Gastón P. Barreto

Microwave Assisted Synthesis of ZnO Nanoparticles: Effect of Precursor Reagents, Temperature, Irradiation Time, and Additives on Nano-ZnO Morphology Development

The effect of different variables (precursor reagents, temperature, irradiation time, microwave radiation power, and additives addition) on the final morphology of nano-ZnO obtained through the microwave assisted technique has been investigated. The characterization of the samples has been carried out by field emission scanning electron microscopy (FE-SEM) in transmission mode, infrared (FTIR), UV-Vis spectroscopy, and powder X-ray diffraction (XRD). The results showed that all the above-mentioned variables influenced to some extent the shape and/or size of the synthetized nanoparticles. In particular, the addition of an anionic surfactant (sodium di-2-ethylhexyl-sulfosuccinate (AOT)) to the reaction mixture allowed the synthesis of smaller hexagonal prismatic particles (100 nm), which show a significant increase in UV absorption.

Thermal Decomposition of Diethylketone Cyclic Triperoxide in Polar Solvents

The thermolysis of diethylketone cyclic triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) was studied in different polar solvents (ethanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, and acetonitrile). The rate constant values (kd) are higher for reactions performed in secondary alcohols probably because of the possibility to form a cyclic adduct with the participation of the hydrogen atom bonded to the secondary carbon. The kinetic parameters were correlated with the physicochemical properties of the selected solvents. The products of the DEKTP thermal decomposition in different polar solvents support a radical-based decomposition mechanism.

THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT

The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 °C temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86% peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1).