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.     

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.     

碟形超声变幅杆的设计

优化超声变幅杆的形状结构可有效地提高水域声场分布和空化区域,提升对水域超声空化效果。通过模拟分析发现传统超声变幅杆在水域中具有声场分布均匀性差、变幅杆端部声压高等特征,不利于声波在水域中传播。基于此,提出并优化设计了一种具有碟形结构的变幅杆,位于变幅杆的最大振幅处的碟形结构,有更大的振动位移;模拟表明其水域声场和声压均衡度显著优于传统变幅杆,铝箔空化腐蚀实验进一步证实了其水域中的声压分布均匀性。同时,实验通过铝箔的空化腐蚀、KI剂量测定及工件表面油渍去除对比了传统变幅杆和碟形变幅杆,分析表明碟形变幅杆所在水域中有较大的空化腐蚀区域,腐蚀速率明显提升,声化学反应速率提高,油渍去除程度增强,说明了设计的碟形变幅杆能够促进空化泡的产生,增加水域空化区域。     

Intensification of sonochemical decolorization of anthraquinonic dye Acid Blue 25 using carbon tetrachloride

In this work, the influence of CCl₄ on the sonochemical decolorization of anthraquinonic dye Acid Blue 25 (AB25) in aqueous medium was investigated using high frequency ultrasound (1700 kHz). This frequency, reputed ineffective, was tested in order to introduce the ultrasound waves with high frequency in the field of degradation or removal of dyes from wastewater, due to its limited use in this field, and to increase the application of high frequency ultrasound wave in the field of environmental protection. The effects of various parameters such as the concentration of CCl₄, frequency (22.5 and 1700 kHz), solution pH, temperature and tert-butyl alcohol adding on the decolorization rate of AB25 was studied. The obtained results clearly demonstrated the significant intensification of AB25 decolorization in the presence of CCl₄. The enhancement effect of CCl₄ increased by decreasing temperature and by increasing the CCl₄ concentration. The pH has a significant influence on the bleaching of dye both in the absence and presence of CCl₄. The three investigated dosimeter methods (KI oxidation, Fricke reaction and H₂O₂ production) well corroborate the improvement of the sonochemical effects in the presence of CCl₄. The best sonochemical decolorization rate of AB25 in aqueous solution both in the absence and presence of CCl₄ is observed to occur at 1700 kHz compared to 22.5 kHz. The sonochemical oxidation of CCl₄ generates oxidizing species in the liquid phase that are highly beneficial for oxidation of hydrophilic and non-volatile pollutant, such as dyes, because they are less susceptible to free radical attack due to lower stability of the generated free radicals.     

Effects of ultrasonic frequency and liquid height on sonochemical efficiency of large-scale sonochemical reactors

The sonochemical efficiency of a cylindrical sonochemical reactor has been investigated as a function of frequency and liquid height. The irradiation frequencies were 45, 129, 231 and 490 kHz. The liquid height was varied from 10 to 700 mm. The sonochemical efficiency of the cylindrical reactor was evaluated by potassium iodide (KI) dosimetry and calorimetry. In our study, the sonochemical efficiency depended on the frequency and liquid height; further, the plots of sonochemical efficiency against liquid height exhibit one or two peaks for each frequency. The sonochemical efficiency up to the first peak increased monotonically with the logarithm of the frequency, and the liquid height for the first peak was inversely proportional to the frequency. From these results, the optimum frequency for a sonochemical reactor can be determined if the liquid height is specified for scale-up of the sonochemical reactor.     

Frequency and power dependence of ultrasonic degassing

We investigated the time variation of ultrasonic degassing for air-saturated water and degassed water with a sample volume of 100 mL at frequencies of 22, 43, 129, 209, 305, 400, 514, 1018, and 1960 kHz and ultrasonic power of 15 W. Ultrasonic degassing was evaluated by dissolved oxygen concentration. Ultrasonic degassing was also investigated at a frequency of 1018 kHz and ultrasonic powers of 5, 10, 15, and 20 W. The dissolved oxygen concentration varied with the ultrasonic irradiation time and became constant after prolonged ultrasonic irradiation. The constant dissolved oxygen concentration value depended on the frequency and ultrasonic power but not the initial dissolved oxygen concentration. The degassing rate at 101.3 kPa was higher in the frequency range of 200 kHz to 1 MHz. The frequency dependence of the degassing rate was almost the same as that of the sonochemical efficiency obtained by the potassium iodide (KI) method. Ultrasonic degassing in the frequency range of 22–1960 kHz was also investigated under reduced pressure of 5 kPa. Degassing was accelerated when ultrasonic irradiation was applied under reduced pressure. However, under a reduced pressure of 5 kPa, the lower the frequencies, the higher is the degassing rate. The sonochemical reaction rate was examined by the KI method for varying dissolved air concentrations before ultrasonic irradiation. Cavitation did not occur when the initial dissolved oxygen concentration was less than 2 mg·L⁻¹. Therefore, the lower limit of ultrasonic degassing under 101.3 kPa equals 2 mg·L⁻¹ dissolved oxygen concentration. A model equation for the time variation of dissolved oxygen concentration due to ultrasonic irradiation was developed, and the degassing mechanism was discussed.     

Degradation of Acid Blue 25 in aqueous media using 1700 kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H2O2 combinations

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700 kHz) for an acoustic power of 14 W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H₂O₂ were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H₂O₂ and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.     

Reaction kinetics of sonochemical oxidation of potassium hexacyanoferrate(II) in aqueous solutions

We studied sonochemical reactions resulting from ultrasonic treatment of potassium hexacyanoferrate(II) in aqueous solutions using a custom-built apparatus working at 536 kHz. We concluded that primary reactions are completely dominated by oxidation of Fe(II) to Fe(III) and did not find any evidences for degradation of cyanide. At the highest concentration used in the present study (0.1 M) we detected formation of pentacyanoaquaferrate(II) complex, which is most probably formed in reactions between hexacyanoferrate(III) anions and hydrogen atoms or hydrated electrons formed in sonochemical processes. We also determined that hydroxyl radicals formation rate in our system, (8.7 ± 1.5)∙10⁻⁸ M∙s⁻¹, is relatively high compared to other reported experiments. We attribute this to focusing of the ultrasonic wave in the sample vessel. Finally, we suggest that oxidation rate of hexacyanoferrate(II) anions can be a convenient benchmark of efficiency of sonochemical reactors.     

Sonochemical reactions at 640 kHz using an efficient reactor. Oxidation of potassium iodide

Ultrasound can be used to oxidize aqueous pollutants. However, due to economic reasons higher oxidation/destruction rates and higher energy efficiency are needed. Recent studies suggest that the higher ultrasound frequencies provide better oxidation rates than the conventional 20 kHz. Another area for improvement is reactor configuration. We have tested two new reactor configurations with proper focusing and reflection of ultrasound for maximum utilization. Reactor configuration plays an important role in the overall efficiency. In the new reactors, transducers and reaction mixture are separated by a polymer acoustic window which allows efficient transfer of ultrasound energy and not the heat from the transducer to the reaction mixture. One reactor at 640 kHz provides a 100% enhancement over the best reported rate for the oxidation of potassium iodide, on a per-Watt basis. Experiments conducted at varying initial KI concentrations show interesting behavior. Increasing the KI concentration by over eight fold merely increases the iodine production rate by two fold. This suggests that in the oxidation region surrounding the bubble, the KI concentration is much different than in the bulk. It is proposed that the hydrophobic bubble region has lower and near saturation KI concentration.     

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.     

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.     

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.     

Ultrasonic degradation of perfluorooctane sulfonic acid (PFOS) correlated with sonochemical and sonoluminescence characterisation

Sonolysis has been proposed as a promising treatment technology to remove per- and polyfluoroalkyl substances (PFASs) from contaminated water. The mechanism of degradation is generally accepted to be high temperature pyrolysis at the bubble surface with dependency upon surface reaction site availability. However, the parametric effects of the ultrasonic system on PFAS degradation are poorly understood, making upscale challenging and leading to less than optimal use of ultrasonic energy. Hence, a thorough understanding of these parametric effects could lead to improved efficiency and commercial viability. Here, reactor characterisation was performed at 44, 400, 500, and 1000 kHz using potassium iodide (KI) dosimetry, sonochemiluminescence (SCL), and sonoluminescence (SL) in water and a solution of potassium salt of PFOS (hereafter, K-PFOS). Then the degradation of K-PFOS (10 mg L⁻¹ in 200 mL solution) was investigated at these four frequencies. At 44 kHz, no PFOS degradation was observed. At 400, 500, and 1000 kHz the amount of degradation was 96.9, 93.8, and 91.2%, respectively, over four hours and was accompanied by stoichiometric fluoride release, indicating mineralisation of the PFOS molecule. Close correlation of PFOS degradation trends with KI dosimetry and SCL intensity was observed, which suggested degradation occurred under similar conditions to these sonochemical processes. At 1000 kHz, where the overall intensity of collapse was significantly reduced (measured by SL), PFOS degradation was not similarly decreased. Discussion is presented that suggests a hydrated electron degradation mechanism for PFOS may occur in ultrasonic conditions. This mechanism is a novel hypothesis in the field of PFAS sonolysis.     

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.     

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.     

Effect of ultrasonic pretreatment on kinetics of gelatin hydrolysis by collagenase and its mechanism

Gelatin is a mixture of soluble proteins prepared by partial hydrolysis of native collagen. Gelatin can be enzymatically hydrolyzed to produce bioactive hydrolysates. However, the preparation of gelatin peptide with expected activity is usually a time-consuming process. The production efficiency of gelatin hydrolysates needs to be improved. In present work, effect of ultrasonic pretreatment on kinetic parameters of gelatin hydrolysis by collagenase was investigated based on an established kinetic model. With ultrasonic pretreatment, reaction rate constant and enzyme inactivation constant were increased by 27.5% and 27.8%, respectively. Meanwhile, hydrolysis activation energy and enzyme inactivation energy were reduced by 36.3% and 43.0%, respectively. In order to explore its possible mechanism, influence of sonication on structural properties of gelatin was determined using atomic force microscopy, particle size analyzer, fluorescence spectroscopy, protein solubility test and Fourier transform infrared spectroscopy. Moreover, hydrogen peroxide was used as a positive control for potential sonochemical effect. It was found that reduction of gelatin particle size was mainly caused by physical effect of ultrasound. Increased solubility and variation in β-sheet and random coil elements of gelatin were due to sonochemical effect. Both physical and chemical effects of sonication contributed to the change in α-helix and β-turn structures. The current results suggest that ultrasound can be potentially applied to stimulate the production efficiency of gelatin peptides, mainly due to its effects on modification of protein structures.     

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.     

Effect of irradiation distance on degradation of phenol using indirect ultrasonic irradiation method

Ultrasound is used as degradation of hazardous organic compounds. In this study, indirect ultrasonic irradiation method was applied to the degradation process of phenol, the model hazardous organic compound, and the effects of irradiation distance on radical generation and ultrasonic power were investigated. The chemical effect estimated by KI oxidation dosimetry and ultrasonic power measured by calorimetry fluctuated for the irradiation distance, and there was a relationship between the period of the fluctuation of ultrasonic effect and the wavelength of ultrasound. The degradation of phenol was considered to progress in the zero-order kinetics, before the decomposition conversion was less than 25%. Therefore, the simple kinetic model on degradation of phenol was proposed, and there was a linear relation in the degradation rate constant of phenol and the ultrasonic power inside the reactor. In addition, the kinetic model proposed in this study was applied to the former study. There was a linear relation in the degradation rate constant of phenol and ultrasonic energy in the range of frequency of 20-30 kHz in spite of the difference of equipment and sample volume. On the other hand, the degradation rate constant in the range of frequency of 200-800 kHz was much larger than that of 20-30 kHz in the same ultrasonic energy, and this behaviour was agreed with the former investigation about the dependence of ultrasonic frequency on chemical effect.     

Sonochemical reaction with microbubbles generated by hollow ultrasonic horn

A microbubble generator with a cylindrical hollow ultrasonic horn (HUSH), gas flow path, and an orifice inside it can produce high ultrasonic pressure around the generated microbubbles. We used this microbubble generator with a HUSH as a sonochemical reactor for the degradation of indigo carmine and evaluated the sonochemical reaction by simply inserting the horn end into a liquid. The experimental results revealed that the ultrasonic irradiation around ultrasonically generated microbubbles effectively degraded indigo carmine in water. In addition, degradation experiments performed by varying the ultrasonic power and gas flow rates indicated that a continuous gas supply and ultrasonic pressure were required for generating the microbubbles, without the generation of millimeter-scale bubbles, to enhance the sonochemical reaction in water.     

Effect of frequency on sonochemical reactions. I: Oxidation of iodide

The effect of continuous sonication on the kinetics of iodine formation in aqueous iodide solutions was studied in the presence of air and argon at two frequencies, 20 and 900 kHz. Most workers in this area assume that frequency has a negligible effect on sonochemical reactions. The present results indicate, however, that there is a significant effect in the above solutions. The rate of sonochemical oxidation of iodide in aqueous solution is 3.1 times greater in presence of air than argon at 900 kHz, in contrast to the situation at 20 kHz, where the ratio is 0.9 A 900 kHz apparatus was specially designed to make it possible to measure the absolute acoustic power delivered into the solution. The rate of oxidation per unit power in this new 900 kHz apparatus can be more than 30 times greater than that at 20 kHz for the oxidation of iodide in the presence of air.