Solution thermodynamics of methocarbamol in some ethanol + water mixtures

Apparent thermodynamic functions, Gibbs energy, enthalpy and entropy of solution and mixing, for methocarbamol in ethanol + water mixtures, were evaluated from solubility data determined at temperatures from 293.15 K to 313.15 K and from calorimetric values of drug fusion. The drug solubility was greatest in the mixtures with 0.70 or 0.80 mass fraction of ethanol and lowest in neat water across all temperatures studied. Non-linear enthalpy-entropy compensation was found for the dissolution processes. Accordingly, solution enthalpy drives the respective processes in almost all the solvent systems analyzed.

Evaluation of the dioxin and furan formation thermodynamics in combustion processes of urban solid wastes

Specific combustion programs (Gaseq, Chemical equilibria in perfect gases, Chris Morley) are used to model dioxin and formation in the incineration processes of urban solid wastes. Thanks to these programs, it is possible to establish correlations with the formation mechanisms postulated in literature on the subject. It was found that minimum oxygen quantities are required to obtain a significant formation of these compounds and that more furans than dioxins are formed. Likewise, dioxin and furan formation is related to the presence of carbon monoxide, and dioxin and furan distribution among its different compounds depends on the chlorine and hydrogen relative composition. This is due to the fact that an increased chlorine availability leads to the formation of compounds bearing a higher chlorine concentration (penta-, hexa-, hepta-, and octachlorides), whereas an increased hydrogen availability leads to the formation of compounds bearing a lower chlorine number (mono, di-, tri-, and tetrachlorides).

Sugarcane crop efficiency in two growing seasons in São Paulo State, Brazil

A conceptual framework for crop production efficiency was derived using thermodynamic efficiency concept, in order to generate a tool for performance evaluation of agricultural systems and to quantify the interference of determining factors on this performance. In Thermodynamics, efficiency is the ratio between the output and input of energy. To establish this relationship in agricultural systems, it was assumed that the input energy is represented by the attainable crop yield, as predicted through simulation models based on environmental variables. The method of FAO's agroecological zones was applied to the assessment of the attainable sugarcane yield, while Instituto Brasileiro de Geografia e Estatística (IBGE) data were used as observed yield. Sugarcane efficiency production in São Paulo state was evaluated in two growing seasons, and its correlation with some physical factors that regulate production was calculated. A strong relationship was identified between crop production efficiency and soil aptitude. This allowed inferring the effect of agribusiness factors on crop production efficiency. The relationships between production efficiency and climatic variables were also quantified and indicated that solar radiation, annual rainfall, water deficiency, and maximum air temperature are the main factors affecting the sugarcane production efficiency.

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.

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.

Colapso da equipartição da energia

This paper discuss the consequences of the equipartition principle when used to calculate the heat capacity of atoms and molecules, a discussion that appeared at the end of XIX century and beginning of the XX century. Classical molecular thermodynamics prediction of the heat capacity is introduced, followed by a presentation of the degrees of freedom of a system. The historical discussion that appeared at the time, by Dulong, Petit, Maxwell, Boltzmann, Rayleigh and Kelvin is discussed afterwards. The necessity of a new theory is also presented as a direct consequence of the equipartition principle collapse.

Química de complexos de (etilenodiaminatetraacetato)rutenato(III/II)

This paper provides a survey of general aspects involved in the coordination chemistry of low-valent (mainly +III,+II), low-spin (d p5,d p6) ruthenium ions with ethylenediamine-N,N,N',N'-tetraacetate (edta) and their substituted derivatives. The topics covered herein include structure, reactivity, kinetics, thermodynamics, electrochemistry and spectroscopy. The contributions from either our research group or the literature over the last three decades are focused in this review.

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.

Review of the synthesis of layered double hydroxides: a thermodynamic approach

The synthesis of layered double hydroxides (LDHs) by hydrothermal-LDH reconstruction and coprecipitation methods is reviewed using a thermodynamic approach. A mixture model was used for the estimation of the thermodynamics of formation of LDHs. The synthesis and solubility of LDHs are discussed in terms of standard molar Gibbs free energy change of reaction. Data for numerous divalent and trivalent metals as well as for some monovalent and tetravalent metals that may be part of the LDH structure have been compiled. Good agreement is found between theoretical and experimental data. Diagrams and tables for the prediction of possible new LDH materials are provided.

Funciones termodinámicas relativas a la transferencia del ketoprófen desde el agua hasta algunos sistemas orgánicos

The thermodynamics of molal partitioning of ketoprofen (KTP) was studied in cyclohexane/buffer (CH/W), octanol/buffer (ROH/W), and dimyristoyl phosphatidylcholine (DMPC), dipalmitoyl phosphatidylcholine (DPPC), and egg lecithin (EGG/W) liposome systems. In all cases the partition coefficients (Kmo/w)were greater than unity; therefore the standard free energies of transfer were negative indicating affinity of KTP for organic media. The Kmo/w values were approximately seventy-fold higher in the ROH/W system compared with the CH/W system. On the other hand, the Kmo/w values were approximately ten or fifty-fold higher in the liposomes compared with the ROH/W system. In all cases, the standard enthalpies and entropies of transfer of KTP were positive indicating some degree of participation of the hydrophobic hydration on partitioning processes.

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.

Diagramas de Ellingham e de Van't Hoff: algumas considerações

The main subject of this article is to show the parallelism betwen the Ellingham and Van't Hoff diagrams. The first one is a graphic representation of the changes in the standard Gibbs free energy (deltarGtheta) as a function of T and was introduced by Ellingham in 1944, in order to study metallurgic processes involving oxides and sulphides. On the other hand, the Van't Hoff diagram is a representation of the function ln K versus (1/T). The equivalence between both diagrams is easily demonstrated, making simple mathematical manipulations. In order to show the parallelism between both diagrams, they are presented briefly and two examples are discussed. The comparison of the both diagrams surely will be helpful to students and teachers in their learning and teaching activities, and will certainly enrich important aspects of chemical thermodynamics.

Determinação do coeficiente de atividade na diluição infinita (g¥) através da micro-extração em fase sólida (SPME)

In this study a new approach, solid phase micro extraction (SPME), is used in the evaluation of the infinite dilution activity coefficient of the solute in a given solvent. It is the purpose of the current work to demonstrate a different approach to obtain the data needed for studying the solution thermodynamics of binary liquid mixtures as well as for designing multi-component separations. The solutes investigated at the temperature 298.15 K were toluene, ethyl benzene and xylene in the solvent methanol.

Calor e trabalho: são estes conceitos invariantes sob a permuta sistema-vizinhança?

It is argued that the invariants associated to the First Law of Thermodynamics and to the concept of identical processes lead to a clear definition of heat and work. The conditions for heat and work to be invariant under a system-surroundings interchange are also investigated. Finally, examples are presented to illustrate the above conditions.

Otto Redlich: chemist and gentleman from the "old school"

The name of Otto Redlich is generally remembered as co-author of one of most used equations of state for the calculation of volumetric and thermodynamic properties of pure substances and their mixtures. Nevertheless, he made also important contributions in different areas of chemistry and chemical engineering. Pursuits of race and religious order forced him and his family to leave his native Austria and emigrate to the United States. His professional career included both academic and industrial research achievements.