Sonochemical reaction

Control of sonochemical reactions is subject to the same limitation that any thermal process has the Boltzmann energy distribution means that the energy per individual molecule wiU vary widely. One does have easy control, however, over the energetics of cavitation through the parameters of acoustic intensity, temperature, ambient gas, and solvent choice. The thermal conductivity of the ambient gas (eg, a variable He/Ar atmosphere) and the overaU solvent vapor pressure provide easy methods for the experimental control of the peak temperatures generated during the cavitational coUapse. 

Abstract Acoustic cavitation is the formation and collapse of bubbles in liquid irradiated by intense ultrasound. The speed of the bubble collapse sometimes reaches the sound velocity in the liquid. Accordingly, the bubble collapse becomes a quasi-adiabatic process. The temperature and pressure inside a bubble increase to thousands of Kelvin and thousands of bars, respectively. As a result, water vapor and oxygen, if present, are dissociated inside a bubble and oxidants such as OH, O, and H2O2 are produced, which is called sonochemical reactions. The pulsation of active bubbles is intrinsically nonlinear. In the present review, fundamentals of acoustic cavitation, sonochemistry, and acoustic fields in sonochemical reactors have been discussed. 

There are two types in acoustic cavitation. One is transient cavitation and the other is stable cavitation [14, 15]. There are two definitions in transient cavitation. One is that the lifetime of a bubble is relatively short such as one or a few acoustic cycles as a bubble is fragmented into daughter bubbles due to its shape instability. The other is that bubbles are active in light emission (sonoluminescence (SL)) or chemical reactions (sonochemical reactions). Accordingly, there are two definitions in stable cavitation. One is that bubbles are shape stable and have a long lifetime. The other is that bubbles are inactive in SL and chemical reactions. There exist... 

Fig. 1.6 The correlation between the bubble temperature at the collapse and the amount of the oxidants created inside a bubble per collapse in number of molecules. The calculated results for various ambient pressures and acoustic amplitudes are plotted. The temperature of liquid water is 20 °C. (a) For an air bubble of 5 pm in ambient radius at 140 kHz in ultrasonic frequency, (b) For an oxygen bubble of 0.5 pm in ambient radius at 1 MHz. Reprinted with permission from Yasui K, Tuziuti T, Iida Y, Mitome H (2003) Theoretical study of the ambient-pressure dependence of sonochemical reactions. J Chem Phys 119 346-356. Copyright 2003, American Institute of Physics...

In some literature, there is a description that a bubble with linear resonance radius is active in sonoluminescence and sonochemical reactions. However, as already noted, bubble pulsation is intrinsically nonlinear for active bubbles. Thus, the concept of the linear resonance is not applicable to active bubbles (That is only applicable to a linearly pulsating bubble under very weak ultrasound such as 0.1 bar in pressure amplitude). Furthermore, a bubble with the linear resonance radius can be inactive in sonoluminescence and sonochemical reactions [39]. In Fig. 1.8, the calculated expansion ratio (/ max / Rq, where f max is the maximum radius and R0 is the ambient radius of a bubble) is shown as a function of the ambient radius (Ro) for various acoustic amplitudes at 300 kHz [39]. It is seen that the ambient radius for the peak in the expansion ratio decreases as the acoustic pressure amplitude increases. While the linear resonance radius is 11 pm at 300 kHz, the ambient radius for the peak at 3 bar in pressure amplitude is about 0.4 pm. Even at the pressure amplitude of 0.5 bar, it is about 5 pm, which is much smaller than the linear resonance radius. 

Fig. 1.9 The calculated results as a function of ambient radius at 300 kHz and 3 bar in ultrasonic frequency and pressure amplitude, respectively. The horizontal axis is in logarithmic scale, (a) The peak temperature (solid) and the molar fraction of water vapor (dash dotted) inside a bubble at the end of the bubble collapse, (b) The rate of production of oxidants with the logarithmic vertical axis. Reprinted with permission from Yasui K, Tuziuti T, Lee J, Kozuka T, Towata A, Iida Y (2008) The range of ambient radius for an active bubble in sonoluminescence and sonochemical reactions. J Chem Phys 128 184705. Copyright 2008, American Institute of Physics...

Similar spatial distribution of active bubbles has been observed in partially degassed water and in pure water irradiated with pulsed ultrasound [67]. For both the cases, the number of large inactive bubbles is smaller than that in pure water saturated with air under continuous ultrasound, which is similar to the case of a surfactant solution. As a result, enhancement in sonochemical reaction rate (rate of oxidants production) in partially degassed water and in pure water irradiated with pulsed ultrasound has been experimentally observed [70, 71]. With regard to the enhancement by pulsed ultrasound, a residual acoustic field during the pulse-off time is also important [71]. 

Tuziuti T, Yasui K, Sivakumar M, Iida Y, Miyoshi N (2005) Correlation between acoustic cavitation noise and yield enhancement of sonochemical reaction by particle addition. J Phys Chem A 109 4869 1872... 

Yasui K, Tuziuti T, Lee J, Kozuka T, Towata A, Iida Y (2008) The range of ambient radius for an active bubble in sonoluminescence and sonochemical reactions. J Chem Phys 128 184705... 

It can be better (but not always) to avoid standing wave conditions by performing sonochemical reactions under high power conditions with mechanical stirring. 

Choose conditions, which allow comparisons between different sonochemical reactions. 

Dahlem O, Reisse J, Halloin V (1999) The radially vibrating horn A scaling up possibility for sonochemical reactions. Chem Eng Sci 54 2829-2838... 

Entezari MH, Kruss P (1996) Effect of frequency on sonochemical reactions n. Temperature and intensity effects. Ultrason Sonochem 3 19-24... 

The chemical reactions induced by ultrasonic irradiation are generally influenced by the irradiation conditions and procedures. It is suggested that ultrasound intensity , dissolved gas , distance between the reaction vessel and the oscillator and ultrasound frequency are important parameters to control the sonochemical reactions. 

Keck A, Gilbert E, Koster R (2002) Influence of particles on sonochemical reactions in aqueous solutions. Ultrasonics 40(l-8) 661-665... 

Following are the important parameters that have to be considered carefully when carrying out sonochemical reactions ... 

If the irradiated water was, however, saturated with hydrogen or carbon monoxide instead of oxygen then no oxides were formed [35]. Under these conditions reduction of nitrogen occurred to afford ammonia [36]. Interestingly, HCN is also observed when carbon monoxide is replaced by methane [37].Thus the result of a sonochemical reaction, in water, depends largely on the nature of the dissolved gases and their concentration. 

Abstract The behaviour of many metal ions which are stable in more than one oxidation states in their aqueous solutions has been studied under sonochemical reaction conditions. Fe(II) is oxidized to Fe(III) and Fe(III) is reduced to Fe(II) with equal ease under sonochemical conditions. Besides, the oxidizing power of Cr2072 is found to be less than the MnO ions, therefore, in a system containing both species, Cr3+ is susceptible to oxidation to Cr61 and the MnO to reduction to Mn2+. 

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