Methods of theoretical study of vibrational phenomena in liquids--comparative analysis

In this review, existing theoretical models of vibrational phenomena in liquids are analyzed and compared. Most attention is paid to sonoluminescence, sonolysis and related phenomena. The criteria of selection of the optimal theoretical model involve analyzing experimental results, its usefulness for evaluation of thermodynamic and other parameters of the liquid under vibration, simplicity of the mathematical solution and the time needed for computing. It is concluded that, according to these criteria, the optimal (between existing models) is the chemical model of vibration in liquid, while the best perspectives are for its combinations with other models.     

Designing and characterizing a multi-stepped ultrasonic horn for enhanced sonochemical performance

The commonly used ultrasonic horn generates localized cavitation below its converging tip resulting in a dense bubble cloud near the tip and limiting diffusion of reactive components into the bubble cloud or reactive radicals out of the bubble cloud. To improve contact between reactive components, a novel ultrasonic horn design was developed based on the principles of the dynamic wave equation. The horn, driven at 20 kHz, has a multi-stepped design with a cone-shaped tip increasing the energy-emitting surface areas and creating multiple reactive zones. Through different physical and chemical experiments, performance of the horn was compared to a typical horn driven at 20 kHz. Hydrophone measurements showed high acoustic pressure areas around the horn neck and tip. Sonochemiluminescence experiments verified multiple cavitation zones consistent with hydrophone readings. Calorimetry and dosimetry results demonstrated a higher energy efficiency (31.3%) and a larger hydroxyl radical formation rate constant (0.36 μM min⁻¹) compared to typical horns. In addition, the new horn degraded naphthalene faster than the typical horn tested. The characterization results demonstrate that the multi-stepped horn configuration has the potential to improve the performance of ultrasound as an advanced oxidation technology by increasing the cavitation zone in the solution.     

The effects of ultrasound on micromixing

The Villermaux–Dushman reaction is a widely used technique to study micromixing efficiencies with and without sonication. This paper shows that ultrasound can interfere with this reaction by sonolysis of potassium iodide, which is excessively available in the Villermaux–Dushman solution, into triiodide ions. Some corrective actions, to minimize this interference, are proposed. Furthermore, the effect of ultrasonic frequency, power dissipation, probe tip surface area and stirring speed on micromixing were investigated. The power and frequency seem to have a significant impact on micromixing in contrast to the stirring speed and probe tip surface area. Best micromixing was observed with a 24 kHz probe and high power intensities. Experiments with different frequencies but a constant power intensity, emitter surface, stirring speed, cavitation bubble type and reactor design showed best micromixing for the highest frequency of 1135 kHz. Finally, these results were used to test the power law model of Rahimi et al. This model was not able to predict micromixing accurately and the addition of the frequency, as an additional parameter, was needed to improve the simulations.     

Treating soil-washing fluids polluted with oxyfluorfen by sono-electrolysis with diamond anodes

This works is focused on the treatment by sono-electrolysis of the liquid effluents produced during the Surfactant-Aided Soil-Washing (SASW) of soils spiked with herbicide oxyfluorfen. Results show that this combined technology is very efficient and attains the complete mineralization of the waste, regardless of the surfactant/soil radio applied in the SASW process (which is the main parameter of the soil remediation process and leads to very different wastes). Both the surfactant and the herbicide are completely degraded, even when single electrolysis is used; and only two intermediates are detected by HPLC in very low concentrations. Conversely, the efficiency of single sonolysis approach, for the oxidation of pollutant, is very low and just small changes in the herbicides and surfactant concentrations are observed during the tests carried out. Sono-electrolysis with diamond electrodes achieved higher degradation rates than those obtained by single sonolysis and/or single electrolysis with diamond anodes. A key role of sulfate is developed, when it is released after the electrochemical degradation of surfactant. The efficient catalytic effect observed which can be explained by the anodic formation of persulfate and the later, a sono-activation is attained to produce highly efficient sulfate radicals. The effect of irradiating US is more importantly observed in the pesticide than in the surfactant, in agreement with the well-known behavior of these radicals which are known to oxidize more efficiently aromatic compounds than aliphatic species.     

Mechanism and dynamic study of reactive red X-3B dye degradation by ultrasonic-assisted ozone oxidation process

The effectiveness of ozone combined with ultrasound techniques in degrading reactive red X-3B is evaluated. A comparison among ozone (O₃), ultrasonic (US), ozone/ultrasonic (O₃/US) for degradation of reactive red X-3B has been performed. Results show that O₃/US system was the most effective and the optimally synergetic factor reaches to 1.42 in O₃/US system. The cavitation of ultrasound plays an important role during the degradation process. It is found that 99.2% of dye is degraded within 6 min of reaction at the initial concentration of 100 mg·L⁻¹, pH of 6.52, ozone flux of 40 L·h⁻¹ and ultrasonic intensity of 200 W·L⁻¹. Ozonation reactions in conjunction with sonolysis indicate that the decomposition followed pseudo-first-order reaction kinetics but the degradation efficiencies are affected by operating conditions, particularly initial pH and ultrasonic intensity. A kinetic model is established based on the reaction corresponding to operational parameters. In addition, the main reaction intermediates, such as p-benzoquinone, catechol, hydroquinone, phthalic anhydride and phthalic acid, are separated and identified using GC/MS and a possible degradation pathway is proposed during the O₃/US process.     

Enhanced sonochemical degradation of azure B dye by the electroFenton process

The degradation of azure B dye (C₁₅H₁₆ClN₃S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H₂O₂ at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe²⁺, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton > Fenton > sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes.     

High-frequency ultrasound treatment of sludge: combined effect of surfactants removal and floc disintegration

Ultrasounds represent an effective technology in many research fields. In sewage sludge treatment, low-frequency ultrasound, particularly at 20 kHz, are widely used for sludge disintegration before the anaerobic digestion, while in the last years novel application of high-frequency ultrasound regards the decontamination of water and wastewater through sonochemical reactions. The innovative approach presented in this paper is the treatment of sewage sludge with ultrasound at 200 kHz for obtaining efficient sludge disintegration and the removal of the linear alkylbenzenesulphonates (LAS) at the same time. Results of the sonolysis experiments showed that native LAS degradation up to 40% can be achieved with low power input in less than 1 h. The degradation pattern was different for each LAS homologue (from C10 to C13), because of their physical-chemical properties, in particular as regards the alkyl chain length. This high-frequency ultrasound irradiation resulted effective also in terms of floc disintegration and soluble organic matter release, in particular for energy inputs higher than 30,000 kJ/kg TS. The disrupting effect of the 200 kHz treatment was also evaluated by microscope analyses and determination of the extracellular polymeric substances release in the liquid phase.     

Effective removal of organics from Bayer liquor through combined sonolysis and ozonation: Kinetics and mechanism

The presence of organic compounds in the waste liquor is of serious environmental concern that has plagued the development of alumina industry (Bayer Process). The present work attempts to develop a green and efficient process for removal of organics utilizing combined effect of sonolysis and ozonation (US/O₃). The effects of reaction duration, ozone concentration and ultrasonic power are assessed for sonolysis (US), ozonation (O₃) and combination of sonolysis and ozonation (US/O₃). The optimal conditions for US/O₃ treatment system is identified to be a reaction duration of 7 h, ozone concentration of 7.65 g/h, and ultrasonic power of 600 W. The total organic carbon (TOC) removal and decolorization are 60.13% and 87.1%, respectively. The process can be scaled-up to industrial scale, which could potentially serve to be a convenient, safe and sustainable alternative to the exisiting treatment technologies. Additionally, the treated waste water can be reused contributing to an improvement in the overall economics.     

Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH₄, C₂H₆, C₂H₄, C₂H₂, CO, CO₂, H₂, H₂O₂, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH₃ and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H₂ did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.