Sonochemical and photochemical oxidation of organic matter

Recent developments in sonochemistry have led us to study its use to treat water and wastewater. The effects of ultrasound wave in hydrophilic chemical oxidations are mainly due to hydroxyl radical production during the cavitation-induced water decomposition. Currently, the sonochemical destruction of aromatic compounds in water solution is obtained with low rates. The aim of this work is to evaluate the efficiency of the sonochemical effect in conjunction with a photochemical irradiation. Taking phenol as an example, the combined action of sonochemistry and photochemistry has been considered in a ‘sonuv’ reactor. An important enhancement of the degradation rate of phenol has been observed. It may be the result of three different oxidative processes: direct photochemical action, high frequency sonochemistry and reaction with ozone (produced by UV irradiation of air). The process has been successfully tested to lower the chemical oxygen demand of a municipal wastewater.     

Effect of sonication on the photo-catalytic mineralization of some chlorinated organic compounds

Effects of the irradiation of ultrasound (US) on the photo-catalytic mineralization of some chlorinated organic compounds such as dichloroethane, tri- and tetrachloroethylenes, chloroacetic acids and chloromethanes were examined in oxygen saturated aqueous solutions suspended titanium dioxide (P25) particles. The yields of the sonochemical mineralization for these compounds were found to be extremely low compared to the photo-catalysis. However, the pre-sonication, US irradiation on the sample solution before the photo-irradiation, enhanced significantly the following photo-catalytic degradation to the complete oxidation. The effect was investigated in detail and it was found that the effect was mainly owing to the increase in the capability of the catalysis of which particles were sparsely dispersed by the sonication. The other contribution of the pre-sonication effect was found to be "pre-sonolysis", the initial formation of some intermediated products sonochemically, which are oxidizable more rapidly further to carbon dioxide than the original compound by the following photo-catalytic reactions. The pre-sonolysis effect was observed remarkably for trichloroacetic acid and tetrachloromethane, both of which are known to be hardly reactive to the photo-catalytic degradation. The photo-catalytic degradation with simultaneous sonication were also carried out for these compounds. The synergetic effect in the mineralization was observed both for carbontetrachloride and for trichloroacetic acid, the higher carbon dioxide yield being obtained in the simultaneous reaction than the sum of the yields in the photo-catalysis and the sonolysis each alone, while no significant synergetic effect was observed in the mineralization of other compounds.     

Grafting modification and structural degradation of multi-walled carbon nanotubes under the effect of ultrasonics sonochemistry

Polyvinyl pyrrolidone (PVP) grafted multi-walled carbon nanotubes (MWCNTs) were prepared by the degradation effect of ultrasonics sonochemistry. PVP macroradicals formed by sonochemical degradation of a PVP solution were trapped by MWCNTs and grafted onto the surface of MWCNTs. It was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis that the PVP was covalently bonded on the MWCNTs. Transmission electron microscopy showed nanotubes in the grafted samples were shorter than the original MWCNTs due to the crushing effect of ultrasonics sonochemistry. Both the decrease in length of the MWCNTs and the PVP grafted onto them are beneficial for their dispersion in solvents.     

Sonochemical degradation of various monocyclic aromatic compounds: relation between hydrophobicities of organic compounds and the decomposition rates

Various aromatic compounds, i.e., nitrobenzene, aniline, phenol, benzoic acid, salicylic acid, 2-chlorophenol, 4-chlorophenol, styrene, chlorobenzene, toluene, ethylbenzene and n-propylbenzene were decomposed under identical ultrasonic irradiation conditions. The relationships between the initial rates of degradation of these aromatic compounds and their physicochemical parameters were systematically investigated. It was revealed that some correlations between the degradation rates and parameters of volatility, Henry's law constant and vapor pressure, were observed only in the limited high range of parameters. It was suggested that the Henry's law constant and vapor pressure had influenced on the rate of degradation for some of the tested aromatic compounds. In contrast, better correlations between the initial rates of degradation and hydrophobic parameters, water solubility and LogP (water-octanol partition coefficient), were observed over the wide range of chosen parameters. These results meant that the hydrophobicity of the compounds significantly affected their accumulation at the gas-liquid interface of the bubbles and it was the most important factor for the sonochemical degradation of aromatic compounds. In particular, for the sonolysis of water-insoluble organic compounds, LogP was found to be the representative parameter for understanding the hydrophobic properties of water-insoluble compounds.     

Ultrasound and polar homogeneous reactions

The effect of ultrasound on the rates of homogeneous heterolytic reactions not switched to a free radical pathway can be explained by the perturbation of the molecular organization of or the solvation in the reacting system. A quantitative analysis of the sonochemical acceleration on the basis of the microreactor concept was carried out. It was found that (1) the Diels-Alder reaction cannot be accelerated by ultrasound except when SET or free radical processes are promoted, (2) the rectified diffusion during cavitation cannot be responsible for the acceleration of reactions, and (3) the sonochemical acceleration of polar homogeneous reactions takes place in the bulk reaction medium. This implies the presence of a 'sound-field' sonochemistry besides the 'hot-spot' sonochemistry. The occurrence of a sonochemical deceleration effect can be predicted.     

The mechanism of sonochemical degradation of a cationic surfactant in aqueous solution

The sonochemical degradation of the cationic surfactant, laurylpyridinium chloride (LPC), in water was studied at concentrations of 0.1-0.6 mM, all below its critical micelle concentration (15 mM). It has been found that the initial step in the degradation of LPC occurs primarily by a pyrolysis pathway. Chemical analysis of sonicated solutions by gas chromatography, electrospray mass spectrometry, and high performance liquid chromatography reveals that a broad range of decomposition products, hydrocarbon gases and water-soluble species, are produced. Propionamide and acetamide were identified as two of the degradation intermediates and probably formed as the result of the opening of the pyridinium ring following OH radical addition. Most of the LPC is eventually converted into carboxylic acids. The complete mineralization of these carboxylic acids by sonolysis is however a comparatively slow process due to the hydrophilic nature of these low molecular weight products.     

Sonochemical fabrication of inorganic nanoparticles for applications in catalysis

Catalysis covers almost all the chemical reactions or processes aiming for many applications. Sonochemistry has emerged in designing and developing the synthesis of nano-structured materials, and the latest progress mainly focuses on the synthetic strategies, product properties as well as catalytic applications. This current review simply presents the sonochemical effects under ultrasound irradiation, roughly describes the ultrasound-synthesized inorganic nano-materials, and highlights the sonochemistry applications in the inorganics-based catalysis processes including reduction, oxidation, degradation, polymerization, etc. Or all in all, the review hopes to provide an integrated understanding of sonochemistry, emphasize the great significance of ultrasound-assisted synthesis in structured materials as a unique strategy, and broaden the updated applications of ultrasound irradiation in the catalysis fields.     

Sonochemistry in non-aqueous liquids

The chemical effects of high-intensity ultrasound on organic liquids are reported. In order to probe the factors which affect sonochemistry in non-aqueous solvents, two very different chemical dosimeters have been used: radical trapping by diphenylpicrylhydrazyl and decomposition of Fe(CO)₅. In both cases, good correlation is found between the logarithm of the sonochemical rate and the solvent vapour pressure. This result is justifiable in terms of the cavitation ‘hot-spot’ mechanism of sonochemistry. Thus, decreasing solvent vapour pressure increases the intensity of cavitational collapse, the peak temperature reached during such collapse, and, consequently, the rates of sonochemical reactions.     

Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation

Sulfonated reduced graphene oxide nanosheets (rGO-SO₃H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO₃H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO₃H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56–95%) the corresponding amides in short reaction times.     

Effects of Na2SO4 or NaCl on sonochemical degradation of phenolic compounds in an aqueous solution under Ar: Positive and negative effects induced by the presence of salts

Sonochemical degradation of 4-chlorophenol, phenol, catechol and resorcinol was studied under Ar at 200 kHz in the absence and presence of Na₂SO₄ or NaCl. The rates of sonochemical degradation in the absence of salts decreased in the order 4-chlorophenol > phenol > catechol > resorcinol and this order was in good agreement with the order of log P (partition coefficient) value of each phenolic compound. The effects of salts on the rates of sonochemical degradation consisted of no effect or slight negative or positive effects. We discussed these unclear results based on two viewpoints: one was based on the changes in pseudo hydrophobicity and/or diffusion behavior of phenolic compounds and the other was based on the changes in solubility of Ar gas. The measured log P value of each phenolic compound slightly increased with increasing salt concentration. In addition, the dynamic surface tension for 4-chlorophenol aqueous solution in the absence and presence of Na₂SO₄ or NaCl suggested that phenolic compounds more easily accumulated at the interface region of bubbles at higher salt concentration. These results indicated that the rates of sonochemical degradation should be enhanced by the addition of salts. On the other hand, the calculated Ar gas solubility was confirmed to decrease with increasing salt concentration. The yield of H₂O₂ formed in the presence of Na₂SO₄ or NaCl decreased with increasing salt concentration. These results suggested that sonochemical efficiency decreased with decreasing gas amount in aqueous solution: a negative effect of salts was observed. Because negative and positive effects were induced simultaneously, we concluded that the effects of salts on the rates of sonochemical degradation of phenolic compounds became unclear. The products formed from sonochemical degradation of 4-chlorophenol were also characterized by HPLC analysis. The formation of phenol and 4-chloro-1,3-dihydroxy benzene was confirmed and these concentrations were affected by the presence of salts.     

Degradation of reactive,acid and basic textile dyes in the presence of ultrasound and rare earths [Lanthanum and Praseodymium]

Degradation of five textile dyes, namely Reactive Red 141 (RR 141), Reactive Blue 21 (RB 21), Acid Red 114 (AR 114), Acid Blue 113 (AB 113) and Basic Violet 16 (BV 16) in aqueous solution has been carried out with ultrasound (US) and in combination with rare earth ions (La³⁺ and Pr³⁺). Kinetic analysis of the data showed a pseudo-first order degradation reaction for all the dyes. The rate constant (k), half life (t_1/2) and the process efficiency (φ) for various processes in degradation of dyes under different experimental conditions have been calculated. The influence of concentrations of dyes (16–40 mg/L), pH (5, 7 and 9) and rare earth ion concentration (4, 12 and 20 mg/L) on the degradation of dyes have also been studied. The degradation percentage increased with increasing rare earth amount and decreased with increasing concentration of dyes. Both horn and bath type sonicators were used at 20 kHz and 250 W for degradation. The sonochemical degradation rate of dyes in the presence of rare earths was related to the type of chromophoric groups in the dye molecule. Degradation sequence of dyes was further examined through LCMS and Raman spectroscopic techniques, which confirmed the sonochemical degradation of dyes to non-toxic end products.     

核燃料后处理中锕系元素的声化学调价研究进展

硝酸水溶液在超声波辐照下产生自由基及活性分子,通过加入辅助试剂或控制硝酸浓度可以选择性地利用这些活性组分氧化或还原铀、镎、钚等锕系元素。在核燃料后处理流程中可利用上述反应对锕系元素进行声化学调价,实现锕系元素调价的无盐化,在某些调价过程中甚至无需额外加入任何试剂。由于上述优点,声化学方法有望在后处理流程的钚、镎调价方面得到应用。     

Numerical simulations for sonochemistry

Numerical simulations for sonochemistry are reviewed including single-bubble sonochemistry, influence of ultrasonic frequency and bubble size, acoustic field, and sonochemical synthesis of nanoparticles. The theoretical model of bubble dynamics including the effect of non-equilibrium chemical reactions inside a bubble has been validated from the study of single-bubble sonochemistry. By the numerical simulations, it has been clarified that there is an optimum bubble temperature for the production of oxidants inside an air bubble such as OH radicals and H₂O₂ because at higher temperature oxidants are strongly consumed inside a bubble by oxidizing nitrogen. Unsolved problems are also discussed.     

Educational aspects of sonochemistry: The role of sonochemistry at high school level

The applications of sonochemistry have attracted a great deal of attention. However, conventional chemistry textbooks used in universities and high schools cover traditional chemistry plus thermo,- photo- and electrochemistry. The effect of sound on chemical systems has completely been ignored. Although the mechanisms of many sonochemical reactions remain unresolved, the rapid expansion of knowledge in sonochemistry has already justified its inclusion in present chemistry curricula. Moreover, the interesting and unusual phenomena encountered under sonication conditions can be used for motivation purposes. Furthermore, exploring and equipping students with a new tool for investigating chemistry is also important based on educational principles. This paper examines some chemical systems (in a high school chemistry syllabus) which are affected by sound energy. It is hoped that these sonochemical applications will facilitate the learning of chemistry in terms of cognitive, psychomotor and affective domains.     

Mechanisms of effective gold shell on Fe3O4 core nanoparticles formation using sonochemistry method

Sonochemical synthesis (sonochemistry) is one of the most effective techniques of breaking down large clusters of nanoparticles (NPs) into smaller clusters or even individual NPs, which ensures their dispersibility (stability) in a solution over a long duration. This paper demonstrates the potential of sonochemistry becoming a valuable tool for the deposition of gold (Au) shell on iron oxide nanoparticles (Fe₃O₄ NPs) by explaining the underlying complex processes that control the deposition mechanism. This review summarizes the principles of the sonochemistry method and highlights the resulting phenomenon of acoustic cavitation and its associated physical, chemical and thermal effects. The effect of sonochemistry on the deposition of Au NPs on the Fe₃O₄ surface of various sizes is presented and discussed. A Vibra-Cell ultrasonic solid horn with tip size, frequency, power output of ½ inch, 20 kHz and 750 W respectively was used in core@shell synthesis. The sonochemical process was shown to affect the surface and structure of Fe₃O₄ NPs via acoustic cavitation, which prevents the agglomeration of clusters in a solution, resulting in a more stable dispersion. Deciphering the mechanism that governs the formation of Au shell on Fe₃O₄ core NPs has emphasized the potential of sonication in enhancing the chemical activity in solutions.     

The sonochemical arylation of active methylene compounds

The sonochemical arylation of active methylene compounds with haloarenes have been studied. The reaction course was found to be dependent on the electron-withdrawing properties of substituent and the leaving group of haloarenes as well as of the character of active methylene compounds. The results of the sonochemical experiments were just slightly better than in the classical ones's, exception being reactions with phenylsulfonylacetonitrile.     

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.     

Sonochemistry of organic compounds in homogeneous aqueous oxidising systems

The influence of ultrasound on the degradation of trichloroethylene, o-chlorophenol and 1,3-dichloro-2-propanol in some Fenton type aqueous systems was investigated. Kinetic analysis of the results revealed that the ultrasonic waves do not really enhance the reactivity of the system, but rather add their own degradation mechanism to the chemical degradation. This effect is comparable to the well known sonochemical switching effect. As a consequence, the degradation rate of the combined systems is the sum of the pure sonochemical degradation rate and the silent chemical degradation rate. The only exception to this rule is the degradation of o-chlorophenol in the presence of hydrogen peroxide, in the absence of catalysts. Care had to be taken in order to avoid artifacts that may arise, e.g., when neglecting temperature effects.