Modeling of gas adsorption equilibrium over a wide range of pressure: A thermodynamic approach based on equation of state

A thermodynamic approach based on the Bender equation of state is suggested for the analysis of supercritical gas adsorption on activated carbons at high pressure. The approach accounts for the equality of the chemical potential in the adsorbed phase and that in the corresponding bulk phase and the distribution of elements of the adsorption volume (EAV) over the potential energy for gas-solid interaction. This scheme is extended to subcritical fluid adsorption and takes into account the phase transition in EAV The method is adapted to gravimetric measurements of mass excess adsorption and has been applied to the adsorption of argon, nitrogen, methane, ethane, carbon dioxide, and helium on activated carbon Norit R I in the temperature range from 25 to 70 C. The distribution function of adsorption volume elements over potentials exhibits overlapping peaks and is consistently reproduced for different gases. It was found that the distribution function changes weakly with temperature, which was confirmed by its comparison with the distribution function obtained by the same method using nitrogen adsorption isotherm at 77 K. It was shown that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of helium expansion at room temperature can lead to erroneous results due to the adsorption of helium in small pores of activated carbon. The approach is a convenient tool for analysis and correlation of excess adsorption isotherms over a wide range of pressure and temperature. This approach can be readily extended to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Allowance for thermodynamic non-ideality in the characterization of protein self-association by frontal exclusion chromatography: hemoglobin revisited

This investigation re-examines theoretical aspects of the allowance for effects of thermodynamic non-ideality on the characterization of protein self-association by frontal exclusion chromatography, and thereby provides methods of analysis with greater thermodynamic rigor than those used previously. Their application is illustrated by reappraisal of published exclusion chromatography data for hemoglobin on the controlled-pore-glass matrix CPG-120. The equilibrium constant of 100/M that is obtained for dimerization of the (02 species by this means is also deduced from re-examination of published studies of concentrated hemoglobin solutions by osmotic pressure and sedimentation equilibrium methods. (C) 2003 Elsevier Science B.V. All rights reserved.

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Thermodynamic and kinetic modelling of the redox properties of tetrahaem cytochromes C3

Dissertação apresentada para obtenção do grau de Doutor em Bioquímica,especialidade Bioquímica-Física, pela Universidade Nova de Lisboa, Faculdade de Cincias e Tecnologia

Rényi entropy and the thermodynamic stability of black holes

Thermodynamic stability of black holes, described by the Rényi formula as equilibrium compatible entropy function, is investigated. It is shown that within this approach, asymptotically flat, Schwarzschild black holes can be in stable equilibrium with thermal radiation at a fixed temperature. This implies that the canonical ensemble exists just like in anti-de Sitter space, and nonextensive effects can stabilize the black holes in a very similar way as it is done by the gravitational potential of an anti-de Sitter space. Furthermore, it is also shown that a Hawking–Page-like black hole phase transition occurs at a critical temperature which depends on the q-parameter of the Rényi formula.

Influences of alternative fuels and EGR on thermodynamic parameters and emissions of a heavy duty engine

Heavy duty Diesel engine, alternative fuels, EGR, exhaust emissions, HC, NOx, FSN

Vaporization behaviour and some thermodynamic properties of the Pd-In, Pd-Pb, Pd-Sn systems

In this study, the vaporization behaviour of solid Pd-rich phases in the Pd-Pb, Pd-In and Pd-Sn systems was investigated by Knudsen-effusion-cell coupled with mass-spectrometry. The Pb, Pd, In vapor pressures [no Sn(g) has been detected in the vapor of Pd-Sn system] were evaluated in the temperatures range 1190-1563 K from the ion intensities measured over two-phases regions. Thermodynamic quantities were derived from vapor pressure data. In particular, for the Pd-Sn binary, the intermediate phase Pd7Sn2, the existence of which has been recently proposed, has been studied here for the first time. Furthermore, preliminary thermochemical data are presented for the diatomic intermetallic molecules PdSn and PdPb, which have been for the first time identified in the vapors in equilibrium over liquid solutions of appropriate composition at higher temperatures (1935-2025 K). (C) 2000 Elsevier Science Ltd. All rights reserved.

Entropy Production In Thermodynamic Climate Models

We present a non-equilibrium theory in a system with heat and radiative fluxes. The obtained expression for the entropy production is applied to a simple one-dimensional climate model based on the first law of thermodynamics. In the model, the dissipative fluxes are assumed to be independent variables, following the criteria of the Extended Irreversible Thermodynamics (BIT) that enlarges, in reference to the classical expression, the applicability of a macroscopic thermodynamic theory for systems far from equilibrium. We analyze the second differential of the classical and the generalized entropy as a criteria of stability of the steady states. Finally, the extreme state is obtained using variational techniques and observing that the system is close to the maximum dissipation rate

Thermodynamic properties of hot nucleonic matter

Phase diagrams for bulk nuclear matter at finite temperatures and variable proton concentrations are presented and discussed. This binary system exhibits a line of critical points, a line of equal concentrations, and a line of maximum temperatures. the phenomenon of retrograde condensation is also possible.

Nonequilibrium thermodynamic fluctuations of black holes

With the aid of the Landau-Lifshitz theory for thermodynamic fluctuations we estimate and comment on the fluctuations in the rates of mass, angular momentum, and other relevant quantities of massive Schwarzschild and Kerr black holes.

Perturbation theory for classical thermodynamic Green's functions

A systematic time-dependent perturbation scheme for classical canonical systems is developed based on a Wick's theorem for thermal averages of time-ordered products. The occurrence of the derivatives with respect to the canonical variables noted by Martin, Siggia, and Rose implies that two types of Green's functions have to be considered, the propagator and the response function. The diagrams resulting from Wick's theorem are "double graphs" analogous to those introduced by Dyson and also by Kawasaki, in which the response-function lines form a "tree structure" completed by propagator lines. The implication of a fluctuation-dissipation theorem on the self-energies is analyzed and compared with recent results by Deker and Haake.

Viral self-assembly as a thermodynamic process

The protein shells, or capsids, of nearly all spherelike viruses adopt icosahedral symmetry. In the present Letter, we propose a statistical thermodynamic model for viral self-assembly. We find that icosahedral symmetry is not expected for viral capsids constructed from structurally identical protein subunits and that this symmetry requires (at least) two internal switching configurations of the protein. Our results indicate that icosahedral symmetry is not a generic consequence of free energy minimization but requires optimization of internal structural parameters of the capsid proteins

Thermodynamic Characterization of Humic Acid-surfactant Interaction: New Insights into the Characteristics and Structure of Humic Acids

ABSTRACT Humic acids (HA) are a component of humic substances (HS), which are found in nearly all soils, sediments, and waters. They play a key role in many, if not most, chemical and physical properties in their environment. Despite the importance of HA, their high complexity makes them a poorly understood system. Therefore, understanding the physicochemical properties and interactions of HA is crucial for determining their fundamental role and obtaining structural details. Cationic surfactants are known to interact electrostatically and hydrophobically with HA. Because they are a very well-known and characterized system, they offer a good choice as molecular probes for studying HA. The objective of this study was to evaluate the interaction between cationic surfactants and HA through isothermal titration calorimetry in a thermodynamic manner, aiming to obtain information about the basic structure of HA, the nature of this interaction, and if HA from different origins show different basic structures. Contrary to what the supramolecular model asserts, HA structure is not loosely held, though it may separate depending on the conditions the HA are subjected to in their milieu. It did not show any division or conformational change when interacting with surfactants. The basic structure of the HA remains virtually the same regardless of the different sources and compositions of these HA.

Thermodynamic investigations in the Si-Ge-rich part of the ruthenium-silicon-germanium system

This paper reports molar heat capacities of Ru50SixGe(50-x) and Ru40SiyGe(60-y) ternary solid solutions determined by differential scanning calorimetry. A second order transition has been characterised for alloys ranging from Ru40Ge60 to Ru40Si10Ge50 at temperatures ranging from 850 to 1040 K, respectively. Tie lines have been established at 1000-900-800-700-600 degrees C by electron microprobe measurements on annealed alloys of the two phase domains: Ru50SixGe(50-x)-Ru40SiyGe(60-y) and Ru40SiyGe(60-y)-SizGe(100-z).