Top Curr Chem (Z) (2016) 374:56

DOI 10.1007/s41061-016-0054-y

REVIEW

Theory of Sonochemistry

Sukhvir Kaur Bhangu1 • Muthupandian Ashokkumar1

Received: 28 May 2016 / Accepted: 12 July 2016 / Published online: 1 August 2016
Ó Springer International Publishing Switzerland 2016

Abstract Sonochemistry refers to ultrasound-initiated chemical processes in liq-

uids. The interaction between bubbles and sound energy in liquids results in
acoustic cavitation. This review presents the fundamental aspects of acoustic cav-
itation and theoretical aspects behind sonochemistry such as dynamics of bubble
oscillation, the rectified diffusion process that is responsible for the growth of
cavitation bubbles, near adiabatic collapse of cavitation bubbles resulting in extreme
reaction conditions and several chemical species generated within collapsing bub-
bles that are responsible for various redox reactions. Specifically, a detailed dis-
cussion on single bubble sonochemistry is provided.

Keywords Sonochemistry  Acoustic cavitation  Single bubble dynamics 

Sonoluminescence

1 Introduction

Ultrasound refers to sound waves beyond the frequency that can be detected by the
human ear. Sound waves with a frequency greater than 20 kHz fall into this
category. Ultrasound is divided into three main regions: low frequency
(20–100 kHz), intermediate frequency (100 kHz–1 MHz) and high frequency
(1–10 MHz) [1]; however, intermediate range is also sometimes referred to as
high frequency. Ultrasound interacts with gas bubbles in liquids to generate
chemical reactions and strong physical forces that can be used for various

This article is part of the Topical Collection‘‘Sonochemistry: From basic principles to innovative
applications’’; edited by Juan Carlos Colmenares Q., Gregory Chatel.

& Muthupandian Ashokkumar

[email protected]
1
School of Chemistry, University of Melbourne, Victoria 3010, Australia

Reprinted from the journal 1 123

 Top Curr Chem (Z) (2016) 374:56

processing applications and for promoting chemical reactions. The driving force for
the generation of chemical and physical forces is acoustic cavitation, which
generates extreme temperatures and pressures. The consequences of these extreme
conditions generated include radical generation, light emission-sonoluminescence
(SL), shock waves, microjets, microstreaming, shear forces and turbulence [1]. As a
result of these strong physical and chemical effects, various applications of acoustic
cavitation have been developed for commercial use including wastewater treatment
[2] and the formation of protein microbubbles which can be used for flavour
encapsulation and drug delivery [3].

2 History

The phenomenon of cavitation was first reported by Thornycroft and Barnaby [4] in
1895. In 1917 Rayleigh published the first mathematical model describing
cavitation in an incompressible liquid [5]. In the 1930s Brohult [6] and other
groups discovered that sonication can be used for the degradation of bio- and
synthetic polymers. In 1935 Frenzel and Schulze [7] reported for the first time that
light emission occurred in water when exposed to intense ultrasound. In 1944 Weiss
[8] observed that the sonication of water leads to the generation of hydrogen and
hydroxyl radicals, and in 1956 Parke and Taylor [9] provided the first experimental
evidence for the formation of OH radicals in aqueous solutions. The first
observations on chemical reactions in organic solutions were made in the early
1950s. It was found that methanol solutions containing diphenylpicrylhydrazyl were
decolourised, indicating the formation of free radicals [10]. Also, the first computer
calculations modelling a cavitation bubble were published by Neppiras and
Noltingk [11] in 1950. Makino et al. [12] used spin trapping agents and electron spin
resonance measurements to verify the formation of H and OH radicals during the
sonication of water. It was reported in 1987 by Henglein [13] that over 80 % of
primary radicals originally generated in the hotspot recombine to produce water
molecules. Since the 1930s, acoustic cavitation has gained popularity as it can be
used for the enhancement of chemical reactions, emulsification of oils, degradation
of chemical and biological pollutants, etc.
A number of books, review articles and book chapters have been published on
acoustic cavitation and its applications are available in the literature. The
fundamentals of an acoustic bubble have been discussed in detail by Leighton
[14] in his book The Acoustic Bubble. Mason and Lorimer [15–17] have published
various review articles and books dealing with different aspects of ultrasound such
as theory of sonochemistry, applications of ultrasound in food technology, uses of
ultrasound in chemical synthesis and physical aspects of sonochemistry. A review
by Leong et al. focuses on the fundamentals of ultrasound-induced physical
processes such as transient and stable cavitation, rectified diffusion, coalescence and
sonoluminescence [18]. The current review provides an overview of various
fundamental processes of acoustic cavitation with a particular emphasis on single
bubble sonochemistry.

123 2 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

3 Acoustic Cavitation

3.1 Bubble Formation

Acoustic cavitation is the phenomenon of formation, growth and violent collapse

induced by the pressure fluctuations generated by sound waves in a liquid medium.
If the intensity of ultrasound is enough to overcome the tensile strength of the
medium, there occurs a point where intermolecular forces are not able to hold the
molecular structure together. This point leads to the formation of a cavity in the
medium. A large amount of energy is required to create a void or cavity. Equation 1
can be used to calculate the critical pressure (PB) required to create a cavity of
radius Re.
0:77r
P B  Ph þ ð1Þ
Re

r is the surface tension of the liquid and Ph is the hydrostatic pressure (could be
approximated to atmospheric pressure under normal experimental conditions). The
equation is valid when 2r/Re  Ph [19]. However, free gas bubbles and gas
molecules trapped in solid impurities are inherently present in liquids, which can act
as nuclei for cavitation. Hence, the actual pressure required for cavitation to occur is
far lower. Hence, in practical terms, acoustic cavitation refers to the growth of pre-
existing gas nuclei followed by the collapse of ‘‘grown’’ bubbles.
There are different mechanisms associated with the formation of bubbles [14].
Firstly, gas molecules trapped in crevices of the container walls, motes or on
hydrophobic dust particles [20] can act as bubble source. Harvey’s crevice model
depicts how an air bubble can be nucleated from cervices. A gas pocket, trapped in a
crevice, responds to alternating compression and the rarefaction cycles of the
applied ultrasound. The gas pocket expands considerably during the negative
pressure cycle. When the gas pocket grows sufficiently it gets detached from the
crevice and leads to the formation of a gas free bubble in the liquid [21]. Dissolved
gas in the liquid then fills the residual gas cavity under the applied sound field and
the cycle is repeated. The second mechanism is based on the skin model where
inherently present bubble nuclei are stabilized against dissolution when their surface
is completely covered with organic materials or surfactants [22]. It has also been
suggested that such bubbles can be stabilized by hydrophobic impurities present in a
liquid. These bubbles tend to grow in an acoustic field by coalescence or rectified
diffusion [23, 24]. Recently Yasui et al. introduced a dynamic equilibrium model for
the stabilization of bubbles covered with hydrophobic materials [25]; the chemical
potential gradient that exists near the edge of hydrophobic materials generates a
dynamic equilibrium state [25]. Another mechanism for the nucleation is
fragmentation of the active cavitation bubbles [26]. The shape instability of a
bubble which is mostly induced by asymmetric collapse leads to the fragmentation
of the bubble into several daughter bubbles which then act as new nuclei for
cavitation [27–30].

Reprinted from the journal 3 123

 Top Curr Chem (Z) (2016) 374:56

Before discussing the growth of an acoustic cavitation bubble, we discuss the

fundamental equations used to study the motion of bubbles in an acoustic field in the
following section.

3.2 Dynamics of Bubble Oscillation

This section focuses on the oscillation dynamics of a gas bubble in an acoustic field.
Further details on this can be found in the book The Acoustic Bubble by Leighton
[14]. The Rayleigh–Plesset equation is used to examine the dynamics of a bubble
oscillating at finite amplitudes [5, 14, 31]. The equation describes the motion of a
spherical bubble in response to a time-varying pressure field in an incompressible
liquid. When time t \ 0, a bubble of radius R0 is at rest in an incompressible viscous
liquid and hydrostatic pressure is p0 which is constant. However, at t [ 0 pressure pt
varies with time and is superimposed on p0, so that the pressure of liquid at certain
point from the bubble, p? = p0 ? pt which results in a change of bubble radius to
some new value Rt. During this process, the liquid shell around the bubble acquires
kinetic energy of
1 1 2
q r r_ 4pr 2 dr ð2Þ
2 R
where shell at radius r has thickness dr, mass = 4pr2qdr (q = density of liquid) and
r_ is the speed.
_ R_ ¼ R2 =r 2 (where R is the radius
Using the liquid incompressibility condition, r=
_
of the bubble when contracted, R is the wall velocity) Eq. 2 can be integrated to give
2pqR3 R_ 2 . Equating this to the difference between the work done at a certain point
from the bubble by p? and the work done by the pressure pL in the liquid outside
the bubble wall gives
R
r ðpL  p1 Þ4pR2 dR ¼ 2pR3 R_ 2 : ð3Þ
R0

Equation (5) is obtained after differentiating Eq. (3) with respect to R, noting that
 2  
o R_ 1 R_ 2
¼ ¼ 2R€ ð4Þ
oR R_ ot

pL  p1 3R_ 2
¼ þ RR€ ð5Þ
q 2
where R_ is the velocity of the cavity, R€ is the acceleration of the cavity.
The liquid pressure pL for a pulsating bubble containing gas and vapour is given
as
  3c
2r R0 2r
pL ¼ p0 þ  pv þpv  ð6Þ
R0 R R

123 4 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

where pv is the vapour pressure of the liquid, r is the surface tension, p0 is the
ambient pressure, c is the ratio of specific heat of gas at constant pressure to that of
constant volume.
Substituting pL from Eq. 6 and p1 ¼ p0 þ pt into Eq. 4 gives
(  3c )
€ 3R_ 2 1 2r R0 2r
RR þ ¼ p0 þ  pv þpv   p0  p t : ð7Þ
2 q R0 R R

The effect of viscosity on the above equation was considered by Poritsky [32],
who found that viscosity effects arise through boundary conditions and not through
the Navier–Stokes equation and obtained Eq. 8.
(  3c )
€ 3R_ 2 1 2r R0 2r 4R_
RR þ ¼ p0 þ  pv þpv    p0  pt ð8Þ
2 r R0 R R R

where g is the viscosity of the liquid.

Equations 5, 7 and 8 are commonly known as Rayleigh–Plesset equations and
they indicate that the motion of a bubble under the acoustic field is non-linear.
A spherical bubble is subjected to the time-varying pressure of amplitude pA and
circular frequency x. Therefore,
pt ¼ pA sinðtÞ: ð9Þ

Substituting Eq. 9 into Eq. 8 gives

(  3c )
€ 3R_ 2 1 2r R0 2r 4R_
RR þ ¼ p0 þ  pv þpv    p0 þ pA sinðtÞ : ð10Þ
2 r R0 R R R

Equation 10 is the fundamental equation used to describe the bubble motion at

different frequencies. Over the past few decades the equation has been extended
significantly to account for damping effects, solution compressibility, condensation,
non-linear evaporation etc. [33, 34].

3.3 Bubble Growth

Bubbles inherently present in liquids tend to grow to a critical size (which is

influenced by several parameters such as acoustic pressure, ultrasonic power and
frequency, viscosity of medium, etc.) in an ultrasonic field. The ultrasound-driven
growth is due to rectified diffusion which is defined as the slow growth of a
pulsating gas bubble due to an average flow of mass (dissolved gases and solvent
vapour) into the bubble as a function of time. Crum [24] explained this
‘‘rectification of mass’’ in terms of two effects, viz. ‘‘area effect’’ and ‘‘shell
effect’’, schematically shown in Fig. 1.
A gas bubble trapped in a liquid tends to expand when the surrounding liquid
experiences negative pressure of the sound wave. At this stage, the low internal
pressure of the bubble results in the evaporation of solvent molecules and diffusion

Reprinted from the journal 5 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 1 Schematic description of the growth of a bubble in an acoustic field by ‘‘area’’ and ‘‘shell’’ effects
(adapted from [35])

of dissolved gases into the bubble from the surrounding liquid. Therefore, the
rarefaction cycle leads to ‘‘intake’’ of gas and vapour molecules. The bubble is
compressed when the surrounding liquid experiences the positive pressure
(compression cycle) of the sound wave. At this stage, the internal pressure of the
bubble is high, which leads to the expulsion of the gas/vapour molecules from the
bubble into the surrounding liquid. Thus, the compression cycle leads to the ‘‘loss’’
of bubble mass. Since the bubble collapse is relatively fast and less surface area is
available for mass transport, the amount of material that diffuses out of the bubble
during the compression cycle is always less that which diffuses into the bubble
during the expansion cycle, thereby leading to the net growth of the bubble. This is
known as the area effect.
A change in the surface area of the bubble alone, however, is not sufficient to
explain rectified diffusion. The concentration of dissolved gases and thickness of the
liquid shell around the bubble change during the expansion and rarefaction cycle.
During the compression half cycle, the bubble contracts and the shell thickness
increases, thereby leading to a decrease in the concentration of gases within the
shell. This generates a concentration difference between the gas at the interface and
bulk. The rate of diffusion of gas in a liquid is proportional to the gradient of the
concentration of the dissolved gas. However, the gas concentration gradient lowers
as the shell thickness increases, which lowers the mass transfer of the gas coming
out of the bubble. When the bubble is in its expanded state, the liquid shell becomes
thinner (relative to the size of the bubble) with a relatively higher gas concentration.
Since the gas concentration inside the bubble is lower, material diffuses into the
bubble from the surrounding liquid shell. Two factors, i.e. gas concentration at the
bubble wall and the shell thickness, work together when the bubble is in the
expanded state and work against each other when the bubble is in the compressed
state, thus resulting in a net bubble growth over time.
Crum [24] noted that both effects have to be considered to theoretically model
the rectified diffusion process. The kinetics of the bubble growth and collapse is also

123 6 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

a crucial factor and expected to control the rectified diffusion. Therefore, a

mathematical solution for the growth of a gas bubble by rectified diffusion requires
equations of bubble motion, diffusion equations and heat conduction equations for
both the liquid and bubble [24]. Consideration of these factors makes it complicated.
Hsieh and Plesset [36] and Eller and Flynn [37] have taken into account the motion
of the bubble wall and a diffusion equation for the concentration of gas dissolved in
the liquid alone. The diffusion of gas in the liquid obeys Fick’s law of mass transfer.
Eller and Flynn [37] showed that the rate of change of number of moles n of the
gas in the bubble with the time is given as
"   1 #
dn R hðRjR0 Þi 2
¼ 4pDR0 C0 þ H ð11Þ
dt R0 pDt

where H is given by
* 4  +* 4 +
Ci R pg;m R
H¼  : ð12Þ
C0 R0 p1 R0

Ci is the concentration of dissolved gas in the liquid far from the bubble, pg,m is
the instantaneous pressure of the gas in the bubble, C0 is the saturation
concentrationof the gas
 in the liquid, D is the diffusivity of the gas, and
 4  4 D E
R pg;m R R
R0 p1 ; R0 and R0 are the time averages.

Crum later extended Eq. 12 to obtain the rate of change of equilibrium bubble
radius as a function of time, which is given as
"    # 1 *    + *  4 +!
dR0 Dd R hðR=R0 Þi 1=2 4r Ci R 4 pg;m R
¼ þ R0 1þ  =
dt R0 R0 pDt 3P1 R0 C0 R0 p1 R0

ð13Þ
where, d = kTC0/P? (K is the universal gas constant, T is the temperature).
The threshold acoustic pressure growth of a gas bubble is obtained by setting
dR0/dt = 0, and results in the equation
 2 2 2 h  2  i
qR0 x0 1  x2 =x20 þb2 x2 =x20 ð1 þ 2r=R0 P1  Ci =C0 Þ
P2A ¼ nh i o : ð14Þ
ð3 þ 4K ÞðCi =C0 Þ  3ðg14Þð3g4Þ þ ð4  3ÞK ð1 þ 2r=R0 P1 Þ

Figure 2 represents the rectified diffusion threshold as a function of radius above

and below the resonance values calculated using Eq. 14.
Later Fyrillas and Szeri [38] developed a new mathematical analysis for
describing the mass transportation during rectified diffusion. They extended the
analysis to incorporate the effect of interfacial resistance to mass transfer caused by
surfactants. Crum’s experimental data was used to estimate the rectified diffusion
growth of the cavitation bubbles. Lee et al. [39] and Leong et al. [18] studied
rectified diffusion growth in the presence of various surfactants. They reported that

Reprinted from the journal 7 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 2 Rectified diffusion threshold as a function of gas bubble radius at different dissolved gas
concentration ratios. The curves can be calculated by Eq. 14, the acoustic frequency used was 1 MHz and
the surface tension was 68 dyn/cm; the liquid is assumed to be water [reprinted with permission from
Elsevier [24], copyright (1984)]

acoustic streaming, caused as a result of surfactant adsorption, plays a major role in

rectified diffusion growth of bubbles in addition to surface activity and the nature of
the head group of surfactants [18].

3.4 Bubble Collapse

Rectified diffusion leads to the growth of the bubble to a critical (resonance) size, at
which the natural bubble oscillation frequency matches that of the driving
ultrasound frequency. A simple relationship between the frequency of ultrasound
and the resonance radius of a bubble is given by Eq. 15, which is called Minnaert’s
equation.
FR3 ð15Þ

F = frequency in hertz, R = radius of the bubble in metres

Yasui [26] suggests that resonance size is not a single value but consists of a
range. While Eq. 15 theoretically predicts the relationship between ultrasound
frequency and resonance size of the bubble, experimental data to support this
equation was only recently reported. A pulsed ultrasound technique can be used to
determine the resonance size range of sonoluminescence (SL) bubbles and
sonochemically (SCL) active bubbles [40–43]. Brotchie et al. [44] have shown
for sonochemically active bubbles that with increasing frequency the mean bubble
size becomes smaller, and the distribution becomes narrower (Fig. 3). SL and SCL

123 8 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 3 Bubble size distributions for 213, 355, 647, 875, 1056 and 1136 kHz. For 875, 1056 and
1136 kHz data have been scaled down by a factor of 4. The acoustic power of all frequencies is
1.5 ± 0.4 W [reprinted with permission from American Physical Society [24]; copyright (2009)]

are discussed later in this review. Other experimental techniques used to measure
the bubble size are laser light diffraction [45], active cavitation detection [46] and
phase-Doppler [47].
Once a critical size is reached, the bubble grows to a maximum in a single
acoustic cycle and implodes (collapses). The bubble implosion, from a thermody-
namic consideration, is important because a large change in bubble volume occurs.
Since the bubble collapse happens in a very short time domain (approx. 1 ls), the
‘‘work done’’ (PdV) leads to a ‘‘near’’ adiabatic heating of the contents of the
bubble, which results in the generation of very high temperatures ([5000 K) and
pressures ([1000 atm) within the bubble.
Rayleigh initially developed the fundamental equation dealing with the collapse
of gas cavity in 1917 for an isothermal process, which can be easily extended for an
adiabatic process. The model was proposed for a bubble of initial radius of Rm and
when R_ = 0, the cavity would collapse, rebound and oscillate between maximum
radius Rmax and minimum radius Rmin. R = Rm and R_ = 0 at the beginning of the
collapse. The pressure of gas inside the bubble is pg,m and temperature is Tm.
Assuming that there is no heat flow across the bubble wall, the gas pressure is given
by Eq. 16, which follows adiabatic law.
 3c
Rm
pg ¼ pg;m ð16Þ
R

As a result of the presence of gases inside the bubble, the decrease in the
potential energy will be equal to the sum of kinetic energy of the liquid and amount
of work done in compressing the liquid when radius changes from Rm to R. The
energy balance is given as

Reprinted from the journal 9 123

 Top Curr Chem (Z) (2016) 374:56

ZR ZR
2 3 _2
 p1 4pR dR ¼ 2pR R q  pL 4pR2 dR: ð17Þ
Rm Rm

The work done can be expressed as

ZR (  )
1 4pR3m Rm 3c1
 pL dV ¼ pg;m 1 : ð18Þ
c1 3 R
Rm

Therefore, Eq. 17 becomes

ZR (  )
1 4pR3m Rm 3c1
p1 4pR2 dR ¼ 2pR3 R_ 2 q  pg;m 1 : ð19Þ
c1 3 R
Rm

If in Eq. 19, vapour pressure and surface tension are negligible and external
pressure is constant, the energy equation described by Noltingk and Neppiras for the
collapse becomes
(  ) (    )
3qR_ Rm 3 1 Rm 3 Rm 3c
¼ p1 1  pg;m  : ð20Þ
2 R 1c R R

This equation can be solved for calculating Rmax and Rmin when the velocity R_ of
the bubble wall is zero.
(  ) (    )
Rm 3 Rm 3c Rm 3
p1 ð c  1Þ 1 ¼ pg;m  ð21Þ
R R R

where R = Rmax or Rmin.

When R = Rmax and if R ¼ Rmin  Rm then Eq. 21 reduces to
 
Rm 3ðc1Þ
pg;m ¼ p1 ðc  1Þ: ð22Þ
Rmin

As PVc and TVðc1Þ are constant during the reversible adiabatic compression, the
maximum pressure Pmax and maximum temperature attained during collapse Tmax
can be obtained from Eq. 22 and are given as
   c
Rm 3c p1 ðc  1Þ c1
Pmax ¼ pg;m  pg;m ð23Þ
Rmin pg;m
 3c1  
Rm p1 ð c  1Þ
Tmax ¼  Tm : ð24Þ
Rmin pg;m

123 10 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 4 Result of the numerical

simulation of the bubble radius
as a function of time for one
acoustic cycle (3.3 ls) when the
frequency and pressure
amplitude of an ultrasonic wave
are 300 kHz and 3 bar,
respectively. The ambient radius
of an isolated spherical air
bubble is 3.5 lm. The dotted
line is the acoustic pressure
(plus the ambient pressure) as a
function of time [reprinted with
permission from AIP Publishing
LLC [48]; copyright (2007)]

Equation 24 for calculating the Tmax tends to overestimate the collapse

temperature because it does not take into account the heat leaking from the bubble
into the surrounding fluid or the thermal conductivity of the gases or the energy
consumed in the decomposition of the vapour/gas within the bubble. Figures 4 and 5
show the results of the numerical simulation of the pulsation of an isolated spherical
air bubble in water irradiated with 300 kHz and 3 bar as calculated by Yasui et al.
[48] using the bubble dynamics equations. The temperature at the end of the bubble
collapse (Rayleigh collapse) increased up to 5100 K (Fig. 5a) whereas pressure
reaches 6 9 109 Pa (Fig. 5b).
The results obtained by Merouani et al. are similar (Fig. 6) [49]. The temperature
and pressure calculated inside a bubble increase suddenly at the end of the bubble
collapse up to 4600 K and 1400 atm (approx. 140 MPa), respectively.
A number of techniques have been developed for the experimental determination
of Tmax. Mišı́k et al. [50], using kinetic isotope effect of the sonolysis of H2O/D2O
mixtures, found that the cavitation temperatures determined were dependent on the
specific spin trap used and are in the range of 1000–4600 K. Mean temperatures in
different regions of a ‘‘hot spot’’ were postulated by Suslick et al. [51], using
comparative rate thermometry in alkane solutions. They proposed a gas phase zone
within the collapsing cavity with an estimated temperature and pressure of
5200 ± 650 K and 500 atm, respectively, and a thin liquid layer immediately
surrounding the collapsing cavity with an estimated temperature of 1900 K [51].
Henglein studied the sonolysis of methane using a methyl radical recombination
(MRR) method to estimate the bubble core temperature [52]. Sonication of methane
leads to the following reactions in the liquid medium:
CH4 ! CH:3 þ H: ðReaction 1Þ

H2 O ! H: þ OH: ðReaction 2Þ

Reprinted from the journal 11 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 5 Results of the numerical simulation. a The bubble radius (dotted line) and the temperature inside
a bubble (solid line). b The pressure (solid line) and the density (dotted line) inside a bubble with
logarithmic vertical axes. Reprinted with permission from AIP Publishing LLC [48]; copyright (2007)

Fig. 6 Bubble radius and temperature and pressure inside a bubble as a function of time during the
collapse phase of the bubble. The horizontal axis is only for 0.6 ls. A maximum bubble temperature and
pressure of about 4600 K and 1400 atm (approx. 140 MPa), respectively, are achieved at the end of the
collapse. Reprinted with permission from Elsevier [49]; copyright (2014)

H: þ CH4 ! CH:3 þ H2 ðReaction 3Þ

OH: þ CH4 ! CH:3 þ H2 O ðReaction 4Þ

123 12 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 7 Rate constants for the formation of ethane and ethylene as a function of temperature (left) and
temperature dependence of the ratio kethylene/kethane (right) [reprinted with permission from Elsevier [52];
copyright (1990)]

CH:3 þ CH:3 ! C2 H6 ðReaction 5Þ

CH:3 þ CH:3 ! C2 H4 þ H2 ðReaction 6Þ

The temperature dependence of the rate constants involved during the formation
of ethane and ethylene (Reactions 5, 6) is shown in Fig. 7. The rate constant for the
formation of ethylene increases with an increase in temperature, whereas that for the
formation of ethane has negligible dependence on the temperature. Figure 7 also
shows the dependence of the ratio kethylene/kethane (=yieldethylene/yieldethane) as a
function of temperature which can used to estimate the bubble temperature.
Temperatures in the range of 1930–2720 K have been estimated using this method.
Tauber et al. estimated the temperature in the range of 2300 and 3600 K using
the MRR method by studying the sonolysis of t-butanol [53]. Grieser and coworkers
[54, 55] noted that cavitation bubble temperature is affected by the surface activity
of alcohols used to generate methyl radicals.

4 Physical and Chemical Effects Generated by Acoustic Cavitation

The sudden violent collapse of a cavitation bubble gives rise to a number of physical
and chemical effects in the liquid such as microstreaming, agitation, turbulence,
microjetting, shock waves, generation of radicals, sonoluminescence etc. [19].
Shock waves are produced when the bubble collapses symmetrically [19]. However,
when the bubble collapses unsymmetrically (mostly at a boundary), it leads to the
formation of a jet in the liquid (Fig. 8) [56] due to the uneven acoustic field around
the bubble.
The microjets have velocities of the order of 100 m/s. The effect of shock waves
and microstreaming together with the transition from high to low flow velocities
away from the bubble surface generates extensive amounts of shear stress [57]. The
generation of very high temperatures on bubble collapse leads to local heating. The

Reprinted from the journal 13 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 8 Microjet formation

when a bubble collapses near a
solid surface; adapted from [57]

Rmax ~ 56 µm R ~ 5 µm
Fig. 9 Relative scattered light
intensity, proportional to the size 0
Relative Intensity

of the bubble, as a function of

time. Bubble growth is a
relatively slow process
compared to the collapse. The
spike observed near the end of
the collapse phase is the SL
emission, adapted from [1]

0 10 20 30 40
time, µs

heat generated can raise the temperature of the core of the bubbles to thousands of
degrees for a short period (micro- to nanoseconds). Such extreme thermal conditions
lead to light emission from the bubbles, referred to as sonoluminescence [58]. It was
first observed in 1933 by Marinesco and Trillant [59]. Frenzel and Schultes [7] and
Griffing and Sette [60] were the first to detect sonoluminescence using photomul-
tipliers with accurate temporal resolution. Sonoluminescence can be divided into
two categories [61]. A large number of cavitation bubbles generates multibubble
sonoluminescence (MBSL). Single bubble sonoluminescence (SBSL) refers to
emission observed from a stably oscillating single bubble in a liquid. The change in
radius of a single bubble within one acoustic cycle is shown in Fig. 9 [1, 61–63].
The relative scattered intensity is proportional to radius of the bubble. A
stroboscopic technique was used to record the images of an oscillating bubble as
shown in Fig. 9. SL emission could also be observed at the end of bubble collapse.
The intensity of SL depends on the nature of the liquid medium [64, 65], amount
of dissolved gases [66, 67], hydrostatic pressure [68], acoustic pressure amplitude
[9, 60] and acoustic frequency [60, 69]. Different theoretical models have been
proposed for SL. One model is based on inward-moving shock waves during bubble
collapse: it is believed that light is emitted from the bubble centre where plasma is
created by the shock-wave convergences [70–72]. Another is quasiadiabatic
compression model, where a bubble is heated by the quasiadiabatic compression
[73, 74]. Both SBSL and MBSL originate from quasiadiabatic compression [62, 75].
However, Yasui proposed that sonoluminescence is originated by the heat generated
from the whole bubble rather than a local point [62, 74] and constructed a

123 14 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

theoretical model for SL. Yasui suggested that SL is due to both electron–ion
radiative recombination and electron–atom bremsstrahlung [75]. The mechanism
behind the SL observed from noble gas bubbles is usually radiative recombination
of electrons and ions and electron–atom bremsstrahlung [62].
The intensity of light emission from cavitation bubbles can be increased
significantly by adding a small amount of luminol in aqueous alkaline solutions.
This emission is referred to as sonochemiluminescence (SCL) [76–79], which arises
because of the reaction between OH radicals and luminol. Thus, SCL indicates a
chemically active region in a reactor. Ashokkumar et al. [78, 79] showed that two
groups of cavitation bubbles exist: one group reaches higher temperatures for SL to
occur and the second group causes chemical reactions (Fig. 10). It can be seen in the
figure that SL occurs only in a small region closer to the liquid–water interface. It
was speculated that these bubbles experience relatively larger acoustic force due to
the reflected waves at the air–liquid interface. Note that chemical activity could also
be observed throughout the reactor from cavitation bubbles that reach a relatively
lower temperature enough to cause chemical reactions (OH radical generation).
The speculation that SL bubbles reach relatively higher temperatures is supported
by the experimental data published later. A comparison between the size
distributions of SL-emitting and sonochemistry-producing cavitation bubbles was
studied by Brotchie et al. [44]. They showed that SL-emitting bubbles are larger
than sonochemically active bubbles (Fig. 11) [44].
Another consequence of the extreme conditions of ultrasound is that it leads to a
variety of chemical reactions (formation of highly reaction radical species). When
an argon-saturated liquid is sonicated, formation of H and OH radicals
(Reaction 2) takes place as the majority of the bubble contents is water vapour.
H radicals are reducing in nature, whereas OH radicals are oxidising in nature.
A number of techniques have been used to confirm the formation and
quantification of radical species. ESR spin traps and chemical dosimeters have
been used for the quantification of the radical produced during sonication
[50, 80, 81]. Another method is the reaction between terephthalic acid and OH

Fig. 10 Sonoluminescence from a water and b an aqueous solution containing luminol;

frequency = 170 kHz; power = 12 W [reprinted with permission from John Wiley and Sons [78];
copyright (2010)]

Reprinted from the journal 15 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 11 Bubble radius distribution of SL and SC bubbles. Frequency = 575 kHz [reprinted with
permission from American Physical Society [44]; copyright (2009)]

radicals which leads to the formation of fluorescent hydroxyterephthalic acid

[81, 82]. The intensity of fluorescence can be utilized to quantify the amount of OH
radicals generated during cavitation. The Weissler method is a simple approach to
quantify OH radicals, which is based on the oxidation of iodide ions [1, 83]. In this
method, OH radicals react to produce hydrogen peroxide (Reaction 7) which can
oxidize iodide ions to molecular iodine (Reaction 8). When excess iodide ions are
present, molecular iodine is converted into the triiodide complex (Reaction 9).
Triiodide has an absorption maximum at 353 nm which can be used to quantify the
amount of iodine, and hence the amount of OH radicals generated.
2OH ! H2 O2 ðReaction 7Þ

H2 O2 þ 2I ! 2OH þ I2 ðReaction 8Þ

I2 þ I ! I
3 ðReaction 9Þ

5 Single Bubble Sonochemistry

In air-saturated water, a variety of radicals and molecular products such as H2O2,

HO2, O, O3, HNO2, HNO3, H2 and OH radicals (Reactions 2, 7, 10–15) are
generated (Fig. 12c).
O2 ! 2O ðReaction 10Þ

O þ O2 ! O3 ðReaction 11Þ

H þ O2 ! HO2 ðReaction 12Þ

123 16 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 12 Calculated results for an initial air bubble at around the end of the bubble collapse only for
0.1 ms. a The bubble radius and the temperature inside a bubble. b The number of molecules inside a
bubble. c The intensity of the light emitted from a bubble [reprinted with permission from AIP Publishing
LLC [89]; copyright (2005)]

2HO2 ! H2 O2 þ O2 ðReaction 13Þ

N2 þ O2 ! 2NO ðReaction 14Þ

2NO þ O2 ! 2NO2 ðReaction 15Þ

The quantification of primary radicals and molecular products in multibubble

systems has been extensively studied [26, 44, 55, 84–88]. Such information for a
single bubble system has also been theoretically studied [48, 49, 89]. Only in the
past decade, experimental details on the amount of radicals and molecular products
generated for single bubble systems became available [62, 76, 90].
Yasui et al. [89] numerically calculated the chemical reaction yield for a single
cavitation bubble. In Fig. 12a, the changes in bubble radius and temperature inside a
bubble are shown. It is seen that the temperature inside a bubble increases at the end
of bubble collapse up to 6500 K, which is much lower than that measured in argon-
saturated bubbles because the molar specific heat of nitrogen and oxygen is larger

Reprinted from the journal 17 123

 Top Curr Chem (Z) (2016) 374:56

than that of argon. Figure 12b shows the number of different molecules produced
inside a bubble. The bubble content mostly consists of nitrogen, oxygen and water
vapour, and the main chemical products obtained in this case are HNO3, HNO2, O
and H2O2. Figure 12c shows the intensity of the light emitted from a bubble. SL is
only emitted at the end of the bubble collapse and has a pulse width of about 60 ps.
The number of photons emitted is 1.53 9 104, which is 20 % less than in the case of
argon-saturated bubbles as the SL intensity is affected by the amount and nature of
the dissolved gases. Yasui observed that these results were consistent with the
experimental observation by Matula and Crum [91].
Didenko and Suslick determined the amount of different chemical products
experimentally. Table 1 shows the average amounts of chemical products per
acoustic cycle. It can be seen from the data shown in Table 2 that the main chemical
products are hydrogen molecule, oxygen atom, hydrogen peroxide, hydrogen atom,
and nitrous acid . According to Didenko and Suslick [90], the number of OH
radicals that diffuse into the liquid after one acoustic cycle is 8.2 9 105, which is
consistent with the calculated result of 6.6 9 105. The generation of NO2 and
further reaction of NO2 with H2O leads to the formation of nitric acid [92]. It is for
this reason that sonication of air-saturated water leads to a decrease in solution pH
[1]. The number of NO2- ions produced in one acoustic cycle was experimentally
determined by Didenko and Suslick [90] as 9.9 9 106 (Table 1). A similar number
was reported by Koda et al. [93], which was found to be larger than the value
numerically calculated by Yasui et al. [89].
In Table 2, the average amount of chemical products diffusing into a liquid per
acoustic cycle for the case of an air bubble is shown. A single bubble trapped at the
pressure antinode of a standing ultrasonic wave initially consists mainly of air, and
its main content gradually changes to argon. Yasui et al. [89] showed that the
average amount of HNO2 (4.0 9 107) dissolving in the liquid per oscillation from
an initial air bubble is an order of magnitude larger than that from an SBSL bubble
in steady state (an argon bubble) and it is even larger than the experimentally
reported value of 9.9 9 106. This suggests that the experimentally reported
production rate of NO2- ions may be the time-averaged value during the course of
the gradual change of the bubble content from air to argon. The amount of OH

Table 1 Amounts of chemical products obtained in a single cavitation bubble at 52 kHz, acoustic
pressure 1.5 atm
Conditions 22 °C 3 °C

Rmax (lm) 28.9 30.5

Number of OH radicals per cycle 6.6 9 105 8.2 9 105
Number of photons per cycle 8.1 9 103 7.5 9 104
Number of NO2- ions per cycle 3.7 9 10 6
9.9 9 106
10
Potential energy at Rmax (eV) 6.4 9 10 7.5 9 1010
6
Energy to form OH radicals (eV per cycle) 3.4 9 10 4.3 9 106
- 6
Energy to form NO2 ions (eV per cycle) 1.6 9 10 4.2 9 106

Reprinted with permission from Nature Publishing Group [90]. Copyright (2002)

123 18 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Table 2 Average amount of chemical products that dissolve into the liquid from the interior of an initial
air bubble in one acoustic cycle
Chemical species Number of molecules per acoustic cycle

HNO2 4.0 9 107

HNO3 3.7 9 107
O 1.6 9 107
H2O2 5.1 9 106
O3 2.7 9 106
HO2 2.3 9 106
NO3 1.1 9 106
H2 1.0 9 106
OH 9.9 9 105
NO2 3.9 9 105
N2O 3.0 9 105
NO 1.3 9 105
H 1.1 9 105
HNO 2.8 9 104
N 2.7 9 103
N2O5 6.8 9 102

Reprinted with permission from AIP Publishing LLC [89]; Copyright (2005)

radicals dissolving into liquid from an initial air bubble (9.9 9 105) is not so
different from that from an SBSL bubble in a steady state (6.6 9 105) and is
consistent with the experimentally reported value of 8.2 9 105.
The main oxidants dissolved in the liquid are oxygen and hydrogen peroxide
besides the OH radicals. In a multibubble system, where a standing wave is
established, many bubbles behave as single spherical SBSL bubbles [87, 89, 94–97].
The reason behind this is Bjerknes force. The radiation force, which acts on the
bubbles, leads to the gathering of bubbles at the regions where the acoustic
amplitude is comparable to the cavitation threshold. It has been concluded that even
in a multibubble system oxidants produced are not only OH radicals but also oxygen
atoms and hydrogen peroxide irrespective of the effect of neighbouring bubbles on
the bubble dynamics, shielding of acoustic field, etc. [89, 98]. According to Yasui
et al. [89], O atoms may have been created by the dissociation of oxygen molecules
and water vapour molecules inside the collapsing bubble as given in Reactions 16–
19 (M is an inert third body).
O2 þ M ! O þ O þ M ðReaction 16Þ

OH þ M ! O þ H þ M ðReaction 17Þ

N2 þ O 2 ! O þ N 2 O ðReaction 18Þ

O2 þ N ! O þ NO ðReaction 19Þ

Reprinted from the journal 19 123

 Top Curr Chem (Z) (2016) 374:56

Fig. 13 Experimental results of

the rate of production of H2O2 in
pure water and I2 in 1 M KI
solution or 1 M KI ? 0.0005 M
ammonium molybdate solution
under different mixtures of
argon and oxygen dissolved in
the solution [reprinted with
permission from American
Chemical Society [102];
copyright (1985)]

Different methods to estimate the amount of oxygen atoms have been reported in
the literature [99–101]. In 1985, Hart and Henglein [102] suggested that O atoms
created inside a bubble may oxidize I- ions in an aqueous KI solution containing a
mixture of argon and O2. In their experimental results (Fig. 13), the amount of I2
produced in aqueous KI solution was considerably larger than that of H2O2
generated in pure water (in the absence of O2). On the basis of this observation, they
concluded that there should be some oxidant such as O in addition to OH radicals
and H2O2. Hart and Henglein [102] as well as Yasui [89] suggested that
considerable amounts of O atoms can be produced in an air-filled collapsing bubble.
Therefore sonochemistry can serve as an important tool to study the chemical
reactions of oxygen atoms in liquids [103].

6 Effect of Ultrasound Frequency on Sonochemistry

The extent of sonochemical reactions (e.g. yield of primary and secondary radicals)
and sonoluminescence intensity produced by acoustic cavitation depend on the
frequency, power, etc. Various methods have been used to estimate the cavitation
yield such as the amount chemical products obtained, Tmax, SL intensity etc. as a
function of acoustic frequency. Yasui et al. [48] estimated the average temperature
and rate of production of the main oxidant OH at different frequencies (20, 100, 300
and 1 MHz) as a function acoustic amplitude (Fig. 14). At lower frequencies (20
and 100 kHz), maximum temperature was reached at relatively lower acoustic

123 20 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 14 Numerical simulations of the rate of production of each oxidant inside an isolated air bubble per
second estimated by the first bubble collapse as a function of acoustic amplitude with the temperature
inside a bubble at the end of the bubble collapse (thick line): a 20 kHz and R0 = 5 lm. b 100 kHz and
R0 = 3.5 lm. c 300 kHz and R0 = 3.5 lm. d 1 MHz and R0 = 1 lm [reprinted with permission from
AIP Publishing LLC [48]; copyright (2007)]

amplitudes. This is due to bubble expansion to a relatively larger volume caused by

the longer acoustic period, resulting in an increase in the amount of water vapour
inside a bubble [104]. For a vaporous bubble, which is defined as a bubble with a
molar fraction of vapour higher than 0.5 at the end of the bubble collapse, the main
oxidant created is OH radicals [48].
The amount of H2O2 produced at 100 kHz is higher compared to that produced at
20 kHz because a high temperature is maintained at 20 kHz for a longer time as
compared to higher frequencies, which can dissociate H2O2 into OH radicals. It has
been shown that Tmax is proportional to Rmax for frequencies greater than 16 kHz
[105]. It has been observed for a gaseous bubble that when the molar fraction of
vapour is less than 0.5, the collapse temperature ranges from 4000 to 6500 K and
the main oxidant is H2O2. However, when the bubble temperature is greater than
6500 K in gaseous bubbles, the main oxidant is O atoms. The consumption of
oxidants took place inside an air bubble by an oxidizing nitrogen when the bubble

Reprinted from the journal 21 123

 Top Curr Chem (Z) (2016) 374:56

temperature is higher than 7000 K, and the main chemical products are HNO2, NO
and HNO3 [48, 106].
While Yasui’s calculations on frequency effect are based on a single bubble
system, the overall chemical activity in a multibubble system should be looked at
with a different approach. While single bubble dynamics calculations provide an
avenue to theoretically calculate bubble temperatures, chemical yield, sonolumi-
nescence intensity, etc., such calculations may not provide insight into multibubble
systems. Single bubble calculations tend to provide overestimates of bubble
temperatures and chemical yields when multibubble systems are considered. This is
due to various factors that include bubble clustering, bubble coalescence,
asymmetric collapse of bubbles, inhomogeneous nature of acoustic field, etc.
It is well known that with an increase in frequency, the number of antinodes and
hence the number of cavitation bubbles generated increase. Figure 15 shows the
schematic and photographic images of the standing waves observed at 37 and
440 kHz, which clearly illustrates the increase in the number of standing waves as
well as the bubble population. It has been noted that the radical yield increases with
an increase in frequency, reaches a maximum value and decreases with further
increase in the frequency. The highest sonochemical yield is obtained between 200
and 800 kHz as demonstrated in various studies [61, 86, 107–109].
Figure 16 presents the OH radical yield as a function of sonication time obtained
by sonicating water with different frequencies (20, 358 and 1062 kHz) at a power of
0.90 W/cm2 [110]. The amount of OH radicals produced was highest at 358 kHz,
whereas a decrease was observed when the frequency was increased to 1062 kHz.
This behaviour is due to a relatively lower bubble temperature generated at
higher frequency and a lower amount of water vapour that could evaporate into a
bubble during the expansion phase [110], as shown in Fig. 17 by theoretical
calculations.
Using the resonance radius of the bubbles at each frequency, researchers could
calculate the amount of water molecules in a monolayer on the surface of bubbles
[110]. As for the evaporation process, a finite time is required. From the time
required for evaporation and expansion cycle and the number of molecules at the

Fig. 15 a, c Schematic representation of the standing wave leading to increase in the number of bubbles
with increasing frequency; b, d Images of sonoluminescence profile at 37 and 440 kHz, respectively
[reprinted with permission from Springer [19]; copyright (2016)]

123 22 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

Fig. 16 Yield of OH radicals as

a function of sonication time for
different ultrasonic frequencies
(filled square 358 kHz, filled
inverted triangle 1062 kHz,
filled circle 20 kHz) at
0.90 W cm-2 [reprinted with
permission from Elsevier [110];
copyright (2008)]

Fig. 17 Mass of water

evaporated from a bubble
surface during a single
expansion phase at various
frequencies [reprinted with
permission from Springer [19];
copyright (2016)]

interface, it can be seen that the mass that evaporates exceeds the amount present in
a monolayer on the bubble surface at lower frequencies. At higher frequencies, the
amount that could evaporate is less than a monolayer, which is due to the very short
expansion time available during bubble oscillations. Though a surge in bubble
population occurs at higher frequency, the size of bubble reduces, thereby leading to
a decrease in the bubble temperature and hence the radical yield. Thus, a
combination of lower bubble temperature and lower amount of water vapour present
inside a collapsing bubble is responsible for the decrease in sonochemical efficiency
at very high frequencies.

7 Summary

This article has provided an overview of the basics and fundamentals of

sonochemistry including the dynamics of bubble motion, growth and collapse as
well as different physical and chemical effects generated after the bubble collapse.
The primary and secondary radicals and physical effects such microjetting,

Reprinted from the journal 23 123

 Top Curr Chem (Z) (2016) 374:56

microstreaming, shear forces and the shock waves generated during acoustic
cavitation have been used in material synthesis, sonochemical degradation of
pollutants, mass transfer enhancement, electrochemistry, food technology, phase
separation, alteration of enzyme activity and removal of deposits and biofilms
[111–116], which will be discussed in various articles of this journal.

References
1. Ashokkumar M, Mason TJ (2007) Sonochemistry. In: Kirk-Othmer encyclopedia of chemical
technology. Wiley, New York. doi:10.1002/0471238961.1915141519211912.a01.pub2
2. Duckhouse H, Mason T, Phull S, Lorimer J (2004) The effect of sonication on microbial disin-
fection using hypochlorite. Ultrason Sonochem 11:173–176
3. Ferrara K, Pollard R, Borden M (2007) Ultrasound microbubble contrast agents: fundamentals and
application to gene and drug delivery. Biomed Eng 9:415–447
4. Thornycroft JI, Barnaby SW (1895) Torpedo-boat destroyers. In: Minutes of the proceedings of the
Institution of Civil Engineers, Thomas Telford-ICE Virtual Library, pp 51–69
5. Rayleigh L (1917) VIII. On the pressure developed in a liquid during the collapse of a spherical
cavity. Lond Edinb Dubl Phil Mag 34:94–98
6. Brohult S (1937) Splitting of the haemocyanin molecule by ultrasonic waves. Nature 140:805
7. Frenzel H, Schultes HF (1935) Luminescenz im Ultraschallbeschickten Wasser. Z Phys Chem
27:421
8. Weiss J (1944) Radiochemistry of aqueous solutions. Nature 153:48–50
9. Parke A, Taylor D (1956) The chemical action of ultrasonic waves. J Chem Phys (Resumed)
1956:4442–4450. doi:10.1039/JR9560004442
10. Schulz R, Henglein A (1953) Notizen: Über den Nachweis von freien Radikalen, die unter dem
Einfluß von Ultraschallwellen gebildet werden, mit Hilfe von Radikal-Kettenpolymerisation und
Diphenyl-pikryl-hydrazyl. Zeitschrift für Naturforschung B 8:160–161
11. Noltingk BE, Neppiras EA (1950) Cavitation produced by ultrasonics. Proc Phys Soc Sect B 63:674
12. Makino K, Mossoba MM, Riesz P (1983) Chemical effects of ultrasound on aqueous solutions.
Formation of hydroxyl radicals and hydrogen atoms. J Phys Chem 87:1369–1377
13. Henglein A (1987) Sonochemistry: historical developments and modern aspects. Ultrasonics
25:6–16
14. Leighton T (2012) The acoustic bubble. Academic, San Diego
15. Lorimer JP, Mason TJ (1987) Sonochemistry. Part 1—the physical aspects. Chem Soc Rev
16:239–274
16. Mason T, Paniwnyk L, Lorimer J (1996) The uses of ultrasound in food technology. Ultrason
Sonochem 3:S253–S256
17. Mason TJ, Lorimer JP (1989) An introduction to sonochemistry. Endeavour 13:123–128
18. Leong T, Wu S, Kentish S, Ashokkumar M (2010) Growth of bubbles by rectified diffusion in
aqueous surfactant solutions. J Phys Chem C 114:20141–20145
19. Ashokkumar M (2016) Ultrasonic synthesis of functional materials. In: SpringerBriefs in green
chemistry for sustainability. Springer, Cham, pp 17–40
20. Crum LA (1982) Nucleation and stabilization of microbubbles in liquids. Appl Sci Res 38:101–115
21. Ashokkumar M (2010) Theoretical and experimental sonochemistry involving inorganic systems.
Springer, Dordrecht
22. Yount DE (1979) Skins of varying permeability: a stabilization mechanism for gas cavitation
nuclei. J Acoust Soc Am 65:1429–1439
23. Lim M, Ashokkumar M, Son Y (2014) The effects of liquid height/volume, initial concentration of
reactant and acoustic power on sonochemical oxidation. Ultrason Sonochem 21:1988–1993
24. Crum L (1984) Acoustic cavitation series: part five rectified diffusion. Ultrasonics 22:215–223
25. Yasui K, Tuziuti T, Kanematsu W, Kato K (2016) Dynamic equilibrium model for a bulk
nanobubble and a microbubble partly covered with hydrophobic material. Langmuir. doi:10.1021/
acs.langmuir.5b04703

123 24 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

26. Yasui K (2002) Influence of ultrasonic frequency on multibubble sonoluminescence. J Acoust Soc
Am 112:1405–1413
27. Bremond N, Arora M, Dammer SM, Lohse D (2006) Interaction of cavitation bubbles on a wall.
Phys Fluids 18:121505
28. Yount D, Gillary E, Hoffman D (1984) A microscopic investigation of bubble formation nuclei.
J Acoust Soc Am 76:1511–1521
29. Calvisi ML, Lindau O, Blake JR, Szeri AJ (2007) Shape stability and violent collapse of
microbubbles in acoustic traveling waves. Phys Fluids 19:047101
30. Wang W, Chen W, Lu M, Wei R (2003) Bubble oscillations driven by aspherical ultrasound in
liquid. J Acoust Soc Am 114:1898–1904
31. Plesset M (1949) The dynamics of cavitation bubbles. J Appl Mech 16:277–282
32. Poritsky P (1952) The collapse or growth of a spherical bubble or cavity in a viscous fluid. In:
Proceedings of the 1st US National Congress in Applied Mathematics, p 813
33. Tomita Y, Shima A (1986) Mechanisms of impulsive pressure generation and damage pit formation
by bubble collapse. J Fluid Mech 169:535–564
34. Yasui K (1998) Effect of non-equilibrium evaporation and condensation on bubble dynamics near
the sonoluminescence threshold. Ultrasonics 36:575–580
35. Grieser F, Ashokkumar M (2006) Sonochemical synthesis of inorganic and organic colloids. In:
Caruso F (ed) Colloids and colloid assemblies: synthesis, modification, organization and utilization
of colloid particles. Wiley-VCH, Weinheim, pp 120–149
36. Hsieh DY, Plesset MS (1961) Theory of rectified diffusion of mass into gas bubbles. J Acoust Soc
Am 33:206–215
37. Eller A, Flynn H (1965) Rectified diffusion during nonlinear pulsations of cavitation bubbles.
J Acoust Soc Am 37:493–503
38. Fyrillas MM, Szeri AJ (1996) Surfactant dynamics and rectified diffusion of microbubbles. J Fluid
Mech 311:361–378
39. Lee J, Kentish S, Ashokkumar M (2005) Effect of surfactants on the rate of growth of an air bubble
by rectified diffusion. J Phys Chem B 109:14595–14598
40. Vinodgopal K, He Y, Ashokkumar M, Grieser F (2006) Sonochemically prepared platinum-
ruthenium bimetallic nanoparticles. J Phys Chem B 110:3849–3852
41. Anandan S, Grieser F, Ashokkumar M (2008) Sonochemical synthesis of Au-Ag core- shell
bimetallic nanoparticles. J Phys Chem C 112:15102–15105
42. Kumar PSS, Manivel A, Anandan S, Zhou M, Grieser F, Ashokkumar M (2010) Sonochemical
synthesis and characterization of gold–ruthenium bimetallic nanoparticles. Colloids Surf A
Physicochem Eng Asp 356:140–144
43. Lee J, Ashokkumar M, Kentish S, Grieser F (2005) Determination of the size distribution of
sonoluminescence bubbles in a pulsed acoustic field. J Am Chem Soc 127:16810–16811
44. Brotchie A, Grieser F, Ashokkumar M (2009) Effect of power and frequency on bubble-size
distributions in acoustic cavitation. Phys Rev Lett 102:084302
45. Burdin F, Tsochatzidis N, Guiraud P, Wilhelm A, Delmas H (1999) Characterisation of the acoustic
cavitation cloud by two laser techniques. Ultrason Sonochem 6:43–51
46. Chen W-S, Matula TJ, Crum LA (2002) The disappearance of ultrasound contrast bubbles:
observations of bubble dissolution and cavitation nucleation. Ultrasound Med Biol 28:793–803
47. Tsochatzidis N, Guiraud P, Wilhelm A, Delmas H (2001) Determination of velocity, size and
concentration of ultrasonic cavitation bubbles by the phase-Doppler technique. Chem Eng Sci
56:1831–1840
48. Yasui K, Tuziuti T, Kozuka T, Towata A, Iida Y (2007) Relationship between the bubble tem-
perature and main oxidant created inside an air bubble under ultrasound. J Chem Phys 127:154502
49. Merouani S, Hamdaoui O, Rezgui Y, Guemini M (2014) Theoretical estimation of the temperature
and pressure within collapsing acoustical bubbles. Ultrason Sonochem 21:53–59
50. Mišı́k V, Miyoshi N, Riesz P (1995) EPR spin-trapping study of the sonolysis of H2O/D2O
mixtures: probing the temperatures of cavitation regions. J Phys Chem 99:3605–3611
51. Suslick KS, Hammerton DA, Cline RE (1986) Sonochemical hot spot. J Am Chem Soc
108:5641–5642
52. Hart EJ, Fischer C-H, Henglein A (1990) Sonolysis of hydrocarbons in aqueous solution. Int J
Radiat Appl Instrum C Radiat Phys Chem 36:511–516
53. Tauber A, Mark G, Schuchmann H-P, Sonntag C (1999) Sonolysis of tert-butyl alcohol in aqueous
solution. J Chem Soc Perkin Trans 2:1129–1136

Reprinted from the journal 25 123

 Top Curr Chem (Z) (2016) 374:56

54. Rae J, Ashokkumar M, Eulaerts O, von Sonntag C, Reisse J, Grieser F (2005) Estimation of
ultrasound induced cavitation bubble temperatures in aqueous solutions. Ultrason Sonochem
12:325–329
55. Ciawi E, Rae J, Ashokkumar M, Grieser F (2006) Determination of temperatures within acousti-
cally generated bubbles in aqueous solutions at different ultrasound frequencies. J Phys Chem B
110:13656–13660
56. Crum L (1994) Sonoluminescence, sonochemistry, and sonophysics. J Acoust Soc Am 95:559–562
57. Mason TJ, Peters D (2002) Practical sonochemistry: power ultrasound uses and applications.
Woodhead, Cambridge
58. Ashokkumar M, Lee J, Kentish S, Grieser F (2007) Bubbles in an acoustic field: an overview.
Ultrason Sonochem 14:470–475
59. Marinesco M, Trillat JJ (1933) Action des ultrasons sur les plaques photographiques. CR Acad Sci
Paris 196:858
60. Griffing V, Sette D (1955) Luminescence produced as a result of intense ultrasonic waves. J Phys
Chem 23:503–509
61. Suslick KS, Crum LA (1998) Sonochemistry and sonoluminescence. Wiley-Interscience, New York
62. Yasui K (1999) Mechanism of single-bubble sonoluminescence. Phys Rev E 60:1754
63. An Y (2006) Mechanism of single-bubble sonoluminescence. Phys Rev E 74:026304
64. Jarman P (1958) Sonoluminescence. Sci Prog 46:632–639
65. Crum L, Walton A, Mortimer A, Dyson M, Crawford D, Gaitan D (1987) Free radical production in
amniotic fluid and blood plasma by medical ultrasound. J Utras Med 6:643–647
66. Finch R (1963) Sonoluminescence. Ultrasonics 1:87–98
67. Weissler A (1953) Sonochemistry: the production of chemical changes with sound waves. J Acoust
Soc Am 25:651–657
68. Chendke P, Fogler H (1983) Sonoluminescence and sonochemical reactions of aqueous carbon
tetrachloride solutions. J Phys Chem 87:1362–1369
69. Chambers LA (1937) The emission of visible light from cavitated liquids. J Chem Phys 5:290–292
70. Wu C, Roberts PH (1993) Shock-wave propagation in a sonoluminescing gas bubble. Phys Rev Lett
70:3424
71. Moss WC, Clarke DB, White JW, Young DA (1994) Hydrodynamic simulations of bubble collapse
and picosecond sonoluminescence. Phys Fluids 6:2979–2985
72. Kondić L, Gersten JI, Yuan C (1995) Theoretical studies of sonoluminescence radiation: radiative
transfer and parametric dependence. Phys Rev E 52:4976
73. Kwak H-Y, Na JH (1996) Hydrodynamic solutions for a sonoluminescing gas bubble. Phys Rev
Lett 77:4454
74. Yasui K (1997) Alternative model of single-bubble sonoluminescence. Phys Rev E 56:6750
75. Yasui K (1999) Single-bubble and multibubble sonoluminescence. Phys Rev Lett 83:4297
76. S-i Hatanaka, Mitome H, Yasui K, Hayashi S (2002) Single-bubble sonochemiluminescence in
aqueous luminol solutions. J Am Chem Soc 124:10250–10251
77. Ashokkumar M (2011) The characterization of acoustic cavitation bubbles—an overview. Ultrason
Sonochem 18:864–872
78. Ashokkumar M, Lee J, Iida Y, Yasui K, Kozuka T, Tuziuti T, Towata A (2010) Spatial distribution
of acoustic cavitation bubbles at different ultrasound frequencies. ChemPhysChem 11:1680–1684
79. Sunartio D, Yasui K, Tuziuti T, Kozuka T, Iida Y, Ashokkumar M, Grieser F (2007) Correlation
between Na* emission and ‘‘chemically active’’ acoustic cavitation bubbles. ChemPhysChem
8:2331–2335
80. Mišı́k V, Riesz P (1996) EPR study of free radicals induced by ultrasound in organic liquids II.
Probing the temperatures of cavitation regions. Ultrason Sonochem 3:25–37
81. Mišı́k V, Riesz P (1996) Recent applications of EPR and spin trapping to sonochemical studies of
organic liquids and aqueous solutions. Ultrason Sonochem 3:S173–S186
82. Mason T, Lorimer J, Bates D, Zhao Y (1994) Dosimetry in sonochemistry: the use of aqueous
terephthalate ion as a fluorescence monitor. Ultrason Sonochem 1:S91–S95
83. Ashokkumar M, Niblett T, Tantiongco L, Grieser F (2003) Sonochemical degradation of sodium
dodecylbenzene sulfonate in aqueous solutions. Aust J hem 56:1045–1049
84. Ashokkumar M, Grieser F (2005) A comparison between multibubble sonoluminescence intensity
and the temperature within cavitation bubbles. J Am Chem Soc 127:5326–5327
85. S-i Hatanaka, Yasui K, Kozuka T, Tuziuti T, Mitome H (2002) Influence of bubble clustering on
multibubble sonoluminescence. Ultrasonics 40:655–660

123 26 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:56

86. Kanthale P, Ashokkumar M, Grieser F (2008) Sonoluminescence, sonochemistry (H2O2 yield) and
bubble dynamics: frequency and power effects. Ultrason Sonochem 15:143–150
87. Yasui K (2001) Temperature in multibubble sonoluminescence. J Chem Phys 115:2893–2896
88. Weninger K, Camara C, Putterman S (2000) Observation of bubble dynamics within luminescent
cavitation clouds: sonoluminescence at the nano-scale. Phys Rev E 63:016310
89. Yasui K, Tuziuti T, Sivakumar M, Iida Y (2005) Theoretical study of single-bubble sonochemistry.
J Chem Phys 122:224706
90. Didenko YT, Suslick KS (2002) The energy efficiency of formation of photons, radicals and ions
during single-bubble cavitation. Nature 418(6896):394–397
91. Matula TJ, Crum LA (1998) Evidence for gas exchange in single-bubble sonoluminescence. Phys
Rev Lett 80:865
92. Kruus P (2000) Sonochemical formation of nitrate and nitrite in water. Ultrason Sono 7:109–113
93. Koda S, Tanaka K, Sakamoto H, Matsuoka T, Nomura H (2004) Sonochemical efficiency during
single-bubble cavitation in water. J Phys Chem A 108:11609–11612
94. Yasui K, Tuziuti T, Iida Y, Mitome H (2003) Theoretical study of the ambient-pressure dependence
of sonochemical reactions. J Chem Phys 119:346–356
95. Vazquez G, Camara C, Putterman S, Weninger K (2001) Sonoluminescence: nature’s smallest
blackbody. Opt Lett 26:575–577
96. Tuziuti T, Yasui K, Sivakumar M, Iida Y, Miyoshi N (2005) Correlation between acoustic cavi-
tation noise and yield enhancement of sonochemical reaction by particle addition. J Phys Chem A
109:4869–4872
97. Matula TJ, Roy RA, Mourad PD, McNamara WB III, Suslick KS (1995) Comparison of multi-
bubble and single-bubble sonoluminescence spectra. Phys Rev Lett 75:2602
98. Mettin R, Akhatov I, Parlitz U, Ohl C, Lauterborn W (1997) Bjerknes forces between small
cavitation bubbles in a strong acoustic field. Phys Rev E 56:2924
99. Lucien E, Greer A (2001) Electrophilic oxidant produced in the photodeoxygenation of 1,2-ben-
zodiphenylene sulfoxide. J Org Chem 66:4576–4579
100. Brown WG, Hart EJ (1972) The oxygen atom: a primary species in irradiated water. Radiat Res
51:249–253
101. Sauer MC Jr, Brown WG, Hart EJ (1984) Oxygen (3P) atom formation by the photolysis of
hydrogen peroxide in alkaline aqueous solutions. J Phys Chem 88:1398–1400
102. Hart EJ, Henglein A (1985) Free radical and free atom reactions in the sonolysis of aqueous iodide
and formate solutions. J Phys Chem 89:4342–4347
103. Thomas KB, Greer A (2003) Gauging the significance of atomic oxygen [O(3P)] in sulfoxide
photochemistry. A method for hydrocarbon oxidation. J Org Chem 68:1886–1891
104. Yasui K (2001) Effect of liquid temperature on sonoluminescence. Phys Rev E 64:016310
105. Toegel R, Gompf B, Pecha R, Lohse D (2000) Does water vapor prevent upscaling sonolumines-
cence? Phys Rev Lett 85:3165
106. Yasui K, Tuziuti T, Iida Y (2004) Optimum bubble temperature for the sonochemical production of
oxidants. Ultrasonics 42:579–584
107. Beckett MA, Hua I (2001) Impact of ultrasonic frequency on aqueous sonoluminescence and
sonochemistry. J Phys Chem A 105:3796–3802
108. Capocelli M, Joyce E, Lancia A, Mason TJ, Musmarra D, Prisciandaro M (2012) Sonochemical
degradation of estradiols: incidence of ultrasonic frequency. Chem Eng J 210:9–17
109. Petrier C, Jeunet A, Luche JL, Reverdy G (1992) Unexpected frequency effects on the rate of
oxidative processes induced by ultrasound. J Am Chem Soc 114:3148–3150
110. Ashokkumar M, Sunartio D, Kentish S, Mawson R, Simons L, Vilkhu K, Versteeg CK (2008)
Modification of food ingredients by ultrasound to improve functionality: a preliminary study on a
model system. Innov Food Sci Emerg 9:155–160
111. Shanmugam A, Chandrapala J, Ashokkumar M (2012) The effect of ultrasound on the physical and
functional properties of skim milk. Innov Food Sci Emer 16:251–258
112. Ashokkumar M, Lee J, Zisu B, Bhaskarcharya R, Palmer M, Kentish S (2009) Hot topic: sonication
increases the heat stability of whey proteins. J Dairy Sci 92:5353–5356
113. Chandrapala J, Zisu B, Palmer M, Kentish S, Ashokkumar M (2011) Effects of ultrasound on the
thermal and structural characteristics of proteins in reconstituted whey protein concentrate. Ultrason
Sonochem 18:951–957
114. Price GJ (1996) Ultrasonically enhanced polymer synthesis. Ultrason Sonochem 3:S229–S238

Reprinted from the journal 27 123

 Top Curr Chem (Z) (2016) 374:56

115. Bhangu SK, Ashokkumar M, Lee J (2016) Ultrasound assisted crystallization of paracetamol:
crystal size distribution and polymorph control. Crys Growth Des 16:1934–1941
116. Mason TJ (2003) Sonochemistry and sonoprocessing: the link, the trends and (probably) the future.
Ultrason Sonochem 10:175–179

123 28 Reprinted from the journal