3370 Ind. Eng. Chem. Res.

2002, 41, 3370-3378

A Sonophotochemical Reactor for the Removal of Formic Acid from

Wastewater
Parag R. Gogate, Sukti Mujumdar, and Aniruddha B. Pandit*
Chemical Engineering Section, U.I.C.T., Matunga, Mumbai 400 019, India

The efficacy of a sonophotochemical reactor coupling ultrasonic irradiation with photocatalytic

oxidation has been evaluated using formic acid degradation as the model reaction. The reactor
used in the present work is a hexagonal flow cell irradiated with multiple-frequency transducers
placed at the wall of the reactor and by ultraviolet radiation positioned at the center of the
reactor. The various operating parameters studied in the present work include the concentration
of the photocatalyst, initial concentration of the pollutant, and effect of aeration for the case of
photocatalytic oxidation. The sonophotochemical operation has been studied in two ways:
simultaneous irradiation and sequential irradiation with the aim of understanding the expected
synergism between the two modes of energy transmission. The effect of the addition of hydrogen
peroxide on the extent of degradation has also been studied. The hybrid technique of
sonophotochemical degradation in the presence of aeration and hydrogen peroxide has been
compared with the individual techniques of photocatalysis, ultrasonic irradiation, and addition
of hydrogen peroxide alone, and recommendations about the effective techniques have been made
for wastewater treatment applications.

1. Introduction power input of 900 W and frequencies of 20, 30, and 50

Pollution is the contamination of water, air, and land
with materials that distract from their ability to support
the ecosystem or provide some human need. Human
activities, industrial processes, and agricultural usage
are the big contributors to the pollution problem. With
new developments in almost all of the fields and the
invention of new molecules which can withstand bio-
logical degradation, it is important to invent and apply
new treatment procedures to keep the balance of the
ecosystem intact. One of the new generation technolo-
gies, quite well established on a laboratory scale, is
acoustic cavitation, i.e., cavitation generated using
ultrasound. During the cavitation phenomenon, very
large magnitudes of temperature and pressure are
generated locally, also releasing large amounts of free
radicals by the dissociation of water, which are capable
of oxidizing/degrading a variety of organic and inorganic
compounds, specifically biorefractory chemicals. The use
of sonochemical reactors for wastewater treatment
applications is not new to researchers.1-10 Excellent
reviews are also available on the use of sonochemical
reactors depicting in detail the mechanism of generation
of cavitation as well as its action, the types of reactors
used, the optimum operating conditions, and different
applications.11-15 It should be noted here that the
majority of the studies are on a laboratory scale, with
the capacity of the reactor on the order of a few
milliliters. It is very unreliable to use this knowledge
to design large-scale reactors for wastewater treatment
applications because of very high scale-up ratios and
also nonsuitability of ultrasonic (US) transducers to
operate at high frequencies and high power dissipation
rates efficiently. In an earlier work,5 a triple-frequency
flow cell was designed with operating conditions of a
* To whom correspondence should be addressed. E-mail:
abp@udct.ernet.in. Phone: 91-22-414 5616. Fax: 91-22-
4145614.
10.1021/ie010711l CCC: $22.00 2002 American Chemical Society
Published on Web 06/07/2002
kHz operating in multiple combinations and was used
for the degradation of formic acid. It was observed that,
although the equipment was able to destroy formic acid
at a reactor capacity of 7 L, the rate of degradation was
quite less (only 6-7% destruction was observed in 2 h
of time) and, hence, the time spans required for achiev-
ing complete degradation of chemical contaminants will
be quite large (the rate of degradation will be further
reduced for complex real effluents where a large variety
of chemicals will be present that would interfere with
the main reaction pathways). Further, it is also impor-
tant to consider the cost of using US irradiation for the
destruction process on an industrial scale. The current
costs for the cleaning of contaminated groundwater with
ultrasound are an order of magnitude higher than those
by an air stripping/active carbon process.7 Thus, it is
important to either find an alternative means for using
cavitation energy efficiently or use acoustic cavitation
(generated by US irradiation) in combination with other
methods, e.g., photocatalytic oxidation, etc., with the
aim of enhancing the rates of degradation.
A promising aspect of photocatalysis with semicon-
ductor materials is the near-complete mineralization of
environmental pollutants in the waste stream under
ambient conditions. Various chalcogenides (oxides such
as TiO2, ZnO, ZrO2, CeO2, etc., or sulfides such as CdS,
ZnS, etc.) can been used as photocatalysts; however, it
should be noted that the best photocatalytic perfor-
mances with maximum quantum yields have always
been reported with titania (Degussa P-25 type, which
is a combination of rutile and anatase grade). There has
been extensive literature on the application of photo-
catalysis to wastewater treatment,16-25 and excellent
reviews are also available on this subject.26-30 In the
case of photocatalytic oxidation, the most common
problem is the reduced efficiency of the photocatalyst
with continuous operation possibly due to the adsorption

of contaminants on the catalyst surface and blocking of
the sites, which makes them unavailable for the de-
struction. Thus, the aim should be to devise a technique
for proper cleaning of the catalyst surface during the
photocatalytic operation. US irradiation can be one such
technique, and it also provides an additional surface
area for the reaction due to fragmentation or deagglom-
eration of the catalyst particles. Ultrasound will play a
profound role in the situations where the adsorption of
pollutants at the specific sites is the rate-controlling
step. Moreover, photocatalytic oxidation is also affected
by severe mass-transfer limitations especially in the
supported catalyst types of reactors, which are generally
preferred over slurry reactors to avoid separation prob-
lems. Turbulence created by the acoustic streaming
produced by ultrasound should eliminate or decrease
the mass-transfer resistance considerably. One more
factor suggesting that the two techniques will give
better results when operated in combination is the fact
that, for both of the techniques, the basic reaction
mechanism is the generation of free radicals and
subsequent attack of these on the pollutant species. If
the two irradiations are operated in combination, a
larger number of free radicals will be available for the
reaction, thereby increasing the rates of reaction, as well
as the degree of oxidation conditions will be compara-
tively higher and hence the hybrid method should be
able to degrade a wider range of pollutants.
There have been many studies depicting the observed
synergism and the enhanced rates of degradation for
the combinatorial operation of sonochemical reactors
and photocatalytic oxidation.31-42 Recently, Toma et al.43
have given a brief overview of different studies pertain-
ing to the effect of ultrasound on photochemical reac-
tions concentrating on the chemistry aspects, i.e.,
mechanisms and pathways of different chemical reac-
tions. It has also been observed that the majority of
studies are restricted to volumes of less than 1 L, and
hence the scale-up of these reactors for actual waste-
water treatment application will be extremely difficult
because the scale-up ratio required is very high. With
a view of moving one step ahead in this direction, it was
thought desirable to study the synergism between
sonochemical and photocatalytic reactors at a large scale
of operation (7 L) in a triple-frequency hexagonal
sonophotochemical flow cell. The system chosen was the
destruction of formic acid because in the majority of the
degradation schemes of organic compounds the end
products are usually lower acids which control the
overall rate of reduction of total organic carbon (TOC)
or chemical oxygen demand. It should be also noted that
the destruction of formic acid leads to a complete
mineralization if operated for longer times (oxalic acid
and hydrogen peroxide, which may be formed in the
course of the reaction, are also susceptible to both US
and ultraviolet (UV) irradiation and hence should be
degraded; the other oxidation products can be carbon
dioxide, water, CO, and H2). Because the main aim of
the present work is to highlight the engineering aspects
of the large-scale operation of sonophotochemical reac-
tors, not much effort was put forward to perform a
detailed kinetic analysis. Much of the information is
available regarding the kinetic studies in the open
literature,33,34,36,37,41 and all of the studies have reported
that the degradation using the combination of US and
UV irradiation follows first-order kinetics with respect
to the pollutant, irrespective of its type.
Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3371
Figure 1. Experimental setup used for studying synergism
between the US and UV irradiations.
The effect of the addition of hydrogen peroxide (it is
an additional source of free radicals) has not been
studied in the literature (except for some papers by the
Fung group33,34,37 at an operating capacity of 4.5 L) for
the combination technique of US and UV irradiation,
and hence some experiments with the addition of
hydrogen peroxide have been performed in the present
work at enhanced capacities.
2. Experimental Section
The experiments were performed in a hexagonal flow
cell depicted schematically in Figure 1. The reactor has
a total capacity of 7.5 L and can be operated in either
batch or continuous mode. In the present work, 7 L of
aqueous formic acid has been used and the operation
was in batch mode.
Each side of the hexagonal flow cell is provided with
three transducers, each with a power dissipation of 150
W/side. The opposite faces of the hexagon have trans-
ducers with irradiating frequencies of 20, 30, and 50
kHz and can be operated either individually or in
combinations. The total maximum power that can be
dissipated in the system is 900 W when all of the
transducers (a combination of 20 + 30 + 50 kHz) are
operated.
In the annular space provided at the center of the
reactor, one tube of UV light was used with a power
dissipation of 8 W. The UV light source was fitted in a
quartz tube placed inside the reactor, and the entire
volume of the reactant is enclosed in an annular space
surrounding the quartz tube and enclosed by the
hexagonal faces. A stirrer was fitted in the reaction zone
to ensure a good dispersion of TiO2 catalyst along with
continuous renewal of the film of the reactants around
the quartz tube for UV irradiation as well as around
the wall of the reactor for US irradiation.
Different concentrations of formic acid, in the range
100-1000 ppm, have been used to study the effect of
the initial concentration on the extent of degradation.
Anatase-grade TiO2 was used as the photocatalyst, and
its concentration was also varied in the range 100-1000
ppm to check for optimum concentration of the same.
The temperature of the reaction mixture was always
maintained in the range of 28-30 C, and continuous
aeration using a sintered multipoint sparger, at a rate
of 1.02 cm3/s, was carried out in all of the experiments.
Some experiments were done in the presence of H2O2
3372 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002
Figure 2. Degradation of formic acid using US irradiation alone.
(concentration in the range 0.1-0.5 mL/L of formic acid)
alone and also in the combination of UV/US/H2O2 to
examine the extent of enhancement observed due to
hydrogen peroxide.
The amount of the formic acid remaining in the
solution was determined using titration with the stan-
dard alkali (NaOH). The concentration of the standard
alkali (NaOH) was so adjusted that the readings of
titration were in the range of 20-25 mL with the least
count of the buret used as 0.1 mL. Moreover, the
titration was repeated two to three times to get accurate
readings, and hence attempts have been made to keep
the errors below 0.1%. The experiments were continued
for up to 2 h of irradiation time, and analysis was done
at intervals of 30 min.
3. Results and Discussion
The experiments with degradation of formic acid
consisted of three parts: US irradiation alone, photo-
catalytic oxidation alone, and a combination of US and
UV irradiation (in two parts: sequential operation, i.e.,
US irradiation followed by UV irradiation and simul-
taneous irradiation of US and UV irradiation). The aim
of comparing the simultaneous and sequential opera-
tions was to check whether any synergism exists
between the two processes or only the individual effects
are contributing to the overall effect. The sequential
operation of UV irradiation followed by US irradiation
was not considered in the present work. This can be
attributed to the fact that the most important contribu-
tion of US irradiation is to regenerate the deactivated
catalyst as well as to increase the surface area of the
catalyst particles available for the adsorption of the
pollutant and subsequent reaction due to the photo-
catalytic oxidation. If UV irradiations were to be used
first, with fresh or the recycled catalyst in the actual
operation, this contribution would not be there and may
result in an even lesser extent of degradation as
compared to the operation of US irradiation followed
by UV irradiation.
3.1. US Irradiation. The results with only US
irradiation of formic acid have been discussed in detail
in the earlier work,5 and only important findings have
been depicted here to give readers better insight into
optimum parameters. Figure 2 gives the variation of
percentage degradation with time of irradiation for the
different combinations studied in the work. It can be
seen from the figure that the extent of degradation
increases with an increase in the frequency of operation;
further, multiple frequencies give better degradation as
compared to single frequencies. The detailed explana-
tion for this observation and also more studies with
Figure 3. Variation of percentage degradation of formic acid with
initial concentration during an irradiation time of 90 min at a
catalyst concentration of 500 ppm.
individual sonochemical degradation of formic acid can
be obtained in the earlier work.5 Moreover, the presence
of air increases the extent of irradiation. The enhance-
ment in the presence of air was observed for all of the
seven combinations studied in terms of frequency;
results are only shown for the multiple-frequency opera-
tion to avoid repetition.
3.2. Photocatalytic Oxidation. The experiments for
individual photocatalytic oxidation studies were per-
formed in two different sets for investigating the effect
of the initial concentration of formic acid and the
concentration of photocatalyst TiO2. Aeration was found
to be essential for the photocatalytic oxidation, and
hence in all of the experiments aeration was used.
3.2.1. Effect of the Initial Concentration of For-
mic Acid. Figure 3 shows the variation in the percent-
age reduction in the concentration of formic acid with
time for different initial concentrations. It can be seen
that the percentage degradation of formic acid is found
to be inversely proportional to the initial concentration
of formic acid (in the range of 100-1000 ppm at a
catalyst loading of 500 ppm). Topalov et al.16 have also
reported that the rate of degradation of metalaxyl (a
typical fungicide) decreases with an increase in the
initial pollutant concentration although the total volume
treated was only 20 mL. Sakthivel et al.,24 with experi-
ments on a leather dye, acid green 16, in a reactor with
a capacity of 90 mL, have obtained similar results. In
the present case, the total volume treated was 7 L, and
thus it can be said that the total volume to be treated
does not have much effect on the trends observed for
the variation in rate constants with the initial concen-
tration of the pollutant.
Further, it was also shown in the earlier work5 that
the rate of sonochemical destruction of formic acid also
shows similar trends, a fact that is very much important
and essential when designing reactors with the combi-
nation of the two modes of irradiation. One must have
similarities in terms of the variation with respect to the
different operating parameters, when the combination
of two techniques has to be used for synergism.
It should be, however, also noted that, even if the
percentage degradation of formic acid is found to be
inversely proportional to the initial concentration of
formic acid, the net number of moles degraded (calcu-
lated as percentage degradation multiplied by the initial
concentration of the pollutant) is greater for the higher
initial concentrations. This may be attributed to the fact
that the variation in the rate of degradation is perhaps
little hampered by the effect of pH of the solution. As
the initial concentration of acid increases, the pH

Figure 4. Variation of the percentage degradation of formic acid
with catalyst concentration during 90 min of irradiation and at
100 ppm initial concentration of acid.
decreases, thereby causing an increase in the expected
rates of degradation (acidic conditions are always
preferred for the photocatalytic oxidation of the pollut-
ants as observed by Tanaka et al.21 and Andreozzi et
al.23). Thus, the observed degradation in the present
case will be somewhat lower as compared to the one
observed with constant pH. Thus, one should always
aim at having a lower initial concentration of the
pollutant for having higher rates of degradation; no
doubt some compromise will have to be done because of
the problems associated with the treatment of higher
volumes of pollutant.
3.2.2. Effect of the Catalyst Concentration. The
effect of the catalyst concentration on the extent of
degradation is shown in Figure 4 (the experimental
conditions are a formic acid initial concentration of 100
ppm and a total time of irradiation of 90 min). It can be
seen from the graph that the percentage degradation
increases with an increase in the catalyst concentration
until an optimum value of 500 ppm, beyond which the
degradation is observed to decrease. The initial increase
in the rate of degradation can be attributed to the fact
that a greater number of electron-hole pairs are formed
because of the large amount of the photocatalyst,
resulting in a greater number of free radicals that attack
the pollutant molecules. Above 500 ppm, however, it is
the opacity of the solution due to the presence of solid
particles which inhibits the transmission of UV light
as well as results in the scattering of the incident UV
light and the enhanced rate of electron-hole pair
recombination which results in reduced rates of degra-
dation. Another factor affecting the degradation might
be the poor dispersion characteristics of the solid pho-
tocatalyst at higher concentrations though the contribu-
tion of this might be quite low as compared to the earlier
two factors.
Similar results have been obtained in the past with
respect to variation of percentage degradation with the
catalyst concentration although for different operating
and geometric conditions. Sakthivel et al.24 have also
reported an optimum value of 250 000 ppm for the
catalyst concentration in the destruction of acid green
16 dye, whereas Andreozzi et al.23 have shown that the
photocatalytic degradation of 4-nitrophenol increases
with an increase in the catalyst concentration until an
optimum value of 40 000 ppm. It can be seen that,
although the trends in the observed variation are same,
the optimum values of the catalyst concentration are
2-3 orders of magnitude different. This can be at-
tributed to the fact that the optimum catalyst concen-
tration value will be a strong function of the geometry
Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3373
Figure 5. Parity plot for the model equation.
of the system (affecting in terms of blockage of the light)
and the operating conditions viz., incident intensity of
UV light and concentration and type of the pollutant
(deciding the optimization in terms of relative rates of
generation and recombination of the electron-hole
pairs). Thus, it is of utmost importance to perform
laboratory-scale experiments for the pollutant in ques-
tion unless data are available in the existing literature
with similarity in the operating conditions and geometry
of the reactor.
3.2.3. Modeling Approach Required for Design.
The data obtained should be modeled to study the effect
of various parameters, and the fitted equation should
give the net degradation of the pollutant. To give an
indication about the type of equations to be developed,
the variation of the extent of degradation with the
catalyst concentration (only until the optimum value)
and the initial concentration of the acid for 30 min of
irradiation has been modeled using regression analysis
and the resulting equation is given as
Ct/C0 ) 0.6631(catalyst concentration)-0.0474
(initial concentration of acid)0.0955 (1)
where Ct is the concentration remaining after time t and
C0 is the initial concentration of acid. The equation
requires that the catalyst as well as the initial concen-
tration of acids be in units of ppm and is valid in the
range of catalyst concentration of 0-500 ppm (500 ppm
is the optimum concentration found in the present work)
and in the range of acid concentration of 100-1000 ppm.
The constant 0.6631 will be a strong function of the time
of irradiation, whereas the exponents may or may not
be dependent on the time of operation. The resultant
model should be checked for accuracy by comparison
with the experimental data, and parity plots (graph of
predicted Ct/C0 against experimentally observed Ct/C0)
as shown in the Figure 5 should be made. It must be
noted at this stage that the present equation has been
developed only to give an indication about the design
strategy and is valid only in a small range of operating
parameters. The generalized equations to be used for
design procedures must be developed considering the
entire range of operating parameters and must contain
a large number of data points to enhance the confidence
in the design.
3.3. Combination of US and UV Irradiation. As
was said earlier, two sets, viz., sequential and simul-
taneous irradiation, were performed in order to inves-
tigate the mechanism of the synergism for the two
techniques under consideration. The simultaneous ir-
radiation technique was studied under different condi-
tions of catalyst concentration and frequencies of irra-
diation.
3.3.1. Comparison of Sequential and Simulta-
neous Operation. In sequential operation, the photo-
catalyst was predispersed using ultrasound, resulting
in an increase in the catalyst surface area by fragmen-
3374 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002
Figure 6. Comparison of sequential and simultaneous irradiation
techniques for sonophotochemical reactors.
Figure 7. Comparison of the combination method with the
individual techniques for degradation of formic acid.
tation/deagglomeration and also cleaning of the catalyst,
and the resultant solution was irradiated by UV light.
The experimental conditions were 100 ppm initial
concentration of the formic acid and 500 ppm catalyst
concentration. In the simultaneous irradiation tech-
nique, as the name suggests, both ultrasound and UV
light were put on simultaneously. The results for these
two techniques are shown in Figure 6. It can be seen
from the graph that the simultaneous irradiation tech-
nique gives better results as compared to the sequential
technique, confirming the fact that not only an increase
in the surface area and precleaning of catalyst are the
important factors but also production of an additional
number of hydroxyl radicals as well as continuous
cleaning of the catalyst surface during the process of
photoactivation under the continuous action of ultra-
sound are equally contributing to the expected enhance-
ment using the combination. To give a quantitative idea,
the extent of degradation of formic acid by the simul-
taneous technique is 30% more as compared to that of
the sequential technique. Similar results have also been
obtained by Stock et al.36 for the degradation of an azo
dye, naphthol blue black (NBB). In their work (640 kHz
sonoreactor with a power input of 240 W and a capacity
of 600 mL has been used), the simultaneous technique
resulted in a decrease of TOC by 75% as compared to
only 50% with the sequential technique. Thus, simul-
taneous use of UV irradiation and ultrasound is recom-
mended for getting better results in terms of the extent
of degradation.
3.3.2. Comparison of Combination with the In-
dividual Techniques. The results for experimentation
with 100 ppm initial concentration of formic acid in the
presence of air for different techniques are shown in
Figure 7. The combination gives about 4 times more
degradation as compared to sonication alone, whereas
the comparison with photocatalytic oxidation alone
follows a somewhat complex nature. The percentage
degradation initially appears to be reduced in the
presence of ultrasound, which can be explained on the
basis of relative contributions of the different factors
underlying the expected synergism between the two
techniques. Initially, fragmentation of the catalyst is the
dominant factor due to large catalyst size as compared
to cleaning as well as enhancement in the formation of
free radicals. The formation of a large number of solid
particles increases the available surface area, but, on
the other hand, it also causes scattering of the UV light
as well as the ultrasound and also inhibits efficient
transmission of both through the medium. This was also
observed visually by way of the appearance of high
turbidity in the initial periods of irradiation. As the time
progresses, a greater number of free radicals are gener-
ated because of the combined action (UV + US), result-
ing in the enhancement, and also continuous cleaning
of the catalyst particle takes place which is absent in
the case of photocatalytic oxidation alone, resulting in
a higher extent of degradation for the combination.
Moreover, as the catalyst size reaches a certain lower
limit (an equilibrium value), further fragmentation does
not take place. It appears that fouling of the catalyst
surface is the controlling factor in the later stages of
the degradation of formic acid by UV light alone as the
extent of degradation almost reaches a constant value
within 2 h of irradiation. In contrast, the extent of
degradation increases continuously in the presence of
ultrasound possibly because of the continuous cleaning
of the catalyst surface.
To validate the above hypothesis of relative contribu-
tions of different effects of ultrasound, the experiments
were repeated with a catalyst concentration of 300 ppm.
For this set, the percentage degradation for the combi-
nation was 12.24%, whereas for photocatalytic oxidation
alone, it was 14.23% in the first 30 min of irradiation
time. Thus, the combination technique gives 14% less
degradation as compared to only photocatalytic oxida-
tion. However, for the case of 500 ppm catalyst concen-
tration, the same technique gives 28% less degradation
as compared to the photocatalytic oxidation. This can
be attributed to the fact that the negative contribution
due to the fragmentation of photocatalyst will be less
in the case of 300 ppm concentration as compared to
500 ppm catalyst concentration. In other words, the time
required for the combination to give better results as
compared to photocatalytic oxidation alone is less as
soon as the fragmentation is reduced. Further confirma-
tion of this fact was obtained when the US irradiation
was restricted to 20 kHz alone instead of a 20 + 30 +
50 kHz combination for the 300 ppm catalyst concentra-
tion. The percentage degradations were found to be
12.24% (for a combination of UV light and 20 + 30 +
50 kHz ultrasound), 15.75% (for a combination of UV
light and 20 kHz ultrasound), and 14.23% (for UV light
alone) in the first 30 min of irradiation time. In this
case, the combination technique shows better results for
30 min of irradiation time as the extent of fragmen-
tation in the case of 20 kHz ultrasound is considerably
lowered (because of a lower intensity of cavitation and
hence the turbulence for the 20 kHz irradiating fre-
quency as compared to a combination of 20 + 30 + 50
kHz ultrasound). It must also be noted at this stage that
all of these results are only at initial stages and

indeed a 20 + 30 + 50 kHz combination gives better
results than 20 kHz alone over extended time periods.
The negative contribution resulting from the scatter-
ing of the waves due to solid particles makes a certain
contribution throughout the irradiation time. This is
evident also from the fact that, in 90 min of irradiation,
a combination gives 15% more degradation as compared
to photocatalytic oxidation for 300 ppm concentration,
whereas for 500 ppm concentration of catalyst, the
enhancement is just 10%, indicating a higher contribu-
tion of fragmentation at higher solid loadings.
It was also observed in the study that 300 ppm
concentration of catalyst in the presence of ultrasound
gives almost the same amount of degradation as com-
pared to 500 ppm catalyst in the absence of ultrasound.
Thus, it can be said that the presence of ultrasound
decreases the required catalyst loading to achieve the
same degradation, which is likely to reduce separation
problems and give some cost benefits. It should also be
noted that the optimum value of the catalyst concentra-
tion (500 ppm for photocatalytic oxidation as observed
in this case) will be different for the combination of US
and UV irradiation because the relative contributions
of different factors (fragmentation, cleaning, and pro-
duction of free radicals) will be strongly dependent on
the catalyst concentration.
3.4. Effect of the Addition of Hydrogen Peroxide.
It can be seen from the above results that the production
of the free radicals and further enhancement in the rate
of generation of the same in the presence of ultrasound
make a crucial impact on the overall rates of degrada-
tion. Thus, with the aim to increase the extent of
degradation further, it was thought of supplying an
additional source for the free radicals in the form of
hydrogen peroxide. It is well-known that hydrogen
peroxide in the presence of US as well as UV irradiation
undergoes a dissociation reaction, forming free hydroxyl
radicals which are strong oxidizing agents.44-48 It must
also be noted here that if one tries to estimate the
dissociation rates alone in the presence of US irradia-
tion, it may not be possible to get measurable rates
because the recombination of the formed free radicals
to form hydrogen peroxide will be the dominant mech-
anism.49
The loading of hydrogen peroxide was restricted in
the range of 0.1-0.5 mL/L of formic acid to be treated.
This can be attributed to the fact that if the concentra-
tion of H2O2 is increased beyond certain limits, ad-
ditional hydrogen peroxide usually recombines with the
dissociated hydroxyl radicals, decreasing the availability
for the pullutant degradation, and it also acts as an
additional pollutant if present in large quantities.
3.4.1. Addition of Hydrogen Peroxide Alone. To
see the contribution of hydrogen peroxide as an oxidiz-
ing agent, experiments were performed with the addi-
tion of 0.5 mL/L of hydrogen peroxide to 7 L of a 100
ppm formic acid solution. It was, however, observed that
the hydrogen peroxide has almost no effect on the
removal of formic acid with a percentage removal of just
1.65% in 90 min of treatment time. Thus, it can be said
that hydrogen peroxide alone is ineffective in the
treatment of formic acid. Further addition of 500 ppm
catalyst (TiO2) with 0.5 mL/L of hydrogen peroxide with
continuous stirring increases this degradation to 6.3%
in the same time of operation. Thus, the rates of
degradation are comparable with US irradiation alone5
Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3375
Figure 8. Results for the combination of hydrogen peroxide and
US irradiation.
but are still quite lower considering the final aim of
designing reactors for effluent treatment.
3.4.2. Combination of Hydrogen Peroxide and
US Irradiation. The results of experiments with the
combination of US irradiation (20 + 30 + 50 kHz
operating simultaneously; power input of 900 W) and
hydrogen peroxide (loading of 0.5 mL/L) are shown in
Figure 8. The degradation for the combination is almost
double as compared to both individual techniques of US
irradiation and the addition of hydrogen peroxide with
the catalyst. Thus, it is now confirmed that, in the
presence of US irradiation, hydrogen peroxide does
dissociate, forming highly reactive hydroxyl radicals and
resulting in an expected enhancement in the overall rate
of degradation. Moreover, the acoustic streaming pro-
duced by US-induced cavitation phenomena50 also helps
in decreasing the effect of mass-transfer limitations
which otherwise severely affect the processes for treat-
ment with hydrogen peroxide alone. Teo et al.8 have also
reported that the initial rate of degradation of a 0.4 mM
p-chlorophenol aqueous solution increases substantially
(by about 3 times for a concentration of hydrogen
peroxide of 15 mM as compared to that in the absence
of hydrogen peroxide) but observed that the addition of
hydrogen peroxide is only facilitated until an optimum
concentration of hydrogen peroxide (40 mM for the
initial concentration of pollutant as 0.4 mM).
It can also be seen from the figure that the extent of
degradation is marginally higher for the catalyst loading
of 500 ppm as compared to 300 ppm, which can be
attributed to the enhanced contribution of surface
cavitation at the surface of solid particles.51 Shirgaonkar
and Pandit32 have also reported that the presence of
TiO2 increases the extent of degradation of 2,4,6-
trichlorophenol for the operation with 22 kHz frequency
and a power input range of 0.4-0.12 W/mL. In the
present case, the operating power density is 0.13 W/mL
and the reactor is irradiated by 20 + 30 + 50 kHz
frequencies operating simultaneously.
3.4.3. Hybrid Technique of UV/US/Hydrogen
Peroxide. Figure 9 shows the extent of degradation of
formic acid for different catalyst loadings at different
times of operation. It can be seen that the presence of
hydrogen peroxide significantly enhances the extent of
degradation (an almost 120% increase is observed for
hydrogen peroxide loading of 0.5 mL/L over the UV/US
combination). This can be very well explained on the
basis of enhanced formation of free radicals from the
dissociation of hydrogen peroxide under the combined
action of US as well as UV irradiation.
Fung et al.37 have also shown that the extent of
degradation of CI reactive red 120 dye increases with
an addition of hydrogen peroxide until loading of 0.2
3376 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002
Table 1. Comparison of the Results Obtained for Different Approaches Used in the Present Work
approach experimental conditions
US irradiation seven different combinations of
frequencies, experiment with the
presence of air
hydrogen peroxide concentration of 0.5 mL/L, additional
experiment with TiO2 catalyst
and stirring
US irradiation + all of the frequencies operating and a
hydrogen peroxide hydrogen peroxide loading of 0.5 mL/L
photocatalytic different initial concentrations of acid
oxidation and catalyst TiO2 in the range of
100-1000 ppm
US irradiation + 100 ppm acid concentration, 500 ppm
UV irradiation of catalyst, all frequencies operating
for US irradiation and UV irradiation;
two different methods of sequential
and simultaneous irradiations
US + UV + 100 ppm acid concentration, 500 ppm
hydrogen peroxide of catalyst, all frequencies operating
for US irradiation and UV irradiation
(simultaneous way); addition of
hydrogen peroxide in the range of
0.1-0.5 mL/L)
Figure 9. Results for the hybrid technique of UV/US/hydrogen
peroxide.
mL/L, whereas for the degradation of Cuprophenyl
Yellow RL, the optimum loading of hydrogen peroxide
was reported to be 0.1 mL/L.33 The operating conditions
used in the experimentation of Poon et al.33 and Fung
et al.37 are US transducers operating at 340 kHz
frequency and UV radiations with a power input of 66
W (six tubes of 11 W each), whereas in the present case,
the frequencies of operation are 20 + 30 + 50 kHz and
a power input of 8 W for UV light. Thus, the rate as
well as the number of formation of hydroxyl radicals
will be much higher in the case of Poon et al.33 and Fung
et al.37 because of more severe conditions as compared
to the present case, and hence the optimum concentra-
tion of hydrogen peroxide (beyond which the scavenging
action of hydrogen peroxide and the recombination of
free radicals are dominant52) will be lower. In the
present case, we have found no decrease in the extent
of degradation with an increase in the hydrogen per-
oxide loading in the range of 0.1-0.5 mL/L. Thus, it can
be said that the optimum loading of hydrogen peroxide
results and comments
multiple frequencies are better as compared
to single frequencies; the presence of air
also increases the extent of degradation by
providing additional nuclei; the maximum
degradation achieved by US alone in the
presence of air is around 6.5%
hydrogen peroxide does not oxidize formic acid
(1.65% destruction in 90 min); stirring in
the presence of TiO2 (500 ppm concentration)
increases degradation to 6.3%
percentage degradation is almost double as
compared to individual techniques,
confirming the release of free radicals due
to dissociation of hydrogen peroxide
rate decreases with an increase in the initial
concentration of pollutant and shows optima
with respect to the catalyst concentration
at 500 ppm; maximum percentage degradation
is observed at 500 ppm catalyst loading and
100 ppm acid initial concentration
results better than the individual techniques
for larger treatment periods; simultaneous
irradiation gives better results as compared
to sequential operation (30% more degradation);
dependency of synergism between the two
techniques on time of operation, more synergistic
at higher treatment times
best treatment approach with maximum
percentage degradation achieved as 55%
in 90 min of treatment time; more enhanced
generation of free radicals due to faster
dissociation of hydrogen peroxide under the
combined action of ultrasound and UV light
is a strong function of the pollutant studied and also of
the reaction conditions.
Thus, it has been conclusively established that the
hybrid technique of sonophotochemical destruction along
with the addition of hydrogen peroxide as a source of
hydroxyl radicals gives excellent results as compared
to individual techniques. Table 1 gives at a glance a look
at the various results obtained in the work and helps
the comparison of the different approaches used in the
study.
5. Conclusions
Destruction of formic acid was found to be more for
the operation with multiple frequencies for US irradia-
tion alone as compared to operation with a single
frequency and was further enhanced by aeration.
Photocatalytic oxidation of formic acid was observed
to increase with an increase in the catalyst concentra-
tion until an optimum value of 500 ppm, whereas a
lower initial concentration of formic acid gives better
results. It must be kept in mind that this optimum
concentration will be different for the hybrid technique.
Net degradation (Ct/C0) has been correlated with these
two parameters, indicating the type of correlations to
be developed using the data available in laboratory-scale
studies, which will then be used in the design of large-
scale reactors.
The common optimum conditions for the two tech-
niques of US irradiation and photocatalytic oxidation
coupled with the similarity in the mechanism of de-
struction and cleaning of photocatalyst due to the
turbulence generated by acoustic streaming make way
for the development of sonophotochemical reactors.
Three important factors, viz., fragmentation of the
catalyst under the action of ultrasound leading to an

increased surface area but at the same time resulting
in more scattering of incident UV and US waves,
cleaning of the fouled catalyst as time proceeds, and
enhancement in the number of free radicals generated,
decide the overall synergism between the two tech-
niques. Initially, fragmentation of the catalyst is the
controlling mechanism, which results in lowering of
degradation rates as compared to the photocatalytic
oxidation alone, but as time progresses, the later two
mechanisms take over, resulting in enhanced degrada-
tion of formic acid. These governing mechanisms have
been conclusively established with an observed in-
creased degradation as soon as the turbulence using
ultrasound is reduced (comparison between 20 kHz and
20 + 30 + 50 kHz operation), lower contribution of
fragmentation for reduced initial concentration of the
catalyst (comparison between 300 and 500 ppm catalyst
concentration), and almost constant percentage degra-
dation at higher time periods in the case of photocata-
lytic oxidation alone indicating fouling of the catalyst.
Moreover, better results with simultaneous operation
as compared to those of the sequential one have also
confirmed that the role of an enhanced amount of free
radicals and continuous cleaning in the reaction period
is crucial.
Addition of hydrogen peroxide increases the extent
of degradation because of the enhanced dissociation of
hydrogen peroxide into hydroxyl radicals under the
action of US and UV irradiation. In the present work,
although it has been observed that the increase is
continuous in the range of 0.1-0.5 mL/L loading, it must
be kept in mind that addition of large quantities of
hydrogen peroxide results in detrimental effects, pos-
sibly because of the recombination of free radicals with
hydrogen peroxide. The optimum value is strongly
dependent on the operating conditions (frequency of
irradiation as well as total power input by both US
transducers and UV irradiation), which decides the rate
of formation of free radicals and also the type of
pollutant studied.
Overall, it can be said that a hybrid technique of UV/
US/hydrogen peroxide gives excellent results as com-
pared to all of the individual techniques and the future
research should be concentrated in evaluating the
efficacy of this hybrid method for a variety of pollutants
and, most importantly, for complex mixtures and real
effluents. It should be also kept in mind that the major
factor controlling the overall efficiency of destruction
will be the stability of the photocatalyst under the effect
of ultrasound, and efforts are required in terms of new
designs, which will protect the catalyst but at the same
time will give enhanced effects.
Acknowledgment
Authors acknowledge the funding of the Department
of Science and Technology, New Delhi, India, for the
research work.
Nomenclature
Ct ) concentration of the pollutant at time t, ppm
C0 ) initial concentration of the pollutant, ppm
t ) time of irradiation, min
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Resubmitted for review March 7, 2002
Revised manuscript received March 7, 2002
Accepted May 3, 2002
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