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High Energy Chemistry, Vol. 38, No. 3, 2004, pp. 135–142. Translated from Khimiya Vysokikh Energii, Vol.

38, No. 3, 2004, pp. 163–170.


Original Russian Text Copyright © 2004 by Margulis.

REVIEWS

Sonochemistry as a New Promising Area


of High Energy Chemistry
M. A. Margulis1
Andreev Institute of Acoustics, State Research Center, ul. Shvernika 4, Moscow, 107005 Russia
Received March 26, 2002

Abstract—Sonochemistry is one of the most intensively developing areas of high energy chemistry in both the-
oretical and applied aspects. There has been considerable progress in sonochemistry: many sonochemical reac-
tions in nonaqueous systems were revealed, power yields for some sonochemical reactions and the initial power
yields of ultrasonic degradation of water were determined, single-bubble sonoluminescence was discovered, the
formation of radicals in an ultrasound field was detected by spin trapping, a method for the generation of pow-
erful low-frequency (of the order of 10–200 Hz) cavitation fields was developed and chemical and physico-
chemical effects in these fields were revealed, high-performance hydrodynamic apparatus were designed and
sonoluminescence and chemical effects were observed in such systems, ultrasound-induced oscillating reac-
tions were discovered, and the generalized electric theory of cavitation processes was elaborated.

1 Among the traditional high-energy chemistry areas rise and chemical effects in such systems were
of principal theoretical and practical importance [1], observed [17], ultrasound-induced oscillating reactions
such as radiation chemistry, plasma chemistry, photo- were discovered [18–20], and the theory of local elec-
chemistry, and laser chemistry, sonochemistry occupies trization was elaborated and generalized for cavitation
a special place as it studies the chemical and physico- processes [21–23]. Another interesting and promising
chemical processes induced by acoustic vibrations in a line of research is the detection of acoustic emission,
medium. which arises in solids under mechanical strain, as well
The chemical effect of ionizing radiation [2] was as upon crack nucleation and propagation [24].
discovered shortly before that of ultrasound [3]; how-
ever, many scientists, not to mention general public,
either have never heard or have a very vague idea of this ENERGETICS OF SONOCHEMICAL
subject. REACTIONS
During the two last decades, five comprehensive
books [4–8] on the issue and hundreds of scientific Only such energy of acoustic vibration as is
papers have been published and eleven international absorbed by a system is sonochemically active [5]. In
conferences on the chemical effects of ultrasound photochemistry, this statement is equivalent to the
(including those of the European Sonochemical Soci- Grotthus–Draper law according to which only
ety) have been held; there is also the international jour- absorbed light is photochemically effective. A part of
nal Ultrasonics Sonochemistry. light flux energy that has not been absorbed by the sys-
tem is not taken into account in calculation. In radioly-
Note the most important advances that enabled con- sis, the power yield is referred to 100 eV of absorbed
siderable progress in this area: many sonochemical energy. In energy calculations in sonochemistry, it is
reactions were found to occur in nonaqueous systems, also reasonable to take into account not all acoustic
power yields for some sonochemical reactions and the energy E input to a solution but only its small portion
initial power yields of ultrasonic degradation of water consumed for the formation of radicals, the chemicoa-
molecules were determined [5], the single-bubble coustic energy Eca. In this connection, by analogy with
sonoluminescence (SL) was discovered [9–12] and the
reason for its difference from multibubble SL was the- radiolysis, we introduced the concept of power yield
oretically substantiated [13, 14], the formation of free F(Y) of a sonochemical-reaction participant Y produced
radicals in an ultrasound field was detected by spin (or disappeared) per 100 eV of Eca [4]. Since it was pos-
trapping [15], a method for generating powerful low- sible to successively consider radical recombination in
frequency (of the order of 10–200 Hz) cavitation fields the cavitation bubble and reaction in the liquid with sol-
was developed [16] and chemical and physicochemical utes, the concept of the initial power yield of the prod-
effects in these fields were revealed [5], high-perfor- uct Y of sonochemical degradation of solvent (water)
mance hydrodynamic apparatus were designed and SL molecules formed per 100 eV of Eca disregarding sec-
ondary reactions in solution, FY , was advanced. The ini-
1 E-mail: margulis@akin.ru tial power yields, the radical recombination factors

0018-1439/04/3803-0135 © 2004 MAIK “Nauka /Interperiodica”


136 MARGULIS

Initial power yields, chemicoacoustic efficiencies,* and radical recombination factors** [5]

FH F HO2 FOH F H2 F H'' 2 O2 F H' 2 O2 F H2 O2 F -H2 O


Gas ηca × 103 βH βOH
molecule (or radical)/100 eV of Eca
Ar 1.5 0.13 – 0.11 1.46 – – 1.47 3.05 11.2 13.4
He 0.22 0.22 – 0.18 1.44 – – 1.46 3.10 6.5 8.1
O2 0.98 – 0.52 1.08 – 1.45 1.17 2.62 3.42 2.8 1.1
* The chemicoacoustic efficiency is defined by ηca ≡ Eca /E.
'' O and F H
** F H ' O are the initial yields of H2O2 produced by the recombination of radicals HO2 and OH, respectively.
2 2 2 2

βH ≡ F H2 /FH and βOH ≡ F H2 O2 /FOH, and the chemicoa- at t = tβ and the radical recombination factor βR ≡
coustic efficiencies in the sonolysis of water and aque- F R2 /FR is obtained. Here, the time tβ is determined by
ous solution in an Ar, He, or O2 atmosphere were the half-width of radical distribution (simplifying con-
obtained (table) [5]. dition for indistinguishable radicals):
bβ = 4Dtβ.
ULTRASONIC ENERGY COMPARED In [27] the following equation was derived for the
WITH OTHER PHYSICAL IMPACTS ON MATTER Gaussian distribution of radicals with initial and final
Considering in the general form the reaction kinet- half-widths b0 and bβ, respectively, at which the radical
ics of radicals produced in an ultrasound field, it is nec- recombination factor β is attained:
essary to take into account the pulse character of their N 0 σ0 bβ – b0
generation and their inhomogeneous distribution in the β = -----------------------
3/2
---------------- ,
bulk. True, local concentrations of radicals significantly 2 ( 8π ) λ b β b 0
exceed the average concentrations. In the core of a cav- where λ is the mean free path of a particle.
itation bubble, the concentration of electrons upon elec-
tric breakdown can be high enough and, thus, can lead This equation can be applied not only to sonochem-
to the formation of both hydrated and “dry” electrons ical reactions but also to studying radiation-chemical,
[5]. A comparative study on the sonolysis and radioly- mechanochemical, and other high-energy chemistry
sis of aqueous solutions was reported in [25, 26]. processes when the initial amount of active species in
the energy deposition region, as well as the half-widths
The radical recombination factor β is a fundamental b0 and bβ of their distribution (or at least the ratio bβ/b0),
characteristic of any type of radiation and a generalized can be estimated. The evaluation of β gave β ≈ 10,
parameter suitable for comparing ultrasound waves which is close enough to the experimental values of βH
with other nonthermal methods of impact on matter. and βOH in an Ar or He atmosphere [5] (see table).
This factor depends on the energy density, the size of its
localization region, the overall number and concentra- The minimal size of the mean cavitation bubble and
tion of produced species, and their spatial distribution, the initial number of particles in this bubble, N0 ≈ 104–
as well as on the physicochemical parameters of the 106, are respectively many orders of magnitude greater
energy release region. In moderate sound fields, the than the dimensions of spurs produced by ionizing radi-
steady-state number density of bubbles oscillating dur- ation and the number of radicals in each spur (e.g., N0 ≤
ing a wave period in 1 cm3 is of the order of 103– 10 under radiolysis [28]) and, moreover, the number of
104 cm–3. The mean distance between neighboring bub- radicals in the “cage” upon photolysis. Figure 1 shows
bles is at least 〈l〉 = 10–2 cm. The time tl taken by the rad- the recombination factors βç and βéç for H and OH
icals to diffuse over a distance 〈l〉 is 〈l〉2/2D (where D is radicals, respectively, as a function of linear energy
the diffusion coefficient). Since tl ≈ 0.5 s  T0 (where transfer ∂E/∂x for different types of ionizing radiation
T0 is the acoustic vibration period), each imploding and includes corresponding data obtained upon US cav-
itation in Ar- and He-saturated water [5]. In terms of the
cavitation bubble and a small volume of liquid with a radical distribution density, ultrasonic cavitation
radius of ρ  〈l〉 that surrounds this bubble may be con- approaches the effect of particulate radiation produced
sidered an isolated region and interactions between rad- in the nuclear reaction
icals produced in neighboring bubble may be ignored.
10B + n 7Li + 4He,
To determine β, we considered the probability of
recombination and diffusion of radicals [27]. In the in which the recoil Li atoms and α-particles separate
presence of a solute with a spherically symmetric dis- with a mean energy of 2.35 MeV (where ∂E/∂x ≈
tribution with respect to the bubble center, the curves 200 eV/nm)), or that of 210Po α-particles but greatly
describing the radical and solute concentration overlap differs from the effect of β-, γ-, and X-rays (∂E/∂x ≈

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


SONOCHEMISTRY AS A NEW PROMISING AREA 137

0.2–2 eV/nm). Like the effect of heavy particles, ultra- logβ


sonic cavitation is also characterized by a high density βH βOH
of energy concentration. With a decrease in the ioniza- 6'
tion and excitation energies of inert gases, the concen-
tration of radicals in a cavitation bubble increases as a 8' 8
1 6
result of excitation transfer and charge exchange;
hence, β(Ar) > β(He). Therefore, it may be expected that 7' 7
βç and βéç will increase through the series He, Ne, Ar,
5'
Kr, Xe, Rn.
5

THE SPECIFICS OF INDUSTRIAL APPLICATION


OF HIGH-POWER ULTRASOUND 4
Unlike the case of radiation-chemical and photo- 0
chemical processes, sonochemistry is free of radioac- 3
tive waste management and radiation protection prob-
lems and does not require the use of light-transparent 2
4'
materials, respectively. Sonochemical processes can be
conducted in reactors made from any engineering mate- 1 3'
rials—in the continuous mode, under pressure, at high
temperatures, etc. In addition, high-intensity cavitation
fields can be created by mechanical or hydrodynamic 2'
means. For some processes, the generator of low-fre- 1'
quency acoustic vibrations in the audio and subsonic
–1 0 1 logdE/dx, [eV/nm]
range (10–200 Hz) that we have designed recently [29]
holds good promise. In the case of low-frequency cavi-
Fig. 1. The logarithmic plot of the recombination factors for
tation, there is no need to use powerful ultrasonic gen- H and OH radicals versus the LET value ∂E/∂x of ionizing
erators and transducers with a high unit power. Low- radiations: (1, 1') γ-radiation, (2, 2') X-rays, (3, 3') deuter-
frequency transducers are nonresonant sources, so that ons, (4, 4') helium ions, (5, 5') 210Po α-particles, (6, 6') B(n,
tunable acoustic vibrations can be generated by their α) recoil particles, and ultrasonic waves in (7, 7') a helium
means (unlike the case of magnetostrictive or piezo- and (8, 8') an argon atmosphere.
electric devices). For such transducers, there is virtually
no limit on the reactor capacity.
of nitrogen oxides upon sonication of water containing
dissolved air or sonolysis of water containing dissolved
CLASSIFICATION OF SONOCHEMICAL ëç3ëééç and nitrogen, etc.). The mechanism of cer-
REACTIONS tain steps of these reactions is similar to that of gas-
phase radiolysis [33].
There are many reactions that significantly change
their rate and product composition under ultrasonic (3) Chain reactions in solution initiated by a sub-
radiation; however, they can proceed without sonica- stance that dissociates in the cavitation bubble (not by
tion (e.g., catalytic oxidation of SO2 [30], oxidation of radical products of water degradation); e.g., the bro-
carboxymethylcellulose [26], etc.). The reasons for mine- or alkyl bromide-initiated isomerization reaction
their strong acceleration are not always understandable; of maleic acid and its esters to fumaric acid.
nonetheless, the chemical effect of ultrasound cannot (4) Reactions involving macromolecules (e.g., deg-
be reduced only to transition to the kinetic region [5]. radation of polymer molecules and induced polymer-
Another group of sonochemical reactions includes the ization by this degradation); these processes resemble
processes that cannot proceed at all without sonication in many respects mechanically initiated or radiation-
Eca. Depending on the mechanism, these reactions can induced polymerization.
be arbitrarily subdivided into the following classes [5]. (5) Initiation of ultrasonic explosion in liquid or
(1) Oxidation–reduction reactions in water occur- solid explosives (e.g., explosions in NI3, tetrani-
ring in the liquid phase between solutes and the prod- tromethane, trinitrotoluene, etc.).
ucts of ultrasonic breakdown of water molecules, (6) Sonochemical reactions in nonaqueous systems.
which are generated in the cavitation bubble and diffuse Until 1963, it was believed that the sonochemical
into solution (the mechanism of sonication effect is reactions could occur only in aqueous solutions, since
indirect [4], as in the case of radiolysis of aqueous sys- “water is the most favorable and unique medium for
tems [31, 32]). radical generation in cavitation fields” [34]. After first
(2) Reactions inside the bubble between dissolved successful works on sonochemistry of nonaqueous sys-
gases and high-vapor-pressure solutes (e.g., synthesis tems [35] (or water-containing systems where the for-

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


138 MARGULIS

% In anhydrous ethylene glycol, peroxide compounds are


100 produced upon sonication at 0°ë in an oxygen atmo-
2 sphere (thermal reactions can be ignored under these
conditions). This reaction did not take place upon the
sonolysis of ethylene glycol in an argon medium.
Detailed determination of methanol sonolysis products
is reported in [46, 47].
Degradation and dimerization of alkyl halides.
60 The ultrasonic treatment of both aqueous solutions and
dry alkyl halides results in the release of halogen atoms.
The release of iodine was observed upon the sonication
of a CHI3 solution in carbon tetrachloride [48], the
addition of dry kaolin sharply increasing the I2 forma-
tion rate. The mechanism of these catalytic effects is
still unclear.
20 Reactions of halogenated derivatives with metals
(Wurtz reaction). When exposed to an ultrasonic field,
1 3 many halogenated organic compounds in the presence
of alkali metals form dimers at a high rate under mild
100 300 500 t, min conditions [49, 50]:
(Li)
Fig. 2. Time dependence for (1) the MePhSiCl2 concentra- RX ))) R–R + LiX,
tion and for the yield of (2) cyclic pentamer and (3) linear
oligomer in toluene in an ultrasonic bath; The sodium where R is alkyl, aryl, benzyl, or benzoyl. It was shown
excess was 50%. [49] that the reaction of Me2Cl2Si or MePhCl2Si with
an Li suspension in mineral oil was considerably
enhanced by ultrasound waves. The products of the
mation of H and OH radicals does not play a significant reaction were linear or cyclic oligomers:
role), the number of publications on sonochemistry of
nonaqueous systems continuously increases. R2
+Li
R1R2SiCl2 ))) ( Si )n + LiCl,
SOME SONOCHEMICAL REACTIONS R1
IN NONAQUEOUS SYSTEMS Ph Ph
Sonochemical reactions in nonaqueous systems are Si Si
Me Me
discussed in detail in the book [8]. Let us consider only Li Ph Ph
some results of theoretical and practical interest. MePhSiCl2 ))) Si Si + LiCl.
Me Me
Pyrolysis [36] and oxidation [37] of saturated Si
hydrocarbons are processes with the highest power Me Me
consumption. In the sonolysis of alkanes under argon,
the principal products were found to be H2, CH4, C2H2, The sonolysis of dialkydichlorosilanes in a tetrahy-
drofuran solution in the presence of sodium gives poly-
C2H4, and C3H6. The same products were formed dur-
organosilanes in a high yield and polymers [51]:
ing pyrolysis [38], electric-discharge treatment [39],
vacuum UV irradiation [40], radiolysis [41], and shock R' R'
wave treatment [42]. The oxidation of some aromatic +Na
Cl Si Cl ))) ( Si )n.
hydrocarbons is enhanced by ultrasound; for example,
the yield of indanone in the oxidation of indan increases R'' R''
from 22 to 78% under certain conditions [43]. In a more close study of the reaction of MePhCl2Si
Oxidation of aliphatic aldehydes proceeds at a with alkali metals, we revealed an interesting effect [52,
substantially higher rate in an ultrasonic field; the selec- 53]: the emergence of a lasting oscillatory reaction
tivity of the reaction of aldehydes that are difficult to with a period of 200 min, which was initiated by ultra-
oxidize increases [44]. sound waves (Fig. 2). In the MePhCl2Si–Na–toluene
Oxidation of alcohols with KMnO4 is accelerated system, the formation of cyclic oligomers and linear
by a factor of 25–40 in an ultrasonic field2 [45]: polymer is observed, where their interconversion
occurs at a certain sonolysis time and methylphenylcy-
OH O clopentasilanes are produced under fairly long sonica-
KMnO4
CH3(CH2)5 CH CH3 ))) CH3(CH2)5 C CH3. tion (Fig. 2). In the absence of ultrasound, the conven-
tional slow parallel reactions of the formation of linear
2 The sign ))) symbolizes the chemical action of ultrasound. polymers proceed to give cyclic oligomers in a low

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


SONOCHEMISTRY AS A NEW PROMISING AREA 139

yield: the oscillating reaction is initiated by ultrasound and magnesium organometallic compounds from vari-
waves. Along with these long-term oscillatory reac- ous alkyl halides:
tions, interesting sonochemical and resonant effects RX + Li RLi + LiX,
[54] were revealed in Belousov–Zhabotinskii oscillat-
ing systems [55]. Further investigation of reactions of RX + Mg RMgX.
this type probably will allow oscillating processes to be When a synthesis reaction is carried out in an ultra-
classified with the seventh group (see the preceding sonic field, there is no need to thoroughly dry and
section). purify the solvent and to use initiator additives, the
Alkylation of aromatic compounds. Various alkyl induction period is strongly shortened, and the process
halides in the presence of an alkali and a phase-transfer becomes safe and reproducible. Ultrasonic waves sub-
catalyst are able to N-alkylate diphenylamine [56] or stantially accelerate and increase the yield of reactions
other aromatic amines at a low rate [57]. Ultrasound of direct synthesis of Al, Zn, Pd, Ga, and other metal
waves increase the rate of these reactions by one or compounds [62–64]; e.g.,
more orders of magnitude [57]. Reacting with various RHal + Al R3AlHal3,
phenols, alkyl halides alkylate the aromatic ring. How-
ever, it was shown [58] that O-alkylation took place in Br + Al ))) Al2Br3.
an ultrasonic field: 3
OH OPr The organic lithium and magnesium compounds
Me Me Me Me obtained can be isolated as desired products and be
PrI/K2CO3 used in various Grignard syntheses. These organome-
)))
tallic compounds can also be used in situ (without iso-
lation). When an alkyl halide is reacted with lithium
Preparation of thioamides and thiocarbamates. and a carbonyl compound (Barbier reaction), the orga-
Thioamides are an interesting class of organic com- nometallic compound is first produced, which rapidly
pounds and are used in many organic syntheses. They reacts with an aldehyde or ketone, and subsequent
are obtained by heating a corresponding amide with hydrolysis yields the corresponding alcohol:
excess P4S10:
R' R' OLi H2O R' OH
RLi + CO ))) C C ,
RCONH2 + P4S10 RCSNH2 + P2O5. R'' R'' R LiOH
R'' R
These reactions take a long time and require a large where R, R', and R" are various alkyls or aryls. The
excess of P4S10 and elevated temperature. The reaction Barbier reaction of allyl or vinyl bromide proceeds
is strongly accelerated by ultrasonic treatment [59]. smoothly and with a high yield; although the formation
of an organic lithium compound with them is not easy
Thiocarbamine acid esters (thiocarbamates) pre- [65]. Side reactions (reduction, enolization, etc.) are
pared by the reaction of salts with alkyl halides have reduced to minimum.
progressively widening application as herbicides. The
reaction slowly proceeds with certain alkyl halides, and The organic Li and Mg compounds RM produced in
temperature elevation is needed. However, salts of thio- an ultrasonic field can rapidly and selectively react in
carbamic acids are thermally unstable, and a yield situ with dimethylformamide in the Bouveault reac-
greater than 50–60% is usually unattainable. We have tion [65] yielding aldehydes or dialdehydes related to
shown [60] that the reaction rate is dramatically the starting alkyl halides:
increased (approximately by a factor of 100) by expo- OLi H+
sure to ultrasound waves: RM + Me2NCHO ))) CO
R
O O
RCHO + NMe2H.
N C SNa + RCl ))) N C SR + NaCl,
Ullmann reaction is strongly accelerated by the
action of ultrasonic waves, and the yield of correspond-
where R is alkyl. The selective acceleration of the ing biphenyl derivatives increases. For example, the
desired reaction in an ultrasound field makes it possible rate of 2,2'-dinitrobiphenyl formation in the reactions
to obtain the product in a quantitative yield and to elim-
inate the product isolation and purification steps. Note NO2 NO2 NO2
that the decomposition products of the starting salt
+Cu
make up to 33% in the 3-h reaction in the absence of I ))) + CuI2
ultrasound.
Synthesis of organometallic compounds. It was increases approximately by a factor of 50 [66] and the
shown [61] that sonication made it possible to signifi- yield reaches 81% against 1.5% under intense mechan-
cantly improve the process of preparation of lithium ical stirring in the absence of ultrasound.

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


140 MARGULIS

Cycloaddition reactions are quite various, many of R(f)I + Zn CuI


))) [R(f)ZnI]
them can be enhanced to increase the product yield. For
example, the yield of the following reactions in an RC≡CH H+
ultrasonic field ))) [R(f)CuZnI] R(f)CH=CHR,
Br CH2 HC Ar Ar where R(f) is the perfluorinated alkyl radical. Such reac-
Zn/I2
O C OEt + N Ar' ))) O N Ar' tions do not proceed at all in the absence of ultrasound.
The number of known ultrasound-induced reactions of
can reach 70–95% [67]. perfluoroalkyl compounds is very great.
Halogen exchange reactions are also induced by
ultrasound. For example, Carbene syntheses usually involve the generation
of the carbene radicals :ëH2 or :CCl2. Their formation
HO
RHal + NaN3 2 ))) RN3 + NaHal, is enhanced by sonication, and they smoothly react with
unsaturated compounds [71]:
where RX is alkyl chloride, alkyl halide, or chloroace-
tonitrile. In the absence of ultrasound, the reaction does R R'
not proceed. The following exchange reaction was :CCl2 + R CH CHR' .
found to be strongly accelerated [68]:
Cl Cl
(R ' N) SO
RHal + KSCN 4 2 4 ))) RSCN + KHal. In [72], we gave an example of preparing a more
The reactions of perfluoroalkyl iodides with a zinc sophisticated set of products via the Simmons–Smith
powder and CuI yields perfluoroalkyl cuprates, which reaction in an ultrasound field. The following products
smoothly react with alkynes [69, 70]: were obtained from vinylidenecyclopropane:

= +
+Zn/Cu
= • = + CH2I2 )))

CH3
I CH2CH
OEt

Nitrile synthesis in an ultrasound field was studied ratory scale experiments long ago; their results are
by Ando et al. [73]. They showed that acyl cyanides or being widely applied in industry.
their dimers were produced in a high yield:
O ACKNOWLEDGMENTS
RCOCl + KCN ))) RC + KCl,
CN
The author is grateful to L.T. Bugaenko for the fruit-
O O CN ful discussions.
2RC ))) RC O C R. This work was supported by the Russian Foundation
for Basic Research, project nos. 02-02-16397A and 03-
CN CN
02-16232, and the International Scientific and Techni-
There are also many other chemical reactions that cal Center, project no. 1471.
are initiated or strongly accelerated in ultrasound fields;
however, their mechanism is basically not understood.
There is also no answer to the fundamental question: REFERENCES
what are particular reactions in nonaqueous media that 1. Pikaev, A.K., Abstracts of Papers, 1 Vserossiiskaya kon-
can be in principle enhanced by ultrasound. Unlike ferentsiya po prikladnym aspektam khimii vysokikh
other processes of high-energy chemistry, the chemical energii (1st All-Russian Conf. on Applied Aspects of
effect of ultrasound waves is more versatile and com- High Energy Chemistry), Moscow, 2001, p. 54.
plex. Many problems await their solution, although 2. Kailan, A., Monatsh. Chem., 1912, vol. 33, p. 71.
there are many processing units that make use of power 3. Richards, W.T. and Loomis, A.L., J. Am. Chem. Soc.,
ultrasound. Within the scope of the present review, it is 1927, vol. 49, p. 3086.
impossible to cover even briefly the aspects of indus- 4. Margulis, M.A., Osnovy zvukokhimii (Fundamentals of
trial application of ultrasound; an interested reader is Acoustic Chemistry), Moscow: Vysshaya Shkola, 1984,
referred to relevant books, e.g. [5, 8]. However, the p. 288.
potential of application of ultrasound in industrial 5. Margulis, M.A., Zvukokhimicheskie reaktsii i sono-
chemistry, medicine, agriculture is far from being lyuminestsentsiya (Sonochemical Reactions and Sonolu-
exhausted. Experimental studies went beyond the labo- minescence), Moscow: Khimiya, 1986, p. 286.

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


SONOCHEMISTRY AS A NEW PROMISING AREA 141

6. Mason, T.J. and Lorimer, J.Ph., Sonochemistry: Theory, 32. Bugaenko, L.T. and Kabakchi, S.A., Metod statsionar-
Application and Uses of Ultrasound in Chemistry, Lon- nykh kontsentratsii v radiatsionnoi khimii (Steady-State
don: Ellis Harwood, 1988. Treatment in Radiation Chemistry), Moscow: Mosk.
7. Ultrasound, Its Chemical, Physical, and Biological Gos. Univ., 1971, p. 101.
Effects, Suslick, K.S., Ed., New York: VCH, 1988. 33. Pshezhetskii, S.Ya., Mekhanizm radiatsionno-khimiches-
8. Margulis, M.A., Sonochemistry and Cavitation, London: kikh reaktsii (Mechanism of Radiation-Chemical Reac-
Gordon and Breach, 1996, p. 543. tions), Moscow: Goskhimizdat, 1962.
9. Gaitan, D.F., Crum, L.A., Churh, C.C., and Roy, R.A., 34. El’piner, I.E., Ul’trazvuk. Fiziko-khimicheskoe i biolog-
J. Acoust. Soc. Am., 1992, vol. 91, no. 6, p. 3166. icheskoe deistvie (Ultrasound. Physicochemical and
10. Crum, L.A. and Reynolds, G.T., J. Acoust. Soc. Am., Biological Effects), Moscow: Fizmatgiz, 1963, p. 420.
1985, vol. 78, no. 6, p. 137. 35. Skorik, Yu.I., Gileva, K.G., Kukharskaya, E.V., and
11. Hiller, R., Putterman, S.J., and Barber, B.P., Phys. Rev. Fedoseev, A.D., Izv. Akad. Nauk SSSR, Ser. Khim., 1963,
Lett., 1992, vol. 69, no. 8, p. 1182. no. 5, p. 932.
12. Barber, B.P., Hiller, R.A., Lofstedt, R., Putterman, S.J., 36. Suslick, K.S., Gawienovski, J.J., Schubert, P.S., and
and Weninger, K.R., Phys. Reports, 1997, vol. 281, p. 65. Wang, H.H., J. Phys. Chem., 1983, vol. 87, no. 13,
13. Margulis, M.A., Usp. Fiz. Nauk, 2000, vol. 173, no. 3, p. 2299.
p. 263. 37. Zil’berg, G.A. and Zodboev, D.D., Ul’trazvukovaya
14. Margulis, I.M. and Margulis, M.A., Dokl. Ross. Akad. Tekh., 1966, no. 3, p. 134.
Nauk, 2002, vol. 385, no. 4, p. 478. 38. Khimiya plazmy (Plasma Chemistry), Smirnov, B.M.,
15. Misik, V. and Riesz, P., J. Phys. Chem., 1994, vol. 98, Ed., Moscow: Atomizdat, 1974.
no. 6, p. 1634. 39. Repic, O. and Vogt, S., Tetrahedron Lett., 1982, vol. 23,
16. Margulis, M.A. and Grundel’, L.M., Zh. Fiz. Khim., p. 2729.
1982, vol. 56, no. 6, p. 1445. 40. Wojnarovits, L. and Foldjak, G., Acta Chim. Hung.,
17. Kurochkin, A.K., Smorodov, E.A., Badikov, Yu.V., and 1980, vol. 10, p. 27.
Margulis, M.A., Zh. Fiz. Khim., 1986, vol. 60, no. 4, 41. Rappoport, S.A. and Gaumann, T., Helv. Chim. Acta,
p. 893. 1973, vol. 57, p. 2861.
18. Margulis, M.A., Los’, G.P., and Zinov’ev, O.I., Zh. Fiz. 42. Lifshitz, A. and Frenklash, M., J. Phys. Chem., 1975,
Khim., 1991, vol. 65, no. 11, p. 3054. vol. 79, no. 7, p. 686.
19. Zinoviev, O.I. and Margulis, M.A., Adv. Sonochem., 43. Cum, G., Galli, G., Gallo G, and Spadaro A., J. Chem.
1993, vol. 3, p. 165. Soc., J. Perkin Trans., 1988, no. 11, p. 375.
20. Maksimenko, N.A. and Margulis, M.A., Dokl. Akad. 44. Mokryi, E.N. and Starchevskii, V.L., Ul’trazvuk v pro-
Nauk SSSR, 1989, vol. 309, no. 6, p. 1399. tsessakh okisleniya organicheskikh soedinenii (Ultra-
21. Margulis, M.A., Zh. Fiz. Khim., 1985, vol. 59, no. 6, sound in Oxidation of Organic Compounds), L’vov:
p. 1497. Vysshaya Shkola, 1987, p. 119.
22. Margulis, M.A., Zh. Fiz. Khim., 1997, vol. 71, no. 10, 45. Yamawaki, J., Sumi, S., Ando, T., and Hanafusa, T.,
p. 1885. Chem. Lett., 1983, no. 4, p. 379.
23. Margulis, M.A. and Margulis, I.M., Ultrasonics 46. Rossochin, D.N., Kovalev, G.V., and Bugaenko, L.T.,
Sonochem., 2002, vol. 9, no. 1, p. 1. J. Am. Chem. Soc., 1995, vol. 117, no. 1, p. 344.
24. Andreikiv, A.E. and Lysak, N.V., Metod akusticheskoi 47. Rossochin, D.N., Bugaenko, L.T., and Kovalev, G.V.,
emissii v issledovanii protsessov razrusheniya (Acoustic Radiat. Phys. Chem., 1995, vol. 45, no. 2, p. 251.
Emission in Investigation of Destruction Processes),
Kiev: Naukova Dumka, 1989, p. 176. 48. Kukharskaya, E.V. and Skorik, Yu.I., Dokl. Akad. Nauk
SSSR, 1964, vol. 159, no. 2, p. 369.
25. Rossochin, D.N., Kovalev, G.V., and Bugaenko, L.T.,
Mendeleev Commun., 1992, p. 103. 49. Boudjouk, P. and Han, B.-H., Tetrahedron Lett., 1981,
vol. 22, no. 39, p. 3813.
26. Rossochin, D.N., Gokjaev, M.B., Bugaenko, L.T., and
Kovalev, G.V., Mendeleev Commun., 1994, p. 25. 50. Han, B.-H. and Boudjouk, P., J. Org. Chem., 1982,
vol. 47, p. 5030.
27. Margulis, M.A., Zh. Fiz. Khim., 1976, vol. 50, no. 4,
p. 897. 51. Price, G.J., Proc. 2nd Meeting Eur. Soc. Sonochemistry,
28. Pikaev, A.K., Impul’snyi radioliz vody i vodnykh ras- Gargnano, 1991, p. 68.
tvorov (Pulse Radiolysis of Water and Aqueous Solu- 52. Margulis, M.A., Los’, G.P., and Zinov’ev, O.I., Zh. Fiz.
tions), Moscow: Nauka, 1965, p. 260. Khim., 1991, vol. 65, no. 11, p. 3054.
29. Margulis, M.A. and Grundel’, L.M., Zh. Fiz. Khim., 53. Zinoviev, O.I. and Margulis, M.A., Adv. Sonochem.,
1982, vol. 56, no. 6, p. 1445. 1993, vol. 3, p. 165.
30. Rossochin, D.N., Kovalev, G.V., Bugaenko, L.T., and 54. Margulis, M.A. and Maximenko, N.A., Adv. Sonochem.,
Rudnev, A.V., Mendeleev Commun., 1992, p. 71. 1991, vol. 2, p. 253.
31. Pikaev, A.K., Sovremennaya radiatsionnaya khimiya. 55. Zhabotinskii, A.M., Oscillations and Travelling Waves
Osnovnye polozheniya, eksperimental’naya tekhnika i in Chemical Systems, Field, R.J. and Burger M., Eds.,
metody (Modern Radiation Chemistry: General Aspects, New York: Wiley, 1985. Translated under the title Kole-
Experimental Equipment, and Methods), Moscow: baniya i begushchie volny v khimicheskikh sistemakh,
Nauka, 1985, p. 375. Moscow: Mir, 1988, p. 720.

HIGH ENERGY CHEMISTRY Vol. 38 No. 3 2004


142 MARGULIS

56. Goodwin, T., Tibbles, J., Butler, C., and Caems, P.W., 65. Luche, J.-L. and Damiano, J.-C., J. Am. Chem. Soc.,
Proc. 1st Meeting of Sonochemistry, Grenoble, 1990, 1980, vol. 102, p. 7926.
p. 58. 66. Lindley, J., Lorimer, J.P., and Mason, T.J., Ultrasonics,
57. Davidson, R.S., Patel, A.M., and Thornwaite, D., Tetra- 1986, vol. 24, p. 292.
hedron Lett., 1983, vol. 24, p. 5904. 67. Bose, A.K., Gupta, K., and Manhas, M.S., J. Chem. Soc.,
58. Mason, T.J., Lorimer, J.P., Turner, A.T., and Harris, A.R., Chem. Commun., 1984, p. 86.
J. Chem. Res., Synop., 1988, vol. 80, p. 68.
68. Reeves, W.-P. and McClucky, J.V., Tetrahedron Lett.,
59. Raucher, S. and Klein, P., Tetrahedron Lett., 1981, 1983, vol. 24, p. 1585.
vol. 46, p. 3558.
69. Ishikawa, N. and Kitazume, T., Synth. Chem. Jpn., 1983,
60. Galiakhmetov, R.N., Kurochkin, A.K., and Margu-
vol. 41, p. 432.
lis, M.A., Zh. Fiz. Khim., 1986, vol. 60, no. 4, p. 1024.
61. Petrier, C., Gemal, A.L., and Luche, J.-L., Tetrahedron 70. Kitazume, T. and Kitazume, T., Chem. Lett., 1982,
Lett., 1982, vol. 23, p. 3361. no. 12, p. 1453.
62. Kuchin, A.V., Nurushev, R.A., and Tolstikov, G.A., Zh. 71. Regen, S.L. and Sign, A., J. Org. Chem., 1982, vol. 47,
Obshch. Khim., 1983, vol. 53, no. 11, p. 2519. p. 1587.
63. Knochel, P. and Normant, J.F., Tetrahedron Lett., 1984, 72. Zefirov, N.S., Lukin, K.A., Politanskii, S.F., and Margu-
vol. 25, p. 1475. lis, M.A., Zh. Org. Khim., 1987, vol. 23, no. 8, p. 1799.
64. Inoue, Y., Yamashita, J., and Hashimoto, H., Synthesis, 73. Ando, T., Kuwate, T., Yamawaki, J., and Hanafuza, T.,
1984, p. 244. Synthesis, 1985, vol. 8, p. 637.

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