Applied Catalysis B: Environmental 29 (2001) 167–176

Review
Ultrasound as a catalyzer of aqueous reaction systems:
the state of the art and environmental applications
N.H. Ince a,∗ , G. Tezcanli a , R.K. Belen a , İ.G. Apikyan b
a Institute of Environmental Sciences, Boǧaziçi University, 80815 Bebek-Istanbul, Turkey
bPISA Textile Dyeing and Finishing Industries, Çobançeşme, Güneşli-Istanbul, Turkey
Received 21 May 2000; received in revised form 26 July 2000; accepted 19 August 2000

Abstract
The work presented here is aimed to guide environmental researchers and engineers in ultrasound-based chemical reaction
systems, which are emerging as promising alternatives for the removal of refractory organics in treated effluents or natural
waters. In accordance, the paper is presented in two parts as: (i) an extensive review of aqueous reaction systems catalyzed by
ultrasonic pressure waves, with emphasis on basic theories, physical/chemical principles, state of the art, and figures-of-merits
of sonochemistry, and (ii) a summary of lab-scale experimental work using ultrasonic reaction schemes for rendering or
catalyzing the destructional removal of organic compounds by oxidation in the bulk liquid upon hydroxylation, and/or by
thermal decomposition in the gaseous bubble. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ultrasound; Cavitation; Microbubbles; Sonochemistry; Advanced oxidation process (AOP); Free radicals; Pyrolysis; Thermal
decomposition; Bubble-liquid interface

1. Introduction Destruction or mineralization of organic compounds

The second half of the last century has witnessed
a rapidly deteriorating water environment as the out-
come of extravagant use of complex organic com-
pounds, the spent parts of which were discharged
into conventionally operated wastewater treatment
systems. Research and development in innovative
technologies during the last decade have shown
that advanced oxidation processes (AOP) are highly
promising for the remediation of such contaminated
water/effluent systems without generating any sludge
or solid material of hazardous character [1–4].
∗ Corresponding author. Tel.: +90-212-263-1500;
fax: +90-212-257-5033.
E-mail address: ince@boun.edu.tr (N.H. Ince).
by these processes is based on oxidative degradation
by free radical attack, particularly by the hydroxyl
radical, which is a far more powerful oxidizing agent
than all commonly known oxidants [5].
Free radicals in AOP practices are generated by
a variety of methods such as: (i) photochemical ir-
radiation with ultraviolet light (coupled with a pow-
erful oxidizing agent and/or a semiconductor), (ii)
Fenton and photo-Fenton catalytic processes, (iii)
␥-radiolysis, (iv) electron beam irradiation techniques
and (v) sonolysis [6–13]. Among these, sonolysis is
rarely used, despite the very unique and “extreme”
conditions generated by ultrasound waves in liquid
media, resulting in a remarkably suitable medium for
“high energy chemistry”. Under well-established con-
ditions, these “extremes” not only promote the oxida-

0926-3373/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 0 ) 0 0 2 2 4 - 1
168 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
tive destruction of target contaminants via free radical
reactions, but also provide an excellent medium for
their thermal decomposition in the gas phase. Hence,
the production of free radical species by sonolysis
extends the goals of AOP beyond aqueous phase
oxidative destruction to gaseous decomposition, ow-
ing to very special effects generated by the forma-
tion and collapse of acoustic cavities in sonicated
water.
The goal of this paper is to review the principles
and state of the art of “ultrasound-based free radical
generation”, to induce “sonochemical” reaction con-
ditions in aqueous systems for potential application
in the remediation of water environments. (Sono-
chemistry is defined as chemical reactivity induced
and/or catalyzed by intense pressure waves in a liquid
medium.) The reason for reviewing so many of basic
principles is due to the fact that ultrasonic systems are
extremely sensitive and vulnerable to operational pa-
rameters, which cannot be controlled without a good
knowledge and understanding of physical and chem-
ical phenomena. The work is further aimed to point
out some lab-scale applications of ultrasonic systems
from the literature, reporting the destructive removal
of hazardous substances in water by free radical
mediated oxidation processes, and/or by thermal
decomposition of the solutes as they diffuse from
the bulk liquid to the gaseous bubble interior.
2. Background theories
Ultrasound is defined as any sound of a frequency
above that to which the human ear has no response (i.e.
above 16 kHz). In practice, three ranges of frequen-
cies are reported for three distinct uses of ultrasound
[14]: (i) high frequency, or diagnostic ultrasound
(2–10 MHz), (ii) low frequency or conventional power
ultrasound (20–100 kHz), and medium frequency, or
“sonochemical-effects” ultrasound (300–1000 kHz). It
is this latter range, where chemical reaction processes
are uniquely catalyzed through very “extreme” tem-
peratures and pressures generated by the formation,
growth and collapse of cavitation bubbles.
When a liquid is exposed to an acoustic field,
the pressure waves of the sonic vibrations create a
time/frequency dependent acoustic pressure, consist-
ing of alternating compression and rarefaction cycles
[15]. If the applied pressure is equal to the negative
pressure developed in the rarefaction cycle of the
wave such that the distance between the molecules
of the fluid exceeds the critical molecular distance
to hold it together, the liquid breaks apart to form
cavities made of vapor and gas-filled microbubbles
[15,16]. The phenomenon called “acoustic cavitation”
consists of at least three distinct and successive stages:
nucleation, bubble growth (expansion), and under
proper conditions implosive collapse [17]. The first
stage is a nucleated process, by which cavitational
nuclei are generated from microbubbles trapped in
microcrevices of suspended particles within the liq-
uid [17,18]. In the second stage, the bubbles grow
and expand in a manner restricted by the intensity
of the applied sound wave. With high-intensity ultra-
sound, a small cavity grows rapidly through inertial
effects, whereas at lower intensities the growth oc-
curs through “rectified diffusion”, proceeding in a
much slower rate, and lasting many more acous-
tic cycles before expansion [17]. The third stage of
cavitation occurs only if the intensity of the ultra-
sound wave exceeds that of the “acoustic cavitational
threshold” (typically a few watts/cm2 for ordinary
liquids exposed to 20 kHz). At this condition, the
microbubbles overgrow to the extent where they can
no longer efficiently absorb energy from the sound
environment to sustain themselves, and implode vio-
lently, therefore, in a so called “catastrophic collapse”
[15,16,18,19].
During this collapse stage, the temperatures and
pressures released are in such extremes that the
entrapped gases undergo molecular fragmentation,
which is the underlying phenomenon in homogenous
sonochemistry [16,20,21]. Furthermore, it has been
observed that just before the catastrophic collapse of
compressed gas-filled cavities in water, the bubbles
produce a flash of light called “sonoluminescence”, as
detected by a peak at 310 nm and a broad continuum
throughout the visible [21,22]. The spectrum of sono-
luminescent water was associated with the formation
of high-energy species (e.g. excited hydroxyl radicals)
from molecular fragmentation of compressed gases,
rather than with black body radiation [19,21,23].
Hence, like photochemistry, sonochemistry involves
the introduction of very large amounts of energy in a
short period of time, but the type of molecular exci-
tation is thermal, unlike the electronic excitation felt
 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
by molecules in photochemical processes [17]. It is
further claimed that sonochemistry lies in between
“high-energy” and “molecular” physics, requiring,
therefore, the use of microscopic description of matter
[18].
At present, no consensus exists for the physical ex-
planation of the collapse phase, except that “extreme
and non-equilibrium” conditions exist during the im-
plosion [16,24]. The most highly favored explanation
is that given by the “hot spot theory”, which suggests
that the collapse is so rapid that the compression of the
gas and vapor inside the bubble is adiabatic [25,26].
Consequently, the temperatures and pressures within
a collapsing microbubble can reach values as high as
4200–5000 K and 200–500 atm, respectively, just be-
fore fragmentation [16,17]. The localized “hot spot”
generated by the rapid collapse of acoustic cavities
is very short lived (<10 ␮s), implying the existence
of extremely high heating and cooling rates in the
vicinities of 1010 K/s [14,17,21]. Hence, sonochem-
istry generated by short-lived cavitational heating is
found similar to shock-tube chemistry or multi-photon
infrared laser photolysis, but it is unique in that
acoustically induced cavitational heating occurs only
at condensed phases of the fluid [24,27].
Less popular than the “hot spot theory” are the “con-
vergent shock-wave” and the “electrical perturbation”
models, which are specifically preferred for explain-
ing the luminescence of a single bubble [28,29]. The
emission of light from a single bubble during col-
lapse was also modeled by Hickling [30] and Le Point,
Le Point-Mullie [24], who compared the phenomenon
with “water freezing” and “microplasma formation”
from tiny electrified jets projected inside the cavity, re-
spectively. Finally, in the “new electrical model” pro-
posed by Marquilis [31], the distortion and splitting
of a cavity into small entities were compared to the
negative picture of the liquid jet distortion in aeresol
sprays.
3. Physicochemical aspects of sonochemistry
A great majority of sonochemical systems with
potential industrial applications are heterogeneous,
where enhancement of chemical reactivity is associ-
ated with the physical effects of ultrasound such as
heat and mass transfer, surface activation, and phase
169
mixing [17,18,32]. Sonocatalysis of liquid–liquid het-
erogeneous reactions is based on the mixing effect
of acoustic streaming, which promotes the emulsi-
fication of non-miscible liquids by enhancing reac-
tion rates upon increased interfaces [18]. When the
system is made of a solid–liquid biphasic medium,
catalysis is a consequence of the disruption of the
solid by the jetting phenomenon associated with the
collapse of cavitation bubbles [18]. It is important
to note that many of such effects are observed when
the heterogeneous medium is irradiated with low fre-
quency, or power ultrasound at the 20–100 kHz range
[18].
Homogenous sonochemistry, however, is induced
directly by the outcome of “extreme” conditions in
collapsing microbubbles [18]. Such extremes are re-
ported to produce very unique catalytic effects, aris-
ing from inherent advantages of the system such as:
(i) the ability to generate high-energy species and (ii)
the mimicry of autoclave reaction conditions (i.e. high
temperatures and pressures) on a microscopic scale
[17]. These effects start in the cavities, which are made
of microbubbles filled with vapor of the liquid medium
and/or dissolved volatile solutes and gases diffused
into them [14]. During the collapse of these cavities
in pure aqueous systems, gaseous water molecules en-
trapped in expanded microbubbles are fragmented as
in pyrolysis to generate highly reactive radical species,
such as hydroxyl radicals [33]. The formation of these
radicals in sonicated water was demonstrated in var-
ious laboratories, using combined spin trapping and
EPR techniques, the Weissler reaction, fluorescence
measurements from 2-hydroxy-terephthalate produced
by hydroxylation of terephthalate ion, DMPO trap-
ping, and sonoluminescence measurements based on
the oxidative degradation of luminol to aminophtalate
by sonolytically produced hydroxyl radicals [34–40].
In non-aqueous organic solvents or aqueous media
containing volatile organic gases and solutes, cavita-
tional collapse not only results in the fragmentation of
water molecules to hydroxyl and hydrogen radicals,
but also in the formation of organic radicals, as con-
firmed by experimental studies with ESR spectroscopy
[41].
The hydroxyl radicals generated by water sonoly-
sis may either react in the gas phase or recombine
at the cooler gas–liquid interface and/or in the solu-
tion bulk to produce hydrogen peroxide and water as
170 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176

Fig. 1. Possible sites of chemical reactions in homogenous reaction media.

shown in [33,42]: available in solution, which in turn is a matter of the

life time and collapse duration of the bubbles, as well
H2 O → • OH + • H (1) as the geometry of the reactor.
• OH + • H → H2 O (2) The more important cavity effects are reported to
occur when the frequency of the wave is equal to the
2• OH → H2 O (3) resonating frequency of the bubble [46]. The reso-
nance radius of a bubble excited by low frequency
2• OH → H2 O2 (4)
waves is reported to be ∼170 ␮m (at 20 kHz), and
2• H → H2 (5) the cavities entrapping such bubbles are said to be
“stable” or long lived, with average life times of
If the solution is saturated with oxygen, peroxyl and ∼10 ␮s [15,44,47]. In this kind of cavitation, the
more hydroxyl radicals are formed in the gas phase collapse stage is delayed till after the elapse of a
(upon the decomposition of molecular oxygen), and number of compression and rarefaction cycles, dur-
the recombination of the former at the cooler sites ing which sufficient volumes of volatile solutes and
(interface or the solution bulk) produces additional solvent vapors in the liquid may flow into the gas
hydrogen peroxide, as shown in [43,44]: phase [15]. The delayed growth and long collapse du-
ration of gas-filled bubbles allow radical scavenging
O2 + • H → • O2 H (6)
and recombination reactions at the interfacial sheath
O2 → O + O (7) (as shown by Eqs. (2)–(5) and 8), thus inhibiting the
mass transfer of hydroxyl and other reactive species
O + H2 O → • OH + • OH (8) into the solution [48]. Hence, low frequency ultra-
•O H sound is expected to induce destructive effects only
2 + • O2 H → H2 O2 + O2 (9)
for hydrophobic solutes, which easily diffuse into the
Experience in homogenous sonochemistry has cavity bubbles to undergo pyrolytic destruction inside
shown that there are three potential sites for chemical the collapsing bubble, or hydroxylation and thermal
reactions in ultrasonically irradiated liquids, as illus- decomposition at its interfacial sheath, where pres-
trated in Fig. 1: (i) the cavitation bubble itself, (ii) the sure gradients and temperatures are still high enough
interfacial sheath between the gaseous bubble and the to induce thermal effects.
surrounding liquid, and (iii) the solution bulk [45]. On the contrary, the resonance radii of bubbles
In water or effluent treatment practices, organic pol- excited by medium frequency (300–1000 kHz) ultra-
lutants may be destroyed either at the first two sites sound waves are extremely small (4.6 ␮m at 500 kHz),
upon combined effects of pyrolytic decomposition and giving rise to very short-lived (0.4 ␮s on the average)
hydroxylation, or in the solution bulk via oxidative and mainly void or vapor-filled “transient” cavitations
degradation by hydroxyl radicals and hydrogen per- [15,27]. The pressures and temperatures developed in
oxide. The extent of oxidation in the latter site is lim- such cavities are much higher than found in “stable”
ited by the quantity of uncombined hydroxyl radicals cavities, and larger energies are released into the sur-
 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
rounding liquid during their more rapid and violent
collapse [46,49,50]. Furthermore, such cavitations
are so short lived and the collapse is so rapid that
the time for appreciable degrees of radical scaveng-
ing reactions in the hot bubble or at its interface is
insufficient. As a consequence, medium frequency
ultrasound waves are highly effective for catalyzing
advanced oxidation processes, which are aimed to
destroy non-volatile organic solutes in solution. The
destructive effect of ultrasound in this condition is
due to the high probability of hydroxyl radical trans-
fer into the surrounding liquid during the collapse
stage of acoustic cavitations [24,35,48].
It is obvious, then that the selection of the right
frequency range (the region of conventional power
ultrasound, or that of “sonochemical effects” ultra-
sound) is of utmost significance for achieving ap-
preciable degrees of decontamination. The choice is
based primarily on the physicochemical properties
of the contaminating species, such as vapor pressure
(or Henry’s constant), solubility and octanol–water
partition coefficient [50,51]. Hydrophobic chemicals
with high vapor pressures have a strong tendency
to diffuse into the gaseous bubble interior, and the
most effective site for their destruction, therefore, is
the bubble-liquid interface and/or the bubble itself
[52–54]. Hence, aqueous solutions contaminated with
volatile pollutants should preferably be exposed to
power ultrasound (whereby long-lived “stable” cavi-
ties are generated) for thermal and oxidation effects in
the gas phase and the gas–liquid interface [45,53–55].
In contrast, hydrophilic compounds with low vapor
pressures and low concentrations tend to remain in
the bulk liquid during irradiation, due to the repulsive
forces exerted to-and-from the slightly hydrophobic
bubble surfaces. The major reaction site for these
chemicals, therefore, is the liquid medium, where
they may be effectively destroyed by oxidative degra-
dation, provided that sufficient quantities of hydroxyl
radicals are ejected into the solution during cav-
ity collapse. As stated previously, maximum radical
transfer into the bulk medium occurs when the col-
lapse is “transient”, or when sonication is carried out
via medium frequency ultrasound waves. Moreover,
at this frequency and at high concentrations of such
solutes, an additional destructive pathway via thermal
decomposition was observed, as demonstrated by the
formation of pyrolysis products along with hydroxy-
171
lated intermediates during sonolysis at 300–500 kHz
[56,57]. The extent of destruction by pyrolytic frag-
mentation of non-volatile contaminants is directly re-
lated to their concentration and hydrophobicity, which
dictates their ability to migrate towards the bubble
and/or to accumulate at the bubble–liquid interface
[33]. Consequently, the probable site for thermal de-
composition of non-volatile solutes is the interfacial
bubble sheath, at which solutes may accumulate via
adsorptive processes during the formation and growth
of acoustic cavities. At appreciable concentrations,
the adsorptive tendency of non-volatile solutes on
non-polar surfaces of cavity bubbles was verified by
the exhibition of saturation type kinetics, typical of
Langmuirian behavior, which is commonly proposed
for describing photocatalytic process kinetics [33].
4. Figures-of-merits for optimizing sonochemical
reaction systems
The main concern of scientists and engineers work-
ing with ultrasonic systems is to accomplish maximum
reaction yields and/or maximum pollutant destruction
at optimal conditions. Research and development in
sonochemical systems exposed the significance of two
basic strategies for maximizing reaction efficiencies:
(i) optimization of power and reactor configuration
and/or (ii) enhancement of cavitation [32,51]. The first
strategy requires a mechanistic approach with fea-
tures like: (i) selection of the transducer (piezoelectric
or magnetic material that converts electrical impulses
to mechanical vibrations) and generator (probe types
for low-frequency, and plate-types for high frequency
effects), (b) configuration and dimensioning of the re-
action cell, and (iii) optimization of the power effi-
ciency (i.e. the effective power density delivered to
the reaction medium). These aspects have been thor-
oughly described and reviewed by others in the last
decade [14,32,51,58,59]. The second strategy, i.e. the
enhancement of cavitation to maximize chemical reac-
tivity involves the addition of different gases and solids
into the system to test and compare their effectiveness
in increasing reaction yields and/or reaction rates.
Aqueous media free of impurities are well known
with their tremendously high cavitation threshold, so
that any kind of interference to create “liquid defects”
in the structure is reported to favor cavitation events
172 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
[32]. The easiest way of creating impurities in soni-
cated water is by saturating the solution with a solu-
ble gas, which speeds up the initialization of cavity
formation via provision of excess nuclei [32], while
enhancing the collapse conditions by increasing the
temperature within cavity bubbles [35,40]. However,
since the first effect of cavitation is degassing, the
solution will rapidly be free of dissolved gases if gas
entrainment is ceased during sonication. It is common
practice, therefore, to bubble the liquid incessantly
with a gas throughout the sonication period to main-
tain a constant gas flow into the bubbles so as to sustain
the “extreme” conditions of collapse. The selection of
this gas is also of significance, because the final tem-
perature of a collapsing bubble is closely related (by a
power function) to a gas parameter, called the “poly-
tropic γ ratio”, i.e. the ratio of specific heats (Cp /Cv )
of the ambient gases entrapped in the bubble [26,40].
The nature of the saturating gas is further important,
due to the inverse relationship between thermal con-
ductivity of a gas and the temperature build-up in a
cavity bubble [35,51]. Sonoluminescence studies with
rare gases have shown that as the thermal conductivity
decreases in the order: Xe < Kr < Ar < Ne < He,
the amount of heat loss to the surrounding liquid
(due to heat conduction in the gas) also decreases,
the collapse approaching perfect adiabatic condi-
tions [40,51]. Hence, sonolytic radical yields increase
with increasing effective temperature of collapsing
bubbles, i.e. with increasing γ ratios, but decrease
with increasing thermal conductivities of ambient
Fig. 2. A typical batch reactior using a horn type sonicator to emit low-frequency ultrasound waves into the reaction medium.
gases [51]. Furthermore, rare gases are more effective
than diatomic gases (and air), owing to higher γ ratios
obtained with monatomic gases in water [20,40,51].
However, despite the equal γ ratios of Argon and
Helium in water, much higher yields of pyrolysis
products were detected with the former, as attributed
to its 10-fold lower thermal conductivity [47].
The addition of solid catalysts, such as glass beads,
ceramic disks, SiO2 , Al2 O3 and talc into the reac-
tion medium is another common method for enhanc-
ing cavitation effects. The presence of such material
is reported to be especially useful for micronization of
species (in ultrasonic cell disruption), and for the abra-
sion, activation and alteration of the chemical proper-
ties of catalyst surfaces during ultrasonic irradiation
of liquid media [32].
5. Applications in environmental remediation
The preliminary steps before application are the se-
lection of material, equipment and sonicator, followed
by the design and configuration of the reactor. For best
results, it is very important that these features are re-
solved by collaborative work between the researcher
and manufacturer through exchange of ideas, defini-
tion of goals, and discussion of expected drawbacks
and outputs. Hence, experimental schemes are usually
goal-specific, but may be broadly generalized in terms
of the operational frequency, which determines the
type of the sonicating device suitable with the prop-
 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
Fig. 3. A typical reaction scheme using a plate type transducer to emit high-frequency ultrasound waves into solution from the bottom of
a batch reactor.
erties of reaction medium and target contaminants. In
accordance, typical reactor schemes used in lab-scale
applications with low and medium frequency irradi-
ation to render ultrasonic destruction of volatile and
non-volatile substrates are suggested in Figs. 2 and 3,
respectively.
Generation of sonochemical reaction conditions in
environmental remediation processes provides pollu-
tant destruction either directly via activating thermal
decomposition reactions, or indirectly by the produc-
tion and/or enhancement of hydroxyl radical yields in
advanced oxidation processes. Many of such studies
are focused on parametric and kinetic analyses of
contaminant degradations, and comparison of reac-
tion efficiencies with those conducted in the absence
of ultrasound. The input concentrations are generally
low (10−9 to 10−3 moles/l), as typical of refractory
organics found in natural waters and conventionally
treated effluents. Most commonly tested chemicals
are those that contain substituted aromatic groups,
like phenol, nitrophenol, chlorophenol, azo-benzene
and toluene. In addition, reports of some specific stud-
ies with chlorinated solvents, herbicides, substituted
ethers, natural organic matter, surfactants, reactive
textile dyestuff, and chlorofluorocarbons are available
in the literature. A brief summary of some of the
reported work is given below.
Irradiation of dilute solutions of phenol with low
and high frequency ultrasound showed that degrada-
173
tion was much faster with high frequency ultrasound
(487 kHz), the pathway being advanced oxidation, as
verified by the formation of typical oxidation inter-
mediates (hydroquinone, cathecol and benzoquinone)
and the lack of pyrolysis products [35,60]. In another
study by Drijvers et al. [54], the decomposition of
phenol and trichloroethylene (TCE) were investigated
under the combined effect of sonolysis at 520 kHz
and chemical oxidation with hydrogen peroxide, using
solid catalysts such as Al2 O3 , ZnO, Ni2 O3 and CuO.
The authors reported that while TCE was not at all
effected by the addition of H2 O2 and solid catalysts,
the degradation of phenol was largely enhanced by the
presence of H2 O2 /CuO. They attributed this different
behavior to the difference in the hydrophobicity of the
two compounds.
A study involving the sonochemical decomposition
of p-nitrophenol (p-NP) in the presence and absence
of strong scavengers of hydroxyl radicals such as hu-
mic acid reported that the rate of degradation was not
significantly affected by the concentration of hydroxyl
scavengers below a threshold value [61]. Hence, it was
suggested that pyrolysis is the main reaction chan-
nel for the decay of this compound during sonication.
The result was consistent with previous work showing
that p-NP decays via first-order reaction kinetics near
the hot interface of cavity bubbles due to its thermal
instability at temperatures over 160◦ C [53]. The au-
thors of the referred study have underlain the pH sen-
174 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
sitivity of the decomposition reactions by addressing
the decrease in the rate of degradation of p-NP upon
increased concentrations of phosphate and bicarbon-
ate ions [53]. They claimed that at pH values higher
than pKa of p-NP, the molecule becomes negatively
charged and is repulsed by bubble surfaces, thus being
displaced away from the interfacial region where the
main decomposition reactions are expected to occur.
Serpone et al. [33] studied the kinetics of 2-, 3-,
and 4-chlorophenol decomposition in air equilibrated
media by low frequency ultrasound irradiation. They
reported that reaction products and kinetics were par-
allel to those observed in heterocatalytic oxidation of
these compounds with semiconductor particles.
Sonochemical treatment of wastewaters contami-
nated with benzene and toluene in a “parallel plate
near field acoustic processor” was shown by Thoma
et al. [62] to be highly effective for the destruction
of both compounds within reasonable energy require-
ments. The authors further found that the degrada-
tion of parent molecules followed first-order reaction
kinetics, and the rate constants in each case were in-
versely proportional to the initial concentration of the
compound.
Petrier et al. [35] studied the degradation of pen-
tachlorophenate in argon, air and oxygen saturated
aqueous solutions under 20 and 530 kHz ultrasonic ir-
radiation. They reported that the higher frequency was
considerably more effective, and the degradation was
faster when the solution was bubbled with argon than
when bubbled with O2 or air.
Kang and Hoffmann [63] studied the kinetics
and mechanism of sonolytic destruction of methyl
tert-butyl ether (MTBE) under the effect of ozone gas
and ultrasonic irradiation at 205 kHz. They reported
that ozone accelerates the first-order degradation rate
of MTBE by sonolysis at decreasing initial concen-
trations of the compound. They also observed that
the presence of carbonate and bicarbonate ions in so-
lution as potential competitive reagents for hydroxyl
radicals did not lower the rate of MTBE degradation,
concluding that the degradation occurred at the inter-
face of the cavitation bubble, not in the liquid bulk.
David et al. [64] reported that the systematic herbi-
cides chlorpropham and 3-chloroaniline are destroyed
more effectively at 482 kHz than at 20 kHz. Chemi-
cal analyses of effluent samples showed that while the
mechanism of destruction for chlorpropham was py-
rolytic decomposition inside the gaseous bubble, 3-
chloroaniline was destroyed mainly by radical mech-
anisms and oxidative degradation in the solution bulk.
The degradation of fulvic acid (as a representative
of natural organic matter) under the combined effect
of low frequency ultrasonic irradiation and ozonolysis
was studied by monitoring the time rate of change
in total organic carbon content of the solution during
contact [65]. The combination was reported to pro-
vide a significant advantage as total mineralization of
organic carbon, which could be achieved neither by
ozone nor ultrasound alone. It was concluded that the
ultrasound/ozone process extends the application of
sonochemical techniques to the catalysis of advanced
oxidation processes for the removal of refractory
organic electrolytes in natural water.
Alegria et al. [52] studied the mechanism and site of
degradation of non-volatile surfactants by ultrasonic
irradiation at 50 kHz, using argon as the saturating
gas. They reported that surfactants orient themselves
radially in the interfacial region with their polar head
groups pointing to the bulk solution. This was veri-
fied by the detection of pyrolysis products and the ob-
servation of a strong inhibition of hydrogen peroxide
production with increasing surfactant concentration,
as opposed to the sonolysis of solutions containing
non-volatile non-surfactants.
Vinodgobal and Kamat [13] reported the results
of three hydroxyl radical mediated oxidation reac-
tions (photocatalysis, ␥-radiolysis and sonolysis) for
the degradation of reactive dye, Acid Orange-7 under
the effect of saturation with O2 . They noted the sim-
ilarity of reaction pathways in all three processes, as
made evident from the single identifiable intermedi-
ate produced in all experiments, and concluded that
textile azo dyes are effectively destroyed by advanced
oxidation, or any hydroxyl radical mediated reaction
pathways. In another study, the authors investigated
the ultrasonic mineralization of a textile dye, Rema-
zol Black-B at 640 kHz under a stream of O2 gas [57].
They reported that dye destruction starts in the solu-
tion bulk with the rupture of the azo-bond by • OH at-
tack, and complete decolorization is accompanied by
total mineralization, provided that sufficient contact is
allowed. The authors concluded that ultrasonic reme-
diation should be considered as a solution alternative
to the reuse and/or recycle of textile dyeing mill efflu-
ents as process water.
 N.H. Ince et al. / Applied Catalysis B: Environmental 29 (2001) 167–176
Joseph et al. [66] investigated the effect of Fenton’s
Reaction on the degradation of azo-benzene and some
related azo dyes at 500 kHz. As in the previous work
of Vinodgobal and Kamat [57], these authors also re-
ported that the first step in the reaction scheme was the
cleavage of the azo-double bond upon hydroxyl rad-
ical attack. Fenton’s Reaction at optimal Fe(II) con-
centrations was found to induce a threefold increase
in the reaction rates. Finally, they reported that satu-
rating the solution with Ar instead of O2 accelerated
the reactions by 10%.
Cheung and Kurup [67] studied the sonochemical
destruction of two chlorofluoro-carbons, CFC11 and
CFC113 in dilute aqueous solutions under the effect
of power ultrasound at 20 kHz. They observed that
the reactions were governed by first-order kinetics,
and the observed rate constants for both compounds
were found to decline slightly with an increase in so-
lution temperature from 5 to 10◦ C. The result being
in agreement with temperature effects observed with
other chlorinated hydrocarbons [68] was attributed to
the decrease in the cavitation intensity with an increase
in solvent vapor pressure. The authors further reported
that the rapid rate of degradation was not affected by
the very slight degree of parent compound volatiliza-
tion (5%) during the experiments.
Gonze et al. [69] investigated the effect of ultrasonic
irradiation (500 kHz) as a pre-treatment operation to
reduce the toxicity, or to improve the biodegradabil-
ity in untreated effluents prior to secondary treatment.
Experiments were carried out with synthetic efflu-
ents contaminated with sodium pentachlorophenate,
and acute toxicity tests were conducted using Vibrio
fischeri and Daphnia magna as test organisms. The
authors reported that ultrasound is a highly effective
pre-treatment tool by virtue of its potential to reduce
the toxicity of untreated wastewaters, while rapidly
improving their biodegradability.
Finally, there is supportive evidence that power
ultrasound provides ultimate bacterial destruction in
infected waters, and the rate of the process increases
with solids addition into the reaction medium [70].
6. Conclusions
Catalysis of chemical reactivity by ultrasonic pres-
sure waves is an emerging technology for water and
175
effluent remediation, owing to the advantages of “high
energy” chemistry induced by “very extreme” condi-
tions achieved during the rapid collapse of cavitation
bubbles. The ability of sound waves to catalyze the de-
composition of refractory organic compounds in water
must be considered a major advantage over currently
practiced advanced treatment technologies, where in-
tensive chemical and energy inputs are required for
acceptable degrees of destruction. Furthermore, sonol-
ysis adds a unique dimension to AO systems, with
the ability of ultrasound waves to be transmitted per-
fectly through opaque systems, unlike that of ultra-
violet light.
If environmental applications of ultrasonic tech-
niques emerge as post-treatment schemes for
destructive removal of refractory compounds in
effluent streams, they will mostly require the use of
medium-frequency ultrasound, since such chemicals
are usually macromolecules with complex molecular
structures and hydrophilic properties. It is fortunate
that reactor systems designed for medium frequency
irradiation are relatively easier to maintain than those
operated with power ultrasound, due to the drawbacks
associated with the latter as noise and cavitational
erosion. Such problems, however, may be overcome
by sound-proof material and the proper selection,
configuration and maintenance of the equipment.
Acknowledgements
The work presented here is part of a State funded
project DPT98K120900. The authors thank the Prime
Ministry of Turkey for the funding.
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