Universal relation for size dependent thermodynamic properties of metallic nanoparticles.
Xiong, Shiyun; Qi, Weihong; Cheng, Yajuan; Huang, Baiyun; Wang, Mingpu; Li, Yejun
2011-06-14
The previous model on surface free energy has been extended to calculate size dependent thermodynamic properties (i.e., melting temperature, melting enthalpy, melting entropy, evaporation temperature, Curie temperature, Debye temperature and specific heat capacity) of nanoparticles. According to the quantitative calculation of size effects on the calculated thermodynamic properties, it is found that most thermodynamic properties of nanoparticles vary linearly with 1/D as a first approximation. In other words, the size dependent thermodynamic properties P(n) have the form of P(n) = P(b)(1 -K/D), in which P(b) is the corresponding bulk value and K is the material constant. This may be regarded as a scaling law for most of the size dependent thermodynamic properties for different materials. The present predictions are consistent literature values.
无
2001-01-01
When species in the solution undergo multiple chemical reactions, the solution may be treated as a solution of all species actually present or as a hypothetical solution composed of elemental species. Based on the fundamental thermodynamic principle, the relationships of mole numbers, molar fractions, thermodynamic properties, partial molar properties, potential and fugacity between the hypothetical solution of elemental species and the equilibrated solution of actual species were derived. The hypothetical elemental solution provides a way of reducing the dimensionality of problem, simplifying the analysis and visualizing the phase behavior.
Thermodynamic properties of cryogenic fluids
Leachman, Jacob; Lemmon, Eric; Penoncello, Steven
2017-01-01
This update to a classic reference text provides practising engineers and scientists with accurate thermophysical property data for cryogenic fluids. The equations for fifteen important cryogenic fluids are presented in a basic format, accompanied by pressure-enthalpy and temperature-entropy charts and tables of thermodynamic properties. It begins with a chapter introducing the thermodynamic relations and functional forms for equations of state, and goes on to describe the requirements for thermodynamic property formulations, needed for the complete definition of the thermodynamic properties of a fluid. The core of the book comprises extensive data tables and charts for the most commonly-encountered cryogenic fluids. This new edition sees significant updates to the data presented for air, argon, carbon monoxide, deuterium, ethane, helium, hydrogen, krypton, nitrogen and xenon. The book supports and complements NIST’s REFPROP - an interactive database and tool for the calculation of thermodynamic propertie...
Covariant Thermodynamics and Relativity
Lopez-Monsalvo, C S
2011-01-01
This thesis deals with the dynamics of irreversible processes within the context of the general theory of relativity. In particular, we address the problem of the 'infinite' speed of propagation of thermal disturbances in a dissipative fluid. The present work builds on the multi-fluid variational approach to relativistic dissipation, pioneered by Carter, and provides a dynamical theory of heat conduction. The novel property of such approach is the thermodynamic interpretation associated with a two-fluid system whose constituents are matter and entropy. The dynamics of this model leads to a relativistic generalisation of the Cattaneo equation; the constitutive relation for causal heat transport. A comparison with the Israel and Stewart model is presented and its equivalence is shown. This discussion provides new insights into the not-well understood definition of a non-equilibrium temperature. The variational approach to heat conduction presented in this thesis constitutes a mathematically promising formalism ...
Phonon spectrum and related thermodynamic properties of microcrack in bcc-Fe
Cao, Li-Xia; Wang, Chong-Yu
2006-09-01
The phonon spectrum and the related thermodynamic properties of microcracks in bcc-Fe are studied with the recursion method by using the Finnis-Sinclair (F-S) N-body potential. The initial configuration of the microcracks is established from an anisotropic linear elastic solution and relaxed to an equilibrium by molecular dynamics method. It is shown that the local vibrational density of states of the atoms near a crack tip is considerably different from the bulk phonon spectrum, which is closely associated with the local stress field around the crack tip; meanwhile, the local vibrational energies of atoms near the crack tip are higher than those of atoms in a perfect crystal. These results imply that the crack tip zone is in a complex stress state and closely related to the structure evolution of cracks. It is also found that the phonon excitation is a kind of local effect induced by microcracks. In addition, the microcrack system has a higher vibrational entropy, which reflects the character of phonon spectrum related to the stress field induced by cracks.
Phonon spectrum and related thermodynamic properties of microcrack in bcc-Fe
Cao Li-Xia; Wang Chong-Yu
2006-01-01
The phonon spectrum and the related thermodynamic properties of microcracks in bcc-Fe are studied with the recursion method by using the Finnis-Sinclair (F-S) N-body potential. The initial configuration of the microcracks is established from an anisotropic linear elastic solution and relaxed to an equilibrium by molecular dynamics method.It is shown that the local vibrational density of states of the atoms near a crack tip is considerably different from the bulk phonon spectrum, which is closely associated with the local stress field around the crack tip; meanwhile, the local vibrational energies of atoms near the crack tip are higher than those of atoms in a perfect crystal. These results imply that the crack tip zone is in a complex stress state and closely related to the structure evolution of cracks. It is also found that the phonon excitation is a kind of local effect induced by microcracks. In addition, the microcrack system has a higher vibrational entropy, which reflects the character of phonon spectrum related to the stress field induced by cracks.
Thermodynamic properties of sea air
R. Feistel
2010-02-01
Full Text Available Very accurate thermodynamic potential functions are available for fluid water, ice, seawater and humid air covering wide ranges of temperature and pressure conditions. They permit the consistent computation of all equilibrium properties as, for example, required for coupled atmosphere-ocean models or the analysis of observational or experimental data. With the exception of humid air, these potential functions are already formulated as international standards released by the International Association for the Properties of Water and Steam (IAPWS, and have been adopted in 2009 for oceanography by IOC/UNESCO.
In this paper, we derive a collection of formulas for important quantities expressed in terms of the thermodynamic potentials, valid for typical phase transitions and composite systems of humid air and water/ice/seawater. Particular attention is given to equilibria between seawater and humid air, referred to as "sea air" here. In a related initiative, these formulas will soon be implemented in a source-code library for easy practical use. The library is primarily aimed at oceanographic applications but will be relevant to air-sea interaction and meteorology as well.
The formulas provided are valid for any consistent set of suitable thermodynamic potential functions. Here we adopt potential functions from previous publications in which they are constructed from theoretical laws and empirical data; they are briefly summarized in the appendix. The formulas make use of the full accuracy of these thermodynamic potentials, without additional approximations or empirical coefficients. They are expressed in the temperature scale ITS-90 and the 2008 Reference-Composition Salinity Scale.
Thermodynamic properties of sea air
R. Feistel
2009-10-01
Full Text Available Very accurate thermodynamic potential functions are available for fluid water, ice, seawater and humid air covering wide ranges of temperature and pressure conditions. They permit the consistent computation of all equilibrium properties as, for example, required for coupled atmosphere–ocean models or the analysis of observational or experimental data. With the exception of humid air, these potential functions are already formulated as international standards released by the International Association for the Properties of Water and Steam (IAPWS, and have been adopted in 2009 for oceanography by IOC/UNESCO.
In this paper, we derive a collection of formulas for important quantities expressed in terms of the thermodynamic potentials, valid for typical phase transitions and composite systems of humid air and water/ice/seawater. Particular attention is given to equilibria between seawater and humid air, referred to as ''sea air'' here. In a related initiative, these formulas will soon be implemented in a source-code library for easy practical use. The library is primarily aimed at oceanographic applications but will be relevant to air-sea interaction and meteorology as well.
The formulas provided are valid for any consistent set of suitable thermodynamic potential functions. Here we adopt potential functions from previous publications in which they are constructed from theoretical laws and empirical data; they are briefly summarized in the appendix. The formulas make use of the full accuracy of these thermodynamic potentials, without additional approximations or empirical coefficients. They are expressed in the temperature scale ITS-90 and the 2008 Reference-Composition Salinity Scale.
Program calculation of thermodynamic properties
Gill, Walter; Filho, Fernando Fachini; Ribeirodeoliveira, Ronaldo
1986-12-01
The determination of the thermodynamic properties are examined through the basic equations such as: state equation (Beattie-Bridgeman Form), saturation pressure equation, specific heat constant pressure or constant volume equation, and specific volume or density of liquid equation.
Kinetics and thermodynamic properties related to the drying of 'Cabacinha' pepper fruits
Hellismar W. da Silva
2016-02-01
Full Text Available ABSTRACT The objective of this study was to determine and model the drying kinetics of 'Cabacinha' pepper fruits at different temperatures of the drying air, as well as obtain the thermodynamic properties involved in the drying process of the product. Drying was carried out under controlled conductions of temperature (60, 70, 80, 90 and 100 °C using three samples of 130 g of fruit, which were weighed periodically until constant mass. The experimental data were adjusted to different mathematical models often used in the representation of fruit drying. Effective diffusion coefficients, calculated from the mathematical model of liquid diffusion, were used to obtain activation energy, enthalpy, entropy and Gibbs free energy. The Midilli model showed the best fit to the experimental data of drying of 'Cabacinha' pepper fruits. The increase in drying temperature promoted an increase in water removal rate, effective diffusion coefficient and Gibbs free energy, besides a reduction in fruit drying time and in the values of entropy and enthalpy. The activation energy for the drying of pepper fruits was 36.09 kJ mol-1.
The Thermodynamic Properties of Cubanite
Berger, E. L.; Lauretta, D. S.; Keller, L. P.
2012-01-01
CuFe2S3 exists in two polymorphs, a low-temperature orthorhombic form (cubanite) and a high-temperature cubic form (isocubanite). Cubanite has been identified in the CI-chondrite and Stardust collections. However, the thermodynamic properties of cubanite have neither been measured nor estimated. Our derivation of a thermodynamic model for cubanite allows constraints to be placed on the formation conditions. This data, along with the temperature constraint afforded by the crystal structure, can be used to assess the environments in which cubanite formation is (or is not) thermodynamically favored.
Thermodynamic properties of modified gravity theories
Bamba, Kazuharu
2016-01-01
We review thermodynamic properties of modified gravity theories such as $F(R)$ gravity and $f(T)$ gravity, where $R$ is the scalar curvature and $T$ is the torsion scalar in teleparallelism. In particular, we explore the equivalence between the equations of motion for modified gravity theories and the Clausius relation in thermodynamics. In addition, thermodynamics of the cosmological apparent horizon is investigated in $f(T)$ gravity. We show both equilibrium and non-equilibrium descriptions of thermodynamics. It is demonstrated that the second law of thermodynamics in the universe can be met when the temperature of the outside of the apparent horizon is equivalent to that of the inside of it.
Thermodynamic and relativistic uncertainty relations
Artamonov, A. A.; Plotnikov, E. M.
2017-01-01
Thermodynamic uncertainty relation (UR) was verified experimentally. The experiments have shown the validity of the quantum analogue of the zeroth law of stochastic thermodynamics in the form of the saturated Schrödinger UR. We have also proposed a new type of UR for the relativistic mechanics. These relations allow us to consider macroscopic phenomena within the limits of the ratio of the uncertainty relations for different physical quantities.
Thermodynamics and statistical mechanics. [thermodynamic properties of gases
1976-01-01
The basic thermodynamic properties of gases are reviewed and the relations between them are derived from the first and second laws. The elements of statistical mechanics are then formulated and the partition function is derived. The classical form of the partition function is used to obtain the Maxwell-Boltzmann distribution of kinetic energies in the gas phase and the equipartition of energy theorem is given in its most general form. The thermodynamic properties are all derived as functions of the partition function. Quantum statistics are reviewed briefly and the differences between the Boltzmann distribution function for classical particles and the Fermi-Dirac and Bose-Einstein distributions for quantum particles are discussed.
Thermodynamic Properties of Supported Catalysts
Gorte, Raymond J.
2014-03-26
The goals of this work were to develop Coulometric Titration as a method for characterizing the thermodynamic redox properties of oxides and to apply this technique to the characterization of ceria- and vanadia-based catalysts. The redox properties of ceria and vanadia are a major part of what makes these materials catalytically active but their properties are also dependent on their structure and the presence of other oxides. Quantifying these properties through the measurement of oxidation energetics was the goal of this work.
Systematic vibration thermodynamic properties of bromine
Liu, G. Y.; Sun, W. G.; Liao, B. T.
2015-11-01
Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.
Generalization of Gibbs Entropy and Thermodynamic Relation
Park, Jun Chul
2010-01-01
In this paper, we extend Gibbs's approach of quasi-equilibrium thermodynamic processes, and calculate the microscopic expression of entropy for general non-equilibrium thermodynamic processes. Also, we analyze the formal structure of thermodynamic relation in non-equilibrium thermodynamic processes.
Composition and Thermodynamic Properties of Air in Chemical Equilibrium
Moeckel, W E; Weston, Kenneth C
1958-01-01
Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.
Schulte, Mitchell D.; Shock, Everett L.
1993-01-01
Aldehydes are common in a variety of geologic environments and are derived from a number of sources, both natural and anthropogenic. Experimental data for aqueous aldehydes were taken from the literature and used, along with parameters for the revised Helgeson-Kirkham-Flowers (HKF) equations of state, to estimate standard partial molal thermodynamic data for aqueous straight-chain alkyl aldehydes at high temperatures and pressures. Examples of calculations involving aldehydes in geological environments are given, and the stability of aldehydes relative to carboxylic acids is evaluated. These calculations indicate that aldehydes may be intermediates in the formation of carboxylic acids from hydrocarbons in sedimentary basin brines and hydrothermal systems like they are in the atmosphere. The data and parameters summarized here allow evaluation of the role of aldehydes in the formation of prebiotic precursors, such as amino acids and hydroxy acids on the early Earth and in carbonaceous chondrite parent bodies.
Nanofluidics thermodynamic and transport properties
Michaelides, Efstathios E (Stathis)
2014-01-01
This volume offers a comprehensive examination of the subject of heat and mass transfer with nanofluids as well as a critical review of the past and recent research projects in this area. Emphasis is placed on the fundamentals of the transport processes using particle-fluid suspensions, such as nanofluids. The nanofluid research is examined and presented in a holistic way using a great deal of our experience with the subjects of continuum mechanics, statistical thermodynamics, and non-equilibrium thermodynamics of transport processes. Using a thorough database, the experimental, analytical, and numerical advances of recent research in nanofluids are critically examined and connected to past research with medium and fine particles as well as to functional engineering systems. Promising applications and technological issues of heat/mass transfer system design with nanofluids are also discussed. This book also: Provides a deep scientific analysis of nanofluids using classical thermodynamics and statistical therm...
Thermodynamic Properties of Mn-C Melts
CHEN Er-bao; WANG Shi-jun
2008-01-01
Carbon solubility in Mn-Fe melts (xMn=0.161-0.706, xFe=0.034-0.633) was measured experimentally at various temperatures. By thermodynamic derivation and calculation, the relationship between activity coefficient of carbon in infinite dilute solution of manganese in Mn-C system and temperature was obtained. Using Gibbs-Duhem relationship, the experimental results of this study, and experimental data reported in references, the relationship between other thermodynamic properties in Mn-C system and temperature were obtained by thermodynamic derivation and calculation.
Thermodynamic properties of triphenylantimony dibenzoate
Markin, A. V.; Smirnova, N. N.; Lyakaev, D. V.; Klimova, M. N.; Sharutin, V. V.; Sharutina, O. K.
2016-10-01
The temperature dependence of the heat capacity of triphenylantimony dibenzoate Ph3Sb(OC(O)Ph)2 is studied in the range of 6-480 K by means of precision adiabatic vacuum calorimetry and differential scanning calorimetry. The melting of the compound is observed in this temperature range, and its standard thermodynamic characteristics are identified and analyzed. Ph3Sb(OC(O)Ph)2 is obtained in a metastable amorphous state in a calorimeter. The standard thermodynamic functions of Ph3Sb(OC(O)Ph)2 in the crystalline and liquid states are calculated from the obtained experimental data: C p ° ( T), H°( T)- H°(0), S°( T), and G°(T)- H°(0) for the region from T → 0 to 480 K. The standard entropy of formation of the compound in the crystalline state at T = 298.15 K is determined. Multifractal processing of the low-temperature ( T topology.
Thermodynamic properties of potassium chloride aqueous solutions
Zezin, Denis; Driesner, Thomas
2017-04-01
Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.
Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium
Hunt, J. L.; Boney, L. R.
1973-01-01
Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.
Thermodynamic properties of water solvating biomolecular surfaces
Heyden, Matthias
Changes in the potential energy and entropy of water molecules hydrating biomolecular interfaces play a significant role for biomolecular solubility and association. Free energy perturbation and thermodynamic integration methods allow calculations of free energy differences between two states from simulations. However, these methods are computationally demanding and do not provide insights into individual thermodynamic contributions, i.e. changes in the solvent energy or entropy. Here, we employ methods to spatially resolve distributions of hydration water thermodynamic properties in the vicinity of biomolecular surfaces. This allows direct insights into thermodynamic signatures of the hydration of hydrophobic and hydrophilic solvent accessible sites of proteins and small molecules and comparisons to ideal model surfaces. We correlate dynamic properties of hydration water molecules, i.e. translational and rotational mobility, to their thermodynamics. The latter can be used as a guide to extract thermodynamic information from experimental measurements of site-resolved water dynamics. Further, we study energy-entropy compensations of water at different hydration sites of biomolecular surfaces. This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft.
Thermodynamic properties of wadsleyite with anharmonic effect
Zhongqing Wu
2015-01-01
The thermodynamic properties of crystals can be routinely calculated by density functional theory calculations combining with quasi-harmonic approximation.Based on the method developed recently by Wu and Wentzcovitch (Phys Rev B 79:104304,2009) and Wu (Phys Rev B 81:172301,2010),we are able to further ab initio include anharmonic effect on thermodynamic properties of crystals by one additional canonical ensemble with numbers of particle,volume and temperature fixed (NVT) molecular dynamic simulations.Our study indicates that phonon-phonon interaction causes the renormalized phonon frequencies of wadsleyite decrease with temperature.This is consistent with the Raman experimental observation.The anharmonic free energy of wadsleyite is negative and its heat capacity at constant pressure can exceed the Dulong-Petit limit at high temperature.The anharmonicity still significantly affects thermodynamic properties of wadsleyite at pressure and temperature conditions correspond to the transition zone.
Thermodynamic properties of organic compounds estimation methods, principles and practice
Janz, George J
1967-01-01
Thermodynamic Properties of Organic Compounds: Estimation Methods, Principles and Practice, Revised Edition focuses on the progression of practical methods in computing the thermodynamic characteristics of organic compounds. Divided into two parts with eight chapters, the book concentrates first on the methods of estimation. Topics presented are statistical and combined thermodynamic functions; free energy change and equilibrium conversions; and estimation of thermodynamic properties. The next discussions focus on the thermodynamic properties of simple polyatomic systems by statistical the
Thermodynamic properties for the lithium dimer
Jia, Chun-Sheng; Zhang, Lie-Hui; Wang, Chao-Wen
2017-01-01
We present an explicit expression of the vibrational partition function for the improved Manning-Rosen potential energy model. We give analytical expressions for the vibrational mean energy, vibrational specific heat, vibrational free energy, and vibrational entropy for diatomic molecules. The properties of these thermodynamic functions for the a3Σu+ state of the 7Li2 molecule are discussed in detail.
Zhao, Leihong; Qu, Xiaolu; Zhang, Meijia; Lin, Hongjun; Zhou, Xiaoling; Liao, Bao-Qiang; Mei, Rongwu; Hong, Huachang
2016-08-01
Failure of membrane hydrophobicity in predicting membrane fouling requires a more reliable indicator. In this study, influences of membrane acid base (AB) property on interfacial interactions in two different interaction scenarios in a submerged membrane bioreactor (MBR) were studied according to thermodynamic approaches. It was found that both the polyvinylidene fluoride (PVDF) membrane and foulant samples in the MBR had relatively high electron donor (γ(-)) component and low electron acceptor (γ(+)) component. For both of interaction scenarios, AB interaction was the major component of the total interaction. The results showed that, the total interaction monotonically decreased with membrane γ(-), while was marginally affected by membrane γ(+), suggesting that γ(-) could act as a reliable indicator for membrane fouling prediction. This study suggested that membrane modification for fouling mitigation should orient to improving membrane surface γ(-) component rather than hydrophilicity.
Li, Wenjiao; Xue, Yongqiang, E-mail: xyqlw@126.com; Cui, Zixiang
2016-08-15
Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.
Consistent thermodynamic properties of lipids systems
Cunico, Larissa; Ceriani, Roberta; Sarup, Bent
Physical and thermodynamic properties of pure components and their mixtures are the basic requirement for process design, simulation, and optimization. In the case of lipids, our previous works[1-3] have indicated a lack of experimental data for pure components and also for their mixtures...... different pressures, with azeotrope behavior observed. Available thermodynamic consistency tests for TPx data were applied before performing parameter regressions for Wilson, NRTL, UNIQUAC and original UNIFAC models. The relevance of enlarging experimental databank of lipids systems data in order to improve...
Industrial Requirements for Thermodynamics and Transport Properties
Hendriks, Eric; Kontogeorgis, Georgios; Dohrn, Ralf
2010-01-01
. The main results are as follows. There is (still) an acute need for accurate, reliable, and thermodynamically consistent experimental data. Quality is more important than quantity. Similarly, there is a great need for reliable predictive, rather than correlative, models covering a wide range...... addressed to or written by industrial colleagues, are discussed initially. This provides the context of the survey and material with which the results of the survey can be compared. The results of the survey have been divided into the themes: data, models, systems, properties, education, and collaboration...... reactive systems (simultaneous chemical and physical equilibrium). Education in thermodynamics is perceived as key, for the future application of thermodynamics in the industry. A number of suggestions for improvement were made at all three levels (undergraduate, postgraduate, and professional development...
The thermodynamic properties of benzothiazole and benzoxazole
Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.
1991-08-01
This research program, funded by the Department of Energy, Office of Fossil Energy, Advanced Extraction and Process Technology, provides accurate experimental thermochemical and thermophysical properties for key'' organic diheteroatom-containing compounds present in heavy petroleum feedstocks, and applies the experimental information to thermodynamic analyses of key hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation reaction networks. Thermodynamic analyses, based on accurate information, provide insights for the design of cost-effective methods of heteroatom removal. The results reported here, and in a companion report to be completed, will point the way to the development of new methods of heteroatom removal from heavy petroleum. Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for benzothiazole and benzoxazole. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, comparative ebulliometry, inclinded-piston gauge manometry, and differential-scanning calorimetry (d.s.c). Critical property estimates are made for both compounds. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 280 K and near 650 K. The Gibbs energies of formation will be used in a subsequent report in thermodynamic calculations to study the reaction pathways for the removal of the heteratoms by hydrogenolysis. The results obtained in this research are compared with values present in the literature. The failure of a previous adiabatic heat capacity study to see the phase transition in benzothiazole is noted. Literature vibrational frequency assignments were used to calculate ideal gas entropies in the temperature range reported here for both compounds. Resulting large deviations show the need for a revision of those assignments. 68 refs., 6 figs., 15 tabs.
The calculation of thermodynamic properties of molecules
van Speybroeck, Veronique; Gani, Rafiqul; Meier, Robert Johan
2010-01-01
Thermodynamic data are key in the understanding and design of chemical processes. Next to the experimental evaluation of such data, computational methods are valuable and sometimes indispensable tools in obtaining heats of formation and Gibbs free energies. The major toolboxes to obtain...... molecules the combination of group contribution methods with group additive values that are determined with the best available computational ab initio methods seems to be a viable alternative to obtain thermodynamic properties near chemical accuracy. New developments and full use of existing tools may lead...... such quantities by computation are quantum mechanical methods and group contribution methods. Although a lot of progress was made over the last decade, for the majority of chemical species we are still quite a bit away from what is often referred to as chemical accuracy, i.e.1 kcal mol-1. Currently, for larger...
Statistical thermodynamics understanding the properties of macroscopic systems
Fai, Lukong Cornelius
2012-01-01
Basic Principles of Statistical PhysicsMicroscopic and Macroscopic Description of StatesBasic PostulatesGibbs Ergodic AssumptionGibbsian EnsemblesExperimental Basis of Statistical MechanicsDefinition of Expectation ValuesErgodic Principle and Expectation ValuesProperties of Distribution FunctionRelative Fluctuation of an Additive Macroscopic ParameterLiouville TheoremGibbs Microcanonical EnsembleMicrocanonical Distribution in Quantum MechanicsDensity MatrixDensity Matrix in Energy RepresentationEntropyThermodynamic FunctionsTemperatureAdiabatic ProcessesPressureThermodynamic IdentityLaws of Th
Thermodynamic and magnetocaloric properties of geometrically frustrated Ising nanoclusters
Žukovič, M., E-mail: milan.zukovic@upjs.sk
2015-01-15
Thermodynamic and magnetocaloric properties of geometrically frustrated Ising spin clusters of selected shapes and sizes are studied by exact enumeration. In the ground state the magnetization and the entropy show step-wise variations with an applied magnetic field. The number of steps, their widths and heights depend on the cluster shape and size. While the character of the magnetization plateau heights is always increasing, the entropy is not necessarily decreasing function of the field, as one would expect. For selected clusters showing some interesting ground-state properties, the calculations are extended to finite temperatures by exact enumeration of densities of states in the energy-magnetization space. In zero field the focus is laid on a peculiar behavior of some thermodynamic quantities, such as the entropy, the specific heat and the magnetic susceptibility. In finite fields various thermodynamic functions are studied in the temperature-field parameter plane and particular attention is paid to the cases showing an enhanced magnetocaloric effect. The exact results on the finite clusters are compared with the thermodynamic limit behavior obtained from Monte Carlo simulations. - Highlights: • We study frustrated spin clusters of various shapes and sizes on a triangular lattice. • Ground-state magnetizations and entropies in a field are exactly determined. • Peculiar behavior of some quantities is studied in zero field and finite temperatures. • Enhanced magnetocaloric effect is observed at relatively low temperatures and fields. • Thermodynamic limit behavior is estimated by Monte Carlo simulations.
Thermodynamic properties of under-cooled silver melts
无
2010-01-01
Differential scanning calorimeter technique combined with the traditional fluxing treatment was used to investigate the specific heat and related thermodynamic properties of under-cooled pure silver melts. The specific heat of the under-cooled melt showed a linear dependence on the temperature in the range of the obtained under-cooling from 0 to 198 K. The related thermodynamic properties of silver, such as the entropy change, the enthalpy change and the Gibbs free energy difference between the under-cooled melt and the solid phase, were derived from the measured specific heat. The relations between the temperature and the thermal diffusion or the thermal conductivity of the under-cooled melt were analyzed respectively.
Thermodynamic properties for the sodium dimer
Song, Xiao-Qin; Wang, Chao-Wen; Jia, Chun-Sheng
2017-04-01
We present a closed-form expression of the classical vibrational partition function for the improved Rosen-Morse potential energy model. We give explicit expressions for the vibrational mean energy, vibrational specific heat, vibrational free energy, and vibrational entropy for diatomic molecule systems. The properties of these thermodynamic functions for the Na2 dimer are discussed in detail. We find that the improved Rosen-Morse potential model is superior to the harmonic oscillator in calculating the heat capacity for the Na2 molecules.
Nonequilibrium thermodynamics and fluctuation relations for small systems
Cao, Liang; Ke, Pu; Qiao, Li-Yan; Zheng, Zhi-Gang
2014-07-01
In this review, we give a retrospect of the recent progress in nonequilibrium statistical mechanics and thermodynamics in small dynamical systems. For systems with only a few number of particles, fluctuations and nonlinearity become significant and contribute to the nonequilibrium behaviors of the systems, hence the statistical properties and thermodynamics should be carefully studied. We review recent developments of this topic by starting from the Gallavotti—Cohen fluctuation theorem, and then to the Evans—Searles transient fluctuation theorem, Jarzynski free-energy equality, and the Crooks fluctuation relation. We also investigate the nonequilibrium free energy theorem for trajectories involving changes of the heat bath temperature and propose a generalized free-energy relation. It should be noticed that the non-Markovian property of the heat bath may lead to the violation of the free-energy relation.
Thermodynamic Properties of $^{56,57}$Fe
Algin, E; Guttormsen, M; Larsen, A C; Mitchell, G E; Rekstad, J; Schiller, A; Siem, S; Voinov, A
2008-01-01
Nuclear level densities for $^{56,57}$Fe have been extracted from the primary $\\gamma$-ray spectra using ($^3$He,$^3$He$^{\\prime}\\gamma$) and ($^3$He,$\\alpha \\gamma$) reactions. Nuclear thermodynamic properties for $^{56}$Fe and $^{57}$Fe are investigated using the experimental level densities. These properties include entropy, Helmholtz free energy, caloric curves, chemical potential, and heat capacity. In particular, the breaking of Cooper pairs and single-quasiparticle entropy are discussed and shown to be important concepts for describing nuclear level density. Microscopic model calculations are performed for level densities of $^{56,57}$Fe. The experimental and calculated level densities are compared. The average number of broken Cooper pairs and the parity distribution are extracted as a function of excitation energy for $^{56,57}$Fe from the model calculations.
AN INTERIM THERMODYNAMIC PROPERTY FORMULATION FOR SUPERCRITICAL n-HEXANE
Azzedine Abbaci
2010-07-01
Full Text Available Accurate information on the thermodynamic properties of supercritical fluids is highly sought for the chemical technology, especially, supercritical extraction technology. The thermodynamic properties of fluids near the critical region are strongly affected by the presence of fluctuations and therefore, can not be described by conventional equation. We have investigated an interim formulation for the behavior of the thermodynamic properties of n-hexane in the vicinity of the critical region. For this reason we have used the so-called “crossover model” to describe the thermodynamic properties of n-hexane in a wide range of temperatures and densities around the critical point.
Moisture sorption isotherms of castor beans. Part 2: Thermodynamic properties
André L. D. Goneli
Full Text Available ABSTRACT Knowledge on the water sorption within agricultural products is extremely important for decision making during post-harvest procedures. In order to improve this knowledge, thermodynamic properties regarding water sorption provide useful data. Thermodynamic properties of castor beans, related to sorption, were determined. Static gravimetric technique under different conditions of temperature (25, 35, 45 and 55 ± 1 °C was used. Saturated salt solutions in the range of 37-87% ± 2% were utilized to create the required controlled humidity environment. After the sorption procedure, differential enthalpy, differential entropy and Gibbs free energy of this process were calculated and decreased with increased values of equilibrium moisture content.
Thermodynamics Properties of Mesoscopic Quantum Nanowire Devices
Attia A.AwadAlla; Adel H.Phillips
2007-01-01
We investigate the thermodynamics properties of mesoscopic quantum nanowire devices, such as the effect of electron-phonon relaxation time, Peltier coefficient, carrier concentration, frequency of this field, and channel width. The influence of time-varying fields on the transport through such device has been taken into consideration. This device is modelled as nanowires connecting to two reservoirs. The two-dimensional electron gas in a GaAs-AlGaAs heterojunction has a Fermi wave length which is a hundred times larger than that in a metal. The results show the oscillatory behaviour of dependence of the thermo power on frequency of the induced field. These results agree with the existing experiments and may be important for electronic nanodevices.
Thermodynamics and Magnetocaloric properties of Fe/Cr Superlattices
Mukherjee, T.; Michalski, S.; Skomski, R.; Sellmyer, D. J.; Binek, Ch.
2011-03-01
We explore MC properties of tailored Fe/Cr superlattices involving simple 3d metals. Our multilayers are fabricated by pulsed laser deposition with emphasis on maximizing magnetic entropy changes near room temperature. We use nanostructuring to tailor magnetic interaction and exploit geometrical confinement in order to fit the FM to paramagnetic transition temperature of the FM constituent films. In concert this leads to an optimized global metamagnetic transition maximizing the isothermal entropy change. Thermodynamic and MC properties of such Fe/Cr superlattices are studied with the help of SQUID magnetometry. Entropy changes are deduced via the Maxwell relation in single phase regions and via the Clausis-Clapeyron relations at first order metamagnetic transitions, X-ray diffraction and X-ray reflectivity are used to correlate structural data with the magnetic properties. Financial support by NRI, and NSF through EPSCoR, Career DMR-0547887, and MRSEC Grant No. 0820521.
Potential Function and Thermodynamic Property of UO
Xiu-lin Zeng; Si-yu Xu; Xue-hai Ju
2013-01-01
Potential energy scan for uranium oxide (UO) was performed by ab initio configuration interaction (CI) method and density functional theory methods at the PBE1 and the B3LYP levels in combination with the (ECP80MWB_AVQZ+2f) basis set for uranium and 6-311+G* for oxygen.The dissociation energies of UO,after being corrected for the zero-point vibrational energy,are 2.38,3.76,and 3.31 eV at the CI,PBE1,and B3LYP levels,respectively.The calculated energy was fitted to potential functions of Morse,Lennard-Jones,and Rydberg.Only the Morse function is eligible for the potential.The anharmonicity constant is 0.00425.The anharmonic frequency is 540.95 cm-1 deduced from the PBE1 results.Thermodynamic properties of entropy and heat capacity at 298.2-1500 K were calculated using DFT-UPBE1 results and Morse parameters.The relationship between entropy and temperature was established.
Thermodynamic properties of α-uranium
Ren, Zhiyong; Wu, Jun; Ma, Rong; Hu, Guichao; Luo, Chao
2016-11-01
The lattice constants and equilibrium atomic volume of α-uranium were calculated by Density Functional Theory (DFT). The first principles calculation results of the lattice for α-uranium are in agreement with the experimental results well. The thermodynamic properties of α-uranium from 0 to 900 K and 0-100 GPa were calculated with the quasi-harmonic Debye model. Volume, bulk modulus, entropy, Debye temperature, thermal expansion coefficient and the heat capacity of α-uranium were calculated. The calculated results show that the bulk modulus and Debye temperature increase with the increasing pressure at a given temperature while decreasing with the increasing temperature at a given pressure. Volume, entropy, thermal expansion coefficient and the heat capacity decrease with the increasing pressure while increasing with the increasing temperature. The theoretical results of entropy, Debye temperature, thermal expansion coefficient and the heat capacity show good agreement with the general trends of the experimental values. The constant-volume heat capacity shows typical Debye T3 power-law behavior at low temperature limit and approaches to the classical asymptotic Dulong-Petit limit at high temperature limit.
Thermodynamical and dynamical properties of charged BTZ black holes
Tang, Zi-Yu; Wang, Bin [Shanghai Jiao Tong University, Department of Physics and Astronomy, Center for Astronomy and Astrophysics, Shanghai (China); Zhang, Cheng-Yong [Peking University, Center for High-Energy Physics, Beijing (China); Kord Zangeneh, Mahdi [Shanghai Jiao Tong University, Department of Physics and Astronomy, Center for Astronomy and Astrophysics, Shanghai (China); Shahid Chamran University of Ahvaz, Physics Department, Faculty of Science, Ahvaz (Iran, Islamic Republic of); Research Institute for Astronomy and Astrophysics of Maragha (RIAAM)-Maragha, P. O. Box: 55134-441, Maragha (Iran, Islamic Republic of); Shiraz University, Physics Department and Biruni Observatory, College of Sciences, Shiraz (Iran, Islamic Republic of); Saavedra, Joel [Pontificia Universidad Catolica de Valparaiso, Instituto de Fisica, Valparaiso (Chile)
2017-06-15
We investigate the spacetime properties of BTZ black holes in the presence of the Maxwell field and Born-Infeld field and find rich properties in the spacetime structures when the model parameters are varied. Employing Landau-Lifshitz theory, we examine the thermodynamical phase transition in the charged BTZ black holes. We further study the dynamical perturbation in the background of the charged BTZ black holes and find different properties in the dynamics when the thermodynamical phase transition occurs. (orig.)
Thermodynamic properties of black holes in de Sitter space
Li, Huai-Fan; Ma, Ya-Qin
2016-01-01
We study the thermodynamic properties of Schwarzschild-de Sitter (SdS) black hole and Reissner-Nordstr\\"{o}m-de Sitter (RNdS) black hole in the view of global and effective thermodynamic quantities. Making use of the effective first law of thermodynamics, we can derive the effective thermodynamic quantities of de Sitter black holes. It is found that these effective thermodynamic quantities also satisfy Smarr-like formula. Especially, the effective temperatures are nonzero in the Nariai limit, which is consistent with the idea of Bousso and Hawking. By calculating heat capacity and Gibbs free energy, we find SdS black hole is always thermodynamically stable and RNdS black hole may undergoes phase transition at some points.
Thermodynamic properties of black holes in de Sitter space
Li, Huai-Fan; Ma, Meng-Sen; Ma, Ya-Qin
2017-01-01
We study the thermodynamic properties of Schwarzschild-de Sitter (SdS) black hole and Reissner-Nordström-de Sitter (RNdS) black hole in view of global and effective thermodynamic quantities. Making use of the effective first law of thermodynamics, we can derive the effective thermodynamic quantities of de Sitter black holes. It is found that these effective thermodynamic quantities also satisfy Smarr-like formula. Especially, the effective temperatures are nonzero in the Nariai limit. By calculating heat capacity and Gibbs free energy, we find SdS black hole is always thermodynamically stable and RNdS black hole may undergoes phase transition at some points.
Thermodynamic properties of the DUPIC fuel and its performance
Park, Kwang Heon; Kim, Hee Moon [Kyung Hee Univ., Seoul (Korea, Republic of)
1997-07-01
This study describes thermodynamic properties of DUPIC fuel and performance. In initial state, DUPIC fuel which contains fissile materials is different from general nuclear fuel. So this study analyzed oxygen potential, thermal conductivity and specific heat of the DUPIC fuel.
THERMODYNAMIC PROPERTIES OF LADDER--LIKE HEISENBERG SYSTEM
蒋青; 潘可扬
1993-01-01
By combining the cumulant expansion method with the double-chain approximation, we study thermodynamic properties of ladder-like He isenberg system. We find the interaction between interchains has different effect in high and low temperature.
Theoretical investigation of the thermodynamic properties of metallic thin films
Hung, Vu Van [Vietnam Education Publishing House, 81 Tran Hung Dao, Hanoi (Viet Nam); Phuong, Duong Dai [Hanoi National University of Education, 136 Xuan Thuy, Hanoi (Viet Nam); Hoa, Nguyen Thi [University of Transport and Communications, Lang Thuong, Dong Da, Hanoi (Viet Nam); Hieu, Ho Khac, E-mail: hieuhk@duytan.edu.vn [Institute of Research and Development, Duy Tan University, K7/25 Quang Trung, Danang (Viet Nam)
2015-05-29
The thermodynamic properties of metallic thin films with face-centered cubic structure at ambient conditions were investigated using the statistical moment method including the anharmonicity effects of thermal lattice vibrations. The analytical expressions of Helmholtz free energy, lattice parameter, linear thermal expansion coefficient, specific heats at the constant volume and constant pressure were derived in terms of the power moments of the atomic displacements. Numerical calculations of thermodynamic properties have been performed for Au and Al thin films and compared with those of bulk metals. This research proposes that thermodynamic quantities of thin films approach the values of bulk when the thickness of thin film is about 70 nm. - Highlights: • Thermodynamic properties of thin films were investigated using the moment method. • Expressions of Helmholtz energy, expansion coefficient, specific heats were derived. • Calculations for Au, Al thin films were performed and compared with those of bulks.
Thermodynamical properties of metric fluctuations during inflation
Bellini, M
2001-01-01
I study a thermodynamical approach to scalar metric perturbations during the inflationary stage. In the power-law expanding universe here studied, I find a negative heat capacity as a manifestation of superexponential growing for the number of states in super Hubble scales. The power spectrum depends on the Gibbons-Hawking and Hagedorn temperatures.
Thermodynamic properties and mixing thermodynamic parameters of two-phase metallic melts
Jian Zhang
2005-01-01
Based on the calculating model of metallic melts involving eutectic, the calculating equations of mixing thermodynamic parameters for two phase metallic melts have been formulated in the light of those equations of homogeneous solutions. Irrespective as to whether the activity deviation relative to Raoultian behavior is positive or negative, or the deviation is symmetrical or unsymmetrical, the evaluated results not only agree well with experimental values, but also strictly obey the mass action law. This testifies that these equations can authentically reflect the structural reality and mixing thermodynamic characteristics of two-phase metallic melts. The calculating equations of mixing thermodynamic parameters for the model of two phase metallic melts offer two practical criteria (activity and mixing thermodynamic parameters) and one theoretical criterion (the mass action law).
Thermodynamic properties and environmental chemistry of chromium
Schmidt, R.L.
1984-07-01
Values of standard entropy, standard enthalpy of formation, and standard free energy of formation for Cr and its solid and aqueous species are tabulated in this report. These values were selected or recalculated after careful evaluation of the best available current thermochemical data. The basis for selection of data centered on conformation with the recent studies of Vasil'ev et al. (1977a,b, 1978, 1980, 1981) for Cr/sup 3 +/ data and O'Hare and Boerio (1975) for CrO/sub 4//sup 2 -/ data. The thermodynamic data presented in this report will be incorporated into the data base of the geochemical computer model, MINTEQ. The distribution of Cr in the environment among its aqueous inorganic species is, according to the thermodynamic data, highly dependent upon pH and Eh and the presence of complexing ligands. The speciation of Cr in natural waters is also controlled by reduction and complexation by organic matter, adsorption and oxidation by Mn-oxide in suspended particulate matter and sediment, and reduction by H/sub 2/S released from anoxic sediments. 89 references, 8 figures, 11 tables.
Mechanical, elastic and thermodynamic properties of crystalline lithium silicides
Schwalbe, Sebastian; Trepte, Kai; Biedermann, Franziska; Mertens, Florian; Kortus, Jens
2016-01-01
We investigate crystalline thermodynamic stable lithium silicides phases (LixSiy) with density functional theory (DFT) and a force-field method based on modified embedded atoms (MEAM) and compare our results with experimental data. This work presents a fast and accurate framework to calculate thermodynamic properties of crystal structures with large unit cells with MEAM based on molecular dynamics (MD). Mechanical properties like the bulk modulus and the elastic constants are evaluated in addition to thermodynamic properties including the phonon density of states, the vibrational free energy and the isochoric/isobaric specific heat capacity for Li, Li12Si7, Li7Si3, Li13Si4, Li15Si4, Li21Si5, Li17Si4, Li22Si5 and Si. For a selected phase (Li13Si4) we study the effect of a temperature dependent phonon density of states and its effect on the isobaric heat capacity.
Thermodynamic properties and mixing thermodynamic parameters of binary homogeneous metallic melts
无
2003-01-01
After the investigation on the thermodynamic properties and mixing thermodynamic parameters of binary ho-mogeneous metallic melts involving compound, peritectic as well as solid solution, it was found that the equations of mix-ing free energy ΔGm and excess free energy ΔGxs of them can be expressed by the following equations:ΔGm = ∑x[∑NiΔGiθ + RT(∑ Nj ln Nj+∑Ni lnNi)] and ΔGxs = ΔGm-RT(alna+blnb), respectively.
Thermodynamic Properties of Liquid Ag-Bi-Sn Alloys
Li, Zuoan; Knott, Sabine; Mikula, Adolf
2007-01-01
As a promising lead-free solder, the thermodynamic properties of the liquid ternary Ag-Bi-Sn system were investigated. Using an appropriate galvanic cell, the partial free energies of Sn in liquid Ag-Bi-Sn alloys were determined as a function of concentration and temperature. Thermodynamic properties were obtained for 27 alloys. Their composition was situated on three cross sections with the constant ratios of Ag:Bi = 2:1, 1:1, and 1:2. The integral Gibbs free energy and the integral enthalpy for the ternary system at 900 K were calculated by Gibbs Duhem integration.
Perturbation theories for the thermodynamic properties of fluids and solids
Solana, J R
2013-01-01
This book, Perturbation Theories for the Thermodynamic Properties of Fluids and Solids, provides a comprehensive review of current perturbation theories-as well as integral equation theories and density functional theories-for the equilibrium thermodynamic and structural properties of classical systems. Emphasizing practical applications, the text avoids complex theoretical derivations as much as possible. It begins with discussions of the nature of intermolecular forces and simple potential models. The book also presents a summary of statistical mechanics concepts and formulae. In addition, i
Organogels thermodynamics, structure, solvent role, and properties
Guenet, Jean-Michel
2016-01-01
This book provides a physics-oriented introduction to organogels with a comparison to polymer thermoreversible gels whenever relevant. The past decade has seen the development of a wide variety of newly-synthesized molecules that can spontaneously self-assemble or crystallize from their organic or aqueous solutions to produce fibrillar networks, namely organogels, with potential applications in organic electronics, light harvesting, bio-imaging, non-linear optics, and the like. This compact volume presents a detailed outlook of these novel molecular systems with special emphasis upon their thermodynamics, morphology, molecular structure, and rheology. The definition of these complex systems is also tackled, as well as the role of the solvent. The text features numerous temperature-phase diagrams for a variety of organogels as well as illustrations of their structures at the microscopic, mesoscopic and macroscopic level. A review of some potential applications is provided including hybrid functional materials ...
Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes
Xingxing Li
2015-07-01
Full Text Available Cuprous oxide (Cu2O nanocubes were synthesized by reducing Cu(OH2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area. The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.
Axiomatic Relation between Thermodynamic and Information-Theoretic Entropies
Weilenmann, Mirjam; Kraemer, Lea; Faist, Philippe; Renner, Renato
2016-12-01
Thermodynamic entropy, as defined by Clausius, characterizes macroscopic observations of a system based on phenomenological quantities such as temperature and heat. In contrast, information-theoretic entropy, introduced by Shannon, is a measure of uncertainty. In this Letter, we connect these two notions of entropy, using an axiomatic framework for thermodynamics [E. H. Lieb and J. Yngvason Proc. R. Soc. 469, 20130408 (2013)]. In particular, we obtain a direct relation between the Clausius entropy and the Shannon entropy, or its generalization to quantum systems, the von Neumann entropy. More generally, we find that entropy measures relevant in nonequilibrium thermodynamics correspond to entropies used in one-shot information theory.
Thermodynamic Product Relations for Generalized Regular Black Hole
Pradhan, Parthapratim
2016-01-01
We derive thermodynamic product relations for four-parametric regular black hole(BH) solutions of the Einstein equations coupled with a non-linear electrodynamics source. The four parameters can be described by the mass ($m$), charge ($q$), dipole moment ($\\alpha$) and quadrupole moment ($\\beta$) respectively. We study its complete thermodynamics. We compute different thermodynamic products i.e. area product, BH temperature product, specific heat product and Komar energy product respectively. Furthermore, we show that some complicated function of horizon areas that is indeed \\emph{mass-independent} and could turn out to be \\emph{universal}.
Thermodynamic properties of bulk and confined water
Mallamace, Francesco, E-mail: francesco.mallamace@unime.it [Dipartimento di Fisica e Scienza della Terra Università di Messina and CNISM, I-98168 Messina (Italy); Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States); Corsaro, Carmelo [Dipartimento di Fisica e Scienza della Terra Università di Messina and CNISM, I-98168 Messina (Italy); Mallamace, Domenico [Dipartimento di Scienze dell' Ambiente, della Sicurezza, del Territorio, degli Alimenti e della Salute, Università di Messina, I-98166 Messina (Italy); Vasi, Sebastiano; Vasi, Cirino [IPCF-CNR, I-98166 Messina (Italy); Stanley, H. Eugene [Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States)
2014-11-14
The thermodynamic response functions of water display anomalous behaviors. We study these anomalous behaviors in bulk and confined water. We use nuclear magnetic resonance (NMR) to examine the configurational specific heat and the transport parameters in both the thermal stable and the metastable supercooled phases. The data we obtain suggest that there is a behavior common to both phases: that the dynamics of water exhibit two singular temperatures belonging to the supercooled and the stable phase, respectively. One is the dynamic fragile-to-strong crossover temperature (T{sub L} ≃ 225 K). The second, T{sup *} ∼ 315 ± 5 K, is a special locus of the isothermal compressibility K{sub T}(T, P) and the thermal expansion coefficient α{sub P}(T, P) in the P–T plane. In the case of water confined inside a protein, we observe that these two temperatures mark, respectively, the onset of protein flexibility from its low temperature glass state (T{sub L}) and the onset of the unfolding process (T{sup *})
Thermodynamic Properties for the Simulation of Crude Oil Primary Refining
Juan Pablo Gutierrez
2014-04-01
Full Text Available Commonly, the use of simulators in the industry is performed without having a proper theoretical support. Sometimes this situation is a consequence of both, lack of time and the dairy dynamism required in the refinery industries. Particularly, the application of thermodynamic models is often not properly considered for the specific process under analysis. An undesirable fact can appear, for example, when a wrong properties package is chosen or even more when this selection step is completely ignored. The aim of this article is to prove that the habitual selection of the thermodynamic models is appropriate or not for the primary refining process. For the purpose, two available simulation softwares and thermodynamic models have been analyzed. The research paper focuses on establishing a guide for plant operators with information that has been previously proven, with theoretical support. In particular, for the oil crude atmospheric distillation (Topping, engineers use almost by default the Peng– Robinson thermodynamic package in Aspen Hysys simulator and Chao–Seader in Aspen Plus. Although the use of the thermodynamic property packages involves a whole theoretical support, this is not considered at the time of their election.
Liang, Zuozhong; Wang, Wei; Zhang, Min; Wu, Fei; Chen, Jian-Feng; Xue, Chunyu; Zhao, Hong
2017-04-01
The structural, mechanical and thermodynamic properties of ZrO2 polymorphs (namely, monoclinic (P21/c), tetragonal (P42/nmc), cubic (Fm 3 bar m), and orthorhombic (Pbca and Pnma)) are investigated systematically by employing DFT functionals (LDA, PBE and PW91). It is found that the structural parameters of ZrO2 polymorphs calculated by PBE and PW91 functionals are highly consistent with previous experiments with low absolute relative error (ARE). Moreover, all considered structures are mechanically stable according to the Born-Huang criterion and the PBE and PW91 functionals are more accurate than the LDA functional in predicting mechanical and thermodynamic properties. Significantly, we described mechanical and thermodynamic properties of ZrO2 polymorphs by introducing the charge density difference of related surfaces, which provides a better understanding of different behaviors of elastic constants (Cij) in various crystal structures of ZrO2.
Thermodynamic Properties of a Trapped Interacting Bose Gas
Shi, Hualin; Zheng, Wei-Mou
1996-01-01
A Bose gas in an external potential is studied by means of the local density approximation. Analytical results are derived for the thermodynamic properties of an ideal Bose gas in a generic power-law trapping potential, and their dependence on the mutual interaction of atoms in the case of a non-ideal Bose gas.
Review and recommended thermodynamic properties of FeCO3
Fosbøl, Philip Loldrup; Thomsen, Kaj; Stenby, Erling Halfdan
2010-01-01
An extensive review of entropy, enthalpy of formation and Gibbs energy of formation, heat capacity, aqueous solubility and solubility constant of FeCO3 is given. A consistent set of thermodynamic properties for FeCO3 and relevant aqeous species is selected and recommended for use. Speciation...
Computer program for calculating thermodynamic and transport properties of fluids
Hendricks, R. C.; Braon, A. K.; Peller, I. C.
1975-01-01
Computer code has been developed to provide thermodynamic and transport properties of liquid argon, carbon dioxide, carbon monoxide, fluorine, helium, methane, neon, nitrogen, oxygen, and parahydrogen. Equation of state and transport coefficients are updated and other fluids added as new material becomes available.
Direct measurement of thermodynamic properties of colloidal hard spheres
Dullens, R.P.A.; Kegel, W.K.; Aarts, D.G.A.L.
2008-01-01
Recently, we have shown how to measure thermodynamic properties of colloidal hard sphere suspensions by microscopy [Dullens et al. (2006) PNAS 103, 529]. Here, we give full experimental details on how to acquire three dimensional snapshots of a colloidal hard sphere suspension over a wide range of d
Quantum Rényi relative entropies affirm universality of thermodynamics
Misra, Avijit; Singh, Uttam; Bera, Manabendra Nath; Rajagopal, A. K.
2015-10-01
We formulate a complete theory of quantum thermodynamics in the Rényi entropic formalism exploiting the Rényi relative entropies, starting from the maximum entropy principle. In establishing the first and second laws of quantum thermodynamics, we have correctly identified accessible work and heat exchange in both equilibrium and nonequilibrium cases. The free energy (internal energy minus temperature times entropy) remains unaltered, when all the entities entering this relation are suitably defined. Exploiting Rényi relative entropies we have shown that this "form invariance" holds even beyond equilibrium and has profound operational significance in isothermal process. These results reduce to the Gibbs-von Neumann results when the Rényi entropic parameter α approaches 1. Moreover, it is shown that the universality of the Carnot statement of the second law is the consequence of the form invariance of the free energy, which is in turn the consequence of maximum entropy principle. Further, the Clausius inequality, which is the precursor to the Carnot statement, is also shown to hold based on the data processing inequalities for the traditional and sandwiched Rényi relative entropies. Thus, we find that the thermodynamics of nonequilibrium state and its deviation from equilibrium together determine the thermodynamic laws. This is another important manifestation of the concepts of information theory in thermodynamics when they are extended to the quantum realm. Our work is a substantial step towards formulating a complete theory of quantum thermodynamics and corresponding resource theory.
Quantum Rényi relative entropies affirm universality of thermodynamics.
Misra, Avijit; Singh, Uttam; Bera, Manabendra Nath; Rajagopal, A K
2015-10-01
We formulate a complete theory of quantum thermodynamics in the Rényi entropic formalism exploiting the Rényi relative entropies, starting from the maximum entropy principle. In establishing the first and second laws of quantum thermodynamics, we have correctly identified accessible work and heat exchange in both equilibrium and nonequilibrium cases. The free energy (internal energy minus temperature times entropy) remains unaltered, when all the entities entering this relation are suitably defined. Exploiting Rényi relative entropies we have shown that this "form invariance" holds even beyond equilibrium and has profound operational significance in isothermal process. These results reduce to the Gibbs-von Neumann results when the Rényi entropic parameter α approaches 1. Moreover, it is shown that the universality of the Carnot statement of the second law is the consequence of the form invariance of the free energy, which is in turn the consequence of maximum entropy principle. Further, the Clausius inequality, which is the precursor to the Carnot statement, is also shown to hold based on the data processing inequalities for the traditional and sandwiched Rényi relative entropies. Thus, we find that the thermodynamics of nonequilibrium state and its deviation from equilibrium together determine the thermodynamic laws. This is another important manifestation of the concepts of information theory in thermodynamics when they are extended to the quantum realm. Our work is a substantial step towards formulating a complete theory of quantum thermodynamics and corresponding resource theory.
Surface tension and related thermodynamic quantities of aqueous electrolyte solutions
Matubayasi, Norihiro
2013-01-01
Surface tension provides a thermodynamic avenue for analyzing systems in equilibrium and formulating phenomenological explanations for the behavior of constituent molecules in the surface region. While there are extensive experimental observations and established ideas regarding desorption of ions from the surfaces of aqueous salt solutions, a more successful discussion of the theory has recently emerged, which allows the quantitative calculation of the distribution of ions in the surface region. Surface Tension and Related Thermodynamic Quantities of Aqueous Electrolyte Solutions provides a d
Thermodynamic properties of a liquid crystal carbosilane dendrimer
Samosudova, Ya. S.; Markin, A. V.; Smirnova, N. N.; Ogurtsov, T. G.; Boiko, N. I.; Shibaev, V. P.
2016-11-01
The temperature dependence of the heat capacity of a first-generation liquid crystal carbosilane dendrimer with methoxyphenyl benzoate end groups is studied for the first time in the region of 6-370 K by means of precision adiabatic vacuum calorimetry. Physical transformations are observed in this interval of temperatures, and their standard thermodynamic characteristics are determined and discussed. Standard thermodynamic functions C p ° ( T), H°( T) - H°(0), S°( T) - S°(0), and G°( T) - H°(0) are calculated from the obtained experimental data for the region of T → 0 to 370 K. The standard entropy of formation of the dendrimer in the partially crystalline state at T = 298.15 K is calculated, and the standard entropy of the hypothetic reaction of its synthesis at this temperature is estimated. The thermodynamic properties of the studied dendrimer are compared to those of second- and fourth-generation liquid crystal carbosilane dendrimers with the same end groups studied earlier.
An approach to get thermodynamic properties from speed of sound
Núñez, M. A.; Medina, L. A.
2017-01-01
An approach for estimating thermodynamic properties of gases from the speed of sound u, is proposed. The square u2, the compression factor Z and the molar heat capacity at constant volume C V are connected by two coupled nonlinear partial differential equations. Previous approaches to solving this system differ in the conditions used on the range of temperature values [Tmin,Tmax]. In this work we propose the use of Dirichlet boundary conditions at Tmin, Tmax. The virial series of the compression factor Z = 1+Bρ+Cρ2+… and other properties leads the problem to the solution of a recursive set of linear ordinary differential equations for the B, C. Analytic solutions of the B equation for Argon are used to study the stability of our approach and previous ones under perturbation errors of the input data. The results show that the approach yields B with a relative error bounded basically by that of the boundary values and the error of other approaches can be some orders of magnitude lager.
Thermodynamic properties of superheated and supercritical steam
Malhotra, A. [Indian Inst. of Technology, New Delhi (India). Dept. of Mechanical Engineering; Panda, D.M.R. [Dadri Gas Power Station, NTPC, Gautam Buddha Nagar (India)
2001-07-01
An existing formulation for steam properties is due to Irvine and Liley. Their equations are convenient to program and do not require excessive computational time to produce results. The properties computed from these equations compare favourably with standard data. An additional advantage of these equations is that they follow prescribed theoretical trends by reducing to perfect-gas behaviour away from the saturation dome. However, a difficulty with these equations is that, at pressures above 10 MPa and close to the saturation dome, unacceptably large errors (above 10%) are produced. These equations are examined in the present work with a view towards enhancing their range of application through the use of additional functions. It is shown that the errors may be reduced to within 1% over the entire range of pressures (both sub-critical and super-critical pressures) required in steam-plant calculations. (author)
Thermodynamic Properties from Corresponding States Theory
Mollerup, Jørgen
1980-01-01
—Leland corresponding-states theory. Different fluid approximations for mixtures have been applied to the various corresponding states approaches. The resulting computation methods have been applied to calculate saturation properties of pure fluids and separation factors in binary mixtures for some fluids commonly...... encountered in natural gas and petroleum refining operations. Finally it is shown that the binary interaction parameters depend only on the fluid approximation and not on the specific form of the potential....
Thermodynamic Properties of Caprolactam Ionic Liquids
JIANG Lu; BAI Liguang; ZHU Jiqin; CHEN Biaohua
2013-01-01
A series of caprolactam ionic liquids (ILs) containing incorporated halide anions were synthesized.Their physical properties,such as melting points,heats of fusion and heat capacities,were measured by differential scanning calorimeter (DSC).The results indicate that these ionic liquids exhibit proper melting points,high value of heats of fusion,and satisfying heat capacities which are suitable for thermal energy storage applications.
Computational Models of Thermodynamic Properties of Uranium Nitride
Mei, Zhi-Gang; Stan, Marius
2014-06-01
The structural, elastic, electronic, phonon and thermodynamic properties of uranium nitride (UN) have been systematically studied by density functional theory (DFT) calculations. The calculated electronic band structure shows that UN is a metallic phase. The ground state structural and elastic properties predicted by DFT agree well with experiments. The thermodynamic properties of UN are studied by quasiharmonic approximation by including both lattice vibrational and thermal electronic contributions to free energies. The calculated enthalpy, entropy, Gibbs energy and heat capacity show an excellent agreement with experimental results. The thermal electronic contribution due to 5f electrons of U is found to be critical to describe the free energy of UN due to its metallic character.
Satoh, Katsuhiko
2013-08-28
The thermodynamic scaling of molecular dynamic properties of rotation and thermodynamic parameters in a nematic phase was investigated by a molecular dynamic simulation using the Gay-Berne potential. A master curve for the relaxation time of flip-flop motion was obtained using thermodynamic scaling, and the dynamic property could be solely expressed as a function of TV(γτ) , where T and V are the temperature and volume, respectively. The scaling parameter γτ was in excellent agreement with the thermodynamic parameter Γ, which is the logarithm of the slope of a line plotted for the temperature and volume at constant P2. This line was fairly linear, and as good as the line for p-azoxyanisole or using the highly ordered small cluster model. The equivalence relation between Γ and γ(τ) was compared with results obtained from the highly ordered small cluster model. The possibility of adapting the molecular model for the thermodynamic scaling of other dynamic rotational properties was also explored. The rotational diffusion constant and rotational viscosity coefficients, which were calculated using established theoretical and experimental expressions, were rescaled onto master curves with the same scaling parameters. The simulation illustrates the universal nature of the equivalence relation for liquid crystals.
Derived thermodynamic properties of alcohol + cyclohexylamine mixtures
IVONA R. RADOVIĆ
2010-02-01
Full Text Available Thermal expansion coefficients, α, excess thermal expansion coefficients, αE, isothermal coefficients of pressure excess molar enthalpy, (∂HE/∂pT,x, partial molar volumes, , partial molar volumes at infinite dilution, , partial excess molar volumes, , and partial excess molar volumes at infinite dilution, , were calculated using experimental densities and excess molar volumes, , data. All calculations are performed for the binary systems of cyclohexylamine with 1-propanol or 1-butanol or 2-butanol or 2-methyl-2-propanol. The Redlich–Kister polynomial and the reduced excess molar volume approach were used in the evaluation of these properties. In addition, the aim of this investigation was to provide a set of various volumetric data in order to asses the influence of temperature, chain length and position of hydroxyl group in the alcohol molecule on the molecular interactions in the examined binary mixtures.
Modelling of physical and thermodynamic properties in systems containing edible oils and biodiesel
Cunico, Larissa; Ceriani, Roberta; Sarup, Bent
The knowledge of physical and thermodynamic properties of pure components and their mixtures is a basic requirement for performing tasks related to process design, simulation, and optimization and also for performing chemical product design using computer aided molecular/mixture design (CAMD) tools...
Intermolecular interactions and the thermodynamic properties of supercritical fluids.
Yigzawe, Tesfaye M; Sadus, Richard J
2013-05-21
The role of different contributions to intermolecular interactions on the thermodynamic properties of supercritical fluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercritical fluids.
Diameter-dependent thermodynamic and elastic properties of metallic nanoparticles
Chandra, Jeewan; Kholiya, Kuldeep
2015-04-01
A simple theoretical model has been proposed to study the diameter-dependent properties of metallic nanoparticles, i.e. Ag, Au, Al, Ni, Pb, Cu and Fe. The diameter-dependent thermodynamic properties includes melting temperature, Debye temperature, evaporation temperature, melting enthapy and melting entropy. The model is also extended to study the diameter-dependent elastic properties including bulk modulus, Young's modulus and thermal expansion coefficient. On comparison with available experimental findings and other theoretical approaches, the results obtained with the present formulation depict a close agreement and demonstrate the validity of the method proposed in the present paper.
Fermi, Enrico
1956-01-01
Indisputably, this is a modern classic of science. Based on a course of lectures delivered by the author at Columbia University, the text is elementary in treatment and remarkable for its clarity and organization. Although it is assumed that the reader is familiar with the fundamental facts of thermometry and calorimetry, no advanced mathematics beyond calculus is assumed.Partial contents: thermodynamic systems, the first law of thermodynamics (application, adiabatic transformations), the second law of thermodynamics (Carnot cycle, absolute thermodynamic temperature, thermal engines), the entr
Ornstein-Zernike derivative relations and thermodynamic functions
Gan, Hin Hark; Eu, Byung Chan
1992-01-01
The consequences of the derivatives of the Ornstein-Zernike relation with respect to the density (ρ) and temperature (T) are examined. An approximate closure for the Ornstein-Zernike relation is used to evaluate the derivatives of the pair-correlation function to all orders without knowing explicitly the correlation functions higher in order than the pair-correlation function. The first- and second-order thermodynamic (ρ or T) derivatives of the pair-correlation function are calculated and compared with the experiments of Egelstaff et al. In addition, the thermodynamic functions involving these derivatives are evaluated to demonstrate the utility and accuracy of the method.
Interactive calculations of thermodynamics properties of minerals in VLab
Kelly, N.; da Silveira, P. R.; Wentzcovitch, R. M.
2009-12-01
We have developed a page within the VLab web site from which calculations of thermodynamics properties of minerals can be performed interactively. Previously published first principles calculations based on qhasiharmonic theory by our group have produced pressure dependent vibrational density of states (VDOSs). These calculations were costly and the essential information they produced, the VDOSs, are now stored on a database. They can be used to regenerate published results or calculate thermodynamics properties using specific user entered information (pressure and temperature range and grids, equation of state type, etc). Results are presented in numerical or graphics format (Gnuplot 4.2.2) that are interactively customized and downloadable. All codes behind the Web container are written in Java.
Thermodynamic properties and diffusion of water + methane binary mixtures
Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au [Centre for Molecular Simulation, Swinburne University of Technology, PO Box 218 Hawthorn, Victoria 3122 (Australia)
2014-03-14
Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methane concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.
Magnetic properties and thermodynamics in a metallic nanotube
Jiang, Wei, E-mail: weijiang.sut.edu@gmail.com; Li, Xiao-Xi; Guo, An-Bang; Guan, Hong-Yu; Wang, Zan; Wang, Kai
2014-04-15
A metallic nanotube composed of the ferromagnetic spin-3/2 inner shell and spin-1 outer shell with a ferrimagnetic interlayer coupling has been studied by using the effective-field theory with correlations (EFT). With both existence of the magnetic anisotropy and transverse field, we have studied effects of them on the magnetic properties and the thermodynamics. Some interesting phenomena have been found in the phase diagrams. At low temperature, the magnetization curves present different behaviors. Two compensation points have been found for the certain values of the system parameters in the system. The research results of metallic nanotubes may have potential applications in the fields of biomedicine and molecular devices. - Highlights: • A hexagonal metallic nanotube is composed of spin-3/2 inner layer and spin-1 outer layer. • Various types of magnetization curves depend on physical parameters and temperature. • We study the effects of physical parameters on the magnetic properties and thermodynamics.
Thermodynamic properties of the blackbody radiation: A Kaniadakis approach
Lourek, Imene; Tribeche, Mouloud
2017-02-01
The thermodynamic properties of the blackbody radiation are revisited, for the first time, within the theoretical framework of the κ-statistics introduced by Kaniadakis. Using the κ-counterpart of the Bose-Einstein distribution, generalized expressions for the free energy, the entropy, the specific heat, and the pressure are obtained. All quantities are shown to recover their standard expressions in the limit κ → 0. The reexamination of the thermodynamic properties of the blackbody radiation shows that it emits more energy with an increase of the value of | κ | in comparison with the standard Planck radiation law. Moreover, the effects of the deformed Kaniadakis statistics are shown to be more appreciable for high temperatures. Our results could be used as a theoretical support for experimental studies implying blackbody radiation such as the study of microwave background radiation.
Thermodynamic properties of stable and metastable phases of Pt metal
PENG Hong-jian; XIE You-qing; NIE Yao-zhuang
2009-01-01
Isometric heat capacity cv and isobaric heat capacity cp of Pt with stable and metastable phases were calculated by using pure element systematic theory. These results are in excellent agreement with of SGTE (Scientific Group Thermodata Europe) database and JANAF (Joint Army-Navy-Air Force) experimental values. The calculation results of cv and cp of Pt metal in natural state are in good agreement with those calculated by FP(first-principles) method. It is found that the electron devotion to heat capacity is important to adjust in OA(one-atom) method while calculating heat capacity. The full information about thermodynamic properties of Pt metal with stable and metastable phases, such as entropy(S), enthalpy(H) and Gibbs energy(G) were calculated from 0 K to random temperature. The results are in good agreement with JANAF experimental value. In contrast to SGTE database, the thermodynamic properties from 0 K to 298.15 K are implemented.
Thermodynamic properties of metastable Ag-Cu alloys
Najafabadi, R.; Srolovitz, D. J.; Ma, E.; Atzmon, M.
1993-09-01
The enthalpies of formation of metastable fcc Ag-Cu solid solutions, produced by ball milling of elemental powders, were determined by differential scanning calorimetry. Experimental thermodynamic data for these metastable alloys and for the equilibrium phases are compared with both calculation of phase diagrams (CALPHAD) and atomistic simulation predictions. The atomistic simulations were performed using the free-energy minimization method (FEMM). The FEMM determination of the equilibrium Ag-Cu phase diagram and the enthalpy of formation and lattice parameters of the metastable solid solutions are in good agreement with the experimental measurements. CALPHAD calculations made in the same metastable regime, however, significantly overestimate the enthalpy of formation. Thus, the FEMM is a viable alternative approach for the calculation of thermodynamic properties of equilibrium and metastable phases, provided reliable interatomic potentials are available. The FEMM is also capable of determining such properties as the lattice parameter which are not available from CALPHAD calculations.
Hrubý Jan
2014-03-01
Full Text Available We present a system of analytical equations for computation of all thermodynamic properties of dry steam and liquid water (undesaturated, saturated and metastable supersaturated and properties of the liquid-vapor phase interface. The form of the equations is such that it enables computation of all thermodynamic properties for independent variables directly related to the balanced quantities - total mass, liquid mass, energy, momenta. This makes it suitable for the solvers of fluid dynamics equations in the conservative form. Thermodynamic properties of dry steam and liquid water are formulated in terms of special thermodynamic potentials and all properties are obtained as analytical derivatives. For the surface tension, the IAPWS formula is used. The interfacial internal energy is derived from the surface tension and it is used in the energy balance. Unlike common models, the present one provides real (contrary to perfect gas approximation properties of steam and water and reflects the energetic effects due to the surface tension. The equations are based on re-fitting the reference formulation IAPWS-95 and selected experimental data. The mathematical structure of the equations is optimized for fast computation.
Hrubý, Jan; Duška, Michal
2014-03-01
We present a system of analytical equations for computation of all thermodynamic properties of dry steam and liquid water (undesaturated, saturated and metastable supersaturated) and properties of the liquid-vapor phase interface. The form of the equations is such that it enables computation of all thermodynamic properties for independent variables directly related to the balanced quantities - total mass, liquid mass, energy, momenta. This makes it suitable for the solvers of fluid dynamics equations in the conservative form. Thermodynamic properties of dry steam and liquid water are formulated in terms of special thermodynamic potentials and all properties are obtained as analytical derivatives. For the surface tension, the IAPWS formula is used. The interfacial internal energy is derived from the surface tension and it is used in the energy balance. Unlike common models, the present one provides real (contrary to perfect gas approximation) properties of steam and water and reflects the energetic effects due to the surface tension. The equations are based on re-fitting the reference formulation IAPWS-95 and selected experimental data. The mathematical structure of the equations is optimized for fast computation.
Molecular Dynamics Simulation on thermodynamic Properties and Transport Coefficients
D.X.Xiong
1996-01-01
Moecular dynamics simulation (MDS) is used to study the thermodynamic properties and transport coefficients of an argon system with Lennend-Jones potential.The results on the velocity distribution,mean free path,mean collison time,specific heat and self0diffusion coefficient agree well with the existing theoretical /experimental data,It shows that molecular dynamics method is another bridge to connect microworld and macreoworld.
Thermodynamic properties of water desorption of forage turnip seeds
Kelly Aparecida Sousa; Osvaldo Resende; André Luis Duarte Goneli; Thaís Adriana de Souza Smaniotto; Daniel Emanuel Cabral de Oliveira
2014-01-01
The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip seeds. The equilibrium moisture content of forage turnip seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within ...
Thermodynamic properties of water desorption of forage turnip seeds
Sousa,Kelly Aparecida de; Resende,Osvaldo; Goneli, André Luis Duarte; Smaniotto,Thaís Adriana de Souza; Oliveira,Daniel Emanuel Cabral de
2015-01-01
The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip seeds. The equilibrium moisture content of forage turnip seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within th...
Prediction Of Refrigerant Thermodynamic Properties By Equations Of State
Moshfeghian, Mahmood Moshfeghian, Mahmood
1992-01-01
The ability of three equations of state (EOS) for calculating the thermodynamic properties of refrigerants has been studied for 35 pure component refrigerants. Three equations of state studied were the Soave-Redlich-Kwong (SRK), Peng-Robinson (PR) and Parameters From Group Contribution (PFGC). For each refrigerant, the vapor pressure, saturated vapor volume, saturated liquid density, and heat of vaporization were calculated and compared with the values reported in the ASHRAE hand-book. For...
Thermodynamic Properties for the Simulation of Crude Oil Primary Refining
Juan Pablo Gutierrez; Leonel Alberto Benítez
2014-01-01
Commonly, the use of simulators in the industry is performed without having a proper theoretical support. Sometimes this situation is a consequence of both, lack of time and the dairy dynamism required in the refinery industries. Particularly, the application of thermodynamic models is often not properly considered for the specific process under analysis. An undesirable fact can appear, for example, when a wrong properties package is chosen or even more when this selection ste...
Composition and thermodynamic properties of dense alkali metal plasmas
Gabdullin, M.T. [NNLOT, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan); Ramazanov, T.S.; Dzhumagulova, K.N. [IETP, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan)
2012-04-15
In this work composition and thermodynamic properties of dense alkali metal plasmas (Li, Na) were investigated. Composition was derived by solving the Saha equations with corrections due to nonideality. The lowering of the ionization potentials was calculated on the basis of pseudopotentials by taking screening and quantum effects into account (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Ab initio interatomic potentials and the thermodynamic properties of fluids
Vlasiuk, Maryna; Sadus, Richard J.
2017-07-01
Monte Carlo simulations with accurate ab initio interatomic potentials are used to investigate the key thermodynamic properties of argon and krypton in both vapor and liquid phases. Data are reported for the isochoric and isobaric heat capacities, the Joule-Thomson coefficient, and the speed of sound calculated using various two-body interatomic potentials and different combinations of two-body plus three-body terms. The results are compared to either experimental or reference data at state points between the triple and critical points. Using accurate two-body ab initio potentials, combined with three-body interaction terms such as the Axilrod-Teller-Muto and Marcelli-Wang-Sadus potentials, yields systematic improvements to the accuracy of thermodynamic predictions. The effect of three-body interactions is to lower the isochoric and isobaric heat capacities and increase both the Joule-Thomson coefficient and speed of sound. The Marcelli-Wang-Sadus potential is a computationally inexpensive way to utilize accurate two-body ab initio potentials for the prediction of thermodynamic properties. In particular, it provides a very effective way of extending two-body ab initio potentials to liquid phase properties.
The thermodynamic properties of alkylated γ-lactones
Emel'Yanenko, V. N.; Verevkin, S. P.; Burakova, E. N.; Roganov, G. N.; Georgieva, M. K.
2009-04-01
The enthalpies of formation of γ-pentanolactone ( I), γ-hexanolactone ( II), and γ-nonanolactone ( III) were determined by combustion calorimetry. The enthalpies of vaporization of these lactones were measured by the transfer method. Conformational analysis was performed and equilibrium structures, sets of fundamental vibrations, moments of inertia, and total energies of the stablest conformers of I, II, and III were calculated by the B3LYP/6-311G( d, p), G3MP2, and CBS-QB3 methods. The experimental IR spectra and calculated vibrational frequencies were used to obtain sets of fundamental vibrations of the stablest conformations. The thermodynamic properties of I- III in the ideal gas state were determined over the temperature range 0-1500 K. Additive and quantum-chemical methods were applied to estimate the Δf H o(g) values of a number of γ-lactones. Composite quantum-chemical methods were used to obtain the energies of monomethyl γ-butyrolactones and estimate their relative stability depending on the position of the methyl substituent in the ring.
Thermodynamic and spectral properties of adiabatic Peierls chains
Weber, Manuel; Assaad, Fakher F.; Hohenadler, Martin
2016-10-01
We present exact numerical results for the effects of thermal fluctuations on the experimentally relevant thermodynamic and spectral properties of Peierls chains. To this end, a combination of classical Monte Carlo sampling and exact diagonalization is used to study adiabatic half-filled Holstein and Su-Schrieffer-Heeger models. The classical nature of the lattice displacements in combination with parallel tempering permit simulations on large system sizes and a direct calculation of spectral functions in the frequency domain. Most notably, the long-range order and the associated Peierls gap give rise to a distinct low-temperature peak in the specific heat. The closing of the gap and suppression of order by thermal fluctuations involves in-gap excitations in the form of soliton-antisoliton pairs and is also reflected in the dynamic density and bond structure factors as well as in the optical conductivity. We compare our data to the widely used mean-field approximation and highlight relations to symmetry-protected topological phases and disorder problems.
Study on thermodynamic properties of actinoid oxides
Tsuji, Toshihide; Miyajima, Nobuyoshi; Kato, Tetsuya; Ochida, Manabu [Nagoya Univ. (Japan). School of Engineering; Mumomura, Tadasumi; Yamashita, Toshiyuki; Nitani, Noriko; Ouchi, Kinji
1996-01-01
Since long-life transuranium elements (TRU) accumulate associated with a progress of high-burnup of fuel, TRU quenching in a reactor or an accelerator has been examined in Japan. To design a fuel for TRU quenching, thermal expansion is an important thermal parameter along with thermal capacity and heat transfer coefficient. Here, lattice constants of PuO{sub 2} ThO{sub 2}, UO{sub 2} and NpO{sub 2} were investigated by high temperature X-ray diffraction, showing that the lattice constants of these dioxides but UO{sub 2} obtained in this study were well coincident with Tailor`s values. The linear expansion coefficients for ThO{sub 2}, UO{sub 2} and PuO{sub 2} agreed with TPRC data and that of NpO{sub 2} with Fahey`s measurement. The linear expansion coefficient of NpO{sub 2} was found to be temperature dependent as well as other three dioxides. Those values were in inverse proportion to their melting points in a higher temperature range, whereas in a lower temperature one, the coefficient of UO{sub 2} was larger than those of NpO{sub 2} and PuO{sub 2}. Therefore, such abnormal behavior of the coefficient in a low temperature range was considered to be related to the lower Debye temperature of UO{sub 2} compared with the other dioxides. (M.N.)
The VLab repository of thermodynamics and thermoelastic properties of minerals
Da Silveira, P. R.; Sarkar, K.; Wentzcovitch, R. M.; Shukla, G.; Lindemann, W.; Wu, Z.
2015-12-01
Thermodynamics and thermoelastic properties of minerals at planetary interior conditions are essential as input for geodynamics simulations and for interpretation of seismic tomography models. Precise experimental determination of these properties at such extreme conditions is very challenging. Therefore, ab initio calculations play an essential role in this context, but at the cost of great computational effort and memory use. Setting up a widely accessible and versatile mineral physics database can relax unnecessary repetition of such computationally intensive calculations. Access to such data facilitates transactional interaction across fields and can advance more quickly insights about deep Earth processes. Hosted by the Minnesota Supercomputing Institute, the Virtual Laboratory for Earth and Planetary Materials (VLab) was designed to develop and promote the theory of planetary materials using distributed, high-throughput quantum calculations. VLab hosts an interactive database of thermodynamics and thermoelastic properties or minerals computed by ab initio. Such properties can be obtained according to user's preference. The database is accompanied by interactive visualization tools, allowing users to repeat and build upon previously published results. Using VLab2015, we have evaluated thermoelastic properties, such as elastic coefficients (Cij), Voigt, Reuss, and Voigt-Reuss-Hill aggregate averages for bulk (K) and shear modulus (G), shear wave velocity (VS), longitudinal wave velocity (Vp), and bulk sound velocity (V0) for several important minerals. Developed web services are general and can be used for crystals of any symmetry. Results can be tabulated, plotted, or downloaded from the VLab website according to user's preference.
WANG Gui-Xiang; GONG Xue-Dong; XIAO He-Ming
2008-01-01
Nitro derivatives of benzene and anilines were optimized to obtain their molecular geometries and electronic structures at a DFT-B3LYP/6-31G* level. Their IR spectra were obtained and assigned by vibrational analysis. Comparing the calculated IR spectra with these of experiments known, all the IR data obtained in this paper were considered to be reliable. Based on the frequencies scaled by 0.96 and the principle of statistic thermodynamics, the thermodynamic properties were evaluated, which were linearly related with the number of nitro and amino groups as well as the temperature, obviously showing good group additivity.
Structural and thermodynamics properties of organo-modified montmorillonite clay
Anoukou, K.; Zaoui, A.; Zaïri, F.; Naït-Abdelaziz, M.; Gloaguen, J. M.
2015-01-01
Polymer clay nanocomposites (PCNs) have been seen as the most novel materials in engineering applications since they exhibit significant improvement in mechanical and physical properties. Indeed, with few amount of organoclay, PCNs exhibit enhanced mechanical, optical, thermal and liquid or gas barrier properties compared to pure polymers and to their counterpart microcomposites. Thus, organoclays are extensively used as precursors in the preparation of PCNs. They are the best candidate in reinforcing PCNs because of the lightweight and the high availability of clay minerals in the nature. However, structure and physical phenomena arising at molecular level in organoclays, and subsequently in PCNs, are not completely or difficultly accessible with existing experimental techniques. In this work, molecular dynamics (MD) simulation was conducted using the combination of two force fields (CLAYFF and CHARMM) to evaluate the thermodynamics and structural properties of organoclay such as heat capacities, isothermal bulk modulus, density, basal spacing and chains arrangement in the interlayer spacing. Our results regarding the basal spacing and density are in fairly good agreement with available experimental data. This allows us to validate the use of the two force fields to represent interactions in organoclays. The effect of the cation exchange capacity (CEC) on the basal spacing and the thermodynamics properties is assessed. We found, through our MD simulation, that the calculated isothermal bulk modulus is in good agreement with the density value of organoclays with two different CEC.
无
2001-01-01
The interaction relation between lanthanum and the constituent elements of Sn-Pb alloy system was analyzed by using the thermodynamic models including Miedema formation energy model for binary system, Tanaka modification by excess entropy and the Chou geometric model for ternary system. The thermodynamic calculaton results show that lanthanum has higher affinity for Sn in the Sn-Pb system. This is an important foundation for the improvement of the metallurgical properties of Sn-Pb solder alloy by adding rare earth elements.
Chemical and Thermodynamic Properties at High Temperatures: A Symposium
Walker, Raymond F.
1961-01-01
This book contains the program and all available abstracts of the 90' invited and contributed papers to be presented at the TUPAC Symposium on Chemical and Thermodynamic Properties at High Temperatures. The Symposium will be held in conjunction with the XVIIIth IUPAC Congress, Montreal, August 6 - 12, 1961. It has been organized, by the Subcommissions on Condensed States and on Gaseous States of the Commission on High Temperatures and Refractories and by the Subcommission on Experimental Thermodynamics of the Commission on Chemical Thermodynamics, acting in conjunction with the Organizing Committee of the IUPAC Congress. All inquiries concerning participation In the Symposium should be directed to: Secretary, XVIIIth International Congress of Pure and Applied Chemistry, National Research Council, Ottawa, 'Canada. Owing to the limited time and facilities available for the preparation and printing of the book, it has not been possible to refer the proofs of the abstracts to the authors for checking. Furthermore, it has not been possible to subject the manuscripts to a very thorough editorial examination. Some obvious errors in the manuscripts have been corrected; other errors undoubtedly have been introduced. Figures have been redrawn only when such a step was essential for reproduction purposes. Sincere apologies are offered to authors and readers for any errors which remain; however, in the circumstances neither the IUPAC Commissions who organized the Symposium, nor the U. S. Government Agencies who assisted in the preparation of this book can accept responsibility for the errors.
Thermodynamic and structural properties of Bi-based liquid alloys
Yadav, S. K.; Jha, L. N.; Adhikari, D.
2015-10-01
Thermodynamic and microscopic structural properties of two Bi-based liquid alloys, such as In-Bi at 900 K and Tl-Bi at 750 K have been studied employing the regular associated solution model. We have estimated the mole fractions of the complexes and the free monomers assuming the existence of complexes In2 Bi in In-Bi melt and TlBi in Tl-Bi melt. The thermodynamic properties have been studied by computing the Gibbs free energy of mixing, enthalpy of mixing, entropy of mixing and activities of the monomers. The compositional contributions of the heat associated with the formation of complexes and the heat of mixing of the monomers to the net enthalpy change has also been studied. The structural properties of the liquid alloys have been studied by computing concentration fluctuation in the long-wavelength limit, chemical short-range order parameter and the ratio of mutual to intrinsic diffusion coefficients. For both of the alloy systems, the theoretical as well as the experimental values of SCC (0) are found to be lower than the corresponding ideal values over the whole composition range, indicating the hetero-coordinating nature of Bi-In and Bi-Tl alloy melts. All the interaction energy parameters are found to be negative and temperature dependent, and both the alloy systems are found to be weakly interacting.
Thermodynamic properties of ultra-small metallic particles
Cheng Nan-Pu; Zeng Su-Min; Chen Zhi-Qian
2005-01-01
The thermodynamic properties of ultra-small metallic particles within an ensemble are affected by the level distribution and the level correlation between the discrete electronic energy levels. The specific heat and spin susceptibility of ultra-small metallic particles in the canonical ensemble with an odd or even number of electrons are numerically calculated by considering the effects of the level statistics, and their behaviour at low and high temperatures is also discussed. As an example, the specific heat and spin susceptibility of nano-Al particles are calculated numerically in this paper.
Thermodynamic and transport properties of underdoped cuprates from ARPES data
Yoshida, T.; Zhou, X.J.; Yagi, H.; Lu, D.H.; Tanaka, K.; Fujimori, A.; Hussain, Z.; Shen, Z.-X.; Kakeshita, T.; Eisaki, H.; Uchida, S.; Segawa, Kouji; Lavrov, A.N.; Ando, Yoichi
2004-09-15
The relationship between photoemission spectra of high-T{sub c} cuprates and their thermodynamic and transport properties are discussed. The doping dependence of the expected quasi-particle density at the Fermi level (E{sub F}) are compared with the electronic specific heat coefficient {gamma} and that of the spectral weight at E{sub F} with the in-plane and out-of-plane superfluid density. We have estimated the electrical resistivity of underdoped cuprates from the momentum distribution curve (MDC) at E{sub F} in the nodal direction. The temperature dependence of the MDC width is also consistent with that of the electrical resistivity.
Interaction potentials and thermodynamic properties of two component semiclassical plasma
Ramazanov, T. S.; Moldabekov, Zh. A.; Ismagambetova, T. N. [Al-Farabi Kazakh National University, IETP, 71 al-Farabi Av., Almaty 050040 (Kazakhstan); Gabdullin, M. T. [Al-Farabi Kazakh National University, NNLOT, 71 al-Farabi Av., Almaty 050040 (Kazakhstan)
2014-01-15
In this paper, the effective interaction potential in two component semiclassical plasma, taking into account the long-range screening and the quantum-mechanical diffraction effects at short distances, is obtained on the basis of dielectric response function method. The structural properties of the semiclassical plasma are considered. The thermodynamic characteristics (the internal energy and the equation of state) are calculated using two methods: the method of effective potentials and the method of micropotentials with screening effect taken into account by the Ornstein-Zernike equation in the HNC approximation.
Thermodynamic properties of gases dissolved in electrolyte solutions.
Tiepel, E. W.; Gubbins, K. E.
1973-01-01
A method based on perturbation theory for mixtures is applied to the prediction of thermodynamic properties of gases dissolved in electrolyte solutions. The theory is compared with experimental data for the dependence of the solute activity coefficient on concentration, temperature, and pressure; calculations are included for partial molal enthalpy and volume of the dissolved gas. The theory is also compared with previous theories for salt effects and found to be superior. The calculations are best for salting-out systems. The qualitative feature of salting-in is predicted by the theory, but quantitative predictions are not satisfactory for such systems; this is attributed to approximations made in evaluating the perturbation terms.
Optical and thermodynamic property measurements of liquid metals and alloys
Weber, J. K. Richard; Krishnan, Shankar; Schiffman, Robert A.; Nordine, Paul C.
Optical properties and spectral emissivities of liquid silicon, titanium, niobium, and zirconium were investigated by HeNe laser polarimetry at λ = 632.8 nm. The metals were of a high purity and, except for zirconium, clean. The more demanding environmental requirements for eliminating oxide or nitride phases from zirconium were not met. Containerless conditions were achieved by electromagnetic levitation and heating. CO2 laser beam heating was also used to extend the temperature range for stable levitation and to heat solid silicon to form the metallic liquid phase. Corrections to previously reported calorimetric measurements of the heat capacity of liquid niobium were derived from the measured temperature dependence of its spectral emissivity. Property measurements were obtained for supercooled liquid silicon and supercooling of liquid zirconium was accomplished. The purification of liquid metals and the extension of this work on liquids to the measurement of thermodynamic properties and phase equilibria are discussed.
Electronic, structural, and thermodynamic properties of actinide dioxides
Ma, Li; Atta-Fynn, Raymond; Ray, Asok K.
2010-03-01
As a continuation of our studies of pure actinide metals using hybrid density functional theory,footnotetextR. Atta-Fynn and A. K. Ray, Europhysics Letters, 85, 27008-p1- p6 (2009); Chemical Physics Letters, 482, 223-227 (2009). we present here a systematic study of the electronic and geometric structure properties of the actinide dioxides, UO2, PuO2 and AmO2, using both density functional and hybrid density functional theories. For the hybrid density functionals, the fractions of exact Hartree-Fock exchange used were 25% and 40%. Each compound has been studied at the nonmagnetic, ferromagnetic and antiferromagnetic configurations, with and without spin-orbit coupling (SOC). The influence of SOC on the properties of the actinide dioxides will be discussed. Thermodynamic properties such as phonon dispersion curves, heat capacity, entropy, internal energy and free energy have been calculated by a coupling of first-principles calculations and lattice dynamics.
Sokolova, Tatiana S.; Dorogokupets, Peter I.; Dymshits, Anna M.; Danilov, Boris S.; Litasov, Konstantin D.
2016-09-01
We present Microsoft Excel spreadsheets for calculation of thermodynamic functions and P-V-T properties of MgO, diamond and 9 metals, Al, Cu, Ag, Au, Pt, Nb, Ta, Mo, and W, depending on temperature and volume or temperature and pressure. The spreadsheets include the most common pressure markers used in in situ experiments with diamond anvil cell and multianvil techniques. The calculations are based on the equation of state formalism via the Helmholtz free energy. The program was developed using Visual Basic for Applications in Microsoft Excel and is a time-efficient tool to evaluate volume, pressure and other thermodynamic functions using T-P and T-V data only as input parameters. This application is aimed to solve practical issues of high pressure experiments in geosciences and mineral physics.
Theoretical study of structural, elastic and thermodynamic properties of CZTX (X = S and Se) alloys
Bensalem, S., E-mail: bensalemse@gmail.com [Centre de Développement des Energies Renouvelables, CDER, BP 62 Route de l’Observatoire Bouzaréah, 16340 Algiers (Algeria); Département de Physique, Faculté des Sciences, Université de Sétif 1, 19000 Sétif (Algeria); Chegaar, M. [Département de Physique, Faculté des Sciences, Université de Sétif 1, 19000 Sétif (Algeria); Laboratoire d’Optoélectronique et Composants, Université de Sétif 1, 19000 Sétif (Algeria); Maouche, D.; Bouhemadou, A. [Laboratoire de Développement de Nouveaux Matériaux et leurs Caractérisations, Université de Sétif 1, 19000 Sétif (Algeria)
2014-03-15
Highlights: • CZTX (X = S, Se) alloys are relatively new absorbers for solar cells applications. • Elastic and thermodynamic properties of these alloys are not well understood. • The considered types “kesterite and stannite” can coexist in experimental samples. • Elastic and thermodynamic properties of both types have been investigated. • Coexistence of both types does not influence the behavior of CZTX-based devices. -- Abstract: By means of first-principles calculation approach, structural parameters, elastic and thermodynamic properties of Copper–Zinc–Tin–(Sulphide, Selenide) or Cu{sub 2}ZnSnX{sub 4} (X = S and Se) alloys for the kesterite (KS) and stannite (ST) types have been investigated. The calculated lattice parameters are in good agreement with experimental reported data. The elastic constants are calculated for both types of both compounds using the static finite strain scheme; the pressure dependence of elastic constants is predicted. The bulk modulus, anisotropy factor, shear modulus, Young’s modulus, Lame’s coefficient and Poisson’s ratio have been estimated from the calculated single crystalline elastic constants. The analysis of B/G ratio shows that Cu{sub 2}ZnSnX{sub 4} or CZTX compounds behave as ductile. Through quasi-harmonic approximation, the temperature dependence of some thermodynamic functions and lattice heat capacity of both compounds for both types have been performed.
Yu, Xiaohua; Zhan, Zhaolin
2014-01-01
This work has considered the intrinsic influence of bond energy on the macroscopic, thermodynamic, and mechanical properties of crystalline materials. A general criterion is proposed to evaluate the properties of nanocrystalline materials. The interrelation between the thermodynamic and mechanical properties of nanomaterials is presented and the relationship between the variation of these properties and the size of the nanomaterials is explained. The results of our work agree well with thermodynamics, molecular dynamics simulations, and experimental results. This method is of significance in investigating the size effects of nanomaterials and provides a new approach for studying their thermodynamic and mechanical properties.
Thermodynamic properties of liquid sodium under high pressure
Li, Huaming; Zhang, Xiaoxiao; Sun, Yongli; Li, Mo
2017-04-01
Acquiring reliable thermodynamic properties in liquid metals at high pressure and temperature is still a challenge in both experiment and theory. Equation of state (EoS) offers an alternative approach free of many of the difficulties. Here using the EoS of a power law form we obtained the thermodynamic properties of liquid sodium under pressure along the isothermal lines, including isothermal buck modulus, thermal expansion coefficient, Grüneisen parameter, and Anderson-Grüneisen parameter. The results are in excellent agreement with available experimental data measured by a piezometer at high temperature and high pressure and sound velocity measurement with pulse-echo technique. We found that the pressure derivative of the isothermal bulk modulus at zero pressure is a monotonic function of temperature and has a value around 4. In addition, unexpected crossing points were found in the isobaric thermal expansion coefficient and Grüneisen parameter; and a minimum in the isobaric heat under isothermal compression was also observed. While some of these detailed predictions are yet to be confirmed by further experiment, our results suggest that the power law form may be a more suitable choice for the EoS of liquids metals.
Gandova V.
2013-01-01
Full Text Available The thermochemical properties of metals and alloys are essential for the chemists to invent and improve metallurgical and materials’ design processes. However, the properties of multicomponent systems are still scarcely known due to experimental difficulties and the large number of related systems. Thus, the modelling of some thermodynamic properties would be advantageous when experimental data are missing. Considering mentioned facts, geometric models to estimate some thermodynamic properties for the liquid phase of the Ni-Bi-Zn systems. The calculations have been performed in a wide temperature range (1000-2000 K. Ternary interaction parameters for the liquid phase allowing molar Gibbs excess energy calculation have been determined.
Structural, elastic and thermodynamic properties of Ti2SC
Hongzhi Fu; Wenfang Liu; Tao Gao
2011-12-01
The structural parameters, elastic constants and thermodynamic properties of Ti2SC were investigated under pressure and temperature by using first-principles plane-wave pseudopotential density functional theory within the generalized gradient approximation. The obtained results are in agreement with the available experimental data. The bulk moduli along the - and -axes, $B_{a}$ and $B_{c}$, almost linearly increase with pressure, and the former is always smaller than the latter. The ratio of $B_{c}/B_{a}$ has a trend of gradual increase as the pressure increases. It is found that the elastic constants, anisotropy and Debye temperature of Ti2SC increase with pressure, while axial compressibility along the - and -axes decreases with pressure. The thermal properties including the equation of state, the Grüneisen parameter , the anisotropies $\\Delta_{p}, \\Delta_{S1}$ and $\\Delta_{S2}$, and the heat capacity are estimated at various pressures and temperatures.
On the thermodynamic properties of the generalized Gaussian core model
B.M.Mladek
2005-01-01
Full Text Available We present results of a systematic investigation of the properties of the generalized Gaussian core model of index n. The potential of this system interpolates via the index n between the potential of the Gaussian core model and the penetrable sphere system, thereby varying the steepness of the repulsion. We have used both conventional and self-consistent liquid state theories to calculate the structural and thermodynamic properties of the system; reference data are provided by computer simulations. The results indicate that the concept of self-consistency becomes indispensable to guarantee excellent agreement with simulation data; in particular, structural consistency (in our approach taken into account via the zero separation theorem is obviously a very important requirement. Simulation results for the dimensionless equation of state, β P / ρ, indicate that for an index-value of 4, a clustering transition, possibly into a structurally ordered phase might set in as the system is compressed.
Stationary Distribution and Thermodynamic Relation in Nonequilibrium Steady States
Komatsu, Teruhisa S.
2010-01-01
We describe our recent attempts toward statistical mechanics and thermodynamics for nonequilibrium steady states (NESS) realized, e.g., in a heat conducting system. Our first result is a simple expression of the probability distribution (of microscopic states) of a NESS. Our second result is a natural extension of the thermodynamic Clausius relation and a definition of an accompanying entropy in NESS. This entropy coincides with the normalization constant appearing in the above mentioned microscopic expression of NESS, and has an expression similar to the Shannon entropy (with a further symmetrization). The NESS entropy proposed here is a clearly defined measurable quantity even in a system with a large degrees of freedom. We numerically measure the NESS entropy in hardsphere fluid systems with a heat current, by observing energy exchange between the system and the heat baths when the temperatures of the baths are changed according to specified protocols.
The new thermodynamic relations of multi-horizons black holes
Xu, Wei; Meng, Xin-he
2014-01-01
We present some general entropy and temperature relations of multi-horizons, even of the "virtual" horizon. These relations are related to product, division and sum of entropy and temperature of multi-horizons. We obtain the additional thermodynamic relations for Schwarzschild-(A)dS black holes and Reissner-Nordstr{\\"o}m-(A)dS black holes, which are found to be held for both AdS and dS black holes. Besides, a new dimensionless, mass-independence and $T_+S_+=T_-S_-$ like relation is presented. It seems to be more universal and does not depend on the mass, electric charge and cosmological constant, as it is a constant in both Schwarzschild-(A)dS black holes and Reissner-Nordstr{\\"o}m-(A)dS black holes. This new relation can be expected to link entropy relations via thermodynamics law and Smarr relation of each horizons and be helpful of understanding microscopically the black hole entropy.
Svehla, R. A.; Mcbride, B. J.
1973-01-01
Program performs calculations such as chemical equilibrium for assigned thermodynamic states, theoretical rocket performance for both equilibrium and frozen compositions during expansion, incident and reflected shock properties, and Chapman-Jouget detonation properties. Features include simplicity of input and storage of all thermodynamic and transport property data on master tape.
Thermodynamics of Paint Related Systems with Engineering Models
Lindvig, Thomas; Michelsen, Michael Locht; Kontogeorgis, Georgios
2001-01-01
Paints are complex materials composed of polymers (binders) dissolved in one or more solvents, pigments, and other additives. The thermodynamics of such systems is essential, for example, for selecting improved solvents and understanding a number of phenomena related especially! to adhesion...... to solid surfaces and drying. Many engineering models have been applied over the last decades for solutions with commoditity polymers. In this work the performance of some of these models is investigated for paint-related systems, focusing on those drying by the so-called " lacquer mechanism " (evaporation...
Thermodynamic and transport properties of superconducting Mg10B2.
Finnemore, D K; Ostenson, J E; Bud'ko, S L; Lapertot, G; Canfield, P C
2001-03-12
Transport and thermodynamic properties of a sintered pellet of the newly discovered MgB2 superconductor have been measured to determine the characteristic critical magnetic fields and critical current densities. Both resistive transition and magnetization data give similar values of the upper critical field, Hc2, with magnetization data giving dHc2/dT = 0.44 T/K at the transition temperature of Tc = 40.2 K. Close to the transition temperature, magnetization curves are thermodynamically reversible, but at low temperatures the trapped flux can be on the order of 1 T. The value of dHc/dT at Tc is estimated to be about 12 mT/K, a value similar to classical superconductors like Sn. Hence, the Ginzburg-Landau parameter kappa approximately 26. Estimates of the critical supercurrent density, Jc, using hysteresis loops and the Bean model, give critical current densities on the order of 10(5) A/cm2. Hence the supercurrent coupling through the grain boundaries is comparable to intermetallics like Nb3Sn.
Molecular Structure, Theoretical Calculation and Thermodynamic Properties of Tebuconazole
MA Haixia; SONG Jirong; HUANG Ting; LU Xingqiang; XU Kangzhen; SUN Xiaohong
2009-01-01
Single crystals of 5-(4-chlorophenyl)-2,2-dimethyl-3-(1,2,4-triazol-1-ylmethyl)-pentom-3-ol (tebuconazole) were obtained in toluene. The single-crystal X-ray diffraction studies showed that it crystallized in the monoclinic system, with space group P2(1)/c and crystal parameters of a= 1.1645(1) nm, b= 1.6768(2) nm, c= 1.7478(2) nm,β=92.055(2)°, Dc= 1.199 g/cm3, Z=4 and F(000)= 1312. Density functional theory (DFT) B3LYP was employed to optimize the structure and calculate the frequencies of tebuconazole. The calculated geometrical parameters are close to the corresponding experimental ones. The specific heat capacity of the title compound was determined with continuous Cp mode of a mircocalorimeter. In the determining temperature range from 283 to 353 K, the special heat capacity of the title compound presents good linear relation with temperature. Using the determined relation-ship of Cp with temperature T, thermodynamic functions (enthalpy, entropy and Gibbs free energy) of the title compound between 283 and 353 K, relative to the standard temperature 298.15 K, were derived through thermody-namic relationship.
Note on electrical and thermodynamic properties of isolated horizons
Chen, Gerui; Wu, Xiaoning; Gao, Sijie
2015-03-01
The electrical laws and Carnot cycle of isolated horizons (IH) are investigated in this paper. We establish Ohm's law and Joule's law of isolated horizons and find that the conceptual picture of black holes (membrane paradigm) can also apply to this kind of quasilocal black holes. We also investigate the geometrical properties near nonrotating IHs and find that under the first-order approximation of r , there exist a Killing vector ∂∂u/ and a Hamiltonian conjugate to it, so this vector can be thought to be a physical observer. We calculate the energy as measured at infinity of a particle at rest outside a nonrotating IH, and we use this result to construct a reversible Carnot cycle with the isolated horizon as a cold reservoir, which confirms the thermodynamic nature of isolated horizons.
A note on electrical and thermodynamic properties of Isolated Horizon
Chen, Gerui; Gao, Sijie
2014-01-01
The electrical laws and Carnot cycle of Isolated Horizon (IH) are investigated in this paper. We establish the Ohm's law and Joule's law of an Isolated Horizon, and find that the conceptual picture of black holes (Membrane Paradigm) can also apply to this kind of quasi-local black holes. We also investigate the geometrical properties near a non-rotating IH, and find that under the first-order approximation of r, there exist a Killing vector and a Hamiltonian conjugate to it, so this vector is a physical observer. We calculate the energy as measured at infinity of a particle at rest outside a non-rotating IH, and use this result to construct a reversible Carnot cycle with the Isolated Horizon as a cold reservoir, which confirms the thermodynamic nature of Isolated Horizon.
Structural and thermodynamic properties of AlB2 compound
Zhou Xiao-Lin; Liu Ke; Chen Xiang-Rong; Zhu Jun
2006-01-01
We employ a first-principles plane wave method with the relativistic analytic pseudopotential of Hartwigsen,Goedecker and Hutter (HGH) scheme in the frame of DFT to calculate the equilibrium lattice parameters and the thermodynamic properties of AlB2 compound with hcp structure. The obtained lattice parameters are in good agreement with the available experimental data and those calculated by others. Through the quasi-harmonic Dcbye model, obtained successfully are the dependences of the normalized lattice parameters a/a0 and c/c0 on pressure P, the normalized primitive cell volume V/Vo on pressure P, the variation of the thermal expansion α with pressure P and temperature T, as well as the Debye temperature θD and the heat capacity CV on pressure P and temperature T.
Thermodynamic properties of rod-like chains: Entropic sampling simulations
Ferreira, L. S.; Jorge, L. N.; Caparica, A. A.; Nascimento, D. A.; Neto, Minos A.; Sousa, J. R.
2016-11-01
In this work, we apply entropic sampling simulations to a three-state model which has exact solutions in the microcanonical and grand-canonical ensembles. We consider N chains placed on an unidimensional lattice, such that each site may assume one of the three states: empty (state 1), with a single molecule energetically null (state 2), and with a single molecule with energy 𝜀 (state 3). Each molecule, which we will treat here as dimers, consists of two monomers connected one to each other by a rod. The thermodynamic properties such as internal energy, densities of dimers and specific heat were obtained as functions of temperature, where the analytic results in the microcanonical and grand-canonical ensembles were successfully confirmed by the entropic sampling simulations.
Electrical Resistivity and Thermodynamic Properties of Iron Under High Pressure
Hieu, Ho Khac; Hai, Tran Thi; Hong, Nguyen Thi; Sang, Ngo Dinh; Tuyen, Nguyen Viet
2017-03-01
In this work, the electrical resistivity and thermodynamic properties of iron under high pressure have been investigated by using the semi-empirical approach. The recently well-established Grüneisen parameter expressions have been applied to derive the Debye frequency and temperature under compression. Using these results combined with the Bloch-Grüneisen law, the resistivity of iron has also been determined up to Earth's core pressures. We show that the electrical resistivity diminished gradually with pressure and saturates at high pressure. Our model gives low electrical resistivity values which are in agreement with the recent experimental measurements. The low resistivity may be attributed to the well-known resistivity saturation effect at high temperature, which was not considered in earlier models of core conductivity.
Thermodynamic properties of lattice hard-sphere models.
Panagiotopoulos, A Z
2005-09-08
Thermodynamic properties of several lattice hard-sphere models were obtained from grand canonical histogram- reweighting Monte Carlo simulations. Sphere centers occupy positions on a simple cubic lattice of unit spacing and exclude neighboring sites up to a distance sigma. The nearestneighbor exclusion model, sigma = radical2, was previously found to have a second-order transition. Models with integer values of sigma = 1 or 2 do not have any transitions. Models with sigma = radical3 and sigma = 3 have weak first-order fluid-solid transitions while those with sigma = 2 radical2, 2 radical3, and 3 radical2 have strong fluid-solid transitions. Pressure, chemical potential, and density are reported for all models and compared to the results for the continuum, theoretical predictions, and prior simulations when available.
Thermodynamic property of gases in the sonoluminescing bubble
AN Yu; LI Guiqin; ZHOU Tieying
2001-01-01
With the theory of statistical physics dealing with chemical reaction (the law of mass action), the different thermodynamic property of noble gases (mono-atomic gases) in a small bubble and diatomic gases in a small bubble semi-quantitatively are analyzed. As bubbles of the mono-atomic and the diatomic gases are compressed, shock waves are produced in both bubbles. Though shock wave leads to sharp increase of pressure and temperature of gases in the bubble, diatomic gas will excitated vibrations and dissociate themselves to mono-atomic gas,these processes will consume many accumulated heat energy and block the further increase of the temperature. Therefore, compare with the mono-atomic gases in the bubble, there will be no enough charged particles ionized to flash for diatomic gases in the bubble, this may be the reason why a bubble of diatomic gases has no single bubble sonoluminescence while a bubble of noble gases has.
Thermodynamic properties for polycyclic systems by non-calorimetric methods
Steele, W.V.; Chirico, R.D.; Klots, T.D.
1993-03-01
A detailed vibrational spectroscopic study of furan, pyrrole, and thiophene has been completed. These compounds form part of the base of five-membered ring systems on which the rest of the research program will be built Several methyl-substituted derivatives were also studied. The results will be used to confirm the model for alkyl- substitution in the ring systems. Gas-phase spectra and fundamental- frequency assignments were completed for 2,3- and 2,5-dihydrofuran. Those compounds initiate work on ring-puckering within the research program. A paper describing the need for third virial estimation, when using the virial equation of state to derive thermodynamic properties at pressures greater than 1 bar was completed.
Molecular dynamics simulation of thermodynamic properties of YAG
Chen Jun; Chen Dong-Quan; Zhang Jing-Lin
2007-01-01
In this paper we study the thermodynamic properties of Y3Al5O12 (YAG) by using molecular dynamic method combined with two- and three-body potentials. The dependences of melting process, elastic constant and diffusion coefficient on temperature of crystal YAG are simulated and compared with the experimental results. Our results show that anion O has the biggest self-diffusivity and cation Y has the smallest self-diffusivity in a crystal YAG. The calculated diffusion activation energies of ions O, Al and Y are 282.55, 439.46, 469.71k J/mol, respectively. Comparing with experimental creep activation energy of YAG confirms that cation Y can restrict the diffusional creep rate of crystal YAG.
Thermodynamic properties of the magnetized Coulomb crystal lattices
Kozhberov, A. A.
2016-08-01
It is thought that Coulomb crystals of ions with hexagonal close-packed lattice may form in the crust of strongly-magnetized neutron stars (magnetars). In this work we are trying to verify this prediction assuming that the direction of the magnetic field corresponds to the minimum of the zero-point energy. We also continue a detailed study of vibration modes and thermodynamic properties of magnetized Coulomb crystals in a wide range of temperatures and magnetic fields. It is demonstrated that the total Helmholtz free energy of the body-centered cubic Coulomb crystal is always lower than that of the Coulomb crystal with hexagonal close-packed or face-centered cubic lattice, which casts doubt on the hypothesis above.
Contribution study of the thermodynamics properties of the ammonia-water mixtures
Kherris Sahraoui
2013-01-01
Full Text Available The full thermodynamic study of the absorption refrigeration units requires the knowledge of the thermodynamic properties of the used mixture. The present work deals with the mathematical modeling of the thermodynamic properties of ammonia-water mixtures using various models. The presented model covers high vapor-liquid equilibrium pressures up to 110 [bar] and temperatures from 230 to 600 [K]. Furthermore, the calculation of the thermodynamic properties of the ammonia-water mixtures and their pure components was carried out. The obtained results were compared with results given in the literature. This shows a good concordance.
Additional energy-information relations in thermodynamics of small systems
Uzdin, Raam
2017-09-01
The Clausius inequality form of the second law of thermodynamics relates information changes (entropy) to changes in the first moment of the energy (heat and indirectly also work). Are there similar relations between other moments of the energy distribution, and other information measures, or is the Clausius inequality a one of a kind instance of the energy-information paradigm? If there are additional relations, can they be used to make predictions on measurable quantities? Changes in the energy distribution beyond the first moment (average heat or work) are especially important in small systems which are often very far from thermal equilibrium. The additional energy-information relations (AEIR's), here derived, provide positive answers to the two questions above and add another layer to the fundamental connection between energy and information. To illustrate the utility of the new AEIR's, we find scenarios where the AEIR's yield tighter constraints on performance (e.g., in thermal machines) compared to the second law. To obtain the AEIR's we use the Bregman divergence—a mathematical tool found to be highly suitable for energy-information studies. The quantum version of the AEIR's provides a thermodynamic meaning to various quantum coherence measures. It is intriguing to fully map the regime of validity of the AEIR's and extend the present results to more general scenarios including continuous systems and particles exchange with the baths.
Thermodynamic Property Model of Wide-Fluid Phase Propane
I Made Astina
2007-05-01
Full Text Available A new thermodynamic property model for propane is expressed in form of the Helmholtz free energy function. It consists of eight terms of the ideal-gas part and eighteen terms of the residual part. Accurate experimental data of fluid properties and theoretical approach from the intermolecular potential were simultaneously considered in the development to insure accuracy and to improve reliability of the equation of state over wide range of pressures and temperatures. Based on the state range of experimental data used in the model development, the validity range is judged from the triple-point of 85.48 K to temperature of 450 K and pressure up to 60 MPa. The uncertainties with respect to different properties are estimated to be 0.03% in ideal-gas isobaric specific heat, 0.2% in liquid phase density, 0.3% in gaseous phase density 1% in specific heats, 0.1% in vapor-pressure except at very low temperatures, 0.05% in saturated-liquid density, 0.02% in speed of sound of the gaseous phase and 1% in speed of sound of the liquid phase.
Ion-specific thermodynamical properties of aqueous proteins
Eduardo R.A. Lima
2010-03-01
Full Text Available Ion-specific interactions between two colloidal particles are calculated using a modified Poisson-Boltzmann (PBequationandMonteCarlo(MCsimulations. PBequationspresentgoodresultsofionicconcentration profiles around a macroion, especially for salt solutions containing monovalent ions. These equations include not only electrostatic interactions, but also dispersion potentials originated from polarizabilities of ions and proteins. This enables us to predict ion-specific properties of colloidal systems. We compared results obtained from the modified PB equation with those from MC simulations and integral equations. Phase diagrams and osmotic second virial coefficients are also presented for different salt solutions at different pH and ionic strengths, in agreement with the experimental results observed Hofmeister effects. In order to include the water structure and hydration effect, we have used an effective interaction obtained from molecular dynamics of each ion and a hydrophobic surface combined with PB equation. The method has been proved to be efficient and suitable for describing phenomena where the water structure close to the interface plays an essential role. Important thermodynamic properties related to protein aggregation, essential in biotechnology and pharmaceutical industries, can be obtained from the method shown here.Interações íon-específicas (dependentes do tipo de íon presente em solução entre duas partículas coloidais são calculadas usando a equação de Poisson-Boltzmann (PB modificada e simulações de Monte Carlo (MC. As equações de PB apresentam bons resultados de perfis de concentração nas proximidades de um macro-íon, principalmente para soluções salinas contendo íons monovalentes. Estas equações incluem não só interações eletrostáticas, mas também potenciais de dispersão, que têm origem nas polarizabilidades de íons e proteínas, permitindo a predição de propriedades íon-específicas de
Ideal gas thermodynamic properties for the phenyl, phenoxy, and o-biphenyl radicals
Burcat, A.; Zeleznik, F. J.; Mcbride, B. J.
1985-01-01
Ideal gas thermodynamic properties of the phenyl and o-biphenyl radicals, their deuterated analogs and the phenoxy radical were calculated to 5000 K using estimated vibrational frequencies and structures. The ideal gas thermodynamic properties of benzene, biphenyl, their deuterated analogs and phenyl were also calculated.
Revisiting the thermodynamic relations in AdS /CMT models
Hyun, Seungjoon; Park, Sang-A.; Yi, Sang-Heon
2017-03-01
Motivated by the recent unified approach to the Smarr-like relation of anti-de Sitter (AdS) planar black holes in conjunction with the quasilocal formalism on conserved charges, we revisit the quantum statistical and thermodynamic relations of hairy AdS planar black holes. By extending the previous results, we identify the hairy contribution in the bulk and show that the holographic computation can be improved so that it is consistent with the bulk computation. We argue that the first law can be retained in its universal form and that the relation between the on-shell renormalized Euclidean action and its free energy interpretation in gravity may also be undeformed even with the hairy contribution in hairy AdS black holes.
1976-01-01
The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.
Thermodynamic response functions and Maxwell relations for a Kerr black hole
Escamilla, L
2015-01-01
Assuming the existence of a fundamental thermodynamic relation, the classical thermodynamics of a black hole with mass and angular momentum is given. New definitions of response functions and $TdS$ equations are introduced and mathematical analogous of the Euler equation and Gibbs-Duhem relation are founded. Thermodynamic stability is studied from concavity conditions, resulting in an unstable equilibrium at all the domain except for a region of local stable equilibrium. Maxwell relations are written, allowing to build the thermodynamic squares. Our results shown an interesting analogy between thermodynamics of gravitational and magnetic systems.
Thermodynamic properties of direct methanol polymer electrolyte fuel cell
Seong, Ji Yun; Bae, Young Chan [Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University, Sungdonggu Haengdangdong 17, Seoul 133-791 (Korea, Republic of); Sun, Yang Kook [Division of Chemical Engineering and Center for Information and Communication, Materials, Hanyang University, Seoul 133-791 (Korea, Republic of)
2005-08-18
A new semi-empirical model is established to describe the cell voltage of a direct methanol fuel cell (DMFC) as a function of current density. The model equation is validated experimental data over a wide range of a methanol concentration and temperatures. A number of existing models are semi-empirical. They, however, have a serious mathematical defect. When the current density, j, becomes zero, the equation should reduce to the open circuit voltage, E{sub 0}. These models, however, do not meet the mathematical boundary condition. The proposed model focuses on very unfavorable conditions for the cell operation, i.e. low methanol solution concentrations and relatively low cell temperatures. A newly developed semi-empirical equation with reasonable boundary conditions includes the methanol crossover effect that plays a major role in determining the cell voltage of DMFC. Also, it contains methanol activity based on thermodynamic functions to represent methanol crossover effect. (author)
ZHANG Jian
2005-01-01
Based on the coexistence theory of metallic melts involving compound formation,the theoretical cal culation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the associated solution model.For Fe-Al,Mn-Al and Ni-Al,the calculated results agree well with the experimental values,testifying that these equations can exactly embody mixing thermodynamic characteristics of these melts.
Koley, Ratna; Pal, Supratik; SenGupta, Soumitra
2009-01-01
Thermodynamic properties of Schwarzschild-Anti de-Sitter (Sch-AdS) and Reissner-Nordstr\\"om-Anti de-Sitter (RN-AdS) blackholes in 3+1 dimensional spacetime are studied critically with special reference to the warped braneworld black holes with non-vanishing cosmological constant on the brane. Explicit dependence of the thermodynamic variables on the parameters of the braneworld model such as the induced three brane cosmological constant as well as the bulk cosmological constant have been determined. Hawking-Page phase transition has been discussed for both Sch-AdS and RN-AdS black holes. At the phase transition point it is shown that the parameters mass, charge and cosmological constant get correlated by an inequality relation which originates from the background warped geometry model.
Thermodynamic Relations for Kiselev and Dilaton Black Hole
Bushra Majeed
2015-01-01
Full Text Available We investigate the thermodynamics and phase transition for Kiselev black hole and dilaton black hole. Specifically we consider Reissner-Nordström black hole surrounded by radiation and dust and Schwarzschild black hole surrounded by quintessence, as special cases of Kiselev solution. We have calculated the products relating the surface gravities, surface temperatures, Komar energies, areas, entropies, horizon radii, and the irreducible masses at the Cauchy and the event horizons. It is observed that the product of surface gravities, product of surface temperature, and product of Komar energies at the horizons are not universal quantities for the Kiselev solutions while products of areas and entropies at both the horizons are independent of mass of the above-mentioned black holes (except for Schwarzschild black hole surrounded by quintessence. For charged dilaton black hole, all the products vanish. The first law of thermodynamics is also verified for Kiselev solutions. Heat capacities are calculated and phase transitions are observed, under certain conditions.
On the thermodynamics of photon gas in Doubly Special Relativity
Faruk, Mir Mehedi
2016-01-01
A particular framework for quantum gravity is the doubly special relativity (DSR) formalism that introduces a new observer independent scale (the Planck scale). We resort to the methods of statistical mechanics in this framework to determine how the deformed dispersion relation effects the thermodynamics of a photon gas. The ensuing modifications to the density of states, partition function, pressure, internal energy, entropy, free energy and specific heat are calculated. These results are compared with the outcome obtained in the Lorentz violating model of Camacho and Murcias (Gen.Relativ.Gravit.39: 1175-1183, 2007). The two types of models predict different results due to different spacetime structure near the Planck scale. The resulting modifications can be interpreted as a consequence of the deformed Lorentz symmetry present in the particular model we have considered.
Chakraborty, Anutosh
2009-02-17
Thermodynamic property surfaces for a single-component adsorbent + adsorbate system are derived and developed from the viewpoint of classical thermodynamics, thermodynamic requirements of chemical equilibrium, Gibbs law, and Maxwell relations. They enable us to compute the entropy and enthalpy of the adsorbed phase, the isosteric heat of adsorption, specific heat capacity, and the adsorbed phase volume thoroughly. These equations are very simple and easy to handle for calculating the energetic performances of any adsorption system. We have shown here that the derived thermodynamic formulations fill up the information gap with respect to the state of adsorbed phase to dispel the confusion as to what is the actual state of the adsorbed phase. We have also discussed and established the temperature-entropy diagrams of (i) CaCl 2-in-silica gel + water system for cooling applications, and (ii) activated carbon (Maxsorb III) + methane system for gas storage. © Copyright 2009 American Chemical Society.
Tušek, Jaka; Engelbrecht, Kurt; Mañosa, Lluis; Vives, Eduard; Pryds, Nini
2016-12-01
This paper presents direct and indirect methods for studying the elastocaloric effect (eCE) in shape memory materials and its comparison. The eCE can be characterized by the adiabatic temperature change or the isothermal entropy change (both as a function of applied stress/strain). To get these quantities, the evaluation of the eCE can be done using either direct methods, where one measures (adiabatic) temperature changes or indirect methods where one can measure the stress-strain-temperature characteristics of the materials and from these deduce the adiabatic temperature and isothermal entropy changes. The former can be done using the basic thermodynamic relations, i.e. Maxwell relation and Clausius-Clapeyron equation. This paper further presents basic thermodynamic properties of shape memory materials, such as the adiabatic temperature change, isothermal entropy change and total entropy-temperature diagrams (all as a function of temperature and applied stress/strain) of two groups of materials (Ni-Ti and Cu-Zn-Al alloys) obtained using indirect methods through phenomenological modelling and Maxwell relation. In the last part of the paper, the basic definition of the efficiency of the elastocaloric thermodynamic cycle (coefficient of performance) is defined and discussed.
Critical, statistical, and thermodynamical properties of lattice models
Varma, Vipin Kerala
2013-10-15
In this thesis we investigate zero temperature and low temperature properties - critical, statistical and thermodynamical - of lattice models in the contexts of bosonic cold atom systems, magnetic materials, and non-interacting particles on various lattice geometries. We study quantum phase transitions in the Bose-Hubbard model with higher body interactions, as relevant for optical lattice experiments of strongly interacting bosons, in one and two dimensions; the universality of the Mott insulator to superfluid transition is found to remain unchanged for even large three body interaction strengths. A systematic renormalization procedure is formulated to fully re-sum these higher (three and four) body interactions into the two body terms. In the strongly repulsive limit, we analyse the zero and low temperature physics of interacting hard-core bosons on the kagome lattice at various fillings. Evidence for a disordered phase in the Ising limit of the model is presented; in the strong coupling limit, the transition between the valence bond solid and the superfluid is argued to be first order at the tip of the solid lobe.
Thermodynamic properties of water desorption of forage turnip seeds
Kelly Aparecida Sousa
2014-11-01
Full Text Available The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip seeds. The equilibrium moisture content of forage turnip seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within the moisture content range of 3.33 to 11.30 (% d.b., varies from 4,222.70 to 2,870.34 kJ kg-1. With the elevation in the equilibrium moisture content, there is an increase in differential entropy and Gibbs free energy, which has positive values, demonstrating non-spontaneity in the process of desorption in the seeds. The theory of enthalpy-entropy compensation can be satisfactorily applied to the sorption phenomenon, and the process of water desorption of forage turnip seeds is controlled by enthalpy.
Thermodynamic Properties of Non-Oxide Composite Refractories
HONG Yanruo; WU Hongpeng; SUN Jialin
2005-01-01
For initiative application of non-oxides in refractories, it is essential to study thermodynamic properties of non-oxides. The stability and stable order of non-oxides under oxidized atmosphere are analyzed firstly and then a new process, "converse reaction sintering", is proposed. The results of study on oxidation mechanism of silicon and aluminum nitrides indicate that the gaseous suboxides can be produced observably when the oxygen partial pressure is lower than "conversion oxygen partial pressure". The suboxides can be deposited near the surface of composite to become a compact layer. This causes the material possessing a performance of "self-impedient oxidation". Metal Si and Al are the better additives for increasing the density and width of compact layer and increasing the ability of anti-oxidation and anti-corrosion. The study on Si3N4-Al2O3, Si3N4-MgO, Si3N4-SiC systems is also enumerated as examples in the paper. The experimental results show that the converse reaction sintering is able to make high performance composites and metal Si and Al not only can promote the sintering but also increase the density and width of compact layer.
Black Hole Thermodynamics in Horava Lifshitz Gravity and the Related Geometry
biswas, Ritabrata; 10.1007/s10509-010-0504-x
2011-01-01
Recently, Ho$\\breve{r}$ava proposed a non-relativistic renormalizable theory of gravity which is essentially a field theoretic model for a UV complete theory of gravity and reduces to Einstein gravity with a non-vanishing cosmological constant in IR. Also the theory admits a Lifshitz scale-invariance in time and space with broken Lorentz symmetry at short scale. On the other hand, at large distances higher derivative terms do not contribute and the theory coincides with general relativity. Subsequently, Cai and his collaborators and then Catiuo et al have obtained black hole solutions in this gravity theory and studied the thermodynamic properties of the black hole solution. In the present paper, we have investigated the black hole thermodynamic for two choices of the entropy function - a classical and a topological in nature. Finally, it is examined whether a phase transition is possible or not.
Thermodynamic properties and phase equilibria of selected Heusler compounds
Yin, Ming
Heusler compounds are ternary intermetallics with many promising properties such as spin polarization and magnetic shape memory effect. A better understanding of their thermodynamic properties facilitates future design and development. Therefore, standard enthalpies of formation and heat capacities from room temperature to 1500 K of selected Heusler compounds X2YZ (X = Co, Fe, Ni, Pd, Rh, Ru; Y = Co, Cu, Fe, Hf, Mn, Ni, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) and half-Heusler compounds XYSn (X = Au, Co, Fe, Ir, Ni, Pd, Pt, Rh; Y = Hf, Mn, Ti, Zr) were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation were compared with those predicted from ab initio calculations and the extended semi-empirical Miedema's model. Trends in standard enthalpy of formation with respect to the periodic classification of elements were discussed. The effect of a fourth element (Co, Cu, Fe, Pd; Ti, V; Al, Ga, In, Si, Ge) on the standard enthalpy of formation of Ni2MnSn was also investigated. Lattice parameters of the compounds with an L21 structure were determined using X-ray powder diffraction analysis. Differential scanning calorimetry was used to determine melting points and phase transformation temperatures. Phase relationships were investigated using scanning electron microscopy with an energy dispersive spectrometer. The isothermal section of the Fe-Sn-Ti ternary system at 873 K was established using equilibrated alloys. Three ternary compounds including the Heusler compound Fe2SnTi were observed. A new ternary compound Fe5Sn9Ti 6 was reported and the crystal structure of FeSnTi2 was determined for the first time.
Comparison of thermodynamic properties of coarse-grained and atomic-level simulation models.
Baron, Riccardo; Trzesniak, Daniel; de Vries, Alex H; Elsener, Andreas; Marrink, Siewert J; van Gunsteren, Wilfred F
2007-02-19
Thermodynamic data are often used to calibrate or test amomic-level (AL) force fields for molecular dynamics (MD) simulations. In contrast, the majority of coarse-grained (CG) force fields do not rely extensively on thermodynamic quantities. Recently, a CG force field for lipids, hydrocarbons, ions, and water, in which approximately four non-hydrogen atoms are mapped onto one interaction site, has been proposed and applied to study various aspects of lipid systems. To date, no extensive investigation of its capability to describe salvation thermodynamics has been undertaken. In the present study, a detailed picture of vaporization, solvation, and phase-partitioning thermodynamics for liquid hydrocarbons and water was obtained at CG and AL resolutions, in order to compare the two types or models and evaluate their ability to describe thermodynamic properties in the temperature range between 263 and 343 K. Both CG and AL models capture the experimental dependence of the thermodynamic properties on the temperature, albeit a systematically weaker dependence is found for the CG model. Moreover, deviations are found for solvation thermodynamics and for the corresponding enthalpy-entropy compensation for the CG model. Particularly water/oil repulsion seems to be overestimated. However, the results suggest that the thermodynamic properties considered should be reproducible by a CG model provided it is reparametrized on the basis of these liquid-phase properties.
Svehla, R. A.; Mcbride, B. J.
1973-01-01
A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.
Hao Ai-Min; Zhou Tie-Jun; Zhu Yan; Zhang Xin-Yu; Liu Ri-Ping
2011-01-01
An investigation of the electronic, elastic and thermodynamic properties of VC under high pressure has been conducted using first-principles calculations based on density functional theory (DFT)with the plane-wave basis set,as implemented in the CASTEP code. At elevated pressures, VC is predicted to undergo a structural transition from a relatively open NaCl-type structure to a more dense CsCl-type one. The predicted transition pressure is 520 GPa.The elastic constant, Debye temperature and heat capacity each as a function of pressure and/or temperature of VC are presented for the first time.
Thermodynamical properties of QED in 1+1 dimensions within light front dynamics
Strauss, S
2008-01-01
We investigate thermodynamical properties of quantum electrodynamics in 1+1 dimensions. Discrete light cone quantization is used to compute the partition function of the canonical ensemble and the thermodynamical potential. The potential is evaluated for different system sizes and coupling strengths. We perform the continuum limit and the thermodynamical limit and present basic thermodynamical quantities as a function of temperature for the interacting system. A more accurate estimation of low lying bound state masses at non-perturbative coupling strength are determined due to the higher harmonic resolution.The results are compared to the idealized cases. The results are compared to the idealized cases.
Experimental thermodynamics experimental thermodynamics of non-reacting fluids
Neindre, B Le
2013-01-01
Experimental Thermodynamics, Volume II: Experimental Thermodynamics of Non-reacting Fluids focuses on experimental methods and procedures in the study of thermophysical properties of fluids. The selection first offers information on methods used in measuring thermodynamic properties and tests, including physical quantities and symbols for physical quantities, thermodynamic definitions, and definition of activities and related quantities. The text also describes reference materials for thermometric fixed points, temperature measurement under pressures, and pressure measurements. The publicatio
Mkanya, Anele; Pellicane, Giuseppe; Pini, Davide; Caccamo, Carlo
2017-09-01
We report extensive calculations, based on the modified hypernetted chain (MHNC) theory, on the hierarchical reference theory (HRT), and on Monte Carlo simulations, of thermodynamical, structural and phase coexistence properties of symmetric binary hard-core Yukawa mixtures (HCYM) with attractive interactions at equal species concentration. The obtained results are throughout compared with those available in the literature for the same systems. It turns out that the MHNC predictions for thermodynamic and structural quantities are quite accurate in comparison with the MC data. The HRT is equally accurate for thermodynamics, and slightly less accurate for structure. Liquid-vapor (LV) and liquid-liquid (LL) consolute coexistence conditions as emerging from simulations, are also highly satisfactorily reproduced by both the MHNC and HRT for relatively long ranged potentials. When the potential range reduces, the MHNC faces problems in determining the LV binodal line; however, the LL consolute line and the critical end point (CEP) temperature and density turn out to be still satisfactorily predicted within this theory. The HRT also predicts with good accuracy the CEP position. The possibility of employing liquid state theories HCYM for the purpose of reliably determining phase equilibria in multicomponent colloidal fluids of current technological interest, is discussed.
Study of Thermodynamic Properties of Nonstoichiometric Phase with Compound Energy Model
无
2002-01-01
Using compound energy model (CEM), the thermodynamic properties of and were evaluated.The evaluation was based on the optimization of ZrO2-CeO2 and ZrO2-CeO1.5 systems, as well as the miscibility gap inCeO1.5-CeO2 system. Except the cubic fluorite structure phase assessed with compound energy model, all the other solutionphases were assessed with subsitutional solution model. The model parameters were evaluated through fitting the selectedexperimental data by means of thermodynamic optimization. A set of parameters with thermodynamics self-consistency wasobtained and satisfactorily described the complex relation between y in and the partial pressure of oxygen atdifferent temperatures, also the interdependence among miscellaneous factors such as temperature, oxygen partial pressure,seem to be reasonable when put into the explanation of pressureless sintering of CeO2-stabilized ZrO2 powder compacts at acontrolled oxygen partial pressure.
Emergence of equilibrium thermodynamic properties in quantum pure states. I. Theory.
Fresch, Barbara; Moro, Giorgio J
2010-07-21
Investigation on foundational aspects of quantum statistical mechanics recently entered a renaissance period due to novel intuitions from quantum information theory and to increasing attention on the dynamical aspects of single quantum systems. In the present contribution a simple but effective theoretical framework is introduced to clarify the connections between a purely mechanical description and the thermodynamic characterization of the equilibrium state of an isolated quantum system. A salient feature of our approach is the very transparent distinction between the statistical aspects and the dynamical aspects in the description of isolated quantum systems. Like in the classical statistical mechanics, the equilibrium distribution of any property is identified on the basis of the time evolution of the considered system. As a consequence equilibrium properties of quantum system appear to depend on the details of the initial state due to the abundance of constants of the motion in the Schrodinger dynamics. On the other hand the study of the probability distributions of some functions, such as the entropy or the equilibrium state of a subsystem, in statistical ensembles of pure states reveals the crucial role of typicality as the bridge between macroscopic thermodynamics and microscopic quantum dynamics. We shall consider two particular ensembles: the random pure state ensemble and the fixed expectation energy ensemble. The relation between the introduced ensembles, the properties of a given isolated system, and the standard quantum statistical description are discussed throughout the presentation. Finally we point out the conditions which should be satisfied by an ensemble in order to get meaningful thermodynamical characterization of an isolated quantum system.
Dorofeeva, O. V.; Ryzhova, O. N.; Moiseeva, N. F.
2008-06-01
The enthalpies of formation, entropies, and heat capacities of 95 organophosphorus derivatives calculated by nonempirical quantum-chemical methods were used to develop the additive method for estimating the thermodynamic properties of these compounds. 86 group contribution values were obtained for estimating the thermodynamic properties of diverse organic derivatives of phosphorus in the oxidation states 3 and 5 (three-and four-coordinate phosphorus atoms).
Moustafa, Sabry Gad Al-Hak Mohammad
Molecular simulation (MS) methods (e.g. Monte Carlo (MC) and molecular dynamics (MD)) provide a reliable tool (especially at extreme conditions) to measure solid properties. However, measuring them accurately and efficiently (smallest uncertainty for a given time) using MS can be a big challenge especially with ab initio-type models. In addition, comparing with experimental results through extrapolating properties from finite size to the thermodynamic limit can be a critical obstacle. We first estimate the free energy (FE) of crystalline system of simple discontinuous potential, hard-spheres (HS), at its melting condition. Several approaches are explored to determine the most efficient route. The comparison study shows a considerable improvement in efficiency over the standard MS methods that are known for solid phases. In addition, we were able to accurately extrapolate to the thermodynamic limit using relatively small system sizes. Although the method is applied to HS model, it is readily extended to more complex hard-body potentials, such as hard tetrahedra. The harmonic approximation of the potential energy surface is usually an accurate model (especially at low temperature and large density) to describe many realistic solid phases. In addition, since the analysis is done numerically the method is relatively cheap. Here, we apply lattice dynamics (LD) techniques to get the FE of clathrate hydrates structures. Rigid-bonds model is assumed to describe water molecules; this, however, requires additional orientation degree-of-freedom in order to specify each molecule. However, we were able to efficiently avoid using those degrees of freedom through a mathematical transformation that only uses the atomic coordinates of water molecules. In addition, the proton-disorder nature of hydrate water networks adds extra complexity to the problem, especially when extrapolating to the thermodynamic limit is needed. The finite-size effects of the proton disorder contribution is
Predictions of titanium alloy properties using thermodynamic modeling tools
Zhang, F.; Xie, F.-Y.; Chen, S.-L.; Chang, Y. A.; Furrer, D.; Venkatesh, V.
2005-12-01
Thermodynamic modeling tools have become essential in understanding the effect of alloy chemistry on the final microstructure of a material. Implementation of such tools to improve titanium processing via parameter optimization has resulted in significant cost savings through the elimination of shop/laboratory trials and tests. In this study, a thermodynamic modeling tool developed at CompuTherm, LLC, is being used to predict β transus, phase proportions, phase chemistries, partitioning coefficients, and phase boundaries of multicomponent titanium alloys. This modeling tool includes Pandat, software for multicomponent phase equilibrium calculations, and PanTitanium, a thermodynamic database for titanium alloys. Model predictions are compared with experimental results for one α-β alloy (Ti-64) and two near-β alloys (Ti-17 and Ti-10-2-3). The alloying elements, especially the interstitial elements O, N, H, and C, have been shown to have a significant effect on the β transus temperature, and are discussed in more detail herein.
A test of systematic coarse-graining of molecular dynamics simulations: thermodynamic properties.
Fu, Chia-Chun; Kulkarni, Pandurang M; Shell, M Scott; Leal, L Gary
2012-10-28
Coarse-graining (CG) techniques have recently attracted great interest for providing descriptions at a mesoscopic level of resolution that preserve fluid thermodynamic and transport behaviors with a reduced number of degrees of freedom and hence less computational effort. One fundamental question arises: how well and to what extent can a "bottom-up" developed mesoscale model recover the physical properties of a molecular scale system? To answer this question, we explore systematically the properties of a CG model that is developed to represent an intermediate mesoscale model between the atomistic and continuum scales. This CG model aims to reduce the computational cost relative to a full atomistic simulation, and we assess to what extent it is possible to preserve both the thermodynamic and transport properties of an underlying reference all-atom Lennard-Jones (LJ) system. In this paper, only the thermodynamic properties are considered in detail. The transport properties will be examined in subsequent work. To coarse-grain, we first use the iterative Boltzmann inversion (IBI) to determine a CG potential for a (1-φ)N mesoscale particle system, where φ is the degree of coarse-graining, so as to reproduce the radial distribution function (RDF) of an N atomic particle system. Even though the uniqueness theorem guarantees a one to one relationship between the RDF and an effective pairwise potential, we find that RDFs are insensitive to the long-range part of the IBI-determined potentials, which provides some significant flexibility in further matching other properties. We then propose a reformulation of IBI as a robust minimization procedure that enables simultaneous matching of the RDF and the fluid pressure. We find that this new method mainly changes the attractive tail region of the CG potentials, and it improves the isothermal compressibility relative to pure IBI. We also find that there are optimal interaction cutoff lengths for the CG system, as a function of
Thermodynamic properties of a quasi-harmonic model for ferroelectric transitions
Mkam Tchouobiap, S E [Laboratory of Research on Advanced Materials and Nonlinear Sciences (LaRAMaNS), Department of Physics, Faculty of Science, University of Buea, PO Box 63, Buea (Cameroon); Mashiyama, H, E-mail: esmkam@yahoo.com [Department of Physics, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512 (Japan)
2011-03-30
Within a framework of a quasi-harmonic model for quantum particles in a local potential of the double Morse type and within the mean-field approximation for interactions between particles, we investigate the thermodynamic properties of ferroelectric materials. A quantum thermodynamic treatment gives analytic expressions for the internal energy, the entropy, the specific heat, and the static susceptibility. The calculated thermodynamic characteristics are studied as a function of temperature and energy barrier, where it is shown that at the proper choice of the theory parameters, particularly the energy barrier, the model system exhibits characteristic features of either second-order tricritical or first-order phase transitions. Our results indicate that the barrier energy seems to be an important criterion for the character of the structural phase transition. The influence of quantum fluctuations manifested on zero-point energy on the phase transition and thermodynamic properties is analyzed and discussed. This leads to several quantum effects, including the existence of a saturation regime at low temperatures, where the order parameter saturates giving thermodynamic saturation of the calculated thermodynamic quantities. It is found that both quantum effects and energy barrier magnitude have an important influence on the thermodynamic properties of the ferroelectric materials and on driving the phase transition at low temperatures. Also, the analytical parameters' effect on the transition temperature is discussed, which seems to give a general insight into the structural phase transition and its nature.
Symmetry, Optical Properties and Thermodynamics of Neptunium(V) Complexes
Rao, Linfeng; Tian, Guoxin
2009-12-21
Recent results on the optical absorption and symmetry of the Np(V) complexes with dicarboxylate and diamide ligands are reviewed. The importance of recognizing the 'silent' feature of centrosymmetric Np(V) species in analyzing the absorption spectra and calculating the thermodynamic constants of Np(V) complexes is emphasized.
Symmetry, Optical Properties and Thermodynamics of Neptunium(V Complexes
Linfeng Rao
2009-12-01
Full Text Available Recent results on the optical absorption and symmetry of the Np(V complexes with dicarboxylate and diamide ligands are reviewed. The importance of recognizing the “silent” feature of centrosymmetric Np(V species in analyzing the absorption spectra and calculating the thermodynamic constants of Np(V complexes is emphasized.
On solutions of loop quantum cosmology and their thermodynamics properties
Sadjadi, H Mohseni
2012-01-01
Loop quantum cosmology is considered in inflationary era. A slow rolling scalar field solution with power law potential is presented in the neighborhood of transition time, i.e. when the universe enters inflationary phase from super-inflation era. The second and the generalized second laws of thermodynamics and their validities and violations are discussed and elucidated through some examples.
Electronic, thermodynamic and elastic properties of pyrite RuO_2
Yang Ze-Jin; Guo Yun-Dong; Wang Guang-Chang; Li Jin; Dai Wei; Liu Jin-Chao; Cheng Xin-Lu; Yang Xiang-Dong
2009-01-01
This paper calculates the elastic, thermodynamic and electronic properties of pyrite (Pa3) RuO_2 by the plane-wave pseudopotential density functional theory (DFT) method. The lattice parameters, normalized elastic constants, Cauchy pressure, brittle-ductile relations, heat capacity and Debye temperature are successfully obtained. The Murnaghan equation of state shows that pyrite RuO_2 is a potential superhard material. Internal coordinate parameter increases with pressure, which disagrees with experimental data. An analysis based on electronic structure and the pseudogap reveals that the bonding nature in RuO_2 is a combination of covalent, ionic and metallic bonding. A study of the elastic properties indicates that the pyrite phase is isotropic under usual conditions. The relationship between brittleness and ductility shows that pyrite RuO_2 behaves in a ductile matter at zero pressure and the degree of ductility increases with pressure.
Thermodynamic and Kinetic Properties of Shocks in Two-Dimensional Yukawa Systems
Marciante, M.; Murillo, M. S.
2017-01-01
Particle-level simulations of shocked plasmas are carried out to examine kinetic properties not captured by hydrodynamic models. In particular, molecular dynamics simulations of 2D Yukawa plasmas with variable couplings and screening lengths are used to examine shock features unique to plasmas, including the presence of dispersive shock structures for weak shocks. A phase-space analysis reveals several kinetic properties, including anisotropic velocity distributions, non-Maxwellian tails, and the presence of fast particles ahead of the shock, even for moderately low Mach numbers. We also examine the thermodynamics (Rankine-Hugoniot relations) of recent experiments [Phys. Rev. Lett. 111, 015002 (2013), 10.1103/PhysRevLett.111.015002] and find no anomalies in their equations of state.
Study of structural, elastic, electronic and thermodynamic properties of NaAlO{sub 3}-perovskite
Bouafia, H. [Laboratoire de Microscope Electronique et Sciences des Materiaux, departement de physique, USTO, BP1505 El m' naouar, Oran (Algeria); Sahli, B. [Laboratoire de Genie Physique, Universite Ibn-Khaldoun, Tiaret 14000 (Algeria); Hiadsi, S. [Laboratoire de Microscope Electronique et Sciences des Materiaux, departement de physique, USTO, BP1505 El m' naouar, Oran (Algeria); Abidri, B., E-mail: b_abidri@hotmail.com [Laboratoire des Materiaux Magnetiques, Universite Djillali Liabes, Sidi Bel-Abbes 22000 (Algeria); Rached, D. [Laboratoire des Materiaux Magnetiques, Universite Djillali Liabes, Sidi Bel-Abbes 22000 (Algeria); Amrani, B. [Departement de Physique, Universite d' Oran es-senia (Algeria)
2012-06-15
The structural, elastic, electronic, and thermodynamic properties of the cubic NaAlO{sub 3}-perovskite are calculated using the full potential linearized augmented plane wave with local orbital (FP-LAPW)+lo. The exchange-correlation energy, is treated in generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) parameterization. The calculated equilibrium parameter is in good agreement with other works. The bulk modulus, elastic constants and their related parameters, such as Young modulus, shear modulus, and Poisson ratio were predicted. The electronic band structure of this compound has been calculated using the Angel-Vosko (EV) generalized gradient approximation (GGA) for the exchange correlation potential. We deduced that NaAlO{sub 3}-perovskite exhibit a wide-gap which it is an indirect from R to {Gamma} point. The analysis of the density of states (DOS) curves shows ionic and covalent character bond for Al-O and Na-O respectively. To complete the fundamental characterization of NaAlO{sub 3} material we have analyzed the thermodynamic properties using the quasi-harmonic Debye model.
Thermodynamic properties of nuclear matter with three-body forces
Somà, V.; Bożek, P.
2009-08-01
We calculate thermodynamic quantities in symmetric nuclear matter within the self-consistent Green's functions method including three-body forces. The thermodynamic potential is computed directly from a diagrammatic expansion, implemented with the CD-Bonn and Nijmegen nucleon-nucleon potentials and the Urbana three-body forces. We present results for entropy and pressure up to temperatures of 20 MeV and densities of 0.32fm-3. While the pressure is sensitive to the inclusion of three-body forces, the entropy is not. The unstable spinodal region is identified and the critical temperature associated to the liquid-gas phase transition is determined. When three-body forces are added we find a strong reduction of the critical temperature, obtaining Tc≃12MeV.
Thermodynamic properties of nuclear matter with three-body forces
Soma, V
2009-01-01
We calculate thermodynamic quantities in symmetric nuclear matter within the self-consistent Green's functions method including three-body forces. The thermodynamic potential is computed directly from a diagrammatic expansion, implemented with the CD-Bonn and Nijmegen nucleon-nucleon potentials and the Urbana three-body forces. We present results for entropy and pressure up to temperatures of 20 MeV and densities of 0.32 fm^-3. While the pressure is sensitive to the inclusion of three-body forces, the entropy is not. The unstable spinodal region is identified and the critical temperature associated to the liquid-gas phase transition is determined. When three-body forces are added we find a strong reduction of the critical temperature, obtaining T_c ~ 12 MeV.
Thermodynamic properties of vitamin B{sub 2}
Knyazev, A.V., E-mail: knyazevav@gmail.com; Letyanina, I.A.; Plesovskikh, A.S.; Smirnova, N.N.; Knyazeva, S.S.
2014-01-10
Graphical abstract: - Highlights: • Temperature dependence of heat capacity of vitamin B{sub 2} has been measured by precision adiabatic vacuum calorimetry. • The thermodynamic functions of the vitamin B{sub 2} have been determined for the range from T → 0 to 322 K. • The energy of combustion of the riboflavin has been measured at 298.15 K. • The enthalpy of combustion Δ{sub c}H° and the thermodynamic parameters Δ{sub f}H°, Δ{sub f}S°, Δ{sub f}G° have been calculated. - Abstract: In the present work temperature dependence of heat capacity of vitamin B{sub 2} (riboflavin) has been measured for the first time in the range from 6 to 322 K by precision adiabatic vacuum calorimetry. Based on the experimental data, the thermodynamic functions of the vitamin B{sub 2}, namely, the heat capacity, enthalpy H°(T) − H°(0), entropy S°(T) − S°(0) and Gibbs function G°(T) − H°(0) have been determined for the range from T → 0 to 322 K. The value of the fractal dimension D in the function of multifractal generalization of Debye's theory of the heat capacity of solids was estimated and the character of heterodynamics of structure was detected. In a calorimeter with a static bomb and an isothermal shield, the energy of combustion of the riboflavin has been measured at 298.15 K. The enthalpy of combustion Δ{sub c}H° and the thermodynamic parameters Δ{sub f}H°, Δ{sub f}S°, Δ{sub f}G° and of reaction of formation of the riboflavin from simple substances at T = 298.15 K and p = 0.1 MPa have been calculated.
Abdel-Naby, Mohamed A; Fouad, Ahmed A; El-Refai, H A
2015-05-01
Cyclodextrin glycosyltransferase (CGTase) was covalently coupled to five oxidized polysaccharides differing in structure and chemical nature. The conjugates were evaluated for the retained activity, kinetic and thermodynamic stability. The conjugated CGTase with oxidized dextran (MW 47000) had the highest retained specific activity (70.05%) and the highest half-life (T1/2) at 80°C. Compared to the native enzyme, the conjugated preparation exhibited higher optimum temperature, lower activation energy (Ea), lower deactivation constant rate (kd), higher T1/2, and higher D values (decimal reduction time) within the temperature range of 60-80°C. The values of thermodynamic parameters for irreversible inactivation of native and conjugated CGTase indicated that conjugation significantly decreased entropy (ΔS*) and enthalpy of deactivation (ΔH*). The results of thermodynamic analysis for cyclodextrin production from starch indicated that The enthalpy of activation (ΔH*) and free energy of activation (ΔG*), (free energy of transition state) ΔG*E-T and (free energy of substrate binding) ΔG*E-S values were lower for the conjugated CGTase. Similarly, there was significant impact on improvement of kcat, kcat/Km values. Both native and conjugated enzyme produce α-cyclodextrin from starch.
Calculation of the thermodynamic properties of liquid Ag–In–Sb alloys
DRAGANA ZIVKOVIC
2006-03-01
Full Text Available The results of calculations of the thermodynamic properties of liquid Ag–In–Sb alloys are presented in this paper. The Redlich–Kister–Muggianu model was used for the calculations. Based on known thermodynamic data for constitutive binary systems and available experimental data for the investigated ternary system, the ternary interaction parameter for the liquid phase in the temperature range 1000–1200 K was determined. Comparison between experimental and calculated results showed their good mutual agreement.
Relativistic thermodynamic properties of a weakly interacting Fermi gas in a weak magnetic field
Men Fu-Dian; Liu Hui; Fan Zhao-Lan; Zhu Hou-Yu
2009-01-01
This paper derives the analytical expression of free energy for a weakly interacting Fermi gas in a weak magnetic field, by using the methods of quantum statistics as well as considering the relativistic effect. Based on the derived expression, the thermodynamic properties of the system at both high and low temperatures are given and the relativistic effect on the properties of the system is discussed. It shows that, in comparison with a nonrelativistic situation,the relativistic effect changes the influence of temperature on the thermodynamic properties of the system at high temperatures, and changes the influence of particle-number density on them at extremely low temperature. But the relativistic effect does not change the influence of the magnetic field and inter-particle interactions on the thermodynamic properties of the system at both high and extremely low temperatures.
Xiang, Hong Wei
2005-01-01
The corresponding-states principle helps the understanding and calculating of thermodynamic, transport, and surface properties of substances in various states, required by our modern lifestyle. The Corresponding-States Principle and its Practice: Thermodynamic, Transport and Surface Properties of Fluids describes the origins and applications of the principle from a universal point of view with comparisons to experimental data where possible. It uses the universal theory to explain present theories. Emphasis is on the properties of pure systems, and the corresponding-states theory can also be e
Thermodynamic properties and phase stability of nanocrystalline metals
SONG Xiaoyan; LI Lingmei; ZHANG Jiuxing
2006-01-01
The fundamental thermodynamic functions of enthalpy, entropy, and Gibbs free energy, as functions of the excess free volume at interfaces, temperature, and grain size, have been derived for single-phase metal nanocrystals. The model was applied to predict the thermal features of nano-grain boundaries and the characteristics of phase transformation in nanocrystalline metals, such as the transformation temperature and the critical grain size for phase transformation at a given temperature. The model predictions have been verified by experimental studies on the β-Co (→) α-Co phase transformation in nanocrystalline Co prepared by ball milling.
Relation between the psychological and thermodynamic arrows of time
Mlodinow, Leonard; Brun, Todd A.
2014-05-01
In this paper we lay out an argument that generically the psychological arrow of time should align with the thermodynamic arrow of time where that arrow is well defined. This argument applies to any physical system that can act as a memory, in the sense of preserving a record of the state of some other system. This result follows from two principles: the robustness of the thermodynamic arrow of time to small perturbations in the state, and the principle that a memory should not have to be fine-tuned to match the state of the system being recorded. This argument applies even if the memory system itself is completely reversible and nondissipative. We make the argument with a paradigmatic system, and then formulate it more broadly for any system that can be considered a memory. We illustrate these principles for a few other example systems and compare our criteria to earlier treatments of this problem.
High-precision thermodynamic and critical properties from tensor renormalization-group flows.
Hinczewski, Michael; Berker, A Nihat
2008-01-01
The recently developed tensor renormalization-group (TRG) method provides a highly precise technique for deriving thermodynamic and critical properties of lattice Hamiltonians. The TRG is a local coarse-graining transformation, with the elements of the tensor at each lattice site playing the part of the interactions that undergo the renormalization-group flows. These tensor flows are directly related to the phase diagram structure of the infinite system, with each phase flowing to a distinct surface of fixed points. Fixed-point analysis and summation along the flows give the critical exponents, as well as thermodynamic functions along the entire temperature range. Thus, for the ferromagnetic triangular lattice Ising model, the free energy is calculated to better than 10(-5) along the entire temperature range. Unlike previous position-space renormalization-group methods, the truncation (of the tensor index range D) in this general method converges under straightforward and systematic improvements. Our best results are easily obtained with D=24, corresponding to 4624-dimensional renormalization-group flows.
High-Precision Thermodynamic and Critical Properties from Tensor Renormalization-Group Flows
Hinczewski, Michael; Berker, A. Nihat
2008-03-01
The recently developed tensor renormalization-group (TRG) method [1] provides a highly precise technique for deriving thermodynamic and critical properties of lattice Hamiltonians. The TRG is a local coarse-graining transformation, with the elements of the tensor at each lattice site playing the part of the interactions that undergo the renormalization-group flows. These tensor flows are directly related [2] to the phase diagram structure of the infinite system, with each phase flowing to a distinct surface of fixed points. Fixed-point analysis and summation along the flows give the critical exponents, as well as thermodynamic functions along the entire temperature range. Thus, for the ferromagnetic triangular lattice Ising model, the free energy is calculated to better than 10-5 along the entire temperature range. Unlike previous position-space renormalization-group methods, the truncation (of the tensor index range D) in this general method converges under straightforward and systematic improvements. Our best results are easily obtained with D=24, corresponding to 4624-dimensional renormalization-group flows. [1] M. Levin and C.P. Nave, Phys. Rev. Lett. 99, 120601 (2007). [2] M. Hinczewski and A.N. Berker, arXiv:0709.2803v1 [cond-mat.stat-mech], Phys. Rev. E, in press.
Xiao-Lin, Zhang; Yuan-Yuan, Wu; Xiao-Hong, Shao; Yong, Lu; Ping, Zhang
2016-05-01
The high pressure behaviors of Th4H15 and ThH2 are investigated by using the first-principles calculations based on the density functional theory (DFT). From the energy-volume relations, the bct phase of ThH2 is more stable than the fcc phase at ambient conditions. At high pressure, the bct ThH2 and bcc Th4H15 phases are more brittle than they are at ambient pressure from the calculated elastic constants and the Poisson ratio. The thermodynamic stability of the bct phase ThH2 is determined from the calculated phonon dispersion. In the pressure domain of interest, the phonon dispersions of bcc Th4H15 and bct ThH2 are positive, indicating the dynamical stability of these two phases, while the fcc ThH2 is unstable. The thermodynamic properties including the lattice vibration energy, entropy, and specific heat are predicted for these stable phases. The vibrational free energy decreases with the increase of the temperature, and the entropy and the heat capacity are proportional to the temperature and inversely proportional to the pressure. As the pressure increases, the resistance to the external pressure is strengthened for Th4H15 and ThH2. Project supported by the Long-Term Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of China.
Naden, Levi N
2015-01-01
We show how thermodynamic properties of molecular models can be computed over a large, multidimensional parameter space by combining multistate reweighting analysis with a linear basis function approach. This approach reduces the computational cost to estimate thermodynamic properties from molecular simulations for over 130,000 tested parameter combinations from over a thousand CPU years to tens of CPU days. This speed increase is achieved primarily by computing the potential energy as a linear combination of basis functions, computed from either modified simulation code or as the difference of energy between two reference states, which can be done without any simulation code modification. The thermodynamic properties are then estimated with the Multistate Bennett Acceptance Ratio (MBAR) as a function of multiple model parameters without the need to define a priori how the states are connected by a pathway. Instead, we adaptively sample a set of points in parameter space to create mutual configuration space o...
Correlating compressor and turbine costs with thermodynamic properties for CAES power plants
Vadasz, P.; Weiner, D.
1987-11-01
Compressed air energy storage (CAES) is a technology that converts excess base load energy into stored pneumatic energy by means of a compressor for a later release through a turbine as premium peaking power. The CAES system consists of a modified gas turbine combined with an underground storage reservoir. Since 1978, such a power plant has operated successfully in Huntorf, West Germany. Others are in construction throughout the world, the largest being constructed in Donbas, Soviet Union (1050 MW). CAES is more economic with respect to other energy storage facilities due to its relatively low installation cost, short construction time, and high reliability. However, since the number of CAES plants all over the world is still small, it is essential for plant planning and optimization to evaluate normative functions for the turbine and compressor cost. The components costs are evaluated from their thermodynamic and turbo-aerodynamic properties, enabling evaluation of the optimal plant parameters.
CHENG Yan; TU Ya-Jing; ZENG Zhao-Yi; GOU Qing-Quan
2008-01-01
Shell model molecular dynamic simulation with interatomic pair potential is utilized to investigate the elastic and thermodynamic properties of gallium nitride with hexagonal wurtzite structure (w-GaN) at high pressure. The calculated elastic constants Cij at zero pressure and 300 K agree well with the experimental data and other calculated values. Meanwhile, the dependences of the relative volume V/Vo, elastic constants Cij, entropy S, enthalpy H, and heat capacities Cv and Cp on pressure are successfully obtained. From the elastic constants obtained, we also calculate the shear modulus G, bulk modulus B, Young's modulus E, Poisson's ratio v, Debye temperature ΘD, and shear anisotropic factor Ashear on pressures.
First-principles calculations for transition phase and thermodynamic properties of GaAs
Lu Lai-Yu; Chen Xiang-Rong; Yu Bai-Ru; Gou Qing-Quan
2006-01-01
The transition phase of GaAs from the zincblende (ZB) structure to the rocksalt (RS) structure is investigated by ab initio plane-wave pseudopotential density functional theory method,and the thermodynamic properties of the ZB and RS structures are obtained through the quasi-harmonic Debye model.It is found that the transition from the ZB structure to the RS structure occurs at the pressure of about 16.3 GPa,this fact is well consistent with the experimental data and other theoretical results.The dependences of the relative volume v/Vo on the pressure P , the Debye temperature θ and specific heat Cv on the pressure P,as well as the specific heat Cv on the temperature T are also obtained successfully.
Dalgıç, Ali Coşkun; Pekmez, Hatice; Belibağlı, Kadir Bülent
2012-08-01
Mint leaves were dried by three different types of dryers, namely; tray, freeze and distributed (indirect)-type solar dryer. Sorption isotherms of fresh, solar, tray and freeze dried mint were determined at temperatures of 15 °C, 25 °C and 35 °C over a range of relative humidities (10-90%). The effect of drying method on the water sorption isotherms of dried mint samples was evaluated. Experimental data were used to determine the best models for predicting the moisture sorption content of mint. Among nine sorption models tested, Peleg, GAB, Lewicki and modified Mizrahi equations gave the best fit to experimental data. The sorption data were analyzed for determination of monolayer moisture content, density of sorbed water, number of adsorbed monolayers, percent bound water, and surface area of adsorbance. The experimental data were also used to determine some thermodynamic properties of mint.
Thermodynamic Properties of Spherically-Symmetric, Uniformly-Accelerated Reference Frames
ZHANG Jian-Bao; HUANG Chao-Guang; LIU Zeng-Rong; SUN Jia-Rui; LI Ying
2008-01-01
We aim to study the thermodynamic properties of the spherically symmetric reference frames with uniform acceleration, including the spherically symmetric generalization of Rindler reference frame and the new kind of uniformly accelerated reference frame. We find that, unlike the general studies about the horizon thermodynamics, one cannot obtain the laws of thermodynamics for their horizons in the usual approaches, despite that one can formally define an area entropy (Bekenstein-Hawking entropy). In fact, the common horizon for a set of uniformly accelerated observers does not always exist, even though the Hawking-Unruh temperature is still well-defined. This result indicates that the Hawking-Unruh temperature is only a kinematic effect, and to gain the laws of thermodynamics for the horizon, one needs the help of dynamics. Our result is in accordance with those from the various studies about the acoustic black holes.
Ben-Naim, Arieh
2017-01-01
This textbook introduces thermodynamics with a modern approach, starting from four fundamental physical facts (the atomic nature of matter, the indistinguishability of atoms and molecules of the same species, the uncertainty principle, and the existence of equilibrium states) and analyzing the behavior of complex systems with the tools of information theory, in particular with Shannon's measure of information (or SMI), which can be defined on any probability distribution. SMI is defined and its properties and time evolution are illustrated, and it is shown that the entropy is a particular type of SMI, i.e. the SMI related to the phase-space distribution for a macroscopic system at equilibrium. The connection to SMI allows the reader to understand what entropy is and why isolated systems follow the Second Law of Thermodynamics. The Second Llaw is also formulated for other systems, not thermally isolated and even open with respect to the transfer of particles. All the fundamental aspects of thermodynamics are d...
A note on the mutual relation between thermodynamics, energy definitions and standard cosmology
Moradpour, H
2016-01-01
In this paper, by solving the Friedman and thermodynamic pressure equations simultaneously, we investigate the relation between the Friedman and thermodynamic pressure equations. Our investigation shows that a prefect fluid, as a suitable solution for the Friedman equations, cannot simultaneously satisfy the thermodynamic pressure equation and Friedman equations. Moreover, we consider various common energy definitions, such as the Komar mass, and try to simultaneously solve the Friedman and thermodynamic pressure equations for various fluids. Our investigation shows that the Komar mass leads to a solution which may unify the primary inflationary and the current accelerating eras into one model. Thereinafter, we consider a general form for the energy of cosmic fluid and combine it with the Friedman and thermodynamic pressure equations to get some new solutions. The cosmological consequences of found solutions are also addressed. In addition, by taking into account a cosmic fluid with the known equation of stat...
Low-Temperature Synthesis and Thermodynamic and Electrical Properties of Barium Titanate Nanorods
Florentina Maxim
2015-01-01
Full Text Available Studies regarding the morphology dependence of the perovskite-type oxides functional materials properties are of recent interest. With this aim, nanorods (NRs and nanocubes (NCs of barium titanate (BaTiO3 have been successfully synthesized via a hydrothermal route at temperature as low as 408 K, employing barium acetate, titanium isopropoxide, and sodium hydroxide as reagents without any surfactant or template. Scanning electron microscopy (SEM, transmission electron microscopy (TEM, and X-ray powder diffraction (XRD, used for the morphology and structure analyses, showed that the NRs were formed by an oriented attachment of the NCs building-blocks with 20 nm average crystallites size. The thermodynamic properties represented by the relative partial molar free energies, enthalpies, and entropies of the oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressure of oxygen, indicated that NRs powders have lower oxygen vacancies concentration than the NCs. This NRs characteristic, together with higher tetragonallity of the structure, leads to the enhancement of the dielectric properties of BaTiO3 ceramics. The results presented in this work show indubitably the importance of the nanopowders morphology on the material properties.
Thermodynamic properties of correlated fermions in lattices with spin-dependent disorder
Makuch, K.; Skolimowski, J.; Chakraborty, P. B.; Byczuk, K.; Vollhardt, D.
2013-04-01
Motivated by the rapidly growing possibilities for experiments with ultracold atoms in optical lattices, we investigate the thermodynamic properties of correlated lattice fermions in the presence of an external spin-dependent random potential. The corresponding model, a Hubbard model with spin-dependent local random potentials, is solved within dynamical mean-field theory. This allows us to present a comprehensive picture of the thermodynamic properties of this system. In particular, we show that for a fixed total number of fermions spin-dependent disorder induces a magnetic polarization. The magnetic response of the polarized system differs from that of a system with conventional disorder.
Cari, C., E-mail: cari@staff.uns.ac.id; Suparmi, A., E-mail: soeparmi@staff.uns.ac.id; Yunianto, M., E-mail: muhtaryunianto@staff.uns.ac.id; Husein, A. S. [Physics Department, Faculty of Mathematics and Science, SebelasMaret University, Jl. Ir. Sutami 36A Kentingan Surakarta 57126 (Indonesia)
2016-02-08
The analytical solution of Ddimensional Dirac equation for Coulombic potential is investigated using Nikiforov-Uvarov method. The D dimensional relativistic energy spectra are obtained from relativistic energy eigenvalue equation by using Mat Lab software.The corresponding D dimensional radial wave functions are formulated in the form of generalized Jacobi and Laguerre Polynomials. In the non-relativistic limit, the relativistic energy equation reduces to the non-relativistic energy which will be applied to determine some thermodynamical properties of the system. The thermodynamical properties of the system are expressed in terms of error function and imaginary error function.
J. D. Pandey
2012-12-01
Full Text Available Thermodynamic properties of liquids and liquid mixtures play very important role in understanding the nature of molecular interactions occurring in the system. In the present work different thermodynamic properties of 15 pure liquids and 34 equimolar binary liquid mixtures of benzene, toluene, p-xylene, chlorobenzene and 1-chloronaphthalene with linear and branched alkanes have been computed with the help of Flory’s statistical theory (FST, Hard sphere equation of state (HSE and Hole theory (HT simultaneously. The calculated values are compared with the experimental findings collected from literature and quite satisfactory results are obtained.
A quantum model for bending vibrations and thermodynamic properties of C3.
Hansen, C. F.; Pearson, W. E.
1973-01-01
The investigation reported was conducted to clarify the thermodynamic properties of C3 by further developing the limit to the partition function suggested by Strauss and Thiele (1967). A quantum solution for the energy levels of a quadratically perturbed square well potential is presented and the consistency of this limit with observed energy levels is established. In the process a more complete physical picture of the bending C3 molecules emerges. The values of entropy deduced from various measurements of graphite pressure are compared with this limit, and the thermodynamic properties predicted for the limiting case are evaluated.
Thermodynamic properties of cyclohexanamines: Experimental and theoretical study
Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry and Department “Science and Technology of Life, Light and Matter”, University of Rostock, Dr-Lorenz-Weg 1, Rostock D-18059 (Germany); Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008 Kazan (Russian Federation); Emeĺyanenko, Vladimir N. [Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008 Kazan (Russian Federation)
2015-05-20
Highlights: • Vapor pressures of four cyclohexanamine derivatives were measured. • Vaporization enthalpies were derived and compared with the literature. • Thermochemical data tested for consistency using additivity rules and computations. • Contradiction between available liquid phase enthalpies of formation was resolved. • Strength of intra-molecular hydrogen bonding in cyclohexyl-1,2-diamines assessed. - Abstract: Vapor pressures of cyclohexanamine, N-methyl-cyclohexanamine, N,N-dimethyl-cyclohexanamine, and N-cyclohexyl-cyclohexanamine were measured using the transpiration method. Molar enthalpies of vaporization of cyclohexanamine derivatives were derived from vapor pressure temperature dependences. Thermodynamic data on cyclohexanamine derivatives available in the literature were collected and treated uniformly. Consistency of the experimental data was proved with a group- contribution method and quantum-chemical calculations. Evaluated vaporization and formation enthalpies of cyclohexanamine derivatives were recommended for practical thermochemical calculations.
Thermodynamic and dynamical properties of dense ICF plasma
Gabdullin Maratbek T.
2016-06-01
Full Text Available In present work, thermodynamic expressions were obtained through potentials that took into consideration long-range many-particle screening effects as well as short-range quantum-mechanical effects and radial distribution functions (RDFs. Stopping power of the projectile ions in dense, non-isothermal plasma was considered. One of the important values that describe the stopping power of the ions in plasma is the Coulomb logarithm. We investigated the stopping power of ions in inertial confinement fusion (ICF plasma and other energetic characteristics of fuel. Calculations of ions energy losses in the plasma for different values of the temperature and plasma density were carried out. A comparison of the calculated data of ion stopping power and energy deposition with experimental and theoretical results of other authors was also performed.
Duan, Yuhua
2012-11-02
Since current technologies for capturing CO{sub 2} to fight global climate change are still too energy intensive, there is a critical need for development of new materials that can capture CO{sub 2} reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO{sub 2} capture applications through a reversible chemical transformation. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO{sub 2} sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO{sub 2} adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO{sub 2} capture reactions by the solids of interest, we were able to screen only those solid materials for which lower capture energy costs are expected at the desired pressure and temperature conditions. Only those selected CO{sub 2} sorbent candidates were further considered for experimental validations. The ab initio thermodynamic technique has the advantage of identifying thermodynamic properties of CO{sub 2} capture reactions without any experimental input beyond crystallographic structural information of the solid phases involved. Such methodology not only can be used to search for good candidates from existing database of solid materials, but also can provide some guidelines for synthesis new materials. In this presentation, we first introduce our screening methodology and the results on a testing set of solids with known thermodynamic properties to validate our methodology. Then, by applying our computational method
Thermodynamic Relations for the Entropy and Temperature of Multi-Horizon Black Holes
Wei Xu
2015-02-01
Full Text Available We present some entropy and temperature relations of multi-horizons, even including the “virtual” horizon. These relations are related to the product, division and sum of the entropy and temperature of multi-horizons. We obtain the additional thermodynamic relations of both static and rotating black holes in three- and four-dimensional (AdS spacetime. Especially, a new dimensionless, charge-independence and T+S+ = T_S_-like relation is presented. This relation does not depend on the mass, electric charge, angular momentum and cosmological constant, as it is always a constant. These relations lead us to obtaining some interesting thermodynamic bounds of entropy and temperature, including the Penrose inequality, which is the first geometrical inequality of black holes. Besides, based on these new relations, one can obtain the first law of thermodynamics and the Smarr relation for all horizons of a black hole.
Thermodynamic properties of 1-butyl-3-methylpyridinium tetrafluoroborate
Safarov, Javid, E-mail: javid.safarov@uni-rostock.de [Institute of Technical Thermodynamics, University of Rostock, Albert-Einstein-Str. 2, D-18059 Rostock (Germany); Department of Heat and Refrigeration Techniques, Azerbaijan Technical University, H. Javid Avn. 25, AZ1073 Baku (Azerbaijan); Kul, Ismail [Department of Chemistry, Department of Biochemistry, Widener University, One University Place, Chester, PA 19013 (United States); El-Awady, Waleed A. [Department of Heat and Refrigeration Techniques, Azerbaijan Technical University, H. Javid Avn. 25, AZ1073 Baku (Azerbaijan); Mechanical Power Engineering Department, Mansoura Univeristy, Mansoura (Egypt); Shahverdiyev, Astan [Department of Heat and Refrigeration Techniques, Azerbaijan Technical University, H. Javid Avn. 25, AZ1073 Baku (Azerbaijan); Hassel, Egon [Institute of Technical Thermodynamics, University of Rostock, Albert-Einstein-Str. 2, D-18059 Rostock (Germany)
2011-09-15
Highlights: > (p, {rho}, T) data of 1-butyl-3-methylpyridinium tetrafluoroborate are estimated. > The measurements were carried out with a vibration-tube densimeter. > The thermomechanical coefficients were calculated. - Abstract: Pressure, density, temperature (p, {rho}, T) data of 1-butyl-3-methylpyridinium tetrafluoroborate [C4mpyr][BF{sub 4}] at T = (283.15 to 393.15) K and pressures up to p = 100 MPa are reported with an estimated experimental relative combined standard uncertainty of {Delta}{rho}/{rho} = {+-}(0.01 to 0.08)% in density. The measurements were carried out with a newly constructed Anton-Paar DMA HPM vibration-tube densimeter. The system was calibrated using double-distilled water, methanol, toluene and aqueous NaCl solutions. An empirical equation of state for fitting of the (p, {rho}, T) data of [C4mpyr][BF{sub 4}] has been developed as a function of pressure and temperature to calculate the thermal properties of the ionic liquid (IL), such as isothermal compressibility, isobaric thermal expansibility, differences in isobaric and isochoric heat capacities, thermal pressure coefficient and internal pressure. Internal pressure and the temperature coefficient of internal pressure data were used to make conclusions on the molecular characteristics of the IL.
S Acharya; J P Hajra
2011-04-01
The four parameter functions are generally considered to be adequate for representation of the thermodynamic properties for the strongly interacting binary systems. The present study involves a critical comparison in terms of applicability of the three well known four-parameter formalisms for the representation of the thermodynamic properties of binary systems. The study indicates that the derived values of the infinite dilution parameters based on the formalisms compare favourably with the computed data available in the literature. The standard deviations in terms of the partial and integral excess functions of all the models lie well within the experimental scatter of the computed data and coincide exactly with each other. The formalisms are useful in representation of the thermodynamic properties of most of the binary systems except for the Mg–Bi and Mg–In systems. In such systems, it appears that the additional compositional terms may be necessary for the formalisms for adequate description of behaviour of the systems. Since the derived values of the thermodynamic properties of all the formalisms match favourably over the entire compositional range for the systems as studied in the present research, any one of them may be used for adequate representation of the properties of the systems.
Thermodynamic Properties of a Reissner-Nordstr(o)m Quintessence Black Hole
WEI Yi-Huan; CHU Zhong-Hui
2011-01-01
The first law of thermodynamics for the three horizons of Reissner-Nordstr(o)m quintessence (RNQ) spacetime is obtained.For a general process of RNQ spacetime,the expressions for the radius changes of the three horizons are derived.When only mass changes,the heat fluxes through the three horizons are equivalent and no heat is left in the black hole region.Finally,a further discussion on the thermal properties of an RNQ black hole is given.Black holes satisfy the four laws of thermodynamics,which indicates a deep connection between gravity and thermodynamics,[1-4] where the entropy of black hole is proportional to the area of event horizon and the temperature of black hole is proportional to the surface gravity of event horizon.For a static and spherically symmetric spacetime,the field equation may be written as the first law of thermodynamics.[5-10]%The first law f thermodynamics for the three horizons of Reissner-Nordstrom quintessence (RNQ) spacetime is obtained. For a general process of RNQ spacetime, the expressions for the radius changes of the three horizons are derived. When only mass changes, the heat fluxes through the three horizons are equivalent and no heat is left in the black hole region. Finally, a further discussion on the thermal properties of an RNQ black hole is given.
Julian Gonzalez-Ayala
2015-06-01
Full Text Available In this work, we present the generalization of some thermodynamic properties of the black body radiation (BBR towards an n-dimensional Euclidean space. For this case, the Planck function and the Stefan–Boltzmann law have already been given by Landsberg and de Vos and some adjustments by Menon and Agrawal. However, since then, not much more has been done on this subject, and we believe there are some relevant aspects yet to explore. In addition to the results previously found, we calculate the thermodynamic potentials, the efficiency of the Carnot engine, the law for adiabatic processes and the heat capacity at constant volume. There is a region at which an interesting behavior of the thermodynamic potentials arises: maxima and minima appear for the n—dimensional BBR system at very high temperatures and low dimensionality, suggesting a possible application to cosmology. Finally, we propose that an optimality criterion in a thermodynamic framework could be related to the 3—dimensional nature of the universe.
Thermodynamics of Association of Structurally Related Amphiphilic Penicillins.
Taboada; Attwood; García; Jones; Ruso; Mosquera; Sarmiento
2000-01-15
Critical micelle concentrations (CMCs) of the penicillins cloxacillin and dicloxacillin in water were determined by conductivity measurements over the temperature range 288.15 to 313.15 K. Both penicillins showed minimum CMCs at temperatures close to 298.15 K. Thermodynamic parameters of aggregate formation were derived from the variation of the CMC with temperature using a modified form of the mass action model applicable to systems of low aggregation number. Values for the enthalpy of aggregate formation, DeltaH(0)(m), calculated by this method showed that the aggregation of both cloxacillin and dicloxacillin became increasingly exothermic with increase in temperature. The predicted DeltaH(0)(m) at 298.15 K was in good agreement with the value determined experimentally by calorimetry for each drug. Copyright 2000 Academic Press.
The simplified Hubbard model in one and two dimensions. Thermodynamic and dynamic properties
Vries, Pedro de; Michielsen, Kristel; Raedt, Hans De
1993-01-01
Thermodynamic and dynamic properties of the one and two-dimensional simplified Hubbard model are studied. At zero temperature and half filling, no metal-insulator transition occurs for nonzero coupling U and the system is an antiferromagnetic insulator. The behavior of the gap in the single-particle
Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J
2016-09-14
The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.
THE SIMPLIFIED HUBBARD-MODEL IN ONE AND 2 DIMENSIONS - THERMODYNAMIC AND DYNAMIC PROPERTIES
DEVRIES, P; MICHIELSEN, K; DERAEDT, H
1993-01-01
Thermodynamic and dynamic properties of the one and two-dimensional simplified Hubbard model are studied. At zero temperature and half filling, no metal-insulator transition occurs for nonzero coupling U and the system is an antiferromagnetic insulator. The behavior of the gap in the single-particle
Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J.
2016-09-01
The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.
Behavior of the Thermodynamic Properties of Binary Mixtures near the Critical Azeotrope
Azzedine Abbaci
2003-12-01
Full Text Available Abstract: In this work we investigate the critical line of binary azeotropic mixtures of acetone-n-pentane. We pinpoint the abnormal behavior of the critical density line as a function of the mole fraction of one of the component and show its influence on other thermodynamic properties such as the volume, the enthalpy and the entropy.
Thermodynamic and Hydrodynamic Properties of Dilute Solutions of Cyclic and Linear Polystyrenes
Hadziioannou, G.; Cotts, P.M.; Brinke, G. ten; Han, C.C.; Lutz, P.; Strazielle, C.; Rempp, P.
1987-01-01
The thermodynamic and hydrodynamic properties of cyclic and linear polystyrenes, ranging from 10000 to 180000 molecular weight, in dilute solutions of cyclohexane have been measured by small-angle neutron scattering (SANS) and dynamic light scattering. The diffusion coefficient D(c) was measured at
Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium.
Treverton, J. A.; Margrave, J. L.
1971-01-01
Some of the thermodynamic properties of liquid cobalt and palladium investigated by means of levitation calorimetry are reported and discussed. The presented data include the specific heats and heats of fusion of the liquid metals, and the emissivities of the liquid metal surfaces.
Microscopic and thermodynamic properties of dense semiclassical partially ionized hydrogen plasma
Ramazanov, T S; Dzhumagulova, K N; Gabdullin, M T [IETP, Al-Farabi Kazakh National University, 96a, Tole Bi St, Almaty, 050012 (Kazakhstan)
2006-04-28
Microscopic and thermodynamic properties of dense semiclassical partially ionized hydrogen plasma were investigated on the basis of pseudopotential models. Radial distribution functions (RDF) of particles were obtained using a system of the Ornstein-Zernike integral equations. The corrections to internal energy and the equation of state were calculated using RDF.
Doiron, Charles; Hencken, Kai
2013-09-01
Computational fluid-dynamic simulations nowadays play a central role in the development of new gas circuit breakers. For these simulations to be reliable, a good knowledge of the pressure and temperature-dependence of the thermodynamic and transport properties of ionized gases is required. A key ingredient in the calculation of thermodynamic properties of thermal plasmas is the calculation of the chemical equilibrium composition of the gas. The general-purpose, open-source software toolkit Cantera provides most functionality required to carry out such thermodynamic calculations. In this contribution, we explain how we tailored Cantera specifically to calculate material properties of plasmas. The highly modular architecture of this framework made it possible to add support for Debye-Hückel non-ideality corrections in the calculation of the chemical equilibrium mixture, as well as to enable the calculation of the key transport parameters needed in CFD-based electric arc simulations: electrical and thermal conductivity, viscosity, and diffusion coefficients. As an example, we discuss the thermodynamic and transport properties of mixtures of carbon dioxide and copper vapor.
Thermodynamic and Optical Properties of CuAlO2 under Pressure from First Principle
ZHANG Liqin; CHENG Yan; JI Guangfu
2015-01-01
The structural stability, thermodynamic and optical properties of delafossite CuAlO2 were investigated using the norm-conserving pseudopotential technique based on the ifrst-principle density-functional theory. The ground-state properties obtained by minimizing the total energy were in favorable agreement with previous works. By using the quasi-harmonic Debye model, the thermodynamic properties including the Debye temperature QD, heat capacity CV, thermal expansion coefifcient a, and Grüneisen parameter g were successfully obtained in the temperature range from 0 to 1 000 K and pressure range from 0 to 80 GPa, respectively. The optical properties including dielectric function e(v), absorption coefifcient a(v), relfectivity coefifcient R(v), and refractive index n(v) were also calculated and analyzed.
Thermodynamic properties of the polarized ideal gas in the presence of a minimal length
Khosropour, B.
2017-07-01
In this work, we attempt to investigate the effect of minimal length on the thermodynamic properties of a polarized ideal gas. The modified electric field in three spatial dimensions based on the Kempf algebra is obtained. The modifications of the thermodynamic parameters of the polarized ideal gas such as the mean energy and entropy are found. Also, we obtain the polarization and dielectric constant in the presence of a minimal length. By considering the values of experimental characteristics, the upper bound on the deformation parameter is estimated.
Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys
Maltsev, Dmitry S.; Volkovich, Vladimir A.; Yamshchikov, Leonid F.; Chukin, Andrey V.
2016-09-01
Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys were studied. Temperature dependences of gadolinium activity in the studied alloys were determined at 573-1073 K employing the EMF method. Solubility of gadolinium in the Ga-Sn and Ga-Zn alloys was measured at 462-1073 K using IMCs sedimentation method. Activity coefficients as well as partial and excess thermodynamic functions of gadolinium in the studied alloys were calculated on the basis of the obtained experimental data.
RNQ黑洞的热力学性质%Thermodynamic property for RNQ black hole
魏益焕
2012-01-01
Thermodynamic property is researched for RNQ black hole, including the first law of thermodynamics, the calculation of its heat capacities and thermal stabilities, The formula for calculating the charge - mass ration of RNQ biack hole is given and the maximum is also obtained.%研究RNQ黑洞的热力学性质.显示RNQ黑洞的热力学第一定律;计算RNQ黑洞的热容量并讨论它的热稳定性质;计算RNQ黑洞的电荷-质量比并获得极端RNQ黑洞电荷-质量比的最大值.
Eichhorn, Ralf; Aurell, Erik
2014-04-01
'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response
Thermodynamic and structural properties of liquid Al-Au alloys
Olajire, B. A.; Musari, A. A.
2017-08-01
The mixing properties of liquid Al-Au alloys with respect to the concentration of each constituent is determined using a method based on hard sphere system and pseudo-potential perturbation. These models were used to get relevant information on mixing properties of the Al-Au alloys like the Gibbs energy and the entropy of mixing. The concentration fluctuations, chemical short range order for the hard sphere mixture (quasi-lattice theory) and the activity are calculated to know the extent of order in the liquid alloys. The results revealed that there is a degree of ordering in liquid Al-Au alloy (hetero-coordinated).
Properties of graphite at melting from multilayer thermodynamic integration
Colonna, F.; Los, J.H.; Fasolino, A.; Meijer, E.J.
2009-01-01
Although the melting of graphite has been experimentally investigated for a long time, there is still much debate on the graphite melting properties, as studies show significant discrepancies. We calculate the melting line by means of LCBOPII, a state-of-the-art interaction potential for carbon. To
Adsorptive Thermodynamic Properties and Kinetics of trans-1,2- Cyclohexandiol onto AB-8 Resin
谢艳新; 侯丽丽; 杨倩; 蒋登高
2012-01-01
AB-8 resin was used as an adsorbent for the removal of trans-1,2-cyclohexandiol（CHD） from aqueous solutions.Batch experiments were carried out to investigate the effect of contact time and temperature on sorption efficiency.The adsorptive thermodynamic properties and kinetics of CHD from water onto AB-8 resin were studied.The Langmuir and Freundlich isotherm models were employed to discuss the adsorption behavior.Thermodynamic parameters such as G,H and S were calculated.The results indicate that the equilibrium data are perfectly represented by Langmuir isotherm model.Thermodynamic study reveals that it is an exothermic process in nature and mainly physical adsorption enhanced by chemisorption with a decrease of entropy process.The kinetics of CHD adsorption is well described by the pseudo second-order model.The adsorbed CHD can be eluted from AB-8 resin by 5% ethanol aqueous solution with 100% elution percentage.
Thermodynamical properties of interacting holographic dark energy model with apparent horizon
Liu, Bin; Deng, Jian-Bo
2011-01-01
We have investigated the thermodynamical properties of the universe with dark energy. It is demonstrated that in a universe with spacial curvature the natural choice for IR cutoff could be the apparent horizon radius. We shown that any interaction of pressureless dark matter with holographic dark energy, whose infrared cutoff is set by the apparent horizon radius, implying a constant effective equation of state of dark component in a universe. In addition we found that for the static observer in space, the comoving distance has a faster expansion than the apparent horizon radius with any spatial curvature. We also verify that in some conditions the modified first law of thermodynamics could return to the classic form at apparent horizon for a universe filled with dark energy and dark matter. Besides, the generalized second law of thermodynamics is discussed in a region enclosed by the apparent horizon.
Monte Carlo simulation of thermodynamic properties for two-dimensional Lennard-Jones fluids
无
2000-01-01
Canonical ensemble Monte Carlo simulations have been carried out to investigate the thermodynamic properties of two-dimensional fluids subjected to truncated Lennard-Jones 12-6 potential. The simulations of thermodynamic states sweep across liquid-vapor regime over a wide range of thermodynamic conditions. Simulated isotherms behave van der Waals loop-like characteristics in the liquid-vapor phase-transition region. It suggests a continuous isothermal phase transition in the case of micro system, in which the system size prohibits phase separation. Two-dimensional dimensionless van der Waals equation of states has been obtained from theoretical analysis. By fitting simulated data to this equation, temperature-dependent parameters in the equation have been determined.
Thermodynamic Properties of Carbon and Manganese in Mn-C and Mn-Fe-C Melts
CHEN Er-bao; WANG Shi-jun
2008-01-01
Carbon solubility in Mn-Fe melts (xMn=0.083-0.706,xFe=0.034-0.715) was measured experimentally at various temperatures.By thermodynamic derivation and calculation,the relationship between activity coefficient of carbon in infinite dilute solution of manganese in Mn-C system and temperature was obtained.Using Gibbs-Duhem relationship,the experimental results of this study,and experimental data obtained by strict thermodynamic derivation and calculation in references,the relationships between other thermodynamic properties (εCC,εCCC,εCFe,eεCCFe,and εCFeCFe) in Mn-Fe-C system and temperature were obtained.
Hidden Relation between Reflection Amplitudes and Thermodynamic Bethe Ansatz
Ahn, C; Rim, C; Ahn, Changrim; Kim, Chanju; Rim, Chaiho
1999-01-01
In this paper we compute the scaling functions of the effective central charges for various quantum integrable models in a deep ultraviolet region $R\\to 0$ using two independent methods. One is based on the ``reflection amplitudes'' of the (super-)Liouville field theory where the scaling functions are given by the conjugate momentum to the zero-modes. The conjugate momentum is quantized for the sinh-Gordon, the Bullough-Dodd, and the super sinh-Gordon models where the quantization conditions depend on the size $R$ of the system and the reflection amplitudes. The other method is to solve the standard thermodynamic Bethe ansatz (TBA) equations for the integrable models in a perturbative series of $1/(const. - \\ln R)$. The constant factor which is not fixed in the lowest order computations can be identified {\\it only when} we compare the higher order corrections with the quantization conditions. Numerical TBA analysis shows a perfect match for the scaling functions obtained by the first method. Our results show ...
Equilibrium properties of blackbody radiation in Doubly Special Relativity
Chandra, Nitin; Vaibhav, Vinay
2016-01-01
Doubly Special Relativity (DSR) is an attempt to incorporate an observer independent energy/length scale in the relativistic theory. We study various thermodynamic properties of blackbody radiation in DSR. We find that the energy density, specific heat etc. follows usual acoustic phonon dynamics as has been well studied by Debye. Other thermodynamic quantities like pressure, entropy etc. has also been calculated. The usual Stefan-Boltzmann law gets modified. The phase-space measure is also expected to get modified for an exotic spacetime, which in turn leads to the modification of Planck energy density distribution and the Wien's displacement law.
Thermodynamic and mechanical properties of curved interfaces : A discussion of models
Oversteegen, S.M.
2000-01-01
Although relatively much is known about the physics of curved interfaces, several models for these kind of systems seem conflicting or internally inconsistent. It is the aim of this thesis to derive a rigorous framework of thermodynamic and mechanical expressions and study their relation to previous
Thermodynamic and mechanical properties of curved interfaces : a discussion of models
Oversteegen, M.
2000-01-01
Although relatively much is known about the physics of curved interfaces, several models for these kind of systems seem conflicting or internally inconsistent. It is the aim of this thesis to derive a rigorous framework of thermodynamic and mechanical expressions and study their relation to
Thermodynamic properties of supercritical carbon dioxide: Widom and Frenkel lines
Fomin, Yu. D.; Ryzhov, V. N.; Tsiok, E. N.; Brazhkin, V. V.
2015-02-01
Supercritical fluids are widely used in a number of important technological applications, yet the theoretical progress in the field has been rather moderate. Fairly recently, a new understanding of the liquidlike and gaslike properties of supercritical fluids has come to the fore, particularly with the advent of the Widom and Frenkel lines that aim to demarcate different physical properties on the phase diagram. Here, we report the results of a computational study of supercritical carbon dioxide, one of the most important fluids in the chemical industry. We study the response functions of CO2 in the supercritical state and calculate the locations of their maxima (Widom lines). We also report the preliminary calculations of the Frenkel line, the line of crossover of microscopic dynamics of particles. Our insights are relevant to physical processes in the atmosphere of Venus and its evolution.
Calculations of the thermodynamic properties of metallurgical solutions
Blander, Milton
Predictive theories for metallurgical solutions are important precursors for computer software in chemical and extractive metallurgy. A limited selection of concepts useful for slags and other ionic systems will be discussed, and include the quasichemical theory, the conformal ionic solution theory, and polymer theory. We emphasize theories which usefully predict solution properties of multicomponent ionic systems, such as silicates and molten salts, to illustrate the range of possible uses.
A REVIEW ON THERMODYNAMICS AND FUNCTIONAL PROPERTIES OF COMPLEX COACERVATES
R. Gupta
2012-12-01
Full Text Available Complex coacervation is defined as associative interactions between oppositely charged functional groups of proteins and polysaccharides, which on separation, form a phase rich in polymeric compounds in equilibrium with another aqueous phase. So coacervates are macro-ionic hydrated complexes of two charged neutralized bioploymers. Voorn and Overbeek developed the first model on complex coacervation by applying Flory-Huggins theory for random mixing of polyions. Alternatively, Veis and Aryani proposed that initially charged pair of symmetrical aggregates forms, followed by phase separation, for modeling diverse range of aggregates. Physicochemical properties such as pH, ionic strength, ratio of protein to polysaccharide, polysaccharide and protein charge, and molecular weight, mechanical properties (shear force and temperature affect the formation and stability of coacervates. Improved structural, rheological, interfacial and delivery properties of these complexes than individual biopolymer can be exploited in numerous domains. This article intends to elucidate the salient features of coacervates which may contribute to better understanding of protein-polysaccharide systems, for their application in foods, cosmetics, pharmaceutical, and medicine.
Porsev, Vitaly V; Bandura, Andrei V; Evarestov, Robert A
2016-06-15
A zone-folding approach is applied to estimate the thermodynamic properties of V2 O5 -based nanotubes. The results obtained are compared with those from the direct calculations. It is shown that the zone-folding approximation allows an accurate estimation of nanotube thermodynamic properties and gives a gain in computation time compared to their direct calculations. Both approaches show that temperature effects do not change the relative stability of V2 O5 free layers and nanotubes derived from the α- and γ-phase. The internal energy thermal contributions into the strain energy of nanotubes are small and can be ignored. © 2016 Wiley Periodicals, Inc.
Mechanical, electronic and thermodynamic properties of full Heusler compounds Fe2VX(X = Al, Ga)
Khalfa, M.; Khachai, H.; Chiker, F.; Baki, N.; Bougherara, K.; Yakoubi, A.; Murtaza, G.; Harmel, M.; Abu-Jafar, M. S.; Omran, S. Bin; Khenata, R.
2015-11-01
The electronic structure, mechanical and thermodynamic properties of Fe2VX, (with X = Al and Ga), have been studied self consistently by employing state-of-the-art full-potential linearized approach of augmented plane wave plus local orbitals (FP-LAPW + lo) method. The exchange-correlation potential is treated with the local density and generalized gradient approximations (LDA and GGA). Our predicted ground state properties such as lattice constants, bulk modulus and elastic constants appear more accurate when we employed the GGA rather than the LDA, and these results are in very good agreement with the available experimental and theoretical data. Further, thermodynamic properties of Fe2VAl and Fe2VGa are predicted with pressure and temperature in the ranges of 0-40 GPa and 0-1500 K using the quasi-harmonic Debye model. We have obtained successfully the variations of the heat capacities, primitive cell volume and volume expansion coefficient.
Thermodynamics and elastic properties of Ta from first-principles calculations
Li Qiang; Huang Duo-Hui; Cao Qi-Long; Wang Fan-Hou; Cai Ling-Cang; Zhang Xiu-Lu; Jing Fu-Qian
2012-01-01
Within the framework of the quasiharmonic approximation,the thermodynamics and elastic properties of Ta,including phonon density of states (DOS),equation of state,linear thermal expansion coefficient,entropy,enthalpy,heat capacity,elastic constants,bulk modulus,shear modulus,Young's modulus,microhardness,and sound velocity,are studied using the first-principles projector-augmented wave method.The vibrational contribution to Helmholtz free energy is evaluated from the first-principles phonon DOS and the Debye model.The thermal electronic contribution to Helmholtz free energy is estimated from the integration over the electronic DOS.By comparing the experimental results with the calculation results from the first-principles and the Debye model,it is found that the thermodynamic properties of Ta are depicted well by the first-principles.The elastic properties of Ta from the first-principles are consistent with the available experimental data.
Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys
B C Anusionwu
2006-08-01
The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation cc(0) and the Warren-Cowley short-range order parameter (1) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In{Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn2 could be present in the Sb-Sn alloy at a temperature of about 770 K.
Rao, Linfeng; Tian, Guoxin; Teat, Simon J.
2010-03-29
Complexation of Np(V) with N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with its diamide analog, N,N,N{prime},N{prime}-tetramethyl-3-oxa-glutaramide (TMOGA), and dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including the stability constant and the enthalpy of complexation, were determined by spectrophotometry and calorimetry. Single-crystal structure of NpO{sub 2}(H{sub 2}O)(DMOGA){center_dot}H{sub 2}O(c) was identified by X-ray diffractometry using synchrotron radiation. Like ODA and TMOGA, DMOGA forms a tridentate Np(V) complex, with three oxygen atoms coordinating to the linear NpO{sub 2}{sup +} moiety via the equatorial plane. The stability constants, enthalpy and entropy of complexation generally decrease in the order ODA > DMOGA > TMOGA, suggesting that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with Np(V) due to the decrease in the entropy of complexation.
Rao, Linfeng; Tian, Guoxin; Teat, Simon J.
2010-03-29
Complexation of Np(V) with N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with its diamide analog, N,N,N{prime},N{prime}-tetramethyl-3-oxa-glutaramide (TMOGA), and dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including the stability constant and the enthalpy of complexation, were determined by spectrophotometry and calorimetry. Single-crystal structure of NpO{sub 2}(H{sub 2}O)(DMOGA){center_dot}H{sub 2}O(c) was identified by X-ray diffractometry using synchrotron radiation. Like ODA and TMOGA, DMOGA forms a tridentate Np(V) complex, with three oxygen atoms coordinating to the linear NpO{sub 2}{sup +} moiety via the equatorial plane. The stability constants, enthalpy and entropy of complexation generally decrease in the order ODA > DMOGA > TMOGA, suggesting that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with Np(V) due to the decrease in the entropy of complexation.
Steele, W. V.; Chirico, R. D.
1989-06-01
Ideal-gas thermodynamic properties for indoline and 2-methylindole based on accurate calorimetric measurements (between 300 to 500 K and 300 to 700 K, respectively) were determined; well into the range of typical chemical process temperatures. The calorimetrically derived values provide a firm basis for the prediction of thermodynamic properties for a large family of structures including many substituted indoles and indolines. Critical-temperature/density measurements obtained using a differential scanning calorimeter (DSC) are reported for 2-methylindole. A critical pressure and acentric factor are derived for 2-methylindole. Group-additivity estimation methods are employed to estimate the Gibbs energies of formation for the reactants, intermediates, and products in a reaction scheme for the hydrodenitrogenation (HDN) of indole. Thermodynamic equilibria calculations on the indole/indoline/hydrogen system are compared with experimental batch-reaction measurements reported in the literature. The interplay between thermodynamics and kinetics in the HDN of indole is discussed. 41 refs., 11 figs., 23 tabs.
Thermodynamic properties and atomic structure of Ca-based liquid alloys
Poizeau, Sophie
To identify the most promising positive electrodes for Ca-based liquid metal batteries, the thermodynamic properties of diverse Ca-based liquid alloys were investigated. The thermodynamic properties of Ca-Sb alloys were determined by emf measurements. It was found that Sb as positive electrode would provide the highest voltage for Ca-based liquid metal batteries (1 V). The price of such a battery would be competitive for the grid-scale energy storage market. The impact of Pb, a natural impurity of Sb, was predicted successfully and confirmed via electrochemical measurements. It was shown that the impact on the open circuit voltage would be minor. Indeed, the interaction between Ca and Sb was demonstrated to be much stronger than between Ca and Pb using thermodynamic modeling, which explains why the partial thermodynamic properties of Ca would not vary much with the addition of Pb to Sb. However, the usage of the positive electrode would be reduced, which would limit the interest of a Pb-Sb positive electrode. Throughout this work, the molecular interaction volume model (MIVM) was used for the first time for alloys with thermodynamic properties showing strong negative deviation from ideality. This model showed that systems such as Ca-Sb have strong short-range order: Ca is most stable when its first nearest neighbors are Sb. This is consistent with what the more traditional thermodynamic model, the regular association model, would predict. The advantages of the MIVM are the absence of assumption regarding the composition of an associate, and the reduced number of fitting parameters (2 instead of 5). Based on the parameters derived from the thermodynamic modeling using the MIVM, a new potential of mixing for liquid alloys was defined to compare the strength of interaction in different Ca-based alloys. Comparing this trend with the strength of interaction in the solid state of these systems (assessed by the energy of formation of the intermetallics), the systems with
无
2007-01-01
In this work, low-grade copper sulfide mine has been treated by the bioleaching process using native cultures of Acidithiobacillus ferrooxidans. The bioleaching experiments were carried out in shake flasks at pH 2.0, 180 r·min-1 and 30°C for mesophilic bacteria. The conductivity of copper bioleaching liquid was determined by the electric conductivity method at temperatures ranging from 298 K to 313 K. The ionic activity coefficients were estimated using Debye-Hücker and Osager-Falkenlagen equations. Meanwhile, the effects of temperature and concentration on the mean ionic activity co efficients were discussed. The relative partial molar free energies, enthalpies and entropies of copper leaching solution at above experimental temperatures were calculated The behaviors of change of relative partial molar quantities were dis cussed on the basis of electrolytic solution theory. Simultaneously, the thermodynamic characters of bioleaching solution with and without mesophilic bacteria were compared. The existence of mesophilic bacteria changed the Fe3+/Fe2+ ratio, which resulted in the difference of ionic interaction. The experimental data show that the determination of the thermody namic properties during the bioleaching processes should be important
Thermodynamics and surface properties of liquid Al-Ga and Al-Ge alloys
Anusionwu, B.C. [Abdus Salam Int. Centre for Theoretical Physics, Trieste (Italy); Federal University of Technology, Department of Physics, Owerri (Nigeria); Adebayo, G.A. [Abdus Salam Int. Centre for Theoretical Physics, Trieste (Italy); University of Agriculture, Department of Physics, Abeokuta (Nigeria); Madu, C.A. [Federal University of Technology, Department of Physics, Owerri (Nigeria)
2009-11-15
The surface properties of Al-Ga and Al-Ge liquid alloys have been theoretically investigated at a temperature of 1100 K and 1220 K respectively. For the Al-Ga system, the quasi chemical model for regular alloy and a model for phase segregating alloy systems were applied, while for the Al-Ge system the quasi chemical model for regular and compound forming binary alloys were applied. In the case of Al-Ga, the models for the regular alloys and that for the phase segregating alloys produced the same value of order energy and same values of thermodynamic and surface properties, while for the Al-Ge system, the model for the regular alloy reproduced better the thermodynamic properties of the alloy. The model for the compound forming systems showed a qualitative trend with the measured values of the thermodynamic properties of the Al-Ge alloy and suggests the presence of a weak complex of the form Al{sub 2}Ge{sub 3}. The surface concentrations for the alloys show that Ga manifests some level of surface segregation in Al-Ga liquid alloy while the surface concentration of Ge in Al-Ge liquid alloy showed a near Roultian behavior below 0.8 atomic fraction of Ge. (orig.)
Thermodynamics and surface properties of liquid Al-Ga and Al-Ge alloys
Anusionwu, B. C.; Adebayo, G. A.; Madu, C. A.
2009-11-01
The surface properties of Al-Ga and Al-Ge liquid alloys have been theoretically investigated at a temperature of 1100 K and 1220 K respectively. For the Al-Ga system, the quasi chemical model for regular alloy and a model for phase segregating alloy systems were applied, while for the Al-Ge system the quasi chemical model for regular and compound forming binary alloys were applied. In the case of Al-Ga, the models for the regular alloys and that for the phase segregating alloys produced the same value of order energy and same values of thermodynamic and surface properties, while for the Al-Ge system, the model for the regular alloy reproduced better the thermodynamic properties of the alloy. The model for the compound forming systems showed a qualitative trend with the measured values of the thermodynamic properties of the Al-Ge alloy and suggests the presence of a weak complex of the form Al2Ge3. The surface concentrations for the alloys show that Ga manifests some level of surface segregation in Al-Ga liquid alloy while the surface concentration of Ge in Al-Ge liquid alloy showed a near Roultian behavior below 0.8 atomic fraction of Ge.
Theoretical investigations on the elastic and thermodynamic properties of rhenium phosphide
Wei, Qun; Zhu, Xuanmin; Lin, Zhengzhe; Yao, Ronghui [Xidian Univ., Xi' an (China). School of Physics and Optoelectronic Engineering; Yan, Haiyan [Baoji Univ. of Arts and Sciences (China). Dept. of Chemistry and Chemical Engineering
2016-04-01
Structural, mechanical, and electronic properties of orthorhombic rhenium phosphide (Re{sub 2}P) are systematically investigated by using first principles calculations. The elastic constants and anisotropy of elastic properties are obtained. The metallic character of Re{sub 2}P is demonstrated by density of state calculations. The quasi-harmonic Debye model is applied to the study of the thermodynamic properties. The thermal expansion, heat capacities, and Grueneisen parameter on the temperature and pressure have been determined as a function of temperature and pressure in the pressure range from 0 to 100 GPa and the temperature range from 0 to 1600 K.
The thermodynamic properties of 2-methylaniline and trans-(R,S)- decahydroquinoline
Steele, W.V.; Chirico, R.D.; Nguyen, A.; Knipmeyer, S.E.
1990-02-01
Measurements leading to the calculation of the ideal-gas thermodynamic properties for 2-methylaniline and trans-(R,S)-decahydroquinoline are reported. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (dsc). Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas at selected temperatures for both compounds. Critical properties were determined for 2-methylaniline with the dsc. Measured combustion enthalpies, vapor pressures, critical properties, and ideal-gas entropies were compared with estimated and experimental literature values. 59 refs., 7 figs., 15 tabs.
Electronic structure and thermodynamic properties of Cu3V2O8 compound
Jezierski, Andrzej; Kaczkowski, Jakub
2015-10-01
The electronic structure and thermodynamic properties of Cu3V2O8 compound for three structures (P-1, P21/c and Cmca) are reported. The calculations are performed by using full-potential local orbital minimum basis method. The total electronic densities of states for all structures have the similar shape but the details are different. The thermodynamic properties (the bulk modulus B, Gibbs free energy, Debye temperature ΘD) are calculated in quasiharmonic Debye-Grüneisen model using the equation of states in the form of Murnaghan, Birch-Murnaghan, Poirier-Tarantola and Vinet. Our ab initio results indicate that α(P-1) phase is stable below 839 K, β(P21/c) and γ(Cmca) phases can exist in the region of 839 K < T < 875 K, however above T = 875 K only γ(Cmca) phase is observed.
Ab initio calculation of structure and thermodynamic properties of Zintl aluminide SrAl{sub 2}
Fu, Zhi-Jian [Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology, Chongqing (China); Chongqing Univ. of Arts and Sciences (China). School of Electrical and Electronic Engineering; China Academy of Engineering Physics (CAEP), Mianyang, Sichuan (China). National Key Lab. of Shock Wave and Detonation Physics; Jia, Li-Jun [Chongqing Univ. of Arts and Sciences Library (China); Xia, Ji-Hong; Tang, Ke; Li, Zhao-Hong [Chongqing Univ. of Arts and Sciences (China). School of Electrical and Electronic Engineering; Sun, Xiao-Wei [Lanzhou Jiaotong Univ. (China). School of Mathematics and Physics; Chen, Qi-Feng [China Academy of Engineering Physics (CAEP), Mianyang, Sichuan (China). National Key Lab. of Shock Wave and Detonation Physics
2015-07-01
The structural and thermodynamic properties of the orthorhombic and cubic structure SrAl{sub 2} at pressure and temperature are investigated by using the ab initio plane-wave pseudopotential density functional theory method within the generalised gradient approximation (GGA). The calculated lattice parameters are in agreement with the available experimental data and other theoretical results. The phase transition predicted takes place at 0.5 GPa from the orthorhombic to the cubic structure at zero temperature. The thermodynamic properties of the zinc-blende structure SrAl{sub 2} are calculated by the quasi-harmonic Debye model. The pressure-volume relationship and the variations in the thermal expansion a are obtained systematically in the pressure and temperature ranges of 0-5 GPa and 0-500 K, respectively.
Theoretical study of the thermodynamic properties of lithium, sodium, and potassium nitrates
Korabel'nikov, D. V.; Zhuravlev, Yu. N.
2013-08-01
The thermal properties of lithium, sodium, and potassium nitrates have been studied in a gradient approximation of the density functional theory using the method of linear combination of atomic orbitals of the CRYSTAL09 program package. The long-wave frequencies and corresponding mode Grüneisen parameters are calculated. The quasi-harmonic Debye-Einstein model is used to calculate the parameters of the equation of states and also the dependences of the thermodynamic potentials, the entropy, the heat capacity, the thermal expansion coefficient, and the Grüneisen parameter on pressure and temperature. The role of external and intramolecular vibrations in the interpretation of thermodynamic properties is determined. The obtained results agree well with the available experimental data.
First-principles calculations on elasticity and the thermodynamic properties of TaC under pressure
Peng, Feng; Han, Ligang; Fu, Hongzhi [College of Physics and Electronic Information, Luoyang Normal University, Luoyang (China); Cheng, Xinlu [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu (China)
2009-07-15
First-principles calculations on the elastic and the thermodynamic properties of TaC have been carried out with the plane-wave pseudopotential density functional method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The dependence of the elastic constants c{sub ij}, the aggregate elastic moduli (B,G,E), and the elastic anisotropy on pressure have been investigated. Moreover, the variation of the Poisson ratio and Debye temperature with pressure have been investigated for the first time. Through the quasi-harmonic Debye model, the thermodynamic properties were also obtained successfully. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Thermodynamic properties of liquid Au–Cu–Sn alloys determined from electromotive force measurements
Guo, Zhongnan; Hindler, Michael; Yuan, Wenxia; Mikula, Adolf
2011-01-01
The thermodynamic properties of the ternary Au–Cu–Sn system were determined with the electromotive force (EMF) method using a liquid electrolyte. Three different cross-sections with constant Au:Cu ratios of 3:1, 1:1, and 1:3 were applied to measure the thermodynamic properties of the ternary system in the temperature range between the liquidus temperature of the alloys and 1023 K. The partial free energies of Sn in liquid Au–Cu–Sn alloys were obtained from EMF data. The integral Gibbs free energy and the integral enthalpy at 900 K were calculated by Gibbs–Duhem integration. The ternary interaction parameters were evaluated using the Redlich–Kister–Muggianu polynomial. PMID:22039311
Thermodynamic properties of liquid Au-Cu-Sn alloys determined from electromotive force measurements.
Guo, Zhongnan; Hindler, Michael; Yuan, Wenxia; Mikula, Adolf
2011-10-20
The thermodynamic properties of the ternary Au-Cu-Sn system were determined with the electromotive force (EMF) method using a liquid electrolyte. Three different cross-sections with constant Au:Cu ratios of 3:1, 1:1, and 1:3 were applied to measure the thermodynamic properties of the ternary system in the temperature range between the liquidus temperature of the alloys and 1023 K. The partial free energies of Sn in liquid Au-Cu-Sn alloys were obtained from EMF data. The integral Gibbs free energy and the integral enthalpy at 900 K were calculated by Gibbs-Duhem integration. The ternary interaction parameters were evaluated using the Redlich-Kister-Muggianu polynomial.
Phase transition and thermodynamic properties of BiFeO3 from first-principles calculations
Li Qiang; Huang Duo-Hui; Cao Qi-Long; Wang Fan-Hou
2013-01-01
The first-principles projector-augmented wave method employing the quasi-harmonic Debye model,is applied to investigate the thermodynamic properties and the phase transition between the trigonal R3c structure and the orthorhombic Pnma structure.It is found that at ambient temperature,the phase transition from the trigonal R3c phase to the orthorhombic Pnma phase is a first-order antiferromagnetic-nonmagnetic and insulator-metal transition,and occurs at 10.56 GPa,which is in good agreement with experimental data.With increasing temperature,the transition pressure decreases almost linearly.Moreover,the thermodynamic properties including Grüineisen parameter,heat capacity,entropy,and the dependences of thermal expansion coefficient on temperature and pressure are also obtained.
Phase transition and thermodynamic properties of SrS via first-principles calculations
Cheng Yan; Lu Lai-Yu; Jia Ou-He; Chen Xiang-Rong
2008-01-01
The phase transition of SrS from NaG1 structure (B1) to CsCl structure (B2) is investigated by means of ab initio plane-wave pseudopotential density functional theory, and the thermodynamic properties of the B1 and the B2 structures are obtained through the quasi-harmonic Debye model. It is found that the transition phase from the B1 to the B2 structures occurs at 17.9 GPa, which is in good agreement with experimental data and other calculated results.Moreover, the thermodynamic properties (including specific heat capacity, the Debye temperature, thermal expansion and Grüneisen parameter) have also been obtained successfully.
Numerical prediction of the thermodynamic properties of ternary Al-Ni-Hf alloys
Romanowska, Jolanta; Kotowski, Sławomir; Zagula-Yavorska, Maryana [Rzeszów University of Technology (Poland)
2014-10-06
Thermodynamic properties of ternary Al-Hf-Ni system, such as {sup ex}G, μ{sub Al}, μ{sub Ni} and μ{sub Zr} at 1373K were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting {sup ex}G values was regarded as the calculation of excess Gibbs energy values inside a certain area (a Gibbs triangle) unless all boundary conditions, that is values of {sup ex}G on all legs of the triangle are known. {sup ex}G and L{sub ijk} ternary interaction parameters in the Muggianu extension of the Redlich-Kister formalism are calculated numerically using Wolfram Mathematica 9 software.
Study of thermodynamic properties of Np-Al alloys in molten LiCl-KCl eutectic
Mendes, E.; Soucek, P.; Malmbeck, R.; Glatz, J. P. [Institute for Transuranium Elements, Karlsruhe (Germany); Caravaca, C. [CIEMAT, DE/DFN/URAA, Madrid (Spain)
2008-08-15
This work is focused on chemical characterisation and determination of thermodynamic properties of Np-Al alloys. The alloys are formed on a solid Al electrode during Np electrodeposition in molten LiCl-KCl Eutectic. Open circuit potential measurements, after small depositions of Np metal onto the Al electrode were used to determine thermodynamic properties of the Np-Al alloys formed (G, H, S, activity of Np in Al) by an e.m.f. method. Galvanostatic electrolyses were carried out on an Al plates. Stable Np-Al deposit was obtained and identified, by XRD analysis, as a mixture NpAl{sub 3} and NpAl{sub 4} alloys.
LDA+ U calculation of structural and thermodynamic properties of Ce2O3
Zhu, Bo; Cheng, Yan; Niu, Zhen-Wei; Zhou, Meng; Gong, Min
2014-08-01
We investigated the structure and thermodynamic properties of the hexagonal Ce2O3 by using LDA+ U scheme in the frame of density functional theory (DFT), together with the quasi-harmonic Debye model. The obtained lattice constants, bulk modulus, and the insulating gap agree well with the available experimental data. We successfully yielded the temperature dependence of bulk modulus, volume, thermal expansion coefficient, Debye temperature, specific heat as well as the entropy at different U values. It is found that the introduction of the U value cannot only correct the calculation of the structure but also improve the accurate description of the thermodynamic properties of Ce2O3. When U = 6 eV the calculated volume (538 Bohr3) at 300 K agrees well with the experimental value (536 Bohr3). The calculated entropy curve becomes more and more close to the experimental curve with the increasing U value.
On the ease of predicting the thermodynamic properties of beta-cyclodextrin inclusion complexes
Apostolakis Joannis
2007-11-01
Full Text Available Abstract Background In this study we investigated the predictability of three thermodynamic quantities related to complex formation. As a model system we chose the host-guest complexes of β-cyclodextrin (β-CD with different guest molecules. A training dataset comprised of 176 β-CD guest molecules with experimentally determined thermodynamic quantities was taken from the literature. We compared the performance of three different statistical regression methods – principal component regression (PCR, partial least squares regression (PLSR, and support vector machine regression combined with forward feature selection (SVMR/FSS – with respect to their ability to generate predictive quantitative structure property relationship (QSPR models for ΔG°, ΔH° and ΔS° on the basis of computed molecular descriptors. Results We found that SVMR/FFS marginally outperforms PLSR and PCR in the prediction of ΔG°, with PLSR performing slightly better than PCR. PLSR and PCR proved to be more stable in a nested cross-validation protocol. Whereas ΔG° can be predicted in good agreement with experimental values, none of the methods led to comparably good predictive models for ΔH°. In using the methods outlined in this study, we found that ΔS° appears almost unpredictable. In order to understand the differences in the ease of predicting the quantities, we performed a detailed analysis. As a result we can show that free energies are less sensitive (than enthalpy or entropy to the small structural variations of guest molecules. This property, as well as the lower sensitivity of ΔG° to experimental conditions, are possible explanations for its greater predictability. Conclusion This study shows that the ease of predicting ΔG° cannot be explained by the predictability of either ΔH° or ΔS°. Our analysis suggests that the poor predictability of TΔS° and, to a lesser extent, ΔH° has to do with a stronger dependence of these quantities on the
Size and shape effects on the thermodynamic properties of nanoscale volumes of water.
Strøm, Bjørn A; Simon, Jean-Marc; Schnell, Sondre K; Kjelstrup, Signe; He, Jianying; Bedeaux, Dick
2017-03-29
Small systems are known to deviate from the classical thermodynamic description, among other things due to their large surface area to volume ratio compared to corresponding big systems. As a consequence, extensive thermodynamic properties are no longer proportional to the volume, but are instead higher order functions of size and shape. We investigate such functions for second moments of probability distributions of fluctuating properties in the grand-canonical ensemble, focusing specifically on the volume and surface terms of Hadwiger's theorem, explained in Klain, Mathematika, 1995, 42, 329-339. We resolve the shape dependence of the surface term and show, using Hill's nanothermodynamics [Hill, J. Chem. Phys., 1962, 36, 3182], that the surface satisfies the thermodynamics of a flat surface as described by Gibbs [Gibbs, The Scientific Papers of J. Willard Gibbs, Volume 1, Thermodynamics, Ox Bow Press, Woodbridge, Connecticut, 1993]. The Small System Method (SSM), first derived by Schnell et al. [Schnell et al., J. Phys. Chem. B, 2011, 115, 10911], is extended and used to analyze simulation data on small systems of water. We simulate water as an example to illustrate the method, using TIP4P/2005 and other models, and compute the isothermal compressibility and thermodynamic factor. We are able to retrieve the experimental value of the bulk phase compressibility within 2%, and show that the compressibility of nanosized volumes increases by up to a factor of two as the number of molecules in the volume decreases. The value for a tetrahedron, cube, sphere, polygon, etc. can be predicted from the same scaling law, as long as second order effects (nook and corner effects) are negligible. Lastly, we propose a general formula for finite reservoir correction to fluctuations in subvolumes.
2011-01-01
Modeling the Thermodynamic and Transport Properties of Decahydronaphthalene/Propane Mixtures: Phase Equilibria , Density, and Viscosity Nathaniel...Decahydronaphthalene/Propane Mixtures: Phase Equilibria , Density, And Viscosity 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18 Keywords: phase equilibria ; modified Sanchez-Lacombe equation of state
Effect of peritectics on thermodynamic properties of homogeneous binary metallic melts
张鉴
2001-01-01
After formulation of the calculating models of mass action concentrations for metallic melts Cu-Al, Ni-Al and Cu-Sn, it is found that in spite of their lower stability than that of compounds with congruent melting point, peritectics are popular structural units in metallic melts, neglecting their presence will make it impossible to study the thermodynamic properties of metallic melts with results which both obey the law of mass action and agree well with practice.
Mahendra P, Verma [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)
2005-07-01
In this paper are presented, the thermodynamic inconsistencies in formulation IAPWS-95 as well as the limitations in the experimental data of the thermodynamic properties of the water. In addition, a new methodology was developed: Verma procedure for the measurement of the calorific capacity of water. Thus, a procedure is presented to calculate other thermodynamic properties of liquids such as water. In the transformation processes of the planet Earth, water is an essential component. Nevertheless, the knowledge about its properties is still very limited. Recently, Verma developed a new program: SteamTablesIIE, to calculate the properties of water as a function of two independent variables between temperatures (T), pressure (P), volume (V), internal energy (U), enthalpy (H), Gibas energy (G) and entropy (S). Yet, thermodynamic inconsistencies were found in the formulation, same that are the limiting factors for the operation of the SteamTablesIIE in all the ranks of the independent variables. [Spanish] En este trabajo se presentan, tanto las inconsistencias termodinamicas en la formulacion IAPWS-95 como las limitaciones en los datos experimentales de las propiedades termodinamicas del agua. Ademas, se desarrollo una nueva metodologia: Procedimiento Verma para la medicion de la capacidad calorifica del agua. Asi, se presenta un procedimiento para calcular otras propiedades termodinamicas de liquidos tales como el agua. En los procesos de transformacion del planeta tierra, el agua es un componente esencial. Sin embargo, el conocimiento acerca de sus propiedades es todavia muy limitado. Recientemente, Verma desarrollo un nuevo programa: SteamTablesIIE, para calcular las propiedades del agua como una funcion de dos variables independientes entre temperaturas (T), presion (P), volumen (V), energia interna (U), entalpia (H), energia Gibas (G) y entropia (S). Con todo, se encontraron inconsistencias termodinamicas en la formulacion, mismas que son las limitantes para el
D.P.Tao
2001-01-01
The coordination numbers in the Molecular Interaction Volume Model can be calcu-lated from the common physical quantities of pure matters.A significant advantage ofthe model lies in its ability to predict the thermodynamic properties of ternary liqmdalloys using only the binary infinite dilute activity coefficients,and the predicted values are in good agreement with the experimental data of ternary liquid alloys,whichshows that the model is reliable,convenient and economic.
Zuber, A; R. F. Checoni; M. Castier
2015-01-01
AbstractThe correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS) is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprise...
Santos, Andrés; de Haro, Mariano López; Yuste, Santos B.
2009-01-01
Different theoretical approaches for the thermodynamic properties and the equation of state for multicomponent mixtures of nonadditive hard spheres in $d$ dimensions are presented in a unified way. These include the theory by Hamad, our previous formulation, the original MIX1 theory, a recently proposed modified MIX1 theory, as well as a nonlinear extension of the MIX1 theory proposed in this paper. Explicit expressions for the compressibility factor, Helmholtz free energy, and second, third,...
Phase Transition and Thermodynamic Properties of Magnesium Fluoride by First Principles
Zhang, Tian; Cheng, Yan; Lv, Zhen-Long; Ji, Guang-Fu; Gong, Min
2014-12-01
The structural stabilities, phase transitions and thermodynamic properties of MgF2 under high pressure and temperature are investigated by first-principles calculations based on plane-wave pseudopotential density functional theory method within the local density approximation. The calculated lattice parameters of MgF2 in all four phases under zero pressure and zero temperature are in good agreement with the existing experimental data and other theoretical results. Our results demonstrate that MgF2 undergoes a series of structural phase transitions from rutile (P42/mnm)→CaCl2-type (Pnnm)→modified fluorite (Pa-3)→cotunnite (Pnam) under high pressure and the obtained transition pressures are in fairly good agreement with the experimental results. The temperature-dependent volume and thermodynamic properties of MgF2 in the rutile phase at 0 GPa are presented and the thermodynamic properties of MgF2 in the rutile, CaCl2-type, modified fluorite and cotunnite phases at 300 K are also predicted using the quasi-harmonic approximation model (QHA) and the quasi-harmonic Debye model (QHD), respectively. Moreover, the partial density of states and the electronic density of the four phases under the phase transition are also investigated.
Bahar, Rim; Azzouz, Soufien; Remond, Romain; Ouertani, Sahbi; Elaieb, Mohamed Taher; El Cafci, Mohamed Afif
2017-05-01
The aim of this paper was to determine the moisture desorption isotherms and essentials thermodynamic properties of two Oak wood varieties. Desorption isotherms were measured using a static gravimetric method at 50, 60, 70 and 80 °C within the range of 5-90 % relative humidity. The equilibrium moisture content decreased with increasing temperature and decreased with decreasing relative humidity at a constant temperature. The `Thermodynamic' sorption equation was found to be the best for describing the experimental moisture sorption isotherms of woods within the range of temperature and water activity investigated. The Fiber saturation point, deduced from the `Thermodynamic' model parameters, depends on the temperature and varying from 22.6 to 54.4 (% kg water/kg dry matter). Isosteric heat of desorption and differential entropy were calculated by applying Clausius-Clapeyron equation to the desorption data fitted by the `Thermodynamic' model. The isosteric heat of desorption and the differential entropy decreased with increasing moisture content according to an exponential law equation and varying from 2.03 to 31.14 kJ/mol and from 73.98 to 4.34 J/(mol K), respectively. The linear relationship between differential enthalpy and entropy satisfied the enthalpy-entropy compensation theory. The sign of Gibbs free energy was found to be positive (+283 J/mol) and (+97 J/mol) for Quercus robur and Quercus canariensis, respectively. The isokinetic temperature was found to be greater than the harmonic temperature. Based on the enthalpy-entropy compensation theory, it could be concluded that the moisture desorption isotherm of Oak wood is a non-spontaneous and enthalpy-controlled process.
Bahar, Rim; Azzouz, Soufien; Remond, Romain; Ouertani, Sahbi; Elaieb, Mohamed Taher; El Cafci, Mohamed Afif
2016-09-01
The aim of this paper was to determine the moisture desorption isotherms and essentials thermodynamic properties of two Oak wood varieties. Desorption isotherms were measured using a static gravimetric method at 50, 60, 70 and 80 °C within the range of 5-90 % relative humidity. The equilibrium moisture content decreased with increasing temperature and decreased with decreasing relative humidity at a constant temperature. The `Thermodynamic' sorption equation was found to be the best for describing the experimental moisture sorption isotherms of woods within the range of temperature and water activity investigated. The Fiber saturation point, deduced from the `Thermodynamic' model parameters, depends on the temperature and varying from 22.6 to 54.4 (% kg water/kg dry matter). Isosteric heat of desorption and differential entropy were calculated by applying Clausius-Clapeyron equation to the desorption data fitted by the `Thermodynamic' model. The isosteric heat of desorption and the differential entropy decreased with increasing moisture content according to an exponential law equation and varying from 2.03 to 31.14 kJ/mol and from 73.98 to 4.34 J/(mol K), respectively. The linear relationship between differential enthalpy and entropy satisfied the enthalpy-entropy compensation theory. The sign of Gibbs free energy was found to be positive (+283 J/mol) and (+97 J/mol) for Quercus robur and Quercus canariensis, respectively. The isokinetic temperature was found to be greater than the harmonic temperature. Based on the enthalpy-entropy compensation theory, it could be concluded that the moisture desorption isotherm of Oak wood is a non-spontaneous and enthalpy-controlled process.
Magnetic and thermodynamic properties of face-centered cubic Fe-Ni alloys.
Lavrentiev, M Yu; Wróbel, J S; Nguyen-Manh, D; Dudarev, S L
2014-08-14
A model lattice ab initio parameterized Heisenberg-Landau magnetic cluster expansion Hamiltonian spanning a broad range of alloy compositions and a large variety of chemical and magnetic configurations has been developed for face-centered cubic Fe-Ni alloys. The thermodynamic and magnetic properties of the alloys are explored using configuration and magnetic Monte Carlo simulations over a temperature range extending well over 1000 K. The predicted face-centered cubic-body-centered cubic coexistence curve, the phase stability of ordered Fe3Ni, FeNi, and FeNi3 intermetallic compounds, and the predicted temperatures of magnetic transitions simulated as functions of alloy composition agree well with experimental observations. Simulations show that magnetic interactions stabilize the face-centered cubic phase of Fe-Ni alloys. Both the model Hamiltonian simulations and ab initio data exhibit a particularly large number of magnetic configurations in a relatively narrow range of alloy compositions corresponding to the occurrence of the Invar effect.
Mnemonic Device for Relating the Eight Thermodynamic State Variables: The Energy Pie
Fieberg, Jeffrey E.; Girard, Charles A.
2011-01-01
A mnemonic device, the energy pie, is presented that provides relationships between thermodynamic potentials ("U," "H," "G," and "A") and other sets of variables that carry energy units, "TS" and "PV." Methods are also presented in which the differential expressions for the potentials and the corresponding Maxwell relations follow from the energy…
Mnemonic Device for Relating the Eight Thermodynamic State Variables: The Energy Pie
Fieberg, Jeffrey E.; Girard, Charles A.
2011-01-01
A mnemonic device, the energy pie, is presented that provides relationships between thermodynamic potentials ("U," "H," "G," and "A") and other sets of variables that carry energy units, "TS" and "PV." Methods are also presented in which the differential expressions for the potentials and the corresponding Maxwell relations follow from the energy…
The Thermodynamics of the Krebs Cycle and Related Compounds
Miller, Stanley L.; Smith-Magowan, David
1990-07-01
A survey is made of the enthalpies of formation, third law entropies and Gibbs energies available for Krebs cycle and related compounds. These include formate, acetate, succinate, fumarate, glycine, alanine, aspartate and glutamate. The potential of the NAD+/NADH couple is recalculated based on the ethanol/acetaldehyde and isopropanol/acetone equilibria. The reported enzyme catalyzed equilibrium constants of the Krebs cycle reactions are evaluated with estimated errors. These 28 equilibria form a network of reactions that is solved by a least squares regression procedure giving Gibbs energies of formation for 21 Krebs cycle and related compounds. They appear to be accurate to ±0.4 kJṡmol-1 for some compounds but ±1 kJṡmol-1 in less favorable cases. This procedure indicates which third law ΔfG and enzyme equilibria are inaccurate, and allows very accurate ΔfG to be determined for compounds related to the Krebs cycle by measuring enzyme equilibrium constants.
Free energy of formation of Mo2C and the thermodynamic properties of carbon in solid molybdenum
Seigle, L. L.; Chang, C. L.; Sharma, T. P.
1979-01-01
As part of a study of the thermodynamical properties of interstitial elements in refractory metals, the free energy of formation of Mo2C is determined, and the thermodynamical properties of C in solution in solid Mo evaluated. The activity of C in the two-phase region Mo + Mo2C is obtained from the C content of iron rods equilibrated with metal + carbide powder mixtures. The free energy of formation of alpha-Mo2C is determined from the activity data. The thermodynamic properties of C in the terminal solid solution are calculated from available data on the solid solubility of C in Mo. Lattice distortion due to misfit of the C atoms in the interstitial sites appears to play a significant role in determining the thermodynamic properties of C in solid Mo.
First-Principles Calculations for Thermodynamic Properties of Perovskite-Type Superconductor MgCNi
ZHANG Wei; LI Zhe; CHEN Xiang-Rong; CAI Ling-Cang; JING Fu-Qian
2008-01-01
The ground state properties and equation of state of the non-oxide perovskite-type superconductor MgCNi,3 are investigated by first-principles calculations based on the plane-wave basis set with the local density approximation (LDA) as well as the generalized gradient approximation (GGA) for exchange and correlation, which agree well with both theoretical calculations and experiments. Some thermodynamic properties including the heat capacity, the thermal expansion coefficient and the Gruneisen parameter for perovskite structure MgCNi,3 are obtained.
Work relation and the second law of thermodynamics in nonequilibrium steady states.
Nakagawa, Naoko
2012-05-01
We extend Jarzynski's work relation and the second law of thermodynamics to a heat conducting system, which is operated by an external agent. These extensions contain a nonequilibrium contribution expressed as the violation of the (linear) response relation caused by the operation. We find that a natural extension of the minimum work principle involves information about the time-reversed operation, and is far from straightforward. Our work relation may be tested experimentally especially when the temperature gradient is small.
Ghebouli, M. A.; Bouhemadou, A.; Ghebouli, B.; Fatmi, M.; Bin-Omran, S.
2011-07-01
Density functional theory pseudo-potential plane-wave calculations are performed in order to predict the structural, elastic and thermodynamic properties of the newly discovered tetragonal intermetallic SrPd 2Ge 2. The computed equilibrium lattice constants and the internal parameter are in good agreement with the experimental findings. The effect of high pressure, up to 40 GPa, on the lattice constants shows that the contraction along the c axis is higher than along the a axis. The single-crystal elastic constants and related properties are calculated using the static finite strain technique. We predicted the bulk modulus, shear modulus, Young's modulus and Poisson's ratio for ideal polycrystalline SrPd 2Ge 2 aggregates, using the Voigt-Reuss-Hill approximations. We estimated the Debye temperature and minimum thermal conductivity of SrPd 2Ge 2 from the average sound velocity. Through the quasi-harmonic Debye model, in which the phononic effects are considered, the temperature and pressure effects on the primitive cell volume, bulk modulus, thermal expansion coefficient, heat capacity and Debye temperature are investigated. This is the first quantitative theoretical prediction of the elastic and thermodynamic properties of the SrPd 2Ge 2 compound, and it still awaits experimental confirmation.
Behnejad, Hassan; Cheshmpak, Hashem; Jamali, Asma
2015-01-01
In this paper, a theoretical method has been introduced for developing the crossover Peng-Robinson (CPR) equation of state (EoS) which incorporates the non-classical scaling laws asymptotically near the critical point into a classical analytic equation further away from the critical point. The CPR EoS has been adopted to describe the thermodynamic properties of some pure fluids (normal alkanes from methane to n-butane and carbon dioxide) such as density, saturated pressure, isochoric heat capacity and speed of sound. Unlike the original method for the crossover transformation made by Chen et al. (Phys Rev A 42:4470-4484, 1990), we have proposed a procedure which adding an additional term into the crossover transformation to obtain the thermophysical properties at the critical point more exactly. It is shown that this new crossover method yields a satisfactory representation of the thermodynamic properties close to the critical point for pure fluids relative to the original PR EoS.
Numerical Prediction of the Thermodynamic Properties of Ternary Al-Ni-Pd Alloys
Zagula-Yavorska, Maryana; Romanowska, Jolanta; Kotowski, Sławomir; Sieniawski, Jan
2016-01-01
Thermodynamic properties of ternary Al-Ni-Pd system, such as exGAlNPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) at 1,373 K, were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting exGAlNiPd values was regarded as calculation of values of the exG function inside a certain area (a Gibbs triangle) unless all boundary conditions, that is values of exG on all legs of the triangle are known (exGAlNi, exGAlPd, exGNiPd). This approach is contrary to finding a function value outside a certain area, if the function value inside this area is known. exG and LAl,Ni,Pd ternary interaction parameters in the Muggianu extension of the Redlich-Kister formalism were calculated numerically using the Excel program and Solver. The accepted values of the third component xx differed from 0.01 to 0.1 mole fraction. Values of LAlNiPd parameters in the Redlich-Kister formula are different for different xx values, but values of thermodynamic functions: exGAlNiPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) do not differ significantly for different xx values. The choice of xx value does not influence the accuracy of calculations.
Thermodynamic properties of liquid Au-Cu-Sn alloys determined from electromotive force measurements
Guo, Zhongnan, E-mail: guozhongn@163.com [Institute of Inorganic chemistry/Material chemistry, University of Vienna, A-1090 Vienna (Austria); Department of Chemistry, School of Chemical and Biological engineering, University of Science and Technology Beijing, 100083 Beijing (China); Hindler, Michael [Institute of Inorganic chemistry/Material chemistry, University of Vienna, A-1090 Vienna (Austria); Yuan, Wenxia [Department of Chemistry, School of Chemical and Biological engineering, University of Science and Technology Beijing, 100083 Beijing (China); Mikula, Adolf [Institute of Inorganic chemistry/Material chemistry, University of Vienna, A-1090 Vienna (Austria)
2011-10-20
Highlights: {yields} A full thermodynamic description of the liquid ternary Au-Cu-Sn system is reported. {yields} The electromotive force method with a liquid electrolyte was used to determine the activity of tin in the alloys. {yields} The partial free energies of tin in this system were calculated from the obtained EMF values. {yields} The Gibbs-Duhem integration was used to calculate the integral Gibbs free energy and integral enthalpy of the entire system. - Abstract: The thermodynamic properties of the ternary Au-Cu-Sn system were determined with the electromotive force (EMF) method using a liquid electrolyte. Three different cross-sections with constant Au:Cu ratios of 3:1, 1:1, and 1:3 were applied to measure the thermodynamic properties of the ternary system in the temperature range between the liquidus temperature of the alloys and 1023 K. The partial free energies of Sn in liquid Au-Cu-Sn alloys were obtained from EMF data. The integral Gibbs free energy and the integral enthalpy at 900 K were calculated by Gibbs-Duhem integration. The ternary interaction parameters were evaluated using the Redlich-Kister-Muggianu polynomial.
First-principles study of structural, elastic, and thermodynamic properties of ZrHf alloy
韦昭; 翟东; 邵晓红; 鲁勇; 张平
2015-01-01
Structural parameters, elastic constants, and thermodynamic properties of ordered and disordered solid solutions of ZrHf alloys are investigated through first-principles calculations based on density-functional theory (DFT). The special quasi-random structure (SQS) method is used to model the disordered phase as a single unit cell, and two lamella structures are generated to model the ordered alloys. Small strains are applied to the unit cells to measure the elastic behavior and mechanical stability of ZrHf alloys and to obtain the independent elastic constants by the stress–strain relationship. Phonon dispersions and phonon density of states are presented to verify the thermodynamic stability of the considered phases. Our results show that both the ordered and disordered phases of ZrHf alloys are structurally stable. Based on the obtained phonon frequencies, thermodynamic properties, including Gibbs free energy, entropy, and heat capacity, are predicted within the quasi-harmonic approximation. It is verified that there are no obvious differences in energy between ordered and disordered phases over a wide temperature range.
Thermodynamic properties and transport coefficients of two-temperature helium thermal plasmas
Guo, Xiaoxue; Murphy, Anthony B.; Li, Xingwen
2017-03-01
Helium thermal plasmas are in widespread use in arc welding and many other industrial applications. Simulation of these processes relies on accurate plasma property data, such as plasma composition, thermodynamic properties and transport coefficients. Departures from LTE (local thermodynamic equilibrium) generally occur in some regions of helium plasmas. In this paper, properties are calculated allowing for different values of the electron temperature, T e, and heavy-species temperature, T h, at atmospheric pressure from 300 K to 30 000 K. The plasma composition is first calculated using the mass action law, and the two-temperature thermodynamic properties are then derived. The viscosity, diffusion coefficients, electrical conductivity and thermal conductivity of the two-temperature helium thermal plasma are obtained using a recently-developed method that retains coupling between electrons and heavy species by including the electron–heavy-species collision term in the heavy-species Boltzmann equation. It is shown that the viscosity and the diffusion coefficients strongly depend on non-equilibrium ratio θ (θ ={{T}\\text{e}}/{{T}\\text{h}} ), through the plasma composition and the collision integrals. The electrical conductivity, which depends on the electron number density and ordinary diffusion coefficients, and the thermal conductivity have similar dependencies. The choice of definition of the Debye length is shown to affect the electrical conductivity significantly for θ > 1. By comparing with literature data, it is shown that the coupling between electrons and heavy species has a significant influence on the electrical conductivity, but not on the viscosity. Plasma properties are tabulated in the supplementary data.
Thermodynamics properties of tachyon cosmology with non-minimal coupling to matter
Farajollahi, H; Abolghasemi, M
2016-01-01
Recently, we have investigated the dynamics of the universe in tachyon cosmology with non-minimal coupling to matter \\cite{faraj}-\\cite{faraj3}. In particular, for the interacting holographic dark energy (IHDE), the model is studied in \\cite{Ravanpak}. In the current work, a significant observational program has been conducted to unveil the model's thermodynamic properties. Our result shows that the IHDE version of our model better fits the observational data than $\\Lambda$CDM model. The first and generalized second thermodynamics laws for the universe enveloped by cosmological apparent and event horizon are revisited. From the results, both first and generalized second laws, constrained by the observational data, are satisfied on cosmological apparent horizon.In addition, the total entropy is verified with the observation only if the horizon of the universe is taken as apparent horizon. Then, due to validity of generalized second law, the current cosmic acceleration is also predicted.
Thermodynamic bounds and general properties of optimal efficiency and power in linear responses.
Jiang, Jian-Hua
2014-10-01
We study the optimal exergy efficiency and power for thermodynamic systems with an Onsager-type "current-force" relationship describing the linear response to external influences. We derive, in analytic forms, the maximum efficiency and optimal efficiency for maximum power for a thermodynamic machine described by a N×N symmetric Onsager matrix with arbitrary integer N. The figure of merit is expressed in terms of the largest eigenvalue of the "coupling matrix" which is solely determined by the Onsager matrix. Some simple but general relationships between the power and efficiency at the conditions for (i) maximum efficiency and (ii) optimal efficiency for maximum power are obtained. We show how the second law of thermodynamics bounds the optimal efficiency and the Onsager matrix and relate those bounds together. The maximum power theorem (Jacobi's Law) is generalized to all thermodynamic machines with a symmetric Onsager matrix in the linear-response regime. We also discuss systems with an asymmetric Onsager matrix (such as systems under magnetic field) for a particular situation and we show that the reversible limit of efficiency can be reached at finite output power. Cooperative effects are found to improve the figure of merit significantly in systems with multiply cross-correlated responses. Application to example systems demonstrates that the theory is helpful in guiding the search for high performance materials and structures in energy researches.
Einstein-Born-Infeld-massive gravity: adS-black hole solutions and their thermodynamical properties
Hendi, S.H. [Physics Department and Biruni Observatory, College of Sciences, Shiraz University,Shiraz 71454 (Iran, Islamic Republic of); Research Institute for Astronomy and Astrophysics of Maragha (RIAAM),P.O. Box 55134-441, Maragha (Iran, Islamic Republic of); Panah, B. Eslam; Panahiyan, S. [Physics Department and Biruni Observatory, College of Sciences, Shiraz University,Shiraz 71454 (Iran, Islamic Republic of)
2015-11-23
In this paper, we study massive gravity in the presence of Born-Infeld nonlinear electrodynamics. First, we obtain metric function related to this gravity and investigate the geometry of the solutions and find that there is an essential singularity at the origin (r=0). It will be shown that due to contribution of the massive part, the number, type and place of horizons may be changed. Next, we calculate the conserved and thermodynamic quantities and check the validation of the first law of thermodynamics. We also investigate thermal stability of these black holes in context of canonical ensemble. It will be shown that number, type and place of phase transition points are functions of different parameters which lead to dependency of stability conditions to these parameters. Also, it will be shown how the behavior of temperature is modified due to extension of massive gravity and strong nonlinearity parameter. Next, critical behavior of the system in extended phase space by considering cosmological constant as pressure is investigated. A study regarding neutral Einstein-massive gravity in context of extended phase space is done. Geometrical approach is employed to study the thermodynamical behavior of the system in context of heat capacity and extended phase space. It will be shown that GTs, heat capacity and extended phase space have consistent results. Finally, critical behavior of the system is investigated through use of another method. It will be pointed out that the results of this method is in agreement with other methods and follow the concepts of ordinary thermodynamics.
Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.
1990-12-01
Catalytic hydrodenitrogenation (HDN) is a key step in upgrading processes for conversion of heavy petroleum, shale oil, tar sands, and the products of the liquefaction of coal to economically viable products. This research program provides accurate experimental thermochemical and thermophysical properties for key organic nitrogen-containing compounds present in the range of alternative feedstocks, and applies the experimental information to thermodynamic analyses of key HDN reaction networks. This report is the first in a series that will lead to an analysis of a three-ring HDN system; the carbazole/hydrogen reaction network. 2-Aminobiphenyl is the initial intermediate in the HDN pathway for carbazole, which consumes the least hydrogen possible. Measurements leading to the calculation of the ideal-gas thermodynamic properties for 2-aminobiphenyl are reported. Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c). Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for selected temperatures between 298.15 K and 820 K. The critical temperature and critical density were determined for 2-aminobiphenyl with the d.s.c., and the critical pressure was derived. The Gibbs energies of formation are used in thermodynamic calculations to compare the feasibility of the initial hydrogenolysis step in the carbazole/H{sub 2} network with that of its hydrocarbon and oxygen-containing analogous; i.e., fluorene/H{sub 2} and dibenzofuran/H{sub 2}. Results of the thermodynamic calculations are compared with those of batch-reaction studies reported in the literature. 57 refs., 8 figs., 18 tabs.
Ozaki, Shunsuke; Nakagawa, Yoshiaki; Shirai, Osamu; Kano, Kenji
2014-11-01
Thermodynamic analysis of the solubility of benzoylphenylurea (BPU) derivatives was conducted to investigate the relative importance of crystal packing and hydration for improving solubility with minor structural modification. The contribution of crystal packing to solubility was evaluated from the change in Gibbs energy on the transition from the crystalline to liquid state. Hydration Gibbs energy was estimated using a linear free-energy relationship between octanol-water partition coefficients and gas-water partition coefficients. The established solubility model satisfactorily explained the relative thermodynamic solubility of the model compounds and revealed that crystal packing and hydration equally controlled solubility of the structural analogs. All hydrophobic substituents were undesirable for solubility in terms of hydration, as expected. On the other hand, some of these hydrophobic substituents destabilized crystal packing and improved the solubility of the BPU derivatives when their impact on crystal packing exceeded their negative influence on hydration. The replacement of a single substituent could cause more than a 10-fold enhancement in thermodynamic solubility; this degree of improvement was comparable to that generally achieved by amorphous formulations. Detailed analysis of thermodynamic solubility will allow us to better understand the true substituent effect and design drug-like candidates efficiently.
Mccarty, R. D.
1980-01-01
The thermodynamic and transport properties of selected cryogens had programmed into a series of computer routines. Input variables are any two of P, rho or T in the single phase regions and either P or T for the saturated liquid or vapor state. The output is pressure, density, temperature, entropy, enthalpy for all of the fluids and in most cases specific heat capacity and speed of sound. Viscosity and thermal conductivity are also given for most of the fluids. The programs are designed for access by remote terminal; however, they have been written in a modular form to allow the user to select either specific fluids or specific properties for particular needs. The program includes properties for hydrogen, helium, neon, nitrogen, oxygen, argon, and methane. The programs include properties for gaseous and liquid states usually from the triple point to some upper limit of pressure and temperature which varies from fluid to fluid.
Structural, mechanical and thermodynamic properties of N-dope BBi compound under pressure
Yalcin, Battal G.
2016-04-01
The structural, mechanical and thermodynamic properties of N-dope BBi compound have been reported in the current study. The structural and mechanical results of the studied binary compounds (BN and BBi) and their ternary alloys BBi1- x N x structures are presented by means of density functional theory. The exchange and correlation effects are taken into account by using the generalized gradient approximation functional of Wu and Cohen which is an improved form of the most popular Perdew-Burke-Ernzerhof. The quasi-harmonic Debye model is used for the thermodynamic properties of studied materials. The basic physical properties of considered structures such as the equilibrium lattice parameter (a 0), bulk modulus (B 0), its pressure derivative (B'), elastic constants (C 11, C 12 and C 44), Kleinman's internal-strain parameter (ƺ), shear modulus anisotropy (A), the average shear modulus (G), Young's modulus (Y) and Poisson's ratio (v), B 0/ G ratio, microhardness parameter (H), Cauchy pressure (C″), and 1st and 2nd Lame constants (λ, μ), debye temperature (θ D), wave velocities (ν l, ν t and ν m), melting temperature (T m) and minimum thermal conductivity (κ min) have been calculated at zero pressure. In order to obtain more information, thermodynamic properties, such as internal energy (U), Helmoltz free energy (F), entropy (S), Debye temperature (θ D), thermal expansion (α), constant volume and pressure heat capacities (C V and C P ), are analyzed under the whole range from 0 to 20 GPa and temperature range from 0 to 1500 K. The obtained results of the studied binary compounds are in coincidence with experimental works.
Dallakyan Sargis
2008-08-01
Full Text Available Abstract Background Gram-negative bacteria use periplasmic-binding proteins (bPBP to transport nutrients through the periplasm. Despite immense diversity within the recognized substrates, all members of the family share a common fold that includes two domains that are separated by a conserved hinge. The hinge allows the protein to cycle between open (apo and closed (ligated conformations. Conformational changes within the proteins depend on a complex interplay of mechanical and thermodynamic response, which is manifested as an increase in thermal stability and decrease of flexibility upon ligand binding. Results We use a distance constraint model (DCM to quantify the give and take between thermodynamic stability and mechanical flexibility across the bPBP family. Quantitative stability/flexibility relationships (QSFR are readily evaluated because the DCM links mechanical and thermodynamic properties. We have previously demonstrated that QSFR is moderately conserved across a mesophilic/thermophilic RNase H pair, whereas the observed variance indicated that different enthalpy-entropy mechanisms allow similar mechanical response at their respective melting temperatures. Our predictions of heat capacity and free energy show marked diversity across the bPBP family. While backbone flexibility metrics are mostly conserved, cooperativity correlation (long-range couplings also demonstrate considerable amount of variation. Upon ligand removal, heat capacity, melting point, and mechanical rigidity are, as expected, lowered. Nevertheless, significant differences are found in molecular cooperativity correlations that can be explained by the detailed nature of the hydrogen bond network. Conclusion Non-trivial mechanical and thermodynamic variation across the family is explained by differences within the underlying H-bond networks. The mechanism is simple; variation within the H-bond networks result in altered mechanical linkage properties that directly affect
Konstantinova, Elena, E-mail: elena.konst@ifsudestemg.edu.br; Sales, José Antonio de
2014-10-01
Creation of magnetic nanodevices leads, in particular, to a growing interest in theoretical investigation of different types of magnetic nanostructures. The purpose of our work is to consider how the properties of such nanomaterials depend on their geometry and on the crystal structure. We report on the Monte Carlo simulation of magnetic nanostructures of different geometric forms, which are based on simple cubic and body-centered cubic cells. The magnetization of spin, magnetic susceptibility and specific heat are investigated for nano-disks, nano-bars and nano-balls of different magnitudes. The combination of dipole and Heisenberg-model interaction are considered for the ferromagnetic case. It is shown that magnetic and thermodynamic properties of nanostructures strongly depend on their geometry. The structures with a body-centered cubic unit cell manifest stronger dependence on size and geometric form. In this case one can interpret the results as an effective reduction of dimension from 3D to 2D for decreasing size of the compound. - Highlights: • Thermodynamic properties of nano-balls are dependent on their size. • Magnetic properties of nano-bars depend on their thickness. • The hysteresis loop is dependent on the geometry of the nanostructure.
Yoozbashi, M.N., E-mail: N_Yoozbashi@sut.ac.ir [Faculty of Materials Engineering, Sahand University of Technology, Tabriz (Iran, Islamic Republic of); Yazdani, S., E-mail: Yazdani@sut.ac.ir [Faculty of Materials Engineering, Sahand University of Technology, Tabriz (Iran, Islamic Republic of)
2010-05-25
Nanostructured, low temperature bainitic steels with remarkable combination of ultimate tensile strength of about 2.5 GPa and high uniform elongation have been developed in the recent decade. To reduce the production cost of these steels, two chemical compositions were designed by using a thermodynamic model which was developed in Cambridge University by Bhadeshia. To attain optimum mechanical properties, the designed steels were transformed isothermally at the temperature range of 200-300 deg. C for different times. The optimum times for each temperature were estimated by evaluation of hardness and XRD results. The measurements of tensile properties and the fracture surface examination by scanning electron microscopy indicated that by modification of chemical composition the cost production of steel not only reduces, but also the mechanical properties particularly total elongation enhances slightly. The results of this study suggest that by using a thermodynamic model and without try and error it is possible to design a new steel with remarkable combination of mechanical properties.
Reference Equations of State for the Thermodynamic Properties of Fluid Phase n-Butane and Isobutane
Bücker, D.; Wagner, W.
2006-06-01
New formulations for the thermodynamic properties of fluid phase n-butane and isobutane in the form of fundamental equations explicit in the Helmholtz energy are presented. The functional form of the correlation equations for the residual parts was developed simultaneously for both substances considering data for the thermodynamic properties of ethane, propane, n-butane, and isobutane. Each contains 25 coefficients which were fitted to selected data for the thermal and caloric properties of the respective fluid both in the single-phase region and on the vapor-liquid phase boundary. This work provides information on the available experimental data for the thermodynamic properties of n- and isobutane, and presents all details of the new formulations. The new equations of state describe the pρT surfaces with uncertainties in density of 0.02% (coverage factor k=2 corresponding to a confidence level of about 95%) from the melting line up to temperatures of 340 K and pressures of 12 MPa. The available reliable data sets in other regions are represented within their experimental uncertainties. The primary data, to which the equation for n-butane was fitted, cover the fluid region from the melting line to temperatures of 575 K and pressures of 69 MPa. The equation for isobutane was fitted to primary data that cover the fluid region from the melting line to temperatures of 575 K and pressures of 35 MPa. Beyond the range described by experimental data, the equations yield reasonable extrapolation behavior up to very high temperatures and pressures. In addition to the equations of state, independent equations for the vapor pressures, the saturated-liquid and saturated-vapor densities, and the melting pressures are given. Tables of thermodynamic properties calculated from the new formulations are listed in Appendix 2. Additionally, a preliminary equation of state for propane is presented that was developed in the course of the simultaneous optimization. This equation has the
Molecular thermodynamics of nonideal fluids
Lee, Lloyd L
2013-01-01
Molecular Thermodynamics of Nonideal Fluids serves as an introductory presentation for engineers to the concepts and principles behind and the advances in molecular thermodynamics of nonideal fluids. The book covers related topics such as the laws of thermodynamics; entropy; its ensembles; the different properties of the ideal gas; and the structure of liquids. Also covered in the book are topics such as integral equation theories; theories for polar fluids; solution thermodynamics; and molecular dynamics. The text is recommended for engineers who would like to be familiarized with the concept
Partanen, Lauri
2017-01-01
Sulfuric and hydrochloric acids participate in several important chemical processes occurring in the atmosphere. Due to its tendency to react with water molecules, sulfuric acid is an important factor in cloud formation and related phenomena. Hydrochloric acid is heavily implicated in stratospheric ozone depletion because of its role as a temporary reservoir for chlorine radicals. In this thesis, the thermodynamics and dynamics of these two acids are investigated. The dynamic part focuse...
Feng, Xuan-Kai; Shi, Siqi; Shen, Jian-Yun; Shang, Shun-Li; Yao, Mei-Yi; Liu, Zi-Kui
2016-10-01
Since Zr-Fe-Sn is one of the key ternary systems for cladding and structural materials in nuclear industry, it is of significant importance to understand physicochemical properties related to Zr-Fe-Sn system. In order to design the new Zr alloys with advanced performance by CALPHAD method, the thermodynamic model for the lower order systems is required. In the present work, first-principles calculations are employed to obtain phonon, thermodynamic and elastic properties of Zr6FeSn2 with C22 structure and the end-members (C22-Zr6FeFe2, C22-Zr6SnSn2 and C22-Zr6SnFe2) in the model of (Zr)6(Fe, Sn)2(Fe, Sn)1. It is found that the imaginary phonon modes are absent for C22-Zr6FeSn2 and C22-Zr6SnSn2, indicating they are dynamically stable, while the other two end-members are unstable. Gibbs energies of C22-Zr6FeSn2 and C22-Zr6SnSn2 are obtained from the quasiharmonic phonon approach and can be added in the thermodynamic database: Nuclearbase. The C22-Zr6FeSn2's single-crystal elasticity tensor components along with polycrystalline bulk, shear and Young's moduli are computed with a least-squares approach based upon the stress tensor computed from first-principles method. The results indicate that distortion is more difficult in the directions normal the c-axis than along to it.
Thermodynamic and relative approach to compute glass-forming ability of oxides
Nouar Boubata; Abdelmalek Roula; Islam Moussaoui
2013-06-01
This study deals with the evaluation of glass-forming ability (GFA) of oxides and is a critical reading of Sun and Rawson thermodynamic approach to quantify this aptitude. Both approaches are adequate but ambiguous regarding the behaviour of some oxides (tendency to amorphization or crystallization). Indeed, ZrO2 and Al2O3 were inappropriately listed by Sun and Rawson to be glassformer oxides while being intermediate ones.We present a non-dimensional approach to value GFA of single oxide by affecting to each one of the coefficients (without measuring units). Obeying to the non-dimensional analysis rules, we introduce a neglected (in all prior thermodynamic models) characteristic: the isobaric heat capacity (p) of oxides, and execute a mathematical treatment of oxides thermodynamic data.We note this coefficient as thermodynamical relative glass-forming ability (ThRGFA) and formulate a model to compute it. Computed values of 2nd, 3rd, 4th and 5th period metal oxides reveal a clear differentiation between them. Indeed, all glass former oxides are characterized by ThRGFA values over 1.709. Moreover, the value intervals confirm the oxides classification into three groups (forming, intermediate and modifier) and sorting of the former ones in distinctive strong and fragile oxides.
Gering, Kevin Leslie
A molecular formulation based on modern liquid state theory is applied to the properties and phase behavior of electrolyte systems containing volatile species. An electrolyte model based on the exponential modification of the Mean Spherical Approximation (EXP-MSA) is used to describe the cation-cation, cation-anion, and anion-anion distributions of the ionic species. This theory represents an improvement over the nonmodified MSA approach, and goes beyond the usual Debye-Huckel theory and Pitzer correlation for treating concentrated solutions. Electrolyte solutions such as water-salt, ammonia-salt, mixed salts, and mixed -solvent systems are investigated over a wide range of temperatures, pressures, and compositions. The usual salt properties, such as osmotic and mean activity coefficients and other thermodynamic properties (enthalpies), are calculated. The predictions are accurate to saturation limits. In addition, an iterative method is presented that is used to predict vapor-liquid equilibria (VLE) and thermodynamic properties of single-salt multisolvent electrolytes of the form solvent-cosolvent-salt. In this method, a local composition model (LCM) and EXP-MSA theory are combined with traditional phase equilibria relations to estimate the pressures and compositions of a vapor phase in equilibrium with a binary-solvent electrolyte. Also, a pseudo-solvent model is proposed as a means of obtaining a variety of averaged liquid phase electrolyte properties. To predict preferential solvation in mixed solvents, a general framework is developed that is based on predicted solvation numbers of each solvent. Preferential solvation will be shown to influence VLE. Results show that phase equilibria is accurately predicted by the above iterative method. Three mixed-solvent electrolyte systems are investigated: water -ethylene glycol-LiBr, ammonia-water-LiBr, and methanol -water-LiCl. Finally, the above electrolyte model is utilized in predicting design criteria for a single
Brustein, Ram; Hadad, Merav
2009-09-04
We show that the equations of motion of generalized theories of gravity are equivalent to the thermodynamic relation deltaQ=TdeltaS. Our proof relies on extending previous arguments by using a more general definition of the Noether charge entropy. We have thus completed the implementation of Jacobson's proposal to express Einstein's equations as a thermodynamic equation of state. Additionally, we find that the Noether charge entropy obeys the second law of thermodynamics if the energy-momentum tensor obeys the null energy condition. Our results support the idea that gravitation on a macroscopic scale is a manifestation of the thermodynamics of the vacuum.
Zhong, Linlin; Wang, Xiaohua; Cressault, Yann; Teulet, Philippe; Rong, Mingzhe
2016-09-01
The metallic vapours (i.e., copper, iron, and silver in this paper) resulting from walls and/or electrode surfaces can significantly affect the characteristics of air plasma. Different from the previous works assuming local thermodynamic equilibrium, this paper investigates the influence of metallic vapours on two-temperature (2 T) air plasma. The 2 T compositions of air contaminated by Cu, Fe, and Ag are first determined based on Saha's and Guldberg-Waage's laws. The thermodynamic properties (including mass density, specific enthalpy, and specific heat) are then calculated according to their definitions. After determining the collision integrals for each pair of species in air-metal mixtures using the newly published methods and source data, the transport coefficients (including electrical conductivity, viscosity, and thermal conductivity) are calculated for air-Cu, air-Fe, and air-Ag plasmas with different non-equilibrium degree θ (Te/Th). The influences of metallic contamination as well as non-equilibrium degree are discussed. It is found that copper, iron, and silver exist mainly in the form of Cu2, FeO, and AgO at low temperatures. Generally, the metallic vapours increase mass density at most temperatures, reduce the specific enthalpy and specific heat in the whole temperature range, and affect the transport properties remarkably from 5000 K to 20 000 K. The effect arising from the type of metals is little except for silver at certain temperatures. Besides, the departure from thermal equilibrium results in the delay of dissociation and ionization reactions, leading to the shift of thermodynamic and transport properties towards a higher temperature.
Thermal stability and related thermodynamic properties of N-ethylthiourea
Ferro, Daniela [CNR, Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Chimica, Universita La Sapienza, P.le A. Moro 5, 00185 Rome (Italy); Badea, Elena [Dipartimento di Chimica IFM, Universita di Torino, Via P. Giuria 9, 10125 Torino (Italy)]. E-mail: elena.badea@unito.it; Jozwiak, Malgorzata [Katedra Chemii Fizycznej, Uniwersytet Lodzki, ul. Pomorska 165, 90-236 Lodz (Poland); Rau, Julietta V. [CNR, Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Chimica, Universita La Sapienza, P.le A. Moro 5, 00185 Rome (Italy)
2007-08-25
The enthalpy and entropy of sublimation of N-ethylthiourea were obtained from the temperature dependence of its vapour pressure measured by both the torsion-effusion and the Knudsen effusion method in the temperature range 360-380 K. The compound undergoes no solid-to-solid phase transition or decomposition below 380 K. The pressure against reciprocal temperature resulted in lg(p, kPa) = (13.40 {+-} 0.27) - (6067 {+-} 102) /T(K). The molar sublimation enthalpy and entropy at the mid interval temperature were {delta}{sub sub} H {sub m}(370 K) = (116.1 {+-} 2.0) kJ mol{sup -1} and {delta}{sub sub} S {sub m}(370 K) = (218.0 {+-} 5.2) J mol{sup -1} K{sup -1}, respectively. The same quantities derived at 298.15 K were (118.8 {+-} 2.1) kJ mol{sup -1} and (226.1 {+-} 5.5) J mol{sup -1} K{sup -1}, respectively.
Intermolecular potentials and the accurate prediction of the thermodynamic properties of water
Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au [Centre for Molecular Simulation, Swinburne University of Technology, PO Box 218, Hawthorn, Victoria 3122 (Australia)
2013-11-21
The ability of intermolecular potentials to correctly predict the thermodynamic properties of liquid water at a density of 0.998 g/cm{sup 3} for a wide range of temperatures (298–650 K) and pressures (0.1–700 MPa) is investigated. Molecular dynamics simulations are reported for the pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, and Joule-Thomson coefficient of liquid water using the non-polarizable SPC/E and TIP4P/2005 potentials. The results are compared with both experiment data and results obtained from the ab initio-based Matsuoka-Clementi-Yoshimine non-additive (MCYna) [J. Li, Z. Zhou, and R. J. Sadus, J. Chem. Phys. 127, 154509 (2007)] potential, which includes polarization contributions. The data clearly indicate that both the SPC/E and TIP4P/2005 potentials are only in qualitative agreement with experiment, whereas the polarizable MCYna potential predicts some properties within experimental uncertainty. This highlights the importance of polarizability for the accurate prediction of the thermodynamic properties of water, particularly at temperatures beyond 298 K.
Intermolecular potentials and the accurate prediction of the thermodynamic properties of water
Shvab, I.; Sadus, Richard J.
2013-11-01
The ability of intermolecular potentials to correctly predict the thermodynamic properties of liquid water at a density of 0.998 g/cm3 for a wide range of temperatures (298-650 K) and pressures (0.1-700 MPa) is investigated. Molecular dynamics simulations are reported for the pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, and Joule-Thomson coefficient of liquid water using the non-polarizable SPC/E and TIP4P/2005 potentials. The results are compared with both experiment data and results obtained from the ab initio-based Matsuoka-Clementi-Yoshimine non-additive (MCYna) [J. Li, Z. Zhou, and R. J. Sadus, J. Chem. Phys. 127, 154509 (2007)] potential, which includes polarization contributions. The data clearly indicate that both the SPC/E and TIP4P/2005 potentials are only in qualitative agreement with experiment, whereas the polarizable MCYna potential predicts some properties within experimental uncertainty. This highlights the importance of polarizability for the accurate prediction of the thermodynamic properties of water, particularly at temperatures beyond 298 K.
Thermodynamic properties of cubic ZrC under high pressure from first-principles calculations
无
2009-01-01
The elastic and thermodynamic properties of Zirconium carbide (ZrC) are investigated by ab initio plane-wave pseudopotential density function theory method. The obtained lattice constant, elastic constant and bulk modulus B are consistent with the experimental and theoretical data. Through the quasi-harmonic Debye model, the dependences of the normalized volume V/V0 and the bulk modulus B on pressure P, as well as the specific heat CV on the temperature T are obtained successfully. The relationships of the thermal expansion α with temperature and pressure are also investigated, which indicate the temperature hardly has any effect on the thermal expansion α at high pressure.
Thermal stability and thermodynamic properties of hybrid proton-conducting polyaryl etherketones.
Marani, D; Di Vona, M L; Traversa, E; Licoccia, S; Beurroies, I; Llewellyn, P L; Knauth, P
2006-08-17
The thermal and structural stability of sulfonated cross-linked PEEK (polyether ether ketone) and its silicon-containing class II hybrid derivatives were characterized by combination of mass spectrometry, infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. Thermodynamic properties of the hybrids were determined, including glass-transition temperature, degree of crystallinity, and thermal stability. The decomposition processes of the hybrid polymers could be consistently interpreted and their energetics quantitatively determined. The introduction of inorganic silanol moieties improves the thermal stability compared to sulfonated products.
Hassanabadi, Hassan
2016-01-01
In this paper, we study the covariant form of the non-relativistic Schrodinger-Pauli equation in the space-time generated by a cosmic string and discuss the solutions of this equation in present of interaction between the magnetic dipole momentum and electromagnetic field. We study the influence of the topology on this system. We obtain the solution of radial part as well as the energy levels. We consider all thermodynamic properties of neutral particle in magnetic cosmic string background by using an approach based on the partition function method.
Santos, Jander P.; Sá Barreto, F. C.
2017-10-01
Thermodynamic and magnetic properties of a trilayer nanostructure of hexagonal lattices described by the spin-1/2 Ising model are investigated by the use of the effective-field theory (EFT) with correlations. The results for the magnetization, the free energy, the internal energy, the entropy, the specific heat and the critical frontiers were obtained. The critical temperature and the compensation temperature are investigated with a negative interlayer coupling, in order to clarify the distinction between the ferromagnetic and ferrimagnetic behaviors. From the thermal variations of the total magnetization, the six compensation types can be found, i.e., L-, Q-, R-, S-, P-, and N-types.
Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys
Kane, Margareet M.; Newhouse, Jocelyn M.; Sadoway, Donald Robert; Kane, Margaret M.
2014-01-01
The variation in the high temperature thermodynamic properties of the Li-Sb system with temperature (425–775ºC) and composition (x[subscript Li] = 0.01–0.75) was determined by electromotive force (emf) measurements in a cell configured as follows: Li-Bi reference electrode (x[subscript Bi] = 0.35) | eutectic of LiCl-KCl or LiCl-LiF | Li-Sb alloy. On the basis of these data the Li-Sb couple was deemed attractive for storage of electrical energy in a liquid metal battery. In addition, an update...
Gangadharan, Rubarani P; Krishnan, S Sampath
2015-06-01
The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6-31G(d, p) and 6-311++G(d,p) basis set by Gaussian program. The results from natural bond orbital (NBO) analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the title molecule. The electron density based local reactivity descriptors such as Fukui functions were calculated. The dipole moment (μ) and polarizability (a), anisotropy polarizability (Δα) and first order hyperpolarizability (β(tot)) of the molecule have been reported. Thermodynamic properties of the title compound were calculated at different temperatures.
Rubarani P Gangadharan; S Sampat H Krishnan
2015-01-01
The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6‐31G(d ,p) and 6‐311+ +G(d ,p) basis set by Gaussian program .The results from natural bond orbital (NBO) analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the ti‐tle molecule .The electron density based local reactivity descriptors such as Fukui functions were calculated . The dipole moment (μ) and polarizability (α) ,anisotropy polarizability (Δα) and first order hyperpolarizability (βtot ) of the molecule have been reported .Thermodynamic properties of the title compound were calculated at different temperatures .
Gonzalez-Perez, Alfredo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)], E-mail: alf@usc.es; Ruso, Juan M. [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Romero, Maria J. [Department of Inorganic Chemistry, Faculty of Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Blanco, Elena [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Prieto, Gerardo [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Sarmiento, Felix [Group of Biophysics and Interfaces, Department of Applied Physics, Faculty of Physics, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain)
2005-06-27
Sodium perfluoroalkyl carboxylates (CnFONa) with n = 6, 9, 10 have been studied by conductivity measurements at different temperatures. The Krafft point was determined for C9FONa and C10FONa at the highest concentration studied by measuring the temperature dependence of the specific conductivity. The critical micelle concentration (cmc) and the ionization degree of the micelle ({beta}) were estimated from conductivity vs. molality plots at different temperatures. Using these data and previous results on temperature dependence of cmc and {beta} of sodium perfluoroheptanoate and perfluorooctanoate, different models were applied to obtain the thermodynamic properties of micellization. The results are discussed in terms of alkyl chain length.
Hassanabadi, H.; Hosseinpour, M. [Shahrood University of Technology, Physics Department, Shahrood (Iran, Islamic Republic of)
2016-10-15
In this paper, we study the covariant form of the non-relativistic Schroedinger-Pauli equation in the space-time generated by a cosmic string and discuss the solutions of this equation in the presence of interaction between the magnetic dipole momentum and electromagnetic field. We study the influence of the topology on this system. We obtain the solution of radial part as well as the energy levels. We consider all thermodynamic properties of a neutral particle in a magnetic cosmic string background by using an approach based on the partition function method. (orig.)
First-Principle Calculations for Elastic and Thermodynamic Properties of Diamond
FU Zhi-Jian; JI Guang-Fu; CHEN Xiang-Rong; GOU Qing-Quan
2009-01-01
The elastic constants and thermodynamic properties of diamond are investigated by using the CRYSTAL03 ture are obtained. The results are in good agreement with the available experimental and theoretical data. Moreover, the relationship between V/V0 and pressure, the elastic constants under high pressure are successfully obtained. Especially, the elastic constants of diamond under high pressure are firstly obtained theoretically. At the same time, the variations of the thermal expansion α with pressure P and temperature Tare obtained systematically in the ranges of 0-870 GPa and 0-1600 K.
Thermodynamic properties of noninteracting quantum gases with spin-orbit coupling
He Li [Jiangsu University of Science and Technology, Zhangjiagang, Jiangsu, 215600 (China); Yu Zengqiang [Institute for Advanced Study, Tsinghua University, Beijing, 100084 (China)
2011-08-15
In this brief report we study thermodynamic properties of noninteracting quantum gases with isotropic spin-orbit coupling. At high temperature, coefficients of virial expansion depend on both temperature T and spin-orbit coupling strength {kappa}. For strong coupling, virial expansion is applicable to the temperature region below the conventional degenerate temperature T{sub F}. At low temperature, specific heat is proportional to {radical}(T) in Bose gases and T in Fermi gases. Temperature dependence of the chemical potential of fermions shows a different behavior when the Fermi surface is above and below the Dirac point.
Elastic and thermodynamic properties of c-BN from first-principles calculations
Hao Yan-Jun; Cheng Yan; Wang Yan-Ju; Chen Xiang-Rong
2007-01-01
The elastic constants and thermodynamic properties of c-BN are calculated using the first-principles plane wave method with the relativistic analytic pseudopotential of the Hartwigen, Goedecker and Hutter (HGH) type in the frame of local density approximation and using the quasi-harmonic Debye model, separately. Moreover, the dependences of the normalized volume V/V0 on pressure P, as well as the bulk modulus B, the thermal expansion α, and the heat capacity CV on pressure P and temperature T are also successfully obtained.
Internet calculations of thermodynamic properties of substances: Some problems and results
Ustyuzhanin, E. E.; Ochkov, V. F.; Shishakov, V. V.; Rykov, S. V.
2016-11-01
Internet resources (databases, web sites and others) on thermodynamic properties R = (p,T,s,...) of technologically important substances are analyzed. These databases put online by a number of organizations (the Joint Institute for High Temperatures of the Russian Academy of Sciences, Standartinform, the National Institute of Standards and Technology USA, the Institute for Thermal Physics of the Siberian Branch of the Russian Academy of Sciences, etc) are investigated. Software codes are elaborated in the work in forms of “client functions” those have such characteristics: (i) they are placed on a remote server, (ii) they serve as open interactive Internet resources. A client can use them for a calculation of R properties of substances. “Complex client functions” are considered. They are focused on sharing (i) software codes elaborated to design of power plants (PP) and (ii) client functions those can calculate R properties of working fluids for PP.
The temperature behaviour of the elastic and thermodynamic properties of fcc thorium
Jaroszewicz, S., E-mail: jaroszew@tandar.cnea.gov.ar [Gerencia de Investigacion y Aplicaciones, Comision Nacional de Energia Atomica, Av. Gral. Paz 1499, San Martin (Argentina); Instituto de Tecnologia Jorge A. Sabato, UNSAM-CNEA (Argentina); Mosca, H.O. [Gerencia de Investigacion y Aplicaciones, Comision Nacional de Energia Atomica, Av. Gral. Paz 1499, San Martin (Argentina); Instituto de Tecnologia Jorge A. Sabato, UNSAM-CNEA (Argentina); Garces, J.E. [DAEE, Centro Atomico Bariloche, Comisin Nacional de Energia Atomica, Av. Bustillo 9500, Bariloche, Rio Negro (Argentina)
2012-10-15
The temperature behaviour of the structural, elastical and thermal properties of fcc thorium have been calculated from a free-parameter Helmholtz free energy developed by computing the cohesive energy from first principles calculations coupled to the Chen-Moebius lattice inversion method and the Debye-Grueneisen quasiharmonic model. The elastic constants, shear modulus, Young modulus, Poisson's ratio and thermodynamic properties of fcc Th as the entropy, the harmonic specific heat, the (P, V, T) equation of state and the thermal lattice expansion are found to be in a very good agreement with experiments and ab initio phonon calculations. The results of this work show the potentiality of the Chen-Moebius method coupled to ab initio calculation of the cohesive energy to develop a free-parameter pair potential capable of giving an overall description of fcc Th properties at T = 0 K with an error similar to ab initio calculations.
Lee, Yongjin; Shin, Moon Sam [School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, Seoul 151-744 (Korea, Republic of); Kim, Hwayong [School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, Seoul 151-744 (Korea, Republic of)], E-mail: hwayongk@snu.ac.kr
2008-11-15
We apply the crossover lattice equation of state (xLF EOS) [M.S. Shin, Y. Lee, H. Kim, J. Chem. Thermodyn. 40 (2007) 174-179] to the calculations of thermodynamic 2nd-order derivative properties (isochoric heat capacity, isobaric heat capacity, isothermal compressibility, thermal expansion coefficient, Joule-Thompson coefficient, and sound speed). This equation of state is used to calculate the same properties of pure systems (carbon dioxide, normal alkanes from methane to propane). We show that, over a wide range of states, the equation of state yields properties with better accuracy than the lattice equation of state (LF EOS), and near the critical region, represents singular behavior well.
Structural properties and thermodynamics of water clusters: a Wang-Landau study.
Yin, Junqi; Landau, D P
2011-02-21
The temperature dependence of structural properties and thermodynamic behavior of water clusters has been studied using Wang-Landau sampling. Four potential models, simple point charge/extended (SPC/E), transferable intermolecular potential 3 point (TIP3P), transferable intermolecular potential 4 point (TIP4P), and Gaussian charge polarizable (GCP), are compared for ground states and properties at finite temperatures. Although the hydrogen bond energy and the distance of the nearest-neighbor oxygen pair are significantly different for TIP4P and GCP models, they approach to similar ground state structures and melting transition temperatures in cluster sizes we considered. Comparing with TIP3P, SPC/E model provides properties closer to that of TIP4P and GCP.
Structural properties and thermodynamics of water clusters: A Wang-Landau study
Yin, Junqi; Landau, D. P.
2011-02-01
The temperature dependence of structural properties and thermodynamic behavior of water clusters has been studied using Wang-Landau sampling. Four potential models, simple point charge/extended (SPC/E), transferable intermolecular potential 3 point (TIP3P), transferable intermolecular potential 4 point (TIP4P), and Gaussian charge polarizable (GCP), are compared for ground states and properties at finite temperatures. Although the hydrogen bond energy and the distance of the nearest-neighbor oxygen pair are significantly different for TIP4P and GCP models, they approach to similar ground state structures and melting transition temperatures in cluster sizes we considered. Comparing with TIP3P, SPC/E model provides properties closer to that of TIP4P and GCP.
Relating biophysical properties across scales.
Flenner, Elijah; Marga, Francoise; Neagu, Adrian; Kosztin, Ioan; Forgacs, Gabor
2008-01-01
A distinguishing feature of a multicellular living system is that it operates at various scales, from the intracellular to organismal. Genes and molecules set up the conditions for the physical processes to act, in particular to shape the embryo. As development continues the changes brought about by the physical processes lead to changes in gene expression. It is this coordinated interplay between genetic and generic (i.e., physical and chemical) processes that constitutes the modern understanding of early morphogenesis. It is natural to assume that in this multiscale process the smaller defines the larger. In case of biophysical properties, in particular, those at the subcellular level are expected to give rise to those at the tissue level and beyond. Indeed, the physical properties of tissues vary greatly from the liquid to solid. Very little is known at present on how tissue level properties are related to cell and subcellular properties. Modern measurement techniques provide quantitative results at both the intracellular and tissue level, but not on the connection between these. In the present work we outline a framework to address this connection. We specifically concentrate on the morphogenetic process of tissue fusion, by following the coalescence of two contiguous multicellular aggregates. The time evolution of this process can accurately be described by the theory of viscous liquids. We also study fusion by Monte Carlo simulations and a novel Cellular Particle Dynamics (CPD) model, which is similar to the earlier introduced Subcellular Element Model (SEM; Newman, 2005). Using the combination of experiments, theory and modeling we are able to relate the measured tissue level biophysical quantities to subcellular parameters. Our approach has validity beyond the particular morphogenetic process considered here and provides a general way to relate biophysical properties across scales.
Measuring Thermodynamic Properties of Metals and Alloys With Knudsen Effusion Mass Spectrometry
Copland, Evan H.; Jacobson, Nathan S.
2010-01-01
This report reviews Knudsen effusion mass spectrometry (KEMS) as it relates to thermodynamic measurements of metals and alloys. First, general aspects are reviewed, with emphasis on the Knudsen-cell vapor source and molecular beam formation, and mass spectrometry issues germane to this type of instrument are discussed briefly. The relationship between the vapor pressure inside the effusion cell and the measured ion intensity is the key to KEMS and is derived in detail. Then common methods used to determine thermodynamic quantities with KEMS are discussed. Enthalpies of vaporization, the fundamental measurement, are determined from the variation of relative partial pressure with temperature using the second-law method or by calculating a free energy of formation and subtracting the entropy contribution using the third-law method. For single-cell KEMS instruments, measurements can be used to determine the partial Gibbs free energy if the sensitivity factor remains constant over multiple experiments. The ion-current ratio method and dimer-monomer method are also viable in some systems. For a multiple-cell KEMS instrument, activities are obtained by direct comparison with a suitable component reference state or a secondary standard. Internal checks for correct instrument operation and general procedural guidelines also are discussed. Finally, general comments are made about future directions in measuring alloy thermodynamics with KEMS.
Mantz, Adam B; Morris, R Glenn; Schmidt, Robert W
2016-01-01
This is the third in a series of papers studying the astrophysics and cosmology of massive, dynamically relaxed galaxy clusters. Our sample comprises 40 clusters identified as being dynamically relaxed and hot (i.e., massive) in Papers I and II of this series. Here we consider the thermodynamics of the intracluster medium, in particular the profiles of density, temperature and related quantities, as well as integrated measurements of gas mass, average temperature, total luminosity and center-excluded luminosity. We fit power-law scaling relations of each of these quantities as a function of redshift and cluster mass, which can be measured precisely and with minimal bias for these relaxed clusters. For the thermodynamic profiles, we jointly model the density and temperature and their intrinsic scatter as a function of radius, thus also capturing the behavior of the gas pressure and entropy. For the integrated quantities, we also jointly fit a multidimensional intrinsic covariance, providing the first observati...
Relating Biophysical Properties Across Scales
Flenner, Elijah; Neagu, Adrian; Kosztin, Ioan; Forgacs, Gabor
2007-01-01
A distinguishing feature of a multicellular living system is that it operates at various scales, from the intracellular to organismal. Very little is known at present on how tissue level properties are related to cell and subcellular properties. Modern measurement techniques provide quantitative results at both the intracellular and tissue level, but not on the connection between these. In the present work we outline a framework to address this connection. We specifically concentrate on the morphogenetic process of tissue fusion, by following the coalescence of two contiguous multicellular aggregates. The time evolution of this process can accurately be described by the theory of viscous liquids. We also study fusion by Monte Carlo simulations and a novel Cellular Particle Dynamics (CPD) model, which is similar to the earlier introduced Subcellular Element Model (Newman, 2005). Using the combination of experiments, theory and modeling we are able to relate the measured tissue level biophysical quantities to s...
Liu, Chun Mei; Xu, Chao [Wuhan University of Science and Technology (China). Dept. of Applied Physics; Duan, Man Yi [Sichuan Normal Univ., Chengdu (China). College of Physics and Electronic Engineering
2015-07-01
SnS has potential technical applications, but many of its properties are still not well studied. In this work, the structural, thermodynamic, elastic, and electronic properties of α-SnS have been investigated by the plane wave pseudo-potential density functional theory with the framework of generalised gradient approximation. The calculated pressure-dependent lattice parameters agree well with the available experimental data. Our thermodynamic properties of α-SnS, including heat capacity C{sub P}, entropy S, and Gibbs free energy relation of -(G{sub T}-H{sub 0}) curves, show similar growth trends as the experimental data. At T=298.15 K, our C{sub P}=52.31 J/mol.K, S=78.93 J/mol.K, and -(G{sub T}-H{sub 0})=12.03 J/mol all agree very well with experimental data C{sub P}=48.77 J/mol.K and 49.25 J/mol.K, S=76.78 J/mol.K, and -(G{sub T}-H{sub 0})=12.38 J/mol. The elastic constants, together with other elastic properties, are also computed. The anisotropy analyses indicate obvious elastic anisotropy for α-SnS along different symmetry planes and axes. Moreover, calculations demonstrate that α-SnS is an indirect gap semiconductor, and it transforms to semimetal with pressure increasing up to 10.2 GPa. Combined with the density of states, the characters of the band structure have been analysed in detail.
Thermodynamic properties for applications in chemical industry via classical force fields.
Guevara-Carrion, Gabriela; Hasse, Hans; Vrabec, Jadran
2012-01-01
Thermodynamic properties of fluids are of key importance for the chemical industry. Presently, the fluid property models used in process design and optimization are mostly equations of state or G (E) models, which are parameterized using experimental data. Molecular modeling and simulation based on classical force fields is a promising alternative route, which in many cases reasonably complements the well established methods. This chapter gives an introduction to the state-of-the-art in this field regarding molecular models, simulation methods, and tools. Attention is given to the way modeling and simulation on the scale of molecular force fields interact with other scales, which is mainly by parameter inheritance. Parameters for molecular force fields are determined both bottom-up from quantum chemistry and top-down from experimental data. Commonly used functional forms for describing the intra- and intermolecular interactions are presented. Several approaches for ab initio to empirical force field parameterization are discussed. Some transferable force field families, which are frequently used in chemical engineering applications, are described. Furthermore, some examples of force fields that were parameterized for specific molecules are given. Molecular dynamics and Monte Carlo methods for the calculation of transport properties and vapor-liquid equilibria are introduced. Two case studies are presented. First, using liquid ammonia as an example, the capabilities of semi-empirical force fields, parameterized on the basis of quantum chemical information and experimental data, are discussed with respect to thermodynamic properties that are relevant for the chemical industry. Second, the ability of molecular simulation methods to describe accurately vapor-liquid equilibrium properties of binary mixtures containing CO(2) is shown.
A class of black holes in dRGT massive gravity and their thermodynamical properties
Ghosh, Suchant G. [Jamia Millia Islamia, Centre of Theoretical Physics, New Delhi (India); University of Kwazulu-Natal, Astrophysics and Cosmology Research Unit, School of Mathematical Sciences, Private Bag 54001, Durban (South Africa); Tannukij, Lunchakorn [Mahidol University, Department of Physics, Faculty of Science, Bangkok (Thailand); Wongjun, Pitayuth [Naresuan University, The Institute for Fundamental Study, Phitsanulok (Thailand); Ministry of Education, Thailand Center of Excellence in Physics, Bangkok (Thailand)
2016-03-15
We present an exact spherical black hole solution in de Rham, Gabadadze, and Tolley (dRGT) massive gravity for a generic choice of the parameters in the theory, and also discuss the thermodynamical and phase structure of the black hole in both the grand canonical and the canonical ensembles (for the charged case). It turns out that the dRGT black hole solution includes other known solutions to the Einstein field equations, such as the monopole-de Sitter-Schwarzschild solution with the coefficients of the third and fourth terms in the potential and the graviton mass in massive gravity naturally generates the cosmological constant and the global monopole term. Furthermore, we compute the mass, temperature and entropy of the dRGT black hole, and also perform thermodynamical stability analysis. It turns out that the presence of the graviton mass completely changes the black hole thermodynamics, and it can provide the Hawking-Page phase transition which also occurs for the charged black holes. Interestingly, the entropy of a black hole is barely affected and still obeys the standard area law. In particular, our results, in the limit m{sub g} → 0, reduced exactly to the results of general relativity. (orig.)
Thermodynamic Properties of the Azeotropic Mixture of Acetone, Cyclohexane and Methanol
WANG Xiu-Rong; NAN Zhao-Dong; TAN Zhi-Cheng
2006-01-01
Molar heat capacities of the pure samples of acetone, methanol and the azeotropic mixture composed of acetone,cyclohexane and methanol were measured by an adiabatic calorimeter from 78 to 320 K. The solid-solid and solid-liquid phase transitions of the pure samples and the mixture were determined based on the curve of the heat capacity with respect to temperature. The phase transitions took place at (126.16±0.68) and (178.96±1.47) K for the sample of acetone, (157.79±0.95) and (175.93±0.95) K for methanol, which were corresponding to the solid-solid and the solid-liquid phase transitions of the acetone and the methanol, respectively. And the phase transitions occurred in the temperature ranges of 120 to 190 K and 278 to 280 K corresponding to the solid-solid and the solid-liquid phase transitions of mixture of acetone, cyclohexane and methanol, respectively. The thermodynamic functions and the excess thermodynamic functions of the mixture relative to standard temperature of 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.
Łapsa, Joanna; Onderka, Bogusław
2016-08-01
The thermodynamic properties of liquid Ag-Sb-Sn alloys were obtained through use of the drop solution calorimetric method and electromotive force (emf) measurements of galvanic cells with a yttria stabilized zirconia (YSZ) solid electrolyte. The experiments were carried out along Ag0.25Sb0.75, Ag0.5Sb0.5 and Ag0.75Sb0.25 sections of the ternary system in the temperature range from 973 K to 1223 K. From the measured emf, the tin activity in liquid solutions of Ag-Sb-Sn was determined for the first time. The partial and integral enthalpy of mixing were determined from calorimetric measurements at two temperatures. These measurements were performed along two cross-sections: Sb0.5Sn0.5 at 912 K and 1075 K, and Ag0.75Sb0.25 at 1075 K. Both experimental data sets were used to find ternary interaction parameters by applying the Redlich-Kister-Muggianu model of the substitutional solution. Consequently, the set of parameters describing the thermodynamic properties of the liquid phase was derived.
The magnetic and thermodynamic properties of a spin-2 Heisenberg ferromagnetic system
Mert, Gülistan, E-mail: gmert@selcuk.edu.tr
2015-01-15
The magnetic and thermodynamic properties such as the magnetization, internal energy, specific heat and susceptibility of spin-2 Heisenberg ferromagnetic system on a square lattice are studied by using Green's function technique. Without including the next nearest neighbor interaction, one doesn't observe the second-order phase transitions. We found that only when the next nearest neighbor interaction is greater than the nearest neighbor interaction, the second-order phase transitions exist for the small single-ion anisotropy values. Indeed, in the case of negative anisotropy which corresponds to first-order phase transitions, the energies have discontinuities. At the same time, the specific heat shows two peaks. - Highlights: • We investigated the magnetic and thermodynamic properties of spin-2 Heisenberg ferromagnetic system. • We applied Green's function technique to the model. • We found that energies have discontinuities in the case of negative anisotropy. • We obtained that specific heat shows two peaks.
First principal studya of structural, electronic and thermodynamic properties of KTaO3-perovskite.
Hiadsi S.
2013-03-01
Full Text Available The results of first-principles theoretical study of structural, elastic, electronic and thermodynamic properties of KTaO3 compound, have been performed using the full-potential linear augmented plane-wave method plus local orbitals (FP-APW+lo as implemented in the Wien2k code. The exchange-correlation energy, is treated in generalized gradient approximation (GGA using the Perdew–Burke–Ernzerhof (PBE96 and PBEsol, Perdew 2008 parameterization. Also we have used the Engel-Vosko GGA optimizes the corresponding potential for band structure calculations. The calculated equilibrium parameter is in good agreement with other works. The elastic constants were calculated by using the Mehl method. The electronic band structure of this compound has been calculated using the Angel-Vosko (EV generalized gradient approximation (GGA for the exchange correlation potential. We deduced that KTaO3-perovskite exhibit an indirect from R to Γ point. To complete the fundamental characterization of KTaO3 material we have analyzed the thermodynamic properties using the quasi-harmonic Debye model.
T. Sajevic
2011-09-01
Full Text Available Structural and thermodynamic properties of the model solution containing charged oligomers and the equivalent number of counterions were studied by means of the canonical Monte Carlo simulation technique. The oligomers are represented as (flexible freely jointed chains or as a linear (rigid array of charged hard spheres. In accordance with the primitive model of electrolyte solutions, the counterions are modeled as charged hard spheres and the solvent as dielectric continuum. Significant differences in the pair distribution functions, obtained for the rigid (rod-like and flexible model are found but the differences in thermodynamic properties, such as, enthalpy of dilution and excess chemical potential, are less significant. The results are discussed in light of the experimental data an aqueous polyelectrolyte solutions. The simulations suggest that deviations from the fully extended (rod-like conformation yield slightly stronger binding of counterions. On the other hand, the flexibility of polyions, even when coupled with the ion-size effects, cannot be blamed for qualitative differences between the theoretical results and experimental data for enthalpy of dilution.
Pattanasiri, Busara; Li, Ying Wai; Landau, David P.; Wüst, Thomas; Triampo, Wannapong
2013-08-01
Understanding protein folding confined by surfaces is important for both biological sciences and the development of nanomaterials. In this work, we study the properties of a confined HP model protein by three different types of surfaces, namely, surfaces that attract: (a) all monomers; (b) only P monomers; and (c) only H monomers. The thermodynamic and structural quantities, such as the specific heat, number of surface contacts, and number of hydrophobic pairs, are obtained by using Wang-Landau sampling. The conformational "transitions", specifically, the debridging process and hydrophobic core formation, can be identified based on an analysis of these quantities. We found that these transitions take place at different temperatures, and the ground state configurations show variations in structural properties when different surface type is used. These scenarios are confirmed by snapshots of typical states of the systems. From our study, we conclude that the thermodynamics of these transitions and the structural changes depend on the combined actions of both the composition of the H monomers and the P monomers in the HP chain and the surface types.
Rong, Yang; Bin, Tang; Tao, Gao; BingYun, Ao
2016-06-01
Hybrid density functional theory is employed to systematically investigate the structural, magnetic, vibrational, thermodynamic properties of plutonium monocarbide (PuC and PuC0.75). For comparison, the results obtained by DFT, DFT + U are also given. For PuC and PuC0.75, Fock-0.25 hybrid functional gives the best lattice constants and predicts the correct ground states of antiferromagnetic (AFM) structure. The calculated phonon spectra suggest that PuC and PuC0.75 are dynamically stable. Values of the Helmholtz free energy ΔF, internal energy ΔE, entropy S, and constant-volume specific heat C v of PuC and PuC0.75 are given. The results are in good agreement with available experimental or theoretical data. As for the chemical bonding nature, the difference charge densities, the partial densities of states and the Bader charge analysis suggest that the Pu-C bonds of PuC and PuC0.75 have a mixture of covalent character and ionic character. The effect of carbon vacancy on the chemical bonding is also discussed in detail. We expect that our study can provide some useful reference for further experimental research on the phonon density of states, thermodynamic properties of the plutonium monocarbide. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160 and 21401173).
Sahli, B. [Laboratoire de Génie Physique, Université Ibn Khaldoun, Tiaret, 14000 (Algeria); Laboratoire des Matériaux Magnétiques, Université Djillali Liabés, Sidi Bel-Abbes 22000 (Algeria); Bouafia, H., E-mail: hamza.tssm@gmail.com [Laboratoire de Génie Physique, Université Ibn Khaldoun, Tiaret, 14000 (Algeria); Abidri, B.; Abdellaoui, A. [Laboratoire des Matériaux Magnétiques, Université Djillali Liabés, Sidi Bel-Abbes 22000 (Algeria); Hiadsi, S.; Akriche, A. [Laboratoire de Microscope Electronique et Sciences des Matériaux, Université des Sciences et de la Technologie Mohamed Boudiaf, département de Génie Physique, BP1505 El m’naouar, Oran (Algeria); Benkhettou, N.; Rached, D. [Laboratoire des Matériaux Magnétiques, Université Djillali Liabés, Sidi Bel-Abbes 22000 (Algeria)
2015-06-25
Highlights: • The ground state properties of SrUO{sub 3}-Perovskite were investigated. • Elastic constants and their related parameters were calculated. • Electronic properties are treated using GGA-PBEsol + U approach. - Abstract: In this paper, we investigate bulk properties of the cubic SrUO{sub 3}-Perovskite in their nonmagnetic (NM), antiferromagnetic (AFM) and ferromagnetic (FM) states using all-electron self consistent Full Potential Augmented Plane Waves plus local orbital (FP-(L)APW + lo) method within PBEsol Generalized Gradiant density approximations. Our calculation allowed us to predict that the more stable magnetic state of the cubic SrUO{sub 3}-Perovskite is that of the ferromagnetic (FM). This work is the first prediction of elastic constants and their related parameters (Young modulus, shear modulus, Poisson ratio, Zener anisotropy and the Debye temperature) for this cubic compound using Mehl method. We have employed the GGA(PBEsol) and GGA(PBEsol) + U to investigate the electronic band structure, density of states and electronic charge density of SrUO{sub 3}-Perovskite. The electronic band structure calculations revealed that SrUO{sub 3} exhibits metallic behavior. On the other hand the charge density plots for [1 1 0] direction indicates a strong ionic character along the Sr–O bond while the U–O bond has strong covalent character. Finally, we have analyzed the thermodynamic properties using the quasi-harmonic Debye model to complete the fundamental characterization of cubic SrUO{sub 3}-Perovskite.
Wang, Han; Nakamura, Haruki; Fukuda, Ikuo
2016-03-21
We performed extensive and strict tests for the reliability of the zero-multipole (summation) method (ZMM), which is a method for estimating the electrostatic interactions among charged particles in a classical physical system, by investigating a set of various physical quantities. This set covers a broad range of water properties, including the thermodynamic properties (pressure, excess chemical potential, constant volume/pressure heat capacity, isothermal compressibility, and thermal expansion coefficient), dielectric properties (dielectric constant and Kirkwood-G factor), dynamical properties (diffusion constant and viscosity), and the structural property (radial distribution function). We selected a bulk water system, the most important solvent, and applied the widely used TIP3P model to this test. In result, the ZMM works well for almost all cases, compared with the smooth particle mesh Ewald (SPME) method that was carefully optimized. In particular, at cut-off radius of 1.2 nm, the recommended choices of ZMM parameters for the TIP3P system are α ≤ 1 nm(-1) for the splitting parameter and l = 2 or l = 3 for the order of the multipole moment. We discussed the origin of the deviations of the ZMM and found that they are intimately related to the deviations of the equilibrated densities between the ZMM and SPME, while the magnitude of the density deviations is very small.
Wang, Han; Nakamura, Haruki; Fukuda, Ikuo
2016-03-01
We performed extensive and strict tests for the reliability of the zero-multipole (summation) method (ZMM), which is a method for estimating the electrostatic interactions among charged particles in a classical physical system, by investigating a set of various physical quantities. This set covers a broad range of water properties, including the thermodynamic properties (pressure, excess chemical potential, constant volume/pressure heat capacity, isothermal compressibility, and thermal expansion coefficient), dielectric properties (dielectric constant and Kirkwood-G factor), dynamical properties (diffusion constant and viscosity), and the structural property (radial distribution function). We selected a bulk water system, the most important solvent, and applied the widely used TIP3P model to this test. In result, the ZMM works well for almost all cases, compared with the smooth particle mesh Ewald (SPME) method that was carefully optimized. In particular, at cut-off radius of 1.2 nm, the recommended choices of ZMM parameters for the TIP3P system are α ≤ 1 nm-1 for the splitting parameter and l = 2 or l = 3 for the order of the multipole moment. We discussed the origin of the deviations of the ZMM and found that they are intimately related to the deviations of the equilibrated densities between the ZMM and SPME, while the magnitude of the density deviations is very small.
Electrochemical thermodynamic measurement system
Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.
2009-09-29
The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.
Dyekjær, Jane Dannow; Jonsdottir, Svava Osk
2003-01-01
Quantitative Structure-Property Relationship (QSPR) models for prediction of various thermodynamic properties of simple organic compounds have been developed. A number of new descriptors are proposed and used alongside with descriptors available within the Codessa program. An important feature in...
First-principles calculations on thermodynamic properties of BaTiO3 rhombohedral phase.
Bandura, Andrei V; Evarestov, Robert A
2012-07-05
The calculations based on the linear combination of atomic orbitals have been performed for the low-temperature phase of BaTiO(3) crystal. Structural and electronic properties, as well as phonon frequencies were obtained using hybrid PBE0 exchange-correlation functional. The calculated frequencies and total energies at different volumes have been used to determine the equation of state and thermal contribution to the Helmholtz free energy within the quasiharmonic approximation. For the first time, the bulk modulus, volume thermal expansion coefficient, heat capacity, and Grüneisen parameters in BaTiO(3) rhombohedral phase have been estimated at zero pressure and temperatures form 0 to 200 K, based on the results of first-principles calculations. Empirical equation has been proposed to reproduce the temperature dependence of the calculated quantities. The agreement between the theoretical and experimental thermodynamic properties was found to be satisfactory.
Kim, Soon Chul; Suh, Song Hyuck; Min, Yoong Ki; Ahn, Eun Ju [Andong National University, Andong (Korea)
2002-03-01
Two non-ionic surfactants, which are the non-ionic surfactants with the polydisperse properties and non-ionic surfactant with the ellipsoidal structure, and which were measured by the small-angle neutron scattering installed in the Korea Atomic Energy Research Institute have been analyzed by using the IGOR Program code. Through the analysis of the SANS data, the strengths and weaknesses of the IGOR program code have been tested in details. To reinforce the IGOR program, the computer programs which are based on the Percus-Yevick, hypernetted-chain, Rogers-Young, and density functional approximation have been developed for the model micelles, and their results have been compared with the computer simulations. It is expected that this study would be applied to study the thermodynamic and structural properties of polymers with the complex structure. 22 refs., 20 figs., 7 tabs. (Author)
Liquidus Temperatures and Thermodynamic Properties of the KCl-{KNO}2
Peng, Qiang; Ding, Jing; Yang, Xiaoxi; Wei, Xiaolan; Yang, Jianping
2013-05-01
Potassium nitrite is very sensitive to temperature, humidity, and the atmosphere, so few studies have been made in this field for the thermodynamic properties of molten salt with nitrite salt. In this article, the liquidus curves of NaCl-{NaNO}2 are calculated by a simple "hard-sphere" ionic interaction model. The calculated liquidus temperatures show good agreement with experimental values, which implies an ideal mixing enthalpy and entropy for the liquid binary systems. In addition to the phase equilibrium data and experimental thermochemical properties of molten salt systems, the activities of these binary systems are determined by the phase diagrams and the analytical integration of the classical Gibbs-Duhem equation.
SteamTablesGrid: An ActiveX control for thermodynamic properties of pure water
Verma, Mahendra P.
2011-04-01
An ActiveX control, steam tables grid ( StmTblGrd) to speed up the calculation of the thermodynamic properties of pure water is developed. First, it creates a grid (matrix) for a specified range of temperature (e.g. 400-600 K with 40 segments) and pressure (e.g. 100,000-20,000,000 Pa with 40 segments). Using the ActiveX component SteamTables, the values of selected properties of water for each element (nodal point) of the 41×41 matrix are calculated. The created grid can be saved in a file for its reuse. A linear interpolation within an individual phase, vapor or liquid is implemented to calculate the properties at a given value of temperature and pressure. A demonstration program to illustrate the functionality of StmTblGrd is written in Visual Basic 6.0. Similarly, a methodology is presented to explain the use of StmTblGrd in MS-Excel 2007. In an Excel worksheet, the enthalpy of 1000 random datasets for temperature and pressure is calculated using StmTblGrd and SteamTables. The uncertainty in the enthalpy calculated with StmTblGrd is within ±0.03%. The calculations were performed on a personal computer that has a "Pentium(R) 4 CPU 3.2 GHz, RAM 1.0 GB" processor and Windows XP. The total execution time for the calculation with StmTblGrd was 0.3 s, while it was 60.0 s for SteamTables. Thus, the ActiveX control approach is reliable, accurate and efficient for the numerical simulation of complex systems that demand the thermodynamic properties of water at several values of temperature and pressure like steam flow in a geothermal pipeline network.
Mogulkoc, Y.; Ciftci, Y. O.; Kabak, M.; Colakoglu, K.
2014-07-01
The structural, elastic, thermodynamic, electronic and vibrational properties of CsCl-type TbMg have been studied by performing ab initio calculations based on density functional theory using the Vienna Ab initio Simulation Package (VASP). The exchange correlation potential within the generalized-gradient approximation (GGA) of projector augmented wave (PAW) method is used. The calculated structural parameters, such as the lattice constant, bulk modulus, its pressure derivative, formation energy and second-order elastic constants are presented in this paper. The obtained results are compared with related experimental and theoretical studies. The electronic band calculations, total density of states (DOS), partial DOS and charge density are also presented. Formation enthalpy and Cauchy pressure are determined. In order to obtain more information the elastic properties such as Zener anisotropy factor, Poisson’s ratio, Young modulus, isotropic shear modulus, Debye temperature and melting point have been carried out. The elastic constants are calculated in zero and different pressure ranges (0-50 GPa) with bulk modulus. We have performed the thermodynamic properties of TbMg by using quasi-harmonic Debye model. The temperature and pressure variation of the volume, bulk modulus, and thermal expansion coefficient have been predicted over a pressure range of 0-25 GPa for of TbMg. Pressure dependence of the anisotropy factors, Young’s modulus, Poisson’s ratios, bulk modulus and axis compressibility of TbMg are presented along different directions and planes. Finally, the phonon dispersion curves are presented for TbMg.
Xu, Yanhui [The Institute of Electrochemical Power Sources, Soochow University, Moye Road 688, Suzhou 215006 (China); Ju, Hua [School of Urban Rail Transportation, Soochow University, Ganjiang East Road 178, Suzhou 215021 (China)
2009-02-15
It is just the best time to compile and compare the experimental data and to explore the possible laws and to discover the relation between the crystallographic parameters, thermodynamic and electrochemical properties, based on lot of the published experimental data about the hydrogen-storage alloys. An empirical correlation between the unit cell volume and the enthalpy change, equilibrium pressure, discharge capacity has been constructed. The violent change of the equilibrium pressure with the unit cell volume might indicate the change in the interaction nature between the host alloy atoms and the intercalated hydrogen atoms. The dependence of unit cell volume vs. average numbers of total electrons for AB{sub 5}-type alloys exhibits same change tendency as that of the Vanderwaals radius vs. atomic numbers from Fe to Se in the elements' periodic table. It is possible that the total numbers of the electrons decides the unit cell volume. (author)
Tchoua, Roselyne B; Qin, Jian; Audus, Debra J; Chard, Kyle; Foster, Ian T; de Pablo, Juan
2016-09-13
Structured databases of chemical and physical properties play a central role in the everyday research activities of scientists and engineers. In materials science, researchers and engineers turn to these databases to quickly query, compare, and aggregate various properties, thereby allowing for the development or application of new materials. The vast majority of these databases have been generated manually, through decades of labor-intensive harvesting of information from the literature; yet, while there are many examples of commonly used databases, a significant number of important properties remain locked within the tables, figures, and text of publications. The question addressed in our work is whether, and to what extent, the process of data collection can be automated. Students of the physical sciences and engineering are often confronted with the challenge of finding and applying property data from the literature, and a central aspect of their education is to develop the critical skills needed to identify such data and discern their meaning or validity. To address shortcomings associated with automated information extraction, while simultaneously preparing the next generation of scientists for their future endeavors, we developed a novel course-based approach in which students develop skills in polymer chemistry and physics and apply their knowledge by assisting with the semi-automated creation of a thermodynamic property database.
Blending Education and Polymer Science: Semiautomated Creation of a Thermodynamic Property Database
Tchoua, Roselyne B.; Qin, Jian; Audus, Debra J.; Chard, Kyle; Foster, Ian T.; de Pablo, Juan
2016-09-13
Structured databases of chemical and physical properties play a central role in the everyday research activities of scientists and engineers. In materials science, researchers and engineers turn to these databases to quickly query, compare, and aggregate various properties, thereby allowing for the development or application of new materials. The vast majority of these databases have been generated manually, through decades of labor-intensive harvesting of information from the literature, yet while there are many examples of commonly used databases, a significant number of important properties remain locked within the tables, figures, and text of publications. The question addressed in our work is whether and to what extent the process of data collection can be automated. Students of the physical sciences and engineering are often confronted with the challenge of finding and applying property data from the literature, and a central aspect of their education is to develop the critical skills needed to identify such data and discern their meaning or validity. To address shortcomings associated with automated information extraction while simultaneously preparing the next generation of scientists for their future endeavors, we developed a novel course-based approach in which students develop skills in polymer chemistry and physics and apply their knowledge by assisting with the semiautomated creation of a thermodynamic property database.
Thermodynamic properties of a geothermal working fluid; 90% isobutane-10% isopentane: Final report
Gallagher, J.S.; Linsky, D.; Morrison, G.; Levelt Sengers, J.M.H.
1987-04-01
We present tables of thermodynamic properties, and dew and bubble properties, of a mixture of 90 mol % isobutane and 10 mol % isopentane, a working fluid in a binary geothermal power cycle. The tables are generated by a formulation of the Helmholtz free energy, in which the mixture properties are mapped onto the known properties of pure isobutane by means of the principle of generalized corresponding states. The data base for the Helmholtz free energy formulation is new. We report data obtained in three different apparatus: critical-line and isopentane vapor pressure data obtained in a visual cell; vapor-liquid equilibria data obtained in a mercury-operated variable-volume cell; and pressure-volume-temperature data for the 90 mol %-10 mol % mixture obtained in a semi-automated Burnett-isochoric apparatus. The principles of the methods, and estimates of the reliability, are discussed and all experimental data are compared with the surface. The results are tables of specific volume, enthalpy, entropy, specific heat and density and temperature derivatives of the pressure at 10 K temperature increments from 240 to 600 K along isobars from 0.01 to 20 MPa. Separate tables are prepared from the dew and bubble properties of the 90-10 mixture. Estimates of the effects of isomeric impurity of isobutane are given in graphical form.
Askari, Omid; Beretta, Gian Paolo; Eisazadeh-Far, Kian; Metghalchi, Hameed
2016-07-01
Thermodynamic properties of hydrocarbon/air plasma mixtures at ultra-high temperatures must be precisely calculated due to important influence on the flame kernel formation and propagation in combusting flows and spark discharge applications. A new algorithm based on the complete chemical equilibrium assumption is developed to calculate the ultra-high temperature plasma composition and thermodynamic properties, including enthalpy, entropy, Gibbs free energy, specific heat at constant pressure, specific heat ratio, speed of sound, mean molar mass, and degree of ionization. The method is applied to compute the thermodynamic properties of H2/air and CH4/air plasma mixtures for different temperatures (1000-100 000 K), different pressures (10-6-100 atm), and different fuel/air equivalence ratios within flammability limit. In calculating the individual thermodynamic properties of the atomic species needed to compute the complete equilibrium composition, the Debye-Huckel cutoff criterion has been used for terminating the series expression of the electronic partition function so as to capture the reduction of the ionization potential due to pressure and the intense connection between the electronic partition function and the thermodynamic properties of the atomic species and the number of energy levels taken into account. Partition functions have been calculated using tabulated data for available atomic energy levels. The Rydberg and Ritz extrapolation and interpolation laws have been used for energy levels which are not observed. The calculated plasma properties are then presented as functions of temperature, pressure and equivalence ratio, in terms of a new set of thermodynamically self-consistent correlations that are shown to provide very accurate fits suitable for efficient use in CFD simulations. Comparisons with existing data for air plasma show excellent agreement.
Structure, thermodynamic properties, and phase diagrams of few colloids confined in a spherical pore
Paganini, Iván E.; Pastorino, Claudio; Urrutia, Ignacio
2015-06-01
We study a system of few colloids confined in a small spherical cavity with event driven molecular dynamics simulations in the canonical ensemble. The colloidal particles interact through a short range square-well potential that takes into account the basic elements of attraction and excluded-volume repulsion of the interaction among colloids. We analyze the structural and thermodynamic properties of this few-body confined system in the framework of inhomogeneous fluids theory. Pair correlation function and density profile are used to determine the structure and the spatial characteristics of the system. Pressure on the walls, internal energy, and surface quantities such as surface tension and adsorption are also analyzed for a wide range of densities and temperatures. We have characterized systems from 2 to 6 confined particles, identifying distinctive qualitative behavior over the thermodynamic plane T - ρ, in a few-particle equivalent to phase diagrams of macroscopic systems. Applying the extended law of corresponding states, the square well interaction is mapped to the Asakura-Oosawa model for colloid-polymer mixtures. We link explicitly the temperature of the confined square-well fluid to the equivalent packing fraction of polymers in the Asakura-Oosawa model. Using this approach, we study the confined system of few colloids in a colloid-polymer mixture.
Aerosol effect on the evolution of the thermodynamic properties of warm convective cloud fields
Dagan, Guy; Koren, Ilan; Altaratz, Orit; Heiblum, Reuven H.
2016-12-01
Convective cloud formation and evolution strongly depend on environmental temperature and humidity profiles. The forming clouds change the profiles that created them by redistributing heat and moisture. Here we show that the evolution of the field’s thermodynamic properties depends heavily on the concentration of aerosol, liquid or solid particles suspended in the atmosphere. Under polluted conditions, rain formation is suppressed and the non-precipitating clouds act to warm the lower part of the cloudy layer (where there is net condensation) and cool and moisten the upper part of the cloudy layer (where there is net evaporation), thereby destabilizing the layer. Under clean conditions, precipitation causes net warming of the cloudy layer and net cooling of the sub-cloud layer (driven by rain evaporation), which together act to stabilize the atmosphere with time. Previous studies have examined different aspects of the effects of clouds on their environment. Here, we offer a complete analysis of the cloudy atmosphere, spanning the aerosol effect from instability-consumption to enhancement, below, inside and above warm clouds, showing the temporal evolution of the effects. We propose a direct measure for the magnitude and sign of the aerosol effect on thermodynamic instability.
Thermodynamic properties of 9-methylcarbazole and 1,2,3,4-tetrahydro-9-methylcarbazole
Steele, W.V.; Knipmeyer, S.E.; Nguyen, A.; Chirico, R.D.
1991-04-01
Removal of carbazole and its derivatives from heavy petroleum has proved to be particularly difficult using present technology. Studies have shown carbazole and its alkyl-homologs are the dominant nitrogen-containing components in clarified slurry oils, thereby indicating their low reactivity and/or formation during cat-cracking processes. The results reported here will point the way to the development of new methods of nitrogen removal from carbazole and its derivatives. Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for 9-methylcarbazole and 1,2,3,4-tetrahydro-9-methylcarbazole. For studies on 1,2,3,4-tetrahydro-9-methylcarbazole experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, vibrating-tube densitometry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c.). Adiabatic heat-capacity and combustion calorimetric studies were reported previously for 9-methylcarbazole. Vapor pressures by comparative ebulliometry and inclined-piston gauge manometry, and heat-capacities for the liquid phase by d.s.c. are reported here. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 298.15 K and near 700 K. The Gibbs energies of formation will be used in a subsequent report in thermodynamic calculations to study the reaction pathway of the initial hydrogenation step in the carbazole/H{sub 2} hydrodenitrogenation network. 52 refs., 9 figs., 15 tabs.
Thermodynamic properties of liquid Al–Li–Zn alloys determined from electromotive force measurement
Trybula, Marcela, E-mail: m.trybula@imim.pl; Fima, Przemysław; Gąsior, Władysław
2014-07-01
Highlights: • Electromotive force (emf) was measured in liquid Al–Li–Zn alloys. • Partial thermodynamic properties (ΔG, ΔH, ΔS) were determined from emf data. • A set of Redlich–Kister (RK) parameters for liquid was optimized using these data. • Partial and mixing ΔG and ΔH were modelled using new and literature RK parameters. • Calculated mixing enthalpy is in good agreement with literature calorimetric data. - Abstract: Electromotive force measurements (emf) were carried out over broad temperature range for liquid ternary Al–Li–Zn alloys. Partial excess thermodynamic functions of lithium: Gibbs energy, enthalpy and entropy in liquid Al–Li–Zn alloys were determined. These data were compared to modelled values obtained using Redlich–Kister–Muggianu (RMK) equation and the set of literature binary and ternary interaction parameters. Mixing Gibbs energy and enthalpy was also computed with the new set of ternary parameters optimized in this work and confronted to available experimentally determined data.
Paganini, Iván E; Pastorino, Claudio; Urrutia, Ignacio
2015-06-28
We study a system of few colloids confined in a small spherical cavity with event driven molecular dynamics simulations in the canonical ensemble. The colloidal particles interact through a short range square-well potential that takes into account the basic elements of attraction and excluded-volume repulsion of the interaction among colloids. We analyze the structural and thermodynamic properties of this few-body confined system in the framework of inhomogeneous fluids theory. Pair correlation function and density profile are used to determine the structure and the spatial characteristics of the system. Pressure on the walls, internal energy, and surface quantities such as surface tension and adsorption are also analyzed for a wide range of densities and temperatures. We have characterized systems from 2 to 6 confined particles, identifying distinctive qualitative behavior over the thermodynamic plane T - ρ, in a few-particle equivalent to phase diagrams of macroscopic systems. Applying the extended law of corresponding states, the square well interaction is mapped to the Asakura-Oosawa model for colloid-polymer mixtures. We link explicitly the temperature of the confined square-well fluid to the equivalent packing fraction of polymers in the Asakura-Oosawa model. Using this approach, we study the confined system of few colloids in a colloid-polymer mixture.
Suzuki, Hal [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan); Inaba, Akira [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan)], E-mail: inaba@chem.sci.osaka-u.ac.jp; Krawczyk, Jan; Massalska-Arodz, Maria [Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Krakow (Poland)
2008-08-15
As a part of a project of clarifying the physical properties and dynamics of cyanobiphenyls with chiral molecules, thermodynamic properties of (S)-4-(2-methylbutyl)-4'-cyanobiphenyl (5*CB) were investigated by adiabatic calorimetry between T = (5 and 350) K. The complicated phase behaviour was solved and the thermodynamic functions were determined. A new glass transition was identified in the phase II (metastable crystal) at T = 105 K. No inversion of the stability between two crystalline phases was found, being contrary to the expectations from the previous neutron scattering studies.
Reiser, Bernhard
We start presenting the extremal principles we will consider: The Statement of Helmholtz 1868 and Rayleigh (SHR) 1913, generalized by Reiser 1996, the Statement of Kelvin (SK) 1849, the Principle of Minimal Entropy Production (PME) of Prigogine 1947 for linear processes, that of Prigogine and Glansdorff 1954 for non-linear processes and finally, the Principle of Maximal Entropy (MEF) of Jaynes, 1957. First we show the relation between SHR and SK. This is a particular example for the property of Irreversible Thermodynamics (TIP) to treat all kinds of movements of fluids, compounds or any type of energy under the engineering term loss, or accurately spoken, entropy production. This possibility to treat different physical effects in the same manner causes by its simplification, considerable economical advantages of treating processes in the frame of TIP. For example, whereas a balance like the momentum balance (Navier-Stokes equation) has to distinguish between inertial, viscous or pressure effects, the PME treats the movements these effects cause with one term, and no pressure coupling or non-linearity is enclosed. Then we generalize the SK from potential velocity fields to general ones and show that it fits into the MEF. We continue with the generalization of the SHR from 1996 to compressible and non-Newtonian fluids. Further, we notice that these principles hold for time-dependent (non-stationary) processes. Therefore, the general fluid dynamical part of the PME 1947 can be generalized from stationary to time-dependent processes. We show that this is possible not only for velocity fields but also for scalar fields using as an example, the temperature in the case of heat conduction. We see that scalar fields need a transformation well known in mathematics. Comparing the PME 1954 with the completely generalized SHR we see that it holds also for non-linear processes. The same holds for the generalized SK. We close the consideration of extremal principles with the
Thermodynamic properties of the liquid Bi-Cu-Sn lead-free solder alloys
Kopyto M.
2009-01-01
Full Text Available The electromotive force measurement method was employed to determine the thermodynamic properties of liquid Bi-Cu-Sn alloys using solid electrolyte galvanic cells as shown below: Kanthal+Re, Bi-Cu-Sn, SnO2 | Yttria Stabilized Zirconia | air, Pt, Po2=0.2:1 atm Measurements were carried out for three cross-sections with constant Bi/Cu ratio equal to: 1/3, 1 and 3 and for various tin content varying every 10%, resulting in a total of 26 different alloy compositions. The temperature of the measurements varied within the range from 973 to 1325 K. A linear dependence of the e.m.f. on temperature was observed for all alloy compositions and the appropriate line equations were derived. Tin activities were calculated as function of composition and temperature. Results were presented in tables and figures.
周世琦
2003-01-01
Based on the functional integral procedure, a recently proposed bridge density function [J. Chem. Phys. 112 (2000) 8079] is developed to calculate global thermodynamic properties of non-uniform fluids. The resulting surface tension of a hard wall-hard sphere interface as a function of the bulk hard sphere fluid density is in good agreement with the available simulation data. The proposed numerical procedure from the approximation of non-uniform first=order direct correlation function to a non=uniform system with excess Helmholtz free energy is of fundamental importance for phase behaviour under the confined condition due to the fact that many available simple approximations in classical density functional theory are for non=uniform first=order direct correlation function.
A. Zuber
2015-09-01
Full Text Available AbstractThe correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.
First-principles study of structural, elastic and thermodynamic properties of AuIn2
Wu, Hai Ying; Chen, Ya Hong; Deng, Chen Rong; Yin, Peng Fei; Cao, Hong
2015-12-01
The structural, elastic and thermodynamic properties of AuIn2 in the CaF2 structure under pressure have been investigated using ab initio plane wave pseudopotential method within the generalized gradient approximation. The calculated structural parameters and equation of state are in excellent agreement with the available experimental and theoretical results. The elastic constants of AuIn2 at ambient condition are calculated, and the bulk modulus obtained from these calculated elastic constants agrees well with the experimental data. The pressure dependence of the elastic constants, bulk modulus, shear modulus and Young’s modulus has also been investigated. The Debye temperature presents a slight increase with pressure. AuIn2 exhibits ductibility and low hardness characteristics, the ductibility increases while the hardness decreases with the increasing of pressure. The pressure effect on the heat capacity and thermal expansion coefficient for AuIn2 is much larger.
Anasuya Kundu; Barnali Chakrabarti; Tapan Kumar Das
2005-07-01
We adopt the potential harmonics expansion method for an ab initio solution of the many-body system in a Bose condensate containing interacting bosons. Unlike commonly adopted mean-field theories, our method is capable of handling two-body correlation properly. We disregard three- and higher-body correlations. This simplification is ideally suited to dilute Bose Einstein condensates, whose number density is required to be so small that the interparticle separation is much larger than the range of two-body interaction to avoid three- and higher-body collisions, leading to the formation of molecules and consequent instability of the condensate. In our method we can incorporate realistic finite range interactions. We calculate energies of low-lying states of a condensate containing 23Na atoms and some thermodynamical properties of the condensate.
Thermodynamic properties and approximate solutions of the ℓ-state Pöschl–Teller-type potential
W.A. Yahya
2016-10-01
Full Text Available In this study, the solutions of the ℓ-state Pöschl–Teller-type potential for the Schrödinger and Klein–Gordon equations are obtained using the parametric Nikiforov–Uvarov method. Solving the Schrödinger and Klein–Gordon wave equations, the energy eigenvalues and wave functions are obtained. For the case ℓ=0, we made comparison with previous results where the solutions of Schrödinger equation for the Pöschl–Teller-type potential were obtained for s-wave (ℓ=0 state. We also obtain the thermodynamic properties such as vibrational mean energy, vibrational specific heat, vibrational mean free energy and vibrational entropy for the Pöschl–Teller-type potential in the classical limit.
Ng, T.Y.; Ren, Y.X. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liew, K.M. [Department of Building and Construction, City University of Hong Kong, Tat Chee Avenue, Kowloon (China)
2010-05-15
In the present work, we present a systematic analysis of the chemisorption process pathway of hydrogen atoms onto the exterior wall of (5,5) carbon nanotubes using the ONIOM2 (B3LYP(6-31+G(d,p):UFF)) scheme, and we avoid the gross assumption of fixing any of the carbon atoms during the simulation. It is shown that the adsorption of hydrogen atoms onto the sidewall of CNTs are energetically favorable and the most stable state is to form two H-C {sigma}-bonds while the original {sigma}-bond between the carbon atoms is totally severed. In particular, we examined the molecular thermodynamics properties for the reaction at a range of temperatures from 77 K to 1000 K, and the results suggests that the reaction is possible at ambient temperature, but it is less favorable than that at lower temperatures. (author)
Hydrogen Absorption Thermodynamic Properties of Rare Earth Based Hydrogen Storage Alloy in Benzene
蔡官明; 陈长聘; 安越; 徐国华; 陈立新; 王启东
2002-01-01
The hydriding/dehydriding thermodynamic properties of the slurry system formed by suspending La-rich mischmetal nickel hydrogen storage alloy (MlNi5) in Benzene (C6H6) were investigated. The pressure-composition isotherms for both the alloy powder and the slurry suspended with MlNi5 were measured at several temperatures(10, 20, 30, 40 ℃). The standard enthalpy of formation ΔH° and standard entropy of formation ΔS° for the alloy powder with and without benzene were determined respectively. The experimental results show that the values of ΔH° and ΔS° for the hydriding reaction of hydrogen storage alloy (MlNi5) of the slurry system and the gas-solid system are all very close.
Thermodynamic properties of isomeric iso-butoxybenzoic acids: Experimental and theoretical study
Jakubczyk, Michał; Sporzyński, Andrzej [Faculty of Chemistry, Warsaw University of Technology, 00-664 Warszawa (Poland); Emel’yanenko, Vladimir N.; Varfolomeev, Mikhail A. [Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Department of Physical Chemistry and Department, Science and Technology of Life, Light and Matter, University of Rostock, D-18059 Rostock (Germany)
2015-09-10
Highlights: • Vapor pressures of butoxy benzoic acid derivatives were measured. • Vaporization, sublimation and fusion enthalpies were derived. • Molar enthalpies of formation were measured by calorimetry. • Thermochemical data tested for consistency using additivity rules and computations. • Simple additivity method suggested for prediction thermochemical properties. - Abstract: Standard (p° = 0.1 MPa) molar enthalpies of formation at the temperature T = 298.15 K of the 2-, 3-, and 4-iso-butoxybenzoic acids were measured using the combustion calorimetry. Standard molar enthalpies of vaporization and sublimation were derived from the vapor pressure temperature dependencies measured by the transpiration method. Molar enthalpies of the solid state phase transitions were measured by the DSC. Thermodynamic data on alkoxy substituted benzoic acids available in the literature were collected and combined with own experimental results. This data set on alkoxybenzoic acids was evaluated by using quantum-chemical and group-additivity methods.
First-principles calculations for electronic,optical and thermodynamic properties of ZnS
Hu CuiE; Zeng Zhao-Yi; Cheng Yan; Chen Xiang-Rong; Cai Ling-Cang
2008-01-01
The electronic,optical and thermodynamic properties of ZnS in the zinc-blende(ZB)and wurtzite(WZ)structures are investigated by using the plane-wave pseudopotential density functional theory(DFT).The results obtained are consistent with other theoretical results and the available experimental data.When the pressures are above 20.5 and 27 GPa,the ZB-ZnS and the WZ-ZnS are converted into indirect gap semiconductors,respectively.The critical point structure of the frequency-dependent complex dielectric function is investigated and analysed to identify the optical transitions.Moreover,the values of heat capacity Cv and Debye temperature ⊙ at different pressures and different temperatures are also obtained successfully.
Studies on Thermodynamic Properties of Adsorption of Theophylline by Phenolic Resin Adsorbents
WANG Zhong; SHI Zuo-qing; SHI Rong-fu; FAN Yun-ge; YAN Yi-Zhong
2004-01-01
In the present work, the equilibrium adsorption of theophylline was studied by phenolic resin adsorbents: JDW-2(made by ourselves) and Duolite S-761 within a temperature range of 303-323 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of theophylline on the two adsorbents, the exponents n＞1 indicate that they are favorable to the adsorptions; the negative values of all the isosteric adsorption enthalpies for the theophylline indicate the exothermic process of the adsorption, while the range(10-40 kJ/mol) of their magnitudes manifests the physisorption process; other thermodynamic properties, the free energy changes and the entropy change associated with adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation.
Zi-iiang Liu; Xiao-wei Sun; Cai-rong Zhang; Jian-bo Hu; Ting Song; Jian-hong Qi
2011-01-01
The thermodynamic and elastic properties of magnesium silicate (MgSiO3) perovskite at high pressure are investigated with the quasi-harmonic Debye model and the first-principles method based on the density functional theory.The obtained equation of state is consistent with the available experimental data.The heat capacity and the thermal expansion coefficient agree with the observed values and other calculations at high pressures and temperatures.The elastic constants are calculated using the finite strain method.A complete elastic tensor of MgSiO3 perovskite is determined in the wide pressure range.The geologically important quantities: Young's modulus,Poisson's ratio,Debye temperature,and crystal anisotropy,are derived from the calculated data.
Díez, A; Largo, J; Solana, J R
2006-08-21
Computer simulations have been performed for fluids with van der Waals potential, that is, hard spheres with attractive inverse power tails, to determine the equation of state and the excess energy. On the other hand, the first- and second-order perturbative contributions to the energy and the zero- and first-order perturbative contributions to the compressibility factor have been determined too from Monte Carlo simulations performed on the reference hard-sphere system. The aim was to test the reliability of this "exact" perturbation theory. It has been found that the results obtained from the Monte Carlo perturbation theory for these two thermodynamic properties agree well with the direct Monte Carlo simulations. Moreover, it has been found that results from the Barker-Henderson [J. Chem. Phys. 47, 2856 (1967)] perturbation theory are in good agreement with those from the exact perturbation theory.
Santos, Andrés; López de Haro, Mariano; Yuste, Santos B
2010-05-28
Different theoretical approaches for the thermodynamic properties and the equation of state for multicomponent mixtures of nonadditive hard spheres in d dimensions are presented in a unified way. These include the theory by Hamad, our previous formulation, the original MIX1 theory, a recently proposed modified MIX1 theory, as well as a nonlinear extension of the MIX1 theory proposed in this paper. Explicit expressions for the compressibility factor, Helmholtz free energy, and second, third, and fourth virial coefficients are provided. A comparison is carried out with recent Monte Carlo data for the virial coefficients of asymmetric mixtures and with available simulation data for the compressibility factor, the critical consolute point, and the liquid-liquid coexistence curves. The merits and limitations of each theory are pointed out.
Thermodynamic Properties of Heusler Fe2-x C ox M n S i
Ito, Masakazu; Furuta, Tatsuya; Kai, Keita; Taira, Atsushi; Onda, Keijiro; Shigeta, Iduru; Hiroi, Masahiko
2017-04-01
We investigated the thermodynamic properties of Heusler compounds Fe2-x C ox m n S i (0.00 ≤ x ≤ 2.00). The specific heats CP(T) for compounds with x ≤ 0.1 exhibit a λ-type anomaly arising from spin rearrangements at TR. With increasing x, TR decreases linearly and vanishes at x ∼ 0.169 . The magnetic entropy, STR, derived from the magnetic specific heat, Cm(T), released at TR decreases by increasing x. This means the canting angle of spins from the [111] direction decreases by the substitution of Fe atoms with Co atoms, based on the magnetic structure model of Fe2MnSi proposed by Miles et al. For compounds with 0.5 ≤ x , CP(T) in the low-T range can be reproduced by Debye T3 law. The electronic specific heat coefficient decreases monotonically with x.
Zaghloul, Mofreh R
2015-01-01
We present computational results and tables of the equation-of-state, thermodynamic properties, and shock Hugoniot for hot dense fluid deuterium. The present results are generated using a recently developed chemical model that takes into account different high density effects such as Coulomb interactions among charged particles, partial degeneracy, and intensive short range hard core repulsion. Internal partition functions are evaluated in a statistical-mechanically consistent way implementing recent developments in the literature. The shock Hugoniot curve derived from the present tables is in reasonable overall agreement with the Hugoniot derived from the Nova-laser shock wave experiments on liquid deuterium, showing that deuterium has a significantly higher compressibility than predicted by the SESAME tables or by Path Integral Monte Carlo (PIMC) calculations. Computational results are presented as surface plots for the dissociated fraction, degree of ionization, pressure, and specific internal energy for d...
Study of thermodynamic water properties and moisture sorption hysteresis of mango skin
Silvio José Ferreira de Souza
2015-03-01
Full Text Available The equilibrium moisture content for adsorption and desorption isotherms of mango skin was determined using the static gravimetric method at temperatures of 20, 26, 33, 38 and 44 oC in the 0.056 to 0.873 water activity range. Both sorption curves show a decrease in equilibrium moisture content as the temperature increasing. The hysteresis effect was observed at constant water activity. The Guggenheim, Anderson, and de Boer (GAB model presented the best fitting accuracy among a group of models and was used to determine the thermodynamic properties of water sorption. Integral enthalpy and integral entropy areas showed inverted values for the adsorption and desorption isotherms over the wide range of water activity studied. These values confirm, in energetic terms, the difference between adsorption and desorption isotherms observed in the hysteresis phenomenon. Finally, the Gibbs free energy revealed that the sorption process was spontaneous for both sorption isotherms.
Thermodynamic properties of solid face centered cubic Rb3C60 at high temperature and pressure
Yang, W.; Sun, J. X.; Liu, H.; Yan, G. F.
2014-03-01
Analytic equation of state and thermodynamic quantities of solid fcc Rb3C60 are derived by using an analytic mean field potential method. For intermolecular forces, the double-exponential potential is utilized. Four potential parameters are determined by fitting experimental compression data of Rb3C60 up to 14 GPa at 296 K. Various physical quantities including isothermals, thermal expansion, isochoric heat capacity, Helmholtz free energy and internal energy are calculated and analyzed. Calculated results are consistent with available experimental data in literature. Furthermore, spinodal temperature for Rb3C60 is found to be 2,860 K. Results verify that analytic mean field potential method is a useful approach to consider the anharmonic effect at high temperatures. Numerous reasonable predictions and the change trend of the properties for Rb3C60 at high temperature and pressure have been given.
Kabadi, V.N.
1995-06-30
The work on this project was initiated on September 1, 1991. The project consisted of two different tasks: (1) Development of a model to compute viscosities of coal derived liquids, and (2) Investigate new models for estimation of thermodynamic properties of solid and liquid compounds of the type that exist in coal, or are encountered during coal processing. As for task 1, a model for viscosity computation of coal model compound liquids and coal derived liquids has been developed. The detailed model is presented in this report. Two papers, the first describing the pure liquid model and the second one discussing the application to coal derived liquids, are expected to be published in Energy & Fuels shortly. Marginal progress is reported on task 2. Literature review for this work included compilation of a number of data sets, critical investigation of data measurement techniques available in the literature, investigation of models for liquid and solid phase thermodynamic computations. During the preliminary stages it was discovered that for development of a liquid or solid state equation of state, accurate predictive models for a number of saturation properties, such as, liquid and solid vapor pressures, saturated liquid and solid volumes, heat capacities of liquids and solids at saturation, etc. Most the remaining time on this task was spent in developing predictive correlations for vapor pressures and saturated liquid volumes of organic liquids in general and coal model liquids in particular. All these developments are discussed in this report. Some recommendations for future direction of research in this area are also listed.
Zhang, Huai-Yong; Zhao, Ying-Qin; Lu, Qing [Sichuan Univ., Chengdu (China). Inst. of Atomic and Molecular Physics; Zeng, Zhao-Yi [Chongqing Normal Univ. (China). College of Physics and Electronic Engineering; Chinese Academy of Engineering Physics, Mianyang (China). National Key Laboratory for Shock Wave and Detonation Physics Research; Cheng, Yan [Sichuan Univ., Chengdu (China). Inst. of Atomic and Molecular Physics; Sichuan Univ., Chengdu (China). Key Laboratory of High Energy Density Physics and Technology of Ministry of Education
2016-11-01
Lattice dynamics, structural phase transition, and the thermodynamic properties of barium titanate (BaTiO{sub 3}) are investigated by using first-principles calculations within the density functional theory (DFT). It is found that the GGA-WC exchange-correlation functional can produce better results. The imaginary frequencies that indicate structural instability are observed for the cubic, tetragonal, and orthorhombic phases of BaTiO{sub 3} and no imaginary frequencies emerge in the rhombohedral phase. By examining the partial phonon density of states (PDOSs), we find that the main contribution to the imaginary frequencies is the distortions of the perovskite cage (Ti-O). On the basis of the site-symmetry consideration and group theory, we give the comparative phonon symmetry analysis in four phases, which is useful to analyze the role of different atomic displacements in the vibrational modes of different symmetry. The calculated optical phonon frequencies at Γ point for the four phases are in good agreement with other theoretical and experimental data. The pressure-induced phase transition of BaTiO{sub 3} among four phases and the thermodynamic properties of BaTiO{sub 3} in rhombohedral phase have been investigated within the quasi-harmonic approximation (QHA). The sequence of the pressure-induced phase transition is rhombohedral → orthorhombic → tetragonal → cubic, and the corresponding transition pressure is 5.17, 5.92, 6.65 GPa, respectively. At zero pressure, the thermal expansion coefficient α{sub V}, heat capacity C{sub V}, Grueneisen parameter γ, and bulk modulus B of the rhombohedral phase BaTiO{sub 3} are estimated from 0 K to 200 K.
Li, Guanchen; von Spakovsky, Michael R
2016-09-01
This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the nonmutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micromechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and near-equilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single-particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in the near-equilibrium realm.
Fisenko, Anatoliy I
2016-01-01
The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these ...
Models of thermodynamic and transport properties of POE VG68 and R410A/POE VG68 mixture
2008-01-01
The thermodynamic properties of a refrigerantoil mixture are the foundation to predict the performance of air-conditioning and refrigeration systems and to evaluate the influence of oil on heat transfer and pressure drop.Models of the thermodynamic and transport properties of POE VG68 and R410A/POE VG68 mixture were provided based on the analysis of state-of-the-art correlations.New models were developed by modifying the coefficients in existing correlations with multiple regression method according to experimental data.The maximum deviation of the predicted values of these models to the experimental data is within 5%.These models can be used for R410A/POE VG68 to obtain accurate and reliable thermodynamic and transport parameters to evaluate the influence of POE VG68 on the performance of an R410A air-conditioning and refrigeration system.
Samujlov E.
2013-04-01
Full Text Available In case of system with chemical reaction the most important properties are heat conductivity and heat capacity. In this work we have considered the equation for estimate the component of these properties caused by chemical reaction and ionization processes. We have evaluated the contribution of this part in heat conductivity and heat capacity too. At the high temperatures contribution in heat conductivity from ionization begins to play an important role. We have created a model, which describe partial and full ionization of gases and gas mixtures. In addition, in this work we present the comparison of our result with experimental data and data from numerical simulation. We was used the data about transport properties of middle composition of Russian coals and the data of thermophysical properties of natural gas for comparison.
Peleties, F. [Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Segovia, J.J. [Grupo de Termodinamica y Calibracion (TERMOCAL), Dpto. Ingenieria Energetica y Fluidomecanica, E.T.S. de Ingenieros Industriales, Universidad de Valladolid, E-47011 Valladolid (Spain); Trusler, J.P.M., E-mail: m.trusler@imperial.ac.u [Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Vega-Maza, D. [Grupo de Termodinamica y Calibracion (TERMOCAL), Dpto. Ingenieria Energetica y Fluidomecanica, E.T.S. de Ingenieros Industriales, Universidad de Valladolid, E-47011 Valladolid (Spain)
2010-05-15
We report measurements of the thermodynamic properties of liquid di-isodecyl phthalate (DIDP) and an equation of state determined therefrom. The speed of sound in DIDP was measured at temperatures between (293.15 and 413.15) K and a pressures between (0.1 and 140) MPa with a relative uncertainty of 0.1%. In addition, the isobaric specific heat capacity was measured at temperatures between (293.15 and 423.15) K at a pressure of 0.1 MPa with a relative uncertainty of 1%, and the density was measured at temperatures between (273.15 and 413.15) K at a pressure of 0.1 MPa with a relative uncertainty of 0.015%. The thermodynamic properties of DIDP were obtained from the measured speeds of sound by thermodynamic integration starting from the initial values of density and isobaric specific heat capacity obtained experimentally. The results have been represented by a new equation of state containing nine parameters with an uncertainty in density not worse than 0.025%. Comparisons with literature data are made.
Probing the Limits: Collected Works on the Second Law of Thermodynamics and Special Relativity
D'Abramo, Germano
2017-01-01
Synopsis: This book brings together the chief results of the research work carried out by the author on the second law of thermodynamics and the theory of special relativity since 2008. The first six chapters are devoted to the research on the epistemological status of the second law of thermodynamics and the connection between thermionic/photoelectric phenomena and the second law: evidence is provided that thermionic emission could, in principle, violate the second law. More precisely, the photoelectric emission induced by the high-frequency tail of black-body radiation at room temperature (heat) can be harnessed to charge a capacitor and provide readily usable energy from a single heat reservoir. Chapter 7 contains some reflections on special relativity. It is the most speculative part of the book and it has not been published elsewhere. Two thought experiments on time dilation in the framework of special relativity are presented. The main contention in this part of the book is that if both postulates of special relativity are assumed to hold concurrently, then the prediction of asymmetric ageing made by Einstein in his 1905 relativity paper appears to be in fact incompatible with them and the fact that time dilation (which is intimately related to "asymmetric ageing") seems to have been experimentally confirmed provides, paradoxically, a refutation rather than a confirmation of the theory of special relativity, at least as interpreted today. A critical assessment of Purcell's basic explanation of magnetic forces, which basically relies on special relativity, is also given at the end of the book.
Nilgün Şen
2016-10-01
Full Text Available The B3LYP/6-311++G(2df,2p density functional theory (DFT method was used to investigate molecular geometry and thermodynamic properties of RDX and RDX derivatives containing Al and B metals. The detonation velocity (D and detonation pressure (P, estimated by using Kamlet–Jacobs and in literature equations, respectively. Total energies (Et, frontier orbital energy (EHOMO, ELOMO, energy gap (ΔELUMO–HOMO and theoretical molecular density (ρ were calculated with Spartan 14 software package program. It was shown that the presence of aluminum and boron atoms affects the good thermal stabilities. The results show that the composite RDX-Al, RDX-B derivatives have higher detonation performance and higher density than RDX. RDX-Al derivatives appeared to be superior to RDX-B mixtures in terms of these parameters. These results provide information on the moleculer design of new energetic materials.
Mechanical, electronic, optical, thermodynamic properties and superconductivity of ScGa3
Parvin, F.; Hossain, M. A.; Ali, M. S.; Islam, A. K. M. A.
2015-01-01
The rare occurrence of type-I superconductivity in binary system ScGa3 has experimentally been shown recently. In the present paper we study the electronic, optical, thermodynamic properties and some aspects of superconductivity of this compound using first-principles calculations. The mechanical properties like elastic constants, bulk modulus, shear modulus, Pugh's ductility index, Young's modulus, Poisson's ratio, elastic anisotropy factor, Peierls stress are calculated for the first time. The material is anisotropic and brittle. Electronic band structure, density of states, Fermi surfaces and bonding nature have also been studied. The optical functions are estimated and discussed for the first time. The high reflectivity is found in the ultraviolet regions up to ~13 eV and thus ScGa3 can serve as a possible shielding material for ultraviolet radiation. Thermal effects on some macroscopic properties of ScGa3 are predicted using the quasi-harmonic Debye model and phonon approximation in the temperature and hydrostatic pressure in the ranges of 0-1000 K and 0-40 GPa, respectively. The calculated electron-phonon coupling constant λ=0.52 yields Tc=2.6 K, which is in very good agreement with the experimentally observed value. The value of the coupling constant and the Ginzburg-Landau parameter (κ=0.09) indicate that the compound is a weak-coupled type-I rare binary BCS superconductor.
Mechanical, electronic, optical, thermodynamic properties and superconductivity of ScGa{sub 3}
Parvin, F. [Department of Physics, Rajshahi University, Rajshahi (Bangladesh); Hossain, M.A. [Department of Physics, Mawlana Bhashani Science and Technology University, Santosh, Tangail 1902 (Bangladesh); Ali, M.S. [Department of Physics, Rajshahi University, Rajshahi (Bangladesh); Islam, A.K.M.A., E-mail: azi46@ru.ac.bd [International Islamic University Chittagong, 154/A College Road, Chittagong 4203 (Bangladesh)
2015-01-15
The rare occurrence of type-I superconductivity in binary system ScGa{sub 3} has experimentally been shown recently. In the present paper we study the electronic, optical, thermodynamic properties and some aspects of superconductivity of this compound using first-principles calculations. The mechanical properties like elastic constants, bulk modulus, shear modulus, Pugh's ductility index, Young's modulus, Poisson's ratio, elastic anisotropy factor, Peierls stress are calculated for the first time. The material is anisotropic and brittle. Electronic band structure, density of states, Fermi surfaces and bonding nature have also been studied. The optical functions are estimated and discussed for the first time. The high reflectivity is found in the ultraviolet regions up to ∼13 eV and thus ScGa{sub 3} can serve as a possible shielding material for ultraviolet radiation. Thermal effects on some macroscopic properties of ScGa{sub 3} are predicted using the quasi-harmonic Debye model and phonon approximation in the temperature and hydrostatic pressure in the ranges of 0–1000 K and 0–40 GPa, respectively. The calculated electron–phonon coupling constant λ=0.52 yields T{sub c}=2.6 K, which is in very good agreement with the experimentally observed value. The value of the coupling constant and the Ginzburg–Landau parameter (κ=0.09) indicate that the compound is a weak-coupled type-I rare binary BCS superconductor.
Mechanical and thermodynamic properties of surfactant aggregates at the solid-liquid interface.
Rabinovich, Yakov I; Vakarelski, Ivan U; Brown, Scott C; Singh, Pankaj K; Moudgil, Brij M
2004-02-01
Surfactants are widely used to stabilize colloidal systems in a variety of industrial applications through the formation of self-assembled aggregates at the solid-liquid interface. Previous studies have reported that the control of surfactant-mediated slurry stability can be achieved through the manipulation of surfactant chain length and concentration. However, a fundamental understanding of the mechanical and energetic properties of these aggregates, which may aid in the molecular-level design of these systems, is still lacking. In this study, experimentally measured force/distance curves between an atomic force microscope (AFM) tip and self-assembled surfactant aggregates on mica or silica substrates at concentrations higher than the bulk critical micelle concentration (CMC) were used to determine their mechanical and thermodynamic properties. The experimental curves were fitted to a model which describes the interaction between a hard sphere (tip) and a soft substrate (surfactant structures) based on a modified Hertz theory for the case of a thin elastic layer on a rigid substrate. The calculated mechanical properties were found to be in the same order of magnitude as those reported for rubber-like materials (e.g., polydimethylsiloxane (PDMS)). By integrating the force/distance curves, the energy required for breaking the surface aggregates was also calculated. These values are close to those reported for bulk-micelle formation.
Theoretical study of elastic, mechanical and thermodynamic properties of MgRh intermetallic compound
S. Boucetta
2014-03-01
Full Text Available In the last years, Magnesium alloys are known to be of great technological importance and high scientific interest. In this work, density functional theory plane-wave pseudo potential method, with local density approximation (LDA and generalized gradient approximation (GGA are used to perform first-principles quantum mechanics calculations in order to investigate the structural, elastic and mechanical properties of the intermetallic compound MgRh with a CsCl-type structure. Comparison of the calculated equilibrium lattice constant and experimental data shows good agreement. The elastic constants were determined from a linear fit of the calculated stress–strain function according to Hooke's law. From the elastic constants, the bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio σ, anisotropy factor A and the ratio B/G for MgRh compound are obtained. The sound velocities and Debye temperature are also predicted from elastic constants. Finally, the linear response method has been used to calculate the thermodynamic properties. The temperature dependence of the enthalpy H, free energy F, entropy S, and heat capacity at constant volume Cv of MgRh crystal in a quasi-harmonic approximation have been obtained from phonon density of states and discussed for the first report. This is the first quantitative theoretical prediction of these properties.
Yuriy Puzachenko
2013-09-01
Full Text Available The paper discusses methods of evaluating thermodynamic properties of landscape cover based on multi-spectral measurements by the Landsat satellites. Authors demonstrate how these methods could be used for studying functionality of landscapes and for spatial interpolation of Flux NET system measurements.
Revisit to Thermodynamic Relations in the AdS/CMT Models
Hyun, Seungjoon; Yi, Sang-Heon
2016-01-01
Motivated by the recent unified approach to the Smarr-like relation of AdS planar black holes in conjunction with the quasi-local formalism on conserved charges, we revisit the quantum statistical and thermodynamic relations of hairy AdS planar black holes. By extending the previous results, we identify the hairy contribution in the bulk and show that the holographic computation can be improved so that it is consistent with the bulk computation. We argue that the first law can be retained in its universal form while the relation between the on-shell renormalized Euclidean action and its free energy interpretation in gravity may be deformed to contain the hairy contribution in hairy AdS black holes.
An introduction to equilibrium thermodynamics
Morrill, Bernard; Hartnett, James P; Hughes, William F
1973-01-01
An Introduction to Equilibrium Thermodynamics discusses classical thermodynamics and irreversible thermodynamics. It introduces the laws of thermodynamics and the connection between statistical concepts and observable macroscopic properties of a thermodynamic system. Chapter 1 discusses the first law of thermodynamics while Chapters 2 through 4 deal with statistical concepts. The succeeding chapters describe the link between entropy and the reversible heat process concept of entropy; the second law of thermodynamics; Legendre transformations and Jacobian algebra. Finally, Chapter 10 provides a
Carlip, S
2014-01-01
The discovery in the early 1970s that black holes radiate as black bodies has radically affected our understanding of general relativity, and offered us some early hints about the nature of quantum gravity. In this chapter I will review the discovery of black hole thermodynamics and summarize the many independent ways of obtaining the thermodynamic and (perhaps) statistical mechanical properties of black holes. I will then describe some of the remaining puzzles, including the nature of the quantum microstates, the problem of universality, and the information loss paradox.
Hallett, Paul; Ogden, Mike; Karim, Kamal; Schmidt, Sonja; Yoshida, Shuichiro
2014-05-01
Soil aggregates are a figment of your energy input and initial boundary conditions, so the basic thermodynamics that drive soil structure formation are needed to understand soil structure dynamics. Using approaches from engineering and materials science, it is possible quantify basic thermodynamic properties, but at present tests are generally limited to highly simplified, often remoulded, soil structures. Although this presents limitations, the understanding of underlying processes driving soil structure dynamics is poor, which could be argued is due to the enormity of the challenge of such an incredibly complex system. Other areas of soil science, particularly soil water physics, relied on simplified structures to develop theories that can now be applied to more complex pore structures. We argue that a similar approach needs to gain prominence in the study of soil aggregates. An overview will be provided of approaches adapted from other disciplines to quantify particle bonding, fracture resistance, rheology and capillary cohesion of soil that drive its aggregation and structure dynamics. All of the tests are limited as they require simplified soil structures, ranging from repacked soils to flat surfaces coated with mineral particles. A brief summary of the different approaches will demonstrate the benefits of collecting basic physical data relevant to soil structure dynamics, including examples where they are vital components of models. The soil treatments we have tested with these engineering and materials science approaches include field soils from a range of management practices with differing clay and organic matters contents, amendment and incubation of soils with a range of microorganisms and substrates in the laboratory, model clay-sand mixes and planar mineral surfaces with different topologies. In addition to advocating the wider adoption of these approaches, we will discuss limitations and hope to stimulate discussion on how approaches could be improved
Thermodynamic properties of copper compounds with oxygen and hydrogen from first principles
Korzhavyi, P.A.; Johansson, B. (Applied Materials Physics, Dept. of Materials Science and Engineering, Royal Inst. of Technology, Stockholm (Sweden))
2010-02-15
We employ quantum-mechanical calculations (based on density functional theory and linear response theory) in order to test the mechanical and chemical stability of several solid-state configurations of Cu1+, Cu2+, O2-, H1-, and H1+ ions. We begin our analysis with cuprous oxide (Cu{sub 2}O, cuprite structure), cupric oxide (CuO, tenorite structure), and cuprous hydride (CuH, wurtzite and sphalerite structures) whose thermodynamic properties have been studied experimentally. In our calculations, all these compounds are found to be mechanically stable configurations. Their formation energies calculated at T = 0 K (including the energy of zero-point and thermal motion of the ions) and at room temperature are in good agreement with existing thermodynamic data. A search for other possible solid-state conformations of copper, hydrogen, and oxygen ions is then performed. Several candidate structures for solid phases of cuprous oxy-hydride (Cu{sub 4}H{sub 2}O) and cupric hydride (CuH{sub 2}) have been considered but found to be dynamically unstable. Cuprous oxy-hydride is found to be energetically unstable with respect to decomposition onto cuprous oxide and cuprous hydride. Metastability of cuprous hydroxide (CuOH) is established in our calculations. The free energy of CuOH is calculated to be some 50 kJ/mol higher than the average of the free energies of Cu{sub 2}O and water. Thus, cuprite Cu{sub 2}O is the most stable of the examined Cu(I) compounds
Yuping, Cang; Xiaoling, Yao; Dong, Chen; Fan, Yang; Huiming, Yang
2016-07-01
The ultrasoft pseudo-potential plane wave method combined with the quasi-harmonic approach have been used to study the electronic, elastic and thermodynamic properties of the tetragonal, monoclinic and orthorhombic Ge3N4. The negative formation enthalpies, the satisfactory of Born's criteria and the linear variations of elastic constants with pressure indicate that the three polymorphs can retain their stabilities in the pressure range of 0-25 GPa. The three Ge3N4 are brittle solids at 0 GPa, while they behave in ductile manners in the pressure range of 5-25 GPa. t- and o-Ge3N4 are hard materials but anisotropic. m-Ge3N4 has the largest ductility among the three phases. The results reveal that m-Ge3N4 belongs to an indirect band gap semiconductor, while t- and o-Ge3N4 have direct band gaps. For the thermal properties, several interesting features can be observed above 300 K. o-Ge3N4 exhibits the largest heat capacity, while m-Ge3N4 shows the highest Debye temperature. The results predicted in this work can provide reference data for future experiments. Project supported by the National Natural Science Foundation of China (Nos. 61475132, 11475143, 61501392, 11304141) and the National Training Programs of Innovation and Entrepreneurship for Undergraduates (No. 201510477001).
Thermodynamic Properties of Compressed CuX (X = Cl, Br) Compounds: Ab Initio Study
Bioud, Nadhira; Kassali, Kamel; Bouarissa, Nadir
2017-04-01
A pseudopotential plane wave method based on the density functional theory has been employed to study some thermodynamic properties of copper chloride (CuCl) and copper bromide (CuBr) compounds under the effect of temperature and pressure. The phase transition pressure, the unit cell volume, the isothermal bulk modulus, the constant volume heat capacity, the entropy, the Debye temperature, the Grüneisen parameter and the volumetric thermal expansion coefficient are studied in the pressure range 0-10 GPa, and for temperatures ranging from 0 K up to 650 K and 750 K for CuCl and CuBr, respectively. The phase transition pressure is found to be around 7.8 and 6.95 GPa for CuCI and CuBr, respectively. These values are respectively in reasonably good agreement with the experimental ones of 8.2 GPa and 6.8 GPa reported in the literature. Moreover, at room temperature and zero pressure, the heat capacity at constant volume and the Grüneisen parameter of both compounds of interest are found to be in good agreement with the available experimental and theoretical data. The information gathered from the present investigation may be useful for the study of the behavior of the fundamental properties of CuCI and CuBr under the influence of high temperature and pressure.
Desgranges, C.; Anderson, P. W.; Delhommelle, J.
2017-02-01
Using molecular simulation, we determine the critical properties of Si as well as the loci for several remarkable thermodynamic contours spanning the supercritical region of the phase diagram. We consider a classical three-body potential as well as a quantum (tight-binding) many-body model, and determine the loci for the ideality contours, including the Zeno line and the H line of ideal enthalpy. The two strategies (classical or quantum) lead to strongly asymmetric binodals and to critical properties in good agreement with each other. The Zeno and H lines are found to remain linear over a wide temperature interval, despite the changes in electronic structure undergone by the fluid along these contours. We also show that the classical and quantum model yield markedly different results for the parameters defining the H line, the exponents for the power-laws underlying the line of minima for the isothermal enthalpy and for the density required to achieve ideal behavior, most notably for the enthalpy.
Atomistic simulations of thermodynamic properties of Xe gas bubbles in U10Mo fuels
Hu, Shenyang; Setyawan, Wahyu; Joshi, Vineet V.; Lavender, Curt A.
2017-04-15
Xe gas bubble superlattice formation is observed in irradiated uranium–10 wt% molybdenum (U10Mo) fuels. However, the thermodynamic properties of the bubbles (the relationship among bubble size, equilibrium Xe concentration, and bubble pressure) and the mechanisms of bubble growth and superlattice formation are not well known. In this work, molecular dynamics is used to study these properties and mechanisms. The results provide important inputs for quantitative mesoscale models of gas bubble evolution and fuel performance. In the molecular dynamics simulations, the embedded-atom method (EAM) potential of U10Mo-Xe (Smirnova et al. 2013) is employed. Initial gas bubbles with low Xe concentration are generated in a U10Mo single crystal. Then Xe atom atoms are continuously added into the bubbles, and the evolution of pressure and dislocation emission around the bubbles is analyzed. The relationship between pressure, equilibrium Xe concentration, and radius of the bubbles is established. It was found that the gas bubble growth is accompanied by partial dislocation emission, which results in a star-shaped dislocation structure and an anisotropic stress field. The emitted partial dislocations have a Burgers vector along the <111> direction and a slip plane of (11-2). Dislocation loop punch-out was not observed. A tensile stress was found along <110> directions around the bubble, favoring the nucleation and formation of a face-centered cubic bubble superlattice in body-centered cubic U10Mo fuels.
Thermodynamic Properties of NH4＋ Fixation in Manured Loess Soil in Shaanxi Province,China
FANXIAOLIN; JUANGTZOCHUAN; 等
1997-01-01
Some thermodynamic properties of NH4+ fixation by loess soil in plowing and clay layers are discussed.The results indicate that the four ion adsorption equations commonly used can describe the properties of NH4+ fixation in these soils under constant temperature.Among the four adsorption equations,the single-surface Langmuir equation is the best.When the concentration of NH4Cl solution is 10-1 mol below,the Freundlich equation can be used. The changes of apparent standard free energy(△G°）,enthalpy(△H°）and entropy(△S°）ilustrate that NH4+ fixation in soil is an endothermic adsorption and spontaneous reaction,and the process can be enhanced by a higher temperature and clay content in soil. The"proper value of NH4+ fixation by soil(K1×qm)imcreased with increasing clay content and temper-ature.The heat of NH4+ fixation in soil(Qm) confirms the conclusions made in this paper.
Zonghua Wang
2013-05-01
Full Text Available Doxorubicin hydrochloride (DOX is an effective anticancer agent for leukemia chemotherapy, although its clinical use has been limited because of its side effects such as cardiotoxicity, alopecia, vomiting, and leucopenia. Attention has been focussed on developing new drug carriers with high adsorption capacity and rapid adsorption rate in order to minimize the side effects of DOX. Graphene oxide (GO, a new type of nanomaterial in the carbon family, was prepared by Hummers method and used as adsorbent for DOX from aqueous solution. The physico-chemical properties of GO were characterized by transmission electron microscope (TEM, Fourier transform infrared spectroscopy (FTIR, zeta potential, and element analysis. The adsorption properties of DOX on GO were studied as a function of contact time, adsorbent dosage, temperature and pH value. The results showed that GO had a maximum adsorption capacity of 1428.57 mg/g and the adsorption isotherm data fitted the Langmuir model. The kinetics of adsorption fits a pseudo-second-order model. The thermodynamic studies indicate that the adsorption of DOX on GO is spontaneous and endothermic in nature.
Influence of volume magnetostriction on the thermodynamic properties of Ni-Mn-Ga shape memory alloys
Kosogor, Anna [National University of Science and Technology “MISiS,” Moscow 119049 (Russian Federation); Institute of Magnetism, 36-b, Vernadsky Str., Kyiv 03142 (Ukraine); Donetsk Institute for Physics and Engineering, Kyiv 03028 (Ukraine); L' vov, Victor A. [Institute of Magnetism, 36-b, Vernadsky Str., Kyiv 03142 (Ukraine); Faculty of Radiophysics, Electronics and Computer Systems, Taras Shevchenko University, Glushkov Str. 4G, Kyiv 01601 (Ukraine); Departament de Fisica, Universitat de les Illes Balears, Ctra. de Valldemossa, km 7.5, 07122 Palma de Mallorca (Spain); Cesari, Eduard [Departament de Fisica, Universitat de les Illes Balears, Ctra. de Valldemossa, km 7.5, 07122 Palma de Mallorca (Spain)
2015-10-07
In the present article, the thermodynamic properties of Ni-Mn-Ga ferromagnetic shape memory alloys exhibiting the martensitic transformations (MTs) above and below Curie temperature are compared. It is shown that when MT goes below Curie temperature, the elastic and thermal properties of alloy noticeably depend on magnetization value due to spontaneous volume magnetostriction. However, the separation of magnetic parts from the basic characteristics of MT is a difficult task, because the volume magnetostriction does not qualitatively change the transformational behaviour of alloy. This problem is solved for several Ni-Mn-Ga alloys by means of the quantitative theoretical analysis of experimental data obtained in the course of stress-strain tests. For each alloy, the entropy change and the transformation heat evolved in the course of MT are evaluated, first, from the results of stress-strain tests and, second, from differential scanning calorimetry data. For all alloys, a quantitative agreement between the values obtained in two different ways is observed. It is shown that the magnetic part of transformation heat exceeds the non-magnetic one for the Ni-Mn-Ga alloys undergoing MTs in ferromagnetic state, while the elevated values of transformation heat measured for the alloys undergoing MTs in paramagnetic state are caused by large MT strains.
Lenz, Dominic A.; Mladek, Bianca M.; Likos, Christos N.; Blaak, Ronald
2016-05-01
We pursue the goal of finding real-world examples of macromolecular aggregates that form cluster crystals, which have been predicted on the basis of coarse-grained, ultrasoft pair potentials belonging to a particular mathematical class [B. M. Mladek et al., Phys. Rev. Lett. 46, 045701 (2006)]. For this purpose, we examine in detail the phase behavior and structural properties of model amphiphilic dendrimers of the second generation by means of monomer-resolved computer simulations. On augmenting the density of these systems, a fluid comprised of clusters that contain several overlapping and penetrating macromolecules is spontaneously formed. Upon further compression of the system, a transition to multi-occupancy crystals takes place, the thermodynamic stability of which is demonstrated by means of free-energy calculations, and where the FCC is preferred over the BCC-phase. Contrary to predictions for coarse-grained theoretical models in which the particles interact exclusively by effective pair potentials, the internal degrees of freedom of these molecules cause the lattice constant to be density-dependent. Furthermore, the mechanical stability of monodisperse BCC and FCC cluster crystals is restricted to a bounded region in the plane of cluster occupation number versus density. The structural properties of the dendrimers in the dense crystals, including their overall sizes and the distribution of monomers are also thoroughly analyzed.
Influence of volume magnetostriction on the thermodynamic properties of Ni-Mn-Ga shape memory alloys
Kosogor, Anna; L'vov, Victor A.; Cesari, Eduard
2015-10-01
In the present article, the thermodynamic properties of Ni-Mn-Ga ferromagnetic shape memory alloys exhibiting the martensitic transformations (MTs) above and below Curie temperature are compared. It is shown that when MT goes below Curie temperature, the elastic and thermal properties of alloy noticeably depend on magnetization value due to spontaneous volume magnetostriction. However, the separation of magnetic parts from the basic characteristics of MT is a difficult task, because the volume magnetostriction does not qualitatively change the transformational behaviour of alloy. This problem is solved for several Ni-Mn-Ga alloys by means of the quantitative theoretical analysis of experimental data obtained in the course of stress-strain tests. For each alloy, the entropy change and the transformation heat evolved in the course of MT are evaluated, first, from the results of stress-strain tests and, second, from differential scanning calorimetry data. For all alloys, a quantitative agreement between the values obtained in two different ways is observed. It is shown that the magnetic part of transformation heat exceeds the non-magnetic one for the Ni-Mn-Ga alloys undergoing MTs in ferromagnetic state, while the elevated values of transformation heat measured for the alloys undergoing MTs in paramagnetic state are caused by large MT strains.
Thermodynamic properties of underdoped YBa2Cu3O6+x cuprates for several doping values
Salas, P.; Solís, M. A.; Fortes, M.; Sevilla, F. J.
2017-05-01
We report the thermodynamic properties of cuprate superconductors YBa2Cu3O6+x, with x ranging from underdoped (x = 0.55) to optimally doped (x = 0.9) regions. We model cuprates as a boson-fermion gas mixture immersed in a layered structure, which is generated via a Dirac-comb potential applied in the perpendicular direction to the CuO2 planes, while the particles move freely in the other two directions. The optimal system parameters, namely, the planes’ impenetrability and the paired-fermion fraction, are obtained by minimizing the Helmholtz free energy in addition to fixing the critical temperature Tc to its experimental value. Using this optimized scheme, we calculate the entropy, the Helmholtz free energy and the specific heat as functions of temperature. Additionally, some fundamental properties of the electronic specific heat are obtained, such as the normal linear coefficient γ(Tc), the quadratic α term and the jump height at Tc. We reproduce the cubic βl term of the total specific heat for low temperatures. Also our multilayer model inherently brings with it the mass anisotropy observed in cuprate superconductors. Furthermore, we establish the doping value beyond which superconductivity is suppressed.
Kumar, Priyank; Bhatt, Nisarg K.; Vyas, Pulastya R.; Gohel, Vinod B.
2016-10-01
The thermophysical properties of rhodium are studied up to melting temperature by incorporating anharmonic effects due to lattice ions and thermally excited electrons. In order to account anharmonic effects due to lattice vibrations, we have employed mean field potential (MFP) approach and for thermally excited electrons Mermin functional. The local form of the pseudopotential with only one effective adjustable parameter rc is used to construct MFP and hence vibrational free energy due to ions - Fion. We have studied equation of state at 300 K and further, to access the applicability of present conjunction scheme, we have also estimated shock-Hugoniot and temperature along principle Hugoniot. We have carried out the study of temperature variation of several thermophysical properties like thermal expansion (βP), enthalpy (EH), specific heats at constant pressure and volume (CP and CV), specific heats due to lattice ions and thermally excited electrons ( and , isothermal and adiabatic bulk moduli (BT and Bs) and thermodynamic Gruneisen parameter (γth) in order to examine the inclusion of anharmonic effects in the present study. The computed results are compared with available experimental results measured by using different methods and previously obtained theoretical results using different theoretical philosophy. Our computed results are in good agreement with experimental findings and for some physical quantities better or comparable with other theoretical results. We conclude that local form of the pseudopotential used accounts s-p-d hybridization properly and found to be transferable at extreme environment without changing the values of the parameter. Thus, even the behavior of transition metals having complexity in electronic structure can be well understood with local pseudopotential without any modification in the potential at extreme environment. Looking to the success of present scheme (MFP + pseudopotential) we would like to extend it further for the
E. Díaz
2007-06-01
Full Text Available Gas chromatography used to calculate the specific retention volume of several hydrocarbons in different chromatographic liquid phases (Squalane, Carbowax-400, Carbowax-1500, Carbowax-4000, Amine-220, Dinonyl phthalate, Tributyl phosphate and Trixylenyl phosphate. Some thermodynamic parameters, such as enthalpy of sorption and Flory-Huggins parameters relating the interaction between liquid phases and solutes, were also calculated from the determined retention volumes. Liquid phase solubility parameters of Squalane, Carbowax-400, Carbowax-1500 and Carbowax-4000 at 80 ºC as well as the polar and apolar components were calculated too. A new model was proposed to correlate polar contribution to the solubility parameter of a liquid phase with the specific retention volume of a solute in this liquid phase.
Lukšič, Miha; Hribar-Lee, Barbara; Vlachy, Vojko; Pizio, O
2012-12-28
The canonical Monte Carlo computer simulations and integral equation theory were applied to examine the structural and thermodynamic properties of a mixture of ions and a core-softened fluid molecules. The positive and negative ions forming a +1:-1 salt were modeled as charged hard spheres, immersed in the dielectric medium. It was shown previously that the core-softened fluid under study is characterized by a set of structural, thermodynamic, and dynamic anomalies. The principal objective of this work was to elucidate how the presence of ions alters this behavior. The structural properties of the mixtures are discussed in terms of the pair distribution functions; in addition, the pair contribution to the excess entropy was calculated. Thermodynamic properties are investigated by using the dependencies of energy and compressibility factor on density, composition of the mixture, and reduced temperature. The heat capacity was also evaluated. Our principal findings concern the description of structural anomalies in the mixture, the dependence of the temperature of maximum density on the ionic concentration, and establishing the regions delimiting the structural and thermodynamic anomalies of the model mixture.
Fisenko, Anatoliy I.; Lemberg, Vladimir F.
2016-09-01
The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these functions have not been established for plutonium carbide. The calculated values for the normal total emissivity of uranium and plutonium carbides at their melting temperatures is in good agreement with experimental data. The obtained results allow to calculate the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides for any size of samples. Based on the model of Hagen-Rubens and the Wiedemann-Franz law, a new method to determine the thermal conductivity of metals and carbides at the melting points is proposed.
Borysow, Jacek, E-mail: jborysow@mtu.edu; Rosso, Leonardo del; Celli, Milva; Ulivi, Lorenzo, E-mail: lorenzo.ulivi@isc.cnr.it [Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, Via Madonna del piano 10, I-50019 Sesto Fiorentino (Italy); Moraldi, Massimo [Dipartimento di Fisica e Astronomia, Università degli Studi di Firenze, Via Sansone 1, I-50019 Sesto Fiorentino (Italy)
2014-04-28
We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.
Borysow, Jacek; del Rosso, Leonardo; Celli, Milva; Moraldi, Massimo; Ulivi, Lorenzo
2014-04-28
We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.
Fisenko, Anatoliy I
2015-01-01
The general analytical expressions for the thermal radiative and thermodynamic properties of a real-body are obtained in a finite range of frequencies at different temperatures. The frequency dependence of the spectral emissivity is represented as a power series. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and total emissivity are expressed in terms of the polylogarithm functions. The general expressions for the thermal radiative and thermodynamic functions are applied for the study of thermal radiation of liquid and solid zirconium carbide. These functions are calculated using experimental data for the frequency dependence of the normal spectral emissivity in the visible-near infrared range at the melting (freezing) point. The gaps between the thermal radiative and thermodynamic functions of liquid and solid zirconium carbide are observed. The g...
Fisenko, Anatoliy I
2014-01-01
Using polylogarithm functions the exact analytical expressions for the radiative and thermodynamic properties of blackbody radiation, such as the Wien displacement law, Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, and pressure in the finite range of frequencies are constructed. The obtained expressions allow us to tabulate these functions in various finite frequency bands at different temperatures for practical applications. As an example, the radiative and thermodynamic functions using experimental data for the monopole spectrum of the Cosmic Microwave Background (CMB) radiation measured by the COBE FIRAS instrument in the 60 - 600 GHz frequency interval at the temperature T = 2.725 K are calculated. The expressions obtained for the radiative and thermodynamic functions can be easily presented in wavelength and wavenumber domains.
Ali, M. A.; Nasir, M. T.; Khatun, M. R.; Islam, A. K. M. A.; Naqib, S. H.
2016-10-01
The structural vibrational, thermodynamical, and optical properties of potentially technologically important, weakly coupled MAX compound, Sc2AlC are calculated using density functional theory (DFT). The structural properties of Sc2AlC are compared with the results reported earlier. The vibrational, thermodynamical, and optical properties are theoretically estimated for the first time. The phonon dispersion curve is calculated and the dynamical stability of this compound is investigated. The optical and acoustic modes are observed clearly. We calculate the Helmholtz free energy (F), internal energy (E), entropy (S), and specific heat capacity (Cv ) from the phonon density of states. Various optical parameters are also calculated. The reflectance spectrum shows that this compound has the potential to be used as an efficient solar reflector.
Wang, Jun-Fei; Fu, Xiao-Nan; Zhang, Xiao-Dong; Wang, Jun-Tao; Li, Xiao-Dong; Jiang, Zhen-Yi
2016-08-01
The structural, elastic, electronic, and thermodynamic properties of thermoelectric material MgAgSb in γ,β,α phases are studied with first-principles calculations based on density functional theory. The optimized lattice constants accord well with the experimental data. According to the calculated total energy of the three phases, the phase transition order is determined from α to γ phase with cooling, which is in agreement with the experimental result. The physical properties such as elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, and anisotropy factor are also discussed and analyzed, which indicates that the three structures are mechanically stable and each has a ductile feature. The Debye temperature is deduced from the elastic properties. The total density of states (TDOS) and partial density of states (PDOS) of the three phases are investigated. The TDOS results show that the γ phase is most stable with a pseudogap near the Fermi level, and the PDOS analysis indicates that the conduction band of the three phases is composed mostly of Mg-3s, Ag-4d, and Sb-5p. In addition, the changes of the free energy, entropy, specific heat, thermal expansion of γ-MgAgSb with temperature are obtained successfully. The obtained results above are important parameters for further experimental and theoretical tuning of doped MgAgSb as a thermoelectric material at high temperature. Project supported by the National Natural Science Foundation of China (Grant No. 11504088), the Fund from Henan University of Technology, China (Grant Nos. 2014YWQN08 and 2013JCYJ12), the Natural Science Fund from the Henan Provincial Education Department, China (Grant No. 16A140027), the Natural Science Foundation of Shaanxi Province of China (Grant Nos. 2013JQ1018 and 15JK1759), and the Science Foundation of Northwest University of China (Grant No. 14NW23).
Electronic, magnetic, elastic and thermodynamic properties of Cu{sub 2}MnGa
Ghosh, Sukriti [Department of Physics, Government Kamla Raja Girls Autonomous Post Graduate College, Gwalior 474001, Madhya Pradesh (India); Condensed Matter Theory Group, School of Studies in Physics, Jiwaji University, Gwalior 474 011, Madhya Pradesh (India); Gupta, Dinesh C., E-mail: sosfizix@gmail.com [Condensed Matter Theory Group, School of Studies in Physics, Jiwaji University, Gwalior 474 011, Madhya Pradesh (India)
2016-08-01
The full-potential linearized augmented plane wave method in the stable Fm-3m phase has been implemented to investigate the structural, elastic, magnetic and electronic properties of Cu{sub 2}MnGa. The optimized equilibrium lattice parameter in stable phase is found to be 5.9495 Å. By the spin resolved density of states calculations, we have shown that the exchange splitting due to Mn atom is the main reason of ferromagnetic behavior of Cu{sub 2}MnGa. The absence of energy gap in both the spin channels predicts that the material is metallic. The total and partial density of states, elastic constants, Shear, Bulk and Young’s moduli, Zener isotropy factor, Cauchy pressure, Pugh's ductility, Kleinman parameter and Poisson's ratio are reported for the first time for the alloy. Cauchy's pressure and Pugh's index of ductility label Cu{sub 2}MnGa as ductile. Cu{sub 2}MnGa is found to be ferromagnetic and anisotropic in nature. The quasi-harmonic approximations have been employed to study the pressure and temperature dependent thermodynamic properties of Cu{sub 2}MnGa. - Highlights: • It is the first attempt to predict a variety of crystal properties of Cu{sub 2}MnGa. • Cu{sub 2}MnGa shows magnetism and hence can prove to be important in modern technology. • Cu{sub 2}MnGa is ductile and hence can attract attention of scientists and technologists.
Ghiaci, M. E-mail: mghiaci@cc.iut.ac.ir; Kia, R.; Kalbasi, R.J
2004-02-01
A study was undertaken to determine the influence of temperature and surfactant concentration on the adsorption of cetyl pyridinium bromide on two ZSM-5 zeolites, and on natural clinoptilolite. The effect of temperature on adsorption and thermodynamic properties was investigated by making measurements at (297, 303, 307, 313) K. The results show that the calculated curves from the general isotherm equation can represent the experimental data very well up to T=313 K. Based on the calculation of the thermodynamics of adsorption, it is evident that the principle contribution to the {delta}G{sup compfn}{sub hm} of negative value is the large positive value of {delta}S{sup compfn}{sub hm} (36 to 52 J {center_dot} mol{sup -1}), whereas {delta}H{sup compfn}{sub hm} is positive and in the range of 1 to 7 kJ {center_dot} mol{sup -1}. Therefore, similar to the micellisation in bulk solution, the second step of surfactant adsorption is an entropy-driven process.
L. O. Olasunkanmi
2013-01-01
Full Text Available Theoretical study of the molecular geometries, electronic and thermodynamic properties of dipyrido-(3,2-a:2,3-c-phenazine (dppz was carried out in the gas phase under standard conditions using PM6 Hamiltonian in semiempirical model. Effects of chlorine substituents on these properties were also investigated. The results showed that all the electronic and thermodynamic properties investigated were affected by the number and relative position of chlorine substituents. Variations in some properties are not significant for some isomeric congeners, having the same number of chlorine substituents, while a number of properties showed general variation with both the number and position of chlorine substituents. Successive addition of one chlorine atom after the other at adjacent position to the last chlorine substituent increases the total energy by 241 eV and decreases the LUMO-HOMO gap by an average value of 0.124 eV. Geometry and energy optimization show that all the molecules considered are planar.
Statistical thermodynamics of alloys
Gokcen, N A
1986-01-01
This book is intended for scientists, researchers, and graduate students interested in solutions in general, and solutions of metals in particular. Readers are assumed to have a good background in thermodynamics, presented in such books as those cited at the end of Chapter 1, "Thermo dynamic Background." The contents of the book are limited to the solutions of metals + metals, and metals + metalloids, but the results are also appli cable to numerous other types of solutions encountered by metallurgists, materials scientists, geologists, ceramists, and chemists. Attempts have been made to cover each topic in depth with numerical examples whenever necessary. Chapter 2 presents phase equilibria and phase diagrams as related to the thermodynamics of solutions. The emphasis is on the binary diagrams since the ternary diagrams can be understood in terms of the binary diagrams coupled with the phase rule, and the Gibbs energies of mixing. The cal culation of thermodynamic properties from the phase diagrams is ...
Bedane, Alemayehu H., E-mail: Alemayehu.Bedane@unb.ca; Xiao, Huining, E-mail: hxiao@unb.ca; Eić, Mladen, E-mail: meic@unb.ca; Farmahini-Farahani, Madjid, E-mail: Madjid.Farahani@unb.ca
2015-10-01
Highlights: • Coating on paper increases the specific surface area but decreases the pore diameter. • Pore size reduction and decrease of hydrophilic property caused reduction in WVTRs. • The low monolayer moisture content of the sample is generally related to the low WVTR. • The net isosteric heats of adsorption decreased with increased sample moisture content. • FT-IR results reveal the formation of water clusters at higher relative humidities. - Abstract: In this study, the surface characteristics, water vapor interactions, and state of water adsorbed on unmodified and coated paper samples were investigated in an attempt to obtain a better understanding of the fundamental principles related to thermodynamics of this process, as well as to provide essential insight that could be used for further improvement of the papers’ barrier properties. Based on the BET measurement, the coated paper samples showed higher specific surface areas than unmodified paper; however, their mean pore diameters are smaller. The BJH method was used for pore size distribution analysis. Hydrophobic properties of the paper samples were determined from experimental isotherms, e.g., monolayer moisture content, and these results have been related to the water vapor transfer rates (WVTRs) showing a complex nature of these relations. The highest peak corresponding to the modified samples with smaller pore sizes was found to be in the range of 1–30 nm, while it was in the 30–100 nm pore size range for unmodified paper. The net isosteric heats of sorption for different unmodified and modified paper samples were determined from water vapor adsorption isotherms measured at 15, 25, and 35 °C. The net isosteric heats of sorption decreased with an increase of moisture content after reaching the maximum values at 12.53, 15.25, 14.71, 23.2, and 22.77 kJ/mol for unmodified, zein grafted, calendered coated, PLA, and PHBV coated papers, respectively. The state of adsorbed water and water
The impact of binding thermodynamics on medicinal chemistry optimizations.
Ferenczy, György G; Keserű, György M
2015-01-01
Ligand binding thermodynamics has been attracted considerable interest in the past decade owing to the recognized relation between binding thermodynamic profile and the physicochemical and druglike properties of compounds. In this review, the relation between optimization strategies and ligand properties is presented based on the structural and thermodynamic analysis of ligand-protein complex formation. The control of the binding thermodynamic profile is beneficial for the balanced affinity and physicochemical properties of drug candidates, and early phase optimization gives more opportunity to this control.
Zhang, JunMin, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn; Lu, ChunRong [School of Automation Science and Electrical Engineering, Beihang University, Beijing 100191 (China); Guan, YongGang, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn; Liu, WeiDong [Department of Electrical Engineering, Tsinghua University, Beijing 100084 (China)
2015-10-15
Because the fault arc in aircraft electrical system often causes a fire, it is particularly important to analyze its energy and transfer for aircraft safety. The calculation of arc energy requires the basic parameters of the arc. This paper is mainly devoted to the calculations of equilibrium composition, thermodynamic properties (density, molar weight, enthalpy, and specific heat at constant pressure) and transport coefficients (thermal conductivity, electrical conductivity, and viscosity) of plasmas produced by a mixture of air, Cu, and polytetrafluoroethylene under the condition of local thermodynamic equilibrium. The equilibrium composition is determined by solving a system of equations around the number densities of each species. The thermodynamic properties are obtained according to the standard thermodynamic relationships. The transport coefficients are calculated using the Chapman-Enskog approximations. Results are presented in the temperature range from 3000 to 30 000 K for pressures of 0.08 and 0.1 MPa, respectively. The results are more accurate and are reliable reference data for theoretical analysis and computational simulation of the behavior of fault arc.
Baggetto, Loic [ORNL; Ganesh, Panchapakesan [ORNL; Sun, Che Nan [ORNL; Meisner, Roberta Ann [ORNL; Zawodzinski, Thomas A [ORNL; Veith, Gabriel M [ORNL
2013-01-01
A detailed comparative study between electrochemical lithiation and sodiation of pure antimony (Sb), relating changes in structural, thermodynamic, kinetic and electrochemical properties has been carried out. For this purpose, a wide range of measurements using electrochemical (galvanostatic cycling, GITT, PITT), x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) methods as well as density functional theory (DFT) based investigations have been undertaken. Assessment of the thermodynamics reveals that the reaction proceeds identically during the first and second cycles for Li whereas it differs between the first and subsequent cycles for Na. For Li the difference between the first and subsequent cycles is rooted in an improvement of the kinetics likely due to the decrease of Sb particle size whereas the reaction with Na proceeds through a different pathway from the first to subsequent cycles and is associated with the formation of amorphous NaxSb phases. For the first time we rationalize the amorphization of NaxSb phases by the long ranged strain propagation due to Na-vacancy compared to Li-Sb. At full discharge, our XRD results show for the first time that a minor fraction of hexagonal Li3Sb forms concomitantly with cubic Li3Sb. The XRD results confirm that Sb crystallizes into hexagonal Na3Sb at full sodiation. The kinetics of the reaction is assessed by rate performance tests which highlight that both Li and Na can diffuse rapidly throughout micron thick films at room temperature. However, it is found that the (de)insertion of Li provides lower overpotentials and larger storage capacities compared to Na. The difference in rate performance is complemented by diffusion coefficient determinations near the 0 V region where both materials are crystallized into M3Sb (M=Li, Na), and the results show that the apparent diffusion coefficients for Li are equivalent or one order of magnitude higher than those for Na. Interestingly, calculations show that the
Iribarne, J V
1973-01-01
The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...
Structural, magnetic, electric, dielectric, and thermodynamic properties of multiferroic Ge V4S8
Widmann, S.; Günther, A.; Ruff, E.; Tsurkan, V.; Krug von Nidda, H.-A.; Lunkenheimer, P.; Loidl, A.
2016-12-01
The lacunar spinel Ge V4S8 undergoes orbital and ferroelectric ordering at the Jahn-Teller transition around 30 K and exhibits antiferromagnetic order below about 14 K. In addition to this orbitally driven ferroelectricity, lacunar spinels are an interesting material class, as the vanadium ions form V4 clusters representing stable molecular entities with a common electron distribution and a well-defined level scheme of molecular states resulting in a unique spin state per V4 molecule. Here we report detailed x-ray, magnetic susceptibility, electrical resistivity, heat capacity, thermal expansion, and dielectric results to characterize the structural, electric, dielectric, magnetic, and thermodynamic properties of this interesting material, which also exhibits strong electronic correlations. From the magnetic susceptibility, we determine a negative Curie-Weiss temperature, indicative for antiferromagnetic exchange and a paramagnetic moment close to a spin S =1 of the V4 molecular clusters. The low-temperature heat capacity provides experimental evidence for gapped magnon excitations. From the entropy release, we conclude about strong correlations between magnetic order and lattice distortions. In addition, the observed anomalies at the phase transitions also indicate strong coupling between structural and electronic degrees of freedom. Utilizing dielectric spectroscopy, we find the onset of significant dispersion effects at the polar Jahn-Teller transition. The dispersion becomes fully suppressed again with the onset of spin order. In addition, the temperature dependencies of dielectric constant and specific heat possibly indicate a sequential appearance of orbital and polar order.
Thermodynamic properties of the liquid Ag-Bi-Cu-Sn lead-free solder alloys
Garzel G.
2014-01-01
Full Text Available The electromotive force measurement method was employed to determine the thermodynamic properties of liquid Ag-Bi-Cu-Sn alloys using solid electrolyte galvanic cells as shown below: Kanthal+Re, Ag-Bi-Cu-Sn, SnO2 | Yttria Stabilized Zirconia | air, Pt, Experiments were made within temperature interval: 950 - 1300K along four composition paths of constant ratios: XAg : XBi : XCu = 1, XAg : (XBi + XCu = 3:2 for XBi = XCu, XBi : (XAg + XCu = 3:2 for XAg = XCu and XCu : (XAg + XBi = 3:2 for XAg = XBi and tin concentration changing from 0.1 to 0.9 mole fractions, every 0.1. Almost all the results were approximated by straight line equations: EMF vs T, and tin activities were then calculated in arbitrary temperature; measurement results were presented by graphs. Unusual activity plot for XBi : (XAg + XCu = 3:2 composition path was most probably caused by miscibility gap detected earlier in Bi-Cu-Sn ternary liquid alloys.
Study of thermodynamic properties of Np-Al alloys in molten LiCl-KCl eutectic
Souček, P.; Malmbeck, R.; Mendes, E.; Nourry, C.; Sedmidubský, D.; Glatz, J.-P.
2009-10-01
Pyrochemical methods are investigated worldwide within the framework of Partitioning and Transmutation concepts for spent nuclear fuel reprocessing. Electroseparation techniques in a molten LiCl-KCl are being developed in ITU to recover all actinides from a mixture with fission products. During the process, actinides are selectively electrochemically reduced on a solid aluminium cathode, forming solid actinide-aluminium alloys. This work is focused on the thermodynamic properties of Np-Al alloys in a temperature range of 400-550 °C and on the characterisation of the structure and chemical composition of deposits obtained by electrodeposition of Np on solid Al electrodes in a LiCl-KCl-NpCl 3 melt. Cyclic voltammetry and open circuit chronopotentiometry have been used to examine the electrochemical behaviour of Np on inert W and reactive Al electrodes. Gibbs energies, enthalpy and entropy of formation and standard electrode potentials of Np-Al alloys were evaluated and compared with ab initio calculations. Galvanostatic electrolyses at 450 °C were carried out to recover Np onto Al plates and the solid surface deposits were characterised by XRD and SEM-EDX analyses. Stable and dense deposits consisting of NpAl 3 and NpAl 4 alloys were identified. In addition, the conversion of NpO 2 to NpCl 3 is described, using chlorination of the oxide in a molten salt media by pure chlorine gas.
Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)
2015-07-14
The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chain stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.
Ana Paula Prette
2013-03-01
Full Text Available The Jackfruit tree is one of the most significant trees in tropical home gardens and perhaps the most widespread and useful tree in the important genus Artocarpus. The fruit is susceptible to mechanical and biological damage in the mature state, and some people find the aroma of the fruit objectionable, particularly in confined spaces. The dehydration process could be an alternative for the exploitation of this product, and the relationship between moisture content and water activity provides useful information for its processing and storage. The aim of this study was to determine the thermodynamic properties of the water sorption of jackfruit (Artocarpus heterophyllus Lam. as a function of moisture content. Desorption isotherms of the different parts of the jackfruit (pulp, peduncle, mesocarp, peel, and seed were determined at four different temperatures (313.15, 323.15, 333.15, and 343.15 K in a water activity range of 0.02-0.753 using the static gravimetric method. Theoretical and empirical models were used to model the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to calculate the isosteric heat of sorption, the differential entropy, and Gibbs' free energy using the Guggenhein-Anderson-de Boer and Oswin models considering the effect of temperature on the hygroscopic equilibrium.
Ya-Ru, Zhao; Hai-Rong, Zhang; Gang-Tai, Zhang; Qun, Wei; Yu-Quan, Yuan
2016-12-01
The elastic anisotropy and thermodynamic properties of the recently synthesized Pnnm-CN have been investigated using first-principles calculations under high temperature and high pressure. The calculated equilibrium crystal parameters and normalized volume dependence of the resulting pressure agree with available experimental and theoretical results. Within the considered pressure range of 0-90 GPa, the dependences of the bulk modulus, Young's modulus, and shear modulus on the crystal orientation for Pnnm-CN have been systematically studied. The results show that the Pnnm-CN exhibits a well-pronounced elastic anisotropy. The incompressibility is largest along the c-axis. For tension or compression loading, the Pnnm-CN is stiffest along [001] and the most obedient along [100] direction. On the basis of the quasi-harmonic Debye model, we have explored the Debye temperature, heat capacity, thermal expansion coefficient, and Grüneisen parameters within the pressure range of 0-90 GPa and temperature range of 0-1600K.
Theoretical Study on Intermolecular Interactions and Thermodynamic Properties of Nitroamine Dimers
JU,Xue-Hai(居学海); XIAO,He-Ming(肖鹤鸣)
2002-01-01
Ab initio self-consistent field (SCF) and Moller-Plesset correlation correction methods emplo ying 6-31G * * basis set have been applied to the optimizations of nitroamine dimers. The binding energies have been corrected for the basis set superposition error (BSSE) and the zero-point energy. Three optimized dimers have been obtained. The BSSE corrected binding energy of the most stable dimer is predicted to be -31.85k J/mol at the MP4/6-31G* *//MP2/6-31G* * level. The energy barriers of the Walden conversion for - NH2 group are 19.7 kJ/mol and 18.3 kJ/mol for monomer and the most stable dimer, respectively. The molecular interaction makes the internal rotation around N1 - N2 even more difficult. The thermodynamic properties of nitroamine and its dimers at different temperatures have been calculated on the basis of vibrational analyses. The change of the Gibbs free energy for the aggregation from monomer to the most stable dimer at standard pressure and 298.2 K is predicted to be 14.05 kJ/mol.
Spectral and thermodynamic properties of the Sachdev-Ye-Kitaev model
García-García, Antonio M
2016-01-01
We study spectral and thermodynamic properties of the Sachdev-Ye-Kitaev model, a variant of the $k$-body embedded random ensembles studied for several decades in the context of nuclear physics and quantum chaos. We show analytically that the fourth and sixth order energy cumulants vanish in the limit of large number of particles $N \\to \\infty$ which is consistent with a Gaussian spectral density. However, for finite $N$, the tail of the average spectral density is well approximated by a semi-circle law. The specific heat coefficient, determined numerically from the low temperature behavior of the partition function, is consistent with the value obtained by previous analytical calculations. For energy scales of the order of the mean level spacing we show level statistics are well described by random matrix theory. Due to the underlying Clifford algebra of the model, the universality class of the spectral correlations depends on $N$. For larger energy separations we identify an energy scale that grows with $N$,...
Xu, Wen-Sheng; Freed, Karl F.
2015-07-01
The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chain stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.
Varshney, Dinesh; Jain, S.; Shriya, S.; Khenata, R.
2016-09-01
Pressure- and temperature-dependent mechanical, elastic, and thermodynamical properties of rock salt to CsCl structures in semiconducting Sr X ( X = O, S, Se, and Te) chalcogenides are presented based on model interatomic interaction potential with emphasis on charge transfer interactions, covalency effect, and zero point energy effects apart from long-range Coulomb, short-range overlap repulsion extended and van der Waals interactions. The developed potential with non-central forces validates the Cauchy discrepancy among elastic constants. The volume collapse ( V P/ V 0) in terms of compressions in Sr X at higher pressure indicates the mechanical stiffening of lattice. The expansion of Sr X lattice is inferred from steep increase in V T/ V 0 and is attributed to thermal softening of Sr X lattice. We also present the results for the temperature-dependent behaviors of hardness, heat capacity, and thermal expansion coefficient. From the Pugh's ratio (ϕ = B T /G H), the Poisson's ratio ( ν) and the Cauchy's pressure ( C 12- C 44), we classify SrO as ductile but SrS, SrSe, and SrTe are brittle material. To our knowledge these are the first quantitative theoretical prediction of the pressure and temperature dependence of mechanical stiffening, thermally softening, and brittle nature of Sr X ( X = O, S, Se, and Te) and still await experimental confirmations.
Determination of thermodynamic properties of aluminum based binary and ternary alloys
Altıntas, Yemliha [Abdullah Gül University, Faculty of Engineering, Department of Materials Science and Nanotechnology, 38039, Kayseri (Turkey); Aksöz, Sezen [Nevşehir Hacı Bektaş Veli University, Faculty of Arts and Science, Department of Physics, 50300, Nevşehir (Turkey); Keşlioğlu, Kâzım, E-mail: kesli@erciyes.edu.tr [Erciyes University, Faculty of Science, Department of Physics, 38039, Kayseri (Turkey); Maraşlı, Necmettin [Yıldız Technical University, Faculty of Chemical and Metallurgical Engineering, Department of Metallurgical and Materials Engineering, 34210, Davutpaşa, İstanbul (Turkey)
2015-11-15
In the present work, the Gibbs–Thomson coefficient, solid–liquid and solid–solid interfacial energies and grain boundary energy of a solid Al solution in the Al–Cu–Si eutectic system were determined from the observed grain boundary groove shapes by measuring the thermal conductivity of the solid and liquid phases and temperature gradient. Some thermodynamic properties such as the enthalpy of fusion, entropy of fusion, the change of specific heat from liquid to solid and the electrical conductivity of solid phases at their melting temperature were also evaluated by using the measured values of relevant data for Al–Cu, Al–Si, Al–Mg, Al–Ni, Al–Ti, Al–Cu–Ag, Al–Cu–Si binary and ternary alloys. - Highlights: • The microstructure of the Al–Cu–Si eutectic alloy was observed through SEM. • The three eutectic phases (α-Al, Si, CuAl{sub 2}) have been determined by EDX analysis. • Solid–liquid and solid–solid interfacial energies of α-Al solution were determined. • ΔS{sub f},ΔH{sub M}, ΔC{sub P}, electrical conductivity of solid phases for solid Al solutions were determined. • G–T coefficient and grain boundary energy of solid Al solution were determined.
Ya-Ru, Zhao; Hai-Rong, Zhang; Gang-Tai, Zhang; Qun, Wei; Yu-Quan, Yuan
2016-01-01
The elastic anisotropy and thermodynamic properties of the recently synthesized Pnnm-CN have been investigated using first-principles calculations under high temperature and high pressure. The calculated equilibrium crystal parameters and normalized volume dependence of the resulting pressure agree with available experimental and theoretical results. Within the considered pressure range of 0–90 GPa, the dependences of the bulk modulus, Young’s modulus, and shear modulus on the crystal orientation for Pnnm-CN have been systematically studied. The results show that the Pnnm-CN exhibits a well-pronounced elastic anisotropy. The incompressibility is largest along the c-axis. For tension or compression loading, the Pnnm-CN is stiffest along [001] and the most obedient along [100] direction. On the basis of the quasi-harmonic Debye model, we have explored the Debye temperature, heat capacity, thermal expansion coefficient, and Grüneisen parameters within the pressure range of 0–90 GPa and temperature range of 0–1600K. PMID:28090376
Cristian F. Costa
2016-06-01
Full Text Available ABSTRACT Jabuticaba is a fruit native of Brazil and, besides containing many nutritional qualities, it also has a good field for use in products such as flour for cakes and biscuits, juice, liqueur, jelly and others. This study aimed to model the drying kinetics and determine the thermodynamic properties of jabuticaba peel at different drying air temperatures. Ripe fruits of jabuticaba (Myrciaria jaboticaba were collected and pulped manually. Drying was carried out in a forced-air circulation oven with a flow of 5.6 m s-1 at temperatures of 40, 50, 60 and 70 °C. Six mathematical models commonly used to represent the drying process of agricultural products were fitted to the experimental data. The Arrhenius model was used to represent the drying constant as a function of temperature. The Midilli model showed the best fit to the experimental data of drying. The drying constant increased with the increment in drying temperature and promoted an activation energy of 37.29 kJ mol-1. Enthalpy and Gibbs free energy decreased with the increase in drying temperature, while entropy decreased and was negative.
Thermodynamics of Aβ16-21 dissociation from a fibril: Enthalpy, entropy, and volumetric properties.
Rao Jampani, Srinivasa; Mahmoudinobar, Farbod; Su, Zhaoqian; Dias, Cristiano L
2015-11-01
Here, we provide insights into the thermodynamic properties of A β16-21 dissociation from an amyloid fibril using all-atom molecular dynamics simulations in explicit water. An umbrella sampling protocol is used to compute potentials of mean force (PMF) as a function of the distance ξ between centers-of-mass of the A β16-21 peptide and the preformed fibril at nine temperatures. Changes in the enthalpy and the entropic energy are determined from the temperature dependence of these PMF(s) and the average volume of the simulation box is computed as a function of ξ. We find that the PMF at 310 K is dominated by enthalpy while the entropic energy does not change significantly during dissociation. The volume of the system decreases during dissociation. Moreover, the magnitude of this volume change also decreases with increasing temperature. By defining dock and lock states using the solvent accessible surface area (SASA), we find that the behavior of the electrostatic energy is different in these two states. It increases (unfavorable) and decreases (favorable) during dissociation in lock and dock states, respectively, while the energy due to Lennard-Jones interactions increases continuously in these states. Our simulations also highlight the importance of hydrophobic interactions in accounting for the stability of A β16-21.
The thermodynamic and ground state properties of the TIP4P water octamer.
Asare, E; Musah, A-R; Curotto, E; Freeman, David L; Doll, J D
2009-11-14
Several stochastic simulations of the TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)] water octamer are performed. Use is made of the stereographic projection path integral and the Green's function stereographic projection diffusion Monte Carlo techniques, recently developed in one of our groups. The importance sampling for the diffusion Monte Carlo algorithm is obtained by optimizing a simple wave function using variational Monte Carlo enhanced with parallel tempering to overcome quasiergodicity problems. The quantum heat capacity of the TIP4P octamer contains a pronounced melting peak at 160 K, about 50 K lower than the classical melting peak. The zero point energy of the TIP4P water octamer is 0.0348+/-0.0002 hartree. By characterizing several large samples of configurations visited by both guided and unguided diffusion walks, we determine that both the TIP4P and the SPC [H. J. C. Berendsen, J. P. Postma, W. F. von Gunsteren, and J. Hermans, (Intermolecular Forces, Reidel, 1981). p. 331] octamer have a ground state wave functions predominantly contained within the D(2d) basin of attraction. This result contrasts with the structure of the global minimum for the TIP4P potential, which is an S(4) cube. Comparisons of the thermodynamic and ground-state properties are made with the SPC octamer as well.
Synthesis and thermodynamic properties of a novel pyridinium-based asymmetrical gemini ionic liquid
Yang, Xuzhao; Wang, Jun; Zou, Wenyuan; Wu, Jinchao [Zhengzhou University of Light Industry, Zhengzhou (China)
2015-12-15
A novel asymmetrical gemini ionic liquid (GIL), [1-(1-pyridinium-yl-hexyl)-6-methylpiperidinium] dihexafluorophosphate ([PyC{sub 6}MPi][PF{sub 6}]{sub 2}) combined with pyridine, 1-methylpiperidine by 1,6-dibromohexane with PF{sub 6} as anion, was synthesized and characterized by 1H NMR and IR. The molar heat capacity of the GIL was measured via differential scanning calorimetry from 298.15 K to 448.15 K under atmospheric pressure. No phase transition or other thermal anomaly was observed in the solid-phase region (298.15 K to 358.15 K) and liquid-phase region (403.15 K to 448.15 K). The basic properties and thermodynamic functions of the GIL, such as melting point, molar enthalpy and entropy of fusion, heat capacity, enthalpy HT-H298.15 K, and entropy S{sub T}-S{sub 298.15} K, were also determined from the experimental data. Thermal decomposition kinetics of [PyC{sub 6}MPi][PF{sub 6}]{sub 2} were investigated by using non-isothermal thermogravimetric analysis in pure nitrogen atmosphere at various heating rates. Thermal decomposition data were, respectively, correlated with Friedman method, Ozawa-Flynn-Wall equation, and ASTM model. The activation energy (E) and pre-exponential factor (logA) values were obtained by using the above three methods.
Nichols, T.T.; Taylor, D.D.
2002-07-18
A status is presented of the development during FY2002 of a database for physical properties models for the simulation of the treatment of Sodium-Bearing Waste (SBW) at the Idaho National Engineering and Environmental Laboratory. An activity coefficient model is needed for concentrated, aqueous, multi-electrolyte solutions that can be used by process design practitioners. Reasonable first-order estimates of activity coefficients in the relevant media are needed rather than an incremental improvement in theoretical approaches which are not usable by practitioners. A comparison of the Electrolyte Non-Random Two-Liquid (ENRTL) and Pitzer ion-interaction models for the thermodynamic representation of SBW is presented. It is concluded that Pitzer's model is superior to ENRTL in modeling treatment processes for SBW. The applicability of the Pitzer treatment to high concentrations of pertinent species and to the determination of solubilities and chemical equilibria is addressed. Alternate values of Pitzer parameters for HCl, H2SO4, and HNO3 are proposed, applicable up to 16m, and 12m, respectively. Partial validation of the implementation of Pitzer's treatment within the commercial process simulator ASPEN Plus was performed.
Thermodynamical and electronic properties of Bx Al1-x N alloys: A first principle study
Kumar, S.; Joshi, Suman; Joshi, B.; Auluck, S.
2015-11-01
A series of first principle calculations were carried out to investigate thermodynamical, electronic and optical properties of cubic Bx Al1-x N ordered alloys using supercell approach within density functional theory (DFT). Here we calculate the lattice constants using van der Waals density functional (vdW-DF) at several concentrations (x) of boron. We find that the vdW-DF prediction shows slightly better agreement with experiment in contrast to local density approximation (LDA)/generalized gradient approximation (GGA). The results show that the direct energy band gap (Γv-Γc) has strong nonlinear dependence on the concentration (x). At x=0.04 and 0.84, Bx Al1-x N has a phase transition from direct to an indirect band gap semiconductor. To describe the alloys' solubility, formation enthalpy were calculated and fitted to quadratic function to obtain interaction parameter. The calculated T-x phase diagram shows a broad miscibility gap with a high critical temperature equal to 3063 K. The calculated dielectric function is explained in terms of band structure and density of states and compared with the available experimental data, showing good agreement.
Dogan, A.; Arslan, H.
2016-05-01
In the present study, Chou's General Solution Model (GSM) has been used to predict the enthalpy and partial enthalpies of mixing of the liquid Ag-In-Sn ternary, Ag-In-Sn-Zn quaternary, and Ag-Au-In-Sn-Zn quinary systems. These are of technical importance to optimize lead-free solder alloys, in selected cross-sections: x In/ x Sn = 0.5/0.5 (ternary), Au-In0.1-Sn0.8-Zn0.1, Ag-In0.1-Sn0.8-Zn0.1 (quaternary), and t = x Au/ x In = 1, x In = x Sn = x Zn (quinary) at 1173, 773, and 773 K, respectively. Moreover, the activity of In content in the ternary alloy system Ag-In-Sn has been calculated and its result is compared with that determined from the experiment, while the activities of Ag contents associated with the alloys mentioned above have been calculated. The other traditional models such as of Colinet, Kohler, Muggianu, Toop, and Hillert are also included in calculations. Comparing those calculated from the proposed GSM with those determined from experimental measurements, it is seen that this model becomes considerably realistic in computerization for estimating thermodynamic properties in multicomponent systems.
Li Zuo Taitano
2012-04-01
Full Text Available Moisture adsorption characteristics of California grown almonds (Nonpareil: pasteurized and unpasteurized almonds; Monterey: pasteurized, unpasteurized and blanched almonds were obtained using the gravimetric method over a range of water activities from 0.11 to 0.98 at 7-50ºC. The weights of almonds were measured until samples reached a constant weight. The relationship between equilibrium moisture content and water activity was established using the Guggenheim-Anderson-de Boer model. The diffusion coefficient of water in almond kernels was calculated based on Ficks second law. The monolayer moisture value of almonds ranged from 0.020 to 0.035 kg H2O kg-1 solids. The diffusion coefficient increased with temperature at a constant water activity, and decreased with water activity at a constant temperature. The thermodynamic properties (net isosteric heat, differential enthalpy and entropy were also determined. The net isosteric heat of adsorption decreased with the increasing moisture content, and the plot of differential enthalpy versus entropy satisfied the enthalpy-entropy compensation theory. The adsorption process of almond samples was enthalpy driven over the range of studied moisture contents.
Thermodynamic properties and cloud droplet activation of a series of oxo-acids
M. Frosch
2010-07-01
Full Text Available We have investigated the thermodynamic properties of four aliphatic oxo-dicarboyxlic acids identified or thought to be present in atmospheric particulate matter: oxosuccinic acid, 2-oxoglutaric acid, 3-oxoglutaric acid, and 4-oxopimelic acid. The compounds were characterized in terms of their cloud condensation nuclei (CCN activity, vapor pressure, density, and tendency to decarboxylate in aqueous solution. We deployed a variety of experimental techniques and instruments: a CCN counter, a Tandem Differential Mobililty Analyzer (TDMA coupled with a laminar flow-tube, and liquid chromatography/mass spectrometry (LC/MS. The presence of the oxo functional group in the α-position causes the vapor pressure of the compounds to diminish by an order of magnitude with respect to the parent dicarboxylic acid, while the CCN activity is similar or increased. Dicarboxylic acids with an oxo-group in the β-position decarboxylate in aqueous solution. We studied the effects of this process on our measurements and findings.
Nichols, Todd Travis; Taylor, Dean Dalton
2002-07-01
A status is presented of the development during FY2002 of a database for physical properties models for the simulation of the treatment of Sodium-Bearing Waste (SBW) at the Idaho National Engineering and Environmental Laboratory. An activity coefficient model is needed for concentrated, aqueous, multi-electrolyte solutions that can be used by process design practitioners. Reasonable first-order estimates of activity coefficients in the relevant media are needed rather than an incremental improvement in theoretical approaches which are not usable by practitioners. A comparison of the Electrolyte Non-Random Two-Liquid (ENRTL) and Pitzer ion-interaction models for the thermodynamic representation of SBW is presented. It is concluded that Pitzer's model is superior to ENRTL in modeling treatment processes for SBW. The applicability of the Pitzer treatment to high concentrations of pertinent species and to the determination of solubilities and chemical equilibria is addressed. Alternate values of Pitzer parameters for HCl, H2SO4, and HNO3 are proposed, applicable up to 16m, and 12m, respectively. Partial validation of the implementation of Pitzer's treatment within the commercial process simulator ASPEN Plus was performed.
Dubey, Gyan Prakash, E-mail: gyan.dubey@rediffmail.com [Department of Chemistry, Kurukshetra University, Kurukshetra 136119 (India); Kumar, Krishan [Department of Chemistry, Kurukshetra University, Kurukshetra 136119 (India)
2011-09-20
Highlights: {yields} Thermodynamic study of diethylenetriamine + 2-methyl-1-propanol, +2-propanol or +1-butanol have been made. {yields} Excess molar volumes and isentropic compressibility were determined. {yields} Types of interactions were discussed based on derived properties. - Abstract: Densities, {rho}, viscosities, {eta}, and speeds of sound, u, were measured for the binary liquid mixtures containing diethylenetriamine with 2-methyl-1-propanol, 2-propanol and 1-butanol at 293.15, 298.15, 303.15, 308.15 and 313.15 K. From density and speed of sound data, excess molar volumes, V{sub m}{sup E} and deviations in isentropic compressibility, {Delta}{kappa}{sub s}, and speed of sound, {Delta}u have been evaluated. Viscosity data were used to compute deviations in viscosity and excess Gibbs energy of activation of viscous flow {Delta}G*{sup E} at 298.15, 303.15 and 308.15 K. A Redlich-Kister type equation was applied to fit the excess molar volumes and deviations in isentropic compressibility, speed of sound and viscosity data. The viscosity data have been correlated with the equations of Grunberg-Nissan, Tamura-Kurata, Heric-Brewer and of Hind et al. All the binary systems of the present study have negative values of excess molar volumes and deviations in isentropic compressibility over whole composition range and at all temperatures which indicates strong interactions between the components of binary mixtures.
Zhao Ya-Ru
2016-12-01
Full Text Available The elastic anisotropy and thermodynamic properties of the recently synthesized Pnnm-CN have been investigated using first-principles calculations under high temperature and high pressure. The calculated equilibrium crystal parameters and normalized volume dependence of the resulting pressure agree with available experimental and theoretical results. Within the considered pressure range of 0–90 GPa, the dependences of the bulk modulus, Young’s modulus, and shear modulus on the crystal orientation for Pnnm-CN have been systematically studied. The results show that the Pnnm-CN exhibits a well-pronounced elastic anisotropy. The incompressibility is largest along the c-axis. For tension or compression loading, the Pnnm-CN is stiffest along [001] and the most obedient along [100] direction. On the basis of the quasi-harmonic Debye model, we have explored the Debye temperature, heat capacity, thermal expansion coefficient, and Grüneisen parameters within the pressure range of 0–90 GPa and temperature range of 0–1600K.
Thermodynamic Properties of Supported and Embedded Metallic Nanocrystals: Gold on/in SiO2
Giannazzo F
2008-01-01
Full Text Available Abstract We report on the calculations of the cohesive energy, melting temperature and vacancy formation energy for Au nanocrystals with different size supported on and embedded in SiO2. The calculations are performed crossing our previous data on the surface free energy of the supported and embedded nanocrystals with the theoretical surface-area-difference model developed by W. H. Qi for the description of the size-dependent thermodynamics properties of low-dimensional solid-state systems. Such calculations are employed as a function of the nanocrystals size and surface energy. For nanocrystals supported on SiO2, as results of the calculations, we obtain, for a fixed nanocrystal size, an almost constant cohesive energy, melting temperature and vacancy formation energy as a function of their surface energy; instead, for those embedded in SiO2, they decreases when the nanocrystal surface free energy increases. Furthermore, the cohesive energy, melting temperature and vacancy formation energy increase when the nanocrystal size increases: for the nanocrystals on SiO2, they tend to the values of the bulk Au; for the nanocrystals in SiO2 in correspondence to sufficiently small values of their surface energy, they are greater than the bulk values. In the case of the melting temperature, this phenomenon corresponds to the experimentally well-known superheating process.
Spectral and thermodynamic properties of the Sachdev-Ye-Kitaev model
García-García, Antonio M.; Verbaarschot, Jacobus J. M.
2016-12-01
We study spectral and thermodynamic properties of the Sachdev-Ye-Kitaev model, a variant of the k -body embedded random ensembles studied for several decades in the context of nuclear physics and quantum chaos. We show analytically that the fourth- and sixth-order energy cumulants vanish in the limit of a large number of particles N →∞ , which is consistent with a Gaussian spectral density. However, for finite N , the tail of the average spectral density is well approximated by a semicircle law. The specific heat coefficient, determined numerically from the low-temperature behavior of the partition function, is consistent with the value obtained by previous analytical calculations. For energy scales of the order of the mean level spacing we show that level statistics are well described by random matrix theory. Due to the underlying Clifford algebra of the model, the universality class of the spectral correlations depends on N . For larger energy separations we identify an energy scale that grows with N , reminiscent of the Thouless energy in mesoscopic physics, where deviations from random matrix theory are observed. Our results are a further confirmation that the Sachdev-Ye-Kitaev model is quantum chaotic for all time scales. According to recent claims in the literature, this is an expected feature in field theories with a gravity dual.
Kinetic and thermodynamic properties of soybean grains during the drying process
Daniel Emanuel Cabral de Oliveira
2013-09-01
Full Text Available The aims of this work were to adjust different mathematical models to experimental data describing the drying of the Valiosa cultivar soybean grain, to determine and to evaluate the effective diffusion coefficient and to obtain the activation energy and the thermodynamic properties of the drying process under different air conditions. The experiments were conducted at the Federal Institute of Education, Science and Technology of Goiás (Instituto Federal de Educação, Ciência e Tecnologia Goiano – Câmpus Rio Verde. The Valiosa cultivar soybean grains, with an initial moisture content on a dry basis of 0.56 (d.b., decimal, were dried in an oven with forced air ventilation at five different temperatures (40, 55, 70, 85 and 100°C until reaching a moisture content of 0.133±0.019 (d.b.. Of the models analyzed, Page’s model was selected to best represent the drying phenomenon. The effective diffusion coefficient of soybeans increased with the air temperature and was described by the Arrhenius equation; an activation energy of 22.77 kJ mol–1 was reported for liquid diffusion in the drying of the soybeans. The enthalpy and entropy decreased with increasing temperature, while the Gibbs free energy increased with increasing drying temperature.
Méndez-Morales, T; Carrete, J; Cabeza, O; Gallego, L J; Varela, L M
2011-09-29
In this work, extensive molecular dynamics simulations of mixtures of alcohols of several chain lengths (methanol and ethanol) with the ionic liquids (ILs) composed of the cation 1-hexyl-3-methylimidazolium and several anions of different hydrophobicity degrees (Cl(-), BF(4)(-), PF(6)(-)) are reported. We analyze the influence of the nature of the anion, the length of the molecular chain of the alcohol, and the alcohol concentration on the thermodynamic and structural properties of the mixtures. Densities, excess molar volumes, total and partial radial distribution functions, coordination numbers, and hydrogen bond degrees are reported and analyzed for mixtures of the ILs with methanol and ethanol. The aggregation process is shown to be highly dependent on the nature of the anion and the size of the alcohol, since alcohol molecules tend to interact predominantly with the anionic part of the IL, especially in mixtures of the halogenated IL with methanol. Particularly, our results suggest that the formation of an apolar network similar to that previously reported in mixtures of ILs with water does not take place in mixtures with alcohol when the chloride anion is present, the alcohol molecules being instead homogeneously distributed in the polar network of IL. Moreover, the alcohol clusters formed in mixtures of [HMIM][PF(6)] with alcohol were found to have a smaller size than in mixtures with water. Additionally, we provide a semiquantitative analysis of the dependence of the hydrogen bonding degree of the mixtures on the alcohol concentration. © 2011 American Chemical Society
Zaghloul, Mofreh R. [Department of Physics, College of Science, United Arab Emirates University, P.O. Box 15551, Al-Ain (United Arab Emirates)
2015-11-15
We present computational results and tables of the equation-of-state, thermodynamic properties, and shock Hugoniot for hot dense fluid deuterium. The present results are generated using a recently developed chemical model that takes into account different high density effects such as Coulomb interactions among charged particles, partial degeneracy, and intensive short range hard core repulsion. Internal partition functions are evaluated in a statistical-mechanically consistent way implementing recent developments in the literature. The shock Hugoniot curve derived from the present tables is overall in reasonable agreement with the Hugoniot derived from the Nova-laser shock wave experiments on liquid deuterium, showing that deuterium has a significantly higher compressibility than predicted by the SESAME tables or by Path Integral Monte Carlo calculations. Computational results are presented as surface plots for the dissociated fraction, degree of ionization, pressure, and specific internal energy for densities ranging from 0.0001 to 40 g/cm{sup 3} and temperatures from 2000 to ∼10{sup 6 }K. Tables for values of the above mentioned quantities in addition to the specific heat at constant pressure, c{sub p}, ratio of specific heats, c{sub p}/c{sub v}, sound speed and Hugoniot curve (for a specific initial state) are presented for practical use.
An adaptive distance-based group contribution method for thermodynamic property prediction.
He, Tanjin; Li, Shuang; Chi, Yawei; Zhang, Hong-Bo; Wang, Zhi; Yang, Bin; He, Xin; You, Xiaoqing
2016-09-14
In the search for an accurate yet inexpensive method to predict thermodynamic properties of large hydrocarbon molecules, we have developed an automatic and adaptive distance-based group contribution (DBGC) method. The method characterizes the group interaction within a molecule with an exponential decay function of the group-to-group distance, defined as the number of bonds between the groups. A database containing the molecular bonding information and the standard enthalpy of formation (Hf,298K) for alkanes, alkenes, and their radicals at the M06-2X/def2-TZVP//B3LYP/6-31G(d) level of theory was constructed. Multiple linear regression (MLR) and artificial neural network (ANN) fitting were used to obtain the contributions from individual groups and group interactions for further predictions. Compared with the conventional group additivity (GA) method, the DBGC method predicts Hf,298K for alkanes more accurately using the same training sets. Particularly for some highly branched large hydrocarbons, the discrepancy with the literature data is smaller for the DBGC method than the conventional GA method. When extended to other molecular classes, including alkenes and radicals, the overall accuracy level of this new method is still satisfactory.
Investigation of thermodynamics properties of chalcopyrite compound CdGeAs2
Huang, Wei; Zhao, Beijun; Zhu, Shifu; He, Zhiyu; Chen, Baojun; Zhen, Zhen; Pu, Yunxiao; Liu, Weijia
2016-06-01
Chalcopyrite of CdGeAs2 single crystal was grown by a modified vertical Bridgman method with sufficient size and quality, and its optical, electrical and thermodynamic properties are characterized. The transmission is recorded in the 2.3-18 μm range, and the band-gap at room temperature is at 0.56 eV. Non-ideal transparency near 5.5 μm which limited its application severely exists in the front of the crystal. The crystal is p type at room temperature with hole concentrations varying from 1014 to 1016 cm-3. From the results of X-ray diffraction measurements carried out over the range 25-450 °C and thermal dilatometer tests, the thermal expansion coefficients are evaluated. And on this basis the Grüneisen parameters at different temperatures are evaluated and also exhibit anisotropic behavior (γa>γc). It is found that γa, γc, and γV have some difference between these two kinds of test methods. Using these Grüneisen parameters, lattice thermal conductivities have been deduced by two correction formulas. Meanwhile, specific heat capacity and thermal conductivity of [204] have been obtained as a function of temperature by experiment.
Zhu, Jinhua; Fu, Qingshan; Xue, Yongqiang, E-mail: xyqlw@126.com; Cui, Zixiang
2017-05-01
Based on the surface pre-melting model, accurate thermodynamic relations of the melting temperature of nanocrystals with different shapes (tetrahedron, cube, octahedron, dodecahedron, icosahedron, nanowire) were derived. The theoretically calculated melting temperatures are in relative good agreements with experimental, molecular dynamic simulation and other theoretical results for nanometer Au, Ag, Al, In and Pb. It is found that the particle size and shape have notable effects on the melting temperature of nanocrystals, and the smaller the particle size, the greater the effect of shape. Furthermore, at the same equivalent radius, the more the shape deviates from sphere, the lower the melting temperature is. The value of melting temperature depression of cylindrical nanowire is just half of that of spherical nanoparticle with an identical radius. The theoretical relations enable one to quantitatively describe the influence regularities of size and shape on the melting temperature and to provide an effective way to predict and interpret the melting temperature of nanocrystals with different sizes and shapes. - Highlights: • Accurate relations of T{sub m} of nanocrystals with various shapes are derived. • Calculated T{sub m} agree with literature results for nano Au, Ag, Al, In and Pb. • ΔT{sub m} (nanowire) = 0.5ΔT{sub m} (spherical nanocrystal). • The relations apply to predict and interpret the melting behaviors of nanocrystals.
Structural, vibrational and thermodynamic properties of Ag(n)Cu(34-n) nanoparticles.
Yildirim, Handan; Kara, Abdelkader; Rahman, Talat S
2009-02-25
We report results of a systematic study of structural, vibrational and thermodynamical properties of 34-atom bimetallic nanoparticles from the Ag(n)Cu(34-n) family using model interaction potentials as derived from the embedded atom method and invoking the harmonic approximation of lattice dynamics. Systematic trends in the bond length and dynamical properties can be explained largely from arguments based on local coordination and elemental environment. Thus an increase in the number of silver atoms in a given neighborhood introduces a monotonic increase in bond length, while an increase of the copper content does the reverse. Moreover, for the bond lengths of the lowest-coordinated (six and eight) copper atoms with their nearest neighbors (Cu atoms), we find that the nanoparticles divide into two groups with the average bond length either close to (∼2.58 Å) or smaller than (∼2.48 Å) that in bulk copper, accompanied by characteristic features in their vibrational density of states. For the entire set of nanoparticles, we find vibrational modes above the bulk bands of copper/silver. We trace a blue shift in the high-frequency end of the spectrum that occurs as the number of copper atoms increases in the nanoparticles, leading to shrinkage of the bond lengths from those in the bulk. The vibrational densities of states at the low-frequency end of the spectrum scale linearly with frequency as for single-element nanoparticles, with a more pronounced effect for these nanoalloys. The Debye temperature is found to be about one-third of that of the bulk for pure copper and silver nanoparticles, with a non-linear increase as copper atoms increase in the nanoalloy.
First-principles study on thermodynamic properties and phase transitions in TiS(2).
Yu, Yonggang G; Ross, Nancy L
2011-02-01
Structural and vibrational properties of TiS(2) with the CdI(2) structure have been studied to high pressures from density functional calculations with the local density approximation (LDA). The calculated axial compressibility of the CdI(2)-type phase agrees well with experimental data and is typical of layered transition-metal dichalcogenides. The obtained phonon dispersions show a good correspondence with available experiments. A phonon anomaly is revealed at 0 GPa, but is much reduced at 20 GPa. The thermodynamic properties of this phase were also calculated at high pressures and high temperatures using the quasi-harmonic approximation. Our LDA study on the pressure-induced phase transition sequence predicts that the CdI(2)-type TiS(2), the phase stable at ambient conditions, should transform to the cotunnite phase at 15.1 GPa, then to a tetragonal phase (I4/mmm) at 45.0 GPa. The tetragonal phase remains stable to at least 500 GPa. The existence of the tetragonal phase at high pressures is consistent with our previous findings in NiS(2) (Yu and Ross 2010 J. Phys.: Condens. Matter 22 235401). The cotunnite phase, although only stable in a narrow pressure range between 15.1 and 45.0 GPa, displays the formation of a compact S network between 100 and 200 GPa, which is evidenced by a kink in the variation of unit cell lengths with pressure. The electron density analysis in cotunnite shows that valence electrons are delocalized from Ti atoms and concentrated near the S network.
Measuring Thermodynamic Length
Crooks, Gavin E
2007-09-07
Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information, and Rao's entropy differential metric. Therefore, thermodynamic length is of central interestin understanding matter out of equilibrium. In this Letter, we will consider how to denethermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.
Thermodynamics of Fractal Universe
Sheykhi, Ahmad; Wang, Bin
2012-01-01
We investigate the thermodynamical properties of the apparent horizon in a fractal universe. We find that one can always rewrite the Friedmann equation of the fractal universe in the form of the entropy balance relation $ \\delta Q=TdS+Td\\tilde{S}$, where $ \\delta Q $ and $ T $ are the energy flux and Unruh temperature seen by an accelerated observer just inside the apparent horizon, and $d\\tilde{S}$ is the entropy production term due to nonequilibrium thermodynamics of fractal universe. This shows that in a fractal universe, a treatment with nonequilibrium thermodynamics of spacetime may be needed. We also study the generalized second law of thermodynamics in the framework of fractal universe. When the temperature of the apparent horizon and the matter fields inside the horizon are equal, i.e. $T=T_h$, the generalized second law of thermodynamics can be fulfilled provided the deceleration and the equation of state parameters ranges either as $-1 \\leq q < 0 $, $- 1 \\leq w < - 1/3$ or as $q<-1$, $w<...
Thermodynamic study of semiconducting related materials by use of EMF method with solid electrolyte
Katayama Iwao
2003-01-01
Full Text Available Electromotive force method with solid electrolyte is briefly explained, and a thermodynamic study of semi conducting compound solid solution ZnTe-CdTe is picked up to show the way how thermodynamic functions of this system are obtained by several experimental methods based on our published papers and recently published data are added for comparison.
Bertoli, Alexandre C; Garcia, Jerusa S; Trevisan, Marcello G; Ramalho, Teodorico C; Freitas, Matheus P
2016-04-01
The use of theoretical calculation to determine structural properties of fulvate-metal complex (zinc, copper and iron) is here related. The species were proposed in the ratio 1:1 and 2:1 for which the molecular structure was obtained through the semi-empirical method PM6. The calculation of thermodynamic stability ([Formula: see text]) predicted that the iron complex were more exo-energetic. Metallic ions were coordinated to the phtalate groups of the model-structure of fulvic acid Suwannee River and the calculations of vibrational frequencies suggested that hydrogen bonds may help on the stability of the complex formation.
Narimani, Mitra; Nourbakhsh, Zahra
2017-03-01
The electronic, thermodynamic and optical properties of XPtSb (X=Lu, Sc) half Heusler compounds are studied based on density functional theory. The calculations are carried out in the presence of spin orbit interaction. The exchange correlation part of total energy is calculated within local density approximation, generalized gradient approximation, Engel-Vosco generalized gradient approximation and modified Becke and Johnson exchange potential with the correlation potential of the generalized gradient approximation. The effect of pressure on the electron density of states and linear coefficient of the electronic specific heat is studied. Using the band structure calculations at different pressures, the band inversion strength and topological phase transition of these compounds are investigated. Some thermodynamic properties of XPtSb compounds by different thermal models using the non-equilibrium Gibbs function are studied and compared with experiment. Furthermore the effect of pressure on dielectric function of XPtSb (X=Lu, Sc) compounds is investigated.
Colon, G.
1981-01-01
The evaluation of the thermodynamic properties of a gas mixture can be performed using a generalized correlation which makes use of the second virial coefficient. This coefficient is based on statistical mechanics and is a function of temperature and composition, but not of pressure. The method provides results accurate to within 3 percent for gases which are nonpolar or only slightly polar. When applied to highly polar gases, errors of 5 to 10 percent may result. For gases which associate, even larger errors are possible. The sequences of calculations can be routinely programmed for a digital computer. The thermodynamic properties of a mixture of neon, argon and ethane were calculated by such a program. The result will be used for the design of the gas replenishment system for the Energetic Gamma Ray Experiment Telescope.
Murtaza, G., E-mail: murtaza@icp.edu.pk [Materials Modeling Laboratory, Department of Physics, Islamia College Peshawar (Pakistan); Gupta, S.K. [Department of Physics, Michigan Technological University, Houghton, MI 49931 (United States); Seddik, T. [Laboratoire de Physique Quantique et de Modélisation Mathématique, Université de Mascara, 29000 Mascara (Algeria); Khenata, R., E-mail: khenata_rabah@yahoo.fr [Laboratoire de Physique Quantique et de Modélisation Mathématique, Université de Mascara, 29000 Mascara (Algeria); Alahmed, Z.A. [Department of Physics and Astronomy, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Ahmed, R. [Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, UTM Skudai, 81310 Johor (Malaysia); Khachai, H. [Physics Department, Djillali Liabes University of Sidi Bel-Abbes (Algeria); Jha, P.K. [Department of Physics, Maharaja Krishnakumarsinhji Bhavnagar University, Bhavnagar 364001 (India); Bin Omran, S. [Department of Physics and Astronomy, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia)
2014-06-01
Highlights: • REGa{sub 3} (RE = Sc or Lu) compounds are mechanical stabile. • Both ScGa{sub 3} and LuGa{sub 3} exhibit metallic behavior just like other REGa{sub 3} compounds. • Melting temperature T{sub m} (K) for ScGa{sub 3} and LuGa{sub 3} are 1244.2 and 1143.8. • High absorption observed in the visible energy region. • The present study would be helpful for future experimental/theoretical explorations. - Abstract: Structural, elastic, optoelectronic and thermodynamic properties of REGa{sub 3} (RE = Sc and Lu) compounds have been studied self consistently by employing state of the art full potential (FP) linearized (L) approach of augmented plane wave (APW) plus local orbitals method. Calculations were executed at the level of Perdew–Burke and Ernzerhof (PBE) parameterized generalized gradient approximation (GGA) for exchange correlation functional in addition to modified Becke–Johnson (mBJ) potential. Our obtained results of lattice parameters show reasonable agreement to the previously reported experimental and other theoretical studies. Analysis of the calculated band structure of ScGa{sub 3} and LuGa{sub 3} compounds demonstrates their metallic character. Moreover, a positive value of calculated Cauchy pressure, in addition to reflecting their ductile nature, endorses their metallic character as well. To understand optical behavior calculations related to the important optical parameters; real and imaginary parts of the dielectric function, reflectivity R(ω), refractive index n(ω) and electron energy-loss function L(ω) have also been performed. In the present work, thermodynamically properties are also investigated by employing lattice vibrations integrated in quasi harmonic Debye model. Obtained results of volume, heat capacity and Debye temperature as a function of temperature for both compounds, at different values of pressure, are found to be consistent. The calculated value of melting temperature for both compounds (ScGa{sub 3} and Lu
Fisenko, Anatoliy I.; Lemberg, Vladimir
2014-07-01
Using the explicit form of the functions to describe the monopole and dipole spectra of the Cosmic Microwave Background (CMB) radiation, the exact expressions for the temperature dependences of the radiative and thermodynamic functions, such as the total radiation power per unit area, total energy density, number density of photons, Helmholtz free energy density, entropy density, heat capacity at constant volume, and pressure in the finite range of frequencies v 1≤ v≤ v 2 are obtained. Since the dependence of temperature upon the redshift z is known, the obtained expressions can be simply presented in z representation. Utilizing experimental data for the monopole and dipole spectra measured by the COBE FIRAS instrument in the 60-600 GHz frequency interval at the temperature T=2.72548 K, the values of the radiative and thermodynamic functions, as well as the radiation density constant a and the Stefan-Boltzmann constant σ are calculated. In the case of the dipole spectrum, the constants a and σ, and the radiative and thermodynamic properties of the CMB radiation are obtained using the mean amplitude T amp=3.358 mK. It is shown that the Doppler shift leads to a renormalization of the radiation density constant a, the Stefan-Boltzmann constant σ, and the corresponding constants for the thermodynamic functions. The expressions for new astrophysical parameters, such as the entropy density/Boltzmann constant, and number density of CMB photons are obtained. The radiative and thermodynamic properties of the Cosmic Microwave Background radiation for the monopole and dipole spectra at redshift z≈1089 are calculated.
Ramachandran, Naveen; Hamborg, Espen S.; Versteeg, Geert F.
2013-01-01
The dissociation constants of protonated monoethanolamine, N-methyldiethanolamine have been determined in aqueous mixtures of methanol, t-butanol–water and sulfolane solvents. The mole fractions of the organic compounds ranged from (0.2 to 0.95) and the temperatures from (283 to 353) K. Standard state thermodynamic properties like ΔrG, were derived from the results. The basic strength of the protonated alkanolamine decreased with decreasing dielectric constant and increase in temperature of t...
Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan
2015-01-01
Computer Aided Molecular Design (CAMD) is an important tool to generate, test and evaluate promising chemical products. CAMD can be used in thermodynamic cycle for the design of pure component or mixture working fluids in order to improve the heat transfer capacity of the system. The safety assessment of novel working fluids relies on accurate property data. Flammability data like the lower and upper flammability limit (LFL and UFL) play an important role in quantifying the risk of fire and e...
Density functional study of the structure, thermodynamics and electronic properties of CdGeAs{sub 2}
Zapol, Peter; Pandey, Ravindra; Seel, Max [Department of Physics, Michigan Technological University, Houghton, MI 49931 (United States); Recio, J. Manuel [Departamento de Quimica Fisica y Analitica, Universidad de Oviedo, 33006-Oviedo (Spain); Ohmer, Melvin C. [Air Force Research Laboratory, Dayton, OH 45433 (United States)
1999-06-14
Structural, thermodynamic and electronic properties of CdGeAs{sub 2} with chalcopyrite structure are investigated in the framework of density functional theory. We employ the linear combination of atomic orbitals method with the Gaussian basis sets and present the results for the equation of state, the Grueneisen constant, the electronic band structure and the pressure coefficients of the valence and conduction levels in CdGeAs{sub 2}. (author)
Plyasunov, Andrey V.
2015-11-01
Thermodynamic modeling of natural processes involving deep aqueous fluids requires the knowledge of the values of chemical potentials (the Gibbs energy) of aqueous species. An accurate prediction of thermodynamic properties at high T and P is a strong challenge. It is shown that geochemical models, including the well-known HKF-model, cannot be recommended for an indiscriminate use at supercritical temperatures to predict chemical potentials of nonelectrolytes at infinite dilution in water. Nevertheless, sufficiently accurate predictions of ϕ2∞ (the fugacity coefficients at infinite dilution in water) of aqueous nonelectrolytes up to 2000 K and water densities up to 1500 kg m-3, i.e. pressure up to 10-12 GPa, can be made relying on known theoretical relations valid at various parts of the phase diagram of water. In essence, the method, proposed in this work, consists in the interpolation of properties between two known limits: the first one, at low water densities, is defined by the values of the second virial coefficients for water-solute interactions, and the second, at high water densities - by predictions of the theory of a mixture of hard spheres. The interpolation at moderate temperatures (700-1300 K) and water densities (500-900 kg m-3) is simplified by sufficiently accurate predictions of properties using a semiempirical variant of a corresponding-states principle. Presented examples of the prediction of fugacity coefficients of "gases" at infinite dilution in water and of an aqueous solubility of corundum over very wide ranges of water densities/pressures demonstrate the potential and generality of the proposed methods of evaluating the thermodynamic properties of aqueous neutral compounds.
Erum, Nazia; Azhar Iqbal, Muhammad
2017-09-01
The effect of pressure variation on stability, structural parameters, elastic constants, mechanical, electronic and thermodynamic properties of cubic SrKF3 fluoroperovskite have been investigated by using the full-potential linearized augmented plane wave (FP-LAPW) method combined with Quasi-harmonic Debye model in which the phonon effects are considered. The calculated lattice parameters show a prominent decrease in lattice constant and bonds length with the increase in pressure. The application of pressure from 0 to 25 GPa reveals a predominant characteristic associated with widening of bandgap with GGA and GGA plus Tran–Blaha modified Becke–Johnson (TB-mBJ) potential. The influence of pressure on elastic constants and their related mechanical parameters have been discussed in detail. Apart of linear dependence of elastic coefficients, transition from brittle to ductile behavior is also observed at elevated pressure ranges. We have successfully computed variation of lattice constant, volume expansion, bulk modulus, Debye temperature and specific heat capacities at pressure and temperature in the range of 0–25 GPa and 0–600 K.
Gonzalez-Ayala, Julian; Cordero, Rubén; Angulo-Brown, F
2015-01-01
In this work we present the generalization of some thermodynamic properties of the black body radiation (BBR) towards an $n-$dimensional Euclidean space. For this case the Planck function and the Stefan-Boltzmann law have already been given by Landsberg and de Vos and some adjustments by Menon and Agrawal. However, since then no much more has been done on this subject and we believe there are some relevant aspects yet to explore. In addition to the results previously found we calculate the thermodynamic potentials, the efficiency of the Carnot engine, the law for adiabatic processes and the heat capacity at constant volume. There is a region at which an interesting behavior of the thermodynamic potentials arise, maxima and minima appear for the $n-d$ BBR system at very high temperatures and low dimensionality, suggesting a possible application to cosmology. Finally we propose that an optimality criterion in a thermodynamic framework could have to do with the $3-d$ nature of the universe.
Introduction to applied thermodynamics
Helsdon, R M; Walker, G E
1965-01-01
Introduction to Applied Thermodynamics is an introductory text on applied thermodynamics and covers topics ranging from energy and temperature to reversibility and entropy, the first and second laws of thermodynamics, and the properties of ideal gases. Standard air cycles and the thermodynamic properties of pure substances are also discussed, together with gas compressors, combustion, and psychrometry. This volume is comprised of 16 chapters and begins with an overview of the concept of energy as well as the macroscopic and molecular approaches to thermodynamics. The following chapters focus o
Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V
2015-07-07
The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.
Crystal structure, thermodynamics, magnetics and disorder properties of Be–Fe–Al intermetallics
Burr, P.A. [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom); Institute of Materials Engineering, Australian Nuclear Science & Technology Organisation, Lucas Heights, New South Wales 2234 (Australia); Middleburgh, S.C. [Institute of Materials Engineering, Australian Nuclear Science & Technology Organisation, Lucas Heights, New South Wales 2234 (Australia); Grimes, R.W., E-mail: r.grimes@imperial.ac.uk [Centre for Nuclear Engineering and Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom)
2015-08-05
Highlights: • DFT atomistic modelling + phonon DOS + Bragg–Williams order/disorder. • A novel Fe–Be binary structure was identified ε-Fe{sub 2}Be{sub 17}. • Small additions of Al stabilises δ-FeBe{sub 5} over ζ-FeBe{sub 2} and ε-Fe{sub 2}Be{sub 17}. • δ-FeBe{sub 5} and ε-Fe{sub 2}Be{sub 17} may accommodate deviations from stoichiometry. - Abstract: The elastic and magnetic properties, thermodynamical stability, deviation from stoichiometry and order/disorder transformations of phases that are relevant to Be alloys were investigated using density functional theory simulations coupled with phonon density of states calculations to capture temperature effects. A novel structure and composition were identified for the Be–Fe binary ε phase. In absence of Al, FeBe{sub 5} is predicted to form at equilibrium above ∼1100 K, while the ε phase is stable only below ∼1500 K, and FeBe{sub 2} is stable at all temperatures below melting. Small additions of Al are found to stabilise FeBe{sub 5} over FeBe{sub 2} and ε, while at high Al content, AlFeBe{sub 4} is predicted to form. Deviations from stoichiometric compositions are also considered and found to be important in the case of FeBe{sub 5} and ε. The propensity for disordered vs ordered structures is also important for AlFeBe{sub 4} (which exhibits complete Al–Fe disordered at all temperatures) and FeBe{sub 5} (which exhibits an order–disorder transition at ∼950 K)
Ismet KAYA; Cigdem Yigit PALA
2014-01-01
In this work,some thermodynamic properties of poly( cyclohexyl methacrylate)were studied by inverse gas chromatography( IGC). For this purpose,the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times(tr)of the probes were determined from the interactions of poly(cyclohexyl methacrylate)with n-pentane,n-hexane,n-heptane,n-octane,n-decane, methanol,ethanol,2-propanol,butanol,acetone,ethyl methyl ketone,benzene,toluene and o-xylene by IGC technique. Then,the specific volume(V0g)was determined for each probe molecule. By using(1/T;lnV0g) graphics,the glass transition temperature of poly( cyclohexyl methacrylate)was found to be 373 K. The adsorp-tion heat under the glass transition temperature(ΔH a ),and partial molar heat of sorption above the glass tran-sition(ΔHS1 ),partial molar free energy of sorption(ΔGS1 )and partial molar entropy of sorption(ΔSS1 )belong-ing to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution(ΔH∞1 ), partial molar free energy of mixing at infinite dilution(ΔG∞1 ),Flory-Huggins interaction parameter(χ∞12 )and weight fraction activity coefficient(a1/w1)∞ values of polymer-solute systems were calculated at different col-umn temperatures. The solubility parameters(δ2 )of the polymer were obtained by IGC technique.
Thermodynamic and mechanical properties of copper precipitates in α-iron from atomistic simulations
Erhart, Paul; Marian, Jaime; Sadigh, Babak
2013-07-01
Precipitate hardening is commonly used in materials science to control strength by acting on the number density, size distribution, and shape of solute precipitates in the hardened matrix. The Fe-Cu system has attracted much attention over the last several decades due to its technological importance as a model alloy for Cu steels. In spite of these efforts several aspects of its phase diagram remain unexplained. Here we use atomistic simulations to characterize the polymorphic phase diagram of Cu precipitates in body-centered cubic (BCC) Fe and establish a consistent link between their thermodynamic and mechanical properties in terms of thermal stability, shape, and strength. The size at which Cu precipitates transform from BCC to a close-packed 9R structure is found to be strongly temperature dependent, ranging from approximately 4 nm in diameter (˜2700atoms) at 200 K to about 8 nm (˜22800atoms) at 700 K. These numbers are in very good agreement with the interpretation of experimental data given Monzen [Philos. Mag. APMAADG0141-861010.1080/01418610008212077 80, 711 (2000)]. The strong temperature dependence originates from the entropic stabilization of BCC Cu, which is mechanically unstable as a bulk phase. While at high temperatures the transition exhibits first-order characteristics, the hysteresis, and thus the nucleation barrier, vanish at temperatures below approximately 300 K. This behavior is explained in terms of the mutual cancellation of the energy differences between core and shell (wetting layer) regions of BCC and 9R nanoprecipitates, respectively. The proposed mechanism is not specific for the Fe-Cu system but could generally be observed in immiscible systems, whenever the minority component is unstable in the lattice structure of the host matrix. Finally, we also study the interaction of precipitates with screw dislocations as a function of both structure and orientation. The results provide a coherent picture of precipitate strength that unifies
J. Romanowska
2011-09-01
Full Text Available Purpose: The interaction of lead-free solders with a copper substrate is an essential issue for the reliability of solder joints. In order to understand this interaction, the knowledge of thermodynamic and other physical properties of several ternary systems such as Ag-Sb-Sn system is necessary. The aim of this work was to determine the activities of all components in Ag-Sb-Sn alloy.Design/methodology/approach: The investigation of this system was carried out using the equilibrium saturation (ES method. The ES measurements were performed at 1273, 1373 and 1473 K. As the latter method is a comparative one, a Sn-Sb alloy was accepted as a reference alloy, where a formula for the Sb activity proposed by Jönsson and verified by Vassiliev was accepted.Findings: In the frame of the presented experiments the activity of Sb was determined by ES method.Research limitations/implications: The activity of Sb was obtained by ES and fitted to the Redlich-Kister-Muggianu (RKM model.Practical implications: A knowledge of multi-component phase equilibrium can provide the alloy developer with specific data enabling finding alloys that meet certain criteria. Phase diagrams are built on the basis of experimental data and the reliability of phase diagrams depends on the reliability of the experimental data used for the optimisation. Hence it is advantageous to use various source of data obtained by several methods and when the data of different source agree (like the ones presented in this paper it proves their reliability. Data presented in this paper will be used for Ag-Sb-Sn phase diagram optimisation in the frame of the COST Action MP0602.Originality/value: Sb activity values in Ag-Sb-Sn alloys obtained by ES and activity values of Sb, Ag and Sn calculated using the RKM model.
Oktavian, Rama; Darmawan, Rhezaldian Eka; Diarahmawati, Ayu; Kartiko, Intan Dyah; Rachmawati, Rizqi Tri
2017-03-01
The increasing consumption of fossil fuel in Indonesia is not followed by the rising on domestic oil production. This will lead to the depletion of fossil fuel reserves that will affect the availability of energy resources. Biofuel is considered as the critical solution to solve this problem in Indonesia. In recent years, alcohol produced from biomass has been used as an oxygenated compound in gasoline to increase the octane number and reduce pollutants resulting from motor vehicle exhaust emissions. However, the use of alcohol as an additive compounds is still limited to ethanol. In fact, the use of higher-chain alcohol such as 1-butanol offers more benefits over ethanol due to its higher calorific value. 1-butanol also has good characteristics for gasoline mixture such as less corrosive than ethanol, more resistant to water contamination, its low vapor pressure which leads to more safety application. This work investigated the effect of 1-butanol addition on the thermodynamic properties of gasoline-ethanol blend, in the form of density values, isobaric expansion coefficient, and the calorific value. The addition of 1-butanol up to 15% weight (80% RON 92-5% ethanol-15% 1-butanol) gives higher density to alcohol-gasoline blend up to 2% compared with pure RON 92 gasoline. Moreover, this addition produces the calorific value of gasoline blend of 11,313 cal/gr compared to pure RON 92 gasoline with the calorific value of 12,117 cal/gram. This blend can reduce the RON 92 gasoline consumption up to 15% from calorific value perspective.
Loverude, Michael E.; Kautz, Christian H.; Heron, Paula R. L.
2002-01-01
Reports on an investigation of student understanding of the first law of thermodynamics. Involves students from a first-year university physics course and a second-year thermal physics course. Focuses on the ability of students to relate the first law to the adiabatic physics course. Discusses implications for thermal physics and mechanics…
Loverude, Michael E.; Kautz, Christian H.; Heron, Paula R. L.
2002-01-01
Reports on an investigation of student understanding of the first law of thermodynamics. Involves students from a first-year university physics course and a second-year thermal physics course. Focuses on the ability of students to relate the first law to the adiabatic physics course. Discusses implications for thermal physics and mechanics…
Menichetti, Roberto; Kanekal, Kiran H.; Kremer, Kurt; Bereau, Tristan
2017-09-01
The partitioning of small molecules in cell membranes—a key parameter for pharmaceutical applications—typically relies on experimentally available bulk partitioning coefficients. Computer simulations provide a structural resolution of the insertion thermodynamics via the potential of mean force but require significant sampling at the atomistic level. Here, we introduce high-throughput coarse-grained molecular dynamics simulations to screen thermodynamic properties. This application of physics-based models in a large-scale study of small molecules establishes linear relationships between partitioning coefficients and key features of the potential of mean force. This allows us to predict the structure of the insertion from bulk experimental measurements for more than 400 000 compounds. The potential of mean force hereby becomes an easily accessible quantity—already recognized for its high predictability of certain properties, e.g., passive permeation. Further, we demonstrate how coarse graining helps reduce the size of chemical space, enabling a hierarchical approach to screening small molecules.
Thermodynamic equilibrium in relativity: four-temperature, Killing vectors and Lie derivatives
Becattini, F
2016-01-01
The main concepts of general relativistic thermodynamics and general relativistic statistical mechanics are reviewed. The main building block of the proper relativistic extension of the classical thermodynamics laws is the four-temperature vector \\beta, which plays a major role in the quantum framework and defines a very convenient hydrodynamic frame. The general relativistic thermodynamic equilibrium condition demands \\beta to be a Killing vector field. We show that a remarkable consequence is that all Lie derivatives of all physical observables along the four-temperature flow must then vanish.
Rusanov, A. I.
2014-12-01
The 21st century has brought a lot of new results related to graphene. Apparently, graphene has been characterized from all points of view except surface science and, especially, surface thermodynamics. This report aims to close this gap. Since graphene is the first real two-dimensional solid, a general formulation of the thermodynamics of two-dimensional solid bodies is given. The two-dimensional chemical potential tensor coupled with stress tensor is introduced, and fundamental equations are derived for energy, free energy, grand thermodynamic potential (in the classical and hybrid forms), enthalpy, and Gibbs energy. The fundamentals of linear boundary phenomena are formulated with explaining the concept of a dividing line, the mechanical and thermodynamic line tensions, line energy and other linear properties with necessary thermodynamic equations. The one-dimensional analogs of the Gibbs adsorption equation and Shuttleworth-Herring relation are presented. The general thermodynamic relationships are illustrated with calculations based on molecular theory. To make the reader sensible of the harmony of chemical and van der Waals forces in graphene, the remake of the classical graphite theory is presented with additional variable combinations of graphene sheets. The calculation of the line energy of graphene is exhibited including contributions both from chemical bonds and van der Waals forces (expectedly, the latter are considerably smaller than the former). The problem of graphene holes originating from migrating vacancies is discussed on the basis of the Gibbs-Curie principle. An important aspect of line tension is the planar sheet/nanotube transition where line tension acts as a driving force. Using the bending stiffness of graphene, the possible radius range is estimated for achiral (zigzag and armchair) nanotubes.
The Classical Thermodynamics of Deformable Materials
McLellan, A. G.
2011-02-01
Part I. The Mathematical Foundations of Finite Strain Theory: 1. Introduction; 2. Mathematical description of homogeneous deformations; 3. Infinitesimal deformation; 4. Transformations describing deformations of a material medium; 5. Forces; 6. Boundary conditions and work; 7. Another unique factorisation of D; 8. Virtual work; 9. Transformation of cartesian tensors; Part II. Non-Hydrostatic Thermodynamics: 10. The thermodynamic basis; 11. Thermodynamic relations; 12. Thermodynamic functions, equations of state; 13. Thermodynamic quantities, definitions, and geometrical situation; 14. Thermal expansion coefficients; 15. Specific heats; 16. Elastic stiffness and compliances; 17. Tensorial forms for the elastic stiffness and compliance matrices; 18. The effects of symmetry on the thermodynamic properties of crystals; 19. Equilibrium and stability conditions for thermodynamic systems; 20. Equilibrium conditions for diffusion in phases under non-hydrostatic stresses; 21. The equilibrium of a stressed solid in contact with a solution of the solid; 22. The thermodynamic stability of a phase; 23. Discussion of the elastic stability conditions; 24. Phase transitions and instability; 25. An example of a phase transition involving a simple shear; 26. Limiting the values of thermodynamic quantities at an instability; 27. The a-β quartz transition; 28. The thermodynamic theory of the growth of Dauphiné twinning in quartz under stress; 29. The tetragonal/cubic ferroelectric transition of barium titanate; References; Index.
EFFECT OF HEATING RATE ON THE THERMODYNAMIC PROPERTIES OF PULVERIZED COAL
Ramanathan Sampath
2000-01-01
This final technical report describes work performed under DOE Grant No. DE-FG22-96PC96224 during the period September 24, 1996 to September 23, 1999 which covers the entire performance period of the project. During this period, modification, alignment, and calibration of the measurement system, measurement of devolatilization time-scales for single coal particles subjected to a range of heating rates and temperature data at these time-scales, and analysis of the temperature data to understand the effect of heating rates on coal thermal properties were carried out. A new thermodynamic model was developed to predict the heat transfer behavior for single coal particles using one approach based on the analogy for thermal property of polymers. Results of this model suggest that bituminous coal particles behave like polymers during rapid heating on the order of 10{sup 4}-10{sup 5} K/s. At these heating rates during the early stages of heating, the vibrational part of the heat capacity of the coal molecules appears to be still frozen but during the transition from heat-up to devolatilization, the heat capacity appears to attain a sudden jump in its value as in the case of polymers. There are a few data available in the coal literature for low heating rate experiments (10{sup 2}-10{sup 3} K/s) conducted by UTRC, our industrial partner, in this project. These data were obtained for a longer heating duration on the order of several seconds as opposed to the 10 milliseconds heating time of the single particle experiments discussed above. The polymer analogy model was modified to include longer heating time on the order of several seconds to test these data. However, the model failed to predict these low heating rate data. It should be noted that UTRC's work showed reasonably good agreement with Merrick model heat capacity predictions at these low heating rates, but at higher heating rates UTRC observed that coal thermal response was heat flux dependent. It is concluded
How Many Types of Thermodynamical Equilibrium are There: Relation to Information Theory and Holism
Koleva, M K
2006-01-01
Major revision of the thermodynamics is made in order to provide rigorous fundament for functional diversity of holistic type. It turns out that the new approach ensures reproducibility of the information as well.
Ramos de Debiaggi, S., E-mail: sbramos@yahoo.com [Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen (Argentina); CONICET (Argentina); Cabeza, G.F. [CONICET (Argentina); Dpto. de Fisica, Universidad Nacional del Sur, Bahia Blanca (Argentina); Toro, C. Deluque [Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen (Argentina); Monti, A.M. [CNEA e Instituto Sabato (Univ. Nac. de San Martin/CNEA), Centro Atomico Constituyentes, Avda. General Paz 1499, B1650KNA, San Martin, Buenos Aires (Argentina); Sommadossi, S. [Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen (Argentina); CONICET (Argentina); Guillermet, A. Fernandez [CONICET (Argentina); Centro Atomico Bariloche e Instituto Balseiro, Avda. Bustillo 9500, (8400) Bariloche (Argentina)
2011-02-17
Research highlights: > Cu{sub 10}In{sub 7} and Cu{sub 11}In{sub 9} are thermodynamically stable with respect to elements at 0 K. > Cu{sub 10}In{sub 7} phase is more stable than the modelled Cu{sub 11}In{sub 9} compound by only 0.92 kJ/mol. > The present ab initio results reproduce very well the available structural data. > Similar DOS for both phases, the most prominent bonding band comes from Cu-d states. > Enhanced relative thermodynamic stability is predicted for phases with 40-45 at.% In. - Abstract: The physico-chemical properties of the intermetallic phases in the Cu-In system have been a matter of considerable theoretical and experimental interest in connection with, i.a., the application of In-Sn alloys as lead-free micro-soldering alloys. Recently, a new binary compound with the chemical formula Cu{sub 10}In{sub 7} has been detected in a study of the {eta}-phase field. The structure of the Cu{sub 10}In{sub 7} phase has been determined as closely related to that of the Cu{sub 11}In{sub 9} compound occurring in the phase diagram, but no experimental or theoretical information on its electronic structure, thermodynamic and equation-of-state properties has yet been reported. In the present work we report the lattice parameters, bulk modulus, energy of formation from the constituent elements and the electronic structure of the new phase, calculated by applying an ab initio density-functional-theory method. Our calculation technique uses the projector augmented wave potentials and the exchange-correlation functions of Perdew and Wang in the generalized gradient approximation. The present results for the Cu{sub 10}In{sub 7} phase are compared with the experimental data available, and with the trends in structural and thermodynamic properties emerging from ab initio calculations also performed in the present study for various structurally related and neighboring compounds in the Cu-In phase diagram, viz., the ideal B8{sub 2}-Cu{sub 2}In, B8{sub 1}-CuIn, B8{sub 2
On Thermodynamical Relation Between Rotating Charged BTZ Black Holes and Effective String Theory
Alexis Larra(~n)aga
2008-01-01
In this paper we study the first law of thermodynamics for the (2+1)-dimensional rotating charged BTZ black hole considering a pair of thermodynamical systems constructed with the two horizons of this solution. We show that these two systems are similar to the right and left movers of string theory and that the temperature associated with the black hole is the harmonic mean of the temperatures associated with these two systems.
Zhang, Suhong [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); College of Science, Yanshan University, Qinhuangdao 066004 (China); Zhang, Xinyu, E-mail: xyzhang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Zhu, Yan [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); College of Physics and Chemistry, Hebei Normal University of Science and Technology, Qinhuangdao 066004 (China); Ma, Mingzhen [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Qin, Jiaqian [Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330 (Thailand); Liu, Riping [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China)
2015-01-15
To give guidance for developing Rh-based superalloys, systematic investigations on structural, elastic and thermodynamic properties of Rh and Rh{sub 3}Zr are conducted by first-principles calculations. The pressure dependence of the basic mechanical parameters is presented covering elastic constants, bulk modulus, shear modulus, Young's modulus, Poisson's ratio, aggregate sound velocities and elastic anisotropy. Additionally, the mechanical stability and ductility/brittleness are also assessed. Compared with Rh, it is found that Rh{sub 3}Zr has higher ductility but lower elastic moduli, lower aggregate sound velocities and higher elastic anisotropy. The variations of the thermal properties including the normalized volume, bulk modulus, thermal expansion coefficient and heat capacity of Rh and Rh{sub 3}Zr in wide pressure (0–40 GPa) and temperature (0–2200 K) ranges are also predicted and analyzed, and a remarkable consistency with experimental results is obtained. - Highlights: • Structural, elastic and thermodynamic properties of Rh and Rh{sub 3}Zr are investigated. • Pressure effects on the structural and elastic properties are presented. • Rh{sub 3}Zr has higher ductility/elastic anisotropy but lower elastic moduli than Rh. • The thermal properties in wide pressure and temperature ranges are predicted.
E. Jäkel
2013-03-01
Full Text Available The sensitivity of passive remote sensing measurements to retrieve microphysical parameters of convective clouds, in particular their thermodynamic phase, is investigated by three-dimensional (3-D radiative transfer simulations. The effects of different viewing geometries and vertical distributions of the cloud microphysical properties are investigated. Measurement examples of spectral solar radiance reflected by cloud sides (passive in the near-infrared (NIR spectral range are performed together with collocated lidar observations (active. The retrieval method to distinguish the cloud thermodynamic phase (liquid water or ice exploits different slopes of cloud side reflectivity spectra of water and ice clouds in the NIR. The concurrent depolarization backscattering lidar provides geometry information about the cloud distance and height as well as the depolarization.
Trinh, Thuat T.; Meling, Nora; Bedeaux, Dick; Kjelstrup, Signe
2017-03-01
We present thermodynamic properties of the H2 dissociation reaction by means of the Small System Method (SSM) using Reactive Force Field (ReaxFF) simulations. Thermodynamic correction factors, partial molar enthalpies and heat capacities of the reactant and product were obtained in the high temperature range; up to 30,000 K. The results obtained from the ReaxFF potential agree well with previous results obtained with a three body potential (TBP). This indicates that the popular reactive force field method can be combined well with the newly developed SSM in realistic simulations of chemical reactions. The approach may be useful in the study of heat and mass transport in combination with chemical reactions.
Zhong Wang; Zuo-qing Shi; Rong-fu Shi; Yun-ge Fan; Yi-zhong Yang
2004-01-01
This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsorbent in hexane solutions within the temperature range of 293-313 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of ethyl benzoate and diethyl phthalate on the adsorbent, since all the correlative factors R' are larger than 0.99. The negative values of all the isosteric adsorption enthalpies for ethyl benzoate and diethyl phthalate indicate that they undergo exothermic processes, while their magnitudes (19-28 kJ/mol) manifest a hydrogen bonding sorption process. Other thermodynamic properties: the free energy changes and the entropy change associated with the adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation.
Fisenko, Anatoliy I
2014-01-01
Using the explicit form of the function to describe the average spectrum of the extragalactic far infrared background (FIRB) radiation measured by the COBE FIRAS instrument in the 0.15 - 2.4 THz frequency interval, the radiative and thermodynamic properties, such as the total emissivity, total radiation power per unit area, total energy density, number density of photons, Helmholtz free energy density, entropy density, heat capacity at constant volume, pressure, enthalpy density, and internal energy density are calculated. The calculated value of the total intensity received in the 0.15 - 2.4 THz frequency interval is 13.6 nW m^-2 sr^-1, and comprises about 19.4 % of the total intensity expected from the energy released by stellar nucleosynthesis over cosmic history. The radiative and thermodynamic functions of the extragalactic far infrared background (FIRB) radiation are calculated at redshift z = 1.5.
The influence of 3d-metal alloy additions on the elastic and thermodynamic properties of CuPd3
Huang Shuo; Zhang Chuan-Hui; Sun Jing; Shen Jiang
2013-01-01
Embedded-atom method (EAM) potentials are used to investigate the effects of alloying (e.g.3d-metals) on the trends of elastic and thermodynamic properties for CuPd3 alloy.Our calculated lattice parameter,cohesive energy,and elastic constants of CuPd3 are consistent with the available experimental and theoretical data.The results of elastic constants indicate that all these alloys are mechanically stable.Further mechanical behavior analysis shows that the additions of Cr,Fe,Co,and Ni could improve the hardness of CuPd3 while V could well increase its ductility.Moreover,in order to evaluate the thermodynamic contribution of 3d-metals,the Debye temperature,phonon density of states,and vibrational entropy for CuMPd6 alloy are also investigated.
Thermodynamic properties of vapor complex Na2ZrCl6
LI Jun-li; YU Jin; YANG Dong-mei; WANG Zhi-chang
2007-01-01
Thermodynamic studies were carried out for the vapor complex of sodium chloride with zirconium tetrachloride at 718-778 K and 0.5-2.5 kPa by using high temperature phase equilibrium-quenching experiments, taking closed Pyrex glass ampoules as the reaction containers. The results show that the sole predominant vapor complex is Na2ZrCl6 for the ZrCl4-NaCl system under the experimental conditions. The thermodynamic equilibrium constants and other thermodynamic functions of the reaction 2NaCl(s)+ZrCl4(g)=Na2ZrCl6(g) have been derived from the measurements. The results for the changes in enthalpy and entropy are △H0=(-70.1±1.5) kJ/mol and △S0=(-105.9±2.0) J/(mol·K) in the temperature range.
Thermodynamic Properties of o-Xylene, m-Xylene, p-Xylene, and Ethylbenzene
Zhou, Yong; Wu, Jiangtao; Lemmon, Eric W.
2012-06-01
Equations of state for the xylene isomers (o-xylene, m-xylene, and p-xylene) and ethylbenzene have been developed with the use of the Helmholtz energy as the fundamental property with independent variables of density and temperature. The general uncertainties of the equations of state are 0.5% in vapor pressure above the normal boiling point, and increase as the temperature decreases due to a lack of experimental data. The uncertainties in density range from 0.1% in the liquid region to 1.0% elsewhere (the critical and vapor-phase regions). The uncertainties in properties related to energy (such as heat capacity and sound speed) are estimated to be 1.0%. In the critical region, the uncertainties are higher for all properties. The behavior of the equations of state is reasonable within the region of validity and at higher and lower temperatures and pressures. Detailed analyses between the equations and experimental data are reported.