Exploring the effects of pulsed ultrasound at 205 and 616 kHz on the sonochemical degradation of octylbenzene sulfonate

Compared to continuous wave (CW) ultrasound, pulsed wave (PW) ultrasound has been shown to result in enhanced sonochemical degradation of octylbenzene sulfonate (OBS). However, pulsed ultrasound was investigated under limited pulsing conditions. In this study, pulse-enhanced degradation of OBS was investigated over a broad range of pulsing conditions and at two ultrasonic frequencies (616 and 205 kHz). The rate of OBS degradation was compared to the rate of formation of 2-hydroxyterephthalic acid (HTA) following sonolysis of aqueous terephthalic acid (TA) solutions. This study shows that sonication mode and ultrasound frequency affect both OBS degradation and HTA formation rates, but not necessarily in the same way. Unlike TA, OBS, being a surface active solute, alters the cavitation bubble field by adsorbing to the gas/solution interface of cavitation bubbles. Enhanced OBS degradation rates during pulsing are attributed to this adsorption process. However, negative or smaller pulse enhancements compared to enhanced HTA formation rates are attributed to a decrease in the high-energy stable bubble population and a corresponding increase in the transient bubble population. Therefore, sonochemical activity as determined from TA sonolysis cannot be used as a measure of the effect of pulsing on the rate of degradation of surfactants in water. Over relatively long sonolysis times, a decrease in the rate of OBS degradation was observed under CW, but not under PW conditions. We propose that the generation and accumulation of surface active and volatile byproducts on the surface and inside of cavitation bubbles, respectively, during CW sonolysis is a contributing factor to this effect. This result suggests that there are practical applications to the use of pulsed ultrasound as a method to degrade surface active contaminants in water.     

Low-MHz frequency effect on a sonochemical reaction determined by an electrical method

The frequency effect of low-MHz ultrasound was studied by using the electrical detection method. The experimental data and theoretical analysis results showed that an appropriate frequency value of ultrasound can be chosen to make a sonochemical reaction give its maximum yield according to the distribution of bubbles in liquid. A Gaussian shape distribution of gas bubble radii is to be expected in a water sample with a normal air atmosphere. In addition, the experimental data indicated that comparison of the effect of frequency on the sonochemical efficiency should be carried out under conditions of not only the same sonic power but also the same sonic intensity.     

Experimental and theoretical investigations on sonoluminescence under dual frequency conditions

The multibubble sonoluminescence (MBSL) intensities from water exposed to the simultaneous ultrasonic irradiation from 20 kHz (fixed at 6.3 W) and 355 kHz (variable power) ultrasound sources have been compared to the MBSL from the individual ultrasound sources under the same power conditions. A synergistic enhancement of the sonoluminescence (SL) signal, >30-fold, at low powers (4.6 W) of the higher frequency was observed. At a higher acoustic power level (15.8 W) the dual frequency operation produced a decrease in the SL signal. These results are in agreement with previously reported data [P. Ciuti, N.V. Dezhkunov, A. Francescutto, F. Calligaris, F. Sturman, Ultrasonics Sonochem. 10 (2003) 337; N.V. Dezhkunov, J. Eng. Phys. Therm. 76 (2003) 142] under similar experimental conditions. Numerical single bubble (SB) dynamics calculations have been used to help interpret the experimental results. It is suggested that the observed effects are caused by a combination of changes to the peak collapse temperature of individual bubbles as well as to changes in the active bubble population.     

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.     

Spatial distribution of sonoluminescence and sonochemiluminescence generated by cavitation bubbles in 1.2 MHz focused ultrasound field

An intensified charge coupled device (ICCD) camera was used to observe the spatial distribution of sonoluminescence (SL) and sonochemiluminescence (SCL) generated by cavitation bubbles in a 1.2 MHz focused ultrasound (FU) field in order to investigate the mechanisms of acoustic cavitation under different sonication conditions for FU therapeutic applications.It was found that SL emissions were located in the post-focal region. When the intensity of SL and SCL increased as the power rose, the growth of SCL was much higher than that of SL. In the post-focal region, the SCL emissions moved along specific paths and formed branch-like streamers. At the beginning of the ultrasound irradiation, cavitation bubbles generated SCL in both the pre-focal and the post-focal region. When the electrical power or the sonication time increased, the SCL in the post-focal region increased and became higher than that in the pre-focal region. The intensity of SCL in the focal region is usually the weakest because of “oversaturation”.The spatial distribution of SCL near a tissue boundary differed from that obtained in free fields. It organized into special structures under different acoustic amplitudes. When the electrical power was relatively low, the SCL emission was conical shape which suggested a standing wave formation at the tissue-fluid boundary. When the electrical power exceeded a certain threshold, only a bright spot could be captured in the focus. The cavitation bubbles which centralized in the focus concentrated energy and hindered the formation of standing waves. With rising electrical power at high levels, besides a bright spot in the focus, there were some irregular light spots in pre-focal region, which indicated some cavitation bubbles or small bubble clusters achieved the threshold of SCL and induced the reaction with the luminol solution.     

Experimental quantification of cavitation yield revisited: focus on high frequency ultrasound reactors

Acoustic cavitation plays an important role in enhancing the reaction rate of chemical processes in sonochemical systems. However, quantification of cavitation intensity in sonochemical systems is generally limited to low frequency systems. In this study, an empirical determination of cavitation yield in high frequency ultrasound systems was performed by measuring the amount of iodine liberated from the oxidation of potassium iodide (KI) solution at 1.7 and 2.4 MHz. Experiments for determining cavitation were carried out at various solute (KI) concentrations under constant temperature, obtained by direct cooling of the solution and variable temperature conditions, in the absence of external cooling. Cavitation yield measurements, reported in this work, extend previously reported results and lend credence to the two step reaction pathway in high frequency systems. Additionally, the concentration of KI and temperature affect the cavitation yield of a system such that the iodine production is proportional to both conditions. It is proposed that direct cooling of sonicated KI solution may be advantageous for optimization of cavitation intensity in high frequency sonochemical reactors.     

Degradation of dichlorvos containing wastewaters using sonochemical reactors

The present work deals with application of sonochemical reactors for the degradation of dichlorvos containing wastewaters. The sonochemical reactor used in the work is a simple ultrasonic horn type operating at 20 kHz with a power rating of 270 W. The effect of different operating parameters such as operating pH, temperature and power density on the extent of degradation has been investigated initially followed by intensification studies using additives such as hydrogen peroxide, Fenton's reagent and CCl(4). It has been observed that low frequency sonochemical reactors can be effectively used for treatment of pesticide wastewaters and acidic conditions and optimum values of temperature and power dissipation favors the degradation of dichlorvos. The efficacy of sonochemical reactors can be further enhanced by using different additives at optimized loadings. Complete removal of the pesticide at the given loading has been obtained using an optimized combination of ultrasound and Fenton's chemistry. The controlling mechanism for the sonochemical degradation has been confirmed to be the free radical attack based on the studies involving radical scavengers. The novelty of the present work is clearly established as there have been no earlier studies dealing with degradation of dichlorvos pesticide using sonochemical reactors operating at low frequency which offers distinct advantage in terms of cost and the stability of the reactor.     

Kinetics of nitrous acid formation in a two-phase tri-n-butylphosphate-diluent/aqueous nitric acid extraction system under the effect of power ultrasound

The kinetics of nitrous acid formation were investigated in two-phase tri-n-butylphosphate (TBP)-diluent/HNO3 (1.5-6.0 mol l-1) systems, where diluent is n-C16H34, n-C12H26, n-C9H20 and i-C8H18, under the effect of power ultrasound at 20 kHz frequency under Ar atmosphere. The rate of HNO2 sonochemical formation decreases with the rise in diluent vapor pressure. The HNO2 formed is distributed between the aqueous and organic phases due to its extraction with TBP. The kinetics of HNO2 sonochemical formation in the two-phase system exhibits induction periods due to NOx (NO + NO2) gas reactions in the HNO3 medium. This induction period decreases with increasing HNO3 concentration and ultrasound intensity. The HNO2 steady-state concentration was obtained under long-time sonication as the result of HNO2 sonochemical decomposition. HNO2 decomposes faster under sonication in the aqueous phase than in the organic phase.     

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.     

Highly efficient sonochemical reaction with a switched spiral focal field

This paper describes an efficient method of inducing sonochemical reactions with focussed ultrasound. A sector-vortex transducer (a phased array transducer with multiple sectors and a geometric focus) is used to produce focal ultrasound fields with spiral-shaped wavefronts. Clockwise and counter-clockwise spiral focal fields, with basically the same ultrasound power distribution but having different wavefront angles, are produced by using the same array transducer. The oxidation of the iodide ions induced from the periodic switching between such a pair of spiral focal fields is investigated at an ultrasound frequency of 750 kHz. The oxidation rate at the optimum switching period (3 ms) is about ten times higher than that at switching periods of 1 s. The optimum switching period and the sonochemical reaction rate are unchanged when the viscosity was adjusted to that of human blood.     

Sonoluminescence and sonochemiluminescence from a microreactor

Micromachined pits on a substrate can be used to nucleate and stabilize microbubbles in a liquid exposed to an ultrasonic field. Under suitable conditions, the collapse of these bubbles can result in light emission (sonoluminescence, SL). Hydroxyl radicals (OH()) generated during bubble collapse can react with luminol to produce light (sonochemiluminescence, SCL). SL and SCL intensities were recorded for several regimes related to the pressure amplitude (low and high acoustic power levels) at a given ultrasonic frequency (200kHz) for pure water, and aqueous luminol and propanol solutions. Various arrangements of pits were studied, with the number of pits ranging from no pits (comparable to a classic ultrasound reactor), to three-pits. Where there was more than one pit present, in the high pressure regime the ejected microbubbles combined into linear (two-pits) or triangular (three-pits) bubble clouds (streamers). In all situations where a pit was present on the substrate, the SL was intensified and increased with the number of pits at both low and high power levels. For imaging SL emitting regions, Argon (Ar) saturated water was used under similar conditions. SL emission from aqueous propanol solution (50mM) provided evidence of transient bubble cavitation. Solutions containing 0.1mM luminol were also used to demonstrate the radical production by attaining the SCL emission regions.     

Acoustic emission spectra and sonochemical activity in a 36 kHz sonoreactor

During ultrasound-induced cavitation in liquids, acoustic emissions at fundamental and harmonic frequencies can be detected. The effect of acoustic emissions at harmonic frequencies on the sonochemical and sonophysical activities has not been explored, especially in large-scale sonoreactors. In this study, the acoustic emissions in the range, 0-250 kHz in a 36 kHz sonoreactor with varying liquid heights were studied and compared with the sonochemical activities. The acoustic pressures at both fundamental and harmonics decreased drastically as the liquid height was increased due to the attenuation of sound energy. It was observed that the increase in input power resulted in only an increase in the acoustic emissions at derivative frequencies such as, harmonics and subharmonics. The sonochemical activity, evaluated in terms of sonochemiluminescence and H₂O₂ yield, was not significantly enhanced at higher input power levels. This suggests that at higher power levels, the “extra” acoustic energy is not effectively used to generate primary cavitation activity; rather it is converted to generate acoustic emissions at harmonic and subharmonic frequencies. This is an important observation for the design of energy efficiency large-scale sonochemical reactors.     

Multibubble sonoluminescence intensity dependence on liquid temperature at different ultrasound intensities.

It is shown that the influence of liquid temperature on the sonoluminescence (SL) intensity is different depending on the ultrasound intensity. At the ultrasound intensities not much higher than the cavitation appearance threshold the SL intensity increases with the temperature. At the ultrasound intensities considerably exceeding the cavitation threshold the SL intensity decreases with an increase of the temperature. At intermediate ultrasound intensities the SL intensity temperature dependence is extreme: the cavitation activity at first increases with temperature, reaches a maximum and then decreases. Continuous and pulsed modes of irradiation at frequencies 880 and 21.9 kHz were used in experiments.     

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     

Intensified dissolution of uranium from graphite substrate using ultrasound

Decontamination of graphite structural elements and recovery of uranium is crucial for waste minimization and recycle of nuclear fuel elements. Feasibility of intensified dissolution of uranium-impregnated graphite substrate using ultrasound has been studied with objective of establishing the effect of operating parameters and the kinetics of sonocatalytic dissolution of uranium in nitric acid. The effect of operating frequency and acoustic intensity as well as the acid concentration and temperature on the dissolution of metal has been elucidated. It was observed that at lower acid concentrations (6 M–8 M), the dissolution ratio increases by 15% on increasing the bath temperature from 45 to 70 °C. At higher acid concentration (>10 M), the increase was only around 5–7% for a similar change in temperature. With 12 M HNO₃, pitting was also observed on the graphite surface along with erosion due to high local reaction rates in the presence of ultrasound. For higher frequency of applied ultrasound, lower dissolution rate of uranium was observed though it also leads to high rates of erosion of the substrate. It was thus established that suitable optimization of frequency is required based on the nature of the substrate and the choice of recycling it. The dissolution rate was also demonstrated to increase with acoustic intensity till it reaches to the maximum at the observed optimum (1.2 W/cm² at 33 kHz). Comparison with silent conditions revealed that enhanced rate was obtained due to the use of ultrasound under optimum conditions. The work has demonstrated the effective application of ultrasound for intensifying the extent of dissolution of metal.     

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.     

Comparison of sonochemiluminescence images using image analysis techniques and identification of acoustic pressure fields via simulation

One common method to determine the existence of cavitational activity in power ultrasonics systems is by capturing images of sonoluminescence (SL) or sonochemiluminescence (SCL) in a dark environment. Conventionally, the light emitted from SL or SCL was detected based on the number of photons. Though this method is effective, it could not identify the sonochemical zones of an ultrasonic systems. SL/SCL images, on the other hand, enable identification of ‘active’ sonochemical zones. However, these images often provide just qualitative data as the harvesting of light intensity data from the images is tedious and require high resolution images. In this work, we propose a new image analysis technique using pseudo-colouring images to quantify the SCL zones based on the intensities of the SCL images and followed by comparison of the active SCL zones with COMSOL simulated acoustic pressure zones.     

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.     

A technique for evaluating the oil/heavy-oil viscosity changes under ultrasound in a simulated porous medium

Theoretically, Ultrasound method is an economical and environmentally friendly or “green” technology, which has been of interest for more than six decades for the purpose of enhancement of oil/heavy-oil production. However, in spite of many studies, questions about the effective mechanisms causing increase in oil recovery still existed. In addition, the majority of the mechanisms mentioned in the previous studies are theoretical or speculative. One of the changes that could be recognized in the fluid properties is viscosity reduction due to radiation of ultrasound waves. In this study, a technique was developed to investigate directly the effect of ultrasonic waves (different frequencies of 25, 40, 68 kHz and powers of 100, 250, 500 W) on viscosity changes of three types of oil (Paraffin oil, Synthetic oil, and Kerosene) and a Brine sample. The viscosity calculations in the smooth capillary tube were based on the mathematical models developed from the Poiseuille’s equation. The experiments were carried out for uncontrolled and controlled temperature conditions. It was observed that the viscosity of all the liquids was decreased under ultrasound in all the experiments. This reduction was more significant for uncontrolled temperature condition cases. However, the reduction in viscosity under ultrasound was higher for lighter liquids compare to heavier ones. Pressure difference was diminished by decreasing in the fluid viscosity in all the cases which increases fluid flow ability, which in turn aids to higher oil recovery in enhanced oil recovery (EOR) operations. Higher ultrasound power showed higher liquid viscosity reduction in all the cases. Higher ultrasound frequency revealed higher and lower viscosity reduction for uncontrolled and controlled temperature condition experiments, respectively. In other words, the reduction in viscosity was inversely proportional to increasing the frequency in temperature controlled experiments. It was concluded that cavitation, heat generation, and viscosity reduction are three of the promising mechanisms causing increase in oil recovery under ultrasound.     

Ultrasonic pretreatment of liquid NaK metal catalyst for side-chain alkenylation of o-xylene with 1,3-butadiene

The effects of sonochemical treatment of a NaK eutectic mixture as catalyst on the side-chain alkenylation of o-xylene with 1,3-butadiene were studied. The parameters studied include ultrasound frequency, insonation time, sonication power as well as the reaction temperature. In addition, the effect of N,N,N',N'-tetramethylethylenediamine (TMEDA) on the reaction was also studied. The results showed that sonochemical treatment of this NaK eutectic mixture catalyst resulted in excellent conversion (up to 83.16%) under mild conditions. The introduction of TMEDA further increased the conversion to 89.4%.