91 resultados para kinetic


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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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The organic fraction of urban solid residues disposed of in sanitary landfills during the decomposition yields biogas and leachate, which are sources of pollution. Leachate is a resultant liquid from the decomposition of substances contained in solid residues and it contains in its composition organic and inorganic substances. Literature shows an increase in the use of thermoanalytical techniques to study the samples with environmental interest, this way thermogravimetry is used in this research. Thermogravimetric studies (TG curves) carried out on leachate and residues shows similarities in the thermal behavior, although presenting complex composition. Residue samples were collected from landfills, composting plants, sewage treatment stations, leachate, which after treatment, were submitted for thermal analysis. Kinetic parameters were determined using the Flynn-Wall-Ozawa method. In this case they show little divergence between the kinetic parameter that can be attributed to different decomposition reaction and presence of organic compounds in different phases of the decomposition with structures modified during degradation process and also due to experimental conditions of analysis.

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Meglumine, (2R,3R,4R,5S)-6-methylaminohexane-1,2,3,4,5-pentol, is a carbohydrate derived from sorbitol in which the hydroxyl group in position one is replaced by a methylamine group. It forms binary adducts with substances having carboxyl groups, which have in common the presence of hydrogen bonding as the main force in the stabilization of these species. During melting, adducts of meglumine with flunixin (2-[[2-methyl-3-(trifluoromethyl)phenyl]amino]pyridine-3-carboxylic acid) polymerize or self-assemble in amorphous supramolecular structures with molecular weights around 2.0 x 10(5) kDa. DSC curves, in a first heating, show isomorphic transitions where the last one at 137 A degrees C for the flunixin-meglumine adduct originated the supramolecular amorphous polymers with glass transition around 49.5 A degrees C. The kinetic parameters for the thermal decomposition step of the polymers were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15, and 20 A degrees C min(-1), the E (alpha) and B (alpha) terms could be determined and, consequently, the pre-exponential factor, A(alpha), as well as the kinetic model, g(alpha).

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Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc. The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn-Wall-Ozawa method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban's samples, but not for leachate's sample. The occurred difference can be attributed to the constituents present in leachate.

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Cellulose can be obtained from innumerable sources such as cotton, trees, sugar cane bagasse, wood, bacteria, and others. The bacterial cellulose (BC) produced by the Gram-negative acetic-acid bacterium Acetobacter xylinum has several unique properties. This BC is produced as highly hydrated membranes free of lignin and hemicelluloses and has a higher molecular weight and higher crystallinity. Here, the thermal behavior of BC, was compared with those of microcrystalline (MMC) and vegetal cellulose (VC). The kinetic parameters for the thermal decomposition step of the celluloses were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and at heating rates of 5, 10, and 20 A degrees C/min, the E(alpha) and B(alpha) terms could be determined and consequently the pre-exponential factor A(alpha) as well as the kinetic model g(alpha). The pyrolysis of celluloses followed kinetic model g(alpha) = [-ln(1 - alpha)](1.63) on average, characteristic for Avrami-Erofeev with only small differences in activation energy. The fractional value of n may be related to diffusion-controlled growth, or may arise from the distributions of sizes or shapes of the reactant particles.

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The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The dehydration, thermal decomposition and transition phase stage of Zn(II)-diclofenac compound were studied by simultaneous TG-DTA and DSC techniques. The TG and DSC curves of this compound were obtained with the mass of sample of 2 and 5 mg. Additionally, DSC curves were carried out in opened and closed alpha-alumina pans under static and nitrogen atmosphere. The DTA and DSC curves show that this compound possesses exothermic transition phase between 170-180 degrees C, which it is irreversible (monotropic reaction) The kinetics study of this transition phase stage was evaluated by DSC under non-isothermal conditions. The obtained data were evaluated with the isoconversional method, where the values of activation energy (E(a) / kJ mol(-1)) was plotted in function of the conversion degree (alpha). The results show that due to mass sample, different activation energies were obtained From these curves a tendency can be seen where the plots maintain the same profile for closed lids and almost run parallel to each other.

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Leachate samples from a sanitary landfill of Araraquara city and composting usine of Vila Leopoldina, São Paulo, Brazil were lyophilized to remove the water content. TG/DTG curves at different heating rates were recorded. The second step of the thermal decomposition of leachate from the Araraquara landfill (CB1), from the composting usine from Vila Leopoldina (CB2) from the organic phase extracted (FO) and aqueous phase (FA) were all kinetically evaluated using the non-isothermal method.By Flynn-Wall isoconversional method the following values were obtained: E=234 +/- 3.65 kJ mol(-1) and logA=29.7 +/- 0.58 min(-1) for CB1; E=129 +/- 1.66 kJ mol(-1) and logA=11.8 +/- 0.10 min(-1) for CB2; E=51.6 +/- 1.35 kJ mol(-1) and logA=6.09 +/- 0.09 min(-1) for FO and E=76.91 +/- 6.33 kJ mol(-1) and logA=8.88 +/- 0.7 min(-1) for FA with 95% confidence level. Applying the procedures of Malek and Koga, SB kinetic model (Sestak-Berggren) is the most appropriate to describe the decomposition of CB1, CB2, FO and FA.