Cavitation, ultrasonic waves

Sonochemistry started in 1927 when Richards and Loomis [173] first described chemical reactions brought about by ultrasonic waves, but rapid development of ultrasound in chemistry really only began in the 1980s. Over the past decades there has been a remarkable expansion in the use of ultrasound as an energy source to produce bond scission and to promote or modify chemical reactivity. Although acoustic cavitation plays... 

For general aspects on sonochemistry the reader is referred to references [174,180], and for cavitation to references [175,186]. Cordemans [187] has briefly reviewed the use of (ultra)sound in the chemical industry. Typical applications include thermally induced polymer cross-linking, dispersion of Ti02 pigments in paints, and stabilisation of emulsions. High power ultrasonic waves allow rapid in situ copolymerisation and compatibilisation of immiscible polymer melt blends. Roberts [170] has reviewed high-intensity ultrasonics, cavitation and relevant parameters (frequency, intensity,... 

Recently, it has been shown that ultrasonic agitation during hydrogenation reactions over skeletal nickel can slow catalyst deactivation [122-124], Furthermore, ultrasonic waves can also significantly increase the reaction rate and selectivity of these reactions [123,124], Cavitations form in the liquid reaction medium because of the ultrasonic agitation, and subsequently collapse with intense localized temperature and pressure. It is these extreme conditions that affect the chemical reactions. Various reactions have been tested over skeletal catalysts, including xylose to xylitol, citral to citronellal and citronellol, cinnamaldehyde to benzenepropanol, and the enantioselective hydrogenation of 1-phenyl-1,2-propanedione. Ultrasound supported catalysis has been known for some time and is not peculiar to skeletal catalysts [125] however, research with skeletal catalysts is relatively recent and an active area. 

Sonication using ultrasonic cleaner baths remains a popular extraction approach particularly for controlled-release products. In sonication, an ultrasonic wave of 20-40 kHz generated by a piezoelectric transducer is used to produce the formation and collapse of thousands of microscopic bubbles (cavitations) in the water bath to facilitate the break up of the solid particles and the subsequent dissolution of the API. Note that parameters such as the wattage power of the sonicator, presence of the perforated tray, depth of the water level, bath temperature and the number of sample flasks sonicated might all affect the extraction rate. For... 

In Chapter 2 we explained why there existed a cavitation threshold i. e. a limit of sound intensity below which cavitation could not be produced in a liquid. We suggested that only when the applied acoustic amplitude (P ) of the ultrasonic wave was sufficiently large to overcome the cohesive forces within the liquid could the liquid be tom apart and produce cavitation bubbles. If degradation is due to cavitation then it is expected that degradation will only occur when the cavitation threshold is exceeded. This is confirmed by Weissler who investigated the degradation of hydroxycellulose and observed that the start of degradation coincided with the onset of cavitation (Fig. 5.21). 

Colloidal potassium has recently been proved as a more active reducer than the metal that has been conventionally powdered by shaking it in hot octane (Luche et al. 1984, Chou and You 1987, Wang et al. 1994). To prepare colloidal potassium, a piece of this metal in dry toluene or xylene under an argon atmosphere is submitted to ultrasonic irradiation at ca. 10°C. A silvery blue color rapidly develops, and in a few minutes the metal disappears. A common cleaning bath (e.g., Sono-clean, 35 kHz) filled with water and crushed ice can be used. A very fine suspension of potassium is thus obtained, which settles very slowly on standing. The same method did not work in THF (Luche et al. 1984). Ultrasonic waves interact with the metal by their cavitational effects. These effects are closely related to the physical constants of the medium, such as vapor pressure, viscosity, and surface tension (Sehgal et al. 1982). All of these factors have to be taken into account when one chooses a metal to be ultrasonically dispersed in a given solvent. 

The ultrasonic irradiation of a solution induces acoustic cavitation, a transient process that promotes chemical activity. Acoustic cavitation is generated by the growth of preexisting nuclei during the alternating expansion and compression cycles of ultrasonic waves. For example, in aqueous liquid, temperatures as high as 4300 K and pressures over 1000 atm are estimated to exist within... 

The effects of ultrasonic irradiation on photochemical reactions have been also reported. In those papers, effects of cavitation were demonstrated. Cavitation means the process in which micro bubbles, which are formed within a liquid during the rarefaction cycle of the acoustic wave, undergo violent collapse during the compression cycle of the wave.5) The dissociation of water to radicals is an example of these effects. Since activated chemical species such as free radicals have high reactivity, chemical reactions proceed. In other words, this phenomenon is a chemical effect of ultrasonic waves. 

However, this commonly accepted theory is incomplete and applies with much difficulty to systems involving nonvolatile substances. The most relevant example is metals. For a heterogeneous system, only the mechanical effects of sonic waves govern the sonochemical processes. Such an effect as agitation, or cleaning of a solid surface, has a mechanical nature. Thus, ultrasound transforms potassium into its dispersed form. This transformation accelerates electron transfer from the metal to the organic acceptor see Chapter 2. Of course, ultrasonic waves interact with the metal by their cavitational effects. 

Absorption is an unavoidable consequence of passing ultrasonic waves through matter. In particular, to reach the cavitation zone in a solution, large-amplitude ultrasound must pass through the solution. Generally, the higher is the viscosity of a solution, the higher is the ultrasonic absorption. There is an additional loss associated with finely divided particles, known as... 

High-Intensity Ultmsonicator. Droplets are disrupted within a field of high-intensity ultrasonic waves. Droplet disruption occurs either due to cavitation or because the frequency of the ultrasonic wave equals the resonance frequencies of the droplets. This causes the droplets to oscillate vigorously. Eventually, the oscillation becomes supercritical and the droplets are disrupted. The effectiveness of sonication, therefore, depends on the nature of the continuous and dispersed phase. The type of oil, as well as the nature of the surfactant, is the limiting factor for the minimal droplet size that can be achieved. 

Sonochemistry (chemical events induced by exposure to ultrasound) occupies an important place in organic chemistry. The chemical effects of high-intensity ultrasound were extensively smdied in aqueous solutions for many years, but is now applied to a variety of organic solvents. The origin of sonochemistry is acoustic cavitation the creation, growth, and implosive collapse of gas vacuoles in solution by the sound field. Acoustic cavitation is the phenomenon by which intense ultrasonic waves induce the formation, oscillation, and implosion of gas... 

High-power ultrasound has been used to disrupt cells, disperse aggregates, and modify food texture and crystallization (Knorr et ah, 2004). The ultrasonic wave causes intense localized heating and this generates gas bubbles which cavitate and result in intense pressure and shear (Povey and Mason, 1998). It is the high pressure and shear which cause physical disruption of food components and materials and can change the rate of chemical reactions. Kentish et ah (2008) used a flow-through power ultrasound systems at 20-24 kHz to produce an oil-in-water emulsion with... 

TTHE ACTION OF ULTRASONIC WAVES IN LIQUIDS can induce or accelerate a wide variety of chemical reactions (1, 2) The chemical effects of ultrasound have been explained in terms of reactions occurring inside, at the interface, or at some distance away from cavitating gas bubbles. In the interior of a collapsing cavitation bubble, extreme but transient conditions exist. Temper-... 

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