Ultrasonics Sonochemistry 15 (2008) 65–77

www.elsevier.com/locate/ultsonch

Thermodynamic and kinetic considerations of nucleation

and stabilization of acoustic cavitation bubbles in water
Pratap S. Bapat, Aniruddha B. Pandit *

Chemical Engineering Department, University Institute of Chemical Technology, Matunga, Mumbai 400019, India

Received 17 July 2006; received in revised form 11 January 2007; accepted 14 January 2007
Available online 3 February 2007

Abstract

Qualitative explanation for a homogeneous nucleation of acoustic cavitation bubbles in the incompressible liquid water with simple
phenomenological approach has been provided via the concept of the desorbtion of the dissolved gas and the vaporization of local liquid
molecules. The liquid medium has been viewed as an ensemble of lattice structures. Validity of the lattice structure approach against the
Brownian motion of molecules in the liquid state has been discussed. Criterion based on probability for nucleus formation has been
defined for the vaporization of local liquid molecules. Energy need for the enthalpy of vaporization has been considered as an energy
criterion for the formation of a vaporous nucleus. Sound energy, thermal energy of the liquid bulk (Joule–Thomson effect) and free
energy of activation, which is associated with water molecules in the liquid state (Brownian motion) as per the modified Eyring’s kinetic
theory of liquid are considered as possible sources for the enthalpy of vaporization of water molecules forming a single unit lattice. The
classical nucleation theory has then been considered for expressing further growth of the vaporous nucleus against the surface energy
barrier. Effect of liquid property (temperature), and effect of an acoustic parameter (frequency) on an acoustic cavitation threshold pres-
sure have been discussed. Kinetics of nucleation has been considered.
 2007 Elsevier B.V. All rights reserved.

PACS: 82.60.Nh; 64.60.Qb; 05.60.Cd; 05.50.+q; 43.35.+d

Keywords: Vaporous nucleus; Thermodynamics; Kinetics; Acoustic cavitation; Threshold pressure; Cubic lattice model

1. Introduction
The possible sources of cavities considered so far in the
acoustic cavitation literature to answer its dynamic behav-
ior are pre-existing gas bubbles in the liquid and the forma-
tion of void in the liquid continuum due to the rupture in
the liquid medium [1] and the local vaporization of liquid
water [2,3]. The literature regarding the existence of these
possibilities has been explained in brief as follows. The lab-
oratory experiments are usually conducted in the standstill
water. Epstein and Plesset [4] derived the mathematical
expression for the time required for the complete dissolu-
*
Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614.
E-mail address: abp@udct.org (A.B. Pandit).
tion of the stand still gas bubbles in a pure liquid (saturated
with the gas) due to the surface tension phenomenon. It
requires few seconds (<10 s) for the complete dissolution
of air bubbles of micrometer size in the pure water.
The other possible source of the cavity is the formation
of a void, which would be created in water when the mol-
ecules are separated by more than the van der Waals dis-
tance (Re = 0.4 nm). The Blake threshold pressure for
such separation is about 1368 · 105 Pa [5]. However the
maximum tensile strength of water found by an experimen-
tal method by Briggs [6] is much lower i.e. in the range of
200 · 105–300 · 105 Pa even though all precautions had
been taken to purify the water to the maximum extent.
In the case of liquid water, which is saturated with air, it
is observed that negative pressure amplitude of 1 · 105–
2 · 105 Pa can form a cavity as reported in the review by

1350-4177/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2007.01.005
66 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
Brenner et al. [7]. The models are developed to explain the
pre-existence of the stable gas bubbles having internal pres-
sure either equal to or lower than the ambient pressure of
the liquid so that these may be stabilized against gaseous
diffusion due to the surface tension phenomenon. The
liquid considered in these models is impure i.e. either con-
taining solid crevices (crevice model) [1,8], or having dis-
solved contaminants exhibiting surfactant properties as
described by Yount in the Varying Permeability model
[9,10]. In the present work, the possibility of a gaseous
nuclei formation by desorbtion of the dissolved gas mole-
cules due to decrease in the liquid pressure has been
considered.
The most widely preferred theory for nucleation due to
the vapor–liquid phase transition is the classical nucleation
theory (hereafter referred as CNT) [2,11]. It accounts for
the requirement of energy for the formation of new surface.
During condensation, enthalpy would be given out from
the initial vapor phase. However during vaporization, an
external energy, equal to the latent heat of vaporization
must be provided to the liquid to change its phase to a
meta-stable state and then to a stable vapor phase. CNT
does not account this for nucleation by vaporization. The
latent heat of vaporization, DH at 20 C for water is
2454.3 kJ/kg [12]. The value of Gibbs free energy barrier
gbar at 20 C for water is 30 kJ/kg as reported by Vortmann
et al. [3]. In the present approach, we have considered the
stable phase change and not the dynamic phase change
(molecules in the liquid state in a cluster may momentarily
change their phase to the vapor state and then may come
back in the liquid state). Thus, DH which, we have used
as the energy barrier in our model is much larger than
the reported gbar based on the critical analysis of the graph
by Vortmann et al. [3] for the variation of Gibbs free
energy against specific volume during the phase change.
Following three possible sources of energy for the
enthalpy of vaporization have been considered in the pres-
ent approach:
a. Potential energy, which would be stored in the liquid
bulk during the propagation of an acoustic sound
energy.
b. Thermal energy of the liquid water bulk, which would
be available due to the Joule–Thomson effect.
c. Free energy of activation, which is associated with a
water molecule in the liquid state as per the Eyring’s
kinetic theory of liquid.
Referring to steam tables of water [12], one can conclude
that about 95% of the total enthalpy change during the
vaporization process of water is due to an increase in the
internal energy alone in the temperature range of 283–
343 K. The properties like internal energy and specific vol-
ume are the state functions, and do not depend upon a path
followed for the change of state. Hence the total energy
change can be considered as an independent of a path to
be followed i.e. either by the supply of heat or by the sup-
ply of sound (pressure) energy in its rarefaction region or
by the surrounding liquid bulk.
In the present approach, water has been viewed as a
cubic lattice structure to estimate the enthalpy of vaporiza-
tion per unit lattice. The cubic lattice approach to model
the liquid state is well known [13]. It is used for successful
prediction of transport phenomenon of liquid water, such
as thermal conductivity, by Bridgman [14] and to explain
the experimentally found relation between self-diffusion
coefficient and viscosity over a temperature range of 0–
55 C [15].
Now onwards we follow a terminology, such as ‘nucleus’
means the presence of a gas/vapor phase in the liquid,
which is not necessarily in mechanical equilibrium with
the surrounding liquid and the ‘cavity’ means a nucleus
in mechanical equilibrium with the surrounding liquid.
Following assumptions have been made:
a. Molecules have been considered to be spherical and
rigid. Nucleus, which would be formed due to desorb-
tion/vaporization, has also been assumed to be of
spherical shape.
b. Intra-molecular interactions are considered in terms
of thermodynamic properties like internal energy
and enthalpy.
c. Classical approach has been adopted which assumes
that the properties of a liquid at macroscopic level
equally hold true even at microscopic level.
Here a term ‘void’ means an empty space available
among the rigid molecules, which can only be occupied
by dissolved gas or vaporizing liquid due to its volume
expansion.
2. Lattice structure approach
In the simple cubic structure particles are placed at the
corners of cubes touching with each other as shown in
Fig. 1. Thus eight water molecules form one cubic lattice.
There is an empty space (void) enveloped by these eight
water molecules. Thus each cube contains one void space
in it. Each water molecule is participating in the formation
of eight adjacent cubes. Hence an effective
 number of par-
ticles (molecules) per unit cube is one ¼ 88 . Hence for the
simple cubic structure, the total numbers of cubes are equal
to the number of molecules present in the liquid bulk.
Fig. 1. Cubic lattice structure approach for the liquid bulk.
 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77 67

Hence the total numbers of unit lattices (void) present in Assume that the actual concentration of the dissolved gas is
the one mol of water are equal to the Avogadro’s number z percentage of its saturation concentration x at a given li-
of molecules. quid temperature. Due to the decrease in the local liquid
pressure Pl in the rarefaction region of the applied acoustic
3. Calculations and inferences wave, solubility of gas (air in the present case) decreases
linearly with decreasing pressure, according to Eq. (3b).
3.1. Formation of gaseous nucleus The required local pressurehat which the liquid wouldi be-
come saturated with gas is 100 z
P l0 þ P Tvap 1  100
z
.
It is difficult to completely degass liquid water. Moholkar Putting this expression for Pl in Eq. (2), the time instant
et al. [16] did one such attempt. They conducted an experi- tA at which the liquid water become super saturated has
ment with partially degassed demineralized water (total gas then been obtained with the use of Eq. (2) and is as follows:
content was below 2 ppm) in an ultrasound bath (driving  
1 P l0 ½100P l0 þP vap ð1100Þ
z z
frequency: 35 kHz, root mean square pressure amplitude: sin PA
1.1 · 105 Pa) to measure the acoustic cavitation intensity tA ¼ : ð4Þ
at various locations. They found that the variation of the 2pf
measured cavitation intensity with location, qualitatively
Thus, in the first half of the rarefaction region, after time
matched well with the calculated variation of the amplitude
instant tA, desorbtion of the dissolved gas would take
of shock wave, which would be emitted by a gas bubble
place. Due to the local desorbtion, there will exist a gas
based on the numerical simulations. This underlines the
phase concentration gradient in the liquid phase. Hence
importance of the consideration of desorbtion of dissolved
the dissolved gas molecules will diffuse towards the des-
gas and its effect in the cavitation phenomena.
orbed gas phase (first nucleus). Thus, the dissolved gas will
Formation of gaseous nucleus i.e. nucleus, which con-
try to appear as a separate gas phase by the diffusion phe-
sisting of gas molecules, in the liquid water bulk has been
nomenon until the saturation level at a new pressure is re-
considered. Consider a gas–liquid system in which two
established again.
phases are separated by a plane surface. Let symbol Pg
In the first half of the rarefaction region pressure
denotes the gas pressure. The saturation concentration of
decreases continuously to the minimum local pressure
the dissolved gas x at Pg is given by the Henry’s law [17]
(Pl0  PA). The corresponding time instant tC is 4f1 . Know-
and is as follows:
ing the instantaneous local pressure at these time instants
Pg i.e. at tA and at tC, we can calculate the average pressure
x¼ ; ð1Þ A tC
H P tavg by using the following general formula:
R tC
where unit of x is mole fraction of dissolved gas in the li- ðP l0  P A  sinð2pftÞÞdt
tA tC t
quid water, H is the Henry’s law constant at a given tem- P avg ¼ A
tC  tA
perature having units of Pascal of gas pressure per mol
fraction of dissolved gas in the liquid phase. P A ½cosð2pftC Þ  cosð2pftA Þ
¼ P l0 þ : ð5Þ
With the propagation of the acoustic wave at a fre- 2pf ðtC  tA Þ
quency f, having a pressure amplitude PA, the instanta- If this average pressure is below the vapor pressure then the
neous local pressure Pl in the liquid bulk changes as a average saturation concentration of the gas during this
sinusoidal function of time t, and is as follows: time period is to be taken as zero (near boiling condition).
P l ¼ P l0  P A  sinð2pftÞ; ð2Þ If the average pressure is above the vapor pressure then the
average saturation concentration of the gas has been found
where Pl0 is the initial liquid pressure at t = 0.
by the following equation, corresponding to the instanta-
In the rarefaction region of the acoustic wave, if the
neous local pressure:
local liquid pressure falls below the vapor pressure P Tvap
A tC
then the local liquid molecules will transform to vapor P tavg  P vap
A tC
xtavg ¼  ðx  0Þ: ð6Þ
phase (boiling). Hence at this condition the saturation sol- P l0  P vap
ubility of the gas has been taken as zero. Thus the satura-
tion solubility of the gas xl at a given temperature has been Let the symbol D indicates the diffusivity of the dissolved
assumed to be a linear function of the local liquid pressure gas. Hence the characteristic length l in the liquid medium
Pl and is as follows: through
p which the desorbtion will take place is equal to
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DðtA  tC Þ. Thus gas molecules in the hypothetical
xl ¼ x when P l ¼ P l0 ; ð3aÞ sphere (or cubic lattice) of radius l will tend to desorb.
x0 Hence the magnitude of total number of gas molecules n,
xl ¼  ðP l  P Tvap Þ when P Tvap 6 P l 6 P l0 ð3bÞ
P l0  P vap which would be desorbed in the given time interval of the
rarefaction region can be calculated as follows:
and  z  4
xl ¼ 0 when P l < P Tvap : ð3cÞ n¼ A t C
 x  xtavg  pl3  qw  N A ; ð7Þ
100 3
68 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
where qw represents the density of liquid water and NA is
the Avogadro’s number. As the size of the vaporous nu-
cleus has been calculated at the vapor pressure, the gaseous
nucleus size Rgas has also been calculated at the vapor pres-
sure for convenience as follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3nkT
Rgas ¼ 3 : ð8Þ
4pP Tvap
A typical acoustic source of intensity 10 W/cm2, which
radiates sound energy at a frequency of 20 kHz with a pres-
sure amplitude PA of 5.42 · 105 Pa, has been considered
for air–water system at initial pressure (Pl0) of
1.01325 · 105 Pa. The Henry’s law constant for the air–
water system is 7.81 GPa of liquid pressure/mol fraction
of dissolved air in an aqueous solution [17]. Diffusivity of
the dissolved air in the liquid water has been taken as
2 · 109 m2/s. (Calculations are done for the estimation
of Rair, but are not shown in the present article as they
are straight forward). At z = 100% and x = 1.3 ·
105 mole fraction of dissolved air, we have tA ¼ 0 s;
tC ¼ 1:25  105 s; P tavg
A tC
¼ 2:44  105 Pa; xtavg
A t C ¼ 0; l ¼
7 4 3
1:58  10 m; qw ¼ 5:56  10 mol=m ; n ¼ 7186; Rair ¼
121 nm. Thus, at 100% saturation condition, Rair works out
to be 121 nm. Fig. 2 represents the effect of the percentage-
dissolved air z on the radius of the gaseous nucleus Rair
formed at the vapor pressure of water at 303 K. As shown
in Fig. 2, Rair decreases with a decrease in the concentra-
tion of the dissolved air expressed as a function of percent-
age saturation at 303 K.
If we consider the effect of surface tension, then there
may be a possibility of coalescence of two or more gaseous
nuclei, which are separated only by a single layer of water
molecules to minimize the surface tension force.
The experimental study of Pandit and Davidson [18]
regarding hydrodynamics of the rupture of thin liquid film
has revealed that below the critical film thickness of
0.07 lm, the liquid film gets rupture naturally without
requirement of any external puncturing device.
Hence referring to the experimental work of Pandit and
Davidson [18], it is very likely that such two or more nuclei
formed in adjacent cubic lattices may coalesce spontane-
ously to produce relatively larger bubble (stable nucleus).
150
100
Rair (nm)
50
0
0 50 100
z
Fig. 2. Plot of Rair against z at 303 K. An acoustic source of intensity
10 W/cm2 having PA = 5.42 Pa and f = 20 kHz has been considered. Rair
is at the vapor pressure of water at 303 K. i.e. 4.23 · 104 Pa.
Recent experimental study of Lee et al. [19] using novel
capillary system demonstrated that with an increase in the
percentage-dissolved air in the liquid water, these exists an
increase in the total bubble volume (gas volume occupied
by uncollapsed or undissolved bubbles) due to the forma-
tion of bubbles and their subsequent coalescence. The coa-
lescence of air nuclei has been quantified later (Section 5).
3.2. Probability of nucleus formation in degassed water
In a real liquid, molecules are not stationary. There
exists a continuous migration of liquid molecules, which
is known as the Brownian motion.
Vaporous nucleus formation is possible only in the rar-
efaction region where the molecules, sitting at the corners
of a cubic lattice are pulled away simultaneously. Each lat-
tice unit is surrounded by other lattices, there has to be a
simultaneous motion of a set of lattices influenced by a suf-
ficient magnitude of the rarefaction pressure, which results
into a finite probability (significantly less than one) of the
nucleus formation.
In the cubic lattice structure, a molecule may vibrate in
the following possible directions as shown in Fig. 3:
a. Along three axes: Along any axis, a molecule can
vibrate in the two directions i.e. positive direction
(away from centre) and negative direction (towards
the centre). Hence the total directions are 6 (=2 · 3).
b. Along planes, which pass through two axes and those
are perpendicular to the third axis. For e.g., in XY
plane a molecule can vibrate in 4 diagonal directions.
There are three such planes, which are X  Y, X  Z,
and Y  Z. Hence the total possible directions are 12
(=4 · 3).
c. Along the diagonals of a three dimensional cube.
There are 8 such directions.
Hence the total directions for a molecular motion in the
cubic lattice structure are 26. However, only 7 directions
allow a molecule to migrate away from the other seven
molecules as shown in Fig. 3. Now, for the possible nucleus
formation, all the eight molecules forming a single lattice
unit must simultaneously move away from the center of
the unit lattice. Thus, the probability of this situation is
78 out of 268 i.e. 1 in 36,224 vibrations of an individual
Fig. 3. Possible directions for migration of a single liquid molecule in a
cubic lattice structure.
 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
molecule (or lattice). Thus one in 36,224 molecular move-
ments may actually lead to the formation of a homoge-
neous nucleation by the evaporation of the water
molecules provided the energy criterion is satisfied.
3.3. Energy criteria for the formation of vaporous nucleus
Energy of vaporization of water molecules forming one
unit lattice, DHlattice has now been calculated using thermo-
dynamic data available in the standard steam tables [12].
Various possible energy sources, discussed earlier have
been considered.
3.3.1. Enthalpy of vaporization per unit lattice
In this calculation it has been assumed that every mole-
cule is participating in the formation of eight adjacent lat-
tice units. Therefore the enthalpy of vaporization per unit
lattice, DHlattice at 303 K has been calculated as follows:
DH g mol
DH lattice ¼ ¼ 7:27  1020 J=void:
NA
Thus the enthalpy of vaporization per unit lattice in the
liquid water at 303 K is 7.27 · 1020 J.
The same calculation procedure has then been repeated
to calculate DHlattice at different temperatures T in the tem-
perature range of 283–343 K. DHlattice is found to decrease
from 7.405 · 1020 J at 283–6.975 · 1020 J at 343 K as
reported in Table 1.
In the following discussion, the considered sources of
energy have been quantitatively evaluated to satisfy the
 
69
An instantaneous power supplied by the acoustic source
is a function of time t and the location of the receiving
point with respect to the source, y. For the time being
the location has been considered to be adjacent to the
vibrating surface of the source (y = 0) as shown in Fig. 4
to neglect the pressure wave damping effect due to the med-
ium impedance on the acoustic energy as a function of dis-
tance. The actual receipt of the energy by one lattice,
located at a distance from the source will be significantly
less. The sound wave, which has been considered in the
present approach, is a simple harmonic plane wave. Hence,
one has to approximate the spherical nucleus, which would
be formed to the cylindrical form, such as the axis of the
cylinder is parallel to the direction of the propagation of
the sound wave. Hence a cylinder whose length lcylinder
and diameter dcylinder are same, and equal to the diameter
of the initial nucleus has been considered. As discussed
later (Section 3.4), the diameter of a vaporous nucleus is
12.34 nm at 303 K. Thus, at 303 K, the linear dimensions
ð9Þ of the hypothetical cylinder are equal to 12.34 nm. Hence,
the surface area of a flat side of the cylinder, Acylinder
through which the sound energy would be transmitted or
accepted is [=p · (dnucleus)2] 1.19 · 1016 m2.
Expression for the total potential energy stored, in the
cylinder during the rarefaction region i.e. from time t equal
to zero to sð¼ 2f1 ¼ 2:5  105 sÞ has been obtained as fol-
lows [20]:
 max 2
1 P th
P:E: ¼ lcylinder  Acylinder  qw  4p2 f 2
2 qw Cf
  

energy need for the vaporization per unit lattice: 1 sin 4pf s  Cy þ sin 4pf Cy
 sþ : ð11Þ
2 4pf
3.3.2. Acoustic irradiation as a possible source
The reported maximum threshold pressure by Briggs [6], Hence, the calculated total potential energy stored in the
P max
th in the degassed water for the stable cavity inception is
cylinder (Eq. (11)) in the rarefaction region of the acoustic
about 295 · 105 Pa. Hence the required intensity I of the sound wave is about 1.65 · 1022 J, which is about two or-
acoustic source at this threshold pressure has been calcu- ders of magnitude less than that required to form one nu-
lated as follows: cleus (7.27 · 1020 J/void) by evaporation. Thus, the sound
2
energy alone cannot be the source for the vaporization and
ðP max
th Þ ð295  105 Þ2 the growth of the cavity.
I¼ ¼
2qw C 2  1000  1:500  103
 3  108 W=m2 ¼ 3  104 W=cm2 : ð10Þ
Thus an acoustic source, which radiates sound energy with
Acoustic horn
intensity of 300 MW/m2 at a frequency f of 20 kHz, has
been considered in this typical case. Liquid water
Spherical
nucleus
Table 1
b coal and Pnucleation (CNT) for liquid water
Calculated values of DH lattice ; R
d Hypothetical
T P Tvap * DHlattice R Rcoal b coal
R Pnucleation Cylinder
(K) ðPaÞ (1020 J) (nm) (nm) ðnmÞ (Pa)
283 1227 7.405 9.12 13.13 8.68 1125
d d
293 2337 7.334 7.44 10.71 8.78 2113
303 4241 7.264 6.17 8.88 8.88 3779
323 12,340 7.121 4.41 6.35 9.06 10,690 Enlarged View
343 31,160 6.975 3.30 4.75 9.23 26,249
Fig. 4. Schematics of the location of the nucleus and its approximation in
*
[12]. the cylindrical form.
70 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77

3.3.3. Thermal energy of a liquid bulk as a possible source  23

6:023  1023
If a fluid is expanded adiabatically at a constant k0 ¼ 3  1:3805  1023  1:500  103
1:808  105
enthalpy H then its temperature drops down. This is
known as the Joule–Thomson effect; and aJT is defined as ¼ 0:6434 W=m K:
follows:
 
DT
aJT ¼ : ð12Þ Thus, the calculated thermal conductivity of liquid water at
DP H 303 K with the use of Eq. (13) is 0.6434 W/m K, which is in
The reported value of aJT for liquid water [21] is in the agreement with the measured value of 0.618 W/(m k) [23].
order of 108 K/Pa. The calculations of thermal conductivity at various temper-
In this section, the possibility of a surrounding liquid atures in the temperature range of 283–343 K have then
bulk as a source of energy supply for the vaporization been compared with the standard reported values [23].
has been explored. The temperature drop required between The difference between the calculated value and the re-
the unit lattice and the surrounding liquid bulk has been ported value is about 10%. This implies that lattice struc-
calculated as follows. Bridgman’s simple theory of energy ture approach appears to be valid.
transport in pure liquids has been taken into consideration. As shown schematically, in Fig. 5 cross-shaded circles
The theory has been explained in brief by Hirchfelder et al. represent two-dimensional view of the selected unit lattice.
[13] and by Bird et al. [14]. According to Bridgman’s the- Four molecules along a length (single shaded circle) are
ory, the expression for a thermal conductivity k 0 is as required to cover the unit lattice. Hence the total number
follows: of molecules required to cover the lattice in the three-
dimensional space are 64 (=43). It has been assumed that
 23
N the instantaneous energy requirement is provided in the
k0 ¼ 3  K  C; ð13Þ form of thermal energy. The thermal energy for vaporiza-
V
  tion is provided with the aid of instantaneous decrease in
where NV is the volume per molecule (cm3/molecule), K is the temperature of these 64 molecules from bulk tempera-
the Boltzman’s constant (1.38 · 1023 J/molecule) and C ture T to temperature Tinst. Hence the temperature of the
represents the velocity of sound in the liquid medium (m/ unit lattice and of the surrounding molecules will be at tem-
s). The velocity of sound increases with an increase in the perature Tinst at the time of vaporous nucleus formation.
acoustic frequency [13]. At lower frequencies (that is lower Due to the temperature difference between 64 molecules
compared to the characteristic frequency of liquid mole- and the remaining liquid molecules; heat transfer will then
cule) the velocity of sound is given by the expression take place. Temperature of the unit lattice at the time of
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi vaporous nucleus formation has been assumed to be at
C P oP 303 K. Specific heat of liquid water bulk at 303 K is
C¼ ; ð14Þ
C V oq T 4.174 · 103 J/kg K. Hence specific heat of a single water
molecule C Pmolecule in the liquid state is 1:247  1022
where the symbols CP and CV represents the specific heat at
constant pressure and at constant volume respectively. The
symbols P and q represent liquid pressure and liquid den-
sity respectively. h oq i
The data of isothermal compressibility xW ¼ q1 oP T
has been taken from Hodgman [22]. At temperature
303 K, the isothermal compressibility of the liquid water
xW is 4.46 · 1010 m2/N. Its density q is 995.7 kg/m3.
Hence
 
oP 1 m2
¼ ¼ 2:25  106 2 :
oq T ¼303 xw q s
Hence the velocity of sound C according to Eq. (14) has
been calculated as follows:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
C ¼ 1  2:25  106 ¼ 1:500  103 m=s:
Mass of one mol of water is 18 g. Hence its molar volume V
is equal to 1.808 · 105 m3/mol. The Avagadro number is
Fig. 5. Schematic of the energy transfer to the nuclei from the surround-
6.023 · 1023 molecules/mol. Hence the thermal conductiv- ing liquid bulk. Cross-shaded circle represents molecules of the nucleus.
ity of liquid water at 303 K has been calculated with the Single-shaded circle represents molecules covering the nucleus. Plain circle
use of Eq. (13) as follows: represents molecule of the liquid bulk.
 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77 71
 3

18
¼ 4:17410
6:0231026
J=molecule K. Hence the equation for the
energy balance is as follows:

DH lattice ¼ 64  C Pmolecule  ðT  T inst Þ: ð15Þ

DHlattice at 303 K is 7.27 · 1020 J. Hence the required

temperature difference (T  Tinst) is 9.1 K. Thus, if the ini-
tial liquid bulk temperature is at 312.1 K, then the vapori-
zation of a unit lattice will take place at 303 K provided the a δ
said temperature drop occurs due to the Joule–Thomson Fig. 6. Eyring’s model for the cubic lattice structure.
effect. The required temperature drop at different vaporiza-
tion temperatures (283–343 K) for the formation of a single adjoining ‘‘hole’’ and the molecules thus move in
nucleus is around 9 K. However as reported previously, the each of the Cartesian coordinate directions in jumps
Joule–Thomson coefficient for liquid water is of the order of length a at a frequency of k* per molecule where
of 108 K/Pa. Thus the theoretical pressure drop required k* is given by the rate equation
to create a temperature differential of 9 K is of the order KT RDGT
of 109 Pa (equivalent to an acoustic intensity of k ¼ e U ð16Þ
h
3.33 · 107 W/cm2), which is very large as compared to the
reported threshold pressure (200 · 105–300 · 105 Pa). where h is the Plank’s constant (6.624 · 1034 Js), K is
Hence the thermal energy (liquid enthalpy) alone as a the Boltzmann constant (1.38 · 1023 J/molecule
pffiffiffi K).
source energy for the enthalpy of vaporization of unit lat- For the cubic lattice structure, a is equal to 2 times
tice is insufficient, though at an acoustic intensity of 3 W/ the diameter of a molecule. Hence the ratio of d to a
cm2, a temperature differential of 3 · 103 K will be created is 0.5.
and may contribute to the overall vaporization process.
The free energy of activation can be calculated from the
3.3.4. Free energy of collision among molecules in the liquid viscosity data against temperature as follows. For a Newto-
state as a possible source nian fluid, the mathematical expression for the viscosity in
In the liquid state, molecules migrate continuously in the terms of ‘‘free energy of activation’’ after the correction
form of collisions with the surrounding molecules. Each suggested by Li and Chang [15] is as follows:
collision is associated with certain energy DE of collision.  2  
nxyz  nxy d hN A DG
There exist a finite number of collisions per second per l¼ exp ; ð17Þ
molecule for a given DE. If it so happen that 8 molecules
2 nxyz a Ve RU T
forming a unit lattice migrate away (Brownian motion) where Ve is the molar volume of the liquid phase, nxy repre-
from the center of the unit lattice, then there exist a possi- sents the total number of (closest) surrounding molecules
bility of vaporization provided the total energy of collisions in a plane and nxyz represents those in space. For the cubic
of 8 molecules (8 · DE) is greater than the earlier estimated lattice structure nxy is equal to 4 and nxyz is equal to 6.
heat of vaporization per unit void. To calculate the value of Hence Eq. (17) for the cubic lattice structure becomes
DE, kinetic theory of liquid developed by Eyring and co-  
1 hN A DG
workers [24] and later improved by Li and Chang [15] l¼ exp : ð18Þ
has been referred. 24 Ve RU T
Postulates of Eyring’s kinetic theory of liquid are as Thus, according to Eq. (18), viscosity changes exponen-
follows: tially with DG. After manipulation of the terms in Eq.
(18) we have
a. In a pure liquid at rest, the motion of the individual !
molecule is largely confined to vibrations of each l Ve 1 DG 1 DG 1
ln ¼ ln þ ¼ 3:178 þ : ð19Þ
molecule within a cage formed by its nearest neigh- hN A 24 RU T RU T
bors as shown in Fig. 6. The cage is represented by
the energy barrier of height NDGA where DG is referred Fig. 7 represents the variation in the left hand side term of
as molar ‘‘free energy of activation’’ and NA is the Eq. (19) against the reciprocal of temperature for liquid
Avogadro’s number. water to obtain the value of DG. The data has been taken
b. Liquid bulk is formed by the formation of layers of from Weast and Astle [25]. The  equation
 of a linear fit
liquid molecules. A distance of d separates these lay- le
for the liquid water is ln N A h ¼ 2:072  103 T 1 
V
ers from each other. In the simple cubic lattice struc-
ture, d is equal to p1ffiffi2 times the diameter of a molecule. 3:178. The regression coefficient of the linear fit is 0.98,
c. Further, Eyring had proposed that a liquid, at rest which indicates that the assumption of the cubic lattice
continually undergoes rearrangements in which one structure is indeed adequate. Hence, the numerical value
molecule at a time escapes from its ‘‘cage’’ into an of DG for the liquid water is 17.227 · 103(=2.072 ·
72 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77

6 Hence the mathematical expression for the number of

vibrations of a single molecule in this
 time period  as per
the Eyring’s theory is given by k   4f1  tnucleous . If these
4 vibrations are equal to or greater than the minimum num-
ber of vibrations required (36,224) for a possible formation
~
μV of a homogeneous nucleation then there is a possibility for
ln
N Ah nucleus inception irrespective of the applied external pres-
2 sure. Therefore the required condition is
 
 1
k   tnucleus P 36; 224: ð20Þ
4f
0
2 3 4 At 303 K, the value of k* has been calculated with the use
-1 -3 -1 of Eq. (16) as follows:
T (10 K )
1:38  1023  303 17:227103
Fig. 7. Hollow circles represent the variation of left hand side term of Eq. k ¼ e 8:314303 ¼ 6:77  109 Hz:
(19) with reciprocal of temperature T for liquid water for cubic lattice 6:624  1034
structure in the temperature range of 273–363 K. Black line presents a
linear trend. Thus, at 303 K, the value of k* is 6.77 GHz for the liquid
water. If we put tnucleus equal to zero in Eq. (20), then the
103 · RU) J/mol as per the cubic lattice structure approach. value of f at 303 K is obtained as follows:
 
Thus, free energy contained by a water molecule DG NA
is k 6:77  109
20 f ¼ ¼ ¼ 46:7 kHz:
2.86 · 10 J/molecule. Hence the total free energy associ- 4  36; 224 4  36; 224
ated with molecules is 22.88 · 1020 J which is about three
times that, required for the vaporization of a unit void Thus, at 303 K the value of f is 46.7 kHz, which represents
(DHlattice = 7.21 · 1020 J at 303 K). DHlattice is about the upper limit of frequency up to which Pnucleus should be
7 · 1020 J in the temperature range 283–343 K as shown independent of the acoustic frequency.
in Table 1. If we consider the energy conservation, then It has been reported [26] that the intensity for a vapor-
the free energy associated with eight molecules forming a ous nucleus formation is independent of the acoustic fre-
unit lattice during the Brownian motion in the liquid state quency below 10 kHz and then increases with an increase
is sufficient for the enthalpy of vaporization of three adja- in the acoustic frequency. The reported intensity [in terms
cent unit lattices into voids. These three lattices may then of pressure Pth using Eq. (10)] against the acoustic fre-
coalesce to form a single vaporous nucleus. quency has been shown in Fig. 8.
Thus the energy associated with Brownian motion of Local applied negative pressure pulls all the molecules
molecules in the liquid state is sufficient for the enthalpy apart from each other, favoring the possibility of simulta-
of vaporization of cubic lattices, provided neous movement of molecules away from each other. With
an increase in the acoustic frequency, number of collisions
a. All the eight molecules migrate away from the center per molecule in the first quarter will decrease. For example,
of the void and at the acoustic frequency of 400 kHz, the number of vibra-
b. the local liquid pressure is below the vapor pressure tions of a 
single molecule  in the first quarter of the acoustic
1 6:77109
at a given temperature. wave are ¼ 4  400103 4230, which is less than the mini-
mum required vibrations (36,224).
Let Pnucleus represents a local pressure at which a vapor- In the absence of an external acoustic field, it has been
ous nucleus tends to form. In the following discussion, the assumed that molecules in the liquid state vibrate ran-
reported effect of an acoustic frequency on Pnucleus [26] has domly. Thus, there is no preferential direction in which
been qualitatively explained based on the cubic lattice model.
1.E+08
3.3.4.1. Effect of an acoustic frequency. The possibility of
the formation of a homogeneous nucleus exists in the first 1.E+07
Pth (Pa)

quarter of the acoustic wave, when the local pressure con- 1.E+06
tinuously decreases below the vapor pressure. At the acous-
tic frequency f, let tnucleus represents the time instant at 1.E+05
which the local instantaneous pressure decreases to Pnucleus 1.E+04
at a given temperature T. Time instant at the end of the 1.E+01 1.E+04 1.E+07
first quarter of the acoustic wave is 4f1 . Thus the total time f (Hz)
period in the first quarter of the acoustic wavein which the  Fig. 8. Reported Variation of the threshold pressure Pth with an
local liquid pressure remains below Pnucleus is 4f1  tnucleus . ultrasonic frequency f [26].
 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
molecules will vibrate. However if the external acoustic
field is applied then the applied pressure will force the mol-
ecules to migrate in a particular fashion i.e. molecules will
be forced to migrate away from each other in the rarefac-
tion region. Hence the possibility of formation of nucleus
will increase. Thus the applied negative pressure amplitude
should increase the possibility of simultaneous migration of
molecules away from each other with an increasing fre-
quency. Hence as shown in Fig. 8, the reported trend [26]
of pressure, Pth increases with an increase in the applied
acoustic frequency above 10 kHz.
3.4. Estimation of an initial nucleus size of acoustic
cavitation bubbles in the degassed water
In the preceding section, an energy criterion for the
enthalpy of vaporization of a single cubic lattice (void)
has been satisfied with the cubic lattice model, hence we
now proceed to estimate its size. Formation of a nucleus
has been defined in this section followed by the estimation
of its size. Effect of the temperature of the bulk liquid on
the initial nucleus size has then been explored.
It has been found from the steam table that the vapor
state volume of one mol of water at 303 K is 0.59274 m3
at its vapor pressure (4.24 · 103 N/m2). Liquid state vol-
ume of one mol of water at 303 K is 1.8 · 105 m3 at its
vapor pressure. The difference between these two volumes
is the increase in the volume among the 6.023 · 1023 mole-
cules as a result of the vaporization process, which occurs
at/below the vapor pressure and at a given temperature.
It has been obtained as 0.59272 m3. As discussed in Section
2, the number of unit lattice (void) in the 6.023 · 1023 mol-
ecules for the simple cubic structure is equal to the Avoga-
dro’s number NA. Hence the volume of each unit lattice
after flashing (vaporization) of water molecules is simply
equal to 0:59274
NA
i.e. 9.84 · 1025 m3. This expanded single
lattice has been treated as an initial nucleus as shown in
Fig. 9. Hence an initial radius of the spherical nucleus is
6.17 nm at 303 K and at the vapor pressure (4.24 ·
103 N/m2) in the liquid water bulk, which is about 20 times
less than the size of the gaseous nucleus (121 nm at 303 K)
formed by desorbtion of dissolved gas molecules at initial
100% saturation condition. If we consider the energy anal-
ysis, then the radius of the vaporous nucleus after coales-
cence of three adjacent nuclei as discussed
p ffiffiffi in Section
3 using Blake formula as follows:
3.3.4 i.e. Rcoal at 303 K is 3R ¼ 1:44  6:17
109 Þ8:88 nm.
Unit lattice Unit lattice in
in liquid state
vapor state
Fig. 9. Increase in volume of unit lattice due to vaporization.
73
3.4.1. Effect of temperature of liquid water bulk
With an increase in the temperature, vapor pressure
increases and there is a decrease in the enthalpy of vapori-
zation and the specific vapor volume [12]. Calculations have
been repeated for different temperatures of liquid water
bulk, T to estimate the corresponding nucleus size Rcoal
formed by the evaporation of three unit lattices in the pure
degassed water at the corresponding vapor pressures
P Tvap . Rcoal decreases from 13.13 nm at 283 K ðP Tvap ¼
1227 N=m2 Þ to 4.75 nm at 343 K ðP Tvap ¼ 31160 N=m2 Þ as
shown in Table 1. Hence, if one wants to evaluate the effect
of temperature on the nucleus size then there should be a
common reference pressure. In the present case the vapor
3
pressure of water at 303 K ðP 303 2
vap ¼ 4:241  10 N=m Þ has
been considered as the reference pressure. Thus the nuclei
sizes Rcoal obtained at different temperatures T have been
corrected as follows. An ideal gas law has been considered.
Hence, the volume of the system (nucleus) is inversely pro-
portional to the local pressure. Hence the mathematical
expression for the corrected radius, R b coal of the spherical
nucleus is as follows:
sffiffiffiffiffiffiffiffiffi
PT
b coal ¼ 3 vap  Rcoal :
R ð21Þ
P 303
vap
b coal corresponding to dif-
The corrected new values of new R
ferent pressures at corresponding temperatures have been
reported in Table 1. With an increase in the liquid temper-
b coal increases marginally from
ature from 283 to 343 K, R
8.68 to 9.23 nm.
3.5. Calculation of the threshold pressure based on the lattice
model
So far we have considered the formation of a vaporous
nucleus i.e. a vapor phase, which do not have a mechanical
stability with the surrounding liquid. Now as already
defined, a cavity means a presence of vapor phase in a
spherical shape, which is in mechanical equilibrium with
the surrounding liquid. Hence the pressure inside the cavity
has to overcome the local pressure of the liquid and the
pressure due to the surface tension (r). The value of the
surface tension at 303 K is 0.072 N/m. Thus for the stable
b coal in the pure degassed
cavitation inception of radius R
water, threshold pressure PT has been calculated at 303 K
0:77  r 0:77  0:072
PT ¼ ¼ N=m2
b coal
R 8:88  109
¼ 62:13  105 N=m2 : ð22Þ
b coal
In the above calculation, corrected value of Rcoal i.e. R
has been used as per Eq. (14) to account for common ref-
erence vapor pressure at 303 K. Thus, the estimated theo-
retical Blake threshold pressure has been found to be
approximately 62 · 105 Pa.
With an increase in the temperature, surface tension
decreases. Following formula, which is mentioned by
74 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77

300 nucleus in the liquid medium. Now we have considered the

P T (10 Pa) Briggs [6] energy required for the formation of a new surface during
200 vaporization via classical nucleation theory approach.
5

Cubic lattice
100 model
4. Classical nucleation theory
0
270 300 330 360 Classical nucleation theory accounts for the requirement
T (K) of energy for the formation of a new surface of radius R
during the phase change due to the surface tension r
Fig. 10. Plot of PT against T for the degassed liquid water.
[2,11]. To fulfill this energy need partially; the initial phase
(i.e. vapor phase in case of condensation or liquid phase in
Carey [27] has been used to calculate the surface tension r case of vaporization) would first shift to meta-stable state
at different liquid temperature T. (super saturation) where excess free energy would be avail-
 1:256
  able. Let DF represents excess free energy per unit volume.
T T Hence the net gain in the free energy of the system DX can
r ¼ 235:8 1  1  0:625 1  ; ð23Þ
T cr T cr be represented as
4
where Tcr is the critical temperature of water in Kelvin DXðRÞ ¼  pR3 DF þ 4pR2 r: ð24Þ
3
(647.3 K).
Calculations have been done at different temperature val- Thus, the variation of DX with R attains maximum value at
ues in the range of 283–343 K to predict the threshold pres- 2r
sures for the cavitation inception. Fig. 10 shows the trend of R ¼  ðLaplace EquationÞ: ð25Þ
DF
the predicted threshold pressure PT for the cavitation incep-
tion in the degassed incompressible pure water against the A nucleus of critical size R* ensures that further growth of
temperature of the liquid water T using (Eqs. (21)–(23)). the nucleus will further decrease the difference between the
With an increase in the temperature (283–343 K), there is free energy available for a given volume of nucleus and the
an increase in R b coal and decrease in the surface tension. energy consumed in the formation of a surface.
Hence, with an increase in the temperature, the predicted From the lattice model approach, the coalescence
threshold pressure to form a single stable cavity also nucleus size at 303 K is 8.88 nm. Surface tension is
decreases. This prediction is qualitatively consistent with 0.0717 N/m. The value of DF has now been calculated
the reported experimental observation [6] over the temper- according to Eq. (26) to ensure its further growth
ature range (283–343 K) as shown in Fig. 10. The experi- 2r 2  0:0717
mentally observed threshold pressure is in the range of DF ¼ ¼ ¼ 16148648 J=m3 : ð26Þ
Rcoal 8:88  109
200 · 105–300 · 105 Pa as reported by Briggs [6]. Thus the
estimated value is much closer to the experimentally Let the degree of super saturation S is defined as
observed threshold pressure than the earlier estimation of P vap
S¼ ; ð27Þ
the cavitation threshold pressure (about 1367 · 105 Pa) P nucleation
based on the separation of water molecules by a distance
where Pvap is the co-existing pressure (vapor pressure) and
greater than the van der Waals distance. However the rate
Pnucleation is the actual local pressure in the vapor phase.
of decrease of the observed threshold pressure is greater
Considering the vapor phase as an ideal gas, the excess
in magnitude than that has been predicted in the present
free energy available per unit volume due to the given
mathematical model, which can be explained as follows.
degree of super saturation in the vapor phase at a given
With an increase in the temperature, number of collisions
temperature T can be expressed as follows:
of a molecule in its Brownian motion in the liquid state
per second i.e. k* for a given free energy of activation DG DF  RU T ql lnðSÞ; ð28Þ
increases exponentially as per Eq. (16). Hence there exists
where RU is the universal gas constant 8.314 J/mol K and ql
a possibility of simultaneous vaporization of three unit
represents molar density of liquid. The density of water at
lattices at two or more locations with an increase in the
303 K is 103 kg/m3 i.e. 106/18 g mol/m3. The degree of super
temperature. If only a single layer of water molecules
saturation has then been calculated as follows (Eq. (28)):
separates these locations then these units may combine to
form one vaporous nucleus. This effect will further lower DF 16148648
lnðSÞ ¼ ¼ ¼ 0:1153;
the predicted threshold pressure with an increase in the RU T ql 8:314  303  106
18
temperature. However in the present investigation this S ¼ 1:122:
probable event has not been considered.
P 4241
So far we have considered the probability consideration Hence P nucleation ¼ vap
S
¼ 1:122 ¼ 3779 N=m2 .
and the criterion of the external energy requirement for the Thus, in conclusion, when the actual local pressure,
enthalpy of vaporization for the formation of the vaporous Pnucleation falls to 3779 Pa at 303 K, the inception of vapor-
 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
ous nucleus of radius of 8.88 nm will take place according
to the energy balance for enthalpy of vaporization as per
lattice model and the nucleus will further grow as further
growth ensures the decrease in the difference between the
energy required for the formation of a new surface during
its growth and the free energy available of the vaporous
nucleus due to the super saturation in the vapor state,
according to CNT.
Table 1 reports the variation of local pressure Pnucleation
below the vapor pressure required for the vaporous nucleus
inception with its further growth with liquid temperature T.
5. Kinetics of homogeneous nucleation of acoustic cavitation
bubbles
In the following, the kinetics of nuclei formation based
on the cubic lattice model and the kinetics of nuclei stabil-
ization based on CNT have been discussed.
In the cubic lattice model, out of the possible 36,224
vibrations of molecules, one could favorably result into
the homogeneous nucleation (Section 3.2). Thus it can be
concluded that out of 36,224 molecules, one molecule can
undergo nucleation. One mol of water occupies 18 cm3.
Hence in 1 cm3 of water,
 the total numbers of water mole-
23
cules are ¼ 6:02310
18
3:346  1022 . As discussed in Section
3.3, the energy associated with the Brownian motion of
molecules in the liquid state is sufficient for the enthalpy
of vaporization of three cubic lattices. The symbol k*
stands for total number of vibrations of a molecule per sec-
ond during its Brownian motion. Hence the rate of forma-
tion of vaporous nucleus per second per cm3 of liquid water
r_ has been expressed as follows.
k
r_ ¼  3:346  1022 : ð29Þ
36; 224
At 303 K, the value of k* is 6.77 GHz for the liquid water
(Section 3.3.4). Hence the rate of nucleation at 303 K is
6.25 · 1027 events per cm3 per second (Cubic Lattice
Model).
The rate of stabilization of nucleus according to CNT is
as follows [2]:
 
DX
J ¼ J 0 exp ; ð30Þ
RU T
where J0 is the pre-exponential factor, RU is the Universal
gas constant [8.314 J/(mol K)], and DX* denotes the maxi-
mum free energy barrier to nucleation. The expressions for
J0 and DX* are given by Eqs. (31) and (32) respectively.
rffiffiffiffiffiffiffi 2 At 100% saturation, the mole fraction of dissolved air in
2r ðqgas Þ
J0  ; ð31Þ
pm ql
where r stands for surface tension, m represents mass of a
single molecule, qgas denotes density of gas phase, and ql
represents density of the liquid phase.
The expression for the free energy barrier, DX* is as
follows:
75
16pr3
DX ¼ : ð32Þ
½3ðRT ql ln SÞ2 
The molar density of the vapor phase has been calculated
according to an ideal gas law, i.e. qgas ¼ P nucleation
RT
.
Hence at a nucleation pressure of 3779 N/m2 at 303 K,
the molar density of the vapor phase is qgas ¼
3779
8:314303
¼ 1:5 mol=m3 . The molar density of liquid water
at 303 K is 5.56 · 104 mol/m3. The mass of a water molecule
is 2.98 · 1026 kg. Hence J0, and DX* have been calculated
with the use of Eqs. (31) and (32) respectively as follows:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2  0:0717 ð1:5Þ2
J0   ¼ 5  107 =ðm3 sÞ;
p  2:98  1026 5:56  104
16  p  ð0:0717Þ3
DX ¼ ¼ 2:368  014 J=mol:
½3ð8:314  303  5:56  104  0:1153Þ2 
Hence with the use of Eq. (30), J has been calculated as
follows:
 
2:368  1014
J ¼ 5  107  exp ¼ 5  107 =ðm3 sÞ:
8:314  303
Thus the rate of stabilization of vaporous nucleus accord-
ing to CNT is 5 · 107/(m3 s) i.e. 50 events per cm3 per
second.
Similar calculations have been done to obtain the rate of
stabilization of gas nuclei of size 121 nm generated at
303 K according to CNT. The mass of an air molecule
(pseudo element) = 4.79 · 1026 kg, z = 100%, r = 0.0717
N/m. Then the calculated values are as follows.
DF = 2.81 · 105 J/m3, S = 1.002, Pnucleation = 1.01123 ·
105 Pa, qair = 40.14 mol/m3, J0 = 9.76 · 1011/(m3 s),
19
DX* = 2.783 · 10 J/mol and J = 2.84 · 104/(cm3 S).
Thus, the rate of stabilization of gas nuclei of size
121 nm at 303 K is 2.84 · 104/(cm3 s) according to CNT.
However this rate is lower by three orders of magnitude
when compared to that of the experimental findings of
Naidu et al. [28] which is equal to 2.64 · 107/(cm3 s) for a
gas bubble of 2 lm. The radius 2 lm was selected [28]
based on the mathematical analysis of size that grows
explosively at the minimum pressure of liquid (Pl0–PA) as
described by Young [1]. Thus CNT is not able to predict
the rate of stabilization of nuclei for a cavitation
phenomenon.
In the following paragraph, a link between the present
approach and the model developed by Naidu et al. [28]
has been established via mass balance of dissolved air mol-
ecules per cm3. The likely coalescence rate of gas nuclei for
their stabilization has also been quantitatively considered.
water is 1.3 · 105 at 303 K. The density of liquid water is
3.349 · 1022 molecules/cm3. Hence the total number of dis-
solved air per cm3 are (=1.3 · 105 · 3.349 · 1022)
4.34 · 1017. Air molecules per nucleus are 7185 (Section
3
3.1). Hence
  the total number of gas nuclei per cm are
17 13
¼ 4:3410
7185
6:04  10 =cm3 . The initial partial pressure
of vapor in the cavity [28] was considered to be equal to
76 P.S. Bapat, A.B. Pandit / Ultrasonics Sonochemistry 15 (2008) 65–77
the vapor pressure (3168 Pa) at an operating temperature
of 298 K. For the mechanical equilibrium, the pressure
inside the bubble has to be 1.73 · 105 Pa. The volume of
the bubble is 3.35 · 1017 m3 (for radius of 2 lm). Hence
with the use of ideal gas law, the total number of air mol-
ecules are 1.38 · 109 per gaseous nuclei. Thus, total air
molecules present in the bubbles per cm3 of liquid are
(=1.38 · 109 · 2.64 · 107) 3.64 · 1016. This value is close
to the total dissolved air molecules (4.34 · 1017) per cm3
at 100% saturation. Thus it is confirmed that the desorbtion
of dissolved gas molecules is responsible for the formation of
gas nuclei. Hence by comparing gas molecules per nucleus
(7185) based on lattice model with gas molecules per
bubble of size 2 lm [28]we obtain  the rate of coalescence
9
of gas nuclei equal to ¼ 1:3810 1:9  105 =s. Thus 1.9 ·
7185
5
10 nuclei of radius 121 nm are likely to coalesce per second
to form a stable bubble of radius 2 lm at 303 K when water
is saturated with air.
Similarly, in the case of vaporous nuclei formation in
acoustic phenomenon, CNT may not be able to predict
the rate of stabilization correctly. Hence we can say that
the rate of formation and stabilization of vaporous nuclei
via coalescence may vary from 50 to 6.25 · 1025 per cm3
per second at 303 K, depending on the quality of the water
and other conditions.
6. Summary and conclusions
In the present investigation a phenomenological
approach to define a nucleus inception of acoustic cavita-
tion bubbles in the liquid water by either the desorbtion of
dissolved gas molecules or the vaporization of local liquid
molecules has been made. The energy criterion for the
enthalpy of local vaporization of water molecules and
the probability consideration in the Brownian motion in
the incompressible liquid bulk has been considered. A
simple approach of cubic lattice structure has been made
to quantify the local vaporization process in terms of unit
lattice and the molecular movement. The vaporous
nucleus has been said to form below the vapor pressure
for a given liquid temperature by the vaporization of eight
water molecules, which form a single unit lattice (void).
The classical nucleation theory has then been considered
to calculate the degree of super saturation, which would
be required in the vapor phase for the growth of the
vaporous nucleus against the energy requirement for the
formation of a new surface. The conclusions have been
summarized as follow:
1. At 100% saturation condition, radius of a gaseous
nucleus, Rair works out to be 121 nm at 303 K, at an
acoustic frequency of 20 kHz with a pressure amplitude
of 5.42 · 105 Pa. There exist 6.04 · 1013 nuclei of size
121 nm per cm3 of water at 303 K base on the mass bal-
ance of dissolved air. It is likely that about 1.9 · 105
nuclei per second per cm3 coalesce to form a stable
bubble of 2 lm based on the findings of Naidu et al.
[28].
2. The total free energy content by eight molecules of water
forming a unit lattice (void) in their Brownian motion
(22.88 · 1020 J) in the incompressible liquid state is suf-
ficient to overcome the enthalpy required for the vapor-
ization of three unit lattices (22 · 1020 J).
3. The predicted nucleus size, which formed by vaporiza-
tion of three unit lattices is in the range of 10 nm.
4. It has been found that the potential energy stored in the
unit lattice by the acoustic source in its rarefaction
region (1022 J) at an acoustic power of 3 · 104 W/
cm2 (at 20 kHz) is insufficient for the enthalpy of vapor-
ization of local water molecules.
5. It has been found that the thermal energy of the sur-
rounding liquid bulk of thickness of a single layer of
water molecules, which would be available due to tem-
perature drop during the pressure change in the rarefac-
tion cycle in the Joule–Thomson effect, is in short supply
of the required enthalpy of vaporization.
6. The predicted threshold pressure based on the nucleus
size required for a stable cavitation inception using the
Blake formula is of the order of 60 · 105 Pa, which is
close to the experimental observations [6].
7. The present approach qualitatively explains the decrease
in the threshold pressure with an increase in the liquid
temperature.
8. The explanation for the observed dependency of the
pressure, which is required for nucleus inception on
the acoustic frequency has also been provided.
9. The CNT is not able to predict the rate of stabilization
correctly. The rate of formation and stabilization of
vaporous nuclei via coalescence may vary from 50 to
6.25 · 1025 per cm3 per second at 303 K depending upon
the quality of water and condition of cavitation.
Acknowledgements
One of the authors (PSB) would like to acknowledge the
financial support provided by the Department of Science
and Technology, India.
References
[1] F.R. Young, Cavitation, McGraw-Hill Book Company, UK,
1989.
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