Research Journal of Chemistry and Environment _________________________________Vol.

16 (4) December (2012)

Res.J.Chem.Environ
Review Paper:

Sonochemical degradation of volatile and Non-volatile

compounds
Goel Mukesh 1, Das Ashutosh 1, Ravikumar K.1*and Nagarajan R. 2
1. Centre for Environmental Engineering, PRIST University, Thanjavur, Tamil Nadu, INDIA
2. Department of Applied Geology, School of Engineering and Science, Curtin University, CDT 250, 98009, Miri, Sarawak, MALAYSIA
* ravikumar.prist.cee@gmail.com

usually measured in cycles per second, or hertz (Hz).

Human hearing is said to lie between 20 Hz and 20 kHz.
The terms sonic, ultrasonic and infrasonic are defined
based on the frequency of sound waves. Ultrasonic waves
refer to the sound of frequencies greater than 20 kHz2. The
upper limit of ultrasonic frequency is not sharply defined
but is usually taken to be 5 MHz for gases and 500 MHz
for solids and liquids3.

Abstract
Destructive technologies for the wastewater treatment
have significant benefits. The advanced oxidation
processes (AOP) promises much in this regard. The
AOP generate free radicals which act as strong
oxidant to destroy the organic pollutants. AOP
includes several methods such as: H2O2/UV, O3/UV
and UV/TiO2. Among the above, ultrasonication is
one of the less studied methods despite its unique and
extreme conditions generated without using
complicated and unsafe process. Ultrasonication
promotes oxidative degradation of the target
compound by hydroxyl radicals and also provides a
possible route for thermal decomposition in the gas
phase. The combination of ultrasonication and other
AOP like photoxidation and ozonation substantially
increases the decomposition rate of organic pollutants
by increasing the amount of hydroxyl radicals
required to oxidize the pollutants. The objective of this
paper is to critically review the efficacy of sonolysis
and its combination with other AOP on the
destruction of undesirable compounds in aqueous
solutions.

Sound waves are longitudinal, i.e. the particles are

displaced parallel to the direction of the motion of the
wave. Therefore, when a sound wave passes through a
liquid or a gas, the molecules in the medium vibrate
longitudinally in the direction of wave propagation.
Pressure variations (rarefaction and compression cycles)
are associated with the movement of the molecules. For a
sinusoidal sound source, the acoustic pressure at any time t
is given by P(t) = Pasin2ft, where Pa = maximum pressure
amplitude, f = frequency of the sound wave. The acoustic
intensity (I) is the rate, at which energy in the wave crosses
a unit area perpendicular to the direction of wave
propagation. It can be expressed as:
I = Pa2/2 c

(1)

where = density of the medium, c = velocity of sound in

that medium (c = f , is the wavelength of the sound
wave; c 1500 m/s for water). For water ( 1 Kg/m3), we
get Pa 1.7 I0.5, Pa is in atm and I in W/cm The sound
attenuation takes place along the distance due to energy
losses.

Keywords: Advanced Oxidation Processes, Sonochemical

Degradation,
Volatile
compounds,
Non-volatile
compounds, Cavitation, Photo-oxidation, Ozonation.

Introduction
In recent years, advanced oxidation processes (AOP) have
emerged as promising new technologies for the degradation
of organic pollutants. AOP processes involve highly
oxidizing agents such as hydroxyl radicals in the
degradation of various organic pollutants. These processes
include photochemical degradation, radiolysis, electron
beam irradiation and sono-chemical degradation. These
technologies involve widely different methods of activation
as well as oxidant generation and can potentially utilize a
number of different mechanisms for organic destruction1.

We get Pa 1.7 I0.5, Pa is in atm and I in W/cm. The sound

attenuation takes place along the distance due to energy
losses. For one dimensional case, the intensity is related to
distance as2:
I = I0 e-2bx

(2)

where I0 is the intensity at the source and bis an overall

attenuation coefficient that includes frictional losses,
thermal conduction losses and losses due to bulk viscosity.
In addition, relaxation and hysteresis processes may be
involved. Attenuation is strongly frequency dependent and
for constant T, b is proportional to f. Therefore, higher
frequency ultrasound is associated with higher energy
losses. For 20 kHz sound waves, energy losses are
negligible for short distances.

Sonochemistry
Sonochemical degradation methods are relatively new and
involve degradation of aqueous solution containing the
organic pollutants by ultrasound. Sound is a waveform
consisting of density variations in an elastic medium,
propagating away from a source. The most immediate
property of sound is its frequency, or pitch, which is
(192)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ

Theory and Fundamentals

The chemical effect of ultrasound is produced through the
phenomenon of cavitation which is caused by the
expansion and contraction of cavitation nuclei due to the
compression and rarefaction cycles of ultrasonic waves.
Cavitation causes the formation, rapid growth and finally
implosive collapse of the bubbles, resulting in unusual
reaction environment in the vicinity of the bubbles4.
Compression of gas and vapour in the bubbles generates
intense heat and can generate local hot spots. Theoretically
it is shown that the temperature inside the cavity could
reach about 5,200 K in the collapsing bubbles and 1,900 K
in the interfacial region between the solution and the
collapsing bubbles5. Sonochemical effect takes place either
due to the pyrolytic degradation inside the bubbles, or by
the reduction and oxidation due to the generation of H. and
OH. radicals at the gas-liquid interface6.

Pmax

3
(dr / dt ) 2
2

pa

p M sin t

2
r

pS

( p0

2 r0 3
)( )
r r

1)

pa
]
p0

(5)

Ultrasound is mainly generated by immersing (i) the

reactor in a sonicating liquid (a reacting vessel in an
ultrasonic bath) or (ii) introducing the source directly in the
reactor (an ultrasonic probe in the reactor). A Cup horn
system uses the features of (i) and (ii). There is also a third
method of generating ultrasound by using a reactor
constructed with ultrasonically vibrating walls. Some of the
most commonly used sonicating systems are summarized
below8:

(3)

Ultrasonic cleaning bath: This is the most widely used

and the least expensive source of ultrasound in the
laboratory. It provides even distribution of energy in the
immersed reaction vessel. Also, it works well with
conventional apparatus like a conical flask and cylinder. It
can be operated under pressure without the need for
elaborate sealing of the ultrasonic source. However, there
are some limitations to the use of an ultrasonic bath. The
ultrasonic intensity supplied to the reaction mixture is very
low due to poor energy transfer. It does not allow proper
temperature control and reproducibility is not very good. In
order to maintain consistent ultrasonic intensity, liquid
level in the bath, solvent level in the reactor and the
position of flask should be fixed. Ultrasonic cleaning
industry employs large-scale ultrasonic bath reactors.

Under adiabatic compression, the maximum temperature is:

T0 [(

pa
]
p0

Reactors

where r0 is the initial radius and r is the radius of cavitation

bubbles at any time t in metre; 0 is the density of liquid in
Kg/m3; pa is the ambient pressure in a liquid in N/m2; pM is
the acoustic pressure amplitude in N/m2; is the surface
tension in N/m; p0 is the initial pressure of gas in the
bubble in N/m2; ps is the saturation pressure of the liquid in
N/m2 and is the polytropic constant = Cp/Cv

T max

1)

Stable cavitation: These bubbles mainly contain gas and

some vapour and are produced at lower intensities. The
time scale allows the mass diffusion of gas along with
condensation and evaporation. When the bubble contracts
the concentration of gas (moles per litre) in the interior of
the bubble increases and gas diffuses from the bubble.
Similarly, when the bubble expands, the concentration of
gas decreases and gas diffuses into the bubble. Because the
diffusion rate is proportional to the surface area, more gas
enters during expansion than leaves during the contraction
of the bubble. Therefore over a complete cycle, there is a
net increase in the amount of gas in the bubble. With the
growth of the bubble, the acoustic and surrounding
conditions will change and the bubble may either ascend to
the surface or collapse. The collapse under these conditions
is not very violent2.

Transient cavitation: These bubbles are voids or vapourfilled bubbles and are produced at high sound intensities.
They exist for a few acoustic cycles and collapsed violently
on compression, resulting into smaller bubbles. Finally, the
bubbles get dissolved into the bulk of the solution. The
transient bubbles are characterized by free evaporation and
condensation of liquid. It is assumed that there is no time
for diffusion of gas into or out of the bubbles. While
calculating the maximum temperature inside the collapsed
cavitation bubbles, assumption of collapse is adiabatic in
nature. Liquid is incompressible and the ultrasonic pressure
wave is exactly sinusoidal7. A simple equation of motion
obtained for the spherical pulsating bubble is:
d 2r
dt 2

p 0 [(

(4)

where T0 is the ambient temperature and maximum

pressure obtained as:

(193)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ

Figure 1: Possible site of chemical reactions

Ultrasonic probe: It produces very high energy compared

to ultrasonic bath and the probe can be directly immersed
in the solution for a better sonochemical effect. Due to its
energy efficiency, it is preferred over an ultrasonic bath. In
this system, the electrical energy is transmitted to the
piezoelectric transducer within the converter, where it is
changed to mechanical vibrations. The longitudinal
vibrations from the converter are intensified by the horn,
creating pressure waves in the liquid which cause
cavitation.

consensus that the mechanical and chemical effects of the

collapsing bubble can be felt in three distinct regions9.
The inside of the bubble is like a high energy microreactor.
The cavitation bubble contains vapor from the solvent (or
any volatile reagent present) which enters as the bubble is
being formed. The bubble implodes, resulting in enormous
increase in both temperature and pressure. When water is
used as a solvent, highly reactive species such as H. and
OH. radicals are produced. In this region, the organic
compounds decompose via a pyrolytic mechanism. The
interface between the bubble and the bulk liquid is a region
where surface active reagents may accumulate or where
species produced in the bubbles will first react with
chemicals in the bulk liquid. Organic compounds present
are decomposed by the combined effect of pyrolytic
degradation and hydroxylation. In the liquid immediately
surrounding the bubble oxidative degradation by hydroxyl
radicals takes place.

Ultrasonic probe system consists of a generator which

supplies power to the transducer housing. The transducer
housing is attached to the sonic horn, which magnifies the
acoustic energy available.
It has two parts; fixed horn element and detachable horn.
The fixed horn is a robust piece of titanium alloy, which is
accurately machined to provide an end face vibrating at
maximum amplitude to which other horns may be attached.
The detachable horn allows the vibration of the fixed horn
to be transmitted through a further length of metal which
can be used to magnify the power delivered to the system.

According to the hot spot theory, the maximum energy is

generated during the transient collapse of the bubbles. In a
particular sound field, bubbles of large radius undergo
stable cavitation, whereas smaller bubbles undergo a
transient collapse. However, if a bubble is very small, the
surface tension pressure inhibits the growth of the bubbles2.
Thus, there exists intermediate size of the bubbles suitable
for transient collapse under the influence of acoustic force.
The concept of cavitation threshold and resonant frequency
is important to understand the effect of frequency on the
overall degradation rate. When the liquid is subjected to
acoustic radiation, the small bubbles in the liquid grow by
rectified diffusion. There are two types of threshold,
namely threshold for rectified diffusion and threshold for
transient cavitation. The threshold from which the tiny
bubbles grow by rectified diffusion after oscillating around
some equilibrium radius is called threshold for rectified
diffusion. Transient cavitation threshold is the threshold at
which the cavity becomes a transient and then expands and
ultimately collapses to generate a large amount of localized
energy10.

Selecting a proper material for horn is the most important

parameter of horn design due to the erosion problem caused
by cavitation. Presently, titanium alloy is the best material
available. The probe system can be used in the continuous
flow mode. A number of probes can be inserted into the
circulating system. The zone of sonochemical influence can
be made uniform throughout the system. It offers the best
possible option for industrial scale sonochemistry.
However, it suffers from the problem of the erosion of
probe tip which can cause contamination in the reaction
mixture.
Another form of reactors is quite useful in making
emulsions i.e. the whistle reactor. Here, liquids are pumped
at a high rate through a narrow gap onto a thin metal blade.
As a result, blade is set into vibration with a sufficiently
high frequency to cause cavitation and hence very efficient
mixing. It is mainly used for making emulsions and for
inducing polymerization and phase transfer reactions.

Resonant frequency is the frequency at which maximum

scattering of the sound wave takes place resulting in the
important cavity effects. There is a resonant radius
corresponding to the resonant frequency. Under the
assumption of negligible heat flow, resonant frequency and

Mechanism of the reaction: Although, the exact nature of

the degradation of compound is not clear, there is overall

(194)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ
bubble radius are related as follows10:

2 rR f

3 Pa

C2HCl3 + Cl.

where f is resonant frequency and rR is the resonant radius.

For air bubbles in water less than one atmosphere equation
6 simply reduces to:
(7)
rR f 3 Hz. m
The bubbles with a radius smaller than the resonant radius
will be expanded by ultrasound and collapsed after
reaching the transient cavitation threshold. Bubbles of the
same size as the resonant radius will pulsate dynamically,
but will not collapse11. Thus, the frequency of the sound
waves becomes a critical parameter in deciding the
transient cavitation threshold. However, the choice of
suitable frequency for effective degradation is also
dependent on the physicochemical properties of the
pollutant present in the water.

Volatile compounds like chlorobenzene14 and CCl415 were

also studied in detail to show that the pyrolytic degradation
takes place. It is found that the degradation of
chlorobenzene results in formation of products like
methane, acetylene, butenyne, butediyne and a broad range
of chlorinated and non-chlorinated mono and dicyclic
hydrocarbons14. The authors mentioned that most of these
products are also formed during thermal degradation or
pyrolysis. The thermal degradation mainly takes place by
the formation of phenyl radicals. The phenyl radicals
further break down into the radicals like C6H4Cl., C4H3.Cl.
and C2H. All the intermediates are explained by the
reactions between these radicals. It was further confirmed
by the addition of 10 mM sodium benzoate, a known
radical scavenger. It did not change the rate constant, which
varied from 0.0182 to 0.0191 min-1.

These properties include vapour pressure, solubility and

partition coefficient. Hydrophilic chemicals have strong
affinity for water and lower vapour pressures and hence
they tend to remain in the water. As mentioned earlier there
are three reaction sites. Due to their affinity with water,
these chemicals do not necessarily go either into the
interfacial layer or inside the bubbles. The majority of
sonochemical reactions for the hydrophilic compounds take
place in the water phase. Hydrophobic chemicals on the
other hand are repulsive towards water and hence mainly
decomposed inside the cavitation bubbles.

Sonochemistry in aqueous solution

In another study, chloroform and carbon tetrachloride have

been experimentally investigated17. The irradiation
frequencies were 35, 74, 170, 300 and 1000 kHz. The
degradation rates of chlorobenzene, chloroform and carbon
tetrachloride were highest at 300 kHz.

Degradation of hydrophobic compounds: By the studies

of volatile organic intermediates in trichloroethylene
degradation, conclusions have been derived that the
pyrolysis mechanism played the dominant role in the
degradation of the volatiles12. They found that the hydroxyl
radicals yield was between 0.0040 mM min-1 - 0.0176 mM
min-1 for air saturated solution at 520 kHz. The hydroxyl
radical concentration corresponds to 7 and 32% of the
initial TCE concentration for 60 minutes of sonication. The
initial TCE concentration used in the experiment was 3.34
mM. This is sufficient to cause fair amount of degradation
of TCE. However, the addition of NaBr (an effective
OH. radical scavenger) proved that TCE was not degraded
in the bulk solution. The reaction constant at 0.03909 min-1
remains the same even after the addition of NaBr. This
proved that TCE is degraded in or at least near the
collapsing microbubbles. The presence of volatile organics
like C2HCl, C2Cl2, C4Cl4 confirmed that the degradation
takes place by C-Cl bond scission. At high temperature,
C2HCl3 breaks down into C2Cl3. radical and HCl as per the
following mechanism:
C2HCl + Cl. ,

(9)

These results are in comparison with the high temperature

pyrolysis and CO2-laser induced degradation of TCE.
These radicals undergo a series of reactions to produce the
variety of intermediates. The authors mentioned that
OH. radical initiated oxidation of TCE results in different
intermediates. Lee and Oh13 reported the ultrasonic
degradation of trichloroethylene (TCE) and carbon
tetrachloride (CT). The enhancement of TCE degradation is
attributed to both the increase of hydroxyl radical
concentration by scavenging of CT for hydrogen atoms and
the generation of chlorine-containing radicals such as CCl3,
CCl2-, Cl- and HClO from pyrolysis of CT during sonolysis
of CT.

(6)

C2HCl3

C2Cl3. + HCl

The sonolytic degradation of dimethoate has yielded the

maximum degradation at 619 kHz. More than 90% toxicity
of dimethoate was reduced within 45 min of sonication.
Similarly high frequency approach has resulted in optimum
to improve the process efficiency by the addition of iron
species.16 Increasing ultrasonic power and temperature has
also intensified the degradation. The degradation was
however reduced in presence of nitrogen gas. This could be
probably due to scavenging effects.
Degradation of several chlorinated compounds and
increasing reaction rate constants with a decrease in vapor
pressures of the C2 compounds19 is observed although the
trend is not very clear (Table 1).
Although kinetic studies on the degradation of volatiles
have been done by many researchers, no attempt has been
made to apply kinetic model to study the degradation rate.
In this study, an attempt is made to study the applicability
of kinetic model on the degradation rate of volatiles.

(8)

(195)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ
Table 1
Variation of rate constants with the vapor pressures of chlorinated compounds
Compound
Rate constant (min-1)
Vapor Pressure at 200C (Torr)
Methylene chloride
0.033
348.9
Chloroform
0.043
160.0
Carbon tetrachloride
0.043
90.00
1,2-dichloroethane
0.021
64.00
Trichloroethylene
0.021
57.80
Perchloroethylene
0.026
20.00

frequency; 487 and 20 kHz was compared. Higher phenol

degradation was achieved at 487 kHz due to higher OH.
radical production. The shorter duration of collapse of the
bubbles at 487 kHz results in the efficient ejection of
radicals in the solution.

A normalization factor is also used to compare the

efficiency of the reactor used.
Degradation of hydrophilic compounds: The intense
energy generated by ultrasonic waves dissociates the water
molecule into the radical species like H., OH., HOO., which
are capable of decomposing organic matter. These radicals
were observed by spin trapping experiments20. They are
produced via the following reactions:
H2O
H. + OH.
(10)
.
2H
H2
(11)
H. + O 2
HO2
(12)
HO2 + HO2
H 2O 2 + O 2
(13)
2OH.
H2O2
(14)
2OH.
H2O + O.
(15)
H. + H2O2
OH. + H2O
(16)

Results obtained from this research demonstrate that

sonochemical reactor at a frequency of 130 kHz and a
power of 400W is capable to some degree of Linear
alkylbenzene sulfonates (LAS) degradation in aqueous
synthetic solutions. The potential of sonochemical reactors
for LAS degradation is evaluated with emphasis on the
effect of sonication time and initial concentration25.
There are few studies on the degradation of non-volatile
compounds using ultrasonic waves. The slow sonochemical
oxidation of non-volatile compounds is a challenge to the
researchers26. Similar observations were found in another
report13. The volatile intermediates during the degradation
of chlorobenzene degraded quite easily, whereas nonvolatile degrades slowly. Decolorization of dye has taken
place within 90 min, but it did not mineralize even up to six
hours of sonication. The use of tertiary butyl alcohol
established that the reaction with hydroxyl radicals was the
main reaction pathway. Substantial inhibition of the
reaction rate was found at higher concentration.

The polar and less volatile compounds like phenol,

chlorophenol etc. degrade mainly by reaction with
OH. radicals in the bulk phase or in the interphase between
the collapsing bubble and the bulk solution, depending on
their hydrophobicity21. Degradation of monochlorophenols
along with the intermediates like hydroquinone,
chlorosorcinol,
chlorohydroquinone,
catechol
and
chlorocatechol was alow studied22. The presence of these
compounds indicates that the degradation is by a reaction
with hydroxyl radicals, since these compounds are OH
adducts. The location of the reaction site was confirmed
with kinetic studies. They found zero-order disappearance
at low concentrations, whereas nonlinear rate indicative of
Langmuir type behavior available in solid/gas systems was
found at higher concentrations.

Even after three hours of sonication, decolorization did not

take place indicating that the reaction stopped far short of
completion. Other non-volatile compounds like thymine28,
formic acid29 and humic acids30 were also studied.
Sonolysis of basic Blue 41 dye in aqueous solution was
performed at 35 kHz using ultrasonic power of 160W and
aqueous temperature of 25C within 180 min31. The TiO2
nanoparticles were used as a catalyst to assist the sonication
process. The effect of experimental parameters such as pH,
H2O2 concentration and initial dye concentration on the
reaction was investigated. Kinetic studies revealed that the
degradation process followed pseudo-first order mechanism
with the correlation coefficient (R2) of 0.9918 under
experimental conditions. It has been noted that crystal
violet ultrasonic degradation in water occurs mainly
through reactions with hydroxyl radicals32. Reaction rates
are strongly affected by pollutant concentration, gas
saturation, applied ultrasonic power and water matrix.

The importance of the hydrophobicity of polar compounds

in sonochemical degradation was reported23.
They
compared the degradation of 2-chlorophenol and phenol. A
higher initial rate was reported for 2-chlorophenol. The
presence of chlorine group increases the hydrophobic
nature of the compound and hence higher degradation. The
rate of hydrogen peroxide formation decrease indicated the
degradation due to reaction with OH. radicals. In a separate
study, the presence of OH adducts like hydroquinone,
catechol and benzoquinone as the primary intermediates for
phenol degradation was evaluated.24 The absence of
products like methane and acetylene confirmed there is no
degradation by pyrolysis. Degradation at two different
(196)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ
irradiation was reported42. The efficiency of degradation
was higher at 20 KHz. This is because of the presence of
TiO2 and SiO2 nanoparticles. Reaction yield is probably
higher due to increased cavitation bubbles at their interface.

Combination of sonolysis and other AOPs

The sonochemical degradation efficiency of organic
compounds is related to their hydrophobicity. It is noted
that the greater is the hydrophobicity, the more efficiently
compounds are destroyed33. The degradation of hydrophilic
compounds is slower and moreover, total degradation is not
achieved. The combinations of ultrasound with other
conventional methods, such as ozonation, wet air oxidation
and electrochemical degradation have obtained much better
results34-35.

The combination of sonolysis and photolysis in the

presence of hydrogen peroxide (H2O2) in a 7-L externalloop airlift sonophotoreactor was used to treat the aqueous
solution of p-aminophenol. The central composite design
(CCD) and response surface methodology (RSM) were
employed to evaluate the interaction effects of the initial
H2O2 concentration (x1 = 100900 mg/L), the ultrasonic
power (x2 = 2565 W), the air flow rate (x3 = 15 L/min)
and the initial concentration of p-aminophenol (x4 = 1050
mg/L) on the p-aminophenol degradation and total organic
carbon (TOC) reduction efficiencies as well as to optimize
operating conditions. The linear, square and interaction
effects of x1, x2, x3 and x4 were also calculated. Genetic
algorithm optimization was employed to maximize the
mineralization efficiency. 79% TOC reduction efficiency
after 90 min and 86.5% p-aminophenol removal efficiency
after 30 min were achieved under recirculating batch mode
at operating conditions of x1 = 740 mg/L, x2 = 65 W, x3 =
5 L/min and x4 = 24 mg/L.
US/O3: A study was conducted on the degradation of
pentachlorophenol (PCP) by the combination of ultrasound
and ozone43. Ozone decomposes into the collapsing
caviation bubble as follows:

US/UV: Hydroxyl radicals and hydrogen peroxides are the

major oxygenating species that are responsible for the
chemical degradation in sonolytic reactions. However,
significant loss of H. and OH. radicals species takes place
due to the recombination of the radicals. The application of
UV light turned the hydrogen peroxide produced by
recombination back into the hydroxyl radicals increasing
the amount of OH. radicals. A significant increase in
phenol degradation rate is reported when the sonolysis was
promoted by photolysis36. The combined effect of US and
UV leads to 99% degradation compared to the 54%
achieved with sonication alone. Similarly, TOC removal
increased from 5% to 20% on the application of UV.
It was also found that the photosonochemical degradation
was the fastest under acidic conditions (pH = 3). These
results are in agreement with the direct photolysis of
phenol37. They also found higher degradation at acidic pH
values. The formation of intermediates like hydroquinone,
catachol, benzoquinone and resorcinol indicated that the
phenol has undergone OH. radical attack. The
photosonochemical degradation of chloro-aromatic
compounds like 4-chlorophenol, 2,4-dichlorophenol, 3chlorobiphenyl and pentachlorophenol was also studied38.
The combined effect of US and UV shows higher
degradation of the above organics as compared to
individual sonolysis and photolysis alone.

O2 + O (3P)

O3
O(3P) + H2O

(17)
2OH.

(18)

However, even with two molecules of hydroxyl radicals

production, the combined effect of sonolysis and
ozonolysis was not different from the ozonolyis alone. This
might be due to the larger rate constant of PCP with ozone
( k O 3 105 M -1s 1 ). The calculation of Hatta number
3

Investigation has been done on the combinative sonolysis

and photocatalysis39 for the degradation of an azo dye,
naphthol blue black (NBB). The combination has a
beneficial effect on the degradation rate. The first order rate
constant for the combined method (0.0183 min-1) is greater
than the one obtained with individual sonolysis (0.0104
min-1) or photocatalysis (0.0056 min-1) experiment. The
toxic compound diethyl phthalate (DEP) was degraded
using the combination of sonolysis and photolysis40. A
synergistic effect of 1.29 and 1.95 was exhibited at the
sonophotocatalytic and sonophotolytic DEP degradation,
leading to the conclusion the benefit of using TiO2
catalysis.

indicates that the PCP is reacting at the gas liquid interface

and negligible amount of O3 will be present in the solution.
Aromatic
intermediates
like
o-chloranil
and
tetrachlorocatechol were found and destroyed. On the other
hand, enhancement in the degradation of MTBE was
observed44 at two frequencies: 205 and 358 kHz. Similar
findings were reported45. In their studies on the oxidation
of azobenzene, they found that the mineralization exceeded
80% at all O3 concentrations on the combined application
of sonication and ozone. The use of ultrasound alone could
only reduce TOC by about 20%.
US/Fenton Method: It is well known that the ferrous
hydrogen peroxide constitutes the Fenton process.
Hydrogen peroxide reacts with water and generates
hydroxyl radicals. The Fenton reaction involves the
following sequence of major steps46:

The degradation of dichlorvos containing wastewaters at a

low frequency was studied. In this study, pH, temperature
and power density affect on degradation. This was one of
the few works detailing low frequency degradation of a
toxic pesticide under pH condition41. The degradation of
the phenylurea monolinuron (MLN) by ultrasound

Fe2+ + H2O2
Fe3+ + H2O2
(197)

Fe3+ + OH- + OH.

Fe-O2H2+

(19)
(20)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ
US/UV

Fe-O2H2+
Fe2+ + .O2H
(21)
It is also found that the high concentration of hydroxyl
radicals produced by Fenton method can enhance the
ultrasonic degradation of 2-chlorophenol. At 10 mg/l of
Fe2+ and 500 mg/l of H2O2, 99% of 2-chlorophenol was
removed, while 0.5 mg/l Fe2+ without H2O2 results in only
31% removal46. It is noted that the coupled US/Fenton
method results in complete degradation of MTBE whereas
only 48% removal has taken place in ultrasonication
alone47.

2. Leighton T.G., The acoustic bubble, Academic Press (1994)

3. Lorimer J.P. and Mason T.J., Sonochemistry, Part 1- The
physical aspects, Chem. Soc. Rev. 16, 239 -274 (1987)
4. Joseph J.M., Destaillats H., Hung H.M. and Hoffmann M.R.,
The sonochemical degradation of azobenzene and related azo
dyes: rate enhancement via Fentons reaction, J. Phys. Chem. A,
104, 301-307 (2000)
5. Suslick K.S., Hammerton D.A. and Cline Jr. R.E., The
sonochemical hot spot, J. Am. Chem. Soc, 108, 5641-5642 (1986)

The potential of the combination of sonication with other

AOPs lies in complete mineralization of target compounds
without using any toxic chemicals or unsafe experimental
practice. However, the synergistic effect of US in
combination with other AOPs is not widely explored in the
destruction of dyes. The dyes create persistent
environmental problems because of their resistance to
degradation. In this study, extensive experimentation are
done on the degradation of eosin B using the combination
of sonication and other AOPs and are compared with the
degradation of volatiles for certain cases.

6. De Visscher A., Van Eenoo P., Drijvers D. and Langenhove

H.V., Kinetic model for the sonochemical degradation of
monocyclic aromatic compounds in aqueous solution, J. Phys.
Chem, 100, 11636-11642 (1996)
7. Noltinkg B.E and Neppiras E.A., Cavitation produced by
ultrasonics, Proc. Phys. Soc., 63B, 674-685 (1950)
8. Mason T.J., Practical Sonochemistry users guide to
applications in chemistry and chemical engineering, Ellis
Horwood Series (1991)
9. Ince N.H., Tezcanli G., Belen R.K. and Apikyan I.G.,
Ultrasound as a catalyzer of aqueous reaction systems: the state of
the art and environmental applications, Appl catalysis B:
Environmental, 29, 167-176 (2001)

Conclusion
In this paper, a comprehensive review of sonochemical
degradation of volatile and nonvolatile compounds under
different process parameters was presented. The
sonochemical effect of ultrasound is a highly exciting and
versatile field. The simplicity and convenience of the
operation is one of the high points of this method.
Ultrasonic irradiation has the potential for use in
environmental decontamination due to the production of
high concentrations of oxidizing species such as OH and
H2O2 in the solution and localized transient high
temperatures and pressures. It 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 the OH. radical.
Hydrophilic compounds are especially difficult to be
degraded alone by sonication.

10. Margulis M.A., Sonochemistry and Cavitation, Gordon and

Breach Publishers (1993)
11. Young F.R., Cavitation, McGraw Hill (1989)
12. Drijvers D, Robrecht D.B., De Visscher A. and Langenhove
H.V., Sonolysis of trichloroethylene in aqueous solution: volatile
organic intermediates, Ultrasonic Sonochemistry, 3, S83-S90
(1996)
13. Lee M. and Oh J., Sonolysis of trichloroethylene and carbon
tetrachloride in aqueous solution, Ultrason Sonochem, 17, 207212 (2010)
14. De Visscher A. and Langenhove H.V., Sonochemistry of
organic compounds in homogenous aqueous oxidizing systems,
Ultrason Sonochem, 5, 87-92 (1998)

Sonochemical processes could be an effective alternative

way for oxidation and completely mineralizing recalcitrant
organic compounds. Also, by converting the pollutants into
less harmful or lower chain compounds, more efficient
biological treatment on the wastewater could be achieved.
Complete mineralization of pollutant is difficult to obtain at
reasonable rates with ultrasound alone. Because the
efficiency of electrical-to-sound-to-thermal conversion is
poor, still faster decomposition is needed to carry out the
oxidation at the industrial level. Therefore much work is
still needed to make the process viable and cost effective.

15. Hua I. and Hoffmann M. R., Kinetics and mechanism of the

sonolytic degradation of CCl4, intermediates and byproducts,
Environ. Sci. Technol., 30, 864-871 (1996)
16. Gyer G.J. and Ince N.H., Degradation of diclofenac in water
by homogeneous and heterogeneous sonolysis, Ultrason
Sonochem, 18, 114119 (2011)
17. Lim M., Son Y. and Khim J., Frequency effects on the
sonochemical degradation of chlorinated compounds, Ultrason
Sonochem, 18, 460465 (2011)

References

18. Chiha M., Hamdaoui Q., Baup S. and Gondrexon N.,

Sonolytic degradation of endocrine disrupting chemical 4cumylphenol in water, Ultrason Sonochem, 18, 1943-1950 (2011)
19. Bhatnagar A. and Cheung H.M., Sonochemical destruction of

1. Bolton J.R, Bircher K.G., Tumas W. and Tolman C.A., Figures

of merit for the technical development and application advanced
oxidation process, J. Adv. Oxi Tech., 1, 13 -17 (1996)

(198)

Research Journal of Chemistry and Environment _________________________________Vol.16 (4) December (2012)

Res.J.Chem.Environ
chlorinated C1 and C2 volatile organic compounds in dilute
aqueous solution, Env. Sci. Tech., 28, 1481-1486 (1994)

251 (1985)
34. Ingale M.N. and Mahajani V.V., A novel way to treat
refractory waste: Sonication followed by wet oxidation, J. Chem.
Tech. Biotechnology, 64, 41-48 (1995)

20. Riesz P. and Takashi F., Free radical formation induced by

ultrasound and its biological implications, Free Rad. Biol. Med,
13, 247-270 (1996)

35. Trabelsi F., Ait-Lyazidi H., Ratsmba B., Wilheim A.M.,

Delmas H.P., Fabre L. and Berlan J., Oxidation of phenol in
waste water by sonoelectrochemistry, Chem. Eng. Sci., 51, 18571865 (1996)

21. Drijvers D., Langenhove H.V. and Beckers M., Decomposition of phenol and trichloroethylene by the ultrasound/H2O2/CuO process, Water Res, 33, 1187- 1194 (1999)
22. Serpone N., Terzian R., Hidaka H. and Pelizzetti E.,
Ultrasonic induced dehalogenation and oxidation of 2-, 3- and 4chlorophenol in air-equilibrated aqueous media. Similarities with
irradiated semiconductor particulates, J. Phys. Chem., 98, 26342640 (1994)

36. Wu C., Liu X., Wei D., Fan J. and Wang L.,
Photosonochemical degradation of phenol in water, Water Res,
35, 3927-3933 (2001)
37. Chun H, Yizhong W. and Hongxiao T., Destruction of phenol
aqueous solution by photocatalysis or direct photolysis,
Chemosphere, 41, 1205-1209 (2000)

23. Petrier C. and Casadonte D., The sonochemical degradation

of aromatic and chloroaromatic contaminants, In Advances in
Sonochemistry, eds., Mason T.J and Tiehm A., Amsterdam,
Elsevier Science (2001)

38. Johnston A.J. and Hocking P., Emerging technologies in

hazardous waste management, Chapt. 6, American Chemical
Society (1993)

24. Petrier C., Lamy M.F., Francony A., Benahcene A. and David
B., Sonochemical degradation of phenol in dilute aqueous
solutions: comparison of the reaction rates at 20 and 487 kHz, J.
Phys. Chem, 98, 10514-10520 (1994)

39. Stock N., Peller J., Vinodgopal K. and Kamat P.V.,

Combinative sonolysis and photocatalysis for textile dye
degradation, Env. Sci. Tech, 34, 1747-1750 (2000)

25. Dehghani M.H., Najafpoor A.A. and Azam K., Using

sonochemical reactor for degradation of LAS from effluent of
wastewater treatment plant, Desalination, 250, 8286 (2010)

40. Na Seungmin, Yun-Gyong Ahn, Mingcan Cui and Jeehyeong

Khim, Significant diethyl phthalate (DEP) degradation by
combined advanced oxidation process in aqueous solution, J. of
Env Manag, 101, 104-110 (2012)

26. Seymour J.D. and Gupta R.B., Oxidation of aqueous

pollutants using Ultrasound: saltinduced enhancement, Ind. Eng.
Chem. Res, 36, 3453-3457 (1997)

41. Golash N. and Gogate P.R, Degradation of Dichlorvos

containing wastewaters using sonochemical reactors, Ultrasonics
Sonochemistry, (2012)

27. Vinodgopal K., Peller J., Makagon O. and Kamat P.V.,

Ultrasonic mineralization of reactive textile azodye, remazol
black B., Water Res, 32, 3646-3650 (1998)

42. Zouaghi R., David B., Suptil J., Djebbar K., Boutiti A. and
Guittonneau S., Sonochemical and sonocatalytic degradation of
monolinuron in water, Ultrason Sonochem, 18, 1107-1112 (2011)

28. Sehgal C.M. and Wang S.Y., Threshold intensities and

kinetics of sonoreaction of thymine in aqueous solutions at low
ultrasonic intensities, J. Am. Chem. Soc., 103, 6606-6611 (1981)

43. Weavers L.K. Malmsdadt N. and Hoffmann M.R., Kinetics

and mechanism of pentachlorophenol degradation by sonication,
ozonation and sonolytic ozonation, Env. Sci. Tech, 34, 1280-1285
(2000)

29. Hart E. J. and Henglein A., Sonolysis of Formic Acid-Water

Mixtures, Radiat. Phys. Chem, 32, 11 (1988)

44. Kang J.W., Hung H-M., Lin A. and Hoffmann M.R.,

Sonolytic destruction of methyl tert. butyl ether by ultrasonic
irradiation: The role of O3, H2O2, frequency and power density,
Env. Sci. Tech, 33, 3199-3205 (1999)

30. Nagata Y., Hirai K., Bandow H. and Maeda Y.,

Decomposition of hydroxybenzoic and humic acids in water by
ultrasonic irradiation, Environ. Sci. Technol, 30, 1133-1138
(1996)

45. Destaillats H., Colussi A.J., Joseph J.M. and Hoffmann M.R.,
Synergistic effect of sonolysis combined with ozonolysis for the
oxidation of azobenzene and methyl orange, J. Phys. Chem. A,
104, 8930-8935 (2000)

31. Abbasi Mahmood et al, Sonochemical degradation of Basic

Blue 41 dye assisted by nanoTiO2 and H2O2, J. of Hazar Mat.,
153, 942947 (2008)

46. Lin J. and Ma Y.S., Oxidation of 2-Chlorophenol in water by

ultrasound/Fenton method, J. Env. Engg., 130-137 (2000)

32. Duque Fernando Guzman, Christian Ptrier, Cesar Pulgarin,

Gustavo Peuela and Ricardo A. Effects of sonochemical
parameters and inorganic ions during the sonochemical
degradation of crystal violet in water Torres-Palma, Ultrasonics
Sonochemistry, 18, 440446 (2011)

47. Neppolian B., Jung H., Choi H., Lee J.H. and Kang J.W.,
Sonolytic degradation of methyl tertbutyl ether: the role of
coupled fenton process and persulfate ion, Water Res, 36, 46994708 (2002).

33. Henglein A. and Kormann C., Scavenging of OH radicals

produced in the sonolysis of water, Int. J. Radiation Biology, 48,

(Received 19th June 2012, accepted 15th September 2012)

(199)