Sonochemistry as a New Promising Area of High Energy Chemistry

Sonochemistry is one of the most intensively developing areas of high energy chemistry in both theoretical and applied aspects. There has been considerable progress in sonochemistry: many sonochemical reactions 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 powerful low-frequency (of the order of 10–200 Hz) cavitation fields was developed and chemical and physicochemical 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 reactions were discovered, and the generalized electric theory of cavitation processes was elaborated.     

Current state of the theory of local electrification of cavitation bubbles

The fundamental propositions of the theory of local electrification of cavitation bubbles, which explains the phenomena of sonoluminescence (SL) and sonochemical reactions, are outlined. Key debatable questions are answered. It is shown that, unlike thermal theories, the local electrification theory agrees with a vast body of experimental data for cavitation clouds. The following experimental results that support this theory are considered: the decisive role of electrokinetic phenomena in initiation of SL, the presence of lines and bands in SL spectra of ultrasonically and laser-induced bubbles in their deformation and splitting, results of experiments with SL quenchers, the asymmetric-in-time profile of SL bursts, the SL at small pulsations of bubbles, etc.     

A comparison between multibubble sonoluminescence intensity and the temperature within cavitation bubbles

Cavitation bubble temperatures have been measured using a methyl radical recombination method and compared with the changes in the sonoluminescence intensity in aqueous ethanol solutions over a range of concentrations. Whereas the sonoluminescence intensity was decreased by more than 90% at low ethanol concentrations (<0.1 M), the measured bubble temperatures seem to be unaffected at this level of additive. The cavitation bubble temperatures were noticeably decreased at substantially higher ethanol concentrations (0.5 M). It has been concluded that the methyl radical recombination method does not report on the true sonoluminescence temperatures. However, it does report on the average bubble temperatures at which sonochemical reactions occur.     

Acoustic emission from cavitating solutions: implications for the mechanisms of sonochemical reactions

The acoustic emission from collapsing cavitation bubbles generated using ultrasound of 20 kHz and 515 kHz frequencies in water has been measured and correlated with sonoluminescence and hydroxyl radical production to yield further information on the frequency dependence of sonochemical reactions. A reasonable correlation was found, and the results suggest differences in the predominant types of cavitation observed under laboratory conditions.     

The range of ambient radius for an active bubble in sonoluminescence and sonochemical reactions

Numerical simulations of nonequilibrium chemical reactions inside an air bubble in liquid water irradiated by ultrasound have been performed for various ambient bubble radii. The intensity of sonoluminescence (SL) has also been calculated taking into account electron-atom bremsstrahlung, radiative attachment of electrons to neutral molecules, radiative recombination of electrons and ions, chemiluminescence of OH, molecular emission from nitrogen, etc. The lower bound of ambient radius for an active bubble in SL and sonochemical reactions nearly coincides with the Blake threshold for transient cavitation. The upper bound is in the same order of magnitude as that of the linear resonance radius. In actual experiments, however, the distribution of ambient radius for active bubbles may be narrow at around the threshold ambient radius for the shape instability. The threshold peak temperature inside an air bubble for nitrogen burning is higher than that for oxidant formation. The threshold peak temperatures depend on ultrasonic frequency and acoustic amplitude because chemical reactions inside a bubble are in nonequilibrium. The dominant emission mechanism in SL is electron-atom bremsstrahlung except at a lower bubble temperature than 2000 K, for which molecular emissions may be dominant.     

Sonochemistry and sonoluminescence in ionic liquids, molten salts, and concentrated electrolyte solutions

Ionic liquids have favorable intrinsic properties that make them of interest as solvents for various chemical reactions. The same properties that make the liquids effective solvents also make them interesting liquids for studies involving sonochemistry, acoustic cavitation, and sonoluminescence. Recent interest in using ultrasound to accelerate chemical reactions conducted in ionic liquids necessitates an understanding of the effects of acoustic cavitation on these solvents. Here, we review our previous results on the effects of cavitation on some room-temperature ionic liquids, including the sonoluminescence spectra of molten salt eutectics and concentrated aqueous electrolyte solutions. In all cases, regardless of the essentially nonexistent vapor pressure of the solution atomic and small molecule emitters are observed in the spectra which arise from sonolysis of the ionic liquids.     

Sonoluminescence quenching of organic compounds in aqueous solution: frequency effects and implications for sonochemistry

Solute-induced quenching of sonoluminescence (SL) is reported for aqueous solutions of two homologous series of methyl esters and ketones using low (20 kHz) and high (515 kHz) ultrasound frequencies. SL data at 20 kHz from aqueous solutions containing alcohols and carboxylic acids are also presented to compare with previously published results at 515 kHz. In addition to supporting the previous findings on the existence of stable and transient bubbles at 515 and 20 kHz, respectively, the results suggest that the hydrogen-bonding characteristics of the solutes also play a major role in the extent of SL quenching. An increase in the SL intensity at low concentrations for most of the solutes suggests that these solutes increase the number of "active" bubbles by hindering the coalescence of bubbles. It is concluded that the effect of the solutes on the SL signal from aqueous solutions at both frequencies is primarily due to the balance of two factors, namely, the incorporation of solute within the bubble, leading to SL quenching, and the prevention of coalescence of the bubbles, leading to SL enhancement. At the higher frequency, SL quenching by the solutes is the main influence on the emission yield. However, at the lower frequency, hindrance to coalescence by the solutes dominates at lower concentrations and leads to SL enhancement. The implications of these results for optimizing conditions for aqueous sonochemical reactions are discussed.     

Multibubble sonolysis and sonoluminescence in molten elementary sulfur and sulfur—styrene mixture

The effect of saturation with argon, as well as styrene and iodine additives on the temperature dependence of multibubble sonoluminescence intensity in molten sulfur at 120–230 °C was studied. The shape of the temperature dependence with a maximum at 170–200 °C is determined by the viscosity variations related to the changes in the molecular structure of molten elemental sulfur. At high temperatures, cyclooctasulfane (S₈) molecules break to radical products, which then undergo polymerization that can be slowed down by the additives. Sulfurization of styrene during sonolysis of a sulfur—styrene mixture resulting in products of the thiophene series was detected. Unlike thermal sulfurization that affords 2,5-diphenylthiophene as a major product, sonochemical sulfurization results mainly in 2,4-diphenylthiophene. The mechanism of 2,4-diphenylthiophene formation initiated by the reaction of styrene molecules with S⁺ ions produced upon fragmentation of S₈ within cavitation bubbles is proposed. The glow of electronically excited S⁺* ions is responsible for the band with a maximum at 560 nm in the sonoluminescence spectrum of molten sulfur, which is suppressed by the styrene additive.     

Organosilicon sonochemistry

Sonochemical reactions involving organosilicon compounds are reviewed. Possible applications of ultrasonic irradiation for acceleration and initiation of various types of reactions are demonstrated along with examples from organic synthesis using organosilicon compounds. Also described are the sonochemical reactions of organic compounds containing the Group IVB elements germanium and tin, chemically related to silicon.     

Mini-review: Ferrite nanoparticles in the catalysis

Recent applications of ferrite nanoparticles as catalysts in organic processes are reviewed. Catalytic applications include the use of mainly cobalt, nickel, copper, and zinc ferrites, as well as their mixed-metal combinations with Cr, Cd, Mn and sometimes some lanthanides. Core–shell nanostructures with silica and titania are also used without loss of magnetic properties. The ferrite nanomaterials are obtained mainly by wet-chemical sol-gel or co-precipitation methods, more rarely by the sonochemical technique, mechanical high-energy ball milling, spark plasma sintering, microwave heating or hydrothermal route. Catalytic processes with application of ferrite nanoparticles include decomposition (in particular photocatalytic), reactions of dehydrogenation, oxidation, alkylation, C–C coupling, among other processes. Ferrite nano catalysts can be easily recovered from reaction systems and reused up to several runs almost without loss of catalytic activity.     

Sonochemiluminescence of aromatic hydrocarbons

Multibubble sonoluminescence of water and a series of aromatic hydrocarbons, viz., benzene, toluene, ethylbenzene, and m-xylene (at 25 °C), and a naphthalene melt (at 110–120 °C) was studied. An analysis of the influence of oxygen and argon on the sonoluminescence intensity and the luminescence spectra of these liquid compounds, as well as the effect of additives of ionol, ethanol, and 9,10-dibromoanthracene on m-xylene sonoluminescence, showed that a considerable contribution to the sonoluminescence of aromatic hydrocarbons is made by chemiluminescence reactions associated with their oxidation. This sonochemiluminescence is observed in both the gas phase of cavitation bubbles and the bulk solution where luminescence is retained for a long time after ultrasonication switching-off (the initial intensity of the residual chemiluminescence is up to 10% of the luminescence intensity during sonolysis). As for thermoinitiated oxidation, the afterglow of m-xylene contains the radical and molecular components.     

Autocatalytic sonolysis of iron pentacarbonyl in room temperature ionic liquid [BuMeIm][Tf2N

The autocatalytic sonochemical reaction of Fe(CO)(5) decomposition in [BuMeIm][Tf(2)N] provides iron nanoparticles in higher yields than in tetralin. Such a difference is explained by the higher decomposition of the intermediate Fe(3)(CO)(12) according to the two-sites model of the sonochemical reactions and the specific properties of the ionic liquid.     

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

The state-of-the-art in the theory of routes for multi-route reactions in the homogeneous catalysis with metal complexes is reviewed. Key problems and the possible approaches to their solution based on the Horiuti-Temkin theory of steady-state reactions, which are useful in constructing the kinetic algebraic models of multi-route processes, are discussed. A classification of the mechanisms of real processes involved in the homogeneous catalysis with metal complexes is presented. The chain mechanisms of catalytic processes, conjugated and associated reactions, and critical phenomena in the dynamics of homogeneous reactions are considered.     

Single bubble sonoluminescence--a chemist's overview.

The phenomenon of sonoluminescence has been known for over 60 years but it is only over the last few years that a better understanding of its origins has emerged. In part the discovery of single bubble sonoluminescence, just over 10 years ago, has been a major contributor to the theoretical advances that have been made to account for the event. This Minireview is from the perspective of a physical chemist and considers the progress that has been made in understanding the role of solutes in affecting the sonoluminescence from a solution exposed to ultrasound. The physicochemical properties of solutes that are important in controlling both single bubble and multibubble sonoluminescence are discussed.     

Sonochemical Reaction of Bifunctional Molecules on Silicon (111) Hydride Surface

While the sonochemical grafting of molecules on silicon hydride surface to form stable Si–C bond via hydrosilylation has been previously described, the susceptibility towards nucleophilic functional groups during the sonochemical reaction process remains unclear. In this work, a competitive study between a well-established thermal reaction and sonochemical reaction of nucleophilic molecules (cyclopropylamine and 3-Butyn-1-ol) was performed on p-type silicon hydride (111) surfaces. The nature of surface grafting from these reactions was examined through contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Cyclopropylamine, being a sensitive radical clock, did not experience any ring-opening events. This suggested that either the Si–H may not have undergone homolysis as reported previously under sonochemical reaction or that the interaction to the surface hydride via a lone-pair electron coordination bond was reversible during the process. On the other hand, silicon back-bond breakage and subsequent surface roughening were observed for 3-Butyn-1-ol at high-temperature grafting (≈150 °C). Interestingly, the sonochemical reaction did not produce appreciable topographical changes to surfaces at the nano scale and the further XPS analysis may suggest Si–C formation. This indicated that while a sonochemical reaction may be indifferent towards nucleophilic groups, the surface was more reactive towards unsaturated carbons. To the best of the author’s knowledge, this is the first attempt at elucidating the underlying reactivity mechanisms of nucleophilic groups and unsaturated carbon bonds during sonochemical reaction of silicon hydride surfaces.     

Ultrasonic evidence of hydrophobic interactions. Effect of ultrasound on benzoin condensation and some other reactions in aqueous ethanol

The kinetics of KCN-catalyzed benzoin condensation of benzaldehyde in water and ethanol-water binary mixtures was investigated both under ultrasound at 22 kHz and without sonication. Thermodynamic activation parameters were calculated from kinetic data obtained at 35, 50, and 65 degrees C. Evidence that ultrasound can retard reactions is reported and hence a direct proof that sonochemical processes occur in the bulk solution. Former results and literature data for ester hydrolyses and tert-butyl chloride solvolysis are involved in the discussion. A quantitative relationship between sonication effects and the hydrophobicity of reagents is presented for the first time. Ultrasound affects hydrophobic interactions with the solvent, which are not manifested in conventional kinetics. When it suppresses the stabilization of the encounter complexes between reagents, sonication hinders the reaction but accelerates it when it perturbs the hydrophobic stabilization of the ground state of a reagent.     

Correlation in spatial intensity distribution between volumetric bubble oscillations and sonochemiluminescence in a multibubble system

The correlation in spatial intensity distribution between volumetric oscillation of multibubble and sonochemiluminescence in an ultrasonic standing-wave field is investigated through the measurements of scattered light from bubbles by changing the measuring position in the direction of sound propagation and sonochemiluminescence with luminol. When a thin light sheet, finer than half the wavelength of sound, is introduced into the cavitation bubbles at the anti-node of the sound pressure, the scattered light intensity oscillates temporally. The peak-to-peak light intensity corresponds to the number of the bubbles which contribute to the sonochemical reaction because the radius for oscillating bubbles at pressure antinode is restrictive in a certain range due to the shape instability and the action of Bjerknes force that expels from anti-node bubbles larger than the resonant size. The experimental results show that at the side near the water surface, the peak-to-peak light intensity is larger in comparison with the intensity near the sound source, and this tendency becomes apparent at higher input power. These light scattering results correspond with the spatial intensity distribution of the sonochemiluminescence with luminol. Therefore, it is interpreted that most of the cavitation bubbles contributing to the sonochemical reactions in the standing wave field exist near liquid surface. Present method of light scattering in reference with the image of the sonochemiluminescence is promising for evaluating spatial distribution of violently oscillating cavitation bubbles effective for sonochemical reactions.     

A sonoluminescent method for on-line monitoring of the natural water quality

Ultrasonic impact on natural waters was applied to identify hydrochemical anomalies from the changes in the characteristics of sonoluminescence generated by ultrasonic cavitation in a flowing water sample. Sonoluminescence excitation spectra characteristic for various natural water pollutants were obtained for the first time. The suitability of changes in the sonoluminescence intensity and in the shape of the sonoluminescence excitation spectra as indicators of hydrochemical anomalies was elucidated.     

Conjugate reactions: New potentials of an old idea

Main concepts of the Shilov–Ostwald theory of conjugate chemical reactions are analyzed from the standpoint of complex reaction kinetics, theory of reaction routes, and thermodynamics of irreversible processes. Classification of conjugate reactions and an algorithm of catalytic system design for conducting these processes are proposed.     

Enlightened sonochemistry

Sonochemistry and photochemistry are initiated by high-energy transient species, which may be prone to mutual interaction. Electronic excitation of solutes by energy transfer from high energy species generated in collapsing bubbles is already supported by experimental evidence. The rates of photochemical reactions can be affected by ultrasound-induced mixing of liquids caused by microstreaming near pulsating cavitation bubbles and shockwaves due to bubble collapse. This may not only improve light absorption but also modify the pathway of reaction by increasing the contact between reagents. Finally, one may speculate about a potentially new chemistry of photoexcited solutes under the extreme conditions inside cavitation microreactors. This work reviews research on the excitation of solutes by sonoluminescence, the combined effects of ultrasound and light on liquid systems and the effect of ultrasound on photocatalytic reactions.