977 resultados para THERMODYNAMIC ANALYSIS
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This survey on calorimetry and thermodynamics of anoxibiosis applies classical and irreversible thermodynamics to interpret experimental, direct calorimetric results in order to elucidate the sequential activation of various biochemical pathways. First, the concept of direct and indirect calorimetry is expanded to incorporate the thermochemistry of aerobic and anoxic metabolism in living cells and organisms. Calorimetric studies done under normoxia as well as under physiological and environmental anoxia are presented and assessed in terms of ATP turnover rate. Present evidence suggests that unknown sources of energy in freshwater and marine invertebrates under long-term anoxia may be important. During physiological hypoxia, thermodynamically grossly inefficient pathways sustain high metabolic rates for brief periods. On the contrary, under long-term environmental anoxia, low steady-state heat dissipation is linked to the more efficient succinate, propionate, and acetate pathways. In the second part of this paper these relationships are discussed in the context of linear, irreversible thermodynamics. The calorimetric and biochemical trends during aerobic-anoxic transitions are consistent with thermodynamic optimum functions of catabolic pathways. The theory predicts a decrease of rate with an increase of thermodynamic efficiency; therefore maximum rate and maximum efficiency are mutually exclusive. Cellular changes of pH and adenylate phosphorylation potential are recognized as regulatory mechanisms in the energetic switching to propionate production. While enzyme kinetics provides one key for understanding metabolic regulation, our insight remains incomplete without a complementary thermodynamic analysis of kinetic control in energetically coupled pathways.
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Activation of methane with a halogen followed by the metathesis of methyl halide is a novel route from methane to higher hydrocarbons or oxygenates. Thermodynamic analysis revealed that bromine is the most suitable halogen for this goal. Analysis of the published data on the reaction kinetics in a CSTR enabled us to judge on the effects of temperature, reactor residence time and the feed concentrations of bromine and methane to the conversion of methane and the selectivity towards mono or dibromomethane. The analysis indicated that high dibromomethane selectivity is attainable (over 90%) accompanied by high methane conversions. The metathesis of dibromomethane can provide an alternative route to the conversion of methane (natural gas) economically with smaller installations than the current syn-gas route. (c) 2005 Elsevier B.V. All rights reserved.
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The magnetoelectric coupling in multiferroic materials is promising for a wide range of applications, yet manipulating magnetic ordering by electric field proves elusive to obtain and difficult to control. In this paper, we explore the prospect of controlling magnetic ordering in misfit strained bismuth ferrite (BiFeO3, BFO) films, combining theoretical analysis, numerical simulations, and experimental characterizations. Electric field induced transformation from a tetragonal phase to a distorted rhombohedral one in strain engineered BFO films has been identified by thermodynamic analysis, and realized by scanning probe microscopy (SPM) experiment. By breaking the rotational symmetry of a tip-induced electric field as suggested by phase field simulation, the morphology of distorted rhombohedral variants has been delicately controlled and regulated. Such capabilities enable nanoscale control of magnetoelectric coupling in strain engineered BFO films that is difficult to achieve otherwise, as demonstrated by phase field simulations.
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Densities, rho, of aqueous solutions of the room temperature protic ionic liquid (PIL), pyrrolidinium nitrate are determined at the atmospheric pressure over the temperature range from (283.15 to 323.15) K and within the whole composition range. The molar isobaric heat capacities, C(p), and refractive index, n(D), of {PIL + water} binary system are measured at 298.15 K. The excess molar volumes V(E), excess molar isobaric heat capacities C(p)(E), and deviation from ideality of refractive index Delta(phi)n, of pyrrolidinium nitrate aqueous solutions were deduced from the experimental results as well as apparent molar volumes V(phi), partial molar volumes (V) over bar (m,i), and thermal expansion coefficients alpha(p). The V(E) values were found to be positive over the entire composition range at all temperatures studied therein, whereas deviations from ideality were negative for refractive index Delta(phi)n. The volumetric properties of binary mixtures containing water and four other protic ionic liquids, such as pyrrolidinium hydrogen sulfate, pyrrolidinium formiate, collidinium formate, and diisopropyl-ethylammonium formate were also determined at 298.15 K. Results have been then discussed in terms of molecular interactions and molecular structures in these binary mixtures. (C) 2009 Elsevier Ltd. All rights reserved.
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Des del seu descobriment, a la molècula C60 se li coneixen una varietat de derivats segons el tipus de funcionalització amb propietats fisicoquímiques específiques de gran interès científic. Una sel·lecció de derivats corresponents a addicions simple o múltiple al C60 s'ha considerat en aquest treball d'investigació. L'estudi a nivell de química computacional de diversos tipus d'addició al C60 s'han portat a terme per tal de poder donar resposta a aspectes que experimentalment no s'entenen o són poc clars. Els sistemes estudiats en referència a l'addició simple al C60 han estat en primer lloc els monoiminoful·lerens, C60NR, (de les dues vies proposades per la seva síntesi, anàlisis cinètic i termodinàmic han ajudat a explicar els mecanismes de formació i justificar l'addició a enllaços tipus [5,6]), i en segon lloc els metanoful·lerens i els hidroful·lerens substituits, C60CHR i C60HR, (raons geomètriques, electròniques, energètiques i magnètiques justifiquen el diferent caràcter àcid ente ambdós derivats tenint en compte una sèrie de substituents R amb diferent caràcter electrònic donor/acceptor). Els fluoroful·lerens, C60Fn, i els epoxid ful·lerens, C60On, (anàlisi sistemàtic dels seus patrons d'addició en base a poder justificar la força que els governa han aportat dades complementàries a les poques que existeixen experimentalment al respecte).
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Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.
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The use of infrared burners in industrial applications has many advantages in terms of technical-operational, for example, uniformity in the heat supply in the form of radiation and convection, with greater control of emissions due to the passage of exhaust gases through a macro-porous ceramic bed. This paper presents an infrared burner commercial, which was adapted an experimental ejector, capable of promoting a mixture of liquefied petroleum gas (LPG) and glycerin. By varying the percentage of dual-fuel, it was evaluated the performance of the infrared burner by performing an energy balance and atmospheric emissions. It was introduced a temperature controller with thermocouple modulating two-stage (low heat / high heat), using solenoid valves for each fuel. The infrared burner has been tested and tests by varying the amount of glycerin inserted by a gravity feed system. The method of thermodynamic analysis to estimate the load was used an aluminum plate located at the exit of combustion gases and the distribution of temperatures measured by a data acquisition system which recorded real-time measurements of the thermocouples attached. The burner had a stable combustion at levels of 15, 20 and 25% of adding glycerin in mass ratio of LPG gas, increasing the supply of heat to the plate. According to data obtained showed that there was an improvement in the efficiency of the 1st Law of infrared burner with increasing addition of glycerin. The emission levels of greenhouse gases produced by combustion (CO, NOx, SO2 and HC) met the environmental limits set by resolution No. 382/2006 of CONAMA
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Biomass is considered the largest renewable energy source that can be used in an environmentally sustainable. From the pyrolysis of biomass is possible to obtain products with higher energy density and better use properties. The liquid resultant of this process is traditionally called bio-oil. The use of infrared burners in industrial applications has many advantages in terms of technical-operational, for example, uniformity in the heat supply in the form of radiation and convection, with a greater control of emissions due to the passage of exhaust gases through a macroporous ceramic bed. This paper presents a commercial infrared burner adapted with an ejector proposed able to burn a hybrid configuration of liquefied petroleum gas (LPG) and bio-oil diluted. The dilution of bio-oil with absolute ethanol aimed to decrease the viscosity of the fluid, and improving the stability and atomization. It was introduced a temperature controller with thermocouple modulating two stages (low heat / high heat), and solenoid valves for fuels supply. The infrared burner has been tested, being the diluted bio-oil atomized, and evaluated its performance by conducting energy balance. The method of thermodynamic analysis to estimate the load was used an aluminum plate located at the exit of combustion gases and the distribution of temperatures measured by thermocouples. The dilution reduced the viscosity of the bio-oil in 75.4% and increased by 11% the lower heating value (LHV) of the same, providing a stable combustion to the burner through the atomizing with compressed air and burns combined with LPG. Injecting the hybrid fuel there was increase in the heat transfer from the plate to the environment in 21.6% and gain useful benefit of 26.7%, due to the improved in the efficiency of the 1st Law of Thermodynamics of infrared burner
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Significant observational effort has been directed to unveiling the nature of the so-called dark energy. However, given the large number of theoretical possibilities, it is possible that this a task cannot be based only on observational data. In this thesis we investigate the dark energy via a thermodynamics approach, i.e., we discuss some thermodynamic properties of this energy component assuming a general time-dependent equation-of-state (EoS) parameter w(a) = w0 + waf(a), where w0 and wa are constants and f(a) may assume different forms. We show that very restrictive bounds can be placed on the w0 - wa space when current observational data are combined with the thermodynamic constraints derived. Moreover, we include a non-zero chemical potential μ and a varying EoS parameter of the type ω(a) = ω0 + F(a), therefore more general, in this thermodynamical description. We derive generalized expressions for the entropy density and chemical potential, noting that the dark energy temperature T and μ evolve in the same way in the course of the cosmic expansion. The positiveness of entropy S is used to impose thermodynamic bounds on the EoS parameter ω(a). In particular, we find that a phantom-like behavior ω(a) < −1 is allowed only when the chemical potential is a negative quantity (μ < 0). Thermodynamically speaking, a complete treatment has been proposed, when we address the interaction between matter and energy dark
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Pós-graduação em Engenharia Mecânica - FEIS
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O objetivo desta dissertação foi verificar a importância dos fatores termodinâmicos na ocorrência de eventos extremos de precipitação na Cidade de Belém (PA) e região metropolitana, no período de agosto de 2008 a dezembro de 2009. Para tal, foram utilizados dados de precipitação e radiossondagens. Para análise das condições termodinâmicas e dinâmicas foram utilizadas imagens de satélite, cartas de superfície e análise do diagrama SKEW T LOG P. O estudo da termodinâmica da atmosfera foi realizado a luz das teorias da Energia Potencial Disponível para a Convecção (CAPE) e, também, da Energia de Inibição da Convecção (CINE). Foi utilizado o método dos decis para classificar os eventos extremos de precipitação a fim de associá-los aos valores da CAPE e da CINE com o objetivo de verificar o valor destes índices quando da ocorrência dos eventos extremos. Verificou-se que a região estudada possui forte atividade convectiva durante todo o ano, haja vista que seus valores médios mensais variam entre 900 J/kg e 1900 J/kg. Foi visto, também, que nem sempre CAPE alta e CINE baixa determinam precipitação. Esta situação determina o potencial para a convecção profunda, mas para converter este potencial em precipitação existe a necessidade da forçante dinâmica. Os resultados mostraram que quando o processo de precipitação dependeu, exclusivamente, da CAPE, foi necessário haver um valor alto para poder gerar convecção profunda e por consequência precipitação, enquanto, que no processo de precipitação com contribuição dinâmica não foi necessário um valor tão significativo da CAPE, neste caso, não ultrapassou a 1000 J/kg. A CINE esteve, sempre, menor no período chuvoso apresentando valores médios mensais menores que 300 J/kg. Isto não quer dizer que quanto menor a CINE maior será a precipitação. Quando a inibição está presente a instabilidade vai crescendo ao longo do dia determinando, com isso, nuvens com um desenvolvimento vertical mais acentuado, assim os pontos onde os inibidores enfraquecem primeiro, serão os pontos preferenciais para o disparo da tempestade. Logo, quando a instabilidade estiver alta e existir o mecanismo inibidor (CINE), em uma grande área, os locais mais propícios aos disparos das tempestades são os pontos onde a CINE e o NCE começam a diminuir e a inversão térmica, que por vezes acontece, começa a ser quebrada. Durante a execução desta pesquisa ficou claro que para a ocorrência de eventos extremos de precipitação, no período chuvoso, existe necessidade da influência da ITCZ e no período seco, conforme se observa no estudo de caso realizado para o mês de outubro o fator dinâmico que mais influencia é a Linha de Instabilidade (LI).
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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This work studies the incorporation of new technologies in the sugarcane sector. Are considered the ethanol steam reforming and the gasification of sugarcane bagasse(by-product) processes associated with combined cycle systems (Gas Turbine + Steam Turbine), aggregating hydrogen production and increased electricity supply in the sector, respectively. To verify the technical feasibility of the incorporation processes was performed a thermodynamic analysis, considering data from a typical Brazilian Sugar Cane Industry. In another step the economic viability study of the hydrogen production process was made, with consideration on hydrated and anhydrous ethanol steam reform, comparing the cost of hydrogen production. Also considered studies of economic engineering of the gasification process and the generation of electricity associated. As conclusions, it follows that the ethanol steam reforming is a great alternative for hydrogen production, presenting production cost relatively low, especially when is considered the steam reforming of hydrated ethanol. For the gasification process associated with combined cycle, can be observed an increase of 8.56 times of the electricity production in the sugar cane industry, indicating a positive annual saving when the sales price of the supply electricity is greater than 0.070 US$/kWh. Finally it can be concluded that the incorporation of these new processes allow greater profitability and operational flexibility of Brazilian sugarcane mills
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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This work evaluates the existing potential in the state of Sao Paulo for the generation of electrical energy using the sugar cane bagasse as fuel. As the bagasse is a by-product of the sugarcane and alcohol industry and it is produced in large scale in the country, mainly in the state of Sao Paulo, it is important to develop researches that aim the best utilization of this input. In order to determine its potential, at first, a study was conducted considering the utilization of the cogeneration, which is a common practice in the plants of the sector. However, it was concluded that the cogeneration could provide a higher quantity of energy if more modern technologies and more efficient processes were used. Another study to estimate the potential considered a system of gasification of the sugar cane bagasse integrated with the combined cycle (BIG/GTCC). It was concluded that this technology can provide a considerable increase in the electrical supply. In this work it was also developed an energetic study based on real data from a plant located in the state of Sao Paulo. A thermodynamic analysis was done in the existing equipment of the cogeneration section of the plant. And another analysis was done considering the implementation of the BIG/GTCC technology to the cogeneration system. Comparing the results of both settings, it was concluded that the utilization of the sugar cane bagasse integrated to a combined cycle increased considerably the efficiency in the generation of electricity of the plant, increasing more than six times its production capacity of electrical energy