Microchemical Journal 80 (2005) 159 – 164

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Sonochemistry and its dosimetry

Y. Iida*, K. Yasui, T. Tuziuti, M. Sivakumar
Ultrasonic Processing Group, Ceramics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),
Nagoya 463-8560, Japan

Received 22 July 2004; accepted 25 July 2004

Available online 12 October 2004

Abstract

The effects of ultrasound originate primarily in acoustic cavitation. The cavitation bubbles collapse violently enough to lead to
interesting chemical effects, known as sonochemistry. There is a great need to relate the efficiency of sonochemical reaction to the energy
of ultrasonic irradiation used to produce them. In this paper, three OH radical dosimeters, Fricke dosimeter, terephthalate dosimeter, and
iodide dosimeter, are compared from the analytical point of view. The dosimeters based on photometry, i.e., Fricke and iodide, produced
reliable and reproducible results, but the sensitivity is not enough for special applications, such as chemical monitoring of single bubble
cavitation. The dosimeter based on fluorometry, terephthalate dosimeter, offered high sensitivity, 1.2
1011 molecules ml1. The effects of
some experimental parameters in sonochemistry, i.e., solution temperature and the dissolved gas species, were evaluated with the
dosimeters.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Sonochemistry; Ultrasound; Dosimeter; OH radical; Fluorescence

1. Introduction one may envisage a decomposition of H2O into H2 and an O

atom by reaction (2)
Acoustic cavitation, the formation and implosive collapse
H2 OYHd þ dOH ð1Þ
of bubbles, occurs when a liquid is exposed to intense
ultrasound. The collapse of these bubbles can be violent
H2 OYH2 þ O ð2Þ
enough to lead to interesting chemical effects, and the
bubbles act as a localized bhotspotQ generating temperatures At high temperature, reaction (3) can readily occur, and the
of about 4000 K and pressures in excess of 1000 O atoms are largely converted into OH radicals through
atmospheres [1]. Combustion and pyrolysis reactions occur reaction (4).
in the vapor phase of the bubbles, which induces and
Hd þ H2 OYH2 þ dOH ð3Þ
accelerates various chemical reactions, known as sono-
chemistry [2]. The sonochemical synthesis of a wide range
O þ H2 OYdOH þ dOH ð4Þ
of nanostructured materials, including nanometer colloids,
nanoporous high surface area aggregates, and nanostruc- An excess of OH over H radicals will be the result. To a
tured oxide-supported catalysts, has been reported [3]. large extent, these radicals react with one another in the gas
When water is irradiated with ultrasound, OH radicals are phase [4].
formed on thermolysis of H2O in the collapsing bubble
dOH þ dOHYH2 O2 ð5Þ
through reaction (1). Besides this homolytic dissociation,
dOH þ dHYH2 O ð6Þ
* Corresponding author. Tel.: +81 52 911 2309; fax: +81 52 916 6992.
E-mail address: y.iida@aist.go.jp (Y. Iida). dH þ dHYH2 ð7Þ
0026-265X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2004.07.016
160 Y. Iida et al. / Microchemical Journal 80 (2005) 159–164
Because of its relatively low stability at high temperature, a
large part of H2O2 is expected to be produced in the liquid
boundary layer that surrounds the bubble and the later stage
of gas phase reaction when the temperature cooled down to
some extent.
The number of these radicals and chemical species
formed by ultrasonic irradiation will considerately depend
on many experimental parameters such as ultrasonic
power and its frequency [5], solution temperature, amount
of dissolved gas [6], existence of radical scavengers, or
surfactants [7], and ultrasonic coupling from the trans-
ducer to the reactor. There is a great need to relate the
efficiency of sonochemical reaction to the energy of
ultrasonic irradiation used to produce them.
Several methods of monitoring the sonochemical effi-
ciency are available. The input electric power to the
ultrasonic transducers is a simple parameter. However, the
energy conversion efficiency depends on a transducer,
coupling from the transducer to the reactor, which is totally
affected by the geometrical design of the ultrasonic reactor,
such as the separation of the vibration plate and the bottom
of the reactor, shape of reactor, and the height of surface
level of the solution. Measurement of sound pressure with a
hydrophone is useful method. However, the sound pressure
is dependent on the sound field, which is dynamic and
distributed in the vessel in the order of the wavelength of
sound. Calorimetry is often used to specify the ultrasound
power dissipated into the solution. It provides a good
measure to evaluate the mechanical and electrical efficiency
of the sonochemical reactor system.
Chemical dosimetry gives the direct sonochemical
efficiency. In this paper, three dosimeters that are sensitive
to OH radicals and related oxidants, i.e., Fricke dosimeter
[8], terephthalate dosimeter [9–12], and iodide dosimeter
[13 14], are compared from the analytical point of view.
Fig. 1. Picture of the sonochemical reactor.
2. Experimental
Terephthalic acid was purified by recrystallization as a
disodium salt. 2-Hydroxyterephthalic acid was synthesized
according to Ref. [10]. Other chemical reagents were
purchased from Wako and used without further purification.
Ultrasonic irradiation was accomplished with a sonochem-
ical reactor (Honda Electronics, HSR-11-45), which is
composed of a water circulating bath of 15
15
15 cm3
dimension and five units of the bolted Langevin-type
transducers settled at the bottom of the bath. The transducers
were driven by a power amplifier (ENI AP400B) with an
operating frequency of 130 kHz. Sample solution of 300 ml
was contained in a 300-ml Erlenmeyer flask that was
immersed in the bath. The bath temperature was kept at
constant temperature by using an electric temperature
controller. Fig. 1 shows the picture of the sonochemical
reactor.
The ultrasonic power dissipated into the solution was
measured with a standard calorimetry by using the following
relation [2]:
PowerðW Þ ¼ ðdT =dt Þð CwM þ CrÞ
where Cw is the heat capacity of water (4.2 J/g deg), M is the
mass of water (g), Cr is the heat content of the reaction vessel
(J/deg), and (dT/dt) is the temperature rise per second (deg/s).
The power efficiency, obtained by the ultrasonic power
dissipated into solution divided by the input electric power,
was estimated as 36.1% at 130 kHz and at 100 W input
condition.
Three chemical dosimetry solutions were prepared by
following the standard manners. The solutions were
saturated with a desired gas by bubbling them for 30
min.
 Y. Iida et al. / Microchemical Journal 80 (2005) 159–164
2.1. Fricke dosimetry
FeSO4(NH4)2SO4d 6H2O 0.392 g (1.0
103 mol),
96% H2SO4 41.1 g (0.4 mol), and NaCl 0.0585 g
(1.0
103 mol) were dissolved in water. This was then
made up to 1 dm3 with water. The absorbance of Fe3+ at
304 nm (the molar absorptivity e=2197 dm3 mol1 cm1)
was measured by using a UV spectrometer (JASCO,
V-530).
2.2. Iodide dosimetry
KI 16.6 g (0.1 mol) was dissolved in water and made up
to 1 dm3 with water. The absorbance of I3 at 355 nm (the
molar absorptivity e=26300 dm3 mol1 cm1) was meas-
ured with the spectrophotometer.
2.3. Terephthalate dosimetry
Terephthalic acid 0.332 g (2.0
103 mol), NaOH
0.200 g (5.0
103 mol), and phosphate buffer (pH 7.4),
prepared from KH2PO4 0.589 g (4.4
103 mol) and
Na2HPO4 0.981 g (7.0
103 mol). The resulting solution
was then made up to 1 dm3 with water. The standard 2-
hydroxyterephthalic acid solution was prepared in a same
manner. The standard was utilized for the calibration. The
fluorescence of each solution was measured using a
spectrofluorometer (Shimazu RF-1500) with an excitation
wavelength of 315 nm and an emission wavelength of
425 nm.
3. Results and discussion
3.1. Fricke dosimetry
2+
In the Fricke dosimeter, Fe is oxidized by OH radicals
and hydrogen peroxide according to reactions (8) and (9),
and Fe3+ is determined photometrically.
S
OH þ Fe2þ þ Hþ YH2 O þ Fe3þ ð8Þ
H2 O2 þ Fe2þ þ Hþ YH2 O þ Fe3þ þSOH ð9Þ
Thus, G value, which denotes the energy-specific yield with
dimension of mol J1, for the Fricke dosimetry can be
written as
GðFe3þ Þ ¼ GðOHÞF þ 2GðH2 O2 ÞF ð10Þ
Fig. 2 shows the typical results of the Fricke dosimetry
obtained with the effect of dissolved gases. The length of
error bar on the Ar plot was estimated from four repeated
measurements. The higher G value for the argon atmosphere
is mainly explainable its higher temperature attained in the
161
.
Fig. 2. Fricke dosimetry in various gas-saturated solutions. Ar ( ), air (E),
and N2 (n).
collapsing bubbles [15]. The temperature inside the collaps-
ing bubble will be greater for gases with the larger c, the
ratio of specific heats Cp/Cv. The temperature can be
estimated, based on a simple adiabatic compression model,
by the following equation
T ~Aexpð3ðc  1ÞÞ
and c=1.67 for monoatomic Ar, 1.40 for diatomic N2 and
O2, and 1.33 for triatomic H2O molecules [16]. In addition,
water vapor and the bimolecular gases are dissociated inside
a collapsing bubble, and the bubble is considerably cooled
by the endothermal heat of dissociation [17].
With the oxygen gas, oxidant other than OH radicals can
be formed in the bubble as indicated in the following
reactions
O 2 YS O þ S O ð11Þ
H þ O2 Y HO2 S
ð12Þ
and HO2 radicals formed by reaction (12) can then oxidize
Fe2+
S
HO2 þ Fe2þ þ Hþ YH2 O2 þ Fe3þ ð13Þ
Therefore, the contribution of d HO2 could be added to
G(Fe3+) as 3G(d HO2) in reaction (10). The difference
between the results obtained in the presence of N2 and in O2
can be attributed to these effects. However, its amount is not
so significant in the experimental condition comparing with
the effects of Ar, as shown in Fig. 2.
The other noticeable feature that can be observed from
Fig. 2 is the gradual decrease of G value from linearity
along with the progress of sonication. This trend can be
explained by the degassing effect by the ultrasound, which
means that the dissolved gases were expelled by the
action of ultrasonic agitation. For example, air-saturated
water can be 50% degassed by sonicating the solution for
30 min.
162 Y. Iida et al. / Microchemical Journal 80 (2005) 159–164

The typical G value obtained for the Fricke dosimetry out in the air-saturated condition. The gradual decrease of
was G(Fe3+)=12.7
1010 mol J1 at 20 8C, air-saturated absorbance in an alkaline solution, ca. above pH 8, is caused
condition, with ultrasonic irradiation of 130 kHz and at 100 by the reaction where the products, i.e., H2O2 and I3, react
W input power. in this pH region [14].

3.2. Iodide dosimetry H 2 O 2 þ I 

3 Y3I þ O2 þ 2H
þ
ð21Þ

In this dosimetry, the generated OH radicals oxidize iodide Whereas, in acidic solution, the iodide ions are oxidized by
ion, giving rise to an iodine atom. This forms a complex with oxygen gas by the following reaction
an iodide ion; the I2 radicals decay, yielding iodine, which
forms the I3 complex by reacting with iodide. I3 is the 2Hþ þ 2I þ 1=2O2 YI2 þ H2 O ð22Þ
species that is monitored in this series of reactions [13].
OH þ I YOH þ I ð14Þ Therefore, the iodide dosimetry should be carried out in a
 relatively limited pH range, i.e., from 4 to 7. Gutierrez et al.
IþI YI
2 ð15Þ
[14] suggested the application of phosphate buffer to keep
2I
2 YI2 þ 2I

ð16Þ the solution at pH 5.9. Fortunately, the solution made by KI
 dissolved in distilled water without pH control falls into this
I2 þ I YI
3 ð17Þ
pH range, as shown by the data points surrounded by an
The G value of the iodide dosimetry can be written as ellipse in Fig. 3.
The typical G value obtained for iodide dosimetry was
GðI
3 Þ ¼ 1=2GðOHÞI ð18Þ
G(I3)=5.5
1010 mol J1 at the same conditions men-
Hydrogen peroxide produced during sonication through tioned in the Fricke dosimetry.
reaction (5) reacts very slowly with iodide ion. However,
with molybdate ions that act as a catalyst, reaction (19) 3.3. Terephthalate dosimetry
proceeds rapidly [18].
H2 O2 þ 2I þ 2Hþ YI2 þ 2H2 O ð19Þ In an alkaline aqueous solution, terephthalic acid
produces terephthalate anions that react with hydroxyl
This feature allows the OH radical yield as well as the H2O2 radicals to generate highly fluorescent 2-hydroxytereph-
yield to be determined from the same sample. The modified G thalate ions (HTA). The mechanism that leads to this
value with molybdate including the H2O2 contribution can be product is complex, which has been elucidated by Mark et
written as al. [12]. The key aspects of this dosimetry are shown in
GðI
3 Þm ¼ 1=2GðOHÞI þ GðH2 O2 ÞI ð20Þ the following scheme. The OH radicals add preferentially
in the 2-position at an almost diffusion-controlled rate
Fig. 3 shows the pH dependence of the observed (reaction (23)). Reaction (24) is rather slow
absorbance value of I3 after the sonication of 200 s carried

and can be accelerated by the reaction in presence of an

oxidant. Mark et al. [12] have used IrCl6 as a potent
oxidant for this purpose. The G value of the terephthalate
dosimetry can be written as

GðHTAÞ ¼ GðOHÞT ð25Þ

Fig. 4a and b shows the effect of temperature on the

.
Fig. 3. Effects of pH on the iodide dosimetry, with (o) and without ( )
molybdate catalyst. The data plots surrounded by an ellipse were obtained
without pH control.
fluorescence intensity obtained in Ar-saturated condition,
Fig. 4a without oxidant and Fig. 4b with an oxidant IrCl6.
In general, sonochemical reactions are accelerated in lower
temperature, as opposed to the usual chemical reactions.
The reasons for these curious trends can be explained as
follows [17]. The degree of heating of the bubble contents
will be less with rising temperature since the proportion of
 Y. Iida et al. / Microchemical Journal 80 (2005) 159–164
Fig. 4. Effects of temperature on the terephthalate dosimetry, without (a)
and with (b) an oxidant IrCl .
6 at 10 8C ( ), 20 8C (E), and 30 8C
(n).
water vapor increases with increasing temperature and
therefore the value of c=Cp/Cv of the vapor mixture
decreases. In Fig. 4a, the sonochemical trends in temper-
ature effects were reversed between 20 and 30 8C. The
results seem to be caused by the slow chemical reaction (24)
was accelerated thermally, as in the usual chemical reaction.
With the addition of the oxidant IrCl6 (2.0
104 mol
dm3), this trend switched into a normal sonochemical
order, 30 8Cb20 8Cb10 8C, as shown in Fig. 4b. Also, the
observed fluorescence intensities were increased by 2–3
times. It should be mentioned about the breakage of linearity
by the progress of reaction in the case with IrCl6. It was
noticed by the naked eye that the brown color of IrCl6
disappeared after 10–15 min. It means that colored IrCl6
was effectively reduced by the action of ultrasound, as in the
case of the nano precious metal particle deposition. The
IrCl6 concentration should be higher or the time of
sonication should be within 10 min.
163
The G value obtained for the terephthalate dosimetry
without oxidant was G(TPA)=0.5
1010 mol J1 at the
same conditions mentioned in the Fricke dosimetry.
3.4. Comparison of three dosimeters
The G value of the Fricke dosimetry G(Fe3+)=12.7
1010
mol J1 was in good agreement with the G value of the iodide
dosimetry G(I3)=5.5
1010 mol J1 from the following
calculation. G(I3)m=7.2
1010 mol J1 from the data shown
in Fig. 2. The G(Fe3+) value estimated from the iodide
dosimetry should be
GðFe3þ Þestimated ¼ GðOHÞ þ 2GðH2 O2 Þ
¼ 2
GðI  
3 Þþ 2
ðGðI3 Þm  GðI3 ÞÞ
and
GðFe3þ Þestimated ¼ 14:4
1010 molJ1 :
On the other hand, the terephthalate dosimetry yielded a
lower G value, G(TPA)=0.5
1010 mol J1. If one adds an
oxidant in the test solution, the G value increases about
three times, as shown in Fig. 4a and b. Therefore, the
difference should be, in part, attributable to the low yield of
2-hydroxyterephthalate from hydroxycyclohexadienyl-type
radicals (reaction (24)). The same tendencies were reported
in the literature where the G values of the Fricke dosimetry
and the terephthalate dosimetry were compared [14]. In
other words, the trapping efficiencies of OH radicals by the
dosimeter chemical reactions are different in the following
order.
GðOHÞF cGðOHÞI NGðOHÞT ð26Þ
3.5. Detection limit and stability
The stabilities of the dosimeters for air bubbling were
checked by long-term, 25-h, bubbling experiments.
Iodide and terephthalate dosimeters were stable and no
signal increase over detection limit was observed in both
cases. For Fricke dosimeter, the absorbance increase of
0.0008 was observed for 40-h bubbling, just around the
detection limit. From these results, the dosimeters are
stable enough for the air bubbling of sonochemical
experiment.
The detection limits for the dosimeters based on the
photometry was calculated from the fluctuation of absorb-
ance 3r=0.001 and the molar absorptivity e=26300 for I3 in
the iodide dosimetry and e=2197 for Fe3+ in the Fricke
dosimetry. The detection limit was 3.8
1011 mol ml1
(2.3
1013 molecules ml1) for the iodide dosimeter and
4.6
1010 mol ml1 (2.7
1014 molecules ml1) for the
Fricke dosimeter, respectively.
The detection limits of the terephthalate dosimeter
based on fluorometry were estimated from the following
164 Y. Iida et al. / Microchemical Journal 80 (2005) 159–164
data; the fluctuation of background emission, 3r=0.3
counts at the background level of 4.8 counts, the
fluorescence intensity of 348 counts at 2.39
107 mol
dm3 of 2-hydroxyterephtalate. The detection limit for the
terephthalate dosimeter was estimated as 2.1
1013 mol
ml1 (1.2
1011 molecules ml1).
Didenko and Suslick [19] have reported a number of OH
radicals produced in single bubble cavitation using tereph-
thalate dosimetry. The typical number was 6.6
105 OH
radicals (15 ml cycle)1 at 52 kHz. It equals to 2.3
109
radicals ml1 s1. From the detection limits estimated
above, about 1-min irradiation was necessary to exceed the
detection limit of terephthalate dosimetry. On the other
hand, at least 170 min is necessary for the iodide dosimeter.
It is clear that such a trace measurement of OH radicals is
fully benefited by its high sensitivity of terephthalate
dosimetry.
Acknowledgement
This work was supported by Industrial Technology
Research Grant Program in ’02 to ’03 from New Energy
and Industrial Technology Development Organization
(NEDO) of Japan.
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