Sonochemistry effect

Birkin P R and SilvaMartinez S 1997 A study on the effects of ultrasound on electrochemical phenomena Ultrasonics Sonochemistry 4 121... 

The chemical effects of ultrasound do not arise from a direct interaction with molecular species. Ultrasound spans the frequencies of roughly 15 kH2 to 1 GH2. With sound velocities in Hquids typically about 1500 m/s, acoustic wavelengths range from roughly 10 to lO " cm. These are not molecular dimensions. Consequently, no direct coupling of the acoustic field with chemical species on a molecular level can account for sonochemistry or sonoluminescence. 

Sonochemistry is strongly affected by a variety of external variables, including acoustic frequency, acoustic intensity, bulk temperature, static pressure, ambient gas, and solvent (47). These are the important parameters which need consideration in the effective appHcation of ultrasound to chemical reactions. The origin of these influences is easily understood in terms of the hot-spot mechanism of sonochemistry. 

The choice of the solvent also has a profound influence on the observed sonochemistry. The effect of vapor pressure has already been mentioned. Other Hquid properties, such as surface tension and viscosity, wiU alter the threshold of cavitation, but this is generaUy a minor concern. The chemical reactivity of the solvent is often much more important. No solvent is inert under the high temperature conditions of cavitation (50). One may minimize this problem, however, by using robust solvents that have low vapor pressures so as to minimize their concentration in the vapor phase of the cavitation event. Alternatively, one may wish to take advantage of such secondary reactions, for example, by using halocarbons for sonochemical halogenations. With ultrasonic irradiations in water, the observed aqueous sonochemistry is dominated by secondary reactions of OH- and H- formed from the sonolysis of water vapor in the cavitation zone (51—53). 

Homogeneous Sonochemistry Bond Breaking and Radical Formation. The chemical effect of ultrasound on aqueous solutions have been studied for many years. The primary products are H2O2 there is strong evidence for various high-energy intermediates, including HO2,... 

Sonochemistry is also proving to have important applications with polymeric materials. Substantial work has been accomplished in the sonochemical initiation of polymerisation and in the modification of polymers after synthesis (3,5). The use of sonolysis to create radicals which function as radical initiators has been well explored. Similarly the use of sonochemicaHy prepared radicals and other reactive species to modify the surface properties of polymers is being developed, particularly by G. Price. Other effects of ultrasound on long chain polymers tend to be mechanical cleavage, which produces relatively uniform size distributions of shorter chain lengths. 

Sostaric JZ (1999) Interfacial effects on aqueous sonochemistry and sonoluminescence. PhD thesis, University of Melbourne, Australia... 

Acoustic cavitation In this case, the pressure variations in the liquid are effected using the sound waves usually ultrasound (16 kHz to 100 MHz). The chemical changes taking place due to the cavitation induced by the passage of sound waves are commonly known as sonochemistry. 

Okitsu K, Suzuki T, Takenaka N, Bandow FI, Nishimura R, Maeda Y (2006) Acoustic multibubble cavitation in water a new aspect of the effect of a rare gas atmosphere on bubble temperature and its relevance to sonochemistry. J Phys Chem B 110 20081-20084... 

The book offers a theoretical introduction in the first three chapters, provides recent applications in material science in the next four chapters, describes the effects of ultrasound in aqueous solutions in the following five chapters and finally discusses the most exciting phenomenon of sonoluminescence in aqueous solutions containing inorganic materials in subsequent two chapters, before ending with a few basic introductory experiments of sonochemistry and sonoluminescence in the concluding chapter. 

The chemical (3) and biological (4) effects of ultrasound were first reported by Loomis more than 50 years ago. In spite of early work in the area of sonochemistry, interest within the chemical community remained... 

The early studies of the chemical effects of ultrasound have been thoroughly reviewed (5-7). Only the most important and most recent research is mentioned here as needed to provide a perspective on sonochemical reactivity patterns. The sonolysis of water is the earliest and most exhaustively studied (3,93,96,98-105). The first observations on the experimental parameters which influence sonochemistry come from these reports. The primary products are H202 and H2, and various data supported their formation from the intermediacy of hydroxyl radicals and hydrogen radicals ... 

In 1981, the first report on the sonochemistry of discrete organometallic complexes demonstrated the effect of ultrasound on iron carbonyls in alkane solutions (174). The transition metal carbonyls were chosen for these initial studies because their thermal and photochemical reactivities have been well characterized. The comparison among the thermal, photochemical, and sonochemical reactions of Fe(CO)5 provides an excellent example of the unique chemistry which homogeneous cavitation can... 

The purpose of this chapter will be to serve as a critical introduction to the nature and origin of the chemical effects of ultrasound. We will focus on organo-transition metal sonochemistry as a case study. There will be no attempt to be comprehensive, since recent, exhaustive reviews on both organometallic sonochemistry Q) and the synthetic applications of ultrasound (2) have been published, and a full monograph on the chemical, physical and biological effects of ultrasound is in press (3). 

Catalysis and Synthesis in the Laboratory. Research on the practical applications of catalysis was not matched in the laboratory. We began a study of metal and non-metal catalyzed reactions early in our sonochemistry program. Our first project was to develop a convenient method of hydrogenating a wide range of olefins. We chose formic acid as our hydrogen source and found it to be effective. For example, with continuous irradiation, palladium catalyzed hydrogenations of olefins are complete in one hour(44). 

Intervention of localized microscopic high temperatures is possible [8, 14, 24], as advocated in sonochemistry to justify the sonochemical effect. There is an inevitable lack of experimental evidence, because we can necessarily have access to macroscopic temperature only. It has been suggested [6, 19] that, in some examples, MW activation could originate from hot spots generated by dielectric relaxation on a molecular scale. 

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