A standard method to calibrate sonochemical efficiency of an individual reaction system

Fricke reaction, KI oxidation and decomposition of porphyrin derivatives by use of seven types of sonochemical apparatus in four different laboratories were examined in the range of frequency of 19.5 kHz to 1.2 MHz. The ultrasonic energy dissipated into an apparatus was determined also by calorimetry. Sonochemical efficiency of Fricke reaction and KI oxidation was defined as the number of reacted molecule per unit ultrasonic energy. The sonochemical efficiency is independent of experimental conditions such as the shape of sample cell and irradiation instruments, but depends on the ultrasonic frequency. We propose the KI oxidation dosimetry using 0.1 moldm(-3) KI solution as a standard method to calibrate the sonochemical efficiency of an individual reaction system.     

用碘释放法研究双束超声辐照的脉冲空化峰

本文使用双束同频脉冲超声水平正交辐照,通过磺释放法检测,发现双束同频水平正交辐照亦可观察到明显的空化峰现象及声化学产额增长。     

空化水中HO2自由基的测定

采用频率为1．8MHz,声强为1－5W／cm2的超声波引发水中的空化效应,通过采用吡啶溶液作为HO2自由基捕获剂,测出了实验条件下空化水中HO2自由基的浓度水平为10－5M。     

Optimisation of 20 kHz sonoreactor geometry on the basis of numerical simulation of local ultrasonic intensity and qualitative comparison with experimental results

The intensity distribution of the ultrasonic energy is, after the frequency, the most significant parameter to characterize ultrasonic fields in any sonochemical experiment. Whereas in the case of low intensity ultrasound the measurement of intensity and its distribution is well solved, in the case of high intensity (when cavitation takes place) the measurement is much more complicated. That is why the predicting the acoustic pressure distribution within the cell is desirable. A numerical solution of the wave equation gave the distribution of intensity within the cell. The calculations together with experimental verification have shown that the whole reactor behaves like a resonator and the energy distribution depends strongly on its shape. The agreement between computational simulations and experiments allowed optimisation of the shape of the sonochemical reactor. The optimal geometry resulted in a strong increase in intensity along a large part of the cell. The advantages of such optimised geometry are (i) the ultrasonic power necessary for obtaining cavitation is low; (ii) low power delivered to the system results in only weak heating, consequently, no cooling is necessary and (iii) the "active volume" is large, i.e. the fraction of the reactor volume with high intensity is large and is not limited to a vicinity close to the horn tip.     

Dosimetry in sonochemistry: the use of aqueous terephthalate ion as a fluorescence monitor

The generation of HO radicals by acoustic cavitation in water was monitored by their reaction with terephthalic acid (TA) anion to produce fluorescent hydroxyterephthalate ions using a cleaning bath (38kHz) and a probe system (20, 40 and 60 kHz) as different sources of ultrasound. When using the ultrasonic bath as a source of energy for sonochemical studies, the shape of the reaction vessel is important. In the case of HO production from water (50 cm³), reaction in a conical flask (100 cm³) produces 2.75 times more radicals than a round-bottomed flask of the same capacity. The fluorescence yield (fluorescence intensity/ultrasound dosage) obtained using the conical flask and ultrasonic bath was similar to that for a probe operating at 40 kHz on the same volume of solution. For a probe system operating at 20, 40 and 60 kHz the greatest sonochemical efficiency was attained at the highest of these frequencies (60 kHz). For the probe system the fluorescence yield is directly proportional to power input and the concentration of TA. The fluorescence yield decreases as the temperature is increased.     

A study on effect of sonochemistry in a reverberation field

In this paper,an ultrasound with frequency of 815 kHz was used to re-search the sonochemical yield in a small-size reverberation field by the methodof fluorescent spectrum analysis.There are two characteristics on the effect ofsonochemistry in the reverberation field:First,the cavitation threshold wasabout 0.3W/cm~2(it was 0.7W/cm~2 in travelling field);Second,when thesound intensity was larger than the threshold,the sonochemical yield increasedas the intensity increased and increased rapidly after the intensity was at1.69-2.13W/cm~2,so that there was a upturned point in the curve of the result(which would tend to saturation in the travelling field).The theoretical analysisshows that the reason of the threshold decrease is that the sound energy densitybecomes high in the reverberation field,and the upturned point results from thedisturbance of the radiation pressure on the liquid surface.Therefore,by exper-iment and theory this paper shows that a reverberation field has to be built forthe higher sonoche     

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.     

Sonoluminescence intensity and ultrasonic cavitation temperature in organic solvents: Effects of generated radicals

Ultrasonic cavitation in organic solvents remains poorly understood in contrast with aqueous systems, largely because of complexities related to solvent decomposition. In this study, we sonicated different types of organic solvents (i.e. linear alkanes, aliphatic alcohols, aromatic alcohols, and acetate esters) under argon saturation. The average temperature of the cavitation bubbles was estimated using the methyl radical recombination method. We also discuss the effects of the physical properties of the solvents, such as vapor pressure and viscosity, on the cavitation temperature. The average cavitation bubble temperature and sonoluminescence intensity were higher in organic solvents with lower vapor pressure; for aromatic alcohols, these values were particularly high. It was found that the specific high sonoluminescence intensities and average cavitation temperatures exhibited in aromatic alcohols are caused by the highly resonance-stable generated radicals. The results obtained in this study are very useful for acceleration of sonochemical reaction in organic solvents, which are indispensable for organic synthesis and material synthesis.     

Advancement of high power ultrasound technology for the destruction of surface active waterborne contaminants

The current paper explores recent advances in sonochemical techniques to improve the ultrasound-mediated degradation efficiency of surface active, waterborne contaminants. Sonochemical degradation efficiency of surface active contaminants generally has a strong dependence on the concentration of contaminant at the gas/solution surface of cavitation bubbles. This in turn depends on the thermodynamic and diffusion/kinetic-controlled adsorption properties of the surfactant at the rapidly pulsating gas/solution surface of acoustic cavitation bubbles. The adsorption properties of surfactants can be exploited to enhance their sonochemical decomposition by varying ultrasound exposure parameters such that changes in the nature of the bubble population (especially the bubble life-time and rate of pulsations) cause changes in the amount of surfactant that adsorbs to the gas/solution interface of cavitation bubbles. Herein we describe recent results on the effect of ultrasound frequency and pulsing mode on sonochemical degradation of surfactants in aqueous solutions and show how the exposure parameters can be adjusted in ways to produce more efficient decomposition of contaminants, even under exposure conditions where seemingly poor sonochemical activity is detected in the bulk solution. The relevance of these results to scale-up of ultrasound decontamination processes is discussed.     

Chemical effect of swirling jet-induced cavitation: degradation of rhodamine B in aqueous solution

The chemical effect of swirling jet-induced cavitation was investigated with the decomposing reaction of rhodamine B in aqueous solution. It was found that rhodamine B in aqueous solution can be degraded with swirling jet-induced cavitation and the degradation can be described by a pseudo-first-order kinetics. The effects of operating conditions such as pressure, temperature, initial concentration of rhodamine B, pH of water on the degradation rate of rhodamine B were discussed. It was found that the degradation rate of rhodamine B increased with increasing pressure and decreased with increasing initial concentration. It was also found that the degradation of rhodamine B was strongly dependent of temperature and pH of aqueous solution. The oxidation efficiency of swirling jet-induced cavitation for rhodamine B degradation was discussed and compared with ultrasonic cavitation. The result indicated that the swirling jet-induced cavitation is more energy efficient as compared to sonochemical cavitation.     

Sonochemical method for producing titanium metal powder

We demonstrate a sonochemical method for producing titanium metal powder. The method uses low intensity ultrasound in a hydrocarbon solvent at near-ambient temperatures to first create a colloidal suspension of liquid sodium–potassium alloy in the solvent and then to reduce liquid titanium tetrachloride to titanium metal under cavitation conditions. XRD data collected for the reaction products after the solvent removal show only NaCl and KCl, with no diffraction peaks attributable to titanium metal or other titanium compounds, indicating either the formation of amorphous metal or extremely small crystallite size. TEM micrographs show that hollow spheres formed of halide salts and titanium metal, with diameters with diameters ranging from 100 to 500 nm and a shell thickness of 20 to 40 nm form during the synthesis, suggesting that the sonochemical reaction occurs inside the liquid shell surrounding the cavitation bubbles. Metal particle sizes are estimated to be significantly smaller than 40 nm from TEM data. XRD data of the powder after annealing and prior to removal of the alkali chloride salts provides direct evidence that titanium metal was formed during the sonochemical synthesis.     

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.     

Sonochemical and sonocatalytic degradation of monolinuron in water

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.     

Effect of particle addition on sonochemical reaction

Enhancement of chemical reaction with a photocatalyst of titanium dioxide (TiO(2)) by ultrasonic irradiation is studied through the absorbance measurements for liberation of iodine from a KI aqueous solution as an index of oxidation reaction. It is well known as a synergetic effect that the addition of TiO(2) fine particles under UV has an ability to enhance the yield in chemical reaction with OH-radical from hot spot at violent collapse of cavitation bubbles with intense ultrasound. In this study, the absorbance is measured after simultaneous irradiation of ultrasound and UV with the addition of TiO(2) much less than the usual concentration by two orders of content. It is shown that, even in case of quite a little TiO(2) addition where the photocatalytic effect is less, the yield is enhanced obviously in comparison with the summation in yield of independent procedure of ultrasound without TiO(2) and UV with TiO(2). The absorbance-peak deviation to the shorter wavelength implies the generation of titanium peroxide (TiO(3)). The effect of particle addition is due to the chemically activated particle surface on the TiO(2) and probably to the increase in the cavitation bubbles that results in promoting a transfer of OH-radical and other oxidants to bulk liquid region at the collapse.     

Quantitative calculation of reaction performance in sonochemical reactor by bubble dynamics

In order to design a sonochemical reactor with high reaction efficiency, it is important to clarify the size and intensity of the sonochemical reaction field. In this study, the reaction field in a sonochemical reactor is estimated from the distribution of pressure above the threshold for cavitation. The quantitation of hydroxide radical in a sonochemical reactor is obtained from the calculation of bubble dynamics and reaction equations. The distribution of the reaction field of the numerical simulation is consistent with that of the sonochemical luminescence. The sound absorption coefficient of liquid in the sonochemical reactor is much larger than that attributed to classical contributions which are heat conduction and shear viscosity. Under the dual irradiation, the reaction field becomes extensive and intensive because the acoustic pressure amplitude is intensified by the interference of two ultrasonic waves.     

Ultrasound-induced cytolysis of cancer cells is enhanced in the presence of micron-sized alumina particles

Micron-sized alumina particles have been shown to enhance sonochemical free radical formation in aqueous solutions and simultaneously increase the solution temperature and acoustic (white) noise, effects attributable to enhanced inertial cavitation [T. Tuziuti, J. Phys. Chem. A 109 (2005) 4869–4872]. In the current study, the same ultrasound exposure system was applied to in vitro cancer cells as a model system to determine the effect of alumina particles on the long-term survival of cells and on the major pathways of cell death, i.e., either apoptosis or necrosis. Following 6 h of incubation after ultrasound treatment, it was found that the cells died mainly through necrosis, irrespective of whether the exposure was conducted in the presence of alumina particles or not. Alumina particles were non-toxic to cells alone, but were found to decrease the long-term survivability of cells that survived the initial exposure. This effect depended on the size and concentration of particles. These results correlated well with the effect of alumina particles on the sonochemical oxidation of KI under the same exposure conditions. Spin-trapping with 5,5-dimethyl-pyroline N-oxide (DMPO) and electron spin resonance spectroscopy indicated that the sonochemical formation of OH radicals increased in the presence of alumina particles. The current study is consistent with the well known observation that micron-sized particles enhance the acoustic cavitation process.     

Mapping of an ultrasonic horn: link primary and secondary effects of ultrasound

The erratic behaviour of cavitational activity exhibited in a sonochemical reactor pose a serious problem in the efficient design and scale-up; thus it becomes important to identify the active and passive zones existing in the reactor so as to enable proper placement of the reaction mixtures for achieving maximum benefits. In the present work mapping of ultrasonic horn has been carried with the help of local pressure measurement using a hydrophone and estimation of amount of liberated iodine using the Weissler reaction and a quantitative relationship has been established. The measured local pressure pulses have been used in the theoretical simulations of the bubble dynamics equations to check the type of cavitation taking place locally and also estimate the possible collapse pressure pulse in terms of maximum bubble size reached during the cavitation phenomena. Relationship has been also established between the observed iodine liberation rates and the maximum bubble size reached. The engineers can easily use these unique relationships in efficient design, as the direct quantification of the secondary effect is possible.     

Measurement of acoustic power in studying cavitation processes

A comparative calorimetric method for measuring the acoustic power generated by a sound source under cavitation conditions and the power absorbed by a liquid with bubbles is developed. The conditions under which the whole of the generated power is absorbed by the liquid with bubbles are determined experimentally. An instrument for power calibration of sound sources operating under cavitation conditions is designed. The instrument is found to provide a high measurement accuracy (3% or better). The requirements on the dimensions of the vessel and on the volume of the liquid in which the sound source operates are formulated to make the power generated under cavitation conditions independent of these parameters. For the first time, it is shown experimentally (by the example of the reaction of nitric oxide formation under the action of sound) that, if these conditions are satisfied and the sound intensity exceeds the threshold intensity, the rate of a number of sonochemical reactions is proportional to the sound intensity in the range from 1.7 to at least 47 W/cm². It is shown that the dependence of the rate of cavitation processes on the sound intensity with a maximum at 8.6 W/cm² and a sharp decrease in the rate with a further intensity increase is determined by the fact that the measured quantity was the electric power at the transducer rather than the acoustic one.     

Investigation of acoustic and geometric effects on the sonoreactor performance

In this work, three design configurations of a sonoreactor are considered under various operating conditions, and the acoustic characteristics during water sonication are investigated while using an immersed-type ultrasonic flat transducer probe in a sonoreactor model. Numerical models are also developed to simulate the sonication process, and they are successfully validated and compared with available data in the literature. Several sets of numerical investigations are conducted using the finite-element method and solved by the computational acoustics module in the COMSOL Multiphysics. The effects of the acoustical and geometrical parameters are investigated, analyzed, and reported, including the ultrasonic frequency, acoustic intensity, and scaling-up the reactor. The present study includes a parametric investigation examining the change of the ultrasonic frequency, intensity, and probe immersion depth on the performance. The results of the parametric study show that the highest cavitation energy corresponds to the maximum magnitude of negative pressure that takes place in the range of 60–80 kHz. The cavitation energy analyses are conducted under the conditions of 20 kHz of frequency and at 36 W input power. It is found that the cavitation energy of 15.87 W could produce 2.98 × 10⁻¹⁰ mol/J of sonochemical efficiency. In addition, the effect of altering the transducer probe depth changes the acoustic pressure field insignificantly. Furthermore, a recommendation is made to improve the sonochemical efficiency by introducing more considerable ultrasound input power while operating the sonoreactor at an ultrasonic frequency lower than 60 kHz. The results presented in this paper provide a comprehensive assessment of different sonoreactors and the feasibility of scaling-up their production rate.     

Kinetics analysis for development of a rate constant estimation model for ultrasonic degradation reaction of methylene blue

Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range.