =2m1 m2 /(m1 +m2 ) is the reduced molec-
ular mass of the two species. n12 = n1 + n2 is the total concen-
tration of two species at the bubble wall. 12 = (1 + 2 )/2 is a
parameter in the potential function characteristic of 1–2 inter-
action, where 1 and 2 are the molecular diameters of water
(1,1)∗
• The specific enthalpy of the water molecules entering the and argon. 12 is a dimensionless correction of first order
bubble from cold bubble interface is, hw = 4kT 0 , where k is that enumerates deviation of the collisional cross-section from
Boltzmann constant and T0 is the ambient temperature. hard sphere cross-section. Values of this parameter are given by
• The specific energy of water molecules in the bubble is the Hirschfelder et al. (1954) as a function of reduced temperature
thermal energy, and is written as of the two species:
   
   
jE
i /T
= Uw = Nw kT 3 + . ∗ T T
jNw exp( i /T ) − 1 T12 = . (18)

/k 1
/k 2
(14)
Values of the potential parameter (
/k) in 0 K are obtained from
• The work done by the bubble is the expansion work: Pi dV , V various texts (Hirschfelder et al., 1954; Reid et al., 1987).
being volume of the bubble.
• (jE/jT ) = CV and (jE/jV ) = 0, as the internal energy 3.5.2. Thermal conductivity
of an ideal gas mixture is a function of its temperature and The estimation of thermal conductivity for the argon–water
composition. vapor mixture is rather complicated due to the fact that it is
a mixture of a monatomic (argon) and polyatomic (water)
With inclusion of various terms above in the overall energy species. The coefficient of thermal conductivity for a pure
balance, we obtain an equation for the change in the temperature monatomic gas can be obtained from rigorous kinetic theory.
of the bubble as However, these formulae cannot be used for the polyatomic
dT dQ dNw gases, as the effect of the internal degrees of freedom on the
CV ,mix = − Pi dV + (hw − Uw ) . (15) thermal conductivity is considerable. However, with Eucken
dt dt dt
correction one can apply the formulae for monatomic gases to
The specific heat of the gas–vapor mixture (CV ,mix ) present in the polyatomic gases.
the bubble is written as The coefficient of thermal conductivity for a monatomic gas

is given as
CV ,mix = CV ,i Ni , (16)
15 k
i
= , (19)
4 m
where CV ,i is the molecular specific heat of species i, and Ni is
the number of molecules of that species present in the bubble. where m is the molecular mass and  is the coefficient of vis-
The CV values for the various species considered in this work cosity, written as
are listed in Table 1. √
5 mkT
= . (20)
16 2 (2,2)∗
3.5. Transport parameters for the argon bubble
For a polyatomic molecule, the corrected thermal conductivity
For an argon bubble, we encounter a binary system, viz. wa- as
 
ter vapor and argon. For such a system, the Chapman–Enskog 15 k 4 Cv 3

Eucken =  + . (21)
theory using Lennard-Jones 12-6 potential (Hirschfelder et al., 4 m 15 R 5
2704 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711

Using above formulae, the thermal conductivity for the mixture formula for monatomic gas. E2 ∼ 1, as argon is a monatomic
of argon and water vapor is calculated using a semi-empirical gas and the experimental value of its thermal conductivity is al-
method (Hirschfelder et al., 1954) described below. most equal to the value determined with the formula. For water
We first define a quantity
12 : vapor, E1 is calculated as E1 =
exp tl /
1 . For the experimental
   value of thermal conductivity of water, we use the correlation
25 kT /12 3 given by Reid et al. (1987):

12 = k. (22)
32   2 (2,2)∗
T ∗ 2
12 12 12

exp tl = 7.341 × 10−3 − 1.013 × 10−5 T
(2,2)∗
12 is again a dimensionless correction for first order, similar
(1,1)∗ + 1.801 × 10−7 T 2 − 9.1 × 10−11 T 3 , (27)
to quantity 12 defined earlier. In terms of this quantity,
and the thermal conductivities of pure components, viz. water where T is in K and
in W/mK.
(
1 ) and argon (
2 ); both being calculated using the formula
for the monatomic gas stated above, a new quantity
mon is 3.6. Transport parameters for the air bubble
calculated as
1+Z In case of air–water vapor mixture we encounter a ternary

mon = . (23)
X+Y system: nitrogen–oxygen–water vapor. Again, we use the
Chapman–Enskog theory for the estimation of transport pa-
X, Y and Z are defined in terms of the mole fractions of two
rameters, however, with a slightly different approach. After
components, x1 and x2 as
determination of binary diffusion coefficient for N2 –H2 O and
x12 2x1 x2 x2 O2 –H2 O binary mixtures using Eq. (17), the overall diffusion
X= + + 2, (24a) coefficient is determined as (Hirschfelder et al., 1954)

1
12
2
x12 2x1 x2 x2 1 N2 O2
Y= U1 + UY + 2 U2 , (24b) = + , (28)

1
12
2 D (1 − H2 O )DN2 .H2 O (1 − H2 O )DO2 .H2 O

Z = x12 U1 + 2x1 x2 UZ + x22 U2 . (24c) where is the mole fraction of the respective species at the
bubble wall.
The quantities U1 , U2 , UY and UZ are given as
For the determination of conductivity of the nitrogen–
 
4 1 12 ∗ m1 1 (m1 −m2 )2 oxygen–water vapor mixture, the viscosity of individual species
U1 = A∗12 − B12 +1 + , (25a) is evaluated first using Eq. (20). Thereafter, the conductivity of
15 12 5 m2 2 m1 m2
species is related to its viscosity using the following formula
 
4 ∗ 1 12 ∗ m2 1 (m2 −m1 )2 that accounts for contribution of internal degree of freedom to
U2 = A12 − B12 + 1 + , (25b) the heat conduction:
15 12 5 m1 2 m1 m 2
     
4 ∗ (m1 + m2 )2
212 15k 4f 3
UY = A12 −
1 12 ∗
B +1
=  + , (29)
15 4m1 m2
1
2 12 5 12 m 30 5
  where f is the number of degree of freedom of the species at
5 12 ∗ (m1 − m2 )2
− ∗ B 12 − 5 , (25c) bubble wall. Values of f for various species are listed in Table 1.
32A12 5 m1 m 2 The effective heat conduction is now written using the following
    formula (Wilke, 1950; Condon and Odishaw, 1958):
4 ∗ (m1 + m2 )2
12
12
UZ = A12 + −1

15 4m1 m2
1
2 i
i

mix =  . (30)
  j i i,j
1 12 ∗ i
− B +1 . (25d)
12 5 12 The parameter  is given as
The quantities A∗12 and B12∗ are functions of the quantities 

   −1/2  1/4 2
defined earlier and are written as A∗12 = (2,2)∗ /(1,1)∗ and 1 mi −1/2 ni mi
∗ = (5(1,2)∗ − 4(1,3)∗ )/(1,1)∗ . Values of A∗ and B ∗ i,j = √ 1+ 1+ , (31)
B12 12 12 8 mj nj mj
are tabulated in Hirschfelder et al. (1954) as a function of the
reduced temperature T ∗ = T /( /k). After determining
mon , where i, j = N2 , O2 and H2 O.
the coefficient of the thermal conductivity for the mixture is
determined using the correlation 3.7. Modeling of pressure variation in nozzle flow

=
mon (x1 E1 + x2 E2 ), (26)
We take approach of discrete calculations while modeling the
where E1 and E2 are the ratios of the experimental value and pressure variation in the nozzle flow. In such an approach, the
the theoretical value of thermal conductivity, determined by the first task is to choose a suitable expression describing variation
 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711 2705

7. The pressure at the nodal points can also be determined by

1 2 N-1 N
successive application of Bernoulli equation between con-
secutive points.
8. The time taken by the fluid element to travel between two
Length of the nozzle (L) nodal points i + 1 and i is
i= 0 1 2 3 N-2 N-1 N
(xi+1 − xi )
Fig. 2. Discretization scheme for calculation of pressure variation in the ti+1 = . (37)
nozzle.
((Ui+1 + Ui )/2)

Time taken by the fluid element to cover the complete length

in the nozzle cross-section area in the direction of flow. We
choose a simple expression such as (Wang and Brennen, 1998)
⎧
  −1/2
⎪
⎪ 1 2x
⎨ 1 − 2  1 − cos L
⎪ for 0 x L,
A(x) =
⎪
⎪ 1 for x < 0 and
⎪
⎩ 3.8. Numerical solution
x > L,
where A is the dimensionless cross-sectional area of the nozzle
normalized by the upstream cross-sectional area (i.e., the area
of the pipe), and L is the length of the nozzle. The procedure
for discrete calculation is described as follows:
1. The flow region between x=0 and L is divided in sufficiently
large number of intervals, say 100 (refer to Fig. 2). These
intervals will have a total of 101 nodes (i = 0.100).
2. The encircled numbers indicate the intervals and dots indi-
cate the node.
3. Values of the distance coordinate, x are then calculated as
 
L If the surrounding liquid is not stagnant, it can induce fragmen-
xi+1 = xi + with x0 = 0 and x101 = L. (33)
100
4. At the different node points, the dimensionless area of the
nozzle is calculated using above expression.
5. To estimate the volumetric flow rate through the nozzle, we
apply Bernoulli equation between points x0 = 0 and x = L/2
(the upstream point and the throat of the nozzle). Taking the
limiting case as the pressure in the liquid at the throat falls
to the vapor pressure of the liquid at given temperature, the
velocity at the throat is calculated as
flow and shape instability, the bubble collapses at first compres-
(P2 − Pv )
Ut = , (34)
(1/2) × 1 × (1 − dt4 /dp4 )
where dt and dp are the diameters of nozzle throat and pipe,
respectively. In the present case, we first assume the pipe
diameter value (as 2 in) and calculate the throat diameter
using the equation for nozzle area. The velocity in the pipe
(i.e., at x0 = 0) can be calculated as
Ut At = Up Ap .
6. Once the velocity in the pipe is determined, the velocity at
other nodal points is calculated in straight forward manner:
Ui Ai = Up Ap .
L of the nozzle is obviously the cumulative time periods.
9. Steps (6) and (7) thus give the time variation of the pressure
in the flow through the nozzle in discrete form. For this
data, a best-fit polynomial equation is obtained, which can
be used in the bubble dynamics simulations.
(32) Eqs. (3)–(6) constitute the complete formulation for radial
motion of bubble with associated heat and mass transfer ef-
fects, which can be solved simultaneously using Runge–Kutta
fourth order–fifth order adaptive step size method (Press et al.,
1992). The initial conditions used for the solution are t =0, R=
R0 , dR/dt = 0, Nw = 0 and T = T0 . We would like to mention
that the phenomenon of bubble collapse (or bubble fragmenta-
tion) depends on many factors such as the surface instability,
local flow conditions, and the bubble population in the vicinity
of the bubble. At the point of maximum compression, when
conditions inside the bubble reach extreme, the bubble is highly
energetic, and hence, unstable. Whether a bubble fragments at
this stage depends on conditions of the ambiance of the bubble.
tation of the bubble. The higher this disturbance, the higher the
chances that bubble would fragment at first compression itself,
without rebouncing. Another instability, which also contributes
to bubble fragmentation is the surface (or shape) instability.
The initial bubble geometry (at the point of introduction in the
flow) is spherical. Small distortions in the spherical geometry
can be induced subsequently during radial motion. These dis-
tortions may grow, depending on other conditions such as am-
plitude of pressure variation driving bubble motion, leading to
fragmentation of the bubble. For the conditions of maximum
sion after an initial expansion. Considering this, the condition
for bubble collapse is taken as the first compression after an
initial expansion. However, it is not necessary that the bubble
collapse at the first compression. For milder instabilities, it may
re-bounce and undergo many oscillations, with the recovery
of pressure of the liquid flow. Equilibrium composition of the
various species formed in the bubble with dissociation of en-
trapped water molecules (i.e., H2 O, H2 , O2 , H, OH, O, H2 O2 ,
HOO, O3 ) at the conditions of temperature and pressure at first
(35)
the compression was calculated using software FACTSAGE,
which uses the free-energy minimization algorithm proposed
by Eriksson (1975). This software has an in-built database of
Cp vs. temperature relationship, entropy and heat of formation
(36) of all the above species.
2706 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711

4. Results and discussion
Simulations were performed to assess the radial bubble mo-
tion and the sonochemical effect produced thereby under vari-
ous combinations of operating and design parameters. Six sets
of parameters were used for simulations, listed in Table 2A. As
mentioned earlier, we consider introduction of two gases, viz.
air and argon, through the sparger. The pressure variation in
the nozzle for these sets of parameters was obtained in the dis-
crete form using algorithm present in previous section, and the
polynomial expression fitted to this data is given in Table 2B.
We would like to mention that the volume fraction of the ex-
ternally introduced bubbles is rather small (∼ 10−5 or less) so
that it does not cause flow instability, as pointed out by Wang
and Brennen (1998). Moreover, it is assumed that the dissolved
gas content of the liquid is quite small, so that the gas released
at the throat of the nozzle due to reduction in pressure does
not change the total volume fraction of the bubbles in the flow
significantly. The representative simulation results (i.e., radius
history of the air and argon bubbles along with associated heat
and mass transfer) for the parameter set 2 are presented in
Figs. 3 and 4. The summary of the simulation results for all the
six parameter sets (i.e., maximum radius attained by the bub-
ble during radial motion, the temperature and pressure peaks
reached in the bubble at the first compression, the number of
water molecules entrapped and the equilibrium composition of
various species) is given in Tables 3 and 4 for argon and air
bubbles, respectively. The simulation results give an elucidation
of the phenomena of radical formation in the bubble; more-
over, the influence of various operating parameters can also be
discerned from these results. Figs. 3 and 4 reveal that larger
amount of water vapor diffuses into the bubble during expan-
sion. Due to extremely fast and nearly adiabatic collapse, not all
of the water vapor is able to escape. The entrapped water vapor
is subjected to extremes of temperature and pressure reached in
the bubble during collapse, causing generation of various radi-
cal species. For the argon bubbles, the dominant radical species
is OHQ . In case of air bubbles, due to presence of oxygen
molecules that act as radical scavenging species, the hydroper-
oxy (HOOQ ) radicals are also present in significant amount.
The influence of following parameters on the radial bubble
motion is assessed in the simulations: (1) upstream pressure
at the nozzle mouth (P2 ); (2) length of the nozzle (L); and
(3) initial bubble radius (R0 ). Before we discuss the effects of
these parameters, we present a general discussion about the
factors that govern the radial bubble motion. For the external
introduction of bubbles in the flow at an upstream position (as
shown in Fig. 1), the minimum gas pressure required would be
greater or equal to the upstream pressure. The initial pressure
in the externally introduced bubble of size R0 in flow would be
the upstream pressure plus the Laplace pressure, 2/R0 . This
bubble then flows with the liquid and expands in the converg-
ing section of the nozzle, with reduction in ambient pressure.
One can easily perceive that the higher the initial pressure in-
side the bubble, the higher the expansion of the bubble till the
throat of the nozzle where the pressure in the flow is assumed
to fall to vapor pressure (Pv ). The subsequent collapse of the
bubble is governed by the inertial forces, and hence, a more
intense collapse (resulting in higher magnitudes of temperature
and pressure peaks reached in the bubble) is seen for a bubble
that expands to a larger extent. Another factor that influences
the bubble motion is the duration of pressure variation. The net

Table 2
Parameters for simulation

Set number P2 (atm) R0 (m) L (in) trec (ms)

(A) Physical parameters

1 1 200 3 4.514
2 1.5 200 3 3.672
3 1.25 200 3 4.029
4 1.25 200 6 8.057
5 1 100 4 21 6.772
6 1 200 4 21 6.772

Constant Set 1 Set 2 Set 3 Set 4 Set 5 Set 6

(B) Best-fit expressiona for pressure variation in flow

A1 0 0 −3.554E + 027 0 0 0
A2 0 0 −4.925E + 026 0 0 0
A3 0 0 8.498E + 024 0 0 0
A4 1.034E + 021 5.4E + 021 −5.464E + 022 4.018E + 019 9.075E + 019 9.075E + 019
A5 −1.4E + 019 −5.95E + 019 1.689E + 020 −9.72E + 017 −1.85E + 018 −1.85E + 018
A6 6.599E + 016 2.28E + 017 −2.589E + 017 8.17E + 015 1.304E + 016 1.304E + 016
A7 −1.19E + 014 −3.36E + 014 2.11E + 014 −2.64E + 013 −3.54E + 013 −3.54E + 013
A8 6.05E + 010 1.383E + 011 −1.369E + 011 2.385E + 010 2.689E + 010 2.689E + 010
A9 −2.81E + 07 −5.233E + 07 1.327E + 07 −1.98E + 07 −1.88E + 07 −1.88E + 07
A10 1.01325E + 05 1.51987E + 05 1.266E + 05 1.2666E + 05 1.01325E + 05 1.01325E + 05

best-fit expression is of the type: A1 t 9 + A2 t 8 + A3 t 7 + A4 t 6 + A5 t 5 + A6 t 4 + A7 t 3 + A8 t 2 + A9 t + A10 . The number format for the constant is as
a The

follows: −3.554E + 027 should be read as −3.554 × 1027 .

 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711 2707

6×1014

No of Water Molecules
4
Radius (R/Ro)

2 3×1014

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless Time (t/trec) Dimensionless Time (t/trec)

2000 40
Temperature (K)

Pressure (atm)
1000 20

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless Time (t/trec) Dimensionless Time (t/trec)

Fig. 3. Simulation results (with parameter set 2) for radial motion of 200 m argon bubble and associated phenomena [time variation of (A) normalized bubble
radius (R/R0 ); (B) number of water molecules in the bubble; (C) temperature in the bubble; and (D) pressure in the bubble].

1×1015
No of Water Molecules

4
Radius (R/Ro)

2 5×1014

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless Time (t/trec) Dimensionless Time (t/trec)
1500 100
Temperature (K)

Pressure (atm)

750 50

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless Time (t/trec) Dimensionless Time (t/trec)

Fig. 4. Simulation results (with parameter set 2) for radial motion of 200 m air bubble and associted phenomena [time variation of (A) normalized bubble
radius (R/R0 ); (B) number of water molecules in the bubble; (C) temperature in the bubble; and (D) pressure in the bubble].

pressure variation (either decreasing in the converging section
or increasing in the diverging section of the nozzle) that a
bubble experiences is |P2 − Pv |. If the duration of the pressure
variation is short, then for a given magnitude of (P2 − Pv ), the
bubble does not get enough time to expand with reduction in
pressure. The ensuing collapse is also less intense, resulting in
the reduction of sonochemical effect produced.
4.1. Effect of upstream pressure
The effect of upstream pressure on the radial motion of
a 200 m bubble in a nozzle of 3 in length can be found by
comparing the results of simulations for parameter set 1 and
2 given in Tables 3 and 4, for an argon and an air bubble,
respectively. It can be seen that the expansion of the bub-
ble increases with increasing upstream pressure, and more
intense is the succeeding collapse, giving rise to higher tem-
perature and pressure peaks. The temperature peak reached
in an argon bubble at collapse is higher than that of an air
bubble and this effect could be attributed to the monatomic
nature of argon. Moreover, the amount of vapor diffus-
ing into the bubble increases with larger expansion of the
bubble. Thus, the amount of water vapor trapped also in-
creases. Overall, the sonochemical effect produced by the
2708 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711

Table 3
Simulation results for argon bubble

Species Parameter set for simulations

Set 1 Set 2 Set 3 Set 4 Set 5 Set 6

Conditions at the first compression of the bubble

(R/R0 )max = 1.802 (R/R0 )max = 3.233 (R/R0 )max = 1.808 (R/R0 )max = 4.049 (R/R0 )max = 5.972 (R/R0 )max = 4.175
Pmax = 0.628 atm Pmax = 20.9 atm Pmax = 1.006 atm Pmax = 12.44 atm Pmax = 59.87 atm Pmax = 16.69 atm
Tmax = 397.4 K Tmax = 1634 K Tmax = 422.9 K Tmax = 1422 K Tmax = 2124 K Tmax = 1553 K
NW T = 7.806E + 013 NW T = 3.16E + 014 NW T = 7.142E + 013 NW T = 6.1E + 014 NW T = 1.17E + 014 NW T = 6.21E + 014

H2 O 1.0000 9.964E − 01 1.0000 9.9992E − 01 9.9509E − 01 9.998E − 01

H2 0 2.1588E − 04 0 4.9437E − 05 2.6889E − 03 1.2196E − 04
O2 0 9.5338E − 05 0 2.2678E − 05 1.0663E − 03 5.4758E − 05
OHQ 0 5.0471E − 05 0 8.1612E − 06 1.1175E − 03 2.4906E − 05
H 2 O2 0 1.9203E − 08 0 2.4748E − 09 6.9725E − 07 8.5422E − 09
HOOQ 0 2.154E − 08 0 1.9265E − 09 1.3975E − 06 8.3684E − 09
HQ 0 2.4792E − 07 0 1.6951E − 08 2.412E − 05 8.7812E − 08
OQ 0 4.5926E − 08 0 2.4026E − 09 6.8873E − 06 1.466E − 08
O3 0 3.1105E − 014 0 6.7337E − 016 2.3287E − 011 6.9351E − 015

Note: In the equilibrium composition, the number format is as follows: 9.964E − 01 should be read as: 9.964 × 10−1 . Species having equilibrium mole fraction
less than 10−20 have been ignored. Notations are as follows: (R/R0 )max = maximum size reached during radial motion, relative to the initial bubble radius;
Pmax = pressure in the bubble at the instance of first compression; Tmax = Temperature in the bubble at the instance of first compression; NW T = water
molecules trapped in the bubble at the instance of first compression.

Table 4
Simulation results for air bubble

Species Parameter set for simulations

Set 1 Set 2 Set 3 Set 4 Set 5 Set 6

Conditions at the first compression of the bubble

(R/R0 )max = 2.58 (R/R0 )max = 3.647 (R/R0 )max = 1.869 (R/R0 )max = 4.462 (R/R0 )max = 6.693 (R/R0 )max = 4.502
Pmax = 1.875 atm Pmax = 48.97 atm Pmax = 0.6557 atm Pmax = 13.19 atm Pmax = 51.49 atm Pmax = 18.16 atm
Tmax = 570.5 K Tmax = 1285 K Tmax = 326.5 K Tmax = 1108 K Tmax = 1740 K Tmax = 1218 K
NW T = 2.36E + 014 NW T = 5.815E + 014 NW T = 1.13E + 014 NW T = 9.16E + 014 NW T = 1.669E + 014 NW T = 8.77E + 014

H2 O 5.753E − 01 6.9049E − 01 3.4193E − 01 8.082E − 01 4.3394E − 01 8.3428E − 01

O2 4.247E − 01 3.095E − 01 6.5807E − 01 1.918E − 01 5.655E − 01 1.6571E − 01
HOOQ 2.4164E − 013 8.1928E − 07 0 7.0777E − 08 2.0887E − 05 2.3262E − 07
OHQ 1.2854E − 013 9.9506E − 06 0 1.1695E − 06 4.8145E − 04 5.1938E − 06
H2 O2 9.2251E − 014 1.3117E − 07 0 1.2411E − 08 1.647E − 06 4.0328E − 08
O3 8.0607E − 018 4.8979E − 010 0 1.4399E − 011 4.2684E − 08 5.5604E − 011
H2 1.1765E − 020 1.1294E − 08 0 7.9648E − 010 2.3769E − 06 8.6266E − 09
OQ 0 1.0708E − 08 0 3.6686E − 010 7.0376E − 06 3.4787E − 09
HQ 0 1.3246E − 011 0 2.3941E − 013 4.5444E − 08 5.9862E − 012

Note: The format for numbers and notations are same as Table 3. Species having equilibrium mole fraction less than 10−20 have been ignored. Species with
nitrogen as a constituent element have been ignored, as they are found in traces and contribute little in the context of induction of radical chemistry.

externally induced bubble increases with increasing upstream
pressure.
4.2. Effect of the nozzle length
The effect of nozzle length on the radial motion of a 200 m
bubble, for an upstream pressure of 1.25 bar, can be found by
comparing the results of simulations for parameter set 3 and 4.
It could be seen that the expansion of the bubble and the tem-
perature and pressure peaks reached in the following collapse
increase with nozzle length. The higher the length of the nozzle,
the larger the duration of the pressure variation driving bub-
ble motion. The values of pressure recovery time (trec ) given
in Table 2A confirms this. As discussed earlier, larger duration
of pressure variation results in higher expansion of the bubble.
Thus, the intensity of the subsequent collapse (driven by inertial
forces) increases. Higher amount of water vapor diffuses into
the bubble, and hence, the water vapor trapping increases. Over-
all, the production of radicals in the bubble, responsible for the
sonochemical effect increases with increasing nozzle length.
 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711
4.3. Effect of initial bubble radius
The effect of initial bubble radius on the radial motion of a
bubble, for an upstream pressure of 1 bar and nozzle length of
4 21 in can be found by comparing the results of simulations for
parameter set 5 and 6. It can be seen that both air and argon
bubbles of 100 m size undergo greater expansion, giving more
intense collapse. This is a manifestation of the initial pressure
in the bubble. The pressure inside the bubble, after its intro-
duction in the flow is P2 + 2/R0 , where P2 is the upstream
pressure and 2/R0 is the Laplace pressure, which depends on
surface tension of the liquid () and the initial radius (R0 ). For
both the bubbles of sizes 100 and 200 m, the parameters P2
and  are same, as both bubbles are introduced at the same point
at upstream of the nozzle and in the same liquid, i.e., water.
It needs to be mentioned that effect of surface tension works
against expansion, however, it is the same for bubble of both
sizes. Due to smaller initial radius (R0 ) the Laplace pressure
inside a 100 m bubble is higher. Both the bubbles are sub-
jected to same reduction in ambient pressure in the converging
section of the nozzle, in response to which they expand. Nev-
ertheless, the higher pressure inside the 100 m bubble drives
it to bigger growth than 200 m bubble. Therefore, a 100 m
bubble undergoes greater expansion than a 200 m bubble, un-
der otherwise similar conditions. Once again, the intensity of
the collapse is smaller for an air bubble than an argon bubble,
for reasons stated earlier.
5. Conclusion
The present work puts forth conceptual design of a new
kind of cavitation reactor, which uses externally induced bub-
bles as nuclei for cavitation and a converging–diverging nozzle
that creates the pressure variation needed for driving the radial
motion of these nuclei. As stated earlier, the principal advan-
tage of such a design is a simple flow geometry, which creates
well-defined pressure variation for driving bubble motion with
minimum pressure loss in the flow. Due to this feature, such
a system is very easy to design and scale up for large-scale
applications. In addition, this system offers good control over
an important parameter in cavitation reactor, i.e., rate of nucle-
ation. By manipulating the rate of gas sparging in the flow, one
can very easily control the rate of nucleation, and hence the
total cavitation intensity produced in the reactor. We have ap-
proached the problem with fundamental perspective, i.e., reck-
oning of the bubble dynamics with different combinations of
operating and design parameters. The results of the simulation
show that a transient motion of the bubbles can be obtained
with the converging–diverging nozzle, giving rise to radical for-
mation in the bubble that induce the sonochemical effect. The
temperature peaks attained in the bubble in a nozzle flow are
somewhat lower than those attained in an orifice flow, where
temperatures of the order of ∼ 5000 K are seen. The maxi-
mum temperature peak that was seen among all parameter sets
of simulations was 2124 K (in set 5). Thus, the cavitation in-
tensity generated by the bubbles in a nozzle flow is moderate,
which is suitable for conducting milder processes such as fatty
2709
oil hydrolysis and water disinfection. Moreover, the simulation
results also establish some definite trends in the sonochemical
effects with operating parameters, which can be used for opti-
mization of the reactor for a given application. One can propose
following strategies for the maximization of the sonochemical
effect produced in the reactor:
• Higher upstream pressures increase the sonochemical effects,
however, the cost of operation also rises, as pumps of higher
capacity are required.
• Use of a monatomic gas like argon for introduction of bub-
bles gives higher sonochemical effect. However, use of ar-
gon as bubbling gas increases operating costs. It needs to be
mentioned that although argon is more expensive than air, for
processes with high economic potential requiring higher cav-
itation intensities, argon may still be a cost-effective option.
• For a given upstream pressure, increasing the length of the
nozzle is a means of intensifying the sonochemical effects.
However, the flow stability criterion puts a limitation on this.
• Reducing the initial size of the bubble is perhaps the easiest
way for raising the sonochemical effect. For this, the gas dis-
tributor (usually a glass frit) should have very fine openings.
In addition to pore size in glass frit, the size of the bubbles
introduced in the flow depends on additional factors. Such
factors are the flow rate of gas and the pressure of gas in the
reservoir (or source) from which gas is withdrawn. Proper
control of these parameters can also reduce the initial size of
the bubbles introduced in the flow.
To conclude, although only a preliminary assessment of the new
design of hydrodynamic cavitation reactor, this work provides
a framework, which could form an origin for more rigorous
modeling and experimentation.
Notation
A dimensionless area of the nozzle
Ap cross-sectional area of the pipe
c velocity of sound in the liquid medium
Cp specific molecular heat capacity (at constant
pressure)
Cp,mix specific heat capacity at constant pressure of a
mixture of species
CV specific molecular heat capacity (at constant vol-
ume)
CV ,mix specific heat capacity at constant volume of a
mixture of species
Cw concentration of water molecules in the bubble
Cw0 initial concentration of water molecules in the
bubble
CwR concentration of water molecules at bubble in-
terface
dp diameter of the pipe
dt diameter of the nozzle throat
D diffusion coefficient of water vapor
E energy content of the bubble
2710 K. Sampath Kumar, V.S. Moholkar / Chemical Engineering Science 62 (2007) 2698 – 2711

f internal degrees of freedom for a species 1 , 2 molecular diameters of water and argon,
h van der Waals hard core radius respectively
hw specific molecular enthalpy of water a accommodation coefficient of water molecules
k Boltzmann constant  angular frequency of pressure variation
ldiff mass diffusion length
lth thermal diffusion length Acknowledgment
L length of the nozzle
m molecular mass of a species Authors gratefully acknowledge Dr. Rudiger Toegel (Physics
n concentration of a species (in molecule/m3 ) at of Fluids Group, Department of Physics, University of Twente,
bubble interface Netherlands) and Dr. Brian Storey (Department of Mechanical
NAr number of argon molecules in the bubble Engineering, Franklin W. Olin College of Engineering, USA)
NN2 number of nitrogen molecules in the bubble for their help in this work.
NO2 number of oxygen molecules in the bubble
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