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.
The influence of reaction vessel diameter on the sonochemical yield was investigated by using reaction vessels with five different diameters. It was revealed that the formation of H(2)O(2) and chloride ion, from the sonolysis of pure water and 1,2,4-trichlorobenzene aqueous solution, was affected by the reaction vessel diameter. That is, these yields increased as the reaction vessel diameter increased up to ø 90 mm and then decreased over ø 90 mm. From the analyses of the measurement of sonochemiluminescence and the calorimetry, it was suggested that active cavitation bubbles were formed at certain zones. In the case of a larger diameter reaction vessel, it was suggested that bubble nuclei that have not grown up to the resonance size, escaped from the sonication zone to the non-sonication zone and dissolved away. As a result, the number of active cavitation bubbles and the yields of H(2)O(2) and chloride ion would decrease in the case of a larger diameter reaction vessel.
The sonochemical decomposition of a low concentration of butyric acid was performed in an aqueous solution by use of 200 kHz ultrasound to discuss the reaction kinetics and molecular behavior during cavitation. Taking into account a Langmuir-type adsorption model, we propose a heterogeneous reaction kinetics model, which is based on the local reaction zone at the interface region of the cavitation bubbles, where the adsorption and desorption of butyric acid molecules from the bulk solution occur during bubble oscillation and then the existing molecules inside the local reaction zone are finally decomposed. To confirm our proposed kinetics model, the rates of decomposition were investigated as a function of the initial concentration of butyric acids in the different pH solutions. It was confirmed that our model could be reasonably applied to explain the obtained results and the pseudo rate constant (k) and the equilibrium constant (K) were able to be calculated: k is 8.0 microM min(-1) (pH 2) and 3.5 microM min(-1) (pH 10), and K is 5.7 x 10(-3) microM(-1) (pH 2) and 8.0 x 10(-3) microM(-1) (pH 10), respectively. By the analysis of the obtained K values, it was clear that the ionized organic acid molecules are relatively difficult to accumulate at the reaction zone, because of their lower hydrophobicity compared with that of the neutral ones. The results obtained in the sonochemical decomposition of benzoic acid were also able to be analyzed with the proposed kinetics model. In addition, we proposed an opinion toward the interpretation of a Langmuir-type adsorption model which has often been applied to explain heterogeneous reaction systems.
Chemical effects of ultrasound have been actively researched in the field of the synthesis of various metal nanoparticles and nanostructured materials. It is very important to understand the reduction mechanism of metal ions, because the reduction processes can be often applied to the synthesis of various materials. In this study, the sonochemical reduction of MnO4- to MnO2 in water under Ar atmosphere was investigated to discuss the reduction mechanism. It has been reported that H, OH, H2 and H2O2 are formed from the sonolysis of water. To understand the roles of H2O2 on the reduction, the reaction of MnO4- with H2O2 without ultrasonic irradiation was investigated. The obtained results suggested the progress of the following reaction: 2MnO4-+3H2O2-->2MnO2+3O2+2OH-+2H2O. In addition, the rates of the sonochemical reduction of MnO4- were investigated in the presence of 1-propanol, where 1-propanol acted as an OH radical scavenger so that the amounts of the sonochemically formed H2O2 molecules were able to be controlled. The results clearly indicated that the sonochemically formed H2O2 molecules as well as H2 molecules and H atoms play an important role for MnO4- reduction. This mechanism was also supported by the analysis of pH changes during ultrasonic irradiation: the pH value increased as the sonochemical reduction of MnO4- proceeded.
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