Optimum bubble temperature for the sonochemical production of oxidants

Numerical simulations of bubble oscillations in liquid water irradiated by an ultrasonic wave are performed for various acoustic amplitudes and various ambient pressures. In the numerical simulations, effect of non-equilibrium evaporation and condensation of water vapor at the bubble wall and that of chemical reactions of gases and vapor inside a bubble are taken into account. The oxidants such as OH radicals, O radicals, H(2)O(2) molecules, and O(3) molecules are created from water vapor inside a heated bubble when a bubble collapses strongly. They are dispersed into the liquid and solutes are oxidized by the oxidants, which is called sonochemical reactions. The computer simulations have revealed that there exists the optimum bubble temperature, which is about 5500 K, for the production of the oxidants inside an air bubble because at higher bubble temperature the oxidants are strongly consumed inside a bubble by oxidizing nitrogen. Correspondingly, there exists an optimum acoustic amplitude for the production of the oxidants, which is about 2.2 atm when the ultrasonic frequency is 140 kHz and the ambient pressure is 1 atm. For an oxygen bubble, on the other hand, the amount of the oxidants created inside a bubble becomes nearly independent of the bubble temperature at the collapse above about 6000 K because nitrogen is absent.     

Sensitivity of free radicals production in acoustically driven bubble to the ultrasonic frequency and nature of dissolved gases

Central events of ultrasonic action are the bubbles of cavitation that can be considered as powered microreactors within which high-energy chemistry occurs. This work presents the results of a comprehensive numerical assessment of frequency and saturating gases effects on single bubble sonochemistry. Computer simulations of chemical reactions occurring inside a bubble oscillating in liquid water irradiated by an ultrasonic wave have been performed for a wide range of ultrasonic frequencies (213–1100 kHz) under different saturating gases (O₂, air, N₂ and H₂). For O₂ and H₂ bubbles, reactions mechanism consisting in 25 reversible chemical reactions were proposed for studying the internal bubble-chemistry whereas 73 reversible reactions were taken into account for air and N₂ bubbles. The numerical simulations have indicated that radicals such as OH, H, HO₂ and O are created in the bubble during the strong collapse. In all cases, hydroxyl radical (OH) is the main oxidant created in the bubble. The production rate of the oxidants decreases as the driving ultrasonic frequency increases. The production rate of OH radical followed the order O₂ > air > N₂ > H₂ and the order becomes more remarkable at higher ultrasonic frequencies. The effect of ultrasonic frequency on single bubble sonochemistry was attributed to its significant impact on the cavitation process whereas the effects of gases were attributed to the nature of the chemistry produced in the bubble at the strong collapse. It was concluded that, in addition to the gas solubility, the nature of the internal bubble chemistry is another parameter of a paramount importance that controls the overall sonochemical activity in aqueous solutions.     

Single-bubble sonoluminescence of aqueous solutions of lanthanide chlorides and models of the sonochemistry of nonvolatile metal salts

The single-bubble sonoluminescence of d-f (Ce³⁺, Pr³⁺) and f-f (Tb³⁺) ions is detected in aqueous solutions of LnCl₃. It has been shown that the luminescence of these ions is sonophotoluminescence, i.e., the reemission of the absorbed short-wavelength part of the radiation spectrum of a blackbody, which appears in a bubble levitating in the field of a standing ultrasonic wave, in the bulk of the solution. In view of the revealed inefficiency of reemission in GdCl₃, the single-bubble sonoluminescence of Gd³⁺ has not been observed. The results indicate the low probability of the penetration of nonvolatile metal ions into the bubble in the hot shell model, which would be valid in single-bubble sonolysis and thereby confirm the validity of the injected droplet model, which explains the penetration to the bubble, electronic excitation, and luminescence of f-f ions Gd³⁺ and Tb³⁺ in multibubble sonolysis with an intensity much higher than the yield of their sonophotoluminescence.     

Energy analysis during acoustic bubble oscillations: Relationship between bubble energy and sonochemical parameters

In this work, energy analysis of an oscillating isolated spherical bubble in water irradiated by an ultrasonic wave has been theoretically studied for various conditions of acoustic amplitude, ultrasound frequency, static pressure and liquid temperature in order to explain the effects of these key parameters on both sonochemistry and sonoluminescence. The Keller–Miksis equation for the temporal variation of the bubble radius in compressible and viscous medium has been employed as a dynamics model. The numerical calculations showed that the rate of energy accumulation, dE/dt, increased linearly with increasing acoustic amplitude in the range of 1.5–3.0 atm and decreased sharply with increasing frequency in the range 200–1000 kHz. There exists an optimal static pressure at which the power w is highest. This optimum shifts toward a higher value as the acoustic amplitude increases. The energy of the bubble slightly increases with the increase in liquid temperature from 10 to 60 °C. The results of this study should be a helpful means to explain a variety of experimental observations conducted in the field of sonochemistry and sonoluminescence concerning the effects of operational parameters.     

Experimental and numerical investigation of the effect of liquid temperature on the sonolytic degradation of some organic dyes in water

This paper presents a comprehensive experimental and numerical investigation of the effects of liquid temperature on the sonochemical degradation of three organic dyes, Rhodamine B (RhB), Acid orange 7 (AO7) and Malachite green (MG), largely used in the textile industry. The experiments have been carried out for an ultrasonic frequency of 300 kHz. The obtained experimental results were discussed using a new approach combining the results of single-bubble event and the number of active bubbles. The single-bubble event was predicted using a model that combines the bubble dynamics with chemical kinetics occurring inside a bubble during the strong collapse. The number of active bubbles was predicted using a method developed in our previous work. The experiments showed that the degradation rate of the three dyes increased significantly with increasing liquid temperature in the range 25–55 °C. It was predicted that the main pathway of pollutants degradation is the attack by OH radicals. The simulations showed that there exists an optimum liquid temperature of about 35 °C for the production of OH inside a bubble whereas the number of active bubbles increased sharply with the rise of the liquid temperature. It was predicted that the overall production rate of OH increased with increasing liquid temperature in the range 25–55 °C. Finally, it was concluded that the effect of liquid temperature on the sonochemical degradation of the three dyes in aqueous phase was controlled by the number of active bubbles in the range 35–55 °C and by both the number of bubbles and the single bubble yield in the range 25–35 °C.     

Production and dispersion of free radicals from transient cavitation Bubbles: An integrated numerical scheme and applications

As an advanced oxidation process with a wide range of applications, sonochemistry relies on acoustic cavitation to induce free radicals for degrading chemical contaminants. The complete process includes two critical steps: the radical production inside the cavitation bubble, and the ensuing dispersion of these radicals into the bulk solution. To grasp the physicochemical details in this process, we developed an integrated numerical scheme with the ability to quantitatively describe the radical production-dispersion behavior. It employs coupled simulations of bubble dynamics, intracavity chemical reactions, and diffusion–reaction-dominated mass transport in aqueous solutions. Applying this method to the typical case of argon and oxygen bubbles, the production mechanism for the main radicals is revealed. Moreover, the temporal-spatial distribution of the radicals in the liquid phase is presented. The results demonstrate that the enhanced radical production observed in oxygen bubbles can be traced to the initiation reaction O₂ + H₂O → OH+HO₂, which requires relatively low activation energy. In the outside liquid region, the dispersion of radicals is limited by robust recombination reactions. The simulated penetration depth of OH is around 0.2 μm and agrees with reported experimental measurements. The proposed numerical approach can be employed to better capture the radical activity and is instrumental in optimizing the engineering application of sonochemistry.     

The size of active bubbles for the production of hydrogen in sonochemical reaction field

The sonication of aqueous solution generates microscopic cavitation bubbles that may growth and violently collapse to produce highly reactive species (i.e. OH, HO₂ and H₂O₂), hydrogen and emit light, sonoluminescence. The bubble size is a key parameter that influences the chemical activity of the system. This wok aims to study theoretically the size of active bubbles for the production of hydrogen in ultrasonic cavitation field in water using a single bubble sonochemistry model. The effect of several parameters such as frequency of ultrasound, acoustic intensity and liquid temperature on the range of sonochemically active bubbles for the production of hydrogen was clarified. The numerical simulation results showed that the size of active bubbles is an interval which includes an optimum value at which the production rate of H₂ is maximal. It was shown that the range of ambient radius for an active bubble as well as the optimum bubble radius for the production of hydrogen increased with increasing acoustic intensity and decreased with increasing ultrasound frequency and bulk liquid temperature. It was found that the range of ambient bubble radius dependence of the operational conditions followed the same trend as those reported experimentally for sonoluminescing bubbles. Comparison with literature data showed a good agreement between the theoretical determined optimum bubble sizes for the production of hydrogen and the experimental reported sizes for sonoluminescing bubbles.     

声致发光气泡内水蒸气的影响

提出了一个单气泡声致发光的简单计算模型.这个模型是在均匀压强近似下，考虑质量和温度在气泡内的非均匀分布，同时考虑了水蒸气在气泡壁上的凝结与蒸发以及水蒸气在气泡内相对惰性气体的质量扩散.通过Saha方程估算气体电离密度，利用电子与离子、电子与中性粒子的轫致辐射，电子与离子的复合辐射公式估算气泡的辐射强度.不考虑化学反应，计算了不同水温时的气泡发光强度，发现当水温在0 ℃时轫致辐射发光模型比较符合实验结果，水温升高时，如水温为20 ℃或以上，轫致辐射发光模型的计算与实验结果出现数量级差别.考虑化学反应，轫致辐射发光模型的计算则总是比实验结果低2个数量级.     

圆锥气泡发光的光谱性质

在改进的U型管装置中观察到一种圆锥气泡声致发光现象。声致发光产生的单个光脉冲的能量可达到约1.4 毫焦. 脉冲宽度约100 毫秒。发光光谱由连续光谱上叠加C2,CN,和CH的激发态光谱构成。这种圆锥气泡声致发光为单泡声致发光和多泡声致发光提供了一种联系。     

Bubble population phenomena in acoustic cavitation

Theoretical treatments of the dynamics of a single bubble in a pressure field have been undertaken for many decades. Although there is still scope for progress, there now exists a solid theoretical basis for the dynamics of a single bubble. This has enabled useful classifications to be established, including the distinction between stable cavitation (where a bubble pulsates for many cycles) and transient cavitation (where the bubble grows extensively over time-scales of the order of the acoustic cycle, and then undergoes an energetic collapse and subsequent rebound and then, potentially, either fragmentation, decaying oscillation or a repeat performance). Departures from sphericity, such as shape and surface oscillations and jetting, have also been characterized. However, in most practical systems involving high-energy cavitation (such as those involving sonochemical, biological and erosive effects), the bubbles do not behave as the isolated entities modelled by this single-bubble theory: the cavitational effect may be dominated by the characteristics of the entire bubble population, which may influence, and be influenced by, the sound field.

The well established concepts that have resulted from the single-bubble theory must be reinterpreted in teh light of the bubble population, an appreciation of population mechanisms being necessary to apply our understanding of single-bubble theory to many practical applications of ‘power’ ultrasound. Even at a most basic level these single-bubble theories describe the response of the bubble to the local sound field at the position of the bubble, and that pressure field will be influenced by the way sound is scattered by neighbouring bubbles. The influence of the bubble population will often go further, a non-uniform sound field creating an inhomogeneous bubble distribution. Such a distribution can scatter, channel and focus ultrasonic beams, can acoustically shield regions of the sample, and elsewhere localize the cavitational activity to discrete ‘hot spots’. As a result, portions of the sample may undergo intense sonochemical activity, degassing, erosion, etc., whilst other areas remain relatively unaffected. Techniques exist to control such situations where they are desirable, and to eliminate this localization where a more uniform treatment of the sample is desired.     

Luminescence of Tb3+ and Gd3+ ions in sonolysis under the conditions of a single bubble moving in aqueous solutions of TbCl3 and GdCl3

Luminescence bands of Tb³⁺ and Gd³⁺ ions are detected during sonolysis in the regime of a moving single bubble in aqueous solutions of TbCl₃ and GdCl₃ salts with concentration 1–2 mol/L. Saturation with argon, low temperatures of solutions (?5°C), and a high concentration of salts are the factors facilitating sonoluminescence of the metal. Comparison with the characteristics of sonoluminescence of lanthanide ions studied earlier in the regimes of multibubble and single-bubble sonolysis with a stationary bubble shows that the electron excitation of metal ions in the given case is associated with translational displacements of the bubble. Our results confirm the validity of the sonochemical model of microdroplet injection, which explains the penetration of nonvolatile salts into cavitation bubbles as a result of their deformation during intense movements.     

Argon rectification and the cause of light emission in single-bubble sonoluminescence

In single-bubble sonoluminescence, repeated brief flashes of light are produced in a gas bubble strongly driven by a periodic acoustic field. A startling hypothesis has been made by Lohse and co-workers [Phys. Rev. Lett. 78, 1359 (1997)] that the non-noble gases in an air bubble undergo chemical reaction into soluble products, leaving only argon. In the present work, this dissociation hypothesis is supported by simulations, although the associated temperatures of about 7000 K seem too low for bremsstrahlung, which has been proposed as the dominant light emission mechanism. This suggests that emission from water vapor and its reaction products, heretofore not included, may play an important role.     

单泡超声空化仿真模型的建立及其动力学过程模拟*

为了模拟单泡超声空化的动力学特性,建立了单泡超声空化的有限元仿真模型,基于流体动力学控制方程和流体体积分数模型,利用有限元分析软件模拟了超声驱动下水中单泡的空化动力学过程。结果表明:单泡随时间的演化规律是先缓慢膨胀到最大后迅速塌缩;泡内压强与气体密度变化与单泡体积变化成反比;在膨胀阶段,泡外压强与气体密度沿着泡的径向向外递减;在压缩阶段,泡外在声压垂直方向的压强与气体密度要大于声压激励方向的压强和气体密度。该文分析结果将为超声空化动力学过程模拟及研究提供参考。     

Porous SiO2 nanoparticles containing ruthenium or sulfur compounds: Sonochemical producing and sonoluminescence in aqueous suspensions

Aqueous suspensions of silicon dioxide porous nanoparticles (average size 10–30 nm, average pore size 5.8 nm) were obtained via ultrasonic dispersing. As was shown through recording SiO molecular lines in a moving single-bubble sonoluminescence spectrum, these nanoparticles penetrate into the bubble and then undergo decay. Similarly, suspensions of SiO₂ nanoparticles, the pores of which were saturated with ruthenium dodecacarbonyl or elemental sulfur, were obtained by impregnation of the initial powder with solutions of these reagents in chloroform followed by evaporation of the solvent. Single-bubble sonoluminescence spectra of these suspensions contain more intense lines of Ru or S and Sⁿ⁺ as compared with the SiO lines. This also proves the involvement of water insoluble ruthenium and sulfur compounds into bubble sonoluminescent reactions in the heterogenic aqueous medium. Using the method of comparing the experimentally obtained and computer simulated luminescent spectra, we determined the effective electronic temperature T_e^Ru, which was 9000 ± 500 K, in non-equilibrium plasma of a bubble levitating in the ultrasonic field.     

A new source of radiation in single-bubble sonoluminescence

An unsolved challenge of sonoluminescence phenomenon is the mechanism of light emission at the moment of collapse. In this article, by considering single-bubble sonoluminescence and based on the hydrochemical model and thermal bremsstrahlung approach, for the first time two different origins of light have numerically been studied to describe the Ar bubble radiation in water at the moment of collapse: (a) radiation from the Ar gas inside the bubble and (b) radiation from the thin layer of the surrounding fluid. The results indicate that, contrary to the previous studies, the radiation from the water shell is dominant, and it is about one order of magnitude stronger than the radiation from the gas inside the bubble. This result can decrease the difference between the theoretical results and the previous experimental data. In addition, based on the role of acoustic pressure amplitude on the characteristics of single-bubble sonoluminescence, various parameters such as degree of ionization, gas pressure, temperature and power were calculated. The results are in excellent agreement with the reported experimental measurements.     

Role of thermal conduction in single-bubble cavitation

Effect of thermal conduction on radiation from a single cavitating bubble has been studied in a hydrochemical framework including variation of heat conductivity of noble gases up to 2500 K. Results of numerical simulation show that thermal conductivity plays an important role in determining ultimate cavitation temperature. Higher thermal conductivity of lighter noble gases causes to more thermal dissipation during the bubble collapse, leading to a lower peak temperature. Moreover, at the same driving conditions, radius of light emitting region is greater for heavier noble bubbles. Therefore, sonoluminescence radiation is more intensive from heavier noble gases. Phase diagrams of single-bubble sonoluminescence have also been calculated and in comparison with available experimental data, there is a relatively good agreement between the theory and experiment for noble gases.     

Study on the spatial distribution of the liquid temperature near a cavitation bubble wall

A simple new model of the spatial distribution of the liquid temperature near a cavitation bubble wall (T_li) is employed to numerically calculate T_li. The result shows that T_li is almost same with the ambient liquid temperature (T₀) during the bubble oscillations except at strong collapse. At strong collapse, T_li can increase to about 1510 K, the same order of magnitude with that of the maximum temperature inside the bubble, which means that the chemical reactions occur not only in gas-phase inside the collapsing bubble but also in liquid-phase just outside the collapsing bubble. Four factors (ultrasonic vibration amplitude, ultrasonic frequency, the surface tension and the viscosity) are considered to study their effects for the thin liquid layer. The results show that for the thin layer, the thickness and the temperature increase as the ultrasonic vibration amplitude rise; conversely, the thickness and the temperature decrease with the increase of the ultrasonic frequency, the surface tension or the viscosity.     

Theoretical estimation of sonochemical yield in bubble cluster in acoustic field

In order to learn more about the physical phenomena occurring in cloud cavitation, the nonlinear dynamics of a spherical cluster of cavitation bubbles and cavitation bubbles in cluster in an acoustic field excited by a square pressure wave are numerically investigated by considering viscosity, surface tension, and the weak compressibility of the liquid.The theoretical prediction of the yield of oxidants produced inside bubbles during the strong collapse stage of cavitation bubbles is also investigated. The effects of acoustic frequency, acoustic pressure amplitude, and the number of bubbles in cluster on bubble temperature and the quantity of oxidants produced inside bubbles are analyzed. The results show that the change of acoustic frequency, acoustic pressure amplitude, and the number of bubbles in cluster have an effect not only on temperature and the quantity of oxidants inside the bubble, but also on the degradation types of pollutants, which provides a guidance in improving the sonochemical degradation of organic pollutants.     

Radical production inside an acoustically driven microbubble

The chemical production of radicals inside acoustically driven bubbles is determined by the local temperature inside the bubbles and by their composition at collapse. By means of a previously validated ordinary differential equations (ODE) model [L. Stricker, A. Prosperetti, D. Lohse, Validation of an approximate model for the thermal behavior in acoustically driven bubbles, J. Acoust. Soc. Am. 130 (5) (2011) 3243–3251], based on boundary layer assumption for mass and heat transport, we study the influence of different parameters on the radical production. We perform different simulations by changing the driving frequency and pressure, the temperature of the surrounding liquid and the composition of the gas inside the bubbles. In agreement with the experimental conditions of new generation sonochemical reactors, where the bubbles undergo transient cavitation oscillations [D. F. Rivas, L. Stricker, A. Zijlstra, H. Gardeniers, D. Lohse, A. Prosperetti, Ultrasound artificially nucleated bubbles and their sonochemical radical production, Ultrason. Sonochem. 20 (1) (2013) 510–524], we mainly concentrate on the initial chemical transient and we suggest optimal working ranges for technological applications. The importance of the chemical composition at collapse is reflected in the model, including the role of entrapped water vapor. We in particular study the exothermal reactions taking place in H₂ and O₂ mixtures. At the exact stoichiometric mixture 2:1 the highest internal bubble temperatures are achieved.