265 resultados para Physical Chemistry problems advanced gas thermodynamics


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Structural and textural studies of a CuO/TiO2 System modified by cerium oxide were conducted using Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N-2 absorption (BET specific surface area). The introduction of a minor amount of CeO2 (Ce0.09Ti0.82O1.91CU0.09 sample) resulted in a material with the maximum surface area value. The results of Raman spectroscopy revealed the presence of only two crystalline phases, TiO2 anatase and CeO2 cerianite, with well-dispersed copper species. TEM micrographs showed a trend toward smaller TiO2 crystallites when the cerium oxide content was increased. The XPS analysis indicated the rise of a second peak in Ti 2p spectra with the increasing amount of CeO2 located at higher binding energies than that due to the Till in a tetragonal symmetry. The CuO/TiO2 system modified by CeO2 displayed a superior performance for methanol dehydrogenation than the copper catalyst supported only on TiO2 or CeO2.

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psi-Condensation of DNA fragments of about 4 kbp was induced by poly(ethylene glycol) (PEG), with degrees of polymerization ranging from 45 to 182, and univalent salt (NaCl). Using circular dichroism spectroscopy, we were able to accurately determine the critical amount of PEG needed to induce condensation, as a function of the NaCl concentration. A significant dependence on the PEG degree of polymerization was found. Phase boundaries determined for the multimolecular condensation were very similar to those observed previously for the monomolecular collapse, with two asymptotic regimes at low and high salt concentrations. We analyze our data using a theoretical model that properly takes into account both the polyelectrolyte nature of the DNA and the liquid crystallinity of the condensed phase. The model assumes that all PEG is excluded from the condensates and shows reentrant decondensation only at low salt. We also systematically study reentrant decondensation and find a very strong dependence on PEG molecular weight. At low PEG molecular weight, decondensation occurs at relatively low concentrations of PEG, and over a wide range of salt concentrations. This suggests that in the reentrant decondensation the flexible polymers used are not completely excluded from the condensed phase.

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A model describing dissociation of monoprotonic acid and a method for the determination of its pK value are presented. The model is based on a mean field approximation. The Poisson-Boltzmann equation, adopting spherical symmetry, is numerically solved, and the solution of its linearized form is written. By use of the pH values of a dilution experiment of galacturonic acid as the entry data, the proposed method allowed estimation of the value of pK = 3.25 at a temperature of 25 degrees C. Values for the complex dimensions and dissociation degree are calculated using experimental pH values for solution concentration values ranging from 0.1 to 60 mM. The present analysis leads to the conclusion that the Poisson-Boltzmann equation or its linear form is equally suited for the description of such systems.

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Silica wet gels were prepared from acid sonohydrolysis of tetraethoxysilane (TEOS) and additions of poly(vinyl alcohol) (PVA)-water solution. Aerogels were obtained from supercritical CO(2) extraction. The samples were studied by thermal gravimetric (TG) analysis, small-angle X-ray scattering (SAXS), and nitrogen adsorption. The structure of wet gels can be described as a mass fractal with dimension D equal to 2.0 on the whole length scale experimentally probed by SAXS, from similar to 0.3 to similar to 15 nm. Pure and low-PVA-addition wet gels exhibit an upper cutoff accounting for a finite characteristic length xi of the mass fractal structure. Additions , of PVA increase without modifying D, which was attributed to a steric effect of the polymer in the structure. The pore volume fraction of the aerogels diminishes typically about 11% with respect to that of the wet gels, although nitrogen adsorption could be underestimating some porosity. The pore size distribution of the aerogels is shifted toward the mesopore region with the additions of PVA, in a straight relationship with the increase of xi in the wet gels. The thermal stability of the pore size distribution of the aerogels was studied up to 1000 degrees C.

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This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula KhFek3+ [Fe2+ (CN)(6)](l)center dot mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H3O+ (hydrated protons) through the channels of the KhFek3+ [Fe2+ (CN)(6)](l) center dot mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K+ or H+ (proton) exchange through the water crystalline structure existing in the channels of the KhFek3+ [Fe2+(CN)(6)](l)center dot mH(2)O structure.

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In this work, carbon-supported Pt70Co30 nanoparticles were prepared by a polyol process using a long-chain diol as reducer (hexadecanediol) and oleic acid and oleylamine as stabilizers. Depending on the synthesis conditions, Pt70Co30/C nanocatalysts with very small particle size (1.9 +/- 0.2 nm) and narrow distribution homogeneously dispersed on the carbon support and having a high degree of alloying without the need of thermal treatments were obtained. The as-prepared catalyst presents an excellent performance as proton exchange membrane fuel cells (PEMFC) cathode material. In terms of mass activity (MA), the Pt70Co30/C electrocatalysts produced single fuel cell polarization response superior to that of commercial catalyst. To analyze alloying effects, the result of thermal treatment at low temperatures (200-400 degrees C) was also evaluated and an increase of average crystallite size and a lower degree of alloying, probably associated to cobalt oxidation, were evidenced.