Single-bubble sonochemiluminescence in aqueous luminol solutions

Sonochemiluminescence (SCL) of luminol due to a single bubble is studied through spectral measurement. No SCL was observed from a stable single bubble that emitted high-intensity sonoluminescence (SL). In contrast, SCL was observed under conditions of an unstable dancing bubble, where a bubble grows and ejects tiny bubbles, making it "dance" by counteraction. Furthermore, SCL was observed from dancing bubbles even when SL was not observed, depending on the dissolved gas content. The instability of bubble collapse is the key parameter governing SCL.     

Influence of bubble clustering on multibubble sonoluminescence

Influence of clustering of cavitation bubbles on multibubble sonoluminescence (MBSL) in standing wave fields is studied through measurement of MBSL intensity with a photomultiplier tube and observation of corresponding bubble behavior with a high-speed video camera and an intensified charge-coupled device one. It is clarified that, when the SL is quenched suddenly at excessive ultrasonic power, the behavior of bubbles clearly changes; the bubbles which form dendritic branches of filaments change into clusters due to the secondary Bjerknes force. The cluster is composed of several bubbles surrounded by many tiny bubbles, in which bubbles repeatedly coalesce and fragment, and run away from pressure antinodes. When the clusters are broken up by forced fluid motion, the quenching of MBSL is suppressed.     

Multibubble Sonoluminescence from a Theoretical Perspective

In the present review, complexity in multibubble sonoluminescence (MBSL) is discussed. At relatively low ultrasonic frequency, a cavitation bubble is filled mostly with water vapor at relatively high acoustic amplitude which results in OH-line emission by chemiluminescence as well as emissions from weakly ionized plasma formed inside a bubble at the end of the violent bubble collapse. At relatively high ultrasonic frequency or at relatively low acoustic amplitude at relatively low ultrasonic frequency, a cavitation bubble is mostly filled with noncondensable gases such as air or argon at the end of the bubble collapse, which results in relatively high bubble temperature and light emissions from plasma formed inside a bubble. Ionization potential lowering for atoms and molecules occurs due to the extremely high density inside a bubble at the end of the violent bubble collapse, which is one of the main reasons for the plasma formation inside a bubble in addition to the high bubble temperature due to quasi-adiabatic compression of a bubble, where “quasi” means that appreciable thermal conduction takes place between the heated interior of a bubble and the surrounding liquid. Due to bubble–bubble interaction, liquid droplets enter bubbles at the bubble collapse, which results in sodium-line emission.     

Multibubble sonoluminescence enhancement by fluid flow

Forced fluid flow can cause the enhancement of multibubble sonoluminescence (SL) under suitable conditions. The effect of directional flow with a circulator is similar to that of rotating flow with a stirrer. The mechanism of the enhancement is that both flows prevent cavitation bubbles from coalescing and clustering, which are responsible for the quenching of SL. The intensity of sonochemiluminescence (SCL) in an aqueous luminol solution increases with flow speed at higher ultrasonic powers more significantly than that of SL in distilled water. However, in the range of low ultrasonic power, the intensities of SL and SCL decrease with flow speed. Therefore, an optimum flow speed exists in relation to ultrasonic power and frequency.     

Enhancement of sonochemical reaction of terephthalate ion by superposition of ultrasonic fields of various frequencies

The ultrasonic reactor with dual frequency was used and the effect of frequency on the fluorescence intensity of terephthalate ion was experimentally investigated in the frequency range from 176 to 635 kHz. The sonochemical reaction fields were visualized by using sonochemical luminescence of luminol solution. Compared with the fluorescence intensity of terephthalate ion for single frequency, the fluorescence intensity for dual frequency increased. The fluorescence intensity ratio of dual frequency to single frequency had maximum value when the frequency of transducer attached at the bottom wall was comparable in magnitude to that at the side wall. In the case of dual frequency, the sonochemical reaction fields became more extensive in the reactor and more intensive around the center of the reactor.     

Generation and consumption rates of OH radicals in sonochemical reactions

In this study, a KI aqueous solution or Methyl Orange (MO) aqueous solution was irradiated by an ultrasonic wave under the same experimental condition. The rates of oxidation of KI and MO by OH radicals differed by an order of magnitude. When the consumption of OH radicals by chemical reactions with species other than KI or MO is taken into account, numerical analysis of chemical kinetics model yields the same generation rate of OH radicals by the action of an ultrasonic wave for the experiments of KI and MO solutions.     

Theoretical study of single-bubble sonochemistry

Numerical simulations of bubble oscillations in liquid water irradiated by an ultrasonic wave are performed under the experimental condition for single-bubble sonochemistry reported by Didenko and Suslick [Nature (London) 418, 394 (2002)]. The calculated number of OH radicals dissolving into the surrounding liquid from the interior of the bubble agrees sufficiently with the experimental data. OH radicals created inside a bubble at the end of the bubble collapse gradually dissolve into the surrounding liquid during the contraction phase of an ultrasonic wave although about 30% of the total amount of OH radicals that dissolve into the liquid in one acoustic cycle dissolve in 0.1 micros at around the end of the collapse. The calculated results have indicated that the oxidant produced by a bubble is not only OH radical but also O atom and H2O2. It is suggested that an appreciable amount of O atom is produced by bubbles inside a standing-wave-type sonochemical reactor filled with water in which oxygen is dissolved as in the case of air.     

Dependence of the characteristics of bubbles on types of sonochemical reactors

Computer simulations of bubble oscillations in liquid water irradiated by an ultrasonic wave have revealed that the characteristic of bubbles depends on types of sonochemical reactors: a horn-type reactor and a standing-wave type reactor. When the acoustic amplitude is large at 20 kHz, the bubble content is mostly water vapor even at the end of the bubble collapse and the temperature inside a bubble at the collapse is relatively low. On the other hand, when the acoustic amplitude is relatively low, the bubble content is mostly noncondensable gas at the end of the bubble collapse and the bubble temperature is relatively high. In a horn-type sonochemical reactor, the former type of bubbles are dominant because many bubbles exist near the horn-tip where the acoustic amplitude is large, while in a standing-wave type reactor the latter type of bubbles are dominant because the Bjerknes force gathers bubbles at a region where acoustic amplitude is relatively low.     

Effect of static pressure on acoustic energy radiated by cavitation bubbles in viscous liquids under ultrasound

The effect of static pressure on acoustic emissions including shock-wave emissions from cavitation bubbles in viscous liquids under ultrasound has been studied by numerical simulations in order to investigate the effect of static pressure on dispersion of nano-particles in liquids by ultrasound. The results of the numerical simulations for bubbles of 5 μm in equilibrium radius at 20 kHz have indicated that the optimal static pressure which maximizes the energy of acoustic waves radiated by a bubble per acoustic cycle increases as the acoustic pressure amplitude increases or the viscosity of the solution decreases. It qualitatively agrees with the experimental results by Sauter et al. [Ultrason. Sonochem. 15, 517 (2008)]. In liquids with relatively high viscosity (～200 mPa s), a bubble collapses more violently than in pure water when the acoustic pressure amplitude is relatively large (～20 bar). In a mixture of bubbles of different equilibrium radius (3 and 5 μm), the acoustic energy radiated by a 5 μm bubble is much larger than that by a 3 μm bubble due to the interaction with bubbles of different equilibrium radius. The acoustic energy radiated by a 5 μm bubble is substantially increased by the interaction with 3 μm bubbles.     

Relationship between the bubble temperature and main oxidant created inside an air bubble under ultrasound

Numerical simulations of nonequilibrium chemical reactions in a pulsating air bubble have been performed for various ultrasonic frequencies (20 kHz, 100 kHz, 300 kHz, and 1 MHz) and pressure amplitudes (up to 10 bars). The results of the numerical simulations have indicated that the main oxidant is OH radical inside a nearly vaporous or vaporous bubble which is defined as a bubble with higher molar fraction of water vapor than 0.5 at the end of the bubble collapse. Inside a gaseous bubble which is defined as a bubble with much lower vapor fraction than 0.5, the main oxidant is H2O2 when the bubble temperature at the end of the bubble collapse is in the range of 4000-6500 K and O atom when it is above 6500 K. From the interior of a gaseous bubble, an appreciable amount of OH radical also dissolves into the liquid. When the bubble temperature at the end of the bubble collapse is higher than 7000 K, oxidants are strongly consumed inside a bubble by oxidizing nitrogen and the main chemical products inside a bubble are HNO2, NO, and HNO3.