988 resultados para chemical kinetics
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Milk supplementation with milk proteins in four different levels was used to investigate the effect on acidification and textural properties of yogurt. Commercial skim milk powder was diluted in distilled water, and the supplements were added to give different enriched-milk bases; these were heat treated at 90 degrees C for 5 min. These mixtures were incubated with the bacterial cultures for fermentation in a water bath, at 42 degrees C, until pH 4.50 was reached. Chemical changes during fermentation were followed by measuring the pH. Protein concentration measurements, microbial counts of Lactobacillus bulgaricus and Streptococcus thermophilus, and textural properties (G`, G ``, yield stress and firmness) were determined after 24 h of storage at 4 degrees C. Yogurt made with milk supplemented with sodium caseinate resulted in significant properties changes, which were decrease in fermentation time, and increase in yield stress, storage modulus, and firmness, with increases in supplement level. Microstructure also differed from that of yogurt produced with milk supplemented with skim milk powder or sodium caseinate. (C) 2009 Elsevier Ltd. All rights reserved.
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The inactivation kinetics of enzymes polyphenol oxidase (PPO) and peroxidase (POD) was studied for the batch (discontinuous) microwave treatment of green coconut water. Inactivation of commercial PPO and POD added to sterile coconut water was also investigated. The complete time-temperature profiles of the experimental runs were used for determination of the kinetic parameters D-value and z-value: PPO (D(92.20 degrees C) = 52 s and z = 17.6 degrees C); POD (D(92.92 degrees C) = 16 s and z = 11.5 degrees C); PPO/sterile coconut water: (D(84.45 degrees C) = 43 s and z = 39.5 degrees C) and POD/sterile coconut water: (D(86.54 degrees C) = 20 s and z = 19.3 degrees C). All data were well fitted by a first order kinetic model. The enzymes naturally present in coconut water showed a higher resistance when compared to those added to the sterilized medium or other simulated solutions reported in the literature. The thermal inactivation of PPO and POD during microwave processing of green coconut water was significantly faster in comparison with conventional processes reported in the literature. (C) 2008 Elsevier Ltd. All rights reserved.
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The electrocatalytic oxidation of ascorbate on a ruthenium oxide hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was investigated at pH 6.9 by using rotating disc electrode (RDE) voltammetry. The influence of the systematic variation of rotation rate, film thickness, ascorbate concentration and the electrode potential indicated that the rate of cross-chemical reaction between Ru(III) centres immobilized into the film and ascorbate controls the overall process. The kinetic regime may be classified as a Sk `` mechanism and the second order rate constant for the surface electrocatalytic reaction was found to be 1.56 x 10(-3) mol(-1) L-1 s(-1) cm. A carbon fibre microelectrode modified with the RuOHCF film was successfully used as an amperometric sensor to monitor the ascorbate diffusion in a simulated microenvironment experiment. (C) 2008 Elsevier B.V. All rights reserved.
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The effects of alkali treatment on the structural characteristics of cotton linters and sisal cellulose samples have been studied. Mercerization results in a decrease in the indices of crystallinity and the degrees of polymerization, and an increase in the alpha-cellulose contents of the samples. The relevance of the structural properties of cellulose to its dissolution is probed by studying the kinetics of cellulose decrystallization, prior to its solubilization in LiCl/N,N-dimethylacetamide (DMAc). Our data show that the decrystallization rate constants and activation parameters are only slightly dependent on the physico-chemical properties of the starting celluloses. This multi-step reaction is accompanied by a small enthalpy and large, negative, entropy of activation. These results are analyzed in terms of the interactions within the biopolymer chains during decrystallization, as well as those between the two ions of the electrolyte and both DMAc and cellulose.
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In this work, TG/DTG and DSC techniques were used to the determination of thermal behavior of prednicarbate alone and associated with glyceryl stearate excipient ( 1: 1 physical mixture). TG/DTG curves obtained for the binary mixture showed a reduction of approximately 37 degrees C to the thermal stability of drug (T(dm/dt-0) (Max)(DTG)). The disappearance of stretching band at 1280 cm(-1) (nu(as) C-O, carbonate group) and the presence of streching band with less intensity at 1750 cm(-1) (nu(s) C-O, ester group) in IR spectrum obtained to the binary mixture submitted at 220 degrees C, when compared with IR spectrum of drug submitted to the same temperature, confirmed the chemical interaction between these substances due to heating. Kinetics parameters of decomposition reaction of prednicarbate were obtained using isothermal (Arrhenius equation) and non-isothermal (Ozawa) methods. The reduction of approximately 45% of activation energy value (E(a)) to the first step of thermal decomposition reaction of drug in the 1:1 (mass/mass) physical mixture was observed by both kinetics methods.
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This work assesses the photocatalytic (TiO(2)/UV) degradation of a simulated reactive dye bath (Black 5, Red 239, Yellow 17, and auxiliary chemicals). Color removal was monitored by spectrophotometry. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 30 min of irradiation, it was achieved 97% and 40% of color removal with photocatalysis and photolysis, respectively. No mineralization occurred within 30 min. A kinetic model composed of two, first-order in-series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 2.6 min(-1) and the second k(2) = 0.011 min(-1). The fast decolorization of Reactive Black 5 dye is an indication that the number of azo and vinylsulfone groups in the dye molecule maybe a determining factor for the increased photolytic and photocatalytic color removal and degradation rates. (C) 2008 Elsevier B.V. All rights reserved.
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The photocatalytic degradation of phenol in aqueous suspensions of TiO(2) under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen- Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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In this work, experimental data for the system Lippia alba + CO2 is presented. The major constituents of the L. alba volatile oil are limonene and carvone. Thus, literature data for the systems limonene + CO2 and carvone + CO2, and the Peng-Robinson equation of state (PR-EOS) were used to select the operating temperature and pressure, which maximize the global yield in L. alba extract. Global yields were determined at 80, 100, and 120 bar and 40, 45, and 50 degrees C. L. alba extracts were also obtained by conventional processes (hydrodistillation, low-pressure ethanol extraction and Soxhlet ethanol). The chemical compositions of the extracts were determined by gas and thin layer chromatography (TLC). The secretor structures of L. alba were observed by scanning electron microscopy (SEM) before and after supercritical extraction. The largest yield (similar to 7%, mass of extract/mass of dry solid) of the CO2-extract was obtained at 318 K and 100 bar. The chemical compositions of the CO2-extracts were different from those of the extracts obtained by Soxhlet and low-pressure solvent extraction (LPSE) because of the co-extraction of heavy substances by ethanol. The operating conditions that maximized the carvone and limomene yields were 80 bar and 323 K (80 mass%) and 120 bar and 323 K (17 mass%), respectively. (c) 2004 Elsevier B.V All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Dilute acid hydrolysis studies were performed on forest residues of Eucalyptus grandis, in a cylindrical reactor of stainless steel. The kinetics of this hydrolysis reaction was investigated employing 0.65% sulfuric acid, a residue/acid solution ratio of 1/9 (w/w), temperatures of 130, 140, 150, and 160 degrees C, and reaction times in the range 20-100 min. The results showed that, under the optimized conditions of acid hydrolysis employed in this study, the variables temperature and reaction time had a strong influence on hemicellulose removal and a small influence on the degree of lignin and cellulose removal. The highest xylose extraction yield was 87.6% attained at 160 degrees C, after 70 min reaction time, simultaneously with the formation of decomposition products, namely 2.8% acetic acid, 0.6% furfural, and 0.06% 5-hydroxymethylfurfural. A similar xylose extraction yield (82.8%) was observed at 150 degrees C after 100 min, with the formation of 3.2% acetic acid, 1.0% furfural, and 0.07% 5-hydroxymethylfurfural. The kinetic parameters determined at 130, 140, 150, and 160 degrees C for degradation of xylan present in the hemicellulose of the eucalyptus forest residue during the formation of xylose were the first-order reaction rate constants (k) for each temperature, 1.22 x 10(-4), 2.12 x 10(-4), 5.43 x 10(-4), and 9.05 x 10(-4) s(-1), respectively, and an activation energy (E-a) of 101.3 kJ mol(-1).
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PbTiO3 thin films were deposited on Si(100) via hybrid chemical method and crystallized between 400 and 700 degreesC to study the effect of the crystallization kinetics on structure and microstructure of these materials. X-ray diffraction (XRD) technique was used to study the structure of the crystallized films. In the temperature range investigated, the lattice strain (c/a) presented a maximum value (c/a = 1.056) for film crystallized at 600 degreesC for I h. Atomic force microscopy (AFM) was used in investigation of the microstructure of the films. The rms roughness of the films linearly increases with temperature and ranged from 1.25 to 9.04 nm while the grain sizes ranged from 130.6 to 213.6 nm. Greater grain size was observed for film crystallized at 600 degreesC for 1 h. (C) 2002 Elsevier B.V. S.A. All rights reserved.