Chapter 1

Fundamentals of Acoustic Cavitation

in Sonochemistry

Jia Luo, Zhen Fang, Richard L. Smith, Jr. and Xinhua Qi

Abstract Acoustic cavitation is the main mechanism for reaction intensification

in sonochemistry. This chapter provides an overview of the dynamics, mechanisms
and theories of acoustic cavitation. Through mathematical simulation and exper-
imental observation, single bubble cavitation theory describes the radial growth,
oscillation and energy behavior of a single bubble in a low frequency acous-
tic field. In multibubble cavitation, the bubble dynamics and energy are greatly
influenced by neighboring bubbles. Many hypotheses, such as rectified diffusion,
bubble coalescence, concerted collapse and bubble cloud theory, and experiment
methods, are used to describe multibubble behavior and energy intensity. Factors
such as liquid properties, acoustic field parameters and heterogeneous character-
istics of reaction system influence acoustic cavitation. Adverse effects from het-
erogeneous characteristics on acoustic cavitation can be analyzed to improve the
efficiency of sonochemical reactors. The introduction of sonication into a chemical
system allows intensification of many reactions, however, proper design of acous-
tic equipment is needed to obtain reliable results.

Keywords Ultrasonic auxiliary · Acoustic cavitation · Bubble dynamics ·

Heterogeneous chemical system

J. Luo · Z. Fang (*)

Biomass Group, Key Laboratory of Tropical Plant Resources and Sustainable Use,
Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences,
Kunming, China
e-mail: [email protected]
R.L. Smith, Jr.
Research Center of Supercritical Fluid Technology, Tohoku University, Sendai, Japan
X. Qi
College of Environmental Science and Engineering, Nankai University, Tianjin, China

© Springer Science+Business Media Dordrecht 2015 3

Z. Fang et al. (eds.), Production of Biofuels and Chemicals with Ultrasound,
Biofuels and Biorefineries 4, DOI 10.1007/978-94-017-9624-8_1
4 J. Luo et al.

1.1 Ultrasound and Acoustic Cavitation

Ultrasound is a longitudinal pressure wave that has a wave frequency higher than
normal human hearing range. In acoustic science, the classification of a sound
wave is according to its oscillating frequency. Waves that have oscillating fre-
quencies from 0.001 to 10 Hz are referred to as infrasonic sound, and waves with
oscillating frequencies from 16 kHz and higher are referred to as ultrasonic sound
or ultrasound [1]. Table 1.1 lists some key parameters including the wavelength,
speed, frequency, amplitude, power, pressure, intensity of acoustic wave, acous-
tic characteristic impedance of medium material and their typical values in sono-
chemistry [1].
Compared with audible sound and other wave phenomena, ultrasound causes
many special physical or chemical effects in materials. Because of the high oscil-
lating frequency of liquid molecules in an ultrasonic field and the high viscosity
of the liquid medium compared with a gas, molecules absorb a large number of
energy from the propagating ultrasonic wave. As shown in Table 1.1 for the acous-
tic pressure, liquid reactants in ultrasonic field can have a high pressure differ-
ence relative to the hydrostatic pressure of fluid [2]. The high energy absorption
and high acoustic pressure make it possible for ultrasonic auxiliary to overcome
intermolecular interactions in a solvent, and produce numerous cavities, which
is referred to as acoustic cavitation. The formed cavities drain and accumulate
ultrasonic energy, and explosively release their energy by the collapse of cavi-
ties. Therefore, there are two main routes that ultrasound provides energy to liquid
reactants: (i) ultrasonic microstreaming (mechanical force) and (ii) acoustic cavi-
tation. However, only acoustic cavitation is believed to activate chemical reactions
with high energy intensity.
As shown in Table 1.1, ultrasound is used in power applications at low fre-
quencies of 20–40 kHz and at high acoustic power (>50 W), or it can be used in
nondestructive detection or measurement at frequencies above 1 MHz and low
acoustic power as commonly used in diagnostics, clinical medicine and biological
processing.
In this chapter, the fundamentals in ultrasound and acoustic cavitation are intro-
duced. The dynamics and influencing factors of cavitation bubbles are summa-
rized. The secondary effects of acoustic cavitation are introduced and discussed.
The knowledge may be useful in studying the intensification mechanism of sono-
chemical reaction of biomass materials. The authors would like to emphasize the
relationship between energy intensity and energy efficiency with sonication. The
ability of cavitating bubbles to focus and concentrate energy, forces and stresses is
the basic of phenomena for ultrasonic auxiliary of biomass-related reactions [3],
while the development of bioenergy requires attentions to special energy intensity
that could activate chemical species and possibly lower energy cost.
1 Fundamentals of Acoustic Cavitation in Sonochemistry 5

Table 1.1  Key parameters in acoustic science and typical parameter values for studies in sono-
chemistry [1]
Parameters (symbol, unit) Physical definition Typical values
Acoustic wavelength (λ, m) Distance between two 3.0–7.5 cm for power ultrasound
neighboring points that have in liquids
the same phase position in an 0.015–0.075 cm for measurement
acoustic wave
Acoustic speed (c, m/s) Acoustic propagation distance Air, 340 m/s
per unit time Liquid, 1,000–2,000 m/s
Solids, 3,000–6,000 m/s
Acoustic frequency (f, Hz) Vibration number per unit 20–40 kHz for power ultrasound
time in liquids
1–20 MHz for measurement
Acoustic amplitude (PA, m) Maximum distance of mass
point at the ultrasonic field
from its balance position
Acoustic power (P, W) Acoustic energy that passes Extremely high power (>1,000 W)
through one surface perpen- for cavitational erosion of solids
dicular to the propagating and metal working
direction per unit time
Optimum acoustic power High power (50–1,000 W) for
depends on sample, reactor ultrasound-assisted conventional
volume and processing needs thermochemical and biochemical
reactions
Low power (1–10 W) for
stimulating biological cells or for
promoting particle aggregation
with low cavitation
Acoustic pressure (Pa, Pa) Difference of dynamic 0.1–1 MPa for ultrasonic cleaner
force per area from its
static value, as the result
of the compressed zone
and rarefacted zone of fluid
formed with sound transport
Pa = PA sin(2πft), where t
refers to the propagating time
Acoustic intensity (I, W/m2) Average acoustic energy that
passes through a unit surface
perpendicular to the propagat-
ing direction per unit time
Vector I = P2A /(2ρc), where ρ
is the medium density
Acoustic characteristic Ratio of acoustic pressure to Gases, 1.1–5.5 × 102 kg/(m2 s)
impedance (Z, kg/(m2 s)) acoustic velocity at one mass Liquids, 0.7–3.2 × 106 kg/(m2 s)
point in the medium Nonmetals, 0.1–1.5 × 107 kg/
(m2 s)
Characteristic of the Metals, 1.0–10.4 × 107 kg/(m2 s)
transmitting medium. Z = ρc,
where ρ is the medium density
6 J. Luo et al.

1.2 Acoustic Cavitation

The energy content of ultrasonic microstreaming is relatively low due to the small
amplitude of the oscillation of fluid elements and it is generally insufficient to
induce chemical reaction in the medium. The wavenumber of ultrasound in liq-
uid is much larger than ultraviolet light, and the excitation of electrons in com-
pound molecules is not possible with sonication. Sonication does not result in the
resonance of chemical molecules or atoms like other methods such as microwave
or infrared radiation, because the oscillating frequency of ultrasound is on the
order of 104–105 Hz. As a result, acoustic cavitation, which could concentrate and
explosively release acoustic energy, is believed to be the dominant mechanism for
process intensification and chemical activation in sonochemical systems.

1.2.1 Dynamics and Energy of Single Bubble Cavitation

The complete process of acoustic cavitation consists of three steps [4, 5]:
1. Formation of cavitation nuclei. Figure 1.1 shows bubble formation, growth and
collapse phenomena for transient and steady cavitation. Negative and posi-
tive acoustic pressure act alternately on one point in the liquid medium in an
ultrasonic cycle with the propagation of ultrasound wave (Fig. 1.1). The nega-
tive acoustic pressure stretches the liquid medium apart to make a relatively
rarefacted zone. If the acoustic pressure is increased to a value that is higher
than certain intensity, the microscopic distance between the liquid molecules
becomes far enough to initiate cavity formation that contains solvent vapors or
dissolved gases. The minimum requirement for acoustic pressure to form a cav-
ity is called the Blake threshold, PB. If the vapor pressure in a bubble can be
ignored, then Eq. 1.1 results [5]:

1/ 2
(2σ/R0 )3

2 (1.1)
PB = P0 +
3 3(P0 + 2σ/R0 )

where P0 is the static pressure on the liquid, R0 is the initial radius of the
formed bubble, and 2σ/R0 is the surface tension of the assumed bubble when
it forms. Low surface tension and low static pressure on a liquid favors the for-
mation and growth of cavitation nuclei. The existence of impurities and hetero-
geneous crevices in liquids decrease the actual pressure threshold of cavitation
by reducing the surface tension. The Blake threshold value for untreated sol-
vents is about 1–10 % of that in ultrapure solvents [4]. The influence of impuri-
ties and heterogeneous crevices on nucleation is kinetic. Similarly to a catalyst,
the presence of surface defects lowers the free energy barriers separating the
metastable liquid state from the vapor phase, and modifies the nucleation
1 Fundamentals of Acoustic Cavitation in Sonochemistry 7

Fig. 1.1  Calculation results of bubble dynamics: a transient cavitation and b steady cavitation:
acoustic pressure, bubble temperature, microturbulence velocity, bubble radius, bubble pressure,
and shockwave amplitude (adapted with permission from [8], Copyright © 2012 Elsevier)

mechanism [6]. As a result, the nucleation rate on surface defects with simple
geometries can be increased by up to five orders of magnitude compared with
that of a flat hydrophobic surface [6]. The presence of surface defects has also
been found to affect the nucleation rate for non-condensable gas as dissolved in
liquids [6]. For bubble nucleation in solutions containing solid substances, the
contact angle of gas bubbles on the solid surface is a critical index to evaluate
the possibility of bubble nucleation. A small contact angle means a low energy
barrier for the nucleation. In recent research by Zhang et al. [7], it was pointed
out that the contact angle of gas bubbles on spherical surfaces could be remark-
ably reduced by several methods such as decreasing the surface tension of the
solution, by reducing the size of solid particles, or by changing the hydrophilic
surface of solid particles to that of a hydrophobic surface.
2. Growth (radial motion) of cavitation bubbles. The formed microbubble contin-
ually grows to a maximum bubble radius of about 2–150 μm until the end of
the negative acoustic pressure phase. The oscillating motion of cavitation bub-
ble can be described with the Rayleigh-Plesset equation [5]:
 
d 2 R 3 dR 2
   3γ  
1 2σ R0 2σ 4µ dR
R 2 + = P0 + − − − P∞ (1.2)
dt 2 dt ρ R0 R R R dt
8 J. Luo et al.

where R is the radius of bubble in motion, dR/dt is the velocity item of bubble
wall away from the bubble center, R0 is the initial radius of bubble, ρ and μ
are the density and viscosity of the liquid, γ refers to the specific heat ratio of
gas in bubble and the P0 and P∞ are the static pressure nearby bubble and at
infinite distance in the liquid. The terms on the left-hand side of the equation
represent the radial motion (expansion or compression) of the bubble wall. On
the right-hand side of the equation, the first term shows the pressure variation
in the bubble, while the second and third terms are the surface tension and the
viscous stresses at the bubble surface, respectively. Equation 1.2 is based on
the assumption that the motion of a bubble is adiabatic and that the liquid is
incompressible [4]. The mass and heat transfer between the bubble and the sur-
roundings is not considered in Eq. 1.2. It is assumed that no chemical reaction
or physical changes occur and that there are no temperature, density or pressure
gradients in cavitating bubble.
3. Collapse or the next oscillation of bubbles. Positive acoustic pressure phase
comes after the negative pressure phase (Fig. 1.1), and under its influence, the
cavitation bubble undergoes contraction. The time required for the bubble to
contract is about 25–0.5 μs, which is half of the reciprocal of ultrasound fre-
quency. According to the literature [9], the oscillating frequency of a bubble in
a liquid, fb, increases with contraction of the bubble radius, R:

1/
2
 
1 3γ 2σ (1.3)
fb = P0 +
2πR ρ R

where ρ is liquid density, γ and 2σ/R are the gas specific heat ratio and sur-
face tension in the bubble and P0 is the static pressure. If the resonant fre-
quency of a bubble, fb, is smaller than the frequency of ultrasonic field, fa, at
the end of the positive acoustic pressure phase, the bubble survives and turns
to growth in a new ultrasonic cycle. The radial motion of the cavitation bub-
ble can be repeated for several acoustic cycles, and is called as steady cavita-
tion (Fig. 1.1b). However, if fb ≥ fa, the bubbles will collapse quickly in several
nanoseconds, and this is called as transient cavitation (Fig. 1.1a). Fragments
generated during the collapse of the parent bubble may become new nuclei for
subsequent cavitation phenomena. Steady and transient cavitation are both pre-
sent in most sonochemical systems, although the properties of the liquid may
favor one type of cavitation.
During the transient collapse of a bubble, work is done by the liquid such that fluid
elements impart energy to the bubble, thus raising its temperature and pressure.
The energy intensity of the cavitation bubble collapse is proportional to the com-
pression ratio of the bubble at the point of minimum radius during radial motion.
At the instance of bubble collapse, energy is released that does not have time to
be transferred to the surroundings and therefore local hotspots are produced [10,
11]. These local hotspots have extremely high temperatures (ca. 5,000 °C) and
1 Fundamentals of Acoustic Cavitation in Sonochemistry 9

Fig. 1.2  Range of duration time, pressure and energy for various energy chemistries (reprinted
with permission from [11], Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim)

pressures (ca. 100 MPa) in its interior, and causes very high rates of local heat-
ing and cooling (>109 °C/s). The energy density of acoustic cavitation can be on
the order of 1015 W/cm3, while the rated acoustic power density used in common
sonochemical reactors is 10−2–10 W/cm3 [12]. Acoustic cavitation also produces
high intensity shockwave and violent flowing of localized liquid.
In Fig. 1.2, the average energy of acoustic cavitation (about 0.1–1 eV) is much
higher than that in conventional heating, so that breaking most of chemical bonds
is possible. However, this energy is not enough for plasma ionization of volatile
molecules and photon production in bubbles. Suslick et al. [13, 14] observed very
strong Ar atomic excitation in the sonication of 95 wt% sulfuric acid solution at
20 kHz at ambient temperature under an Ar atmosphere. The emission temperature
of Ar excitation in bubble was estimated at about 8,000 °C. However, the thermal
excitation of Ar atom needed very high energy of >13 eV, and thus Ar atom could
not be thermally excited at 8,000 °C, which shows that the distribution of tempera-
ture and pressure in a bubble is not uniform. Figure 1.3 shows the physical struc-
ture of a bubble and the active zones for sonochemistry. Optically opaque plasma
probably exists at the core of a collapsing bubble at extreme conditions, and the
collision of higher energy electrons in this plasma zone is believed to result in the
excitation of an Ar atom. Spectral lines of Ar excitation are emitted just on the
outer zone of the plasma ionization (emissive shell) and can be detected by ultravi-
olet-visible spectroscopy [14]. The emissive shell is optically transparent and has a
temperature that is much lower than the plasma zone.
On the other hand, the energy intensity of bubbles is also influenced by the
mass and heat transfer of the surrounding liquid. It is believed that the vapor or gas
10 J. Luo et al.

Fig. 1.3  Physical structure of collapsing bubble and active zones for sonochemistry (adapted
with permission from [14], Copyright © 2011 Elsevier)

in the cavity can not escape into the surroundings before bubble collapse occurs.
However, the evaporation of liquid molecules at the interface between bubbles
and surroundings is possible and materials flowing into the bubbles can change
the vapor composition in a bubble. Dissociation and chemical reactions of volatile
molecules in the bubble can occur and this will consume the energy of the bubble
and reduce its energy release when it collapses. For example, sonication in alcohol
solution under Ar atmosphere at the frequencies of 20, 363 and 1,056 kHz gives
contradictory results [15]. Much less energy is released in a high frequency acous-
tic field of 1,056 kHz than at low frequencies, which is determined by the volume
change of bubbles when bubbles collapse. However, the calculated temperature of
the cavitation bubbles has the following order of high to low according to frequen-
cies of 1,056 > 363 > 20 kHz. It is highly possible that the evaporation of sol-
vent in the acoustic field of 20 kHz is more than that at 1,056 kHz, because of the
longer acoustic cycle and larger bubble size during the radial motion of bubbles
under sonication at 20 kHz.
Therefore, it is necessary to modify the Rayleigh-Plesset equation (Eq. 1.2),
because Eq. 1.2 deals with slow bubble motions, and many of the assumptions on
which Eq. 1.2 is based are invalid at the time of rapid collapse of bubbles [16].
Equation 1.2 does not take mass transfer, heat transfer, chemical reactions, non-
equilibrium phase changes and non-uniform pressures in the bubble interior into
account, so that modeling results have large deviations from their true values.
Boundary layer approximation on the basis of physical observations allows simpli-
fication of the theory.
1 Fundamentals of Acoustic Cavitation in Sonochemistry 11

For example, considering the compressibility of liquid and the acoustic attenu-
ation, the bubble motion can be described by the Keller-Miksis equation (Eq. 1.4)
[17, 18]:

dR/dt d 2 R 3 dR/dt dR 2
 
(1 − )R 2 + (1 − )
c dt 2 3c dt
  
1 dR/dt   R dPb 2σ 4µ dR
= (1 + ) Pb − (Pam − PA sin 2πft) + − −
ρ c c dt R R dt
(1.4)
where R is the radius of bubble in motion, dR/dt is the velocity item of bubble
wall away from the bubble center, ρ is the liquid density, μ is the dynamic vis-
cosity of the liquid (μ = ρν, ν is kinematic viscosity), and the c, f and PA are the
speed, frequency and pressure amplitude of the sound wave in liquid, respectively.
In Eq. 1.4, 2σ/R is the surface tension of the bubble according to the liquid tem-
perature, Pam is the ambient pressure (1 atm), Pb is the pressure inside the bubble,
and its time derivative is given by a van der Waals type equation of state as Eq. 1.5
[17, 18]:
Ntot (t)kTb
Pg (t) =
(1.5)
 3 
4π
(R(t))3 − Req (t)/8.86

3

In Eq. 1.5, k is the Boltzmann constant, Ntot is the total number of vapor molecules
in the bubble due to the condensation and evaporation, Tb is the temperature of
bubble contents and Req is the equilibrium radius of the bubble.
Other important parameters for numerical simulation of bubble motion are
the mass diffusion and non-equilibrium phase change of water vapor during the
sonication in water. In 2000, Storey and Szeri [16, 19] proposed a two-step pro-
cess that consisted of the diffusion of vapor molecule to the bubble wall and the
condensation of vapor at the bubble wall, along with three important time scales,
namely, the time scale of bubble dynamics (tosc), the time scale of mass diffusion
(tdif) and the time scale of condensation (tcond) as follows:
R
tosc =
|dR/dt|
R2 1
tdif = ReSc M ≈ ReSc √ , Re = ρ0 R0 v0 /µ0 , Sc = µ0 /ρ0 Davg
DH2 O R Tb
 (1.6)
R 2πMH2 O
tcond =
σ 9M0 T0

where Tb is the temperature of the bubble, DH M

2O
is the diffusion coefficient of
water vapor in the gas mixture, Re and Sc are Reynolds number and Schmidt num-
ber, respectively. In Eq. 1.6, ρ0, R0, v0 and μ0 are the initial values of liquid den-
sity, bubble radius, bubble wall velocity and gas viscosity, respectively. Davg is the
12 J. Luo et al.

average binary coefficient matrix of the diffusion coefficients of vapor mixture,

which is dimensionless. T0 is the temperature of the bubble interface and the MH2 O
and M0 are the molecular mass of water and the initial molecular mass of the bub-
ble contents, respectively.

tosc ≫ tdif, tcond, so that bubble motion is slow enough to allow the completion of
For mass diffusion of water vapor, in the earlier phase of bubble collapse,

one cycle of mass transfer between liquid and bubble interior, which results in uni-

tosc ≪ tdif, the bubble motion is so rapid that the water vapor has insufficient time
form bubble composition [18, 19]. Then, with the acceleration of the bubble wall,

to diffuse to the bubble wall that results in nearly unchanged composition of vapor

For condensation of water vapor, if tosc ≫ tcond, the condensation is in quasi-

content in the bubble [18, 19].

equilibrium with respect to the bubble motion. If tosc ≪ tcond, the phase change
will be non-equilibrium, which results in the entrapment of water molecules in the

tosc ≪ tdif is reached well before tosc ≪ tcond during bubble collapse and so the
bubble [18, 19]. However, Storey and Szeri [19] demonstrated that the condition

slow mass diffusion is responsible for trapping water vapor in the bubble.
Actually, during bubble oscillation, the surface temperature of the bubble exceeds
the temperature of bulk water only for a very brief moment [17, 18]. Therefore, the
bubble is divided into two parts, a “cold” boundary layer in thermal equilibrium
with liquid and an eventually hot homogeneous core. Based on this assumption, the
instantaneous diffusive penetration depth ldif is taken to be Eq. 1.7 [17, 18]:

ldif = Dtosc (1.7)

where D is the diffusion coefficient.

The analysis [17] shows that the penetration depth exceeds the bubble radius
(ldif ≥ R) during the expansion and a major part of the afterbounce in bubble
motion, and the total volume of bubble interior is in equilibrium with the liq-
uid. Since ldif is only 0.01R during bubble collapse, this implies that the thick-
ness of the boundary layer is negligible compared with the total bubble volume.
Therefore, the bubble can be regarded as being homogeneous in both cases, and
then the rate of change of water molecules in the bubble (NH2 O ) when the velocity
of the bubble wall is non-zero is given by Eq. 1.8 as:
 
dNH2 O 2 ∂CH2 O 2 CH2 O,eq − CH2 O
= 4πR D |r=R ≈ 4πR D (1.8)
dt ∂r ldif

where CH2 O and CH2 O,eq are the actual concentrations of water molecules in the
bubble core and the equilibrium concentration of water molecules at bubble wall,
respectively. The CH2 O,eq is calculated from the vapor pressure of water at bulk
temperature (Tl).
At the instant that the bubble stops growing, the velocity of the bubble wall is
zero, and the upper limit of the diffusion length can be calculated [17, 18]:
1 Fundamentals of Acoustic Cavitation in Sonochemistry 13

 R
ldif = min( Dtosc , ) (1.9)
π
For diffusion of heat in analogy with diffusion of mass, in the earlier phases of
bubble collapse when the time scale of bubble oscillation is longer than that for
heat transfer, sufficient heat transfer helps to keep the bubble interior at ambient
liquid temperature, while during bubble collapse, the bubble motion is so rapid
that bubble collapse behaves nearly adiabatically with negligible outflow of bub-
ble energy [19]. Equation 1.10 provides a method to estimate the rate of heat loss
across a bubble wall during its motion [17, 18]:
  
dQ 2 T0 − T R Rκ
= 4πR tc , lth = min( , ),
dt lth π |dR/dt|
n (1.10)
tc 
κ= , ρmix Cp, mix = ρi Cpi
ρmix Cp, mix
i=1

where λtc is the thermal conductivity of bubble contents and T0 is the temperature
of the cold bubble surface that is nearly the same with the temperature in the liq-
uid. In Eq. 1.10, lth is the thermal diffusion length, κ is the thermal diffusivity and
terms ρi and Cpi are the density and molecular specific heat of compound i, respec-
tively. The ρmix and Cp,mix in Eq. 1.10 are the density and molecular specific heat
of the vapor mixture in the bubble, respectively.
The overall energy balance for the bubble as an open system can be written as
Eq. 1.11 [18]:
dE dQ dW dNH2 O
= − + h H2 O (1.11)
dt dt dt dt
where dW/dt refers to the work done by the bubble. The enthalpy per water mol-
ecule that condenses at the cold bubble surface is given by hH2 O = 4kT0, where k
is the Boltzmann constant. Equation 1.11 can be rewritten as [17, 18]:
dT dQ dV   dNH2 O
Cv,mix = − Pi + hH2 O − UH2 O
dt dt dt  dt 
∂E  θi T
UH2 O = = NH2 O kT 3 +
∂NH2 O exp (θi /T ) − 1 (1.12)
n
Cv,mix = Cv,i Ni
i=1
where UH2 O is the internal energy, namely, the specific energy of water molecules
in the bubble, Pi is the pressure in the bubble interior, θi is the characteristic vibra-
tional temperature of species i, Ni is the number of molecules of component i and
Cv,i and Cv,mix are the specific heats of individual component i and the mixture,
respectively.
14 J. Luo et al.

Equation 1.12 can be used to estimate the temperature change of a bubble dur-
ing its motion, and it gives better results in the numerical simulation of the sono-
chemical phenomena [17].
In summary, cavitation behavior of a single bubble under a high intensity ultra-
sonic field has been discussed along with fundamental relationships. Information
on the formation, growth, collapse and energy change of single bubble as the
result of certain ultrasonic field parameters in a sonochemical reactor has been
highlighted. By solving related mathematical equations, the motion and energy
behavior of a single bubble can be estimated theoretically. By trapping a single
bubble of gas in partially degassed liquid by a standing acoustic wave and then
driving it into highly nonlinear oscillation, single bubble cavitation can be realized
and studied in the laboratory [20], which demonstrates that cavitation takes place
when the acoustic intensity is higher than the Blake threshold, and it provides
much higher energy intensity than conventional acoustic streaming. The energy
intensity of cavitation bubble depends on the compression ratio of bubble radius
and also the net heat capacity of the bubble content. However, the entrapment of
solvent vapor in the bubble at the moment of collapse consumes the heat capac-
ity of the bubble through evaporation, which lowers the temperature attained at
the moment of minimum radius during collapse. Moreover, dissociation of solvent
vapor mainly involves endothermic reactions that further consume energy and con-
tribute to the lowering of the peak temperature attained at collapse.

1.2.2 Multibubble Cavitation

In an actual sonochemical reaction, there are numerous active bubbles (ca. 104 bub-
bles/1 mL water) for sonication at 20 kHz [2]. Bubbles at different positions of
acoustic field follow different cavitation behavior and have different cavitation
energy due to spatial diversity of the acoustic pressure intensity. Bubble behavior
is influenced not only by the acoustic field, but also by the cavitation behavior of
neighboring bubbles. As a result, multibubble cavitation shows statistical results of
cavitation behavior and gives rise to the interactions between bubbles.
In multibubble cavitation, the intensity and efficiency of acoustic cavitation
is determined by the number density of effective bubbles in the liquid. Rectified
diffusion, bubble coalescence and concerted collapse influence the behavior of
bubbles.
Rectified diffusion. In acoustic cavitation, two possibilities exist for the newly
formed bubble nuclei—dissolution in the liquid phase if the ultrasonic intensity
is below a threshold value, or growth to a larger size under the action of nega-
tive acoustic pressure. If the size of the bubble expands to over a critical (reso-
nance) size, the bubbles will quickly collapse in the following positive acoustic
pressure stage, which initiates sonochemical reactions. However, several or tens of
acoustic cycles may be necessary for a significant number of bubbles to reach the
critical size (Fig. 1.4) [21]. Rectified diffusion is the main way to enlarge the sizes
1 Fundamentals of Acoustic Cavitation in Sonochemistry 15

of bubbles to a critical size, whether in single bubble cavitation or in multibub-

ble cavitation. Rectified diffusion refers to the unequal mass transfer through the
cavitation bubble wall in an acoustic cycle. In the expansion phase of bubbles, gas
concentration in the bubbles decrease, which drives the mass transfer from bulk
liquid to bubble interior. During the shrinkage of bubbles, materials in the bubbles
diffuse out of the bubbles. The expansion process of bubbles is relatively slow,
while shrinkage of bubbles is rapid. In bubble expansion, the surface area of the
bubble is much higher than that during shrinkage. Volumetric work done by the
shrinkage of bubble is converted to the evaporation heat of liquid molecules at the
bubble/liquid boundary, namely more liquid molecules transform into vapor con-
tent of the bubble. Since materials flowing into the bubble are more than materials
flowing out in the acoustic cycles, net growth of cavitation bubbles occurs [21].
Bubble coalescence. Compared with the slow progress of rectified diffusion,
bubble coalescence can be regarded as a rapid progress in which bubbles grow to
the critical size. Bremond et al. [22] used photography that showed the coalescence
of two bubbles subjected to a negative pressure of −2 MPa. The work demonstrated
that if the distance of two bubbles is in the range for weak interaction (400 μm for
instance), collapse of the two bubbles will be delayed due to the partially shielding
of acoustic pressure by each other, but the coalescence would not occur. However,
if the two bubbles are initially closer to each other (ca. 200 μm), or if the intensity
of negative pressure increases, the two bubbles will lose their spherical shape and
join to form a single bubble. The significant interaction of cavitating bubbles with
their neighbors is governed by secondary Bjerknes forces derived from the nonlin-
ear oscillations of bubbles [23, 24]. A threshold distance exists for the merging of
bubbles. The secondary Bjerknes forces become dominant and attract two bubbles
to move towards each other only when the distance of the two bubbles is within a
threshold value [23]. High acoustic pressure accelerates the approach and merging
of bubbles. The threshold distance is 200 μm when the acoustic pressure is 10 kPa,
while it increases to 500 μm when the acoustic pressure is 40 kPa [23]. Bubble
interactions reversely affect the nonlinear motions of each bubble and thus influ-
ences cavitation phenomena and sonochemical yields [24].
An interesting work on the experimentally observation and control of bubble
coalescence was performed by Ashokkumar [15] and Ashokkumar et al. [21].
They used pulse ultrasound instead of continuous ultrasound. The growth of bub-
bles in the measuring system was stimulated when the ultrasound was applied,
however, during the off time, some small bubbles became dissolved in the liquid,
while others that had sizes large enough to live through the pulse off period, con-
tinued to grow in the next acoustic pulse. As mentioned before, most bubbles need
several or tens of acoustic cycles to reach the critical size, which is also referred
to as an “induction period” for the achievement of steady cavitation. As shown in
Fig. 1.4b, the number of acoustic pulses required for steady cavitation in water
under a pulse ultrasonic field at 515 kHz is about 10, while with the addition of
surfactants—methanol (Fig. 1.4c) and sodium dodecyl sulfonate (SDS, Fig. 1.4d),
the number of acoustic pulses increases to about 20 and 40, respectively. The
addition of surfactants seems to change the surface properties of the bubbles, and
16 J. Luo et al.

Fig. 1.4  Bubble growth in surfactant solution under sonication: a bubble growth as the function
of time in water and sodium dodecyl sulfonate (SDS) solution at acoustic pressure of ~0.022 MPa
and frequency of ~22 kHz; b sonoluminescence (SL) intensity as the function of acoustic pulse
number in water under pulse ultrasonic field at 515 kHz; c SL intensity as the function of acous-
tic pulse number in 1 M aqueous methanol solution under pulse ultrasonic field at 515 kHz; d SL
intensity as the function of acoustic pulse number in 0.75 mM aqueous SDS solution under pulse
ultrasonic field at 515 kHz (adapted with permission from [21], Copyright © 2007 Elsevier)

hinders coalescence of small bubbles to larger ones. As a result, the growth of bub-
bles through bubble coalescence requires more sonication time or more acoustic
pulses in surfactant solutions. On the other hand, for high concentration of SDS,
the adsorption of SDS at the bubble/liquid interface is thought to restrict outflow
of chemical matters in the bubbles during bubble shrinkage. Therefore, the growth
of bubbles via rectified diffusion route is promoted and accelerated with the addi-
tion of surfactants.
Concerted collapse. In a bubble cloud, the collapse of a bubble emits strong
shockwaves. The produced shockwave elevates the ambient pressure or external
energy intensity on neighboring bubbles, and accelerates the collapse of neigh-
boring bubbles and other bubbles in the cloud. This assumption is referred to as
1 Fundamentals of Acoustic Cavitation in Sonochemistry 17

concerted collapse [2, 25]. Concerted collapse starts at the boundary of a bub-
ble cloud and proceeds until collapse of bubbles at the cloud center occurs. As
a result, shockwaves from multiple bubbles converge together and form a single
shockwave directing towards the solid surface with much higher shockwave inten-
sity (several hundreds of kPa) than the collapse of multiple single bubbles.
In a practical sonochemical reactor, the behavior of bubbles is influenced by
the pattern of ultrasonic streaming. Some sonochemical systems show interfer-
ence characteristics in ultrasonic wave propagating in the whole reactor space,
which means numerous alternate or fixed regions with strong or weak ultrasonic
intensity. An example is the common ultrasonic bath with special depths (integral
multiples of quarter-wavelength of ultrasound wave) from the bath bottom to the
liquid surface. For this type of sonochemical reactor, the collapse of bubbles are
generally concentrated at points that have high ultrasonic intensity (antinodes) in
the reactor space, which gives high cavitation activities as shown in Fig. 1.5 [26,
27]. Regions with long-term low or even zero ultrasonic intensity (nodes) may
favor the growth of bubbles via rectified diffusion and coalescence. At these nodes,
the size of the bubbles may increase beyond the critical size. The bubbles pos-
sibly survive even for long time after the ultrasound is shut off [21]. The behavior
of bubbles at antinodes or nodes is also used in distinguishing the intensification
mechanism of cavitation from that of ultrasonic streaming [28].
Because of the uncertainties in the spatial distribution of bubble size and bub-
ble density as well as the complex interaction between bubbles, the determina-
tion of cavitation in a multibubble system is more involved than that for a single
bubble system [15, 20]. Several effective methods have been developed for ana-
lyzing cavitation in multibubble systems [14, 15, 29, 30]. These methods are
summarized in Table 1.2. Acoustic frequency spectroscopy (AFS, Fig. 1.6) is

Horizontal plane
8 cm
Vertical direction from the
bottom of ultrasonic bath

6 cm

4 cm

2 cm

0 cm

Fig. 1.5  Cavitation erosion pattern on aluminum foil vertically positioned in ultrasonic bath
(water depth of 10 cm) at 20 kHz (adapted with permission from [27], Copyright © 2009
Elsevier)
18 J. Luo et al.

Table 1.2  Qualitative and quantitative approaches for measuring ultrasonic cavitation and
secondary effects
Method Sensor Principle of measurement Reference
Spectroscopic
Acoustic frequency Hydrophone Steady and transient bubbles [27, 31]
oscillating at subharmonics,
harmonics and ultraharmonics
frequencies produce variation of
local acoustic pressure
Sonoluminescence Light intensity Light intensity is detected and [14, 15, 29]
plotted as the function of scanning
wavelength from 300–900 nm
(ultraviolet-visible range)
Chemical
Iodine method ·OH radical H2O → ·OH + ·H, [30]
I− + ·OH → I2− → I3−
I3− concentration determined by
ultraviolet spectroscopy
Fricke method H2O → ·OH + ·H,
Fe2+ + ·OH → Fe3+ + OH−
Fe3+ concentration determined by
ultraviolet spectroscopy
Salicylic acid method Hydroxylation of salicylic acid by
·OH radical
Salicylic acid concentration deter-
mined by high performance liquid
chromatography
Terephthalic acid p-C6H4(COOH)2 + ·OH → C6H3
method OH(COOH)2
Hydroxyterephthalic acid concen-
tration determined by fluorescence
spectroscopy
Sonochemiluminescence 3-Aminophthalhydrazide (lumi-
nol) + ·OH → 3-aminophthalate,
in alkaline solution
Blue light emission of 3-ami-
nophthalate proportional to
concentration
Physical
Aluminum foil erosion Al foil Indentations on foil and weight [27, 30]
loss
Laser scattering Light Volumetric concentration of bub- [32, 33]
attenuation bles from Beer-Lambert law
Laser phase-Doppler Frequency Velocity of bubbles from [33, 34]
variation frequency variation between
scattering and incident waves
while bubble size by phase
displacement between scattering
and reflected waves
1 Fundamentals of Acoustic Cavitation in Sonochemistry 19

Fig. 1.6  Average acoustic

frequency spectra under f (a)
sonication of 22 kHz: h
a strong cavitation intensity
sh h
in water; b medium cavitation
intensity in water; c weak
cavitation intensity in
water; d no cavitation (b)
intensity in silicon oil. f
f fundamental frequency
(22 kHz); h harmonic
h h
frequencies; sh subharmonic sh
frequencies (adapted with
permission from [31],
Copyright © 2000 American f (c)
Institute of Chemical
Engineers [AIChE])
h
h

(d)
f

a direct but approximate way for measuring the occurrence of acoustic cavita-
tion. Hydrophones are placed in liquid under sonication, and record the inten-
sity of pressure pulse at local place as the function of scanning frequency. AFS
results reflect the change of acoustic parameters as the result of acoustic activa-
tion. Since it uses hydrophones for detection of sound waves, AFS needs com-
plex mathematical transformation and processing to obtain useful information
from the as-received spectra [27]. AFS spectrum with high intensity peaks at the
harmonic, higher harmonic, or even subharmonic frequencies proved the occur-
rence of cavitation [27, 31]. Chemical measurements are normally used in the
quantitative determination of cavitation yield and cavitation efficiency [12, 30].
In common horn- and bath-type reactors, the cavitation yields are determined as
3.5 × 10−9 and 5.8 × 10−7 g/J, respectively, which give relatively low energy effi-
ciency (5–20 %) of acoustic cavitation [12]. Because of less energy requirement,
the results from chemical measurement represent the less violent energy character-
istics in bubble dynamics than that from sonoluminescence [15]. Erosion analysis
of aluminum foil of several micrometer thickness is used to evaluate the cavitation
number (punching number on foil) and cavitation intensity (weight loss of foil).
20 J. Luo et al.

Results from chemical methods and erosion analysis describe the intensity of ·OH
radical and shockwave, secondary effects of cavitation, respectively.
Advanced technologies such as pulsed multibubble sonoluminescence (MBSL),
laser diffraction [32, 33], laser phase-Doppler [33, 34], methyl radical recombina-
tion and others are widely used in analyzing multibubble cavitation in recent years,
and these methods give the scale or distribution of energy, number, size, velocity
of bubble clusters. For MBSL, light emitted at certain wavelength relates to the
formation of special plasma. Light intensity is proportional to the energy intensity
of bubbles. By fitting the emission spectra of special plasma, the emission tem-
perature of plasma in bubbles can be estimated, which indicates the energy level of
bubble cavitation. However, the analysis of multibubble cavitation is still challeng-
ing. In fact, as the time for bubble collapse is short, cavitation bubbles analyzed by
various methods are mainly in growth or in oscillating, which does not apply to the
bubbles before collapse. For laser phase-Doppler, the number and volume factions
of bubbles are plotted against to the motion velocity and size of bubbles at certain
plane in acoustic field. Velocity of bubbles is determined by frequency variation
between scattering and incident waves, while bubble size is determined by phase
displacement between scattering and reflected waves. Laser scattering and laser
phase-Doppler are both direct methods to determine the cavitation number.
In multibubble cavitation, the production of cavitation bubbles means the for-
mation of another immiscible phase besides the liquid medium. The intensity of
ultrasonic energy is scattered and weakened for a heterogeneous liquid containing
high concentrations of insoluble solid particles or gas microbubbles. High acous-
tic intensity produces high number density of bubbles (bubble cloud) in the liq-
uid phase, while high number density of bubbles greatly influence the delivery of
acoustic intensity to the entire reactor space. These two opposing effects have con-
tradictory consequences [26]. For example, in a horn type sonochemical reactor, a
high density of bubble cloud gathers at the region near the tip of the transducer, and
results in inefficient cavitation in sonochemical processing [35]. Thus, the system
with a controlled concentration of cavitation nuclei gives much higher cavitation
intensity than the system with too many nuclei and the system suffering completely
denucleation [26]. Appropriate number of cavitation nuclei uses energy efficiently.
The formation and distribution of cavitating bubbles in the whole space of a
sonochemical reactor is not uniform and is greatly influenced by ultrasonic
streaming. Ultrasonic streaming occurs according to the geometry of the reactor
and the variation of its ultrasonic parameters. By using high-speed photography
[36] and chemical methods such as the iodine method [37] and sonochemilumi-
nescence [38], it is possible to observe and record the spatial distribution of active
bubbles. Bubbles are forced to migrate directionally in the acoustic field due to
primary Bjerknes forces. The primary Bjerknes force is defined as the translational
force on a cavitating bubble in a liquid when the nonlinear oscillation of the cavi-
tating bubble is interacting with the acoustic pressure field [39]. Parlitz et al. [40]
demonstrated that when the amplitude of the acoustic pressure was not high, cavi-
tating bubbles tended to move along the direction of pressure rise (pressure anti-
node). This deduction is consistent with the phenomenon that is described in the
1 Fundamentals of Acoustic Cavitation in Sonochemistry 21

section dealing with concerted collapse (Fig. 1.5). However, when the amplitude
is further increased, the primary Bjerknes force may change, and the high pres-
sure amplitude region may become repulsive for the bubbles because of nonlinear
oscillation of bubbles [36, 40]. As a result, in an acoustic field near a sonotrode
with the pressure amplitude of greater than 190 kPa [36], cavitation bubbles tend
to move along the direction of pressure drop. This creates different spatial distribu-
tions and migration features of bubbles in a reactor that is commonly referred to as
acoustic cavitation structure.
Typical acoustic cavitation structures can be conical bubble structure (CBS),
smoker bubble structure, tailing bubble structure (TBS), jet-induced bubble struc-
ture (JBS) and acoustic Lichtenberg figure (ALF). Acoustic cavitation structure
CBS (Fig. 1.7a) [36] and smoker (Fig. 1.7b) [41] are two common forms that

Fig. 1.7  Acoustic cavitation structures: a conical bubble structure; b smoker bubble structure;
c tailing bubble structure; d jet-induced bubble structure; e acoustic Lichtenberg figure (a, b, d
and e are reprinted with permission from [36], Copyright © 2014 Elsevier. c is reprinted with
permission from [42], Copyright © 2014 Elsevier)
22 J. Luo et al.

occur in a relatively strong acoustic field. CBS is produced by sonotrode. When

the sonotrode vibrates with moderate amplitude, the radiating surface is covered
by bubbly web structures and the CBS is composed of filament structures, while as
the vibrating amplitude of the sonotrode increases, the CBS becomes a homogene-
ous distribution of bubbles and the radiating surface is covered by a bubbly film
[36]. Smoker, which only appears on a radiating surface such as the bottom of a
cleaning bath or on the surface of transducer submerged in liquid, is bound to the
surface with a small tip and a big tail [41]. TBS (Fig. 1.7c) and JBS (Fig. 1.7d) are
two new acoustic cavitation structures produced by artificially implanting nuclei
in a strong acoustic field [42]. For TBS, acoustic radiation forces make the cav-
itation bubbles move away from the radiating surface to form a cloud tail [42].
For JBS, the submerged liquid jet and acoustic radiation forces both determine the
direction of the bubble translation [42]. ALF (Fig. 1.7e) occurs in an ultrasonic
field with relatively weak intensity [40, 43]. Bubbles in ALF translate towards the
pressure antinodes one after another that causes a dendritic bubble structure and
self-organization. The nuclei sources of CBS and smoker are mainly small air bub-
bles trapped within crevices or non-condensed air microbubbles in the liquid. The
nuclei sources of TBS and JBS are small air bubbles that originate from foreign
impurities or the submerged liquid jet [36]. The above acoustic cavitation struc-
tures are closely interrelated to each other and can be interchanged under special
conditions. By artificially implanting nuclei, one can create controllable distribu-
tions of cavitation bubbles over an entire reactor space that is favorable for pro-
moting sonochemical reaction [42].
In summary, this section has discussed statistical cavitation behavior of bubbles
formed under the application of ultrasound to a reactor. The spatial characteristics
in number density or volume fraction of bubbles with certain sizes or velocities in
the uneven acoustic intensity field have been mainly considered. The number and
size distribution of bubbles greatly influence cavitation behavior of neighboring
bubbles and thus it strongly affects the product yields in sonochemical reactions.

1.2.3 Physical and Chemical Effects of Cavitation

The oscillation and transient collapse of cavitation bubbles produce many special
secondary physicochemical phenomena, including shockwave, microturbulence,
microjet, radical effects and sonoluminescence, which can have great influence on
the dynamics and process equilibrium in a system. Mass and heat transfer coef-
ficients of a reacting system can be multiplied by sonication with the predomi-
nant reason for enhancement being related to acoustic cavitation and its secondary
effects [28, 44]. The collapse of transient bubbles produces local hot spots with
temperature and pressure that is much higher than that of the surrounding liquid.
The huge temperature and pressure drop generates strong shockwaves towards
bubble outsides [45]. The shrinkage and transient collapse of bubbles creates
large voids in the liquid, while the quick influx of liquid stream to the voids forms
1 Fundamentals of Acoustic Cavitation in Sonochemistry 23

Fig. 1.8  Schematic representations of secondary effects: a microjet, b radical formation and

c shockwave and microturbulence in ultrasonic cavitation

violent microturbulence in local liquid. Microjet refers to the unsymmetrical col-

lapse of bubbles at a broad solid/solvent interface (>200 μm) that produces high
speed impact (>100 m/s) oriented towards the solid surface [2]. Schematic repre-
sentation of several secondary effects is given in Fig. 1.8. As shown in Fig. 1.1, the
collapse of transient bubbles produces secondary effects that have a much higher
intensity than the oscillating motion from steady bubbles [8]. Transient bubbles
have a more violent change in bubble size during the acoustic cycle. Therefore, the
intensities of shockwave and microturbulence emitted by transient bubbles become
about 3,000 and 40 times, respectively, of that from steady bubbles (Fig. 1.1).
During cavitation, high-temperature dissociation of gaseous water molecules
generates radical ·OH, while the burning of gaseous N2 with gaseous O2 gener-
ates ion NO2− in bubbles as bubbles shrink or collapse. And light is emitted from
the emissive shell (sonoluminescence). In the sonication of water at 22 °C and
52 kHz, a single cavitating bubble with a maximum radius of 28.9 μm produces
6.1 × 10−18 mol NO2−, 1.1 × 10−18 mol ·OH and 1.3 × 10−20 mol photons in an
acoustic cycle [20]. However, the negligible amounts of these spontaneous species
has less influence on the performance of general sonochemistry [46].
It should be clarified that ultrasound wave, acoustic cavitation and these sec-
ondary effects have their action range. Most cavitation activity and high sono-
chemical yields appear within the distance of about one wavelength, namely
several centimeters, away from the sound-emitting surface such as the ultrasonic
horn [47, 48]. In some texts [1], according to the distance X away from the sound-
emitting surface, the action zone for ultrasound in sonochemical reactor is divided
as near-surface zone (X < wavelength λ), streaming zone (X ~ λ) and far-field zone
(X > λ). Only the near-surface zone is suitable for effective cavitation and sono-
chemical reactions, while the streaming zone is suitable for particle aggregation
24 J. Luo et al.

and emulsion separation under low intensity ultrasound by standing wave prin-
ciple. The action ranges of acoustic cavitation and relevant secondary effects
are much shorter. The surrounding liquid absorbs much of the cavitation energy,
while the reactive radicals generated by cavitation are easily quenched and cannot
migrate far from the location of the collapsed bubble. The attenuation of the pres-
sure pulse for the bubbles is greater than 5 μm, which makes the pressure ampli-
tude measured at 1 mm from the bubble center only 10−3 of its actual value [31].
In a heterogeneous system, such as in systems containing a high concentration
of small-size solid particles, the absorption of cavitation energy by the surround-
ings become significant due to the scattering effects. Near the surface of the solid
materials, the shockwave that has high temperature and high pressure from bub-
ble collapse, impacts the solid surface and changes the morphology and properties
of solid surface. The high energy shockwave lasts for short time of about 200 ns
and this happens within a short distance of only tens of nanometers from the solid
surface [2]. However, the energy from many shockwaves can be concentrated and
enhanced due to concerted collapse. Therefore, it is possibly for ultrasound wave
to make indentations of 10–100 μm on solid surface even if the solid surface is
exposed under acoustic cavitation for a short period of time [2].
As shown in Fig. 1.3, the active zones for acoustic cavitation and most of the
derived physicochemical effects can be divided into four parts—bubble interior,
bubble/liquid interface, nearby zone and far-distance zone. The bubble interior
allows the access of volatile chemicals and dissolved gases. The bubble generates
high temperatures and pressures in its interior during the nearly adiabatic com-
pression process, and initiates ionization, thermolysis and violent radical reactions
of vapor molecules. Radical reactions not only occur in the bubble interior, but
also at the bubble/liquid interface and in the nearby liquid, especially for nonvola-
tile compounds. In the sonochemical degradation of phenol in water, the increase
of relative concentration of nonvolatile phenol at the bubble/liquid interface pro-
motes the degradation efficiency of phenol multiply even though the concentration
of phenol in the bulk liquid remains almost unchanged [49]. This demonstrates
that the bubble/liquid interface plays a vital role in radical-induced chemical reac-
tions of nonvolatile compounds under sonication. However, it does not mean that
the chemical reactions of nonvolatile compounds cannot take place in the bubble
interior. In the study of sonoluminescence in concentrated H3PO4 solution, peaks
assigned to radicals ·OH and PO· are both significantly visible in the ultraviolet
spectrum [29]. In the sonoluminescence of H3PO4, radical PO· must be produced
from nonvolatile H3PO4 in the plasma zone, namely the deepest core in the bubble
structure. There are probably two different types of cavitating bubbles that exist
in sonicated H3PO4 solution [29]: (1) stationary bubbles that undergo highly sym-
metrical collapse and produce radical ·OH and (2) rapidly moving bubbles that
have less symmetrical collapse. In the second type of bubbles, nanodroplets of
liquid containing H3PO4 might be injected into the bubble interior due to capil-
lary wave action, microjetting, or bubble coalescence in the asymmetry collapse
of bubbles [29]. However, the ratio of chemical reactions of nonvolatile species in
bubbles is not large. As the collapse of transient bubble occurs, numerous active
1 Fundamentals of Acoustic Cavitation in Sonochemistry 25

radicals are released into the nearby liquid which initiate radical reactions such as
the oxidative degradation of chemical materials in wastewater or are captured by
chemical reagent in determining cavitation activity. For the nearby zone which is
within 100 μm from the bubble boundary, the dominant ultrasound-intensification
mechanism is physical, such as shockwave and microturbulence. High impact and
high temperatures that result from shockwave and high-speed microjet are respon-
sible for the modification of solid surfaces under high-energy ultrasound, such
as surface erosion, particle breakage, metal melting and peeling of surface oxide
coating [2, 50]. Microturbulence promotes dispersion and fine emulsification in
immiscible liquid mixtures and helps to dislodge substances that adhere onto solid
surfaces (ultrasonic cleaning). In the far-distance zone, cavitation and shockwaves
lose their strength, while microturbulence may be the main mechanism for ultra-
sonic intensification of chemical processing such as emulsification [48].
Most sonochemical reactions do not occur in the interior of active bubbles.
The intensification of these sonochemical reactions is through the action of sec-
ondary effects, but not the cavitation behavior of bubbles themselves. However,
the energy intensity of secondary effects greatly depends on the behavior of the
bubbles, as well as the liquid properties and heterogeneous characteristics of the
reaction system. For chemical reactions that are related to biomass conversion, the
effective intensification/activation zones are mainly the zones that are nearby the
bubbles and the zones that have distance within one wavelength from the bubbles.
Therefore, the physical mechanism should be applicable to the discussion of ultra-
sound-enhanced biomass processing, and intensification of the mass transfer.

1.2.4 Factors that Influences the Energy

of Acoustic Cavitation

For most practical sonochemical reactions, it is necessary to know the factors that
could influence acoustic cavitation, and these factors include the physicochemical
properties of liquids, acoustic operation and heterogeneous characteristics of reac-
tion system [4, 5, 51, 52]. The selection and optimization of those factors allows
proper energy intensity to be applied and gives higher energy efficiency. Table 1.3
describes some important factors and their effects on cavitation. Energy efficiency
for cavitation is related to the proper design of sonochemical reactors that provide
a uniform acoustic energy field for bubble cavitation. Generally, the influence of
the factors shown in Table 1.3 can be divided into four categories:
1. Influence on acoustic environment for the occurrence of cavitation. Factors
such as heterogeneous characteristics, acoustic frequency and liquid tempera-
ture influence the propagation and attenuation of acoustic energy in the liquid
and thus affect the intensity and uniformity of the acoustic field. The charac-
teristics of acoustic streaming in different reactors also influences the spatial
distribution of acoustic energy [54].
26 J. Luo et al.

2. Influence on the occurrence of cavitation, namely cavitation threshold and

cavitation density. Dissolved gases and volatile liquids provide cavitation
nuclei, which lower cavitation threshold and make the occurrence of cavitation
easier. Relatively high acoustic frequency increases the number of useful cavi-
tation events in per unit of time by shortening the duration of an acoustic cycle.
3. Influence on growth and energy accumulation of bubbles. High acoustic
frequency reduces time for the expansion and compression of bubbles, and
influences the work done onto the bubble during compression and the energy
concentration generated thereby. The properties of liquids such as surface ten-
sion and viscosity limit the growth and maximum size of bubbles. The con-
centration of organic liquids and surfactants influences the growth of bubbles
through rectified diffusion and bubble coalescence.
4. Influence on the release of bubble energy during their shrinkage and col-
lapse. The evaporation of liquid in bubbles and the chemical reactivity of liquid
and dissolved gases both consume the energy obtained during bubble growth
and these buffer the released intensity of cavitation and the secondary effects
[53]. Heterogeneous characteristics and high viscosity in liquid absorb the
intensity of secondary effects and result in their rapid reduction.
Many factors may promote acoustic cavitation in one aspect but may have adverse
effects on another aspect. Representative cases appear in the discussion of acoustic
frequency [51] and bubble cloud effects [26], which are mentioned in Table 1.3
and Sect. 1.2.3, respectively. Thus comprehensive analysis and evaluation of the
factors influencing acoustic cavitation (Table 1.3) is needed. For practical sono-
chemical processes, the purpose of chemical treatment often determines the selec-
tion and optimization of ultrasonic parameters [51]. High ultrasonic frequency
of >100 kHz weakens the physical or mechanical effects generated by acoustic
cavitation [55], however, it promotes advanced oxidation reactions through radi-
cal reaction pathways [56]. Furthermore, the conditions with the highest cavitation
efficiency are not necessarily the optimal conditions for achieving highest product
yields in sonochemical reactions. The best of reaction temperature must be appro-
priate for both cavitation effects and the chemical dynamics [51].
The heterogeneous characteristics in cavitating systems are especially impor-
tant. Strictly speaking, no cavitation happens in an absolutely single phase. Even
for acoustic cavitation mediums such as concentrated H2SO4 or H3PO4 solution
or ionic liquids that have a very low vapor pressure, the cavitating system is het-
erogeneous [29, 57–59]. Much of the literature has demonstrated that high cavi-
tation intensity can be obtained with only very small numbers of bubble nuclei.
More importantly, compared with water and common organic liquids that have
high volatility, cavitation in low-vapor-pressure and nonpolyatomic vapor liquids
such as concentrated H3PO4 solutions reduces excessive energy consumption due
to solvent evaporation, polyatomic vibrations, rotations, and especially endother-
mic bond dissociations. As a result, high cavitation intensity is obtained in concen-
trated H3PO4 solutions, which emits bright MBSL intensity that could be visible
under fluorescent lamp [29].
1 Fundamentals of Acoustic Cavitation in Sonochemistry 27

Table 1.3  Factors influencing acoustic cavitation [4, 5, 51–53]

Factor Direct effect Remarks
1. Liquid properties
Compressibility Cavitation bubble dynamics High compressibility reduces cavitation
intensity
Vapor pressure 1. Cavitation threshold High vapor pressure makes cavitation easier,
2. Vapor composition in bubble but decreases energy intensity of bubble
3. Intensity of bubble collapse collapse due to liquid evaporation during
acoustic cycles
Surface tension 1. Cavitation threshold High surface tension increases cavitation
2. Bubble size threshold, but gives bubble collapse with
high energy intensity
Viscosity 1. Cavitation threshold 1. Cavitation occurring in low viscosity is
2. Bubble oscillation mainly transient
2. High viscosity induces steady or no cavi-
tation. High cavitation energy in single bub-
ble and high attenuation of acoustic energy,
shockwave and microturbulence
Chemical 1. Radical formation Reaction of active compounds consumes the
reactivity 2. Intensity of bubble collapse energy released by cavitation
Pretreatment Cavitation threshold Degassing and nucleation influence acoustic
cavitation
2. Properties of gas in liquid
Gas solubility 1. Number of cavitation events 1. Dissolved gas acts as cavitation nuclei
2. Vapor composition in bubble facilitating cavitation
2. Cavitation intensity is inversely propor-
tional to amount of dissolved gas
Specific 1. Heat transfer between bubble Low thermal conductivity of gas leads to
heat, thermal and liquid high local heating during bubble collapse
diffusivity 2. Energy of cavitation bubbles
Chemical 1. Radical formation Reaction of compounds decreases the energy
reactivity 2. Intensity of bubble collapse intensity of bubble collapse
3. Liquid temperature
1. Bubble dynamics 1. Complex influences. Liquid temperature
2. Liquid properties, gas increases cavitation intensity due to volatil-
solubility ity effect in most cases
3. Sound propagation 2. Chemical reactions need appropriate tem-
perature for efficient coupling of cavitation
effects with chemical dynamics
4. Static pressure
1. Cavitation threshold High cavitation threshold and violent bubble
2. Bubble dynamics collapse occur at high static pressure
Increasing static pressure allows one to
distinguish between acoustic microstreaming
and cavitation mechanism
5. Existence of solid particles
1. Spatial distribution of acous- High concentration of solid microparti-
tic intensity cles decreases cavitation efficiency and
2. Intensity of secondary effects intensity of secondary effects due to acoustic
scattering
(continued)
28 J. Luo et al.

Table 1.3  (continued)
Factor Direct effect Remarks
6. Acoustic intensity
1. Bubble dynamics 1. High acoustic intensity promotes cavitation
2. Number of cavitation events 2. Capacity for indefinite increase of acous-
tic intensity depends on material stability
of transducer and the properties of liquid
medium. Acoustic intensity is determined
according to reaction requirement
3. Bubble cloud effect seriously decreases
cavitation efficiency at high acoustic inten-
sity. Additional auxiliaries such as mechani-
cal agitation avoid bubble clouds gathering
in zones that have high acoustic intensity
7. Acoustic frequency
1. Acoustic cycle 1. Cavitation threshold increases with acous-
2. Bubble dynamics tic frequency
3. Cavitation threshold 2. High acoustic frequency of >1 MHz
4. Sound attenuation means short acoustic cycle and insufficient
time for the generation, growth and collapse
of bubbles
3. High frequency increases attenuation of
ultrasonic energy in liquid
4. Number of useful cavitation events per
unit time increases for acoustic frequency
of <200 kHz. This increases cavitation
efficiency
5. Longer duration of bubble motion and
larger bubble size exist with low frequency.
This increases the evaporation of liquid at
the bubble surface and chemical reaction of
vapor content in bubble, which consumes
energy in cavitation bubble, and decreases
the energy intensity of transient collapse

It can be concluded that in “homogeneous” liquids, the concentration of micro-

bubbles that are artificially produced by researchers determines the cavitation
intensity in sonochemical reactors. This conclusion is obtained for microbubbles
from vapor that is produced by solvent volatilization, but the conclusion is also
applicable to liquid containing noncondensable gases. In the latter case, non-
condensable gases displace vapor molecules as the main source of microbubble
nuclei, while the content of noncondensable gases in liquids can be controlled by
properly degassing and removal of gas microbubbles trapped in crevice (denucle-
ation) [26]. Aqueous solutions that are not degassed give relatively poor cavita-
tion intensity according to acoustic emission spectrum results, and this is due to
the acoustic attenuation and acoustic energy scattering in the bubble-rich liquid.
Aqueous solutions that are completely pre-denucleated show no cavitation inten-
sity as no microbubble is available as cavitation nuclei. As a result, the highest
1 Fundamentals of Acoustic Cavitation in Sonochemistry 29

acoustic emission intensity is observed in the liquid that is degassed but not denu-
cleated which contains a controlled concentration of noncondensable air [26]. In
most cases, degassing before sonochemical treatment enhances the intensity of
cavitation and dramatically improves cavitation distribution. Cavitation is con-
centrated more closely to transducers when sonication is performed in tap water,
while it is highly dispersed and evenly in the whole reactor space when sonication
is performed in boiled water [60]. Nuclei concentration effects seem to artificially
regulate cavitation intensity in homogeneous liquids.
For solid-liquid heterogeneous systems, especially patterned geometry of
defects on solid surfaces, the size and concentration of the solid micro-/nanoparti-
cles are important for selective production or control of cavitation intensity [6, 7].
As mentioned in Sect. 1.2.1, smart design of surface defects can enhance the
nucleation rate by several orders of magnitude [6]. In biomass reactions handing
lignocellulose particles, appropriate particle size (several tens to several hundreds
of micrometers) [61, 62] and solid concentration (<5 wt%) [51] seems to promote
efficient reaction.
Another interesting heterogeneous system is the hot-pressed solvents such as
subcritical CO2 [63]. Acoustic cavitation only occurs below the critical point of
liquid, because no phase boundary exists above the critical point. Compared to
ambient water, acoustic cavitation in subcritical CO2 requires a lower threshold
pressure, as the high vapor pressure of CO2 counteracts the hydrostatic pressure.
The Blake threshold for subcritical CO2 at 20 °C and 5.82 MPa is only 0.1 MPa,
while water needs 5.9 MPa for the same conditions [63]. Theoretical calcula-
tions show that with stimulation of ultrasound at 20 kHz, liquid CO2 at 20 °C and
5.82 MPa gives high cavitation intensity, with the maximum bubble radius compa-
rable to that in water at 20 °C and ambient pressure [63]. The acoustic cavitation
in subcritical CO2 is already used in radical-induced chemical reactions, such as
polymer synthesis.

1.3 Conclusions and Future Outlook

Ultrasound can be an effective technology for process intensification by acoustic

cavitation in many chemical reactions. Acoustic cavitation accumulates and explo-
sively releases energy through the growth, radial motion and collapse of bubbles.
The intensity of released energy is enough to break chemical bonds and even to
generate plasma and photons. However, in many practical reactions, second-
ary effects generated by cavitation become the primary and direct cause for pro-
cess intensification under sonication, while the intensity of secondary effects also
depend on the behavior of bubbles themselves and the influence from the proper-
ties of the sonication medium. The analysis of influencing factors must be com-
prehensive and be directed towards specific situations. Ultrasonic streaming and
heterogeneous characteristics of sonochemical systems have great influence on
the efficiency of acoustic cavitation, namely the transformation ratio of ultrasonic
30 J. Luo et al.

energy to cavitation energy. Some qualitative and quantitative approaches are

recommended for measuring ultrasonic cavitation and secondary effects, which
will help to understand the regularity of cavitation energy and its distribution in
specific reactors. Optimization of chemical reactions under sonication can be
achieved through combined knowledge of the regularities in cavitation energy,
ultrasonic operation and reaction requirement.
Acoustic cavitation can vary greatly between reactor types and different son-
ochemical systems. Mechanics and fluid dynamics help to develop mathematical
models for acoustic cavitation and provide some possible theoretical frameworks.
However, experimental methods are needed to examine many hypotheses that
are used in the design of practical reactors. In the last decade, new technologies
such as multibubble sonoluminescence and advanced photography have greatly
elevated the progress of experimental acoustics, and advanced application of ultra-
sound in biomass conversion. However, new studies are still needed to help many
of the intrinsic characteristics and nature of acoustic cavitation. Research areas
that are probably fruitful for exploration are: (1) acoustic cavitation in multibub-
ble systems, (2) cavitation in special liquid mediums such as viscous liquid, ionic
liquids and near-critical fluids, (3) acoustic cavitation occurring on the solid/liq-
uid interface both on experimental and theoretical level, (4) characteristic analysis
of acoustic fields in new sonochemical reactors with different geometric arrange-
ments and (5) mechanisms of sonochemistry for special reactions.
Especially, the experimental mapping and theoretical study of the spatial dis-
tribution of active cavitation in reactor space needs more attention. Further, the
combination of sonochemistry with general chemistry methods should be given
attention within educational environments.
In practical chemical processes that are enhanced by ultrasonic energy, the most
important consideration will be the system performance and energy efficiency
of the applied ultrasound. New advances in the statistic analysis and purpose-
ful design of the energy of cavitation bubbles will allow the design of efficient
systems.

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