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High Energy Chemistry. 2004, 38, 135-142 PDF
High Energy Chemistry. 2004, 38, 135-142 PDF
REVIEWS
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
Initial power yields, chemicoacoustic efficiencies,* and radical recombination factors** [5]
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 ≈
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.
= +
+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.
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.
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.