Synthetically useful sonochemical reactions in solution

Examples of sonochemical reactions in solution with synthetic potential have recently been published. The free radical mechanism of some of them seems to be clearly established, in accordance with the empirical sonochemistry rules. Cases exist, however, where this simple interpretation is difficult. This is particularly true for cycloaddition reactions. In the case of [2 + 2] cycloaddition, the steric course is modified. In [4 + 2] reactions, positive results have been recorded with quinones as the dienophile. A few questions left open using current theories are identified and possible mechanistic pathways are discussed considering the radiomimetic effect of sonication.     

Sonocatalytic and sonophotocatalytic degradation of rhodamine 6G containing wastewaters

The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocatalytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium dioxide (TiO₂) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been investigated by varying the loading over the range of 1.5–4.5 g/L. It has been observed that the maximum degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO₂ maximum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with presence of radical scavengers such as methanol (CH₃OH) and n-butanol (C₄H₉OH) indicated lower extents of degradation confirming the dominance of radical mechanism. The combined approach of ultrasound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real conditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO_2, respectively. Studies using combination of UV and US irradiations have also been carried out using the optimal concentration of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US and UV with TiO₂ (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give higher extent of degradation as compared to the individual processes based on US or UV irradiations.     

Sonochemical preparation of carbon spheres

Spherical morphology of carbon with 150–400 nm size is produced by sonication (480 kHz, 2.5 W) of toluene with water under ambient conditions. Medium range of frequency and weak power of ultrasound is found to be the appropriate conditions for preparing the carbon spheres. Morphological and structural analysis of the product is carried out with TEM, SEM, elemental analysis, TGA, and FT-IR spectroscopy.     

Sonochemical removal of trihalomethanes from aqueous solutions

In this research, ultrasound irradiation was employed to degrade the trihalomethanes, THMs: CHCl₃, CHBrCl₂, CHBr₂Cl, CHBr₃, and CHI₃. The kinetics reaction rates and removal efficiencies of the THMs compounds, as a sole component in the aqueous solutions, were studied. Batch experiments were conducted at an ultrasonic frequency of 20 kHz and acoustic intensity of 3.75 W/cm². The first-order degradation rate constants and the sonolysis efficiencies followed the decreasing order of CHCl₃ > CHBrCl₂ > CHBr₂Cl > CHBr₃ > CHI₃. Up to 100% of the CHCl₃ was removed, while only 60% of the CHI₃ was sonodegraded, after 180 min sonication. The THMs vapor pressure was found to be the most important parameter affecting the sonodegradation kinetics and efficiency, while the bond dissociation energy and hydrophilic/hydrophobic characteristics of the THMs compounds were found to be of secondary importance.     

Effects of ultrasonic disintegration of excess sewage sludge

Ultrasonic disintegration of excess sludge is used as a process preceding the stabilization of sludge in wastewater treatment plants. It has a task of intensifying the anaerobic digestion of the organic fraction of sludge due to the fragmentation of its particles and destruction of microorganisms. Amount of energy put into process is the strongest factor determining type and intensity of disintegration. Physicochemical properties of sludge, operational variables and construction of installation have to be considered as well. The research have shown the effects of disintegration of various sludge conducted in disintegrators of varying heads and emitter structures, but at the same energy density E_V kW h m⁻³.     

Improved sonolytic hydrolysis of peptides in aqueous solution with addition of 1,4-benzenedithiol

Described here is the sonolytic hydrolysis of peptides achieved by treatment of aqueous solution to which the radical scavenger 1,4-benzenedithiol (1,4-BDT), which has hydrogen donating ability, has been added. Mass spectrometric analysis of the products of sonolytic hydrolysis gave information about amino acid sequence of the peptides without any byproducts. The additive 1,4-BDT improves the sonolytic hydrolysis of peptides in terms of the rate of hydrolysis reaction and the amount of additive required when compared to catechol, a previously reported additive. The sonolytic hydrolysis of peptides differs from both acid hydrolysis and hydrogen atom-induced dissociation named matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD), in characteristics. We propose a mechanistic reaction for the sonolytic hydrolysis of peptides, based on the mechanisms of both acid hydrolysis and MALDI-ISD processes. The sonolytic hydrolysis of peptides upon addition of hydrogen donating radical scavengers can be rationalized via the attachment of a hydrogen atom to the carbonyl oxygen with subsequent hydrolysis.     

Decomposition of chlorofluorocarbons and hydrofluorocarbons in water by ultrasonic irradiation

The sonochemical degradation of CFC-113 (F₂ClC---CCl₂F), HCFC-225ca (F₃C---CF₂CCl₂H), HCFC-225cb (F₂ClC---CF₂---CClFH) and HFC-134a (F₃C---CF₂H) in water was investigated. The decomposition rates of CFC-113 increased with increasing the concentration of the CFC and at high concentration the rates far exceeded the rate of OH radical formation by water sonolysis, and OH radicals seemed to have little effect on the decomposition. The pyrolysis in the cavitation bubbles was suggested.     

Sonolysis of per- and poly fluoroalkyl substances (PFAS): A meta-analysis

Human ingestion of per- and polyfluoroalkyl substances (PFAS) from contaminated food and water is linked to the development of several cancers, birth defects and other illnesses. The complete mineralisation of aqueous PFAS by ultrasound (sonolysis) into harmless inorganics has been demonstrated in many studies. However, the range and interconnected nature of reaction parameters (frequency, power, temperature etc.), and variety of reaction metrics used, limits understanding of degradation mechanisms and parametric trends. This work summarises the state-of-the-art for PFAS sonolysis, considering reaction mechanisms, kinetics, intermediates, products, rate limiting steps, reactant and product measurement techniques, and effects of co-contaminants. The meta-analysis showed that mid-high frequency (100 – 1,000 kHz) sonolysis mechanisms are similar, regardless of reaction conditions, while the low frequency (20 – 100 kHz) mechanisms are specific to oxidative species added, less well understood, and generally slower than mid-high frequency mechanisms. Arguments suggest that PFAS degradation occurs via adsorption (not absorption) at the bubble interface, followed by headgroup cleavage. Further mechanistic steps toward mineralisation remain to be proven. For the first time, complete stoichiometric reaction equations are derived for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) sonolysis, which add H₂ as a reaction product and consider CO an intermediate. Fluorinated intermediate products are derived for common, and more novel PFAS, and a naming system proposed for novel perfluoroether carboxylates. The meta-analysis also revealed the transition between pseudo first and zero order PFOA/S kinetics commonly occurs at 15 – 40 µM. Optimum values of; ultrasonic frequency (300 – 500 kHz), concentration (>15 – 40 μM), temperature (≈20 °C), and pH range (3.2 – 4) for rapid PFOX degradation are derived by evaluation of prior works, while optimum values for the dilution factor applied to PFAS containing firefighting foams and applied power require further work. Rate limiting steps are debated and F⁻ is shown to be rate enhancing, while SO₄²⁻ and CO₂ by products are theorised to be rate limiting. Sonolysis was compared to other PFAS destructive technologies and shown to be the only treatment which fully mineralises PFAS, degrades different PFAS in order of decreasing hydrophobicity, is parametrically well studied, and has low-moderate energy requirements (several kWh g⁻¹ PFAS). It is concluded that sonolysis of PFAS in environmental samples would be well incorporated within a treatment train for improved efficiency.     

Lipase-catalyzed diacylglycerol production under sonochemical irradiation

The present paper describes a protocol for production of diacylglycerol by the partial hydrolysis of soybean oil catalyzed by lipase under ultrasound irradiation. Better yields and shorter reaction times were obtained under sonication as compared to the thermal process.