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.     

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.     

Sonoluminescence of aqueous solutions of lanthanide salts

The influence of salts (TbCl₃, Tb(NO₃)₃, PrCl₃, EuCl₃, CeCl₃, and DyCl₃) on the spectrum and intensity of multi-bubble sonoluminescence (SL) of water was observed at a frequency of 20 kHz. Luminescence bands of the lanthanide ions were detected in the SL spectra of concentrated solutions of the Ce^III, Tb^III, and Dy^III chlorides (0.1—1 mol L^–1). No luminescence was observed for solutions of the other salts, and the shape of the spectra is due to the absorption of the water SL by the lanthanide ions. Possible mechanisms of the appearance of SL of lanthanides were considered. The first mechanism is the excitation of the lanthanide aqua ions in the solution bulk due to the absorption of the short-wave portion of glow of the excited water molecules and OH radicals emitted from the cavitation gas-vapor bubbles. The second mechanism involves the transfer of the lanthanide ions to the gas phase from the liquid layer adjacent to the cavitation bubble and their excitation in the bubble volume upon collisions with other hot or electron-excited particles.     

Sonoluminescence of aqueous solution of gadolinium chloride

A line of the Gd^III ion was detected at 311 nm in the multibubble sonoluminescence spectrum of a concentrated (1 mol L⁻¹) solution of gadolinium chloride. A comparison with the earlier studied sonoluminescence of the Ce^III and Tb^III ions shows that the Gd^III ion is excited in the volume and/or on the surface of cavitation bubbles upon collisions with “hot” particles. The efficiency of excitation of the lanthanide ions via this mechanism depends on the type of electron transition. For the same energy of the excited state, the efficiency of Gd^III excitation (f-f transition) exceeds by at least 50 times that of Ce^III excitation (f-d transition). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1341–1344, June, 2005.     

Multibubble sonoluminescence of europium(III) chloride in heavy water

A weak glow in the region of the Eu³⁺ photoluminescence spectrum was detected against the background of the continuum of the solvent emission during multibubble sonolysis of air- or argon-saturated EuCl₃ solutions (0.1 mol L⁻¹) in heavy water. No characteristic sonoluminescence of the europium ion in aqueous solutions was observed earlier. Possible reasons for the low yield of Eu³⁺ sonoluminescence compared with other lanthanide ions (Ln³⁺) are discussed and the influence of europium on the spectrum of the solvent continuum related, in particular, to quenching of the electron-excited sonolysis products H₂O* (D₂O*) and Eu³⁺* in electron transfer reactions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1793–1796, September, 2008.     

Sonoluminescence of aqueous solutions of sulfuric acid and sulfur dioxide

Sonoluminescence (SL) of aqueous solutions of sulfuric acid and sulfur dioxide enhances with an increase in their concentration and reaches a maximum at 16 and 0.05 mol L^–1, respectively. The further increase in the concentration of these substances decreases the SL intensity. The SL spectra of the solutions have a broad maximum at 450 nm. Excited SO₂ molecules formed in sulfuric acid due to sonolysis are luminescence emitters. The proposed mechanism of bright SL in these systems is based on the energy transfer from the electron-excited sonolysis products to the SO₂ molecules in cavitation bubbles.     

Sonoluminescence Spectra in the First Tens of Seconds of Sonolysis of [BEPip][NTf2], at 20 kHz under Ar

Following recent works on the sonochemical degradation of butyl ethyl piperidinium bis-(trifluoromethylsulfonyl)imide ([BEPip][NTf₂]), monitoring of sonoluminescence (SL) spectra in the first tens of seconds of sonolysis was needed to better characterize the formed plasma and to question the correlation of the SL spectra with the viscosity. A very dry [BEPip][NTf₂] ionic liquid (IL) and a water-saturated liquid are studied in this paper. In both cases, IL degradation is observed as soon as SL emission appears. It is confirmed that the initial evolution of the SL intensity is closely linked to the liquid viscosity that impacts the number of bubbles; however, other parameters can also play a role, such as the presence of water. The water-saturated IL shows more intense SL and faster degradation. In addition to the expected bands, new emission bands are detected and attributed to the S₂ B-X emission, which is favored in the water-saturated ionic liquid.     

Eco-friendly synthesis of esters under ultrasound with p-toluenesulfonic acid as catalyst

The present work describes the efficient ultrasound-assisted synthesis of saturated aliphatic esters from synthetic aliphatic acids in methanol or in ethanol, using p-toluenesulfonic acid as a catalyst. The esters were isolated in good yields after short reaction times under mild conditions. The compounds were analyzed by high resolution mass spectrometry (HRMS), which give a fragmentations pathway common for these molecules.     

The effects of ultrasonic irradiation on the preparation and properties of Ormosils

Organically modified silicates (Ormosils), derived from silica and polydimethylsiloxane (PDMS), have been prepared by the sol-gel method with ultrasonic irradiation. Tetraethoxysilane (TEOS), PDMS, water and HCl were mixed and exposed to 20 kHz ultrasonic waves under various conditions. Ultrasonic irradiation shortened the gelation time and made it possible to obtain gels without the addition of solvent (e.g. alcohol and tetrahydrofuran (THF)). The reaction mechanism of the ultrasonic irradiated Ormosil solution was investigated by liquid state ²⁹Si NMR. The densities of the gels prepared under ultrasonic irradiation were found to be much higher than those without irradiation. The effect of solvent addition on the properties of gels was also investigated.     

Production of O Radicals from Cavitation Bubbles under Ultrasound

In the present review, the production of O radicals (oxygen atoms) in acoustic cavitation is focused. According to numerical simulations of chemical reactions inside a bubble using an ODE model which has been validated through studies of single-bubble sonochemistry, not only OH radicals but also appreciable amounts of O radicals are generated inside a heated bubble at the violent collapse by thermal dissociation of water vapor and oxygen molecules. The main oxidant created inside an air bubble is O radicals when the bubble temperature is above about 6500 K for a gaseous bubble. However, the concentration and lifetime of O radicals in the liquid water around the cavitation bubbles are unknown at present. Whether O radicals play some role in sonochemical reactions in the liquid phase, which are usually thought to be dominated by OH radicals and H2O2, should be studied in the future.