Ind. Eng. Chem. Res.

2001, 40, 4681-4715 4681

REVIEWS

Sonochemistry: Environmental Science and Engineering

Applications
Yusuf G. Adewuyi*
North Carolina A and T State University, Department of Chemical Engineering,
Greensboro, North Carolina 27411

Sonochemical engineering is a field involving the application of sonic and ultrasonic waves to
chemical processing. Sonochemistry enhances or promotes chemical reactions and mass transfer.
It offers the potential for shorter reaction cycles, cheaper reagents, and less extreme physical
conditions, leading to less expensive and perhaps smaller plants. The amount of things that
can be accomplished with sonochemistry is, at this stage, only limited by the minds of those
working in this exciting field. Existing literature on sonochemical reacting systems is chemistry-
intensive, and applications of this novel means of reaction in environmental remediation and
pollution prevention seem almost unlimited. For example, environmental sonochemistry is a
rapidly growing area that deals with the destruction of organics in aqueous solutions. However,
some theoretical and engineering aspects are not fully understood. This paper reviews the field
comprehensively by combining the existing knowledge from chemistry with insights into the
pathways and kinetic analysis of environmental sonochemical reacting systems and with
challenges for large-scale applications. The review is intended to advance our understanding
and outline directions for future research.

Contents 6. Concluding Remarks 4711

1. Introduction
2. Theory
2.1 Fundamentals of Ultrasound
2.2 Factors Affecting Aqueous
Sonochemical Processes
2.3 Fundamentals of Sonochemical
Reactions
3. Types of Pollutants
4. Prior Literature
4.1 Aromatic Compounds
4.2 Chlorinated Aliphatic
Hydrocarbons
4.3 Explosives
4.4 Herbicides and Pesticides
4.5 Organic Dyes
4.6 Organic and Inorganic Gaseous
Pollutants
4.7 Organic Sulfur Compounds
4.8 Oxygenates and Alcohols
4.9 Other Organic Compounds
4.10 Other Environmental
Applications
5. Discussion
5.1 Reaction Pathways and Kinetics
5.2 Effects of Water Quality
5.3 Sonication Byproducts and
Toxicity Effects
5.4 Efficiency and Scale-up Issues
7. Literature Cited 4712
4681
4682
4682 1. Introduction
4682 When ultrasonic (or sonic) energy at high powers
more than 1/3 W/cm2 for water at room temperaturesis
4683 applied to a liquid, a “cold boiling” termed cavitation
takes place. Simply put, cavitation is the formation,
4686 growth, and sudden collapse of bubbles in liquids.1,2
Ultrasonic vibration reduces the thickness of liquid
4686
films, enhances gas transfer, and reduces bubble coa-
4686 lescence, which increases the interfacial area for gas
4700 transfer.3-6 For example, the diffusion of liquids through
porous media is enhanced by ultrasound. Ultrasound
4702 can be used to separate gases because lighter molecules
4703 in an ultrasonic field will travel further than heavier
4704 ones. Ultrasonic energy is also used to remove contami-
nants from air and to break down toxic compounds in
4704 water and soil.6 Nearly half of the 189 hazardous air
pollutants (“air toxics”) regulated by the Clean Air Act
4706 Amendment (CAAA) of 1990 are volatile organic com-
4706 pounds (VOCs). This diverse list includes common
4706 solvents or halogenated aliphatic compounds, such as
4707 methylene chloride, chloroform, and trichloroethylene,
all of which are mineralized by ultrasonic irradiation.
7-14 The term mineralization implies the final products
4707 of degradation reactions, which are carbon dioxide,
4708 short-chain organic acids, and/or inorganic ions. Ben-
4708 zene, well-known for its resistance to the action of strong
4709
* Phone: 336-334-7564.Fax: 336-334-7904.E-mail: adewuyi@
4709 ncat.edu.

10.1021/ie010096l CCC: $20.00 © 2001 American Chemical Society

Published on Web 10/04/2001
4682 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
Table 1. Some Advanced Oxidation Technologies
(i) Fenton-Type Reactions
Fe2+ + H2O2 f •OH + Fe3+ + OH-
(ii) Ozone-Peroxide-UV Systems
O3 + -OH f O2- f •OH
3O3 + UV (<400 nm) f 2 •OH
H2O2 + UV (<400 nm) f 2 •OH
H2O2 + O3 f 2•OH
H2O2 + O3 + UV f •OH
(iii) Semiconductor Oxides-UV Systems
TiO2 + hv f TiO2 (h+ + e-)
H+ + OH- f •OH
(iv) Radiolysis (High-Energy Beams):
H2O f e-aq + H• + •OH + (H2, H2O2, H3O+)
(v) Wet Oxidation (WO) Systems:
RH + O2 f R• + HO2•
RH + HO2• f R• + H2O2
H2O2 + M f 2 OH•
RH + OH• f R• + H2O
R• + O2 f ROO•
ROO• + RH f ROOH + R•
(vi) Sonolysis (Ultrasound)
H2O f H• + •OH
oxidants, succumbs under ultrasonication in aqueous
medium.15 Sonochemical oxidation techniques involve
the use of sonic or ultrasonic waves to produce an
oxidative environment via cavitation that yields local-
ized microbubbles and supercritical regions in the
aqueous phase.16 The collapse of these bubbles leads to
surprisingly high local temperatures and pressures.
Locally, the high temperature and pressure may reach
up to and above 5000 K and 1000 atm, respectively.17,18
These rather extreme conditions are very short-lived but
have shown to result in the generation of highly reactive
species including hydroxyl (OH•), hydrogen (H•) and
hydroperoxyl (HO2•) radicals, and hydrogen peroxide.19-23
These radicals are capable of initiating or promoting
many fast reduction-oxidation (REDOX) reactions.
These reactions with inorganic and organic substrates
are fast and often near the diffusion-controlled rate.24-25
Sonochemistry is an example of advanced oxidation
processes (or AOPs).26,27 As shown in Table 1, AOPs owe
their enhanced reactivity, as least in part to the genera-
tion of reactive free radicals, the most important of
which is the excited hydroxyl radical (•OH).
A number of studies have documented the role of
sonochemistry in homogeneous and heterogeneous
chemistry.28-30 Although the phenomena of sonochem-
istry has been recognized for many years and despite
its recent advances, the mechanisms of homogeneous
and heterogeneous sonochemistry are not fully under-
stood. It is only recently that applications in synthesis
and pollution control have prompted interest in indus-
trial scale operation.31,32 Thompson and Doraiswamy33
and Moholkar et al.34 recently reviewed the fundamen-
tals and science and engineering aspects of ultrasound
and its applications to organic synthesis. Luche28 dis-
cusses the use of sonochemistry in organometallic
synthesis, biphasic systems, catalytic reactions, and
organic electrochemistry and the practical consider-
ations for process optimization. However, the applica-
tions of this novel means of reaction in environmental
remediation and pollution prevention seem almost
unlimited. Sonication improves mass transfer and chemi-
cal reaction and is expected to reduce or eliminate
chemical usage, resulting in minimal sludge and dis-
posal problems. This paper reviews the field of envi-
ronmental sonochemistry comprehensively by combin-
ing the existing knowledge from chemistry with insights
into the pathways and kinetic analysis of environmental
sonochemical reacting systems and with challenges for
long-term reliability and economical scaleup.
2. Theory
2.1. Fundamentals of Ultrasound. Ultrasound are
waves at frequencies above those within the hearing
range of the average person, i.e., at frequencies above
16 kHz (16 000 cycles per second).1,2 Ultrasonic energy
(high frequency sound waves) produces an alternating
adiabatic compression and rarefaction of the liquid
media being irradiated. In the rarefaction part of the
ultrasonic wave (when the liquid is unduly stretched
or “torn apart”), microbubbles form because of reduced
pressure (i.e., sufficiently large negative pressures).
These microbubbles contain vaporized liquid or gas that
was previously dissolved in the liquid. The microbubbles
can be either stable about their average size for many
cycles or transient when they grow to certain size and
violently collapse or implode during the compression
part of the wave. The critical size depends on the liquid
and the frequency of sound; at 20 kHz, for example, it
is roughly 100-170 µm. The implosions are the spec-
tacular part of sonochemistry. The energy put into the
liquid to create the microvoids is released in this part
of the wave, creating high local pressures up to 1000
atm and high transitory temperatures up to 5000 K.17-21
This energy-releasing phenomena of the bubble forma-
tion and collapse is simply called cavitation or (“cold
boiling”), or for the case described above, acoustic
cavitation.1,35-37 Cavitation can also be achieved by
throttling a valve downstream from a pump. When
pressure at an orifice or any other mechanical constric-
tion falls below the vapor pressure of liquid, cavitations
are generated which then collapse downstream with a
recovery of pressure, giving rise to high temperature
and pressure pulses. Cavitation achieved from this
mechanism is termed hydrodynamic cavitation.38
2.2. Factors Affecting Aqueous Sonochemical
Processes. Sonochemistry is complicated by the fact
that the nature or the physicochemical properties of the
solvent, solute, or gas in the bubble can have dramatic
effect on the cavitational collapse.37 Cavities are more
readily formed when using solvents with high vapor
pressure (VP), low viscosity (µ), and low surface tension
(σ); however, the intensity of cavitation is benefited by
using solvents of opposite characteristics (i.e., low VP;
high µ, σ, and density, F). The intermolecular forces in
the liquid must be overcome in order to form the
bubbles. Thus, solvents with high densities, surface
tensions, and viscosities generally have higher threshold
for cavitation but more harsh conditions once cavitation
begins.35 There are several properties of gases that can
affect sonochemical activities.5 The heat capacity ratio
(Cp/Cv) or polytropic ratio (γ) of the gas in the bubble
affects the amount of heat released and, hence the final
temperature produced in an adiabatic compression and
the cause of reaction. Assuming adiabatic bubble col-
lapse, the maximum temperatures and pressures within
the collapsed cavitation bubbles (eqs 1 and 2) are
predicted by Noltingk and Nepprias from approximate
solutions of Rayleigh-Plesset equations.39-40
[ ]
Pa(γ - 1)
Tmax ) To (1)
Pv

{Pa(γ - 1)
} the temperature, and the pressure on collapse are all
[γ/γ-1]
Pmax ) Pv (2)
Pv
where To ) ambient (experimental) temperature or
temperature of bulk solution, Pv ) pressure in the
bubble at its maximum size or the vapor pressure of
the solution, Pa ) pressure in the bubble at the moment
of transient collapse (i.e., acoustic pressure), and γ )
polytropic index of the cavity medium.5 As seen from
these equations, higher temperatures and pressures are
generated with monatomic gases with higher γ than
those with polyatomic gases with lower γ. Another
parameter that affects cavitational collapse is the
thermal conductivity of the gas. Although compression
is adiabatic in the sonochemical process, small amounts
of heat are transferred to the bulk liquid. A gas with
low thermal conductivity reduces heat dissipation from
cavitation site following adiabatic collapse and should
favor higher collapse temperature compared with high
thermal conductivity gas. In addition, the gas with the
higher thermal conductivity reduces the temperature
achieved in a collapse. The solubility of the gas in the
liquid used is also an important aspect; the more soluble
the gas, the more likely it is to diffuse into the cavitation
bubble. Dissolved gases form the nuclei for cavitation.
Soluble gases should result in the formation of larger
number of cavitation nuclei and extensive bubble col-
lapse since these gases are readily forced back to the
aqueous phase.
As expected from sonochemical reactions, lowering
temperature increases the rate of reaction unlike most
chemical reacting systems. This is attributed to the
lowering of the solvent vapor pressure which increases
the intensity of cavitation. At low vapor pressure, less
vapor has an opportunity to diffuse into the bubble and
thus cushion the cavitational collapse, therefore making
the implosion more violent. Also, as liquid temperature
decreases, the amount of gas dissolved increases and
the vapor pressure of the liquid decreases. Very volatile
solvents lead to relatively high pressures in the bubble
and also “cushion” the collapse. In some cases, the
increase of temperature may favor the reaction kinetics
to a point and further increase in reaction temperature
leads to a decrease in the reaction rate.41
In the case of a progrssive planar or spherical wave,
the acoustic (or sound) intensity (in W m-2) is directly
related to acoustic pressure by eq 3:
2 due to the fact that higher frequency may actually
Pa
I) (3)
2Fc
where F is the density of the fluid (e.g., water) and c is
the speed of sound in the fluid (1500m/s in water). The
acoustic power (W) represents the intensity emitted by
a given surface. The term Fc represents the acoustic
impedance (Z) of the medium. Values of Z for air, water,
benzene, and ethanol are 400, 1.5 × 106, 1.1 × 106, and
0.95 × 106, kg m-2 s-1 respectively.28 The literature
points to the conclusion that some increase in the
pressure of the system should increase the reaction rate
due to the magnified effect of cavitation implosions.
However, as pressure increases, the intensity must be
increased to obtain cavitation in the first place. Too
much pressure reduces the rate of reaction by decreas-
ing the frequency or efficiency of bubble formations.37
An increase in ultrasound intensity means an increase
in the acoustic amplitude (i.e., Pa). The collapse time,
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4683
dependent on acoustic amplitude; the cavitation bubble
collapse will be more violent at higher acoustic ampli-
tudes. An increase in intensity will thus result in
greater sonochemical effects in the collapsing bubble.5,28
The power delivered to a system depends to some extent
on the frequency level. In most cases, as the power is
increased, the reaction rate also increases. At a critical
power level, increasing the power will decrease the rate
of reaction.42 Power input to the system is dependent
on the amplitude. By increasing the amplitude, the
power is also increased.42,43 Sonochemical activity rises
with increasing intensity to an optimum above which
efficiency falls. According to Raleigh, the main condition
of effective action for ultrasonic cavitation is that the
time of cavity collapse should be smaller than half the
ultrasonics period (τ < T/2), as shown in eq 4.44,45 For a
bubble under constant external pressure (hydrostatic)
from an initial or maximum radius, Rmax, to some final
radius, the relation is given by
τ ≈ 0.915Rmax ( )
F
Ph
1/2
<
T
2
(4)
where τ ) time of cavitation bubble collapse, Rmax ) the
maximum radius of cavitation bubble, T ) ultrasonic
period, Ph ) hydrostatic pressure, and F ) density of
liquid.28,44-45
When the acoustic power increases and simulta-
neously increases amplitude of vibration, the maximum
radius of the cavity bubble also increases, as well as its
time of collapse, τ, and this bubble is not able to collapse
within time equal half of the period. That is, before the
sound field reverses itself, and the rarefaction phase
begins acting on the collapsing bubble.
Frequency has significant effect on the cavitation
process because it alters the critical size of the cavita-
tional bubble.46-51 At very high frequencies, the cavi-
tational effect is reduced because either (i) the rarefac-
tion cycle of the sound wave produces a negative
pressure which is insufficient in its duration and/or
intensity to initiate cavitation or (ii) the compression
cycle occurs faster than the time for the microbubble to
collapse. Lower frequency ultrasound produces more
violent cavitation, leading to higher localized temper-
atures and pressures. However, current research indi-
cates that in reactions such as oxidations, higher
frequencies may lead to higher reaction rates. This is
increase the number of free radicals in the system
because although cavitation is less violent, there are
more cavitation events and thus more opportunities for
the free radicals to be produced. Francony and Petrier
observed the ultrasonic degradation of carbon tetra-
chloride was enhanced and the yield of products faster
when using 500 kHz ultrasound compared with 20
kHz.48 But at very high frequencies, the cavitation
process is decreased. Entezari and Kruus studied the
sonochemical reaction rate of oxidation of iodide at
different temperatures (0-50 °C) and with different
ultrasonic horns at low frequency (20 kHz) and with a
high-frequency (900 kHz) apparatus.50 The results
showed that at 900 kHz the rate of oxidation increased
up to 30 °C at lower power levels whereas at 20 kHz,
the rate of oxidation decreased with increasing temper-
ature.
2.3. Fundamentals of Sonochemical Reactions.
The influence of ultrasonic energy on chemical activity
4684 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
Figure 1. Three reaction zones in the cavitation process.
may involve any or all of the following: production of
heat, promotion of mixing (stirring) or mass transfer,
promotion of intimate contact between materials, dis-
persion of contaminated layers of chemicals, and pro-
duction of free-chemical radicals.1-3,52-53 The physical
effects of ultrasound can enhance the reactivity of a
catalyst by enlarging the surface area or accelerate a
reaction by proper mixing of reagents. The chemical
effects of ultrasound enhance reaction rates because of
the formation of highly reactive radical species formed
during cavitation.4,21 Homogeneous sonochemistry ex-
amines, mainly in the liquid phase, the activity of the
radicals or excited species formed in the bubble gas
phase (OH•, H•, X•, C2•, CN/, etc.) during the violent
implosion and their possible release into the liquid.28
The cavitation event also gives rise to acoustic micros-
treaming or formation of miniature eddies that en-
hances the mass and heat transfer in the liquid, and
also causes velocity gradients that results in shear
forces. In heterogeneous sonochemistry, the mechanical
effects of cavitation resulting from the erosion action of
microjets formed during asymmetric collapse of bubbles
at the vicinity of interfaces are also important.28 So far,
four theories have been proposed to explain the sono-
chemical events: (1) hot-spot theory; (2) “electrical”
theory; (3) “plasma discharge” theory, and (4) super-
critical theory. These have led to several modes of
reactivity being proposed: pyrolytic decomposition, hy-
droxyl radical oxidation, plasma chemistry, and super-
critical water oxidation. The “hot-spot” theory suggests
that a pressure of thousands of atmosphere (up to 1000
atm) is generated and a temperature of about 5000 K
results during the violent collapse of the bubble.17-19
Both Margulis54 and Lepoint55 advocate that the ex-
treme conditions associated with fragmentative collapse
are due to the intense electrical fields. The “electrical”
theory by Margulis suggests that during bubble forma-
tion and collapse, enormous electrical field gradients are
generated and these are sufficiently high to cause bond
breakage and chemical activity.22,54 The “plasma theory”
by Lepoint and Mullie also suggests the extreme condi-
tions associated with the fragmentative collapse is due
to intense electrical fields and seems not to involve a
true implosion. They liken the origin of cavitation
chemistry to corona-like discharges caused by a frag-
mentation process and supported their views by drawing
numerous analogies between sonochemistry and corona
chemistry and indicating the formation of microplasmas
inside the bubbles.55 The supercritical theory recently
proposed by Hoffmann56 suggests the existence of a
layer in the bubble-solution interface where tempera-
ture and pressure may be beyond the critical conditions
of water (647 K, 22.1 MPa) and which may have
physical properties intermediate between those of a gas
and a liquid. They showed that supercritical water is
obtained during the collapse of cavitation bubbles
generated sonolytically.
In general, most studies in environmental sonochem-
istry have adopted the “hot spot” concepts to explain
experimental results. This theory considers a sonochem-
ical reaction as a highly heterogeneous reaction in which
reactive species and heat are produced from a well-
defined microreactor, “the bubble of cavitation.21,57 In
the “structured hot spot” model shown in Figure 1, three
regions for the occurrence of chemical reactions are
postulated: (1) a hot gaseous nucleus; (2) an interfacial
region with radial gradient in temperature and local
radical density; and (3) the bulk solution at ambient
temperature. Reactions involving free radicals can occur
within the collapsing bubble, at the interface of the
bubble, and in the surrounding liquid. Within the center
of the bubble, harsh conditions generated on bubble
collapse cause bond breakage and/or the dissociation of
the water and other vapors and gases, leading to the
formation of free radicals or the formation of excited
states. Solvent and/or substrates suffer homolytic bond
breakage to produce reactive species. The high temper-
atures and pressures created during cavitation provide
the activation energy required for the bond cleavage.
The radicals generated either react with each other to
form new molecules and radicals or diffuse into the bulk
liquid to serve as oxidants. The second reaction site is
 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4685

Table 2. Proposed Kinetic Mechanisms

A. Water Dissociation
H2O f H• + •OH R1 •OH + •OH f H2O2 R7 H• + H2O2 f •OH + H2O R13
H• + H• f H2 R2 •OH + •OH f H O + O•
2 R8 H• + H2O2 f H2 + HO2• R14
H• + O2 f HO2• R3 •OH + •HO f H O + O
2 2 2 R9 •OH + H O f HO • + H O
2 2 2 2 R15
HO2• + HO2• f H2O2 + O2 R4 O• + O• f O2 R10 •OH + H f H O + H•
2 2 R16
HO2• + HO2• f H2O + 3/2O2 R5 1/2O2 + 2H• f H2O R11 H2O + •OH f H2O2 + H• R17
H• + HO2• f H2O2 R6 H• + OH• f H2O R12
B. Under N2 Atmosphere
As in R1 Plus
N2 f 2N• R18 NO + NO2 f N2O3 R25 NO + NO f N2O + O R32
N• + •OH f NO + H• R19 N2O3 + H2O f 2HNO2 R26 N2O + O• f 2NO (or N2 + O2) R33
NO + •OH f HNO2 R20 N• + H• f :NH R27 N2O + N2 f O• R34
NO + •OH f NO2 + H• R21 :NH + :NH f N2 + H2 R28 N• + O2 f NO + O• R35
NO + H• f N• + •OH R22 N2 + •OH f N2O + H• R29 NO + O f NO2• R36
2 NO2(aq) + H2O f HNO2 + HNO3 R23 N2 + O• f N2O (or NO + N•) R30 2NO + O2 f 2NO2 R37
NO2 + •OH f HNO3 R24 N• + NO f N2 + O R31
C. Under O2 Atmosphere
As in R1 Plus
O2 f 2O• R38 O• + H2 f •OH + H• R42 O3 + O f 2O2 R46
O• + H2O f 2•OH R39 O• + HO2• f •OH + O2 R43 2HO2• f H2O2 + O2 R47
O• + O2 fO3 R40 O• + H2O2 f •OH + HO2• R44 2•OH f H2O2 R48
H• + O2 f •OH + O• (or HO2•) R41 HO2• f •OH + O• R45 2•OH f O• + H2O R49
D. Under Ar Atmosphere
As in R1 plus
•OH + •H + M f H2O + M R50 O• + H2O + M f H2O2 + M R55 O• + H2O f 2•OH R60
2•OH f •O + H2O R51 O2 + H• + M f HO2• + M R56 Ar f Ar/ R61
2•OH + M f H2O2 + M R52 •OH + H O f HO • + H O
2 2 2 2 R57 Ar/ + H2O f H2O/ + Ar R62
2H• + M f H2 + M R53 2HO2• f H2O2 + O2 R58 H2O/ f H• + •OH R63
2O• + M f O2 + M R54 HO2• + H• f H2O + O• R59
E. Under Air Atmospehre
As in B and C Plus
N2 + O2 f 2NO R64 NO2• + O• f NO3 R66 N2O5 + H2O f 2HNO3 R68
N2O• + O• f 2NO R65 NO2 + NO3 f N2O5 R67
F. Under H2 Atmosphere
As in R1 Plus
H2 f H• + H• R69 H2 + •OH f H2O + H• R70
G. Under CO2 Atmosphere
As in R1 Plus
CO2 + •H f CO + •OH R71 O • + O • f O2 R74 CO2 + H• f HCOO• R76
CO2 f CO + O• R72 CO + O• f CO2 R75 HCOO• + H• f HCHO + O• R77
2H• + O• f H2O R73

the liquid shell immediately surrounding the imploding
cavity, which has been estimated to heat up to ap-
proximately 2000 K during cavity implosion. In this
solvent layer surrounding the hot bubble, both combus-
tion and free-radical reactions (involving •OH derived
from the decomposition of H2O) occur.23 Reactions here
are comparable to pyrolysis reactions. Pyrolysis (i.e.,
combustion) in the interfacial region is predominant at
high solute concentrations, while at low solute concen-
trations, free-radical reactions are likely to predominate.
At this interface between the bubble and bulk liquid,
surface-active reagents also accumulate and species
produced in the bubble first react with chemicals in the
bulk liquid. It has been shown that the majority of
degradation takes place in the bubble-bulk interface
region.58,59 The liquid reaction zone was estimated to
extend ∼200 nm from the bubble surface and had a
lifetime of <2 µs.17-19 In the bulk liquid, no primary
sonochemical activity takes place although subsequent
reactions with ultrasonically generated intermediates
may occur. A small number of free radicals produced in
the cavities or at the interface may move into the bulk-
liquid phase and react with the substrate present
therein in secondary reactions to form new products.
Depending on their physical properties and concentra-
tions, molecules present in the medium will be “burned”
in close to the bubble or will undergo radical reactions.
For example, reactions R4 and R7 in Table 2 do not
occur in the gaseous phase (where H2O2 is unstable)
because of the prevailing high temperatures and pres-
sures. Rather, these reactions occur at the relatively
cooler interfacial region.
Some of the sonochemical reactions identified in the
cavitational events are summarized in Table 2. The
formation of •H and •OH is attributed to the thermal
dissociation of water vapor present in the cavities during
the compression phase (R1). Sonolysis of water also
produces H2O2 and hydrogen gas, via hydroxyl radicals
and hydrogen atoms (R2-R7). The presence of oxygen
improves sonochemical activities, but it is not essential
for water sonolysis, and sonochemical oxidation and
reduction can proceed in the presence of any gas.
However, in the presence of oxygen acting as a scaven-
ger of hydrogen atom (and thus suppressing the recom-
bination of •H and •OH), the hydroperoxyl radical (HO2•)
is additionally formed which is an oxidizing agent (R3).
This radical causes a number other reactions to occur
resulting in the formation of H2O2, O2, O, and H2 as
products (R4-R9). Thermal dissociation of oxygen mol-
ecule may also occur, leading to the generation of
additional hydroxyl radicals (R38-R39). In the absence
of •OH scavengers, the main product of the sonolysis of
water is H2O2 (R7). H2O2 can also be produced in an
“inert” atmosphere but only at the expense of •OH
4686 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
radical (R51). Formation of atomic nitrogen and oxygen,
nitrogen fixation (with HNO2 as the major acid compo-
nent formed) can occur in the cavity.60 Nitrogen mol-
ecules inside the cavitation bubble may react at high
temperature with hydroxyl radicals and oxygen atoms
to give nitrous oxide and nitrogen oxide by a mechanism
analogous to that in combustion chemistry (R19, R29-
R30). N2O is unstable under the high-temperature
conditions of the cavitation bubble and is further
decomposed in the gas phase and may be transformed
to NO (R33).60 NO may undergo further reactions either
in the gas-phase of acoustic cavities or free-radical
reactions in the cooler interfacial zone, ultimately
resulting in the formation of nitrous and nitric acids
(R20-R23). Nitrogen fixation is inhibited by H2 and CO
under a hydrogen atmosphere; oxidation reactions are
almost completely suppressed owing to the strong
reducing ability of •H. The inhibiting effect of CO on
nitrogen is as follows. The oxygen formed in the irradi-
ated water is used up in the oxidation of the CO
introduced into the water with subsequent formation
of CO2 (R74). The presence of CO (or CO2 in small
amount) may cause formation of HCHO in the cavita-
tion bubble (R75-R76). If CO is introduced with N2 and
H2, then HCN and HCHO are major products. HCN,
NH3, and HCHO can be formed from solutions saturated
with N2, CO, and H2.60 Another mechanism suggested
is that in which inert gases penetrating into a cavity
can contribute to the transfer of electron excitation to
water or hydrogen molecules.22,44,60 For example, the
excited argon atom (Ar*) can participate in energy
transfer reactions, as shown in reactions (R60-R62). In
the presence of H2, argon also facilitates the formation
of ‚H by direct dissociation of H2 within the cavitation
bubble.
3. Types of Pollutants
A number of previous studies have examined the
transformation of pollutants by ultrasonic irradiation
or combined ultrasound and other advanced oxidation
techniques to organic techniques to organic intermedi-
ates with mineralizaton to inorganic ions, CO2, and
short-chain organic acids as final products in some
cases. The pollutants studied and other environmental
applications include:
(1) Aromatic Compounds
• Phenol, 2-, 3-, 4- and 2,4-chlorophenols, p-nitrophenol,
and p-nitrophenyl acetate (PNPA)
• Benzene, toluene, ethylbenzene, 1,3,5-trimethylben-
zene (mesitylene), xylene, fluoro-, bromo-, iodo- and
chlorobenzene, hydroxybenzoic acids, humic acids,
nitrobenzene, nitro- and chloro-toluene, and styrene
• Polycyclic aromatic hydrocarbons (PAHs),- anthracene,
phenanthrene, pyrene, byphenyl, and dioxin
• Mixtures of chlorophenol and chlorobenzenes
(2) Chlorinated Aliphatic Hydrocarbons (CAHs)
• Trichloroethylene (TCE) and tetra- or perchloroethyl-
ene (PCE)
• Carbon tetrachloride (CCl4), chloroform (CHCl3), dichlo-
romethane (CH2Cl2), and methylene chloride (CH3-
Cl)
• 1,1,1-Trichloro and 1,2-dichloroethane
• Chloral hydrate
• Mixtures of CAHs with phenols, BTEX, or chloroben-
zenes
(3) Explosives
• 2,4,6-Trinitrotoluene (TNT)
• Cyclotrimethylene-trinitramine (RDX)
• HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)
(4) Herbicides and Pesticides
• Herbicides: atracine, alachlor, chlorpropham (isopro-
pyl-3-chlorocarbanilate 3-chloraniline)
• Pesticides: pentachlorophenol (PeCP) and pentachlo-
rophenate (PCP), polychlorophenyls (PCBs), par-
athion (O5-O-diethylo-p-nitrophenyl-thiophosphate),
and phenyltrifluoromethyl ketone (PTMK)
(5) Organic Dyes
• Azo dye, remazol black (RB)
• Azo dye, naphthol blue black (NBB)
(6) Organic and Inorganic Gaseous Pollutants
• Greenhouse gasessfluorotrichlormethane (CFC 11),
trifluorotrichloro ethane (CFC 113), nitrous oxide, and
carbon dioxide
• Hydrocarbonssacetylene, methane, ethane, propane
• Hydrogen sulfide
• Ozone
(7) Organic Sulfur Compounds
• Carbon disulfide
• Di-n-butylsulfide
(8) Oxygenates and Alcohols
• Methyl tert-butyl ether (MTBE), methanol, and etha-
nol
• Mixtures of alcohols and chloromethanes
• Mixtures of alcohols (i.e., ethanol), polyvinlpyrrolidone
(PVP), and tetranitromethane (TNM)
(9) Other Organic Compounds
• Surfactantsstert-octylphenoxy polyethoxyethanol (Tri-
ton X-100), polyoxyethylene alkyl ether (SS 70)
• Formic acid and formates
• Acetate
• Thymine
(10) Other Environmental Applications
• Industrial wastes of a cyclohexane oxidation unit
• Natural groundwater and organic matter
• Biological treatment systems: toxicity reduction and
disinfection
4. Prior Literature
Studies involving the use of sonochemical or pho-
tosonochemical processes to treat a variety of chemical
contaminants mostly in aqueous systems are sum-
marized in Table 3, highlighting the chemical oxidation
schemes and experimental conditions utilized, removal
effectiveness, and intermediates and degradation prod-
ucts observed.
4.1. Aromatic Compounds. The ultrasonic degrada-
tion of phenol, chlorophenols, and nitrophenols have
been studied by a number of investigators. The inter-
mediates and products of the sonochemical oxidation of
phenol usually include hydroquinone, catechol, p- and
o-benzoquinone, 2,5-dioxohexen-3-dioic, muconic, ma-
leic, succinic, formic, propanoic, oxalic and acetic acids,
and CO2. Berlan et al.61 observed that primary degrada-
tion products such as dihydroxybenzenes and quinones
are further degraded upon time into the low molecular
carboxylic acids under mild external conditions (room
temperature, atmospheric pressure) due to local extreme
conditions resulting from cavitation, without the need
for any chemical reagent. Petrier et al.62 found the rate
of sonochemical phenol degradation to proceed more
rapidly at higher (i.e., 487 kHz) than low (i.e., 20 kHz)
frequency with concomitant better release of •OH in the
Table 3. Studies Utilizing Sonochemical and Photosonochemical Degradation of Aqueous Organic and Inorganic Pollutants
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Adewuyi carbon disulfide (CS2) 6.4-7.0 × 10-4 ultrasound: 20 temp, 1-50 °C; in air :sulfate in the degradation rates in the
and Collins, M, 10.5 × 10-4 kHz, 14-50 W irradiating pH range 8-11 irradiating gases is in the
2001a,b M, 13.2-13.6 gases, Air, Ar, order He > Air > N2O > Ar
× 10-4 M He, N2O; pH
8-11
Alippi et carbon tetrachloride 1.0-5.0 M ultrasound (US) temp, room, Free iodine and Cl2 in 5.0 × 10-3 - 3.0 × 10-3 (mol
al., 1992 (CCl4), chloroform CCl4, 1.0 M (300 W) irradiation the case of CCl4. HCl dm-3) free iodine yield.
(CHCl3) dichloromethane KI time, 1-3h inferred from pH
(CH2Cl2), (in aqueous decrease. No Cl2 formed
solution of KI) with CHCl2 and CHCl2.
Barbier and 4-nitrophenol (4-Np) 0.5 mM ultrasound/ temp, 20 ( 2 4-nitrocatechol, CO2 ultrasound-enhanced
Petrier, ozonation °C; pH 2; O3 minerilization potential
1996 ultrasound, 20 irradiating potential of substrate
kHz (30 W), 500 gas, O3/O2
kHz (30 W); O3 (2-3% O3)
concentration,
1.72 × 10-4 M at
20 kHz, 1.58 ×
10-4 M at 500
kHz
Berlan et phenol; aniline; 100 mg/L ultrasound (30 temp, 27 ( 2 hydroquinone, catechol, Total degradation after 100
al., 1994 2-chlorophenol W), intensity, 1 W °C; pH 6; p-benzoquinone, oxalic min at 541 kHz, unchanged
cm-2 at 541 kHz dissolved gas, maleic, acetic, formic at 20 kHz. Mineralization
and 27 W cm-1 at air, O2, and Ar; and propanoic acids, of phenol improved with
20 kHz solid catalyst and CO2 Raney nickel.
Bhatnagar methylene chloride; 50-350 mg/L ultrasound (20 temp, 25 °C; No chlorinated products 72-99.9% destruction in
and chloroform, CHCl3; aqueous solutions kHz, 0.1 kW/L) pH 6-5, 7, 9 detected. HCl inferred 20-40 min. First-order
Cheung, carbon tetrachloride, of VOCs and from pH decrease. degradation kinetics varies
1994 CCl4; 1,2-dichloroethane, mixtures from 0.021 to 0.046 min-1.
DCA;
1,1,1-trichloroethane, TCA;
trichloroethylene (TCE);
perchloroethylene (PCE)
Buttner et methanol-water mixtures 0-100 vol. % ultrasound (US) irradiation H2, CH2O, CO, CH4, degradation efficiency not
al., 1991 CH3OH (1-MHz, 2 time, 10 min C2H4, C2H6 under explicitly given
W/cm2) argon; CO2, CO,
HCOOH, CH2O, H2O2,
H2 under oxygen
Catallo and chlorpyrifos, 3,3′,4,4′- 3 µg/mL ultrasound (1.6 temp, 4-12 °C; dechlorination products not explicitly given
Junk, 1995 tetrachloroazoxybenzene kW h) sonication time, 6-10 h detected for all
(TCAOB), at 5-100 psi. compounds (except for
2-chlorobiphenyl, Sparged under TCAOB and TCDF)
2,4,8-trichlorodibenzofuran Ar for 1 h prior under minimal
(TCDF), lindane, aldrin, to run. sonochemical
hexachlorobenzene (HCB), conditions
mixture of chlorinated
olefins, parafins and
aromatics
Chen et al., phenol (PhOH), sewer PhOH, ultrasound, 25, temp, 22 °C; hydroquinone, catechol oxidation proceeded toward
1971 waste treatment effluent 100-700 55, and 800 kHz; irradiating completion at the high
mg/L, solid intensity, 0-33.3 gas, air; frequency
catalysts, W/cm2 catalysts,
20-200 mg V2O5, PtO2,
Ag2O, MnO2,
and RuO2
Chendke carbon tetrachloride (pure 0-100 vol. % ultrasound irradiation major products, HCl 7.5-20.0% CCl4 consumed
and Fogler, CCl4, two-phase CCl4 time, 15 and HOCl; minor
1983 water-CCl4 solution, min; pressure, products, C2Cl4 or
saturated water solution in 1-20 atm C2Cl6
CCl4)
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4687
Table 3. (Continued)
4688

chemical degradation degradation

contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Cheung et methylene chloride, carbon 100-1000 ultrasound (250 temp, 15-20 Products not explicitly Methylene chloride
al., 1991 tetrachloride, mg/L aqueous W) °C reported. HCl dropped from 120 to 25
1,1,1-trichloroethane, solutions formation inferred from ppm in 40 min. First-order
trichloroethylene pH drop. rate constant of 3.93 × 10-2
min-1 calculated.
Cheung fluorotrichloromethane 50 mg/L ultrasound (20 temp, 5-10 °C HCl, HF or other acidic almost 100% in 40 min for
and Kurup, (CFC11), aqueous kHz), batch CR at 5 psi g species (inferred from CR and 10 min for batch
1994 trifluorotrichloroethane solution reactor pH drop) reactor
(CFC113) (160 W/4.6
W/mL),
circulating
reactor (CR),
0.64 W/mL
Cost et al., p-nitrophenol (in the 2 × 10-5 M ultrasound (20 temp, 10 °C; 4-nitrocatechol degradation not affected by
1993 presence of common kHz, 50 W) pH 5.5; chemicals of natural water
chemicals of natural water) irradiation
medium, air
Dahi, 1976 Rhodamine B, E. coli E. coli, sonozonation; temp, 18 °C; not determined ultrasonic treatment of
106-107 ultrasound, 20 pH 7.2; effluent from biological
bacteria per kHz ozone, irradiation sewage reduced the
mL 3.68-3.94 medium, sterilization dose of O3 by
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001

mg min-1 L-1 O2/O3 50% and decoloration

zero-order rate constant of
Rhodamine B by 55%
David et al., chlorpropham (isopropyl- 0.1 mM sonolysis, probe temp, 20 °C; 3-chloroaniline, Degradation efficiency was
1998 3-chlorocarbanilate), aqueous transducer (20 & irradiation HCOOH, CO, CO2, Cl- 100% after 45 min at 482
3-chloroaniline solutions 482 kHz, 40 W) medium, air for chlorpropham; Cl-, kHz and 60% at 20 kHz.
NO2-, NO3-, CO, CO2 Efficient elimination of
for 3-chloroaniline both compounds at 482
kHz.
De Visscher trichloroethylene (TCE), TCE, 3.34 ultrasound (518 solution temp, not reported H2O2 enhanced o-CP
and o-chlorophenol (o-CP), mM; o-CP, kHz, 18.2W) 30 °C; degradation rate by
Langenhove 1,3-dichloro-2-propanol 0.362 and with/without irradiation 20-25%. TCE and DCP
1998 (DCP) 0.724 mM; Fenton reagent, medium, air unaffected by H2O2.
DCP, 0.29 hydrogen Presence of t-BuOOH and
mM; H2O2, 0, peroxide (H2O2) t-Bu-OO-t-Bu
1, 10, 100 or organic inhibited degradation.
mM; peroxides
CuSO4, 10,
41mM
De Visscher ethylbenzene (EB) 0.5-1mM ultrasound (518 solution temp, benzene, toluene, styrene, Rates are first-order.
et al., 1997 aqueous ( 1 kHz, 13 W 30 ( 1 °C cumene propylbenzene, Pyrolysis is an
solution per 150 cm3 diphenylmethane, important pathway.
solution) 1,2-diphenylethane,
benzaldehyde
acetophenone, phenylacetylene
De Visscher benzene (B), ethyl benzene B, 3.38, 1.69, ultrasound (520 temp, 29 ( 1 not reported first-order kinetic rates, k
et al., 1996 (EB), styrene (S), 0.9, and 0.45 kHz) °C; pH 7 (min-1): B, 0.0271; EB,
o-chlorotoluene (OC) mM; EB, 1, 0.0622; OC, 0.0431; S,
0.5, and 0.33 0.0446
mM; OC,
0.68, 0.34,
0.17mM; S,
0.97, 0.49,
and 0.25 mM
Drijvers et trichloroethylene (TCE) TCE, 0.84, ultrasound, 520 temp, 29.5 + products from mixture TCE, 3.34 to 0.1 in 90 min.
al., 1999 chlorobenzene (CB) 1.67, and 3.37 kHz (14.23 ( 0.73 W) 0.5 °C; of TCE and CB, Sonolysis rates of TCE and
mixtures of TCE and CB mM; CB, 086, solution pH 7 C8H4Cl2, C8H6,Cl2, CB depend on initial
1.72, and 3.44 mM C8H5,Cl3, and C8H4Cl4. concentration of TCE and CB
Table 3. (Continued)
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/ other
authors degraded concentration scheme conditions products results or remarks
Drijvers et chlorobenzene 1.72mM ultrasound, 520 temp, 29.5 ( methane, acetylene, Argon accelerated
al., 1998 aqueous kHz (14.23 ( 0.73 W, 0.095 W 0.5 °C; butenyne, butadiyne, degradation rates
solution. ml -1) solution pH, phenylacetylene, compared with air.
4.7, 7, 10; benzene,
irradiation non-chlorinated
gas, Ar, air mono- and dicyclic
hydrocarbons,
chlorophenols, CP (in
the presence of air only)
Drijvers et trichloroethylene (TCE) 3.34 mM ultrasound, 520 temp, 29-32 C2HCl, C2Cl2, C4Cl2, Concentration decreased
al., 1996 aqueous kHz (0.095 °C; pH, C2Cl4, C4HCl3, C4Cl4, from 3.34 to 0.25 mM at
solution W/mL), 20 kHz 4.7, 7, 10; C4HCl5, C4Cl6 520 kHz and 3.34 to 0.5
(0.43 W/mL) irradiation mM at 20 kHz in 60 min.
gas, air, Ar
D’Silvia et benzo [a}pyrene (B[a]P, PAHs, 8.9-15 ultrasound (18 PAH solutions PAH and Dioxin, fine B[a]P in 20% aqueous
al., 1990 benzo [ghi]perylene, mg/L, pure or kHz, 50 W) typically carbonaceous deposits; ethanol, 99.1%, 94.1% and
coronene (PAHs) and neat TCE and sonicated for TCE and TCA, brown 22% degradation rates after
2-chlorodibenzo-p-dioxin TCA over 2 h period polymeric materials 60 min for initial
(in 20% ethanol-water), concentrations of 1.1, 8.9
trichloroethylene (TCE), and 21.5 ppm respectively,
1,1,1-trichloroethane (TCA) significantly lower for 100%
ethanol solution alone.
Eiler, 1994 VOCs, trichlorothylene TCE, CAVOX system, H2O2 added organic acids, halides, removal efficiencies greater than
(TCE) primarily; BTEX, 1475-2000; sequential before the CO2 and H2O 99.9% for TCE and BTEX
Benzene (Bz); toluene (TL); Bz, 240-500; hydrodynamic cavitation
ethylbenzene (EB); xylenes TL, 8-11; XL, cavitation (360 chamber
(XL) up to 100 (all W, 5 & 10 kW)
in ppb) and UV
photolysis
(low-pressure Hg
lamp, 2.5-10
kW)
Entezari et carbon disulfide (CS2) pure CS2 ultrasound, 900 temp, -50 to + amorphous carbon and effect of irradiating gas on
al., 1997 kHz (29 W) and 10 °C; monoclinic sulfur rate, He >H2 > Air > O2,
20 kHz (49 W) irradiating negligible rate at 900 kHz
gas, Ar, H2, air,
He, O2, CO2
Gondrexon pentachlorophenol (PCP) 10-4 M three-stage temp, 20 ( 2 No products and conversion rates up to 80%
et al., 1999 aqueous sonochemical °C; solution intermediates for ultrasonic units in
solutions reactor (500 kHz pH 7 determined. series
each, 0-100 W)
Gonze et al., Sodium 0.1 mM sequential temp, 20 ( 2 degradation products Ultrasonic irradiation
1999 pentachlorophenate ultrasonic/ °C solution, not reported decreased immensely the
(NaPCP) as wastewater biological pH 6.8-7.5; toxicity of NaPCP to
model compound. Bacteria treatment; operating microorganisms and could
(vibrio fischeri). Daphnids Electrical wattage, be used as preoxidation
(Daphnia magna). generator, 500 55-65 W step before biological
kHz, 0-100W treatment.
Gutierrez poly(vinylpyrrolidone) PVP, 0-0.1 ultrasound (300 irradiating PVP and EtOH, CH4, The decomposition of TNM
and (PVP), ethanol (EtOH) and M EtOH, kHz, 2 W cm-2) medium, Ar C2H6, CH2O, CH3CHO, is one of the fastest
Henglein, tetranitromethane (TNM) 0-0.5 M C2H6, CO, CO2; TNM, sonochemical reactions.
1988 in aqueous solution TNM, 4.5 × C(NO2)3-, NO2-, NO3-, Maximum rates of PVP
10-3 M and 5 N2, CO, CO2 occurred at about 0.04 M
× 10-3 M (in
water plus
glycol,
glycerin, or
propanol-2)
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4689
Table 3. (Continued)
4690

chemical degradation degradation

contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Gutierrez et aqueous acetate solutions 0-0.8 ultrasound, 300 temp, room ( 2 °C ; major, succinic, glycolic At acetate concentration greater
al., 1986 mol/dm3 kHz (16 W) irradiating gas, Ar; and glyoxylic acid, and than 0.4 mol/dm3, CO2 and CO
acetate irradiating smaller amounts of became the predominant
time, 30 min HCHO, CO2; minor, CH4 products of sonolysis.
Hamlin et carbon tetrachloride (CCl4) 2 mL CCl4 or ultrasonic temp, 20 °C; CCl4: CO2, O2, Cl2, with CCl4 alone (no water),
al., 1961 and chloroform (CHCl3) in CHCl3 in 20 generator, irradiating HCl, C2Cl6, C2Cl4; cavitation occurred but
aqueous suspension mL H2O medical (15 W, gas, Ar; CHCl3: HCl, C2Cl6, there was no reaction
1mc-sec, 3 irradiating C2Cl4
W/cm2), electric time, 15-180
(5 W, 300 kc/s) min
Harada, carbon dioxide (CO2) CO2 in ultrasound (200 temp, 5-45 °C; gaseous products; the decreasing rate for CO2
1998 distilled kHz, 200 W) irradiation major, CO, H2; minor, followed the order Ar > He
water gas, Ar, He, O2 H2 > N 2
(0.0-0.60 H 2, N 2
mole fraction)
Hart et al., acetylene in aqueous 0-10-2 M ultrasound irradiating H2, CO, CH4, HCOOH, Products similar to those in
1990 solutions quartz generator medium, Ar CH3COOH, HCHO, pyrolysis and combustion.
(1 MHz, 2W/cm2) CH3CHO, other C2-C8 Maximum rate occurred at
hydrocarbons, insoluble 2 × 10-3 M or 5 vol % of
soot, C6H6, styrene, C2H2
naphthalene, and
phenylacetylene
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001

Hart et al., methane (CH4), ethane water ultrasound, 300 irradiation major products, maximum decomposition
1990 (C2H6) containing kHz, 2 W/cm2 gas, Ar hydrogen, acetylene, occurs at 15% for methane
2-100 vol % ethylene, ethane; and 10% for ethane
CH4 or C2H6 minor, CO, propane,
in Ar propene
Hart and formic acid-water mixtures 0-30 M ultrasound (300 gas medium, major, H2CO2, CO; At 15 M HCOOH, overall
Henglein, 1988 aqueous kHz, 2 W/cm2) Ar minor, oxalic acid rate of decomposition is 540
solution mM min-1.
Hart and ozone (O3) in aqueous O3, 353 & 628 ultrasound, 300 temp, 33 °C; H2O2 formation rapid decomposition rate of
Henglein, solutions mM, 1.6 mM kHz irradiation ozone (3 mM/min) occurred
1986 gas, Ar + at [O3] ) 1 mM
O2/O3 mixture
Hart and nitrous oxide (N2O) water ultrasound, 300 irradiation N2, O2, NO2-, NO3- maximum yield obtained at
Henglein, containing kHz gas, Ar Ar/N2O vol % ratio of 85:15
1986 0-100 vol %
N2O in Ar
Hart and solutions of KI and sodium HCO2-, ultrasound, 300 irradiating KI: iodine, H2O2; H2 the yield of H2O2 was about
Henglein, formate (HCO2Na) in pure 0.001, 0.01 & kHz; O3, 31.8 & gas, Ar, O2, also formed in the 4 times greater under
1985 and ozonized water 0.1 M KI; 0.1 67.4 mM and Ar/O2 absence of O2. HCO2Na: H2O2, H2, Ar/O2 mixture (70/30%)
M mixture; CO2 and oxalate in the absence than under the pure gases
solution pH of O2; H2O2 and CO2
6.32-12.07 (absence of O2)
Henglein, carbon dioxide (CO2), CO2-N2O- ultrasound, 300 bulk solution CO2: major, CO; minor, No chemical effects
1985 nitrous oxide (N2O), CH4 kHz (3.5 W/cm2) temp, 20 °C; HCOOH. N2O: N2, occurred during irradiation
methane (CH4) containing aq. irradiating nitrite, nitrate. CH4: under an atmosphere of
solutions gas, Ar C2H6, C3- and C4- pure CO2, N2O, or CH4.
(0.0.1 mole hydrocarbons, CO, CO2, Sonochemistry
fraction); CH2O characterized by a strong
Ethanol linkage between the
(0.05M); KI sonolysis of water and the
(0.1 M) gas.
Hirai et al., CFC-113 (F2ClC-CCl2F), CFC-113, ultrasound (200 irradiation CO, CO2, Cl-, F- CFCs and HCFCs are
1996 HCFC-225ca 25-1000 ppm; kHz, 6 W/cm2) medium, Ar, readily decomposed
(F3C-CF2-CCl2H), HCFC- air ∼CFC-113 degradation
HCFC-225cb 225ca,cb, 100 faster under argon than air
(F2ClC-CF2-CClFH) and ppm;
HFC-134a (F3C-CF2H) in HFC-134a,
water 300 ppm
Table 3. (Continued)
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Hua et al., p-nitrophenol (p-Np) in 100 µM near-field temp, 22-25 4-nitrocatechol first-order rate constants at
1995 aqueous solution acoustical °C; solution (4-NC); other products 1.4W/cm2 higher in Ar than
processor (NAP), pH 4.5-5.0; not reported here in O2, kO2 ) 5.19 × 10-4 s-1
16 and 20 kHz, irradiation kAr ) 7.94 × 10-4 s-1
0-1775W medium, Ar,
O2, mixture of
Ar/O2
Hua et al., 1995 p-nitrophenyl acetate 100 µM immersion-probe temp, 25 °C major, hydrolysis products; hydrolysis rate constants
(PNPA) in aqueous solution ultrasound (115 solution pH minor, NO2-, NO3- varies from 9.8 × 10-5 to 3.8
W, 96 W/cm2) 3-8; × 10-4 s-1, depending on
irradiation dissolved gas, accelerated
gas, Kr, Ar, He by ultrasound
Hua and carbon tetrachloride (CCl4) CCl4, 1.95 × ultrasound (20 solution pH CCl4: C2Cl4, C2Cl6, Cl-, CCl4: 90% and 99%
Hoffmann and p-nitrophenol (p-Np) + 10-4 and 1.95 kHz, 135 or 112.5 11.8; HOCl, p-Np; reduction after 12 and 90
1996 CCl4 in water with/without × 10-5 mol L-1; W/cm2) irradiation 4-nitrocatechol (4-NC) min, respectively; not
saturation with Ozone (O3) p-Np, 100 µM gas, Ar affected by O3. Degradation
of p-Np enhanced
significantly by CCl4 and
4-nitrocatechol
accumulation minimized
Hung et al., nitrobenzene (NB) 25 µM ultrasound (US)/ temp, 15 ( 2 intermediates: with US, combination of ultrasound
2000 Fe°. US, 20 °C; initial pH 6 o-, p-, m-nitrophenol and Fe° had synergistic
kHz (139 W/L); and 4-nitrocatechol; effect on the reduction of
Fe°, 0-88 g/L with Fe°, nitrobenzene, nitrobenzene
aniline
Hung and carbon tetrachloride (CCl4) 0.1 mM ultrasound (US)/ temp, 15 °C; intermediates: US/Fe°, combined US/Fe° system
Hoffmann, Fe°. US, 20 kHz irradiation C2Cl4 and C2Cl6; Fe° had a positive synergistic
1998 (62 W/285 L); Fe°, gas, Ar; initial (only), CHCl3, and effect on CCl4
0-24.49 g/L pH 7 CH2Cl2 dehalogenation
(powder) 0-42
g/L (turnings)
Inazu et al., trichloroethylene (TCE), 10 ppm ultrasound irradiation in air or O2, Cl-, H2, Over 75% initial amount
1993 tetrachloroethylene (PCE), generator/barium gas, Ar, O2, or CO2, negligible CO; in decomposed in 10 min.
1,1,1-trichloroethane titanate air argon, Cl-, H2, CO, CO2 Order of degradation rates:
(TCA), chloroform (CHCl3), oscillator (200 in argon, TCE > TCA > PCE;
carbon tetrachloride (CCl4) kHz, 6 W/cm2) in air, CCl4 > CHCl3
Ingale et al., refractory component in COD, 1000 sequential sonication at formation of acetic acid hybrid system more
1995 the industrial waste of a mg dm-3 sonication/wet 30 and 50 °C as byproduct effective than sonication-
cyclohexane oxidation unit oxidation with CuSO4 66% in COD reduction
(SONIWO); (6.26 × 10-4 (1473 to 499 mg dm-3) vs
ultrasonic catalyst for 1 36% (1533 to 980) for Cu2+
cleaning bath (40 h; WO, 250 °C, system
kHz, 150/300W) 0.69 MPa
Johnston pentachlorophenol (PCP), PCP, 2.4 × simultaneous UV temp, 35 ( 2 PCP: chloride Sonication of UV-irradiated
and 3-chlorobiphenyl 10-4 M; 3-CB, (Hg bulb-100W, °C; TiO2: catalyst solution
Hocking, (3-CB), 4-chlorophenol 4 × 10-4 M; 7000W/cm2/ultra surface area, significantly improved
1993 (4-CP), 2,4-dichlorophenol 4-CP, 7 × 10-3 sound (20 kHz, 55 ( 10 m2/g; rates.
(DCP) M; DCP, 2 × 475 amount, 0.2%
10-3 M W)/photocatalytic W/W
(TiO2) treatment catalyst/
solution
Kang and methyl tert-butyl ether 0.01-1.0 mM simultaneous temp, 20 °C; tert-butyl formate (8%), the presence of O3
Hoffmann, (MTBE) sonolysis/ solution pH tert-butyl alcohol (5%), accelerated MTBE
1998 ozonation, 6.6-6.8; methyl acetate (3%), degradation rates
ultrasound (205 irradiation acetone (12%) substantially, enhancement
kHz, 200 WL-1), gas, O2/O3; by 1.5-3.9 depending on
[O3]o ) 0.26-0.34 irrad. time, [MTBE]o
µM 0-60 min
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4691
Table 3. (Continued)
4692

chemical degradation degradation

contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Khenokh benzene (Bz), toluene (TL), Bx, 2.4, 5.0 & ultrasound, 435 temp, 40 °C Bz & TL, HCHO, HCHO yields increased
and phenol (PhOH) (saturated 10.2 × 10-4 M; kc phenolic hydroxyls with initial concentration of
Lapinskaya, aqueous solution) PhOH, 0.01, Bz or TL and time
1956 0.08 & 0.32 M
Koike, 1992 alcohol-water mixtures, 10-80 vol % sonication bath argon bubbled typical products, CH4, order of yield for CH4 was
CH3OH, C2H5OH, (SB), 50 kHz, 120 for 15 min C2H6, C3H6, C2H4, C2H5OH > CH3OH >
n-C3H7OH, i-C3H7OH W before C2H2 i-C3H7OH ∼ n-C3H7OH
sonication
Koszalka et synthetic carbon 13.6-15.8 ultrasonic probe temp, 25-35 intermediates, CCl4 reduced from 13.6 to
al., 1992 tetrachloride CCl4), ppm (475 W) °C; pressure, chloroform, 1.71 ppm (g90%
contaminated water (sonication at 15-45 psig; dichloromethane, destruction) by sonolysis,
250 W), irradiation, air, Ar, H2; chloromethane; final 15.8 ppm to <0.5 ppb with
unknown irrad. time, products, methane, sonolysis plus chemical
chemical agent 0-5 min chlorine/chloride agent.
Kotronarou parathion (O,O-diethyl saturated ultrasound (20 temp, 30 °C; p-nitrophenol (p-Np), initial parathion was
et al., 1992 O-p-nitrophenyl aqueous kHz, 75 W cm-2) solution pH SO42-, PO42-, oxalate degraded e 2 h since
thiophosphate) parathion 6.0; final pH (C2O42-), NO2-, NO3- [SO42-]o was originally
solution (82 after 2 h equal 82 µM
µM) sonication, 3.7
Kotronarou p-nitrophenol (p-Np) in 100 µM ultrasound (20 temp, 30 °C NO2-, NO3-, first-order rate constants
et al., 1991 oxygenated aqueous kHz, 84 W) solution pH p-benzoquinone decreased from 3.67 ×
solutions 2.12; (p-BQ), hydroquinone,
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001

10-4s-1 (pHo 5) to 2.0 × 10-4

irradiation 4-nitrocatechol, s-1 (pHo 8).
gas, air formate (HCO2-),
oxalate
Kotronarou hydrogen sulfide (H2S) 92,100 and 20 probe ultrasound temp, 25 °C sulfate (SO42-), sulfite S(-II) completely oxidized
et al., 1992 (S[-II] ) [H2S] + [HS-] + µM (20 kHz, ∼75 solution pH (SO32-), thiosulfate in less than 30 min
[S2-]) W/cm2 or ∼85W) 10.6-7.4; (S2O32-) in the mole
irradiation ratio 2.2:2.7:1
gas, air respectively
Kruger et natural groundwater 350 µg/L ultrasound [361 temp, 22-31 chloride complete destruction
al., 1999 containing mainly kHz (60 W), 620 °C; solution within 60 min
1,2-dichloroethane kHz (75 W), and pH 6.2-7;
(1,2-DCA) 1086 kHz (105 irradiation
W) gas, air
Ku et al., 2-chlorophenol (2-CP) in 1.26 × 10-4 M probe ultrasound temp, 17-60 chlorohydroquinone, apparent pseudo first-order
1997 aqueous solution (20 kHz, 0-550 °C; pH 3, 5, 7, catechol, chloride at pH rate constant ranged from
W); intensity, 9, and 10; 11, but glyoxilic acid 3.3 to 1.5 × 10-3 in the pH
38.1 W/cm2 irrad. gas, air, also detected at pH 3 range 3-11 at 24 ( °C
O2, N2
Lin et al., 2-chlorophenol (2-CP) 10 and 100 ultrasound (20 temp, 25 °C; not explicitly given; 2-CP decomposition was
1996 mg/L kHz, 160 pH 3, 7, 11; total organic carbon 99%, 62%, and 15% at pH 3,
W)/H2O2 (200 catalyst, (TOC) monitored 7, and 11, respectively, at
mg/L) process FeSO4 350 min, and was enhanced
by FeSO4 as catalyst.
Lin et al., 2-chlorophenol (2-CP) 100 mg/L ultrasound (20 temp, 25 °C; not explicitly given; H2O2 improved 2-CP
1996 kHz, 0, 125, and solution pH 3, total prganic carbon decomposition, 57% over
160 W)/H2O2 (0, 5, 7, 9, 11 (TOC) monitored the control with 500 mg/L
100, 200, and 500 H2O2
mg/L) process
Lur′e, 1962 phenol (PhOH), benzene PhOH, ultrasound, 800 solution temp, PhOH: catechol, Prolonged treatment
25-300 mg/L; kc/s, 1500 W; 40-60 °C; pyrogallol, o-quinone; resulted in rapid oxidation
Bz, 200-500 Intensity, 4-7 treatment Bz; phenol, pyrogallol, of catechol to muconic acid.
mg/L W/cm2 (350 time, 40 min to catechol, formaldehyde
mL solution) 5 h.
Mead et al., thymine (aerated aqueous 2 × 10-3-2 × ultrasound (447.5 solution temp, cis- and trans-5, A value of 1.8 ( 0.3 × 10-5
1975 solutions) 10-2 M ( 0.6 kHz, 5 W 25 °C 6-dihydroxy-5,6- M min-1 was obtained for
cm-2) dihydrothymine, the zero-order rate
5-hydroxymethyluracil constant.
and urea
Table 3. (Continued)
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Nagata et monohydroxybenzoic acid 100 µM/L ultrasound, 200 temp, 25 °C; only CHCl3 measured Rates of the HBAs were
al., 1996 (HBA); kHz, 200 W irradiating faster in Ar than in air but
3,4-dihydroxybenzoic acid gas, air & Ar rates of TA and HA were
(3,4-DHBA); gallic or faster in air.
3,4,5-trihydroxybenzoic
acid (GA); tannic acid (TA);
humic acid (HA)
Nagata et 2-, 3-, & 4-chlorophenol 100 µM/L ultrasound, 200 irradiating chloride Degradation of CPOHs and
al., 2000 (CPOH), kHz, 200 W gas, air & Ar, PCP were almost 100%
pentachlorophenol (PCP) presence of Fe(II) under Ar and 80-90%
under air after 1 h.
Olson and fulvic acid (FA) and FA, 10 mg/L sonolysis/ temp, 25 °C; CO2 91% TOC removed as CO2
Barbier, naturally colored TOC; NCG, ozonolysis groundwater pH 8.6; (from FA) after 60 min.
1994 groundwater (NCG) contains (sonozone irradiating Sonozone is more effective
2.5-3.0 mg/L process); gas, 2.1% O3 in than ozone or ultrasound
(dissolved ultrasound, 55 W, O2 (3.2 mg/min) alone
organic 20 kHz
carbon)
Okouchi et phenol (PhOH) 100 ppm ultrasonic temp, 25 °C; catechol, hydroquinone degradation rates increased
al., 1992 (mg/dm3) generator (200 W; catalyst, Fe2+, in the order O2 > air > He,
19.5, 50, 200, and MnO2 irradiating N2 and enhanced by
600 kHz) gas, Air, O2, N2, He catalyst
Orzechowska carbon tetrachloride CCl4, 40 ppm; ultrasound (20 solution temp, chloride and formate At 20 min, the pH decreased
et al., 1995 (CCl4), chloroform (CHCl3), CHCl3, 37 kHz); cup horn, 27-40 °C; ions; chloride: CCl4, 2.80 by 2.3 units for CCl4
trichloroethylene (TCE), ppm; TCE, 37 100 W; horn deionized and ppm; CHCl3, 4.55 ppm; solutions.
chlorobenzene (CB), ppm; CB, 94 probe, 120 W tap water (pH TCE, 2.80 ppm; CB,
polychlorobiphenols (PCBs) ppm; PCB, 55 6.3-8.37); 0.50 ppm; PCB, 0.30
Triton X-100 (TX) ppm; TX, 1% sonication ppm; TX, 0.30 ppm;
aq. soln. time, up to 60 formate, <1.00 ppm for
min. each
Petrier et pentachlorophenate (PCP) 10-4 M ultrasonic disk temp, 24 ( 1 CO2, (CO in Ar only), fast cleavage of the C-Cl
al., 1992 transducer (530 °C; pH 7; Cl-, NO2-, and NO3- bond, releasing Cl- and
kHz, 20 W) irradiation mineralization of PCP to
gas, Ar, air, CO2 in 100 minutes
O2
Petrier et phenol (PhOH) 0.05-10 mM ultrasound (30 temp, 25 °C; CO2 as the only rate is dependent on
al., 1994 (a) W): disk irradiation gaseous product, [PhOH]0 with maximum
transducer, 487 gas, air hydroquinone (HQ), value reaching limits of:
kHz titanium catechol (CC) 11.6 × 10-6 M min-1 (for
probe, 20 kHz benzoquinone (BQ) 487 kHz) and 1.84 × 10-6 M
min-1 (for 20 kHz)
Petrier et atrazine (ATZ), ATZ, 0.1 mM; ultrasound: temp, 20 °C; ATZ: dealkylation the degradation proceeded
al., 1996 pentachlorophenol (PCP) PCP, 0.1 mM immersion probe, pH 7 (for PCP); products of atrazine, 7.8 times (for ATZ) and 4.8
20 kHz, 18.5 W; dissolved gas, CO2, chloride; PCP: times (for PCP) more
ultrasonic air; irradiation chloride rapidly at 500 kHz than at
emitter, 500 kHz, time, ATZ 120 20 kHz
18.5 W min, PCP 180
min
Petrier et chloroform (CHCl3), MeOH: 1% ultrasound irradiation acidic degradation chloromethanes extensively
al., 1994 (b) dichloromethane (CH2Cl2), CCl4; BuOH: (30W), Vibracell gas, O2 and products detected with decomposed MeOH and
carbon tetrachloride 0.5% CCl4; emitter, 20 kHz; argon β-carboline (10-4-10-5 BuOH remained stable, but
(CCl4), and dilute mixtures Et(OH)2: 0.02 Undatim M) especially for Et(OH)2 oxidized
of CCl4 in methanol and 0.05% Irradiation solutions of CCl4 in
(MeOH), butanol (BuOH), CCl4 system, 500 kHz alcohol
and 1,2-Ethanediol
[Et(OH)2]
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4693
Table 3. (Continued)
4694

chemical degradation degradation

contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Petrier et aqueous solutions of CIBZ and ultrasound (30 temp, 20 °C; CIBZ: Cl-, CO, CO2, Chloroaromatic hydrocarbons
al., 1998 chlorobenzene (CIBZ), CIPH, 0.5 mM; W), disk water C2H2; 4-CIPH: Cl-, and yielded g 89% Cl- as product in 150
4-chlorophenol (4-CIPh), 1,2-DCB, 0.4 transducer (500 equilibrated hydroxlated min. For the mixture, CIBZ
1,2-dichlorobenzene mM 1,3-DCB, kHz), titanium air intermediates degrades before 4-CIPH
(1,2-DCB), 0.05 mM; probe (20 kHz) (hydroquinone, (100 vs 300 min). 1,2-DCB,
1,3-dichlorobenzene 1,4-DCB, 0.2 mM; 4-chlorocatechol, etc.) 1,3-DCB, 1,4-DCB,
(1,3-DCB), 1,3,5-TCB, 1,3,5-TCB, and 1-CN more
1,4-dichlorobenzene 0.02 mM; 1-CN, efficiently destroyed.
(1,4-DCB), 0.04 mM
1,3,5-trichlorobenzene,
(1,3,5-TCB),
1-chloronaphthalene
(1-CN) and mixture of
CIBZ and CIPh
Petrier and phenol (Ph), carbon Ph, 10-3 ultrasound (30 temp, 20 °C; Ph hydroquinone, degradation rates for CCl4
Francony, 1997 tetrachloride (CCl4) mol/L; CCl4, W), titanium solution pH 2; catechol; CCl4: Cl-, and increase with frequency,
4-4.6 × 10-4 horn, 20 kH; O2-saturated CO2 but maximum for PhOH at
mol/L piezo-electric solutions 200 kHz
disk, 200, 500
and 800 kH
Phull et al., bacterial cells (E. coli) 676 bacterial ultrasound (US) temp, 20 °C; dead bacterial cells ultrasound amplified the
1997 colonies per and/or sonication biocidal effects and reduced
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001

cm3 (1/10 chlorination. US, time, 1, 2, 5, the amount of chlorine

dilution) 20 kHz (8 W 10, or 20 min required for disinfection
cm-2) & 800 kHz
(15 W cm-2);
chlorination,
0.01-30 ppm
Popa and chloromethanes in aqueous 1.5 cm3 ultrasound, 1 temp, 25 °C; C2H2Cl4, C2HCl5, the sonolytic reaction fairly
Ionesu, 1992 media (CH2Cl2/H2O, samples megacycles/s, 584 irradiation C2Cl6 obeys zero-order kinetics.
CHCl3/H2O, CCl4/H2O) (chloro- W gas, argon; pH The rate constants were
methane) in 6 1.73 × 10-7, 2.22 × 10-7, and
98.5 cm3 H2O 2.78 × 10-7 Ms-1 for CCl4,
CHCl3, and CH2Cl2,
respectively.
Price et al., chlorobenzene (CB), saturated horn ultrasound temp, 20 °C not explicitly reported At 20.9 W/cm2, the rate
1994 1,4-dichlorobenzene, solutions (M): (22 kHz), (ambient); constants for 1,4-DCB, NT,
(1,4-DCB), naphthalene CB, 4.1 × intensities solution, pH AN, and PR are 0.038,
(NT), anthracene (AN), 10-3; DCB, (W/cm2), 13.5, 5.48-4.50 (not 0.015, 0.033, and 0.016
pyrene (PR) 6.2 × 10-5; NT, 11.7, 20.9, and controlled by (min-1), respectively, and
2.36 × 10-4; 38.9 buffer) 0.022 for CB at 23.9 W/cm2
AN, 2.30 ×
10-7; PR, 6.4
× 10-7
Rajan et al., water-KI-CCl4 system 1%, 16.6%, horn ultrasound temp, 34 °C; I2, Cl2, Cl, HOCl, HCl, Model developed predicted
1998a,b (KI-water solution and 25% KI (25 kHz) irradiation CO2, and O2 well the rates observed for
saturated with CCl4) solutions gases, air, N2, CCl4 suspension in KI
containing 5.2 O2 solution.
× 10-3 M CCl4
Reinhart et trichloroethylene (TCE) 5-20 ppm sonolysis/ temp, 25 °C; not explicitly reported combined sonolysis/Fe rates
al., 1996 zerovalent Fe. irradiation Cl- inferred was 3 times that of Fe alone
US: 20 kHz, 90 & gas, N2
180 W; iron (Fe),
1&3 g/L
Sakai et al., chloral hydrate (CH) 0.1 M in ultrasound (29 temp, 30 °C; solution chloride ion (Cl-) kinetic rate expression
1977 aqueous and 400 kHz); saturated with obtained for the formation
solutions power output, 0.5 air and mixtures of HCl agreed with
W/cm (20/80 and experimental result
2/98) of O2 and
N2
Table 3. (Continued)
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Sehgal and thymine (THY) 0.1 mM ultrasound (1-7 temp, 20-70 not determined At an aeration rate of 50
Wang, 1981 W cm2) °C; aeration mL/min at 34 °C, [THY] is
medium, air reduced to half in 30 min.
Serpone et 2-, 3-, and 4-chlorophenols 4-CPOH, 75.1 horn ultrasound temp, 33 ( 2 4-CPOH, hydroquinone (HQ), total degradation in 10 h for
al., 1994 (2-CPOH, 3-CPOH, and µM; 3-CPOH, (20 kHz, 49.5 °C; air 4-chlororesorcinol (4CR), 2-CPOH and 3-CPOH and
4-CPOH) 77.8 µM; W, 52.1 W/cm2) equilibrated; 4-chlorocatechol (4-CC); 15 h for 4-CPOH with rates
2-CPOH, 83.1 natural solution 3-CPOH, Cl-, [4.8 ( 0.4, 4.4 ( 0.5, and
µM pH: 4-CPOH, 5.1; chlorohydroquinone 3.3 + 0.2] × 10-3 min-1,
3-CPOH, 5.4; (CHQ), 4-3-CC, respectively.
2-CPOH, 5.7 carbonaceous species;
C-CPOH, CHQ, 3-CC,
catechol (CC)
Serpone et phenol (PhOH) and PhOH, 75 µM immersion horn 30 ( 2 °C; pH PhOH, appearance (in At pH 12, neither HQ, CC
al., 1992 intermediates, catechol (pH 12), 68 ultrasound 200 3, 5.4, 5.7, 12; 9h) and subsequent or BC were detected from
(CC) hydroquinone (HQ), µM (pH 3) kHz, 25, 50, or 75 open to air disappearance of CC, the insonation of PhOH
p-benzoquinone (BQ) and 51 µM W/cm2 HQ and BQ BQ, HQ + since they were unstable.
(pH 5.7); HQ, unidentified species CO2 could not be detected.
44 µM, pH 3; HQ, BQ + unidentified
BQ, 43 µM, species
pH 3; CC, 54
µM, pH 3
Sierka, trinitrotoluene (TNT) and 70/30 mg/L ultrasound temp, 25-59 not explicitly ultrasound inhibited
1985 cyclotrimethylene TNT/RDX; (5-50W at °C; pH 5.84-10.0 determined kinetics at high temp and
-trinitramine (RDX) aqueous 852-863 kHz, pH due to radical-radical
solutions 60.6-1,007 extinguishment reaction
kHz)/ozone (72.91
mg O3/min)
Sierka and humic acid (HA) solution unknown ultraviolet/ irradiating trihalomethanes O3-US-UV system proved
Amy, 1985 concentration ultrasound/O3; gas, O3/O2; formation potential to be most effective reaction
US, 40 kHz, 300 pHo 4.0, 7.1, (THMFP), and conditions, followed by
W; UV lamp, and 10.0 nonvolatile total O3-UV, O3 alone, and
253.7 nm; O3, 4.3 organic carbon O3-US, providing 93%,
mg/L (2 min), (NVTOC) monitored as 86%, 75%, and 71%
21.6 mg/L (10 byproducts reduction in THMFP levels,
min) and 43.2 respectively, in 20 min.
mg/L (20 min)
Soudagar and toluene (T), nitrotoluene mixture of 20 KMnO4; temp, 30-35 T, benzoic acid; O-T T studied in detail among
Samant, (NT), O-chlorotoluene mmol of ultrasonic cleaner °C and MTB, the arylalkanes. The
1995 (O-T), O-p-xylene, KMnO4; and (23 kHz, 120W) corresponding optimal time for oxidation
mesitylene (1,3,5- 10 mmol of carboxylic acids of T was 3 h. KMnO4
trimethylbenzene (MTB), arylalkane in accelerates oxidation in the
and isopropyl- 50 cm3 water presence of ultrasound.
tert-butylbenzene
(IPB,TBB)
Spurlock et carbon tetrachloride saturated ultrasound, temp, 20 °C; CCl4, CO, CO2, HOCl, irradiation of products R2
al., and (CCl4); di-n-butyl sulfide aqueous 280-800 kHz at irradiation and hexachloroethane SO and R2SO2 yielded
Reifneider (R2S) solution of 5-11 W/cm2) gases, O2 and (C2Cl6) (in AR only); RSO3H as principal product
1970, 1971 CCl4 Ar Minor, R2SO2, RSO3H, only at 800 kHz
butyric acid, CO, C2H4,
C2H2, and CH4
Stock et al., azo dye, naphthal blue 50 ( 5 µM sonolysis/ temp, 20 ( 5 °C NBB intermediates Degradation rate for
2000 black (NBB) photocatalysis; minerilized to sonolysis was about 2 times
US, 640 kHz, 250 inorganic species faster than that of
W; TiO2 (P.25), 1 photocatalysis.
g/L
Suzuki et surfactant, 100 ppm in ultrasound/ temp, 25 °C; not explicitly significant enhancement in
al., 2000 polyoxyethylene-alkyl 1000 mL aqueous photocatalysis, irradiation determined TOC the photocatalytic reaction
ether (SS-70) sample 200 kHz/200 W, gas, air; irrad. monitored observed when combined
TiO2/Hg lamp time, 60 min with US irradiation
(253.7 nm/20W)
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4695
 4696

Table 3. (Continued)
chemical degradation degradation
contaminants oxidation experimental intermediates/ efficiency/other
authors degraded concentration scheme conditions products results or remarks
Takizawa et phenol (Ph), 2-naphthol 8.0 × 10-3 M ultrasound (200 temp, 25 °C; Ph, CC, hydroquinone Hydroxylated products
al., 1996 (2-Nph), 4-methylphenol in water and kHz) irradiation (HQ); 4-mpH yields ranged from 15% to Ph and
(4-mPh), catechol (CC), water- time, 12-18 h; 4-methylcatechol; 4-HAN have the highest
resorcinol (RS), ethanol irradiation 4-HAN, hydroquinone; yields of products, Ph 30%
3-tert-butyl-4-hydroxyanisole (3-tb-4-HAN), mixture (1:1 gas, O2 2-NpH CC and 26% HQ in 12 h;
3-methyl-4-hydroxyanisole V/V, 100 mL) 2,3-dihydronaphthol; 4-HAN, 50% HQ in 12 h.
(3-m-4-HAN) CC and RS, pyrogallol;
3-tb-4-HAN,
tert-butyl-HQ;
3-m-4-HAN, metyhl HQ
Tauber et 4-nitrophenol 5 × 10-3 ultrasound, 321 irradiation pH 10, 4-nitrocatechol, thermolysis products
al., 2000 mol/dm3 kHz, 170 W/kg gas, Ar; pH 4 & hydroquinone + observed at low pH
10 benzoquinone, nitrite; compared with OH-induced
pH 4, products at pH 10 reactions at high pH.
+ phenol, nitrate, CO,
CO2, H2
Theron et phenyltrifluoromethyl 160 µmol/L TiO2 temp, 293 K; CF3COOH and the amount of CF3COOH
al., 1999 ketone (PTMK) aq. solution photocatalysis pH 6-6.5 hydroxlated PTMK was 8 times lower in
and/or (natural sonicated solutions than in
ultrasound (US); water) UV-irradiated TiO2
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001

TiO2, 3.5 g/L; US, suspension at both

30 & 515 kHz, frequencies
16 W
Thoma et benzene (Bz), toluene (T) 4, 40, and 80 near-field air or O2 not reported rate constants for 4 to 80
al., 1998 mg/L; Bz, acoustic saturated mg/L solutions; Bz, 0.01-0.003
51-1030 µM; processor (NAP), solutions min-1; T, 0.028-0.004 min-1
T, 43.5-870 200-800 W,
µM 16-20 kHz, 1.3
W/mL-1
Toy et al., 1,1,1-trichloroethane 3.6 and 2500 cup-horn temp, ambient; chloride (Cl-) decomposition more
1990 (CCl3CH3, or TCA) ppm ultrasound (20 pH 3 extensive with combined
kHz)/Hg/Xe lamp photolysis and sonolysis
(200 W) (photosonolysis) than each
[photolysis only
and/or sonolysis]
Toy et al., 1,1,1-trichloroethane (CCl3CH3 1.06 and 10 immersion horn temp, chloride (Cl-) disappearance of TCA was
1992 or TCA) ppm ultrasound ambient; open 91.4 in 18 min.
(475 W, 20 kHz) to atmosphere
Trabelsi et phenol 89-100 mg/L sonolysis, SS (20 temp, 27 ( 2 maleic acid (MA), oxalic At 20 kHz, 5% conversion
al., 1996 and 500 kHz, °C; solution acid (OA), muconic acid with sonolysis alone
20 W)/electrolysis, ES (current saturated with (MCA), p-benzoquinone compared with 755 for SEO
density ) air for 20 min (BQ), hydroquinone in 10 min. SEO’s conversion
68A/m2) (HQ), catechol (CC), is 95% at 500 kHz in 10
[sonoelectro- CO2 min and 100% in 60 min.
oxidation (SEO)] HQ, CC, and BQ disappear
after 2 h at 540 kHz
Vinodgopal azo dye, remazol black B 33 µM ultrasound (640 temp, oxalate (C2O42-) RB disappeared in 90 min
et al., 1998 (RB) kHz, 240 W) ambient; with rate constant of 2.9 ×
under 10-2 min-1 and 60%
constant mineralization achieved in
bubbling of O2 6 h.
Weavers and ozone in aqueous solutions 85 ( 5 to 245 ultrasound direct temp, 23 ( 3 not explicitly first-order degradation rate
Hoffmann, ( 3 µM O3 probe, 20 kHz; °C; irradiating determined constants are 0.84 and 0.66
1998 saturated 263 W L-1 gas, O2/O3 min-1, respectively, at 20
solutions ultrasonic mixture; pH 2 kHz and 500 kHz at [O3]o )
transducer, 500 245 µM
kHz, 96 WL-1
 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4697

solution in the former case. Okouchi et al.63 observed

the degradation of phenol in less than 100 min to

W cm-2 (s-1) are: 2-PCB, 2.1

× 10-3 ( 2.8 × 10-5; 4-PCB,

2,4,5-PCB, 2.6 × 10-3 ( 9.4

destruction efficiencies in 6

first-order rate constant of

proceed with pseudo first-order rate and the addition

constants at 20 kHz/30.8

1.6 × 10-3 ( 3.4 × 10-5;

results or remarks
of Fe2+ and MnO2 to increase the rates in aqueous

products remains to be

pseudo-first-order rate
the toxicity of reaction
efficiency/other

min with an average

solutions. Serpone et al.64 noticed the disappearance of
degradation

0.7 min-1 at 25 °C
phenol at the initial concentration range of ∼30 to 70

greater than 99%

µM to follow a zero-order kinetics with k ) 0.08 µM/

determined.
min at [phenol]initial ) 51 µM and pH 5.7 and slower at
an alkaline pH of 12. They also observed three principal

× 10-5
intermediate species formed at pH 3 (catechol, hydro-
quinone (HQ), p-benzoquinone (BG)), only catechol (CC)
and HQ at natural pH 5.4-5.7, and no intermediates
detected at pH 12. The mechanism is given as
PA, phenanthrene diol;

k1
8 •OH + H•
not explicitly reported

H2O + ))) 79

phenol, propylphenol,
(5)
BP, ortho, meta, and

di-tert-butyl phenol,
k
intermediates/

-1
para-1,1 biphenols
degradation

dibutylbiphenyl,
diethylbiphenyl,
products

biphenyl, ethyl
k2
•
OH 98 1/2H2O2 (6)
benzene,

chloride
k3
•
H 98 1/2H2 (7)
k4
•
OH + phenol 98 products (8)
power intensity,

power intensity,
to atmosphere)
experimental

mL/min (open
conditions

1-22 W/cm2;
temp, 21-27

temp, 20-60

temp, 15 °C;
°C; pH 3-9;
reactor, 100

30.8 W/cm2;
°C; air flow

irradiating

irradiating
gas, air

gas, Ar
(20 kHz, 27 W/cm2)

(PUS), 20 kHz for

and 1071 kHz for

probe ultrasound

probe ultrasound
all PCBs; also at
oxidation
chemical

205, 358, 618,

scheme

(147 W/cm2)

2-PCB only
ultrasound

For a constant phenol concentration, the rate of loss of

phenol as a function of sonocation time was found
linearly related to the sonocation power, P, according
to

k1k4[phenol]
Rate ) (10)
PA or BP, 0.39

2,4,5-PCB, 7.6
concentration

•
k2[ OH] + k4[phenol]
and 130 pm

µM; 4-PCB,
0.53, 1.6, 8,
mg/310 mL

2-PCB, 4.6

× 10-2 µM
5.4 µM;

At low concentrations of phenol, k2 [•OH] > k4[phenol],

water

and at low constant P, the rate follows first-order

kinetics; at high concentration, where k2 [•OH] ,
k4[phenol], the rate follows zero-order kinetics at con-
stant P. However, contrary to the zero-order kinetic
behavior observed at 25 and 50 W/cm2, the sono-
carbon tetrachloride (CCl4)

polychlorinated biphenyls
(2-PCB), 4-chlorobiphenyl
(PCBs), 2-chlorobiphenyl

oxidation of phenol was found to be only first-order at

hydrocarbons (PAHS),

75 W/cm2. Over a pH range of 3-9, Lur’e et al.65 found

2,4,5-chlorobiphenyl
contaminants

phenanthrene (PA),
polycyclic aromatic

the decomposition of phenol to be practically indepen-

degraded

dent of pH. Chen et al.66 also found that at high

biphenyl (BP)

concentrations ([PhOH] > 300 ppm) the conversion was

(2,4,5-PCB)

zero-order and become first-order at very low concentra-

(4-PCB),

tion (<100 ppm). The rate was also found to be negli-

gible at low frequency and the oxidation proceeded
toward completion at high frequency. Trabelsi et al.67
Table 3. (Continued)

investigated the oxidation of phenol in a screened

reactor with ultrasound alone at 20 kHz and with
ultrasound associated with electrolysis. They found that
Tumeo, 1997
Wheat and

Zhang and

the electrochemical oxidation of phenol in NaCl media

Hua, 2000
authors

Wu et al.,

combined with sonication at 20 kHz resulted in 75%

1992

conversion of the initial phenol within 10 min and led

to the formation of toxic p-quinone. At a higher fre-
quency of 500 kHz, a conversion of 95% was obtained
4698 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
within the same treatment time with acetic and chlo-
rocrylic acids as final products of degradation. However,
sonoelectrooxidation at high frequency allowed total
degradation in 20 min with no toxic aromatic intermedi-
ates. They also observed that high frequency ultrasound
enhanced mass transfer substantially up to 70-fold the
mass transfer by diffusion, and without ultrasound
dimerization of phenol radicals yielded polymeric species
which built on the electrodes and passivated them.
The sono-oxidation intermediates and products of 2-,
3-, and 4-chlorophenols (2-,3-,4-CPOH) and 2,4-dichlo-
rophenol (2,4-DCP) in air equilibrated media generally
include chlorohydroquinone (CHQs), catechols (CC),
chlorocatechols, chlororesorcinols (CRSs), and chlorides.
In addition, 2,4-dichlorophenol has been found to pro-
duce some 2- and 4-chlorophenols as intermediates. The
major mechanism of oxidation for these chlorophenols
is a radical attack similar to equations for phenol (eqs
5-9).64 Serpone et al.68 obtained CHQ as the major
intermediate for both 2-CPOH and 3-CPOH sonolysis,
with a small quantity of catechol (CC) in the case of
2-CPOH. By contrast, the principal intermediate for
4-CPOH was found to be HQ with a small amount of
4-CRS. Ku et al.69 in the sono-oxidation of 2-CPOH with
oxygen purging at various solution pH levels identified
CHQ, CC and glycoxilic acid as intermediates at pH 3
but only CHQ and CC at pH 11. Lin et al.70 found that
the combination of ultrasound with H2O2 increased the
efficiency of 2-CPOH decomposition significantly. With
the ultrasound/H2O2 process, they observed that with
pH controlled at 3, the rate of 2-CPOH decomposition
(i.e., 99%) was enhanced up to 6.6-fold and TOC removal
(i.e., 63%) up to 9.8-fold compared with values at pH
controlled at 11. The variations in decomposition rates
at the different pH values were attributed to the pKa
value of 8.49 for 2-CPOH at 25 °C. The 2-CPOH is
almost completely in the ionic form when the pH exceeds
the pKa value of 8.49 but exists in molecular form when
pH < pKa, the fraction in molecular state increasing
with pH drop. In ionic state, 2-CPOH does not vaporize
into the cavitation bubbles, and oxidation reaction
occurs with OH radicals outside the bubble film. How-
ever, in the molecular state, reactions occur by both
thermal cleavage inside the bubble and oxidation with
OH radicals outside, leading to more effective decom-
position. Lin et al.71 also studied the effect of H2O2
concentration on decomposition. It was shown that the
more the H2O2 that was added, the greater the degrada-
tion efficiency. In a particular study with 500 mg/L of
H2O2 and initial 2-CPOH concentration of 100 mg/L,
they observed, after a reaction time of 30 min, an
improvement as great as 57% over the control, i.e.,
without H2O2 addition. The result was attributed to
increase in OH radicals generated on addition of H2O2.
However, the increase in degradation rates was not
significant between the additions of 200 and 500 mg/L
H2O2, suggesting the concentration saturation of OH
radicals at the 200 mg/L level. Petrier et al.72 studied
the sonochemical degradation of 4CPOH and concluded
that the release of end products (i.e., Cl-) and formation
of hydroxylated intermediates (HQ, CC) were evidence
of a two-step reaction involving OH radicals with
substrate in the liquid layer surrounding the cavitation
bubble. The dechlorination yields were also found to be
higher at 500 kHz (using undatim ultrasonic source)
than with the common 20 kHz ultrasonic probe. The
dechlorination rates for 4-chloro-3,5-dimethyl-phenol
were found to be approximately 2 orders of magnitude
lower than that of 2,4-chlorophenol (2,4-DCP), and this
was attributed to the fact that the formation of aryne
intermediates is blocked by the ortho methyl groups.73
Nagata et al.74 found the first-order ultrasonic degrada-
tion rates of 2-, 3-, and 4-chlorophenol to be faster under
argon atmosphere compared to air atmosphere. With 0.1
mM initial concentrations, the rates for 2-CPOH,
3-CPOH, and 4-CPOH were 6.0, 7.2, and 7.0 µM min-1,
respectively, in argon compared to 5.0, 6.6, and 4.5 µM
min-1 in air atmosphere. The rate was even faster for
3-CPOH (k ) 20.0 µM min-1) with an initial concentra-
tion of 1 mM in argon atmosphere. The faster degrada-
tion of 3-CP compared to 2-CP and 4-CP was attributed
to the fact that with 3-CP, there are three points of
simultaneous ortho and para orientation to Cl and OH
groups where, due to the electrophilic character of OH,
OH radical addition would easily occur. Johnston and
Hocking75 investigated the photocatalytic and photolytic
degradation of 2,4-DCP with and without sonication.
They found that the use of sonication (1 × 10-3 M, 2,4-
DCP, or 0.2% or 0.05% TiO2) in photolysis resulted in
the enhancement of chloride release rate by a factor of
4 compared with that of UV irradiation only.
The main sonooxidation products of p-nitrophenol (p-
Np) are nitrates (NO2-), nitrates (NO3-), short-chain
carboxylic acids, formic acid (or formate, HCO2-), acetic
acid (or acetate), and oxalic acid (or oxalate) with
intermediates such as 4-nitrocatechol (4-NP), hydro-
quinone, and benzoquinone. Kotronarou et al.76 and
Hoffmann et al.58 found that in the presence of ultra-
sound, p-nitrophenol solutions was denitrated to yield
NO2- and NO3- by two independent mechanisms: (a)
via the gas-phase reaction, which takes place in pure
water, and (b) from the decay of p-NP molecules. It was
shown that while NO3- did not interfere with the
sonochemical reactions of p-NP, NO2- appeared to affect
the decay of p-nitrophenol and the formation of 4-ni-
trocatechol (4-NP). Ultrasonic irradiation of a solution
containing 100 µM p-NP and 100 µM NaNO2 was found
to result in a slower disappearance of p-NP (k1 ) 2.0 ×
10-4 s-1) when compared to a kinetic run in the absence
of NO2- (k1 ) 3.67 × 10-4 s-1). On the basis of the
products and kinetic observations, it was concluded that
the degradation of p-NP involved high-temperature
reactions of p-NP in the interfacial region of cavitation
bubbles and that the main pathway was carbon-
nitrogen bond cleavage with hydroxyl radical reaction
providing a secondary reaction channel. Hua et al.77
studied the sonochemical degradation of p-NP using
high-power ultrasonic system (parallel-plate near field
acoustical processor, NAP, with 0-1775W) in the pres-
ence of argon (Ar) and oxygen (O2) in order to investigate
the effect of power per area. They found pseudo-first-
order constant for p-NP degradation in the presence of
pure O2, (k2 ) 5.19 × 10-4s-1) was lower than that in
the presence of pure Ar, (kAr ) 7.94 × 10-4s-1). The
highest degradation rate was in the presence of Ar/O2
(4:1 v/v) mixtures (kAr/O2 ) 1.20 × 10-3s-1) at the same
intensity of 1.4 W/cm2. Cost et al.78 also studied the
sonochemical reactions of p-NP in solutions containing
particulate matter, phosphate (total ions: HPO42- +
H2PO4-, and a pH 6.8), bicarbonate (HCO3- ions, and
pH 8), and humic acid and in solutions from lake water
(natural water). They also observed first-order rate
constants, kobs, for p-NP of 4.4 × 10-4 in deionized water
and 3.4-3.2 × 10-4 s-1 in water with bicarbonate

concentration: 10-4 e [HCO3-] e 10-2 M. They found
the degradation rate was unaffected by chemicals of
natural water. They rationalized the results by indicat-
ing that for pollutants such as p-NP which decay via
thermal reactions near the interface or inside of cavi-
tating bubbles, the high-temperature denitration reac-
tions in this case are not significantly affected by
common chemicals of natural waters. Barbier and
Petrier79 investigated the ultrasonic degradation and
minerilization of 4-nitrophenol (4-NP) at two ferquencies
(20 kHz and 500 kHz) and in water saturated with
oxygen or an oxygen-ozone gas mixture. They found the
coupling of ultrasound and O3 increased the potential
of ozonation to mineralize 4-NP degradation products.
At low pH (pH 2), where the ozone auto-decomposition
radical pathway is suppressed, they observed 4-NP
mineralization at 500 kHz was 1.8 times faster than at
20 kHz for the same O3 consumption and attributed the
enhanced rate to increased O3 utilization occurring at
the higher frequency. Tauber et al.80 found the sonolytic
degradation of 4-nitrophenol (4-NP) in argon-saturated
aqueous solution (321 kHz) was fully due to OH-radical-
induced reactions at pH 10, where 4-nitrophenol is
deprotonated (pKa ) 7.1) and nonvolatile 4-nitrophe-
nolate predominates. At pH 4 and with the neutral form
of 4-nitrophenol, oxidative-pyrolytic degradation pre-
dominated, resulting in large yields of CO, CO2, and H2.
Takizawa et al.81 sonicated various phenolic com-
pounds in aqueous media (water and water-ethanol) at
215 °C for 12-18 h. using 200 kHz ultrasound in the
presence of oxygen and isolated various hydroxylated
phenols as products of ultrasonic oxidation (Table 3).
They also identified catechol and hydroquinone as the
oxidation products of phenol. They postulated the fol-
lowing mechanism for the production of hydroquinone
from phenol: The phenolic benzene ring was attacked
by the hydroxyl radical produced in water sonochemi-
cally. The attack took place at the carbon attached to
the methoxy group at the p-position of phenolic hydroxy
group and the methoxy group was eliminated with
hydrogen radical to give hydroquinone and methanol.
Hua et al.56 observed that ultrasonic irradiation acceler-
ated the rate of hydrolysis of p-nitrophenyl acetate (p-
NPA) in aqueous solution by 2 orders of magnitude over
the pH range of 3-8 compared to the same hydrolysis
under ambient conditions at 25 °C. The first-order rate
constants were independent of pH and ionic strength.
They explained their observations by considering the
existence of transient supercritical water (SCW) around
the collapsing cavitation bubbles during sonolysis as an
important factor in the acceleration of chemical reac-
tions due to higher concentration of OH- at the hot
bubble interface resulting from higher ion product, Kw,
of supercritical water.
The main chemical degradation intermediates and
products from benzene usually include phenol, catechol
(CC), hydroquinone (HQ), p- and o-benzoquinone (p- and
o- BQ), 1,2,3-trihydroxybenzene, maleic and muconic
acid, formalaldehyde, and acetylene.82-85 Chlorobenzene
transforms into 4-chlorophenol, chlorophenol, 4-chloro-
catechol, hydroquinone, benzene, butenyne, butadiyne,
nonchlorinated mono- and dicyclic hydrocarbons, CH4,
and C2H2 upon ultrasonic irradiation in air-saturated
solutions.84 De Visscher et al.82 investigated the sono-
chemical degradation of monocyclic aromatic com-
pounds, benzene, ethylbenzene, styrene, and o-chloro-
toluene, in aqueous solutions and found the first-order
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4699
reactions to be dependent on initial concentrations of
the substrates and the sonication time. Pyrolysis is
expected to be the main reaction path for the degrada-
tion of polar compounds. De Visscher et al.83 analyzed
the reaction products of the sonochemical degradation
of ethylbenzene in aqueous solutions and found them
to be typical of high-temperature pyrolysis reactions.
The reaction rates were also found to be first-order.
Unlike ethylbenzene, both pyrolysis and radical attack
appear to be important pathways of benzene and
chlorobenzene degradations. Drijvers et al.84 observed
that chlorobenzene was mainly degraded thermally and
that the first-order degradation rates for the sonolysis
was not influenced by the pH of the aqueous solution
while saturating the solution with argon instead of air
accelerated the degradation. It was also suggested that
chlorophenol (CP), the only oxygen-containing interme-
diate detected, was not formed directly by the reaction
of OH radicals with chlorobenzene but resulted from the
addition of oxygen to chlorophenyl radicals in the
interface since chlorobenzene could not break down in
the bulk solution itself. Price et al.86 obtained a first-
order rate constant of 0.055 min-1 and 0.08 min-1,
respectively, for the sonication of chlorobenzene (CB)
and 1,4-dichlorobenzene (1,4-DCB) at about 39 Wcm-2
and observed that 1,4-DCB was totally consumed after
40-50 min. For a given intensity (i.e., 20.9 W/cm2), the
reaction rate of 1,4-DCB was found to be faster com-
pared with those of CB, naphthalene (NT), anthracene
(AN), and pyrene (PR). Drijvers et al.85 compared the
sonolysis at 520 kHz (9.4 or 0.063 Wml-1) and 25 °C of
four monohalogenated benzenes, fluorobenzene (FB),
chlorobenzene (CB), bromobenzene (BB), and iodoben-
zene (IB), at different initial concentrations, 0.5, 1, and
2 mM. They found all four to degrade by similar
mechanisms and the sonolysis rates to depend on initial
concentrations. Petrier et al.72 also studied the sonochem-
ical degradation of chlorobenzene (CB). On the basis of
the chloride ion evolution, the low level of hydroxylated
intermediates, and the formation of gaseous stable
products (CO2, CO, C2H2), they suggested a thermal
degradation inside the cavitation bubble as the prefer-
ential reaction pathway, with C2H2 formed by ther-
molytic ring cleavage. The formation of brown carbon-
aceous particles was attributed to soot formation under
pyrolytic conditions, phenyl radical combination, or
C2H2 reactions at high temperatures. For a mixture of
the hydrophobic CB and the hydrophilic 4-CPOH at 0.5
mM each, CB decayed first, and the 4-CPOH transfor-
mation started only when CB reached a low level (0.02
mM). The results also indicated that the presence of
hydrophobic compound with high vapor pressure (Hen-
ry’s law constant, H, for CB ) 3.77 × 10-3 atm.m3mol-1)
hinders efficiently the degradation of hydrophilic com-
pound with less vapor pressure (H ) 2.4 × 10-3
atm.m3mol-1) or the less volatile solute, 4-CPOH.
Khenokh and Lapinskaya87 observed that the oxidative
processes arising from the ultrasonic irradiations of
benzene and toluene in aqueous solutions resulted in
the destruction of the six-membered ring compounds,
with the formation of formaldehyde and other simulta-
neous reactions leading to the formation of phenol.
Thoma et al.88 studied the sonochemical treatment of
benzene and toluene in water using a parallel plate near
field acoustic processor (NAP). They found the magne-
tostrictive system to be capable of degrading both
contaminants in a continuous stirred tank reactor
4700 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
configuration with the rate constant inversely propor-
tional to the target pollutant concentration. They also
observed that the apparent first-order rate constant
increased approximately linearly with the power input
(measured from the wall) to the system.
Hung et al.89 found the rate of reduction of nitroben-
zene by Feo enhanced in the presence of ultrasound
(US). For example, the first-order rate constant for the
ultrasonic degradation of nitrobenzene in the absence
of Feo was found to be 1.8 × 10-3 min-1 compared to
7.8 × 10-3 min-1 in the presence of 70 g/L Feo. They
described the overall rate of nitrobenzene disappearance
by the linear relation:
d[NB]
- ) kus[NB] + kFeo[NB] + k′[NB] )
dt
(kUS + kFeo + k′)[NB] (11)
where kus, kFeo, and k′ are, respectively, the first-order
degradation rate constants for sonolysis, reduction by
Feo, and the synergistic kinetic effect achieved by
combining the two systems. They also obtained the
following relation from eq 11:
-ln
[ ]
[NB]
[NB]o
1
) (kus + kFeo)t + kseckpt2
2
(12)
where ksec, kp ) xoka, xo, and ka are the average second-
order rate constant for the reaction between the Feo
surface sites or the reaction intermediates and ni-
trobenzene, a zero-order rate constant that increases
with added [Feo], the initial activated Feo surface before
the application of ultrasound, and a proportionality (dx/
dt ) kax, x ) surface area of Feo at time t), respectively.
They attributed the faster degradation rates in the
combined US/Feo system to several causes. These in-
clude the indirect chemical effects associated with the
continuous ultrasonic cleaning and activation of the Feo
surface, the accelerated rates of mass transport result-
ing from the turbulent effects of cavitation, and the
acidity produced by H+ released from HNO3, a product
of sonolysis of nitrobenzene and water. The intermedi-
ates such as 4-nitrocatechol and benzoquinone usually
observed when Feo is used for reduction were negligible
in the combined US/Feo system. They also found the
sonolytic degradation of aniline to be a first-order
reaction with apparent rate constant of 2.4 × 10-3 min-1
at 20 kHz and 139 WL-1 with or without Feo.
Soudagar and Samant90 evaluated the ultrasound-
catalyzed oxidation of various aryl alkanes (eg., toluene,
nitro- and o-chloro-toluene, p-xylene) to the correspond-
ing aryl carboxylic acids using aqueous KMnO4 under
heterogeneous conditions and optimized parameters
such as quantity of KMnO4, stirring rate and reaction
time. It was shown that heterogeneous oxidation of
unsubstituted aryl alkanes was significantly accelerated
using aqueous KMnO4 at ambient temperatures and in
the presence of ultrasound. While under optimized
conditions o-chlorotoluene and mesitylene (1,3,5-tri-
methylbenzene) were effectively converted into the
corresponding carboxylic acids, isopropyl benzene and
tert-butyl benzene did not undergo oxidation and were
recovered unreacted. Nagata et al.91 investigated the
aqueous sonochemical degradation of hydroxybenzoic
acids such as monohydroxbenzoic acids (HBAs), 3,4-
dihydroxybenzoic acid (3,4-DHBA), 3,4,5-trihydroxyben-
zoic acid (gallic acid, GA), tannic acid (TA), and humic
acids (HA) under air or argon atmosphere. They found
the pseudo-first-order constants for 2-HBA, 3-HBA, and
4-HBA to be 3.0 × 10-2, 4.9 × 10-2 and 5.1 × 10-2 min-1,
respectively, under Ar and 2.7 × 10-2, 3.4 × 10-,2 and
3.1 × 10-2 min-1 under air. However, the rate constants
of GA and TA were higher under air irradiation (5.5 ×
10-2 and 16.4 × 10-2 min-1) compared with irradiation
under Ar (2.6 × 10-2 and 6.4 × 10-2 min-1). The rate
constant for 3,4-DHBA was the same under both
atmospheres (1.9 × 10-2 min-1). The decomposition of
3-HBA was almost completely quenched in the presence
of t-BuOH at a concentration of 0.1 mM. They argued
that the sonolytic degradation of the HBA under Ar
atmosphere proceeded mainly via reactions with OH
radicals in the bulk solution. Whereas under air oxygen
molecules contributed to the decomposition of the poly-
hydroxybenzoic acids at the interface, thermal decom-
position in cavitation bubbles or interfacial regions
played a negligible role in both atmospheres. They also
suggested that the participation of oxygen molecules
accounted for the faster decomposition rates of GA and
TA in air, the rates in air facilitated with an increasing
number of OH groups (kTA > kGA) as expected with
oxidation of phenolic compounds with oxygen. D-Silva
et al.92 observed the rapid destruction of polycyclic
aromatic hydrocarbons (PAHs) and dioxin when solu-
tions of benzo[a]pyrene (B[a]P), benzo[ghi]perylene,
coronene, or 2-chlorodibenzo-p-dioxin in 20% ethanol-
water at approximately 10-15 ppm levels were sub-
jected to high-intensity sonication. It was shown that
the sonolytic decomposition of PAH and dioxin was
accompanied by the formation of a black carbonaceous
residues. It was also shown that the effect of ultrasound
on a 100% ethanol solution of B[a]P was not as pro-
nounced as in water-ethanol mixture.
4.2. Chlorinated Aliphatic Hydrocarbons (CAHs).
The sonochemical reactivity of chlorinated hydrocarbons
in aqueous solutions is attributed to their volatility and
their low solubility in water, properties facilitating their
concentration in the cavitation bubbles resulting in
rapid decomposition by high temperature and high
pressure. The sonication of 15 mL of neat chlorinated
solvents 1,1,1-trichloroethane (TCA) and trichloroeth-
ylene (TCE) produced a yellow color (presumably due
to elemental chlorine) in 10 min and in 2 h produced a
brown suspension indicating the solvents have polym-
erized due the treatment.92 Inazu et al.93 found that
aqueous solutions of trichloroethylene (TCE), tetrachlo-
roethylene (PCE), 1,1,1-trichloroethane (1,1,1-TCA),
chloroform (CHCl3), and carbon tetrachloride (CCl4)
decomposed rapidly to chloride anions (Cl-), hydrogen,
carbon monoxide, and carbon dioxide by ultrasonic
irradiation in the presence of argon, O2, or air. They
suggested that the main reactions were thermal decom-
position or combustion in cavitation bubbles and not
reactions by OH radicals or H atom. It was also shown
that the main products of TCE degradation products
under Ar were Cl-, CO, and H2. The minor products of
the decomposition under Ar were CO2, CH4, C2H4, and
a trace amount of dichloroethylene. Under the sonica-
tion of O2 or air, considerable amount of CO2 evolved,
and no CO was observed. Drijvers et al.94 identified the
following volatile products of TCE sonication at 50
kHz: chloroacetylene (C2HCl), dichloroacetylene (C2Cl2),
dichlorodiacetylene (C4Cl2), tetrachloroethylene (C2Cl4),
two isomers of trichlorobutenyne (C4HCl3), tetrachlo-
robutenyne (C4Cl4), pentachlorobutadiene (C4HCl5), and

hexachlorobutadiene (C4Cl6). It was also shown that the
degradation rate of TCE was more energetically efficient
at 520 kHz than at 20 kHz. Reinhart et al.95 studied
the combined effects of sonication and zerovalent iron
on the destruction rate of TCE and found ultrasound to
increase the rate significantly. For example, they ob-
tained first-order rate constants, k (hr-1), of 0.0147,
0.0218, and 0.0426, respectively, for ultrasound alone,
iron alone (3 g/L), and the combined system, respec-
tively.
The main intermediates of the sonication of the
aqueous carbon tetrachloride (CCl4) are tetrachloro-
ethylene (C2Cl4) and hexachloroethane (C2Cl6) with
trace amounts of dichlorocarbene, dichlromethane,
trichloroethylene, tetrachloroethane, pentachloroethane,
hexachloropropene, hexachlorobutadiene, and chloro-
form, and the final products are usually chlorine,
chlorides (or HCl), chlorohydric acid, hypochlorous acid
(HOCl), CO, and CO2.96-100 Jennings et al.97 investi-
gated the sonochemical reactions of CCl4-H2O mixtures
in an argon atmosphere and compared results with
those of CHCl3-H2O mixtures. They observed cavitation
when CCl4 was sonicated alone, but there was no
reaction. In the presence of as little as 1 mL H2O per
100 mL of CCl4, reaction ensued, and the total inorganic
chlorine yield was found not to be significantly sensitive
to large changes in the CCl4 to H2O ratios. The observed
products from the CCl4 reaction included: CO2, O2, Cl2,
HCl, C2Cl6, and C2Cl4 compared with products of
CHCl3: HCl, C2Cl6, and C2Cl4. Hua and Hoffman99
studied the sonolytic destruction of aqueous CCl4 in the
absence or presence of ozone (O3). The observed first-
order degradation rates in argon-saturated aqueous
solutions were 3.3 × 10-3 and 3.9 × 10-3 s-1 with CCl4
initial concentration of 1.95 × 10-4 and 1.95 × 10-5 mol
L-1, respectively. It was shown that the presence of O3
did not affect the degradation rate significantly but
inhibited the accumulation of C2Cl4 and C2Cl6 interme-
diates. However, sonication of p-nitrophenol in Ar-
saturation aqueous solution in the presence of CCl4
resulted in the degradation rate enhancement of p-NP
by a factor of 4.5 compared to sonication without CCl4
and the reduction of 4-nitrocatechol, an aromatic deg-
radation product. The improvement in rate and mini-
mization of 4-nitrocatechol formation were shown to be
due to the presence of HOCl, a product of CCl4 sonolysis.
Koszalka et al.100 obtained 98% reduction of CCl4 in
the presence of H2, air, or Ar and observed the ultrasonic
destruction to be an exponential process. It was shown
that the initial reaction products: chloroform, dichlo-
romethane, and chloromethane were further degraded
to methane and chlorine/chloride. Total halogen analy-
ses of unreacted and reacted CCl4-contaminated samples
also confirmed Cl balance, indicating that CCl4 was not
volatilized or masked by the chemistry of the process.
Wu et al.7 studied the destruction of CCl4 under dis-
solved air and varied process parameters such as pH,
irradiation, time, steady-state temperatures, and ultra-
sonic intensity. It was shown that CCl4 destruction rate
was significantly affected by the intensity of the ultra-
sonic energy, the rate increasing proportionally to the
intensity. However, the addition of H2O2 as an oxidant
with or without ultrasonic irradiation was also found
to have negligible effect upon the rate. This was at-
tributed to the predominance of the thermal dissociation
reaction in the cavitation holes under supercritical
conditions compared to the bulk-liquid-phase reactions
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4701
involving CCl4 and oxidants such as OH radicals. The
bulk-liquid rate constants (e.g., 107 M-1 min-1) were
found to be about several times smaller than those in
the cavities (e.g., 1012 M-1 min-1). On the basis of a
detailed chemical reaction mechanism and assuming a
batch reactor, they described the destruction of CCl4 in
water by the following differential equations using
second-order rate constants and concentrations in the
bulk-liquid phase and cavity respectively:
-d[CCl4]
) kI[OH][CCl4] + kII[H][CCl4] +
dt
kIII[HO2][CCl4] + kIV[O][CCl4] (13)
d[CCl4]
) kckv[CCl4][M] (14)
dt
where M is any collision partner and kc is the system
adjustment coefficient, which is a function of bubble
concentration, bubble radius concentration, mixing ex-
tent of the system, etc. The results of this model
formulation via a series of elementary reactions were
found to be in general in agreement with experimental
data. They obtained the value of kc to be constant at
2.5 × 10-11 by fitting experimental data to the model,
assuming constant vessel size, steady-state tempera-
ture, and power. Hung and Hoffmann101 investigated
the degradation of CCl4 by combined ultrasound (US)
and iron (Feo) in Ar-saturated solutions and observed a
40-fold enhancement in overall rate for the coupled
system compared with US alone. The first-order ultra-
sonic rate constant for CCl4 was 0.107 min-1 at 62 W
(20 kHz) in 285 mL solution, whereas the apparent rate
constant in the presence of Feo was found to depend on
the total surface area of elemental iron as follows:
kobs ) (kus + kFeoAFeo) min-1 (15)
where kus ) 0.107 min-1, kFeo ) 0.105 L m-2 min-1, and
AFeo is the reactive surface area of Feo in units of m2/L.
Rajan et al.102,103 investigated experimentally and by
modeling of the water-KI-CCl4 system and attributed
the significant increase in oxidation rates observed in
a suspension of CCl4 liquid in KI solution to the release
of Cl2, Cl, and HOCl, which act as a separate source of
reactants to yield I2. They used a complex mathematical
model that included detailed kinetics of CCl4 to predict
the extent of degradation of dissolved CCl4 and the large
enhancements in the rate of oxidation of aqueous iodine
ion (I-) in the presence of CCl4. A similar study of the
CCl4/KI (1.0 M solution) system by Alippi et al.9 found
the yield of free iodine to increase linearly with soni-
cation time.
Petrier et al.104 studied the sonolysis of chloromethane
and their dilute mixtures in alcohols under saturation
with Ar or O2 and found the zero-order rate constants
to be greater in Ar atmosphere. Since the sonochemical
cleavage of the alcohols were found to be weak, the
initial step in the transformation (faster in Ar) was
attributed to the C-Cl cleavage, in constrast to the
reaction in water, where sonochemical cleavage of the
solvent plays a major role. They also explained that the
sonolysis, probably in the cavitation bubble of CCl4 and
which was more efficient in alcohols than in the pure
state, could result from the preferential vaporization of
this apolar molecule into a bubble formed in a hydrogen-
bonded structured liquid. Toy et al.12,13 investigated the
4702 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
decomposition of aqueous 1,1,1-trichloroethane (1,1,1-
TCA) under sonolysis, photolysis, and the synergistic
combination of the two and reported more extensive
decomposition with combined photolysis and sonolysis
(photosonolysis) than UV photolysis or sonolysis alone.
It was also shown that TCA (CCl3CH3) decomposed into
gases, VOCs, and ionic species, and as the volume of
the same concentration was increased, the sonolysis
digestion efficiency decreased. Cheung et al.8 examined
the sonochemical destruction of methylene chloride
(CH3Cl), TCA, TCE, and CCl4 and attributed the rapid
decrease of reactor solution pH in all cases to the
probable formation of HCl from the chlorinated reac-
tants with the hydrogen source being water. Bhatnagar
and Cheung10 studied the kinetic behavior of individual
VOCs in the presence of other VOCs by sonicating
mixtures of (1) two chloromethanes (CH3Cl + CCl4) and
(2) CH2Cl2, CCl4 (C1 compounds) + 1,1,1-TCA (C2
compound). The first-order rate constants for the com-
pounds were essentially unchanged by the presence of
other reacting species. Petrier and Francony105 com-
pared the decomposition rates of CCl4 and phenol at
different frequencies (20-800 kHz) and observed that
irrespective of frequency, it was easier to decompose the
hydrophobic and volatile CCl4 than the hydrophilic
phenol with a low vapor pressure. For the phenol, they
found that degradation proceeded faster at 200 kHz and
that the addition of an excess of 1-butanol (10-fold
phenol initial concentration), used to scavenge hydroxyl
radicals totally inhibited the reaction. The rate of
disappearance of CCl4 on the other hand was found to
increase slightly with increase in frequency, and the
addition of 1-butanol (10-fold CCl4 initial concentration)
did not affect the rate of CCl4 destruction. It was also
shown that both phenol degradation and H2O2 forma-
tion involving reactions with OH radical at the interface
increased with frequency reaching an optimal value at
200 kHz. Drijvers et al.106 investigated the mutual
influence of TCE and chlorobenzene by sonicating dilute
aqueous mixtures of the two volatile organic compounds
and found the sonolysis rates to depend strongly on the
initial concentration of TCE and CB. The presence of
CB was found to lower the sonolysis rate of TCE, while
the sonolysis rate of CB (with initial concentration 3.44
mM) was enhanced by the presence of 0.84 mM TCE.
They attributed the different effects of both volatile
organics on each other’s sonolysis to the difference in
reaction rate of TCE and CB with the radicals formed
during sonolysis. They suggested that the effect of TCE
on the sonolysis rate of CB (i.e., the lowering of the γ
value of the gas present in the cavitation bubble and
consequently the temperature during collapse) was
compensated by an increased indirect degradation of CB
by radicals formed out of TCE.
De Visscher and Van Langelove107 explored the influ-
ence of Fenton-type oxidants on the aqueous sonochemi-
cal degradation of trichloroethylene (TCE), o-chlorophe-
nol (o-CP), and 1,3-dichloro-2-propanol (DCP). It was
shown that di-tert-butyl peroxide inhibited the sonolysis
of both TCE and CP by scavenging OH radicals and by
lowering the maximum temperature generated during
a cavitation event. However, 10 mM tert-butyl hydro-
peroxide had no considerable effect on the sonochemical
degradation of TCE but inhibited completely the deg-
radation of o-CP. The effect of TCE was interpreted to
mean that the amount of tert-butyl hydroperoxide in the
cavitation bubbles (where TCE is degraded) was too low
to change the conditions of a cavitation event signifi-
cantly. The effect on o-CP indicated that tert-butyl
hyroperoxide scavenged OH radicals without producing
any radicals that entered the liquid phase where oxida-
tion was expected to occur. Unlike the less polar, organic
peroxides, the presence of H2O2 did not affect the
degradation of TCE and DCP but enhanced the degra-
dation of o-CP on the order of 20-25%. The degradation
of both o-CP and DCP (with low Henry’s constant) are
expected to occur by radical attack. Hence, they at-
tributed the low reactivity of DCP toward OH to the
lack of aromatic rings on which the radicals can add
and to the presence of Cl atoms on DCP that could lead
to electronic repulsion toward the OH radical. They also
observed that in the presence of H2O2 and copper ions,
the sonochemical degradation of o-CP is the sum of the
effect of the ultrasound and the chemical oxidation effect
and likened the overall degradation mechanisms to
sonochemical switching effect. That is, sonication in-
duces a specific reactivity and silent chemical, and
sonochemical degradations follow separate paths. The
CAV-OX has been shown to degrade TCE and BTEX
in contaminated groundwater with efficiencies better
than 99.9% when varied principal opearting parameters
such as H2O2 dose, pH, and flow rate are used.14 The
process involves the use of sequential hydrodynamic
cavitation and direct UV photolysis of H2O2 to generate
hydroxyl and hydroperoxyl radicals. Orzechowska et
al.108 monitered and compared the chloride release
tendencies of CCl4, CHCl3, TCE, aromatic chloro com-
pounds (e.g., CB, polyaromatic chloro compounds, PCBs,
4,4′- and 3,3′-dichlorobiphenyl) and TritonX-100 (a sur-
factant) upon sonication and found that CB and PCBs
did not release Cl- as readily as did CCl4, CHCl3, and
TCE. They attributed the results to possible hydroxy-
lation reactions at an open position of aromatic ring,
i.e., oxidation of PCBs and CB by OH radical without
dehalogenation. The presence of humic substances was
also found not to affect Cl- yields. Catallo and Junk109
studied the sonochemical transformation of hazardous
chlorinated chemicals and a mixture of chlorinated
olefins, paraffins, and aromatics from a Louisiana
superfund site (LSS) and observed dechlorination via
aryl C-Cl bond heterolysis and hydroxylation reactions
to be the main reaction pathways. Dechlorination and/
or other transformations were observed for chlorinated
alkanes (e.g., CCl4) 2,4-dichlorophenol, chlorpyrifos, and
lindane (hexachlorocyclohexane, γ-isomer) and a for
range of chlorinated aromatic and aliphatic chemicals
in the LSS mixture. The herbicide byproducts, chlorpy-
rifos, 3,3′,4,4-tetrachloroazoxybenzene (TCAOB), and
trichlorodibenzofuran (TCDF), were not dechlorinated.
However, TCAOB appeared to deoxygenate sonochemi-
cally to the 3,3′,4,4 tetrachloroazobenzene. Sakai et al.110
studied the sonochemical degradation of aqueous solu-
tions of chloral hydrate (CCl3CH(OH)2 or simply CH)
and found the rate to be proportional to the square of
oxygen concentration at low concentrations, while at
relatively high concentration, the rate is independent
of the oxygen concentration. They also found the reac-
tion rate to be proportional to the square root of the
concentration of chloral hydrate and to the intensity of
the ultrasound regardless of the concentration of oxygen
gas dissolved in the solutions.
4.3. Explosives. Sierka111 investigated the treatment
of aqueous solutions of trinitrotoluene (TNT) and cy-
clotrimethylene-trinitramine (RDX) in the weight ratio

of 70:30 (typical of munitions wastewater) at 25-59 °C
using a combination of ozone and ultrasound in the pH
range of 5.84-10.00. They demonstrated the synergistic
effects of both ozone and ultrasound. While the maxi-
mum destruction of both TOC and TNT was observed
at 859 kHz and 50W, experiments performed without
O3 at these same conditions resulted in no TNT or TOC
removals. The increased removal with O3/ultrasound
systems was explained partially by the increased tem-
perature in the reactor. While at 25 °C, the TNT
destroyed after 60 min of ozonation was 23%; 99% was
destroyed when temperature averaged 59 °C. Removal
rates of both TNT and TOC increased directly with
increases in reaction temperature and initial pH. How-
ever, it was shown that at solution pH values main-
tained in excess of 9.6, the combination of high pH and
temperature was not beneficial. This was attributed to
the fact that ultrasound inhibited kinetics at high
temperatures and pH by promoting radical-radical
extinguishment reaction. But ultrasound was also shown
to have an additional benefit potential in that it can act
as a catalyst by enhancing the autodecomposition of O3
to free radicals once the ozone has been dissolved in the
aqueous phase. Sonolysis was evident in the degrada-
tion of residues of the military explosives TNT (2,4,6-
trinitrotoluene) and HMX (octahydro-1,3,5,7-tetranitro-
1,3,5,7-tetrazocine), as indicated by release of nitrate
(NO3-) during treatment.73 Hoffmann and co-work-
ers16,58 112 investigated the sonochemical degradation of
TNT at 20 and 500 kHz to acetate, formate, glycolate,
oxalate, CO2, NO2-, and NO3- as products with 1,3,5-
trinitrobenzene as intermediate and found the overall
degradation rate to follow an apparent first-order rate
law. The overall reaction stoichiometry for the auto
oxidation of TNT was found to be:
)))))
C7H5(NO2)3 + 9O2 98
7CO2 + H2O + 3H+ + 3NO3- (16)
where ))) denotes ultrasonic irradiation. They found
TNT degradation to be more efficient at 500 kHz than
20 kHz, irrespective of the background gas. The first-
order kinetic rates vary by a factor up to 3, depending
on the nature of dissolved gases and also on the
ultrasonic frequency: kO2 ) 1.67 × 10-5 s-1, kAr ) 4.50
× 10-5 s-1, and kO2/O3 ) 5.50 × 10-5 s-1 (with 99/1 vol
% O2/O3 mixture as cavitating gases) at 20 kHz com-
pared with kO2 ) 2.00 × 10-5 s-1, kAr ) 7.17 × 10-5 s-1,
and kO2/O3 ) 8.50 × 10-4 s-1 at 500 kHz.
4.4. Herbicides and Pesticides. The sonolysis of the
systemic herbicide, chlorpropham (isopropyl-3-chloro-
carbanilate) in air equilibrated aqueous solutions lead
to the formation of hydroxylated products and 3-chlo-
roaniline as intermediates, and subsequent mineraliza-
tion of intermediates to Cl-, NO2-, NO3-, CO, and CO2.
David et al.113 observed that the ultrasonic treatment
of chlorpropham at 482 and 20 kHz led to a highly
drastic degradation with the initial rate at the high
frequency (13.0 × 10-8 M s-1), much higher than that
at the low frequency (4.2 × 10-8 M s-1). They also
noticed a complete degradation after 45 min at 482 kHz
compared with 1/3 of chlorpropham remaining after 60
min at 20 kHz. It was also shown that the yield of Cl-
was about 98% after 80 min at 482 kHz, indicating the
C-Cl bond cleavage is a major primary process. Two
pathways deduced to be involved in the transformation,
the oxidation by OH• and pyrolysis near the cavitation
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4703
bubbles. The formation of hydrated products (e.g.,
3-chlorohydroquinone) indicated the involvement of the
hydroxyl radical in the degradation of chloropropham.
Petrier et al.114 investigated the ultrasonic degradation
of atrazine, CIET [2,4-diamino-6-chloro-N-ethhyl-N′-(1-
methylethyl)-1,3,5 triazine] and pentachlorophenol (PCP)
at 500 kHz and 20 kHz and demonstrated in both cases
that degradations were more efficient and complete at
the higher frequency. Sonochemical degradation of
atrazine resulted in dealkylation product: CIAT [2,4-
diamino-6-chloro-N-(1-methylethyl)-1,3,5 triazine],
CEAT[2,4-diamino-6-chloro-N-ethyl-1,3,5 triazine], and
CAAT[2,4-diamino-6-chloro-1,3,5- triazine], which are
typical oxidation products of atrazine from degradation
by ozone, Fentons reagent, or TiO2 photocatalysis. Long
irradiation times (3 h) resulted in the formation of CO2
(13% of initial atrazine) and chloride. They observed fast
reactions for PeCP (10-4 M aqueous solution at pH 7)
at both frequencies, yielding 98% of the theoretical
amount of chloride and 20% theoretical carbon as CO2
recovered after 180 min for the reaction conducted at
500 kHz. However, the addition of n-pentanol (10 mM)
inhibited completely both atrazine and PeCP degrada-
tion at high and low frequency, suggesting reactions
with OH• radicals escaping from the cavitation bubble.
Koshkinen et al.115 found the sonochemical degradation
of atrazine to be slower than that of alachlor (70-fold)
at 20 kHz at the same concentration (e.g., 3.1 µmol/L)
and temperature (30 °C). The first-order rate constants
and extrapolated half-lives were 8.01 × 10-3 min-1 and
86 min and 2.1 × 10-3 min-1 and 330 min for alachlor
and atrazine, respectively. They also attributed the
decomposition of both atrazine and alachlor to the
attack by hydroxyl free radicals. Nagata et al.74 found
the aqueous sonochemical degradation of 0.1 mM pen-
tachlorophenol (PeCP) to be faster under argon atmo-
sphere compared with air atmosphere (first-order rate
constant of 6.4 vs 4.5 µM min-1).
Gondrexon et al.116 studied the sonochemical degra-
dation of PeCP in a three-stage, continuous flow,
laboratory-scale ultrasonic reactor and obtained a con-
version up to 80%. Johnston and Hocking75 investigated
the photocatalytic and photolytic degradation of PeCP
(2.4 × 10-4 M solution) with and without sonication.
They observed the initial rate of chloride formation due
to photocatalysis using TiO2 to be about 2.7 times faster
with sonication than without. In the absence of sonica-
tion, the percent degradation measured by Cl- release
reached a value of 40% after 50 min, beyond which
continued irradiation up to 200 min did not significantly
affect increase in degradation. In contrast, combined
sonication, UV, and photolysis resulted in a rapid initial
degradation, with near quantitative release of chloride
after 120 min. They attributed their observation to
possible poisoning of catalyst active sites during pho-
todegradation by inert intermediates formed but which
are removed from active sites by sonication, allowing
further degradation or decrease in pH during photolysis,
leading to significant decrease in a photochemical
degradation process. Petrier et al.117 also studied the
sonochemical degradation of pentachlorophenate (PCP)
at 530 kHz in aqueous solutions saturated with air,
oxygen, or argon and observed the degradation and the
resulting toxicity decrease to be faster under argon
bubbling (PCP disappeared in 50 min) than under air
or oxygen. The ultrasonic degradation of PCP was also
attributed to a rapid cleavage of carbon-chlorine bond
4704 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
to release Cl- (90% chlorine recovered as Cl- in 150
min). This was followed by degradation to CO2 in air-
or oxygen-saturated solutions (or CO in argon-saturated
solutions) and nitrite and nitrate in solutions aerated
with air or oxygen. They also postulated that because
of the high temperature inside the cavitation bubble,
the formation of CO in the presence of argon was due
to reactions of the type:
CO2 + Ar f CO + O + Ar and
CO2 + •H f CO + •OH
Wheat and Tumeo118 studied the aqueous sonolysis of
two polycyclic aromatic hydrocarbons or PAH’s (phenan-
threne and biphenyl), and the results obtained suggest
polychlorinated biphenyls (PCB’s) may be susceptible
to hydroxyl radical substitution reactions under the
vigorous reaction conditions supplied by high-intensity
ultrasound. The principal products of biphenyl reaction
identified through mass spectral analysis were [1,1-
biphen]-2-ol, [1,1-biphen]-3-ol and [1,1-biphen]-4-ol, and
the principal products of phenanthrene appeared to be
di-hydroxy substituted phenanthrene. The phenolic
products produced from these hydrophobic compounds
were considered consistent with a free radical attack
by hydroxyl free radicals (OH•) on the hydrocarbon
skeleton. Zhang and Hua119 also observed that poly-
chlorinated biphenyls (2-, 4-, and 2,4,5-chlorobiphenyls)
dechlorinated rapidly to chloride ion during sonolysis
at 20 kHz with 99% destruction of 2-PCB, 4-PCB, and
2,4,5-PCB in 36, 47, and 29 min, respectively. The
chloride recovery ratio defined as [Cl-] /([M]i - [M]f) ×
n, where n is the number of chlorine atoms per cogener
in each sample and [M]i and [M]f are initial and final
concentrations of parent compound (i.e., mol/L PCB),
were 77%, 79%, and 70%, respectively, for 2-PCB,
4-PCB, and 2,4,5-PCB, respectively. They also identified
products such as biphenyl, toluene, ethylbenzene, phe-
nol, trichlorophenol, hexenyldiphenol, and other phenols
(Table 3). They investigated the role of aqueous hydroxyl
radical in the decomposition of 2-PCB at 205, 358, 618,
and 1071 kHz. It was shown that ultrasonic irradiation
was optimal at 358 kHz but chloride recovery was
optimal at 1071 kHz. They proposed that both ther-
molysis and free radical attack are important pathways
of PCB destruction but that free radical attack (espe-
cially •OH) in the aqueous phase played a more signifi-
cant role at 358 kHz than at other three frequencies.
Johnston and Hocking75 investigated the photo catalytic
/photolytic degradation of PCB isomer 3-chlorobiphenyl
at 75 ppm level (4 × 10-4 M) by monitoring the chloride
formation. TiO2 (0.2% w/w) and 30 mL aliquots were
subjected to UV irradiation and to combined UV/
ultrasound irradiation. They found a linear rate of
appearance of chloride with time for both conditions,
but rates with sonication were approximately 3 times
greater that without sonication, and they attributed the
enhanced rates partially to the highly hydrophobic
nature (i.e., low solubility) of substrate. They also
attributed the significant increase in degradation rates
and efficiency of the concurrent UV/ultrasonic irradia-
tion to cavitational effects, bulk, and localized mass
transport effects and sonochemical reactions.
Kotronarou et al.120 showed that the sonolysis of
parathion (o,o-diethyl o-p-nitro phenyl thiophosphate)
led to its transformation to sulfate, nitrate, nitrite,
phosphate, oxalate and p-nitrophenol, p-NP (parathion
hydrolysis product) with complete degradation in e2 h.
They proposed that parathion transformation proceeded
via thermal decomposition in the hot interfacial region
of the collapsing bubbles with secondary reactions with
•OH radicals. Theron et al.121 determined the removal
rates of phenyltrifluoromethyl ketone (160 µmol L-1
PTMK) by sonolysis at 30 and 515 kHz, by UV-
irradiated TiO2 (Degussa P25 and Rhodia), and by
simultaneous photocatalysis and ultrasonic irradiations.
The PTMK first-order removal rate constant was found
to be 14 times greater at the higher frequency compared
with that at the lower frequency at the same energy
level and 2.5 times higher when synthesized Rhodia
TiO2 was used instead of Degussa P25. The amount of
trifluoroacetic acid (CF3COOH or TFA), an undesirable
and stable product of TiO2-treated CF3-containing pol-
lutants, was about 8 times lower in sonicated solutions
than in UV-irradiated suspensions, for both frequencies.
4.5. Organic Dyes. Vinodgopal et al.122 studied the
sonochemical degradation of a reactive black dye (Azo
dye, Remazol Black B or RB) at high frequency (640
kHz) in O2-saturated aqueous solution. They found
sonolysis as a feasible method to achieve both decolori-
zation and 65% degradation of the dye in 6 h as
measured by the decrease in the in total organic content.
The pseudo-first-order rate constant for the disappear-
ance of the dye was determined to be 2.9 × 10-2min-1.
They also observed that degradation stopped far short
of completion when performed in an aqueous solution
of about 2% tert-butyl alcohol, an excellent OH radical
scavenger, and attributed the conversion of the dye to
oxalate (C2O42-) to •OH radical-initiated oxidative deg-
radation. They also compared photocatalytic and radi-
olytic methods of degradation to sonolysis. Their results
suggested that sonochemical degradation rates of Azo
dyes were substantially faster and led to better destruc-
tion of the dye compared to photocatalysis. Stock et al.123
investigated the degradation of an azo dye, naphthol
blue black (NBB), using sequential combination of high-
frequency sonolysis and photocatalysis in four different
configurations: (1) sonolysis only, (2) photocatalysis
only, (3) simultaneous sonolysis and photocatalysis, and
(4) sequential sonolysis and photocatalysis. They ob-
served that for individual techniques, sonolysis was
effective for inducing faster degradation of the parent
dye, while TiO2 photocatalysis was effective for promot-
ing degradation. For example, photocatalysis was re-
sponsible for 68% conversion compared to 35% for
sonolysis after 12 h. It was also shown that the first-
order rate was enhanced by the combined systems
(simultaneous and sequential). For example, pseudo-
first-order rate constant was 1.83 × 10-2 min-1 for the
combined case compared with 1.04 × 10-2 min-1 for
sonolysis or 0.56 × 10-2 min-1 for photocatalytic experi-
ments.
4.6. Organic and Inorganic Gaseous Pollutants.
Cheung and Kurup124 investigated the sonochemical
destruction of fluorotrichloromethane (CFC11) and tri-
fluorotrichloroethane (CFC113) in dilute aqueous solu-
tions in a batch and circulating reactor. They found the
rates to be fairly rapid with less than 5% of the original
CFC’s undergoing volatilization and the bulk of material
destroyed in the liquid phase. In these preliminary
studies, they also observed the rates to be slightly higher
at 5 °C than at 10 °C and rapid drops in pH (initial value
of 7.4 to about 5.4), indicating the formation of acidic
species. Hirai et al.125 evaluated a number of CFC’s and

HFC’s and found them to be readily decomposed
sonochemically with high efficiency to inorganic prod-
ucts (CO, CO2, Cl-, F-). It was also shown that CFC-
113 decomposed faster under argon atmosphere (with
higher CP/Cv ratio) than air atmosphere and that its
decomposition rate was not significantly affected by the
addition of tert-butyl alcohol (tert-BuOH), a known
effective OH radical scavenger. Hart and Henglein126
studied the sonochemistry of Ar/N2O mixtures and the
pure gases in aqueous solutions at high frequency, 300
kHz, and observed products of decomposition of N2O to
be N2, O2, NO2- (or HNO2), and small amount of NO3-
(or HNO3). It was also observed that the maximum yield
of decomposition occurred at an Ar/N2O vol % ratio of
85:15. However, the rate of N2O decomposition was very
low when water was sonicated under pure nitrous oxide,
as expected with a triatomic gas. The yield of HNO2 was
much higher than observed in the irradiation of water
under air and under mixtures of nitrogen and argon,
and this was attributed to the decomposition of N2O of
the type: 3N2O + H2O f 2HNO2 + 2N2. Henglein127
studied the ultrasonic irradiation of water under argon
atmosphere containing small amounts of CO2, N2O and
CH4. They observed no chemical effects in the irradia-
tion under atmosphere of pure CO2, N2O, or CH4.
However, they showed that sonochemistry in an argon
atmosphere containing small amount of any of the
polyatomic gases was characterized by a strong linkage
between the sonolysis of water and the added gas. The
main products of the sonolysis of CO2 were CO and
small amount of formic acid, about 30 times smaller
than CO yield. The main products of N2O sonolysis were
N2, NO2- and NO3- in this study.127 In the N2O-Ar
containing solutions, they observed the yields of the
products NO2- and NO3- were about 10 times greater
than the amounts formed in the ultrasonic irradiation
of aerated water and greater than the amounts in water
irradiated in the presence of both N2O and O2. Hara-
da128 investigated the sonolysis of CO2 dissolved in
water (0.0-0.6 mole fraction CO2 in water) at 5-45 °C
using an ultrasonic generator (200 kHz, 200 W) and Ar,
He, H2, and N2 as the irradiating gases. While irradia-
tion of ultrasound had hardly any sonochemical effect
under CO2 atmosphere, the most favorable atmosphere
for reducing was CO2-Ar mixture with 0.03 mole
fraction of CO2 in gas phase, a concentration considered
an equal mixture of CO2 and Ar in water because CO2
is more soluble than Ar. The amount of CO2 in CO2-
Ar was found to decrease to about half at 5 °C, and the
decreasing rate for CO2 followed the order Ar > He >
H2 > N2. They also observed that dissolved CO2 was
deoxidized to carbon monoxide (CO2 f CO + O) by
sonolysis and showed that the hydrogen carbonate or
bicarbonate ion (HCO3-) played an important role
compared to the carbonate ion (CO32-). Since hydrogen
is also obtained from the solvent (water) and both CO
and H2 are fuel gases, which also react to produce C1
compounds such as methanol, they proposed sonication
as a useful and potential technique to reduce CO2 and
produce fuel.
The main oxidation products of the methane-contain-
ing solutions were oxygen-containing gases such as CO,
CO2, and compounds with oxygen, such as C2H4, C2H6,
and C3 and C4 compounds, and the production of large
amounts of H2. Hart et al.129 also identified H2, C2H2,
C2H4, and C2H6 as major products and C3-C4 hydro-
carbons (e.g., propane, propene, 2-methylpropane, n-
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4705
butane, 1-butene, 2-methyl,1-butane and butadiene) and
CO as other products of CH4 sonolysis under argon
atmosphere. They found the products for the sonolysis
of the C2H6 to be the same as CH4 except that they were
produced in higher yields. Hart et al.130 also observed
the sonochemical degradation of acetylene to be rapid
(90% consumption of C2H2 at time g 80 min) with
formation of large products. In addition to small gas
molecules such as CO and CH4, various hydrocarbons
with intermediate C atom numbers, such as benzene
and other C6H6 isomers, high C atom numbers such as
naphthalene are formed.
Kotronarous et al.131 found the ultrasonic irradiation
of H2S or S(-II), [[S(-II) ) [H2S] + [HS-] + [S2-]]
solutions to result in rapid oxidation and the formation
of sulfate (SO42-), sulfite (SO32-), and thiosulfate (S2O32-)
as products at pH g 10 with the initial mole ratio of
2.2:2.7:1, respectively. They also found oxidation of S(-
II) at pH 10 to be zero order with respect to [S(-II)]
with the zero-order rate constant, kO, dependent on
initial concentration of S(-II) and increasing linearly
with [S(-II)]O up to [S(-II)]O = 450µM (where kO = 12
µM min-1) and remaining constant thereafter. However,
at low pH e 8.5 (e.g., pH 7.4), the rate of ultrasonic
oxidation of S(-II) was first order with respect to [S(-
II)], the rate of oxidation increased with a decrease in
pH, and measured concentrations of SO42-, SO32-, and
S2O32- could not account for the total observed decrease
in S(-II), especially at the short sonication times. The
discrepancy between the [Sox] measured and the [Sox]
expected was attributed to the formation of sulfur (S8)
that was not analytically measured but increased the
turbidity of the solution. The apparent zero-order
dependence on [S(-II)] suggested that the rate-deter-
mining step (or the main pathway) in the overall
reaction was the reaction of HS- and the oxidation
intermediates with •OH radical in the liquid phase as
it diffused out of the cavitation bubble (HS- + •OH f
HSOH-) and the observed decrease in the zero-order
rate constant at the pH > 10 was attributed partly to
the dissociation of •OH in the alkaline solutions and
since the oxide radical ion (•O-) reacts more slowly with
the same substrate than •OH according to the reaction:
•OH +OH- S O•- + H O, where the forward rate, k )
2 f
1.2 × 1010m-1s-1 and the backward rate, kb ) 9.3 ×
107s-1. At pH e 8.5, thermal decomposition of H2S
within or near collapsing cavitation bubbles was con-
sidered the important reaction pathway. Kotronarou
and Hoffmann132 also developed a comprehensive aque-
ous-phase mechanism for the free-radical chemistry of
the S(-II) + ‚OH + O2 system and used the mechanism
to successfully model the oxidation of S(-II) at 20 kHz
and 75 W/cm2 and at pH g 10, assuming a continuous
and uniform ‚OH (3.5 µM/min) input into the solution
from the imploding cavitation bubbles.
When water was irradiated with ultrasound under an
atmosphere containing O2 and O3, an extremely rapid
decomposition of O3 was found to take place, leading to
a yield of H2O2 up to a factor of 6 higher than in water
containing oxygen only.133 Weaver and Hoffmann3 in-
vestigated the sonolytic degradation of O3 aqueous
solutions at pH 2 using both closed and open continuous
flow systems and the mass transfer mechanisms occur-
ring in sonolytic ozonation and their effects on chemical
reactivity. They found the sonochemical degradation of
O3 to follow apparent first-order kinetics with typical
rate constants of 0.84 ( 0.07 and 0.66 ( 0.08 min-1,
4706 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
respectively, at 20 and 500 kHz and an initial O3
concentration of 245 ( 3 µM. It was also shown that
both the sonochemical degradation of O3 and the
increase in O2/O3 gas flow rate enhanced mass transfer
at 20 kHz. This effect was attributed partially to
turbulence induced by acoustic streaming.
4.7. Organic Sulfur Compounds. Spurlock and
Reifsneider96,134 investigated the ultrasonic irradiation
of diakyl sulfides at 20 °C using 280-, 610-, and 800-
kHz transducers and 5-11 W/cm2 intensities under
oxygen and argon atmospheres and in suspensions in
pure water and in saturated aqueous solutions of CCl4.
The principal products of the irradiation of 0.06 M
aqueous suspension of di-n-butyl sulfide (R2S) at 800
kHz and 9.4w/cm2 were di-n-butyl sulfoxide (R2SO) and
n-butyl sulfonic acid (RSO3H) in the yield ratios of 85/
15 and 80/10 in O2 and Ar, respectively. Minor products
observed included di-n-butyl sulfone (R2SO2), butyric
acid, carbon monoxide, ethylene, acetylene, and meth-
ane.
Entezari et al.135 sonicated 50 mL of pure carbon
disulfide (CS2) at 20, 50, and 900 kHz frequencies under
the atmosphere of different gases (Ar, H2, Air, He, O2,
CO2) in a temperature range of -50 to +10 °C. They
observed that ultrasonic sonication at 900 and 50 kHz
(up to 4 h) led to no visible or chemical changes due to
the sonication while irradiation of CS2 at 20 kHz
frequency resulted in the formation of heterogeneous
mixture of amorphous carbon and monoclinic sulfur. The
dissociation of CS2 was proposed to be due to the
extreme conditions resulting from the collapse of the
cavity bubbles, the low thermal conductivity of CS2
ensuring the high-temperature persisted long enough
to result in the breakage of the C-S bond to form
elemental carbon and sulfur. The dissociation rate was
also found to be rapid and efficient at lower tempera-
tures and higher intensities but at the same power
(49W) and under helium and hydrogen gas than under
air, argon, or oxygen. The fact that the sonochemical
activity was higher in He than in Ar (with lower heat
conductivity) was attributed to other properties of gases,
especially solubility. Adewuyi and Collins136,137 studied
the kinetics of the sonochemical degradation of aqueous
carbon disulfide in a batch reactor at 20 kHz and the
effects of process parameters (e.g., concentration, tem-
perature, ultrasonic intensity) on the degradation pro-
cess. They found the reaction rate to be zero-order in
the temperature range 20-50 °C and first-order at lower
temperature. The zero-order rate constant for the
degradation at 20 °C, at 14 W, and in air was 2.27 ×
10-5 min-1. At the same initial concentrations and
temperature of 20 °C and in the presence of air, the
degradation rate of CS2 at 50 W (39.47 W/m2) was more
than 2 times that at 14 W (11.04 W/m2). The rate of
sonochemical degradation of CS2 in the presence of the
different gases was on the order of He > Air > N2O >
Ar; the rate with helium was found to be about 3 times
that of argon. They found the formation of sulfate as a
product to be enhanced at the lower pH and also at
lower temperatures when solutions from experiments
in the pH range 8-11 and temperatures 5-50 °C were
analyzed.
4.8. Oxygenates and Alcohols. Kang and Hoff-
mann138 studied the sonolysis, ozonolysis and the com-
bined sonolysis/ozonation of methyl tert-butyl ether
(MTBE) in the concentration range of 0.01-1.0 mM and
demonstrated that the addition of O3 to the influent O2
gas ([O3]0 ) 0.26-0.34 mM in solution) accelerated the
degradation of MTBE by a factor of 1.5-3.9, depending
on the initial concentration of MTBE. The sonochemical
first-order degradation rate constant for the loss of
MTBE was found to increase from 4.1 × 10-4 at
[MTBE]0 ) 1.0 mM (90% conversion in 93 min) to 8.5
× 10-4s-1 as the concentration of MTBE decreases to
0.01 mM (90% conversion in 45 min). The O3-ultrasound
system was shown to effectively degrade the MTBE into
innocuous and biodegradable products with tert-butyl
formate (TBF), tert-butyl alcohol (TBA), methyl acetate
(MA), and acetone identified as primary intermediates
and byproducts of the degradation reaction. Acetone,
which was formed from the oxidation of TBF (degrada-
tion rate constant, kTBF ) 1.87 × 10-3s-1) and TBA, was
found as the intermediate product with the highest yield
(12%). Using measured values of MTBE and TBF rate
constants, a reaction mechanism involving tree parallel
pathways: (1) direct pyrolytic decomposition of MTBE,
(2) direct reaction of MTBE with O3, and (3) reaction of
MTBE with •OH radical were proposed and used to
obtain the following kinetic rate expression:
[MTBE]
-d ) (kpyr + kI + kII + kIII)[MTBE] )
dt
ko[MTBE] (17)
where kpyr, kI, kII, and kIII are the pseudo-first-order rate
constant for the direct pyrolysis, thermal degradation
leading to O-CH3 bond breakage, direct reaction with
ozone, and other direct routes to products formation,
respectively.
Koike139 studied the sonolysis of alcohol-water mix-
tures using CH3OH, C2H5OH, n-C3H7OH, and i-C3H7-
OH and found each mixture to form gaseous products,
including CH4, C2H6, C2H4, C2H2, and C3H6. Koike139
found the product yields to increase to a maximum at
alcohol composition of about 20 vol % in the water
solution and to decrease thereafter for each of the
alcohol-water mixture. Buttner et al.140 studied the
sonolysis of water-methanol mixtures under argon and
oxygen and obtained similar results. With increasing
methanol concentration the product yields first in-
creased as methanol is a reactant and decreased with
increasing concentration leading to a maximum in the
yields versus composition curves. In solutions containing
more than 80% methanol, they observed almost no
chemical reactions. They detected typical pyrolysis and
combustion products of methanol (H2, CH2O, CO, CH4,
and traces of C2H4 and C2H2 under argon, and CO2, CO,
HCOOH, CH2O, H2O2 and traces of H2 under oxygen).
Gutierrez and Henglein141 compared the sonolysis of
aqueous solutions of ethanol (as volatile and soluble
solute), poly(vinylpyrrolidine) PVP (as nonvolatile sol-
ute), and tetranitromethane TNM (as volatile and
almost insoluble solute) under Ar irradiation (at 300
kHz and 2W/cm2). They explained the formation of
products in all three cases (such as CH4, C2H4, C2H6,
CO, and CO2 from ethanol and PVP; and NO2-, NO3-,
N2, CO, CO2 from TNM) in terms of pyrolysis in or close
to the cavitation bubbles.
4.9. Other Organic Compounds. Suzuki et al.142
examined the effect of ultrasound (200 kHz, 200W) at
298 K on the degradation rate of the surfactant, poly-
oxyethylene-alkyl ether (C14H29O(CH2CH2)7H), under
three different conditions: ultrasonic irradiation only
(sonoprocess), photocatalytic reaction using TiO2 (0.25

g/mL of P25) and low-pressure mercury (20W, 253.7 nm)
lamp (photoprocess), and the combination of the two
processes (photosonoprocess). They observed the decom-
position rate in the photosonoprocess was faster than
the photoprocess or sonoprocess alone. A significant
acceleration in the degradation of TOC was also ob-
served when stirring speed was increased from 100 to
500 rpm. The significantly enhanced rate in the pho-
tosonoprocess compared to the sonoprocess alone was
attributed to the redispersion of the agglomerated
catalyst particles under ultrasonic irradiation. They also
successfully separated solid catalyst particles agglomer-
ated by ultrasonic irradiation at 28 kHz in the presence
of glass beads.
Hart and Henglein143 evaluated the sonolysis of
mixtures of formic acid and water at concentrations of
0-30 M. The main reaction products under an argon
atmosphere were H2, CO2, CO, and very small amounts
of oxalic acid. Hart and Henglein144 also studied the
irradiation of aqueous solutions of potassium iodide and
sodium formate under the atmosphere of argon, oxygen
and argon-oxygen mixtures of varying composition. The
sono products of formate solutions were H2O2 and CO2
in the presence of O2 and H2, CO2, and oxalate in the
absence of O2. Gutierrez et al.145 found the products of
sonolysis of acetate to include succinic acid (as a product
of attack of OH radicals on acetate), glyoxylic and
glycolic acids, smaller amounts of HCHO, CO, and CO2,
and CH4 as a minor product.
Thymine (Thy) was found to degrade sonochemically
in aqueous solutions at 450 kHz into six products: cis-
and trans-5, 6-dihydroxy-dihydrothymine (cis- and trans-
thymine glycols), 5-hydroxymethyluraacid, urea, and
possibly N-formyl-N′-pyruvelurea plus an unidentified
product.41 Mead et al.146 also found the degradation to
vary linearly with sonication time with a zero-order rate
constant of 1.8 ( 0.3 × 10-5 M.min-1. Sehgal and
Wang41 found that at an aeration rate of 50 mL/min and
at 34 °C, the concentration of thymine is reduced to half
its value in 30 min, implying that an average of 3 ×
10-8mol or 1.8 × 1016 molecules of Thy reacted per
second per liter. The studies also indicated there was a
change in kinetics of reaction of Thy from first to zero
order as temperature of solution changed from 0 to 50
°C, and they suggested that the sono reaction took place
in the bubble-liquid interphase.
4.10. Other Environmental Applications. Ingale
et al.147 investigated the degradation of a refractory
component in the industrial waste of a cyclohexene
oxidation unit using a hybrid system, namely, sonication
followed by catalytic wet oxidation (SONIWO). It was
shown that sonication in the presence of CuSO4 as
catalyst resulted in an accelerated degradation of the
unknown compound which was refractory to wet oxida-
tion at 225 °C compared with sonication without a
catalyst.
Kruger148 investigated the sonolysis of natural ground-
water containing 1,2-didhloroethane (1,2-DCA) as the
main organic contaminants (350 µg/L), and trichlo-
romethane, cis-1,2-dichloroethane, trichloroethane and
tetrachloroeathane, trichloroethene, tetrachloroethene
in trace amounts (total of ∼85 µg/L), and Fe (3-17 mg/
L) and Mn (0.4-0.9 mg/L) as the main inorganic
products. They observed almost complete destruction of
1,2-DCA in all cases after 60 min and pseudo-first-order
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4707
rate constants of 0.062, 0.063, and 0.044 min-1, for the
sonication at 361, 620, and 1086 kHz respectively at
105W.
Olson and Barbier149 studied the effectiveness of the
“sonozone” process (i.e., combined ultrasound ozonolysis)
in degrading refractory electrolytes such as humic
materials using purified fulvic acid, FA (as a substrate)
and naturally colored groundwater sample with pH 8.6.
The combined system was found to significantly en-
hance TOC removal and mineralization rates. Sierka
and Amy150 also studied the singular and combined
effects of ultraviolet (UV) light and ultrasound (US) on
the ozone (O3) oxidation of humic substances, the most
important of the trihalomethane (THM) precursors.
They found that the combination of O3-US-UV proved
to be the most effective reaction condition, followed by
O3-UV, O3 alone, and O3-US, providing 93%, 86%,
75%, and 71% reduction in trihalomethane formation
potential (THMFP) levels, respectively, in the reaction
time of 20 min.
Gonze et al.151 investigated the use of the ultrasonic
process as a preoxidation step before a classical biologi-
cal treatment used for further mineralization. They
simultaneously monitored the toxicity for sodium pen-
tachlorophenate solution (NaPCP) on marine bacteria
(Vibrio fischeri) and on daphnids (Daphniamagna), and
the biodegradability of the pollutant solution during
ultrasonic irradiation at 500 kHz. The pollution degra-
dation was found to follow an apparent first-order
kinetic:
( )
Pth
[NaPCP] ) [NaPCP]o exp -kth t (18)
V
i.e., the disappearance rate is proportional to the power
density applied, and the kinetic pseudo first-order rate
constant, kth (m3 J-1) is representative of ultrasonic
efficiency. In general, they demonstrated that ultrasonic
irradiation decreased the toxicity of NaPCP and could
be considered a preoxidation step without which the
NaPCP could not be degraded by activated sludge for
up to 28 days.
Dahi152 studied the ozonation process with and with-
out simultaneous sonication at 20 kHz in regard to the
disinfections of microorganism (Escherichia coli) and
oxidation of organic (e.g., Rhodamine B). The ultrasonic
treatment was found to intensify the action of ozone in
the oxidation of chemicals and in the inactivation of
microorganisms. The enhanced performance of the
simultaneous sonozonation process was attributed to (1)
sonochemical degradation of O3, causing augmentation
of activities of free radicals in water, and (2) increase
in the aeration parameter (kLa value) and intensified
mass transfer resulting from sonication. Phull et al.153
reported the biocidal effects of ultrasound alone (at 20-
25 kHz and 800 kHz) or in conjunction with chlorine
on microorganisms. Ultrasound was found to signifi-
cantly amplify the biocidal effects of normal chlorination
and to reduce the amount of chlorine required for
disinfections.
5. Discussion
As reviewed above, the results of most studies seem
to demonstrate that while ultrasound is effective in
degrading pollutants, total mineralization is difficult to
obtain with ultrasound alone, in particular, with recal-
4708 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
citrant pollutants or mixtures of pollutants. Moreover,
where the final products are determined to be carbon
dioxide, short-chain organic acids, and/or inorganic ions,
the time scale and the dissipated power necessary to
obtain the complete minerilization of the hazardous
pollutants are currently not economically or practically
acceptable. Combinations of ultrasound with other
advanced oxidation processes (AOPs) or conventional
biological processes are found to be effective in degrad-
ing some recalcitrant compounds; however, the econom-
ics are poorly understood. This section discusses some
of the problems related to sonochemical reaction kinet-
ics, byproducts, and ecological effects and to technical-
scale application and implementation of the ultrasound
for water treatment and the need to address them.
5.1. Reaction Pathways and Kinetics. In general,
three distinct pathways have been determined in the
sonochemical degradation of chemical compounds. These
include oxidation by hydroxyl radicals, pyrolytic decom-
position, and supercritical water oxidation.58 The ultra-
sonic degradation of organic compounds in dilute aque-
ous solutions depends to a large extent on the nature
of the organic material. The specific nature of the
saturating gas also influences the relative proportion
of the pyrolytic or free radical steps. Hydrophobic and
volatile organic compounds tend to partition into the
collapsing cavitation bubbles and degrade mainly by
direct thermal decomposition leading to the formation
of combustion byproducts. The sonochemical oxidation
of polar organics (e.g., phenol) is slow compared to that
of nonpolar, volatile organics such as CCl4.56,58 Hydro-
philic and less volatile or nonvolatile compounds de-
grade to form oxidation or reduction byproducts by
reacting with hydroxyl radicals or hydrogen atoms
diffusing out of the cavitation bubbles. Thermal de-
struction processes are not considered important for
nonvolatile substrates because they do not partition
appreciably into the bubbles. The efficiency with which
a solute reacts with hydroxyl radicals generated in
ultrasonic reaction mixtures is related to its hydropho-
bicity; the greater the hydrophobicity is, the more
efficient the solute can act a radical scavenger.154 The
time scales of treatment in simple batch reactors
reported in the literature are generally in the range of
minutes to hours for complete degradation. Most inves-
tigators have observed the kinetics of sono degradation
of pollutants to be first- or zero-order. For pollutants
with first-order degradation rates, the first-order rate
constants tend to decrease as the initial substrate
concentrations increase.112,131 In contrast, for pollutants
displaying zero-order substrate disappearance, the rate
constants increase as the initial substrate concentration
increases. A change in reaction order from zero-order
(at high initial substrate concentration) to first-order
(at lower initial substrate concentration) has also been
observed.66 The change in rate constants with initial
substrate concentration is ascribed to radical scaveng-
ing/recombination, i.e., a combination of a first order
thermal destruction processes and a zero order reaction
with hydroxyl radicals.112,131 Sehgal and Wang41 ob-
served change in reaction order from first to zero as
temperature increased. Cost et al.78 indicated that zero-
order kinetics are typical of hydroxyl radical reactions
since the free radicals are generated at constant rate
under ultrasonic irradiation and suggested the slow
degradation of humic acid occurred mainly by radical
attack.
Generally, improvements in technology are needed to
oxidize organics especially polar compounds more ef-
ficiently. If degradation rates can be enhanced, reaction
times will be reduced for equivalent final contaminant
concentrations, translating to reduction in reactor sizes.
Consequently, the cost of application of this technology
to industrial or field-scale projects would be significantly
reduced. The manipulation of macroscopic parameters
has been shown to lead to enhancement of cavitation
chemistry as the number of cavitation bubbles and
chemical events at each bubble are varied. Hoffmann
and co-workers77 optimized the degradation rates of
aqueous-phase organic compounds with acoustical pro-
cessors by adjusting the energy density, energy inten-
sity, and the nature and properties of the saturating
gas in solution. They observed that the first-order
degradation rates increase as the energy density and
intensity increased to a saturation value. Continuous
gassing conditions also induce a greater number of
cavitation events in homogeneous systems and assist
cavitation in heterogeneous systems.28 Susuki et al.155
investigated the influence of aeration, bubble distribu-
tion, and frequency on the degradation rate of surfactant
SS-70 (initial concentration, 50 ppm; critical micelle
concentration, 52.2 ppm) at 298°K using cylindrical-type
(26 kHz) and disk-type (100 kHz, 300 kHz) ultrasonic
transducers and showed that the degradation rates were
enhanced by aeration (i.e., aeration bubbles generated)
and the shape of the reactors used. It is also well-known
that ultrasonic degradation of phenolic compounds
involve •OH radical attack, and hence, the use of high-
frequency ultrasound (e.g., 500 kHz) has proven to be
more advantageous compared with low-frequency ul-
trasound. Higher ultrasonic frequencies are more favor-
able for the generation of hydroxyl radicals possibly due
to faster production rates.46,48-50 Weaver et al.156 ex-
amined the first-order sono degradation kinetics of three
similar aromatic compounds, nitrobenzene (NB), 4-ni-
tophenol (4-NP), and 4-chlorophenol (4-CP), by ultra-
sound at frequencies of 20 and 500 kHz. They found that
in the 20 kHz reactor, NB degraded the fastest and 4-NP
the slowest, but in the 500 kHz reactor, 4-CP was the
fastest while 4-NP was the most resistant to sonolytic
destruction. They attributed the results to the greater
degree of vapor-phase pyrolysis at the lower frequency
due to high temperatures achieved during bubble col-
lapse, while higher frequency favored ‚OH production.
Using 20 kHz ultrasound, large salt-induced enhance-
ments in oxidation/destruction rates have been ob-
served: 6-fold for chlorobenzene, 7-fold for p-ethylphe-
nol, and 3-fold for phenol oxidation, in sodium chloride
solutions (0, 0.17, 0.67, and 1.38 mol/L).59 The enhance-
ment was ascribed to the fact that the presence of the
salt increased the residence of the aromatice compounds
in or at the surface of the cavitation bubbles. The rate
of the sonochemical degradation of 3-chlorophenol was
enhanced 2.4 times by the addition of appropriate
amount of Fe(II) concentrations (e.g., 1 mM). The
enhancement was attributed to the probable regenera-
tion of OH radicals from H2O2, which would otherwise
formed from recombination of OH radicals and contrib-
uted to lesser degradation.74 More such inexpensive
approaches for improving process efficiency should be
investigated in the future to make sonochemical oxida-
tion an economically viable remediation technology.
5.2. Effects of Water Quality. This section discusses
how measures of water quality (i.e., matrix components)

such as alkalinity, particulate matter (dissolved organic
and inorganic), and mixtures of compounds affect the
rates of sono-reactions. Sonchemical oxidation reactions
like other AOPs should generally be inhibited by high
alkalinity usually resulting from the presence of large
concentrations of radical scavengers such as bicarbon-
ates and carbonates. This significantly reduces process
efficiency. However, Cost et al.78 observed that added
alkalinity did not affect the rates of destruction of
p-nitrophenol (p-Np) or p-nitrocatechol by ultrasound.
According to models on bubble nucleation in liquids,
suspended particles are expected to affect cavitation,
and hence, the rates of ultrasonic degradation of pol-
lutants because of the formation and stabilization of gas
bubbles in the crevices of the particles. Large particles
might be expected to decrease the rate because of sound
attenuation. Fine particles containing gas- and vapor-
filled crevices might enhance the rate by providing
additional nuclei for bubble formation.157 However,
Kotronarou112 investigated the effect of large sand
particles (500 µm average) and fine particles (7 nm
average) on the sonication of sulfide oxidation and
observed no significant effect for the sizes and concen-
trations studied. Cost et al.78 also noted that particulate
matter (sea sand or Fe2O3 particle) did not significantly
affect the degradation rate of p-Np. Orzechowska et
al.108 observed that the presence of humic substances
did not affect Cl- yields in the sonication of aqueous
chlorinated hydrocarbons. However, Taylor et al.158
found the presence of fulvic acid (FA) to significantly
inhibit the sonochemical degradation of PAHs (in the
concentration range of 0.1-0.5 µM) at 20 kHz (600W)
and at 20 °C. In the presence of approximately 50 µM
FA, the first-order rate constants (k, s-1) of anthracene,
phenanthrene, and pyrene decreased by factors of 3.7
(0.015 vs 0.0041), 3.3 (0.006 vs 0.0018), and 2.3 (0.006
vs 0.0026), respectively.
Multicomponent waste streams are more realistic
matrices to consider for practical treatment situations.
Hua and Hoffmann99 found that sonication of a mixture
of CCl4 and p-NP resulted in the enhancement of p-NP
degradation, demonstrating that ultrasound is not
limited to single-solute solutions. They also found that
the effect of CCl4 in a mixed waste stream was particu-
larly interesting in that it released a residual oxidant,
which could continue to attack other refractory mol-
ecules in solution after the ultrasonic irradiation was
halted. Drijvers et al.106 also showed that volatile
organic compounds could strongly affect each other’s
sonolysis rates. However, as indicated earlier, the
presence of hydrophobic compound CB hindered the
degradation of hydrophilic compound, 4-CPOH.72 Zhang
and Hua159 found moderate decreases in degradation
efficiency when a mixture containing 10µM chloropicrin
(CCl3NO2 or CP), 10µM trichloroacetonitrile (C2Cl3N or
TCA), and 0.5 mM bromobenzene (BB) was sonicated
at both 20 kHz (30.8 Wcm-2) and 358 kHz in a complex
aqueous matrix (i.e., river water) compared to reagent
grade water. Differences in rate constants observed
during sonication of the mixture and individual com-
pounds were also minimal. The first-order rate con-
stants at 20 kHz for TCA, CP, and BB were, respec-
tively, 4.7 × 10-2 ( 6.5 × 10-4, 5.3 × 10-2 ( 4.4 × 10-4,
and 4.4 × 10-2 ( 7.5 × 10-4 min-1 when sonicated
individually. The rates were 4.4 × 10-2 ( 7.2 × 10-4,
5.0 × 10-2 ( 8.8 × 10-4, and 4.1 × 10-2 ( 9.1 × 10-4
min-1 in a mixture. Since both industrial waste streams
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4709
and contaminated waters (surface and groundwater)
generally contain a wide array of both pollutant and
nonpollutant chemicals, more studies on the effects of
water quality on sonochemical oxidation rates are
needed to advance our understanding.
5.3. Sonication Byproducts and Toxicity Effects.
If ultrasound is to be used in the destruction of hazard-
ous wastes on an industrial scale, the associated reac-
tions must be ecologically acceptable. Hence, the toxicity
of the reaction products obtained from sonochemical
treatments is a factor that should be considered prior
to subsequent utilization of treated water. In most
studies so far, the toxicity of the reaction products
produced by treatment remains to be determined.
Special attention must be paid to the types of products
formed and their toxicity and resistance to further
ultrasonic cleavage or other secondary treatments. Total
organic carbon (TOC) analysis is one method that has
been used extensively to determine quantitatively
whether the sono degradation of the organic compound
results in complete minerilization to the relatively
harmless CO2 (g) or some product that presents toxic
features. However, TOC analyses do not give the entire
picture with respect to toxicity because a given hazard-
ous substance may also degrade to carbon deposits135
or be converted into other benign substrates that are
acceptable end-products. A quick minerilization of an
organic contaminant should be the goal to minimize the
survival time of toxic intermediates. The use of ultra-
sound in combination with other advanced oxidation
processes or conventional biological processes has been
found to be effective in reducing toxicity. For example,
Gonze et al.151 demonstrated that ultrasonic irradiation
when used as a pretreatment step decreased the toxicity
of sodium pentachlorophenol (NaPCP) solution im-
mensely allowing degradation by biological activated
sludge process. Other possible ways include the coupling
of H2O2, O3, or UV photocatalysis and solution chemistry
modification to enhance the efficiency of free radical
generation through cavitation. Hoffmann and col-
leagues138 demonstrated that the combination of ultra-
sound with ozonation or other AOPs effectively degraded
recalcitrant pollutants such as MTBE into innocuous
and biodegradable products. Trabelsi et al.67 showed
that the combination of electrochemistry and high-
frequency sonication allowed a total degradation of
phenol within 20 min with no production of toxic
aromatic intermediates. It appears that using a combi-
native AOP approach is certainly a positive step toward
achieving quick minerilization and more such studies
should be considered in future efforts to address and
mitigate the byproduct toxicity problems.
5.4. Efficiency and Scaleup Issues. The ultrasonic
system transforms electrical power into vibrational or
ultrasonic energy, i.e., mechanical energy.31-32 160-161
This mechanical energy is then transmitted into the
sonicated reaction medium. The efficiency of the energy
transformation depends not only on the equipment itself
but also on the ultrasonication conditions. Therefore,
the amount of acoustic energy delivered into the liquid
medium cannot be measured solely by measuring the
amount of electrical energy expended to produce the
mechanical vibration. Sonolysis is relatively inefficient
with respect to total input energy. This is because part
of the total energy input is lost to produce heat and
another part produces cavitation. But not all of the
cavitational energy produces chemical and physical
4710 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
Figure 2. Energy conversion in sonochemical processes.
effects. Some energy is consumed in sound re-emission
(i.e., harmonics and sub-harmonics).32,57 The low ef-
ficiency of the conversion sequence electrical energy f
acoustic energy f chemical effects may preclude the use
of this method as a primary treatment. As illustrated
by Kotronarou et al.,131 the limitation of sonolysis for
the control of H2S and other trace contaminants in
water is that it is relatively inefficient with respect to
the energy input. Their calculations indicated only a
small portion of the total energy supplied to the system
resulted in “useful” free-radical reactions. The energy
transformation losses within the system are shown in
Figure 2. At each stage in the transmission of power,
there is an inefficiency whereby sonochemical benefit
is lost to heat or sound. Hence, it can be appreciated
that the determination of an energy balance is not easy.
The sonochemical yield (SY ) measured effect/input
power (W)) is measured in moles of products generated
per second. Despite the difficulty in ascertaining ac-
curate energy balance, “SY” is defined in general this
way similar to the definition of “photochemical
yield”.31,32,162 Hence, the acoustical power transferred
to the reaction mixture is less than the overall power
input into the power generators (i.e., the power drawn
from the wall supply). The challenge is to harness these
energy losses to useful purposes, e.g., pollution treat-
ment. In addition to knowledge of the characteristics of
the reaction mixtures and kinetics of reaction, effective
scaleup procedure is necessary and requires that all
parameters affecting cavitation efficiency be studied
well, properly quantified and optimized.
The majority of the reported studies to date employed
laboratory-scale piezoelectric probe (0.25-0.5 in.) batch
reactors with small volumes (20-200 mL) for ultrasonic
degradation of pollutants45,160 The probe type reactor
is widely used due to its ability to deliver high power
output and the ease of operation to give optimum
performance at different amplitudes. However, Kotron-
arou and Hoffmann111,132 found that the same energy
input dispersed over a broader area resulted in a
significant enhancement in reaction rate and energy
utilization efficiency. It was also shown that sonolysis
reactors with larger radiating surfaces are more energy
efficient the direct immersion probe reactor, which has
a small (1 cm2) radiating surface. In addition to the low-
energy utilization efficiency, the probe type reactor
system is also not an optimal reactor configuration for
the efficient generation of transient cavitation for two
other reasons. First, sonication efficiency is reduced due
to blanketing effect caused by intense generation of
cavitation bubbles at the tip. Second, the probe type
transducer tips have relatively short life before the
titanium tip requires replacement. For these reasons,
the application of direct probe sonolysis to special
applications such as groundwater remediation or pre-
treatment of industrial hazardous wastes is not eco-
nomically feasible. In their studies of H2S ultrasonic
oxidation, Hoffmann and co-workers131,132 found a direct
linear relationship between the applied power at a fixed
frequency and the observed rate of loss of S(-II),
indicating a continuous-flow stirred-tank probe reactor
could attain significant conversion efficiencies. Their
initial tests indicated that the use of large high-powered
sonicators in the CSTR mode could result in viable
degradation efficiencies. Hua et al.77 found that a near-
field acoustical processor or NAP (where liquid flows
between two high intensity vibrating plates) was more
efficient than a probe reactor for the degradation of
p-nitrophenol. They observed that NAP provided about
1.5 times the power per unit volume of the probe reactor
but resulted in 19 times more p-nitrophenol destruction
per kilojoule energy imparted on the system. It was also
shown that the G value for the probe reactor is ap-
proximately 1 order of magnitude less than that in the
NAP, although the degradation rate constants were the
same magnitude. The G value is an efficiency measure
used in radiation chemistry and for each species in
neutral water is defined as the number of molecules
undergoing reaction for each 100 eV electrical energy
transferred.25 The NAP parallel-plate reactor allows for
a lower sound intensity but a higher acoustical power
per unit volume than those of the conventional probe-
type reactor. However, limited work has been reported
on the NAP and tank reactors, and comparison of their
performance data with the probe reactor are scarce.
Gondrexon et al.116 observed a conversion rate for
pentachlorophenol (PCP) up to 80% using a three-stage
laboratory-scale sonochemical reactor (each equipped
with 500 kHz piezoelectric disk) and operating in the
continuous flow mode. Operation in continuous-flow
mode also has the advantage of short residence time,
especially for pollutants that are degraded quickly.

However, as they indicated, the scaleup of such an
experimental system would not be easy, and a lot of
technical problems remain to be overcome. But increas-
ing commercial interest in sonochemical processes
should reduce cost in the very near future. Problems
related to technical-scale application and implementa-
tion of sonochemical steps into conventional water
treatments must be considered in future investiga-
tions.31,32,160
6. Concluding Remarks
Ultrasonic irradiation shows promise and has the
potential for use in environmental remediation due the
production of high concentrations of oxidizing species
such as •OH and H2O2 in solution and localized transient
high temperatures and pressures. In terms of conven-
ience and simplicity of operation, sonolysis could prove
to be economically competitive and far superior to many
alternative approaches. These include high-temperature
catalytic combustion or incineration, activated carbon
or zeolite adsorption, supercritical fluid extraction or
oxidation, substrate-specific biodegradation, membrane
separation, electron-beam irradiation, UV-photolytic,
and other chemical degradation methods.26,163-164 Some
of these techniques are cost-intensive and require
transference of the target molecule from an aqueous
phase. Biodegradation provides a promising method for
environmental remediation. However, currently avail-
able processes are slow and produce unpredictable
results. Aerobic biological oxidation is also limited when
the feed is either recalcitrant to bidegradation, or
inhibitory or toxic to the bioculture.164 The sonochemical
approach also has the advantage of being adaptable to
mixed solid-liquid wastes. Ultrasonic degradation is
several times (about 10 000-fold) faster than natural
aerobic oxidation, for example.115 Also, sonochemical
degradation occurs over wide range concentrations
(varying by order of magnitude), unlike certain biologi-
cal systems that are inhibited by relatively low sub-
strate concentrations. In a recent economic analysis of
a dilute p-nitrophenol aqueous waste treatment, the cost
of sonochemical oxidation was found to be comparable
to that of incineration.77 The relative efficiency of
ultrasound in terms of p-nitrophenol degraded per liter
of water was also shown to be far superior to conven-
tional UV-photolytic degradation.58 Calculated G value
efficiencies from the literature also indicate sonochemi-
cal systems are competitive with other AOPs such as
UV photocatalysis and supercritical water oxida-
tion.87,163,165 Sonolysis does not require the addition of
chemical additives to achieve viable degradation rates.
However, some chemicals may be utilized as an effective
sonolytic catalyst for reactions involving ‚OH radical for
example.
As obvious from the degradation products in Table 3,
complete mineralization of recalcitrant pollutant is
difficult to obtain at reasonable rates with ultrasound
alone. Because the efficiency of electrical-to-sound-to-
thermal conversion is poor, even faster decomposition
is needed to carry out the oxidation at the commercial
level. Moreover, other barriers remain to the large-scale
implementation of this technology for pollution degra-
dation. The economics are poorly understood. The
scaleup of sonochemical reactors remains problematic
because few studies have been done to determine which
measures of reactor efficiency correlates best with
pollutant destruction rates. Several studies have noted
Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001 4711
the change in biodegradability of a waste subjected to
prior chemical oxidation.164 Integration of destructive
processes for recalcitrant or inhibiting contaminant
conversion is advantageous conceptually. However,
substantial research efforts are needed to develop
efficient processes through coupling of biological ap-
proaches with chemical and physical treatments. The
design key for such a coupled system lies in choosing
processes that complement each other and leads to a
synergistic effect. Sonochemical oxidation technologies
are most advantageously used in combination with other
advanced oxidation processes and/or biological treat-
ment.
Ultrasound has other environmental science and
engineering applications. Low permeability geomateri-
als such as clay or silt are difficult to remediate because
of low transport rates and high adsorption potential. It
has been shown that ultrasonic vibrations enhance
removal of volatile organic compounds (VOCs) and
liquid contaminants from low permeability geologic
formations that have been pneumatically or hydrauli-
cally fractured.166 Mukherjee et al.167 and Liu et al.168
also showed that sonication could be used as a pretreat-
ment step to improve the release of organic matter
associated with the particulate phase into the soluble
aqueous phase enhancing its bioavailability during the
anaerobic biodegradation of aquatic sediments. Also, in
the desorption of phenol from activated carbon and
polymeric resin, Rege et al.169 found sonication at 40
kHz and 1.44 MHz to significantly increase desorption
rates, and the rates were also favored by decreased
temperature, aerated medium, and increased ultrasonic
intensity. They also found desorption rates in the
absence of ultrasound was limited by pore diffusion,
whereas those under ultrasonic irradiations were lim-
ited by surface reaction. The improvement in desorption
rates were attributed to an enhancement in diffusional
transport due to the acoustic microstreaming caused
within the pores.
The amount of things that can be accomplished with
sonochemistry is, at this stage, only limited by the
minds of those working in this exciting field. It is a
whole new field of research that is growing very fast,
with exciting prospect for any researcher. The review
of the environmental aspects of sonochemistry high-
lighting remediation processes, reaction pathways, and
kinetic studies presented here indicates a large scope
for further experimental and theoretical investigations
on all aspects of this important medium of reaction.
More research and developmental studies, both experi-
mental and theoretical and encompassing kinetics,
reaction mechanisms, reactor design, and energy con-
servation, are needed to improve reliability and mini-
mize costs for scale-up and long-term use.170-172 De-
staillat et al.173 demonstrated the effectiveness of a novel
pilot-plant scale sonochemical reactor (UES 4000C
Pilotstation) recently developed for large-scale reme-
diation applications. A budget analysis of this system
(612 kHz, 3 kW) indicated that nearly one-third of the
applied power is converted into sonochemical activity.
It is hoped that this review has stimulated thinking
beyond the cases presented and should spur future
engineering-based research in the continued use of
sonochemical oxidation as an environmentally benign
process for the removal of inorganic and organic species
from industrial wastewater streams and remediation of
contaminants in subsurface environments.
4712 Ind. Eng. Chem. Res., Vol. 40, No. 22, 2001
Acknowledgment
The author thanks Air Force Office of Scientific
Research (Grant. No. F.49620-95-1-0541) and Depart-
ment of Energy (Grant No. DE-FC04-90AL66158) for
financial support.
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Received for review January 30, 2001
Revised manuscript received July 18, 2001
Accepted August 13, 2001
IE010096L