RESUMEN

A series of CrOx-ZrO2-SiO2 (CrZrSi) catalysts was prepared by a "one-pot" template-assisted evaporation-induced self-assembly process. The chromium content varied from 4 to 9 wt.% assuming Cr2O3 stoichiometry. The catalysts were characterized by XRD, SEM-EDX, temperature-programmed reduction (TPR-H2), Raman spectroscopy, and X-ray photoelectron spectroscopy. The catalysts were tested in non-oxidative propane dehydrogenation at 500-600 °C. The evolution of active sites under the reaction conditions was investigated by reductive treatment of the catalysts with H2. The catalyst with the lowest Cr loading initially contained amorphous Cr3+ and dispersed Cr6+ species. The latter reduced under reaction conditions forming Cr3+ oxide species with low activity in propane dehydrogenation. The catalysts with higher Cr loadings initially contained highly dispersed Cr3+ species stable under the reaction conditions and responsible for high catalyst activity. Silica acted both as a textural promoter that increased the specific surface area of the catalysts and as a stabilizer that inhibited crystallization of Cr2O3 and ZrO2 and provided the formation of coordinatively unsaturated Zr4+ centers. The optimal combination of Cr3+ species and coordinatively unsaturated Zr4+ centers was achieved in the catalyst with the highest Cr loading. This catalyst showed the highest efficiency.

RESUMEN

Chlorate ion ClO3- is formed as a result of the complex chemical interaction of ozone with chloride ion in aqueous solution. In neutral and basic solutions, chlorate is the main product. In acid solutions, the main product is molecular chlorine Cl2, and the yield of chlorate is 50-100 times lower. Dependencies have been studied of chlorate formation rate on significant experimental factors: concentrations of initial substances, ozone and chloride ion, acidity (pH), ionic strength and temperature of the reaction solution. The kinetic laws of chlorate generation have been established, and the expressions are given for rate constants of chlorate formation as functions of temperature and ionic strength. When tert-butanol is added to the reaction system, the formation of chlorate ceases, which is an evidence of the crucial role of free radical reactions in this process.

Asunto(s)

RESUMEN

The experimental dissociation constants of strong acids are notoriously ill-defined, and it is necessary to rely on theoretical methods for their evaluation. We present a methodology for the theoretical evaluation of the dissociation constants, and the values of Ka for perchloric and sulfuric acids have been estimated. It has been shown that the acid dissociation constant Ka can be expressed as a product of two terms, Ka = Ka' × fHA∞, where Ka' is the apparent dissociation constant and fHA∞ is the infinite dilution activity coefficient of undissociated molecule of acid in liquid solution. The values of Ka' can be computed from readily available reference data. The limiting activity coefficients fHA∞ for strong acids can be determined by theoretical methods only. The following estimate for the limiting activity coefficients of perchloric and sulfuric acids has been obtained, -2.5 < log10 fHA∞ < -1.3. The ranges of values of the dissociation constants of HClO4 and H2SO4 at 25 °C have been determined; log10 Ka(HClO4) = 10.8-12.3; log10 Ka1(H2SO4) = 4.5-8.6.