A segunda lei da termodinâmica

Considering intrinsic characteristics of the system exclusively, both statistical and information theory interpretations of the second law are used to provide more comprehensive meanings for the concepts of entropy, temperature, and Helmholtz and Gibbs energies. The coherence of Clausius inequality to these concepts is emphasized. The aim of this work is to re-discuss the second law of thermodynamics in accordance to homogeneous processes thermodynamics, a temporal science which is the very special oversimplification of continuum mechanics for spatially constant intensive properties.

Uma teoria termodinâmica para brisas: teste utilizando simulações numéricas

O objetivo deste trabalho foi testar uma teoria termodinâmica em brisas marítimas-terrestres acopladas com brisas de vale-montanha através de simulações numéricas tridimensionais em uma região da costa leste do Nordeste Brasileiro, considerando a presença e a ausência da topografia. Embora o contraste de temperatura entre as superfícies seja importante na formação da brisa, a eficiência termodinâmica é fundamental na determinação da sua intensidade. Tem-se que a inclinação faz com que a diferença de pressão entre dois pontos fique maior durante o dia e menor durante a noite contribuindo para a formação de brisas marítimas mais intensas e de brisas terrestres menos intensas, respectivamente. A máxima queda de pressão ocorre por volta de três horas antes da máxima intensidade da brisa. Isso porque grande parte da energia disponibilizada para as circulações é gasta para vencer dissipação, principalmente, no período diurno, quando esses processos são realmente efetivos. Do ponto de vista puramente termodinâmico a inclinação da montanha atua para intensificar a brisa durante o dia e para enfraquecê-la durante a noite.

Análise termodinâmica de uma central de biomassa lenhosa

Dissertação para obtenção do Grau de Mestre em Engenharia Mecânica

Proposta e avaliação termodinâmica de soluções para o aproveitamento da exergia na regaseificação de GNL

Uma vez que o gás natural liquefeito (GNL) é transportado a uma temperatura criogénica de -162 °C e como os gasodutos recebem o gás natural (GN) à temperatura ambiente, existe neste sistema exergia que pode ser usada na produção de energia elétrica. A presente dissertação consiste na proposta, avaliação e comparação termodinâmica de diferentes ciclos para produção de energia elétrica, através do aproveitamento da exergia do GNL, aquando da sua transformação em GN, para introdução nos gasodutos. Neste trabalho, considerou-se como caso de estudo o terminal de GNL de Sines, em Portugal, que atualmente não tem implementada nenhuma solução para o aproveitamento da exergia disponível. Considerando os critérios de projeto, definidos de acordo com as características do terminal de Sines e, usando água do mar como fonte de calor, simularam-se e compararam-se os seguintes tipos de ciclos: o ciclo existente no terminal (CE), sem produção de energia; o ciclo de expansão direta do GN (CED); os ciclos tipo Rankine (CTR); os ciclos tipo Rankine com expansão direta (CTR+ED); e os ciclos tipo Rankine com apoio de energia solar (CTRS). Consideraram-se sete fluidos de trabalho (FT) diferentes: propano, etano, etileno, dióxido de carbono, R134a, R143a e propileno. As potências líquidas máximas obtidas para cada ciclo demonstram que: com o CE gastam-se cerca de 1182 kW para fazer o processamento de GNL; com o CED é possível gastar apenas 349 kW; com os CTR é possível obter uma potência líquida positiva ao processar o GNL, produzindo até 2120 kW (usando propileno como FT); com os CTR+ED é possível produzir 2174 kW (também usando propileno com FT); e com os CTRS é possível produzir até 3440 kW (valor médio anual) (usando etano como FT). Fez-se a otimização multi-objetivo dos ciclos tendo-se considerado alguns aspetos económicos. Além da maximização da potência líquida, para os CED, CTR e CTR+ED minimizou-se a área de transferência de calor total dos permutadores de calor e para os CTRS minimizou-se a área de coletores solares instalada.

A formulação ab-initio da segunda lei da termodinâmica

This paper deals with Carathédory's formulation of the second law of thermodynamics. The material is presented in a didatical way, which allows a second year undergraduate student to follow the formalism. An application is made to an ideal gas with two independent variables. A criticism to Carnot formulation of the second law and an investigation of the historical origins of the Carathéodory formalism are also presented.

Termodinâmica estatística de líquidos com o método de Monte Carlo. I. Metodologia

Statistical mechanics Monte Carlo simulation is reviewed as a formalism to study thermodynamic properties of liquids. Considering the importance of free energy changes in chemical processes, the thermodynamic perturbation theory implemented in the Monte Carlo method is discussed. The representation of molecular interaction by the Lennard-Jones and Coulomb potential functions is also discussed. Charges derived from quantum molecular electrostatic potential are also discussed as an useful methodology to generate an adequate set of partial charges to be used in liquid simulation.

Termodinâmica estatística de líquidos com o método de Monte Carlo. II. O líquido clorofórmio

Thermodynamic properties and radial distribution functions for liquid chloroform were calculated using the Monte Carlo method implemented with Metropolis algorithm in the NpT ensemble at 298 K and 1 atm. A five site model was developed to represent the chloroform molecules. A force field composed by Lennard-Jones and Coulomb potential functions was used to calculate the intermolecular energy. The partial charges needed to represent the Coulombic interactions were obtained from quantum chemical ab initio calculations. The Lennard-Jones parameters were adjusted to reproduce experimental values for density and enthalpy of vaporization for pure liquid. All thermodynamic results are in excelent agreement with experimental data. The correlation functions calculated are in good accordance with theoretical results avaliable in the literature. The free energy for solvating one chloroform molecule into its own liquid at 298 K and 1 atm was computed as an additional test of the potential model. The result obtained compares well with the experimental value. The medium effects on cis/trans convertion of a hypotetical solute in water TIP4P and chloroform solvents were also accomplished. The results obtained from this investigation are in agreement with estimates of the continuous theory of solvation.

Sobre a primeira lei da termodinâmica

Entropy is a concept that has long stimulated human curiosity, resulting in an huge intelectual production. The same has not occurred for the first law of thermodynamics, perhaps because of its apparent obviousness. In this article the first law presentation, as displayed in most traditional physical chemistry textbooks, is criticized. An alternative view is suggested, in accordance with temporal thermodynamics. The time derivative local form of the second law is used to stress the entropy concept implications on the notion of internal energy.

Reflexões sobre a contribuição da Carnot à primeira lei da termodinâmica

The classical interpretations of Nicolas Léonard Sadi Carnot on some physical principles involved in the operation of heat engines were fundamental to the development and formulation of the Second Law of Thermodynamics. Moreover, an accurate historical survey clearly reveals that Carnot was, by that time, also well aware about some new concepts, which were further worked out by other scientists to lead to what was, some time later, known as the mechanical equivalent of heat and the conservation of energy. Benoit Paul Émile Clapeyron recognized these original concepts in the first of Carnot´s monographs, published in 1824, but no explicit citation is found in any post-Carnot classical texts dealing with the First Law of Thermodynamics, including those by Julius Robert Mayer, James Prescott Joule and Hermann Ludwig Ferdinand von Helmholtz. The main objective of the present work is to point out some historical evidences of the pioneering contribution of Carnot to the modern concept of the First Law of Thermodynamics.

Sobre a primeira lei da termodinâmica: as diferenciais do calor e do trabalho

We treat some subtleties concerning the First Law of Thermodynamics and discuss the inherent difficulties, namely the interpretation of the heat and the work differentials. By proposing a new differential equation for the First Law, which is written using both system and neighborhood variables, we overcome the mentioned difficulties and establish a criterion for the definition of heat and work.

Aplicação de Zr/Ti-PILC no processo de adsorção de Cu(II), Co(II) e Ni(II) utilizando modelos físico-químicos de adsorção e termodinâmica do processo

The aim of this investigation is to study how Zr/Ti-PILC adsorbs metals. The physico-chemical proprieties of Zr/Ti-PILC have been optimized with pillarization processes and Cu(II), Ni(II) and Co(II) adsorption from aqueous solution has been carried out, with maximum adsorption values of 8.85, 8.30 and 7.78 x10-1 mmol g-1, respectively. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data with a linear regression process. The energetic effect caused by metal interaction was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.

A primeira lei da termodinâmica dos processos homogêneos

Thermodynamics of homogeneous processes, which corresponds to the very special situation in thermodynamics of continuous media, is used to discuss the first law. An important part of this work is the exposition of some typical mathematical errors, frequently found in the traditional presentation of thermodynamics. The concepts of state and process functions are discussed, as well as reverse and reversible processes, temporality and its implications on thermodynamics, energy reservoirs and symmetry. Our proposal is to present the first law by using a time dependent viewpoint coherent with mechanics and the foundations of that viewpoint.

Remoção dos corantes azul brilhante, amarelo crepúsculo e amarelo tartrazina de soluções aquosas utilizando carvão ativado, terra ativada, terra diatomácea, quitina e quitosana: estudos de equilíbrio e termodinâmica

This work compared activated carbon, activated earth, diatomaceous earth, chitin and chitosan to removal acid blue 9, food yellow 3 and FD&C yellow nº 5 dyes from aqueous solutions with different pH values (2-10). In the best process condition for each dye, equilibrium studies were carried out at different temperatures (from 298 to 328 K) and Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich models were fitted with experimental data. In addition, entropy change, Gibbs free energy change and enthalpy change were obtained in order to verify the thermodynamic adsorption behavior.

Modelagem termodinâmica por extração por solvente de metais divalentes em meio sulfato usando D2EHPA

The extraction of divalent metals (Mn2+, Ni2+, Co2+ and Cu2+) in the system MSO4 - H2SO4 - H2O - D2EHPA in isoparaffin (17/21) was studied by a thermodynamic model based on chemical equilibria with mass and charge balance equations. The activity coefficients of all solutes in the aqueous phase were calculated by Davies equation. By applying this model, the equilibrium concentrations of solutes were calculated from de concentration of divalent metals and pH. The predicted distribution coefficients for the divalents metals were in good agreement with experimental results.

A segunda lei da termodinâmica

Considering intrinsic characteristics of the system exclusively, both statistical and information theory interpretations of the second law are used to provide more comprehensive meanings for the concepts of entropy, temperature, and Helmholtz and Gibbs energies. The coherence of Clausius inequality to these concepts is emphasized. The aim of this work is to re-discuss the second law of thermodynamics in accordance to homogeneous processes thermodynamics, a temporal science which is the very special oversimplification of continuum mechanics for spatially constant intensive properties.