Intermolecular potentials and the accurate prediction of the thermodynamic properties of water.
Shvab, I; Sadus, Richard J
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(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. PMID:24320337
Intermolecular potentials and the accurate prediction of the thermodynamic properties of water
NASA Astrophysics Data System (ADS)
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.
Intermolecular potentials and the accurate prediction of the thermodynamic properties of water
Shvab, I.; Sadus, Richard J.
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.
Sprenger, K G; Jaeger, Vance W; Pfaendtner, Jim
2015-05-01
We have applied molecular dynamics to calculate thermodynamic and transport properties of a set of 19 room-temperature ionic liquids. Since accurately simulating the thermophysical properties of solvents strongly depends upon the force field of choice, we tested the accuracy of the general AMBER force field, without refinement, for the case of ionic liquids. Electrostatic point charges were developed using ab initio calculations and a charge scaling factor of 0.8 to more accurately predict dynamic properties. The density, heat capacity, molar enthalpy of vaporization, self-diffusivity, and shear viscosity of the ionic liquids were computed and compared to experimentally available data, and good agreement across a wide range of cation and anion types was observed. Results show that, for a wide range of ionic liquids, the general AMBER force field, with no tuning of parameters, can reproduce a variety of thermodynamic and transport properties with similar accuracy to that of other published, often IL-specific, force fields. PMID:25853313
Velasco, Inmaculada; Rivas, Clara; Martínez-López, José F; Blanco, Sofía T; Otín, Santos; Artal, Manuela
2011-06-30
Quasicontinuous PρT data of CO(2), ethane, propane, and the [CO(2) + ethane] mixture have been determined along subcritical, critical, and supercritical regions. These data have been used to develop the optimal experimental method and to determine the precision of the results obtained when using an Anton Paar DMA HPM vibrating-tube densimeter. A comparison with data from reference EoS and other authors confirm the quality of our experimental setup, its calibration, and testing. For pure compounds, the value of the mean relative deviation is MRD(ρ) = 0.05% for the liquid phase and for the extended critical and supercritical region. For binary mixtures the mean relative deviation is MRD(ρ) = 0.70% in the range up to 20 MPa and MRD(ρ) = 0.20% in the range up to 70 MPa. The number of experimental points measured and their just quality have enable us to determine some derivated properties with satisfactory precision; isothermal compressibilities, κ(T), have been calculated for CO(2) and ethane (MRD(κ(T)) = 1.5%), isobaric expasion coefficients, α(P), and internal pressures, π(i), for CO(2) (MRD(α(P)) = 5% and MRD(π(i)) = 7%) and ethane (MRD(α(P)) = 7.5% and MRD(π(i)) = 8%). An in-depth discussion is presented on the behavior of the properties obtained along subcritical, critical, and supercritical regions. In addition, PuT values have been determined for water and compressed ethane from 273.19 to 463.26 K up to pressures of 190.0 MPa, using a device based on a 5 MHz pulsed ultrasonic system (MRD(u) = 0.1%). With these data we have calibrated the apparatus and have verified the adequacy of the operation with normal liquids as well as with some compressed gases. From density and speed of sound data of ethane, isentropic compressibilities, κ(s), have been obtained, and from these and our values for κ(T) and α(P), isobaric heat capacities, C(p), have been calculated with MRD(C(p)) = 3%, wich is within that of the EoS. PMID:21639086
NASA Astrophysics Data System (ADS)
Hrubý, Jan
2012-04-01
Mathematical modeling of the non-equilibrium condensing transonic steam flow in the complex 3D geometry of a steam turbine is a demanding problem both concerning the physical concepts and the required computational power. Available accurate formulations of steam properties IAPWS-95 and IAPWS-IF97 require much computation time. For this reason, the modelers often accept the unrealistic ideal-gas behavior. Here we present a computation scheme based on a piecewise, thermodynamically consistent representation of the IAPWS-95 formulation. Density and internal energy are chosen as independent variables to avoid variable transformations and iterations. On the contrary to the previous Tabular Taylor Series Expansion Method, the pressure and temperature are continuous functions of the independent variables, which is a desirable property for the solution of the differential equations of the mass, energy, and momentum conservation for both phases.
The thermodynamic cost of accurate sensory adaptation
NASA Astrophysics Data System (ADS)
Tu, Yuhai
2015-03-01
Living organisms need to obtain and process environment information accurately in order to make decisions critical for their survival. Much progress have been made in identifying key components responsible for various biological functions, however, major challenges remain to understand system-level behaviors from the molecular-level knowledge of biology and to unravel possible physical principles for the underlying biochemical circuits. In this talk, we will present some recent works in understanding the chemical sensory system of E. coli by combining theoretical approaches with quantitative experiments. We focus on addressing the questions on how cells process chemical information and adapt to varying environment, and what are the thermodynamic limits of key regulatory functions, such as adaptation.
Computing Thermodynamic And Transport Properties
NASA Technical Reports Server (NTRS)
Mcbride, B.; Gordon, Sanford
1993-01-01
CET89 calculates compositions in chemical equilibrium and properties of mixtures of any chemical system for which thermodynamic data available. Provides following options: obtains chemical-equilibrium compositions and corresponding thermodynamic mixture properties for assigned thermodynamic states; calculates dilute-gas transport properties of complex chemical mixtures; obtains Chapman-Jouguet detonation properties for gaseous mixtures; calculates properties of incident and reflected shocks in terms of assigned velocities; and calculates theoretical performance of rocket for both equilibrium and frozen compositions during expansion. Rocket performance based on optional models of finite or infinite area combustor.
Integrated 3-parameter diagram for determining thermodynamic properties of fluids
NASA Astrophysics Data System (ADS)
Zhao, Guochang; Deng, Xiaoxue; Zhu, Mingshan
1987-04-01
The importance of thermodynamic properties of fluids has motivated recent studies in developing methods of calculating thermodynamic properties. Among the various methods, the use of computational diagrams is a commonly used engineering method. Conventional diagrams do not take into consideration the internal relationships among the various thermodynamic properties. The internal relationships of various thermodynamic properties are considered. The Lee-Kessler three-parameter equations were used to construct an integrated three-parameter diagram for determining the thermodynamic properties of fluids; the curves were generated using an ai-M/6 microcomputer with an attached Sr 6602 plotter. The diagram is considered sufficiently accurate for engineering calculations.
Predict amine solution properties accurately
Cheng, S.; Meisen, A.; Chakma, A.
1996-02-01
Improved process design begins with using accurate physical property data. Especially in the preliminary design stage, physical property data such as density viscosity, thermal conductivity and specific heat can affect the overall performance of absorbers, heat exchangers, reboilers and pump. These properties can also influence temperature profiles in heat transfer equipment and thus control or affect the rate of amine breakdown. Aqueous-amine solution physical property data are available in graphical form. However, it is not convenient to use with computer-based calculations. Developed equations allow improved correlations of derived physical property estimates with published data. Expressions are given which can be used to estimate physical properties of methyldiethanolamine (MDEA), monoethanolamine (MEA) and diglycolamine (DGA) solutions.
Thermodynamic Properties of HCFC-124
NASA Astrophysics Data System (ADS)
Fukushima, Masato; Watanabe, Naohiro
Thermodynamic properties of HCFC-124, such as saturated densities, vapor pressures and PVT properties, were measured and the critical parameters were determined through those experimental results. The correlations for vapor pressure, saturated liquid density and PVT properties deduced from those experimental results were compared with the measured data and also with the estimates of the other correlations published in literatures. The thermodynamic functions, such as enthalpy, entropy, heat capacity, etc., can reasonably be calculated from the correlation equations in this paper.
Thermodynamic properties of cerium mononitride
NASA Astrophysics Data System (ADS)
Aristova, N. M.; Belov, G. V.
2014-09-01
Data on the thermodynamic properties of cerium mononitride CeN in the solid state are analyzed. Relations approximating the temperature dependence of the thermodynamic functions of CeN(cr.) in the temperature range of 298.15-2900 K are obtained. Using the relations of thermodynamics known for this temperature range, the thermodynamic functions of cerium mononitride (entropy, Gibbs energy, and enthalpy variation) are calculated. The resulting data is entered into the database of the IVTANTHERMO software package and is used to analyze the thermal stability of CeN(cr.), and to estimate its boiling point at atmospheric pressure.
The Thermodynamic Properties of Cubanite
NASA Technical Reports Server (NTRS)
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 gadolinium disilicide
Lukashenko, G.M.; Polotskaya, R.I.
1986-11-01
The authors determine the Gibbs energy, enthalpy, formation heat, and other thermodynamic properties of gadolinium disilicide by measuring the electromotive force in the 830-960 K temperature range in electrolytes consisting of molten tin and various chlorides. The relationship of these properties to crystal structure is briefly 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.
Thermodynamic properties of minerals
Robie, Richard A.
1962-01-01
In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.
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 thermodynamic properties of benzothiazole and benzoxazole
NASA Astrophysics Data System (ADS)
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.
Thermodynamic Properties of Actinides and Actinide Compounds
NASA Astrophysics Data System (ADS)
Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean
The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.
NASA Astrophysics Data System (ADS)
Pliego, Josefredo R.; Riveros, José M.
2000-03-01
Clusters of hydroxide ion, HO-(H2O)n=1-4, have been studied by high level ab initio calculations in order to better understand the first coordination shell of OH- ions. Geometry optimizations were performed at Hartree-Fock, density functional theory and second order Møller-Plesset perturbation theory levels using the 6-31+G(d,p) basis set. Single point energy calculations were carried out on the optimized geometries using the more extended 6-311+G(2df,2p) basis set and a higher level of electron correlation, namely fourth-order Møller-Plesset perturbation theory. For the n=1-3 clusters, only structures with the hydroxide ion hydrogen bonded to all waters molecules were considered. For the n=4 cluster, three minima were found; the most stable species has all four waters directly bound to the hydroxide ion, while the other two clusters have only three waters in the first coordination shell. In addition, the transition state connecting the cluster containing four waters in the first coordination shell to the species having three waters in the coordination shell was characterized. The barrier for this rearrangement is very low (1.82 kcal/mol), and we predict this process to occur on the picosecond time scale. The thermodynamic properties (enthalpy, entropy and Gibbs free energy) for the formation of the clusters have been calculated for all the species (including the fully deuterated clusters). Comparison of our calculations with experimental data reveals good agreement in the free energy. Nevertheless, our ab initio results suggest that for the n>1 clusters, both -ΔH0 and -ΔS0 are larger than those reported from experiment and new experiments may be necessary to obtain accurate experimental values.
Thermodynamic Properties of Dimethyl Carbonatea)
NASA Astrophysics Data System (ADS)
Zhou, Yong; Wu, Jiangtao; Lemmon, Eric W.
2011-12-01
A thermodynamic property formulation for dimethyl carbonate has been developed with the use of available experimental thermodynamic property data. The equation of state was developed with multiproperty fitting methods involving pressure-density-temperature (pρT), heat capacity, vapor pressure, and saturated-liquid density data. The equation of state conforms to the Maxwell criterion for two-phase liquid-vapor equilibrium states, and is valid for temperatures from the triple-point temperature (277.06 ± 0.63) K to 600 K, for pressures up to 60 MPa, and for densities up to 12.12 mol dm-3. The extrapolation behavior of the equation of state at low and high temperatures and pressures is reasonable. The uncertainties (k = 2, indicating a 95% confidence level) of the equation of state in density are 0.05% for saturated-liquid states below 350 K, rising to 0.1% in the single phase between 278 K and 400 K at pressures up to 60 MPa. Due to the lack of reliable data outside this region, the estimated uncertainties increase to 0.5% to 1% in the vapor and critical regions. The uncertainties in vapor pressure are 0.6% from 310 K to 400 K, and increase to 1% at higher temperatures and to 2% at lower temperatures due to a lack of experimental data. The uncertainty in isobaric heat capacity and speed of sound in the liquid phase at saturation or atmospheric pressure is 0.5% from 280 K to 335 K. The uncertainties are higher for all properties in the critical region. Detailed comparisons between experimental and calculated data, and an analysis of the equation, have been performed.
Thermodynamic and Properties of Nanophases
Wunderlich, Bernhard {nmn}
2009-01-01
A large volume of today s research deals with nanophases of various types. The materials engineer, chemist, or physicist, however, when dealing with applications of nanophases is often unaware of the effect of the small size on structure and properties. The smallest nanophases reach the limit of phase definitions by approaching atomic dimensions. There, the required homogeneity of a phase is lost and undue property fluctuations destroy the usefulness of thermodynamic functions. In fact, itwas not expected that a definite nanophasewould exist belowthe size of a microphase.Aneffort ismadein this reviewto identify macrophases, microphases, and nanophases. It is shown that nanophases should contain no bulk matter as defined by macrophases and also found in microphases. The structure and properties of nanophases, thus, must be different from macrophases and microphases. These changes may include different crystal and amorphous structures, and phase transitions of higher or of lower temperature. The phase properties are changing continuously when going from one surface to the opposite one. The discussion makes use of results from structure determination, calorimetry, molecular motion evaluations, and molecular dynamics simulations.
NASA Technical Reports Server (NTRS)
Liu, Yen; Vinokur, Marcel
1989-01-01
This paper treats the accurate and efficient calculation of thermodynamic properties of arbitrary gas mixtures for equilibrium flow computations. New improvements in the Stupochenko-Jaffe model for the calculation of thermodynamic properties of diatomic molecules are presented. A unified formulation of equilibrium calculations for gas mixtures in terms of irreversible entropy is given. Using a highly accurate thermo-chemical data base, a new, efficient and vectorizable search algorithm is used to construct piecewise interpolation procedures with generate accurate thermodynamic variable and their derivatives required by modern computational algorithms. Results are presented for equilibrium air, and compared with those given by the Srinivasan program.
Thermodynamic properties of modified gravity theories
NASA Astrophysics Data System (ADS)
Bamba, Kazuharu
2016-06-01
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 nonequilibrium 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 transport properties of fluids
NASA Technical Reports Server (NTRS)
Fessler, T. E.
1980-01-01
Computer program subroutine FLUID calculates thermodynamic and transport properties of pure fluids in liquid, gas, or two-phase (liquid/gas) conditions. Program determines thermodynamic state from assigned values for temperature and density, pressure and density, temperature and pressure, pressure and entropy, or pressure and enthalpy.
Tables of thermodynamic properties of sodium
Fink, J.K.
1982-06-01
The thermodynamic properties of saturated sodium, superheated sodium, and subcooled sodium are tabulated as a function of temperature. The temperature ranges are 380 to 2508 K for saturated sodium, 500 to 2500 K for subcooled sodium, and 400 to 1600 K for superheated sodium. Tabulated thermodynamic properties are enthalpy, heat capacity, pressure, entropy, density, instantaneous thermal expansion coefficient, compressibility, and thermal pressure coefficient. Tables are given in SI units and cgs units.
Thermodynamics and statistical mechanics. [thermodynamic properties of gases
NASA Technical Reports Server (NTRS)
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.
Accurate Prediction of Binding Thermodynamics for DNA on Surfaces
Vainrub, Arnold; Pettitt, B. Montgomery
2011-01-01
For DNA mounted on surfaces for microarrays, microbeads and nanoparticles, the nature of the random attachment of oligonucleotide probes to an amorphous surface gives rise to a locally inhomogeneous probe density. These fluctuations of the probe surface density are inherent to all common surface or bead platforms, regardless if they exploit either an attachment of pre-synthesized probes or probes synthesized in situ on the surface. Here, we demonstrate for the first time the crucial role of the probe surface density fluctuations in performance of DNA arrays. We account for the density fluctuations with a disordered two-dimensional surface model and derive the corresponding array hybridization isotherm that includes a counter-ion screened electrostatic repulsion between the assayed DNA and probe array. The calculated melting curves are in excellent agreement with published experimental results for arrays with both pre-synthesized and in-situ synthesized oligonucleotide probes. The approach developed allows one to accurately predict the melting curves of DNA arrays using only the known sequence dependent hybridization enthalpy and entropy in solution and the experimental macroscopic surface density of probes. This opens the way to high precision theoretical design and optimization of probes and primers in widely used DNA array-based high-throughput technologies for gene expression, genotyping, next-generation sequencing, and surface polymerase extension. PMID:21972932
Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium
NASA Technical Reports Server (NTRS)
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
NASA Astrophysics Data System (ADS)
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
NASA Astrophysics Data System (ADS)
Wu, Zhongqing
2015-02-01
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.
Prediction of Thermodynamic Properties for Halogenated Hydrocarbon
NASA Astrophysics Data System (ADS)
Higashi, Yukihiro
The predictive methods of thermodynamic properties are discussed with respect to the halogenated hydrocarbons using as working fluids for refrigeration and heat pump cycles. The methods introduced into this paper can be calculated by the limited information; critical properties, normal boiling point and acentric factor. The results of prediction are compared with the experimental values of PVT property, vapor pressure and saturated liquid density. On the basis of these comparisons, Lydersen's method for predicting the critical properties, the generalized vapor pressure correlation by Ashizawa et, al., and Hankinson-Thomson's method for predicting saturated liquid density can be recommended. With respect to the equation of state, either Soave equation or Peng-Robinson equation is effective in calculating the thermodynamic properties except high density region.
NASA Astrophysics Data System (ADS)
Garrison, Stephen L.
2005-07-01
The combination of molecular simulations and potentials obtained from quantum chemistry is shown to be able to provide reasonably accurate thermodynamic property predictions. Gibbs ensemble Monte Carlo simulations are used to understand the effects of small perturbations to various regions of the model Lennard-Jones 12-6 potential. However, when the phase behavior and second virial coefficient are scaled by the critical properties calculated for each potential, the results obey a corresponding states relation suggesting a non-uniqueness problem for interaction potentials fit to experimental phase behavior. Several variations of a procedure collectively referred to as quantum mechanical Hybrid Methods for Interaction Energies (HM-IE) are developed and used to accurately estimate interaction energies from CCSD(T) calculations with a large basis set in a computationally efficient manner for the neon-neon, acetylene-acetylene, and nitrogen-benzene systems. Using these results and methods, an ab initio, pairwise-additive, site-site potential for acetylene is determined and then improved using results from molecular simulations using this initial potential. The initial simulation results also indicate that a limited range of energies important for accurate phase behavior predictions. Second virial coefficients calculated from the improved potential indicate that one set of experimental data in the literature is likely erroneous. This prescription is then applied to methanethiol. Difficulties in modeling the effects of the lone pair electrons suggest that charges on the lone pair sites negatively impact the ability of the intermolecular potential to describe certain orientations, but that the lone pair sites may be necessary to reasonably duplicate the interaction energies for several orientations. Two possible methods for incorporating the effects of three-body interactions into simulations within the pairwise-additivity formulation are also developed. A low density
Thermodynamic properties of hydrogen-helium plasmas.
NASA Technical Reports Server (NTRS)
Nelson, H. F.
1972-01-01
Calculation of the thermodynamic properties of an atomic hydrogen-helium plasma for postulated conditions present in a stagnation shock layer of a spacecraft entering the atmosphere of Jupiter. These properties can be used to evaluate transport properties, to calculate convective heating, and to investigate nonequilibrium behavior. The calculations have been made for temperatures from 10,000 to 100,000 K, densities of 10 to the minus 7th and .00001 g cu cm, and three plasma compositions: pure hydrogen, 50% hydrogen/50% helium, and pure helium. The shock layer plasma consists of electrons, protons, atomic hydrogen, atomic helium, singly ionized helium, and doubly atomized helium. The thermodynamic properties which have been investigated are: pressure, average molecular weight, internal energy, enthalpy, entropy, specific heat, and isentropic speed of sound. A consistent model was used for the reduction of the ionization potential in the calculation of the partition functions.
Computing Thermodynamic And Transport Properties Of Air
NASA Technical Reports Server (NTRS)
Thompson, Richard A.; Gupta, Roop N.; Lee, Kam-Pui
1994-01-01
EQAIRS computer program is set of FORTRAN 77 routines for computing thermodynamic and transport properties of equilibrium air for temperatures from 100 to 30,000 K. Computes properties from 11-species, curve-fit mathematical model. Successfully implemented on DEC VAX-series computer running VMS, Sun4-series computer running SunOS, and IBM PC-compatible computer running MS-DOS.
Thermodynamic properties of hydrogen-helium plasmas
NASA Technical Reports Server (NTRS)
Nelson, H. F.
1971-01-01
The thermodynamic properties of an atomic hydrogen-helium plasma are calculated and tabulated for temperatures from 10,000 to 100,000 K as a function of the mass fraction ratio of atomic hydrogen. The tabulation is for densities from 10 to the minus 10th power to 10 to the minus 6th power gm/cu cm and for hydrogen mass fraction ratios of 0, 0.333, 0.600, 0.800, and 1.0, which correspond to pure helium, 50 percent hydrogen per unit volume, 75 percent hydrogen per unit volume, 89 percent hydrogen per unit volume, and pure hydrogen plasmas, respectively. From an appended computer program, calculations can be made at other densities and mass fractions. The program output agrees well with previous thermodynamic property calculations for limiting cases of pure hydrogen and pure helium plasmas.
NASA Technical Reports Server (NTRS)
Nguyen, Huy H.; Martin, Michael A.
2004-01-01
The two most common approaches used to formulate thermodynamic properties of pure substances are fundamental (or characteristic) equations of state (Helmholtz and Gibbs functions) and a piecemeal approach that is described in Adebiyi and Russell (1992). This paper neither presents a different method to formulate thermodynamic properties of pure substances nor validates the aforementioned approaches. Rather its purpose is to present a method to generate property tables from existing property packages and a method to facilitate the accurate interpretation of fluid thermodynamic property data from those tables. There are two parts to this paper. The first part of the paper shows how efficient and usable property tables were generated, with the minimum number of data points, using an aerospace industry standard property package. The second part describes an innovative interpolation technique that has been developed to properly obtain thermodynamic properties near the saturated liquid and saturated vapor lines.
Thermodynamic properties of gaseous ruthenium species.
Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie
2015-05-21
The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points. PMID:25905631
Thermodynamic properties of Heisenberg magnetic systems
NASA Astrophysics Data System (ADS)
Qin, Wei; Wang, Huai-Yu; Long, Gui-Lu
2014-03-01
In this paper, we present a comprehensive investigation of the effects of the transverse correlation function (TCF) on the thermodynamic properties of Heisenberg antiferromagnetic (AFM) and ferromagnetic (FM) systems with cubic lattices. The TCF of an FM system is positive and increases with temperature, while that of an AFM system is negative and decreases with temperature. The TCF lowers internal energy, entropy and specific heat. It always raises the free energy of an FM system but raises that of an AFM system only above a specific temperature when the spin quantum number is S >= 1. Comparisons between the effects of the TCFs on the FM and AFM systems are made where possible.
Specification and thermodynamical properties of semigroup actions
NASA Astrophysics Data System (ADS)
Rodrigues, Fagner B.; Varandas, Paulo
2016-05-01
In the present paper, we study the thermodynamical properties of finitely generated continuous subgroup actions. We propose a notion of topological entropy and pressure functions that do not depend on the growth rate of the semigroup and introduce strong and orbital specification properties, under which the semigroup actions have positive topological entropy and all points are entropy points. Moreover, we study the convergence and Lipschitz regularity of the pressure function and obtain relations between topological entropy and exponential growth rate of periodic points in the context of semigroups of expanding maps, obtaining a partial extension of the results obtained by Ruelle for ℤd-actions [D. Ruelle, Trans. Am. Math. Soc., 187, 237-251 (1973)]. The specification properties for semigroup actions and the corresponding one for its generators and the action of push-forward maps are also discussed.
The thermodynamic properties of thianthrene and phenoxathiin
Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.
1993-04-01
Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for thianthrene (Chemical Abstracts registry number [92-85-3]) and phenoxathiin (registry number [262-20-41]). 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.). Critical properties were estimated for both materials based on the measurement results. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 298.15 K and 700 K. The property-measurement results reported here for thianthrene and phenoxathiin provide the first experimental gas-phase Gibbs energies of formation for tricyclic diheteroatom-containing molecules.
The thermodynamic properties of thianthrene and phenoxathiin
NASA Astrophysics Data System (ADS)
Steele, W. V.; Chirico, R. D.; Knipmeyer, S. E.; Nguyen, A.
1993-04-01
Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for thianthrene and phenoxathiin. 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.). Critical properties were estimated for both materials based on the measurement results. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for both compounds for selected temperatures between 298.15 K and 700 K. The property-measurement results reported here for thianthrene and phenoxathiin provide the first experimental gas-phase Gibbs energies of formation for tricyclic diheteroatom-containing molecules.
A generalized model for the thermodynamic properties of mixtures
Lemmon, E.W.; Jacobsen, R.T.
1999-05-01
A mixture model explicit in Helmholtz energy has been developed which is capable of predicting thermodynamic properties of mixtures containing nitrogen, argon, oxygen, carbon dioxide, methane, ethane, propane, n-butane, i-butane, R-32, R-125, R-134a, and R-152a within the estimated accuracy of available experimental data. The Helmholtz energy of the mixture is the sum of the ideal gas contribution, the compressibility for real gas contribution, and the contribution from mixing. The contribution from mixing is given by a single generalized equation which is applied to all mixtures studied in this work. The independent variables are the density, temperature, and composition. The model may be used to calculate the thermodynamic properties of mixtures at various compositions including dew and bubble point properties and critical points. It incorporates accurate published equations of state for each pure fluid. The estimated accuracy of calculated properties is {+-}0.2% in density, {+-}0.1% in the speed of sound at pressures below 10 MPa, {+-}0.5% in the speed of sound for pressures above 10 MPa, and {+-}1% in heat capacities. In the region from 250 to 350 K at pressures up to 30 MPa, calculated densities are within {+-}0.1% for most gaseous phase mixtures. For binary mixtures where the critical point temperatures of the pure fluid constituents are within 100 K of each other, calculated bubble point pressures are generally accurate to within {+-}1 to 2%. For mixtures with critical points further apart, calculated bubble point pressures are generally accurate to within {+-}5 to 10%.
EquilTheTA: Thermodynamic and transport properties of complex equilibrium plasmas
Colonna, G.; D'Angola, A.
2012-11-27
EquilTheTA (EQUILibrium for plasma THErmodynamics and Transport Applications) is a web-based software which calculates chemical equilibrium product concentrations from any set of reactants and determines thermodynamic and transport properties for the product mixture in wide temperature and pressure ranges. The program calculates chemical equilibrium by using a hierarchical approach, thermodynamic properties and transport coefficients starting from recent and accurate databases of atomic and molecular energy levels and collision integrals. In the calculations, Debye length and cut-off are consistently updated and virial corrections (up to third order) can be considered. Transport coefficients are calculated by using high order approximations of the Chapman-Enskog method.
Accurate simulation of optical properties in dyes.
Jacquemin, Denis; Perpète, Eric A; Ciofini, Ilaria; Adamo, Carlo
2009-02-17
Since Antiquity, humans have produced and commercialized dyes. To this day, extraction of natural dyes often requires lengthy and costly procedures. In the 19th century, global markets and new industrial products drove a significant effort to synthesize artificial dyes, characterized by low production costs, huge quantities, and new optical properties (colors). Dyes that encompass classes of molecules absorbing in the UV-visible part of the electromagnetic spectrum now have a wider range of applications, including coloring (textiles, food, paintings), energy production (photovoltaic cells, OLEDs), or pharmaceuticals (diagnostics, drugs). Parallel to the growth in dye applications, researchers have increased their efforts to design and synthesize new dyes to customize absorption and emission properties. In particular, dyes containing one or more metallic centers allow for the construction of fairly sophisticated systems capable of selectively reacting to light of a given wavelength and behaving as molecular devices (photochemical molecular devices, PMDs).Theoretical tools able to predict and interpret the excited-state properties of organic and inorganic dyes allow for an efficient screening of photochemical centers. In this Account, we report recent developments defining a quantitative ab initio protocol (based on time-dependent density functional theory) for modeling dye spectral properties. In particular, we discuss the importance of several parameters, such as the methods used for electronic structure calculations, solvent effects, and statistical treatments. In addition, we illustrate the performance of such simulation tools through case studies. We also comment on current weak points of these methods and ways to improve them. PMID:19113946
Thermodynamic properties of average-atom interatomic potentials for alloys
NASA Astrophysics Data System (ADS)
Nöhring, Wolfram Georg; Curtin, William Arthur
2016-05-01
The atomistic mechanisms of deformation in multicomponent random alloys are challenging to model because of their extensive structural and compositional disorder. For embedded-atom-method interatomic potentials, a formal averaging procedure can generate an average-atom EAM potential and this average-atom potential has recently been shown to accurately predict many zero-temperature properties of the true random alloy. Here, the finite-temperature thermodynamic properties of the average-atom potential are investigated to determine if the average-atom potential can represent the true random alloy Helmholtz free energy as well as important finite-temperature properties. Using a thermodynamic integration approach, the average-atom system is found to have an entropy difference of at most 0.05 k B/atom relative to the true random alloy over a wide temperature range, as demonstrated on FeNiCr and Ni85Al15 model alloys. Lattice constants, and thus thermal expansion, and elastic constants are also well-predicted (within a few percent) by the average-atom potential over a wide temperature range. The largest differences between the average atom and true random alloy are found in the zero temperature properties, which reflect the role of local structural disorder in the true random alloy. Thus, the average-atom potential is a valuable strategy for modeling alloys at finite temperatures.
Thermodynamic Properties in Triangular-Lattice Superconductors
NASA Astrophysics Data System (ADS)
Ma, Xixiao; Qin, Ling; Zhao, Huaisong; Lan, Yu; Feng, Shiping
2016-06-01
The study of superconductivity arising from doping a Mott insulator has become a central issue in the area of superconductivity. Within the framework of the kinetic-energy-driven superconducting (SC) mechanism, we discuss the thermodynamic properties in the triangular-lattice cobaltate superconductors. It is shown that a sharp peak in the specific heat appears at the SC transition temperature T_c, and then the specific heat varies exponentially as a function of temperature for temperatures T
FLUID- THERMODYNAMIC AND TRANSPORT PROPERTIES OF FLUIDS (IBM PC VERSION)
NASA Technical Reports Server (NTRS)
Fessler, T. E.
1994-01-01
The accurate computation of the thermodynamic and transport properties of fluids is a necessity for many engineering calculations. The FLUID program was developed to calculate the thermodynamic and transport properties of pure fluids in both the liquid and gas phases. Fluid properties are calculated using a simple gas model, empirical corrections, and an efficient numerical interpolation scheme. FLUID produces results that are in very good agreement with measured values, while being much faster than older more complex programs developed for the same purpose. A Van der Waals equation of state model is used to obtain approximate state values. These values are corrected for real-gas effects by model correction factors obtained from tables based on experimental data. These tables also accurately compensate for the special circumstances which arise whenever phase conditions occur. Viscosity and thermal conductivity values are computed directly from tables. Interpolation within tables is based on Lagrange's three point formula. A set of tables must be generated for each fluid implemented. FLUID currently contains tables for nine fluids including dry air and steam. The user can add tables for any fluid for which adequate thermal property data is available. The FLUID routine is structured so that it may easily be incorporated into engineering programs. The IBM 360 version of FLUID was developed in 1977. It is written in FORTRAN IV and has been implemented on an IBM 360 with a central memory requirement of approximately 222K of 8 bit bytes. The IBM PC version of FLUID is written in Microsoft FORTRAN 77 and has been implemented on an IBM PC with a memory requirement of 128K of 8 bit bytes. The IBM PC version of FLUID was developed in 1986.
FLUID- THERMODYNAMIC AND TRANSPORT PROPERTIES OF FLUIDS (IBM VERSION)
NASA Technical Reports Server (NTRS)
Fessler, T. E.
1994-01-01
The accurate computation of the thermodynamic and transport properties of fluids is a necessity for many engineering calculations. The FLUID program was developed to calculate the thermodynamic and transport properties of pure fluids in both the liquid and gas phases. Fluid properties are calculated using a simple gas model, empirical corrections, and an efficient numerical interpolation scheme. FLUID produces results that are in very good agreement with measured values, while being much faster than older more complex programs developed for the same purpose. A Van der Waals equation of state model is used to obtain approximate state values. These values are corrected for real-gas effects by model correction factors obtained from tables based on experimental data. These tables also accurately compensate for the special circumstances which arise whenever phase conditions occur. Viscosity and thermal conductivity values are computed directly from tables. Interpolation within tables is based on Lagrange's three point formula. A set of tables must be generated for each fluid implemented. FLUID currently contains tables for nine fluids including dry air and steam. The user can add tables for any fluid for which adequate thermal property data is available. The FLUID routine is structured so that it may easily be incorporated into engineering programs. The IBM 360 version of FLUID was developed in 1977. It is written in FORTRAN IV and has been implemented on an IBM 360 with a central memory requirement of approximately 222K of 8 bit bytes. The IBM PC version of FLUID is written in Microsoft FORTRAN 77 and has been implemented on an IBM PC with a memory requirement of 128K of 8 bit bytes. The IBM PC version of FLUID was developed in 1986.
Thermodynamic properties for R-404A
Fujiwara, K.; Nakamura, S.; Noguchi, M.
1999-01-01
An 18-coefficient modified Benedict-Webb-Rubin equation of state has been developed for R-404A, a ternary mixture of 44% by mass of pentafluoroethane (R-125), 52% by mass of 1,1,1-trifluoroethane (R-143a), and 4% by mass of 1,1,1,2-tetrafluoroethane (R-134a). Correlations of bubble point pressures, dew point pressures, saturated liquid densities, and saturated vapor densities are also presented. This equation of state has been developed based on the reported experimental data of PVT properties, saturation properties, and isochoric heat capacities by using least-squares fitting. These correlations are valid in the temperature range from 250 K to the critical temperature. This equation of state is valid at pressures up to 19 MPa, densities to 1,300 kg {center_dot} m{sup {minus}3}, and temperatures from 250 to 400 K. The thermodynamic properties except for the saturation pressures are calculated from this equation of state.
Thermodynamic Properties of the Group IA Elements
NASA Astrophysics Data System (ADS)
Alcock, C. B.; Chase, M. W.; Itkin, V. P.
1994-05-01
This review describes thermodynamic properties of condensed phases of the alkali metals, excluding francium for which the amount of information is too limited. The properties considered are: heat capacities from 0 to 1600 K, temperatures and enthalpies of fusion and martensitic transformation in Li and Na; discussion on the Debye temperature and electronic heat capacity coefficient at absolute zero temperature is also included. The paper is the second part of a series. Similar to our previous assessment of the II A group, this paper considers original studies, especially with respect to factors which influence the accuracy and reliability of results. Recommendations derived from such analyses are compared with most advanced previous reviews made at the Institute for High Temperatures (Moscow) and the National Institute of Standards and Technology (Washington). The properties of individual elements of the group are compared and suggestions are made for experimental studies which should improve poorly measured quantities. The review is supplemented by an IBM PC database which contains references, assessed data, brief description of studies, and has facilities for fitting and plotting of data and for adding new information. §
Thermodynamic Properties of Organometallic Dihydrogen Complexes for Hydrogen Storage Applications
NASA Astrophysics Data System (ADS)
Abrecht, David Gregory
The mechanism and thermodynamic properties of hydrogen binding to the solid-state complexes [M(CO)dppe2][BArF24] (M = Mn, Re, Tc) and [M'Hdppe2][NTf2] (M' = Fe, Ru, Os) were investigated experimentally and computationally over the temperature range 298K-373K and pressure range 0-2800 torr, based on the Sieverts method. The bulk absorption behavior was found to be accurately described by Langmuir isotherms. Enthalpy and entropy values of ΔH° = -52.2 kJ/mol and ΔS° = -99.6 J/mol-K were obtained experimentally for hydrogen absorption onto [Mn(CO)dppe2][BArF24] from the Langmuir equilibrium constant, and values obtained from electronic structure calculations using the LANL2DZ-ECP basis set were found to successfully reproduce both the pressure-temperature-composition behavior and the thermodynamic values to within 5% of those obtained through experiment. Results from simulations for all complexes yielded large enthalpy values similar to metal hydride formation enthalpies for all complexes studied, and the substitution of the metal center reproduced qualitative binding strength trends of 5d>3d>4d consistent with those previously reported for the group 6 metals. X-ray diffraction patterns and Mössbauer spectra were taken to determine the thermal decomposition pathway for [FeH(η2-H 2)dppe2][NTf2]. Simulations at the B3LYP/TZVP level of theory and experimental Mössbauer spectra confirmed the direct thermal decomposition from singlet-state [FeH(η2-H 2)dppe2][NTf2] to triplet-state [FeHdppe 2][NTf2] under vacuum conditions at 398K. Evaluation of the partial quadrupole splitting values of Q(H2) = -0.245 mm/s from Mössbauer spectroscopy significantly differ from typical values obtained for hydrides, indicating an underutilized mechanism for identification of dihydrogen ligands. Singlet-state thermodynamic values from simulation were consistent with experimental observations for Ru and Os, and ruthenium complexes were found to have thermodynamic properties within
Accurate thermodynamic properties of gas phase hydrogen bonded complexes.
Hansen, Anne S; Maroun, Zeina; Mackeprang, Kasper; Frandsen, Benjamin N; Kjaergaard, Henrik G
2016-08-24
We have measured the infrared spectra of ethanol·dimethylamine and methanol·dimethylamine complexes in the 299-374 K temperature range, and have determined the enthalpy of complex formation (ΔH) to be -31.1 ± 2 and -29.5 ± 2 kJ mol(-1), respectively. The corresponding values of the Gibbs free energy (ΔG) are determined from the experimental integrated absorbance and a calculated oscillator strength of the OH-stretching vibrational transition to be 4.1 ± 0.3 and 3.9 ± 0.3 kJ mol(-1) at 302 and 300 K, respectively. The entropy, ΔS is determined from the values of ΔH and ΔG to be -117 ± 7 and -111 ± 10 J (mol K)(-1) for the ethanol·dimethylamine and methanol·dimethylamine complexes, respectively. The determined ΔH, ΔG and ΔS values of the two complexes are similar, as expected by the similarity to their donor molecules ethanol and methanol. Values of ΔH, ΔG and ΔS in chemical reactions are often obtained from quantum chemical calculations. However, these calculated values have limited accuracy and large variations are found using different methods. The accuracy of the present ΔH, ΔG and ΔS values is such that the benchmarking of theoretical methods is possible. PMID:27523902
Effects of Thermodynamic Properties on Slab Evolution
NASA Astrophysics Data System (ADS)
Wada, I.; King, S. D.; Caddick, M. J.; Ross, N.
2012-12-01
We perform a series of numerical experiments to investigate the effects of thermodynamic properties on the geometrical evolution of subducting slabs. We calculate density (ρ), thermal expansivity (α), and heat capacity (cp) of mantle mineral assemblages of a harzburgite composition over a range of pressure and temperature conditions applicable to the Earth's mantle, using the thermodynamic database of Stixrude and Lithgow-Bertelloni [2011] and the thermodynamic calculation code Perple_X [Connolly, 2009]. Following Nakagawa et al. [2009], we assume that thermal diffusivity (κ) follows a power-law relationship with density (κ=κ0(ρ/ρ0)3, where κ0 and ρ0 are reference diffusivity and density, respectively). The calculations show that ρ, α, and κ change significantly along mantle geotherms; the ranges of their values are 3300-5100 km/m3, 1.5-3.5 10-5/K, and 3-17 W/m K, respectively. The change in cp is small (< 5%). We incorporate the pressure and temperature (PT) dependence of these thermodynamic properties into a 2-D finite element code with compressible convection formulations under the truncated anelastic liquid approximation [Lee and King, 2009] and develop a dynamic subduction model with kinematic boundary conditions. In the model, we use a composite mantle rheology that accounts for both diffusion and dislocation creep with flow law parameterization of wet olivine [Hirth and Kohlstedt, 2003]. Following Billen and Hirth [2007] and Lee and King [2011], we adjust the flow law parameter values for the lower mantle to test the effects of viscosity contrast between the upper and lower mantle on slab evolution. We use a reference model with a constant ρ, κ α, and cp, which is equivalent to using the incompressible extended Bousisnesq approximation. Preliminary results show that incorporating PT-dependent ρ enhances the vigor of the buoyancy driven flow compared to the reference model. Further, lithostatic pressure at a given depth is higher than in the
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. PMID:21523307
Thermopower Puck for Measurement of Thermodynamic Properties
NASA Astrophysics Data System (ADS)
Vargas, Andres; Fukuda, Ryan; Soliz, Nicholas; Ho, Pei-Chun
2014-03-01
A thermopower puck was created in order to measure the thermoelectric power and thermal conductance of strongly correlated electron materials from 10K to 300K. The puck consists of a 2k Ω resistivity heater and 2 thermometers. The heater is connected to the top of the sample and applies heat until thermal equilibrium is reached. This creates a temperature gradient across the sample and is read by the 2 thermometers, one reading the hotter temperature and the other reading the colder temperature. The wire that is used as the thermal anchor for the high temperature thermometer, which is electrically isolated from thermometer, is also used as one of the leads to measure the thermal voltage produced across the sample. To calibrate the measurement probe, the thermoelectric power and thermal conductance of a nickel sample, which was purchased from Quantum Design, was measured. The data obtained qualitatively agrees with the literature data provided to us by Quantum Design. For future work, we will be using the measurement probe to investigate the thermodynamic properties of intermetallic compounds. Research at CSU-Fresno is supported by NSF DMR-1104544. Felipe Vargas is also supported by Undergraduate Research Grant at CSU Fresno.
Composition and Thermodynamic Properties of Air in Chemical Equilibrium
NASA Technical Reports Server (NTRS)
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.
A method for the accurate and smooth approximation of standard thermodynamic functions
NASA Astrophysics Data System (ADS)
Coufal, O.
2013-01-01
A method is proposed for the calculation of approximations of standard thermodynamic functions. The method is consistent with the physical properties of standard thermodynamic functions. This means that the approximation functions are, in contrast to the hitherto used approximations, continuous and smooth in every temperature interval in which no phase transformations take place. The calculation algorithm was implemented by the SmoothSTF program in the C++ language which is part of this paper. Program summaryProgram title:SmoothSTF Catalogue identifier: AENH_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AENH_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 3807 No. of bytes in distributed program, including test data, etc.: 131965 Distribution format: tar.gz Programming language: C++. Computer: Any computer with gcc version 4.3.2 compiler. Operating system: Debian GNU Linux 6.0. The program can be run in operating systems in which the gcc compiler can be installed, see http://gcc.gnu.org/install/specific.html. RAM: 256 MB are sufficient for the table of standard thermodynamic functions with 500 lines Classification: 4.9. Nature of problem: Standard thermodynamic functions (STF) of individual substances are given by thermal capacity at constant pressure, entropy and enthalpy. STF are continuous and smooth in every temperature interval in which no phase transformations take place. The temperature dependence of STF as expressed by the table of its values is for further application approximated by temperature functions. In the paper, a method is proposed for calculating approximation functions which, in contrast to the hitherto used approximations, are continuous and smooth in every temperature interval. Solution method: The approximation functions are
Measurement of Thermodynamic Properties of Titanium Aluminum Alloys
NASA Technical Reports Server (NTRS)
Mehrotra, Gopal
1995-01-01
This final report is a summary of the work done by Professor Mehrotra at NASA Lewis Research Center. He has worked extensively on the measurement of thermodynamic properties of titanium aluminum alloys over the past six years.
Thermodynamic properties of UF6 at high temperatures
NASA Technical Reports Server (NTRS)
Hassan, H. A.; Deese, J. E.
1974-01-01
The equilibrium composition and the thermodynamic properties of the mixture resulting from the decomposition of uranium hexafluoride is calculated for temperatures ranging from 600 K to 4000 K at pressures from 0.01 atmospheres to 10 atmospheres.
NASA Technical Reports Server (NTRS)
Nguyen, Huy H.; Martin, Michael A.
2003-01-01
The availability and proper utilization of fluid properties is of fundamental importance in the process of mathematical modeling of propulsion systems. Real fluid properties provide the bridge between the realm of pure analytiis and empirical reality. The two most common approaches used to formulate thermodynamic properties of pure substances are fundamental (or characteristic) equations of state (Helmholtz and Gibbs functions) and a piecemeal approach that is described, for example, in Adebiyi and Russell (1992). This paper neither presents a different method to formulate thermodynamic properties of pure substances nor validates the aforementioned approaches. Rather its purpose is to present a method to be used to facilitate the accurate interpretation of fluid thermodynamic property data generated by existing property packages. There are two parts to this paper. The first part of the paper shows how efficient and usable property tables were generated, with the minimum number of data points, using an aerospace industry standard property package (based on fundamental equations of state approach). The second part describes an innovative interpolation technique that has been developed to properly obtain thermodynamic properties near the saturated liquid and saturated vapor lines.
Accuracy Based Generation of Thermodynamic Properties for Light Water in RELAP5-3D
Cliff B. Davis
2010-09-01
RELAP5-3D interpolates to obtain thermodynamic properties for use in its internal calculations. The accuracy of the interpolation was determined for the original steam tables currently used by the code. This accuracy evaluation showed that the original steam tables are generally detailed enough to allow reasonably accurate interpolations in most areas needed for typical analyses of nuclear reactors cooled by light water. However, there were some regions in which the original steam tables were judged to not provide acceptable accurate results. Revised steam tables were created that used a finer thermodynamic mesh between 4 and 21 MPa and 530 and 640 K. The revised steam tables solved most of the problems observed with the original steam tables. The accuracies of the original and revised steam tables were compared throughout the thermodynamic grid.
Thermodynamic and transport properties of sodium liquid and vapor
Fink, J.K.; Leibowitz, L.
1995-01-01
Data have been reviewed to obtain thermodynamically consistent equations for thermodynamic and transport properties of saturated sodium liquid and vapor. Recently published Russian recommendations and results of equation of state calculations on thermophysical properties of sodium have been included in this critical assessment. Thermodynamic properties of sodium liquid and vapor that have been assessed include: enthalpy, heat capacity at constant pressure, heat capacity at constant volume, vapor pressure, boiling point, enthalpy of vaporization, density, thermal expansion, adiabatic and isothermal compressibility, speed of sound, critical parameters, and surface tension. Transport properties of liquid sodium that have been assessed include: viscosity and thermal conductivity. For each property, recommended values and their uncertainties are graphed and tabulated as functions of temperature. Detailed discussions of the analyses and determinations of the recommended equations include comparisons with recommendations given in other assessments and explanations of consistency requirements. The rationale and methods used in determining the uncertainties in the recommended values are also discussed.
Thermodynamical properties of graphene in noncommutative phase–space
Santos, Victor; Maluf, R.V.; Almeida, C.A.S.
2014-10-15
We investigated the thermodynamic properties of graphene in a noncommutative phase–space in the presence of a constant magnetic field. In particular, we determined the behaviour of the main thermodynamical functions: the Helmholtz free energy, the mean energy, the entropy and the specific heat. The high temperature limit is worked out and the thermodynamic quantities, such as mean energy and specific heat, exhibit the same features as the commutative case. Possible connections with the results already established in the literature are discussed briefly.
Felmy, Andrew R.; Mason, Marvin; Qafoku, Odeta; Xia, Yuanxian; Wang, Zheming; MacLean, Graham
2003-03-27
Developing accurate thermodynamic models for predicting the chemistry of the high-level waste tanks at Hanford is an extremely daunting challenge in electrolyte and radionuclide chemistry. These challenges stem from the extremely high ionic strength of the tank waste supernatants, presence of chelating agents in selected tanks, wide temperature range in processing conditions and the presence of important actinide species in multiple oxidation states. This presentation summarizes progress made to date in developing accurate models for these tank waste solutions, how these data are being used at Hanford and the important challenges that remain. New thermodynamic measurements on Sr and actinide complexation with specific chelating agents (EDTA, HEDTA and gluconate) will also be presented.
Thermodynamic properties of alloys of the vanadium-nitrogen system
Lukashenko, G.M.; Khaenko, B.V.; Sidorko, V.R.
1985-08-01
This paper discusses the results of work on the thermodynamic properties of alloys of the V-N system studied by measuring the electromotive forces of galvanic concentration cells in KC1NaC1 melts in the range, 953 - 1123/sup 0/K, at nitrogen concentrations in the alloys of less than 50 at.%. As a result of this investigation, partial thermodynamic functions for both components and integral functions of alloy formation in a wide range of compositions have been obtained.
Thermodynamic properties of high-pressure mantle minerals
NASA Astrophysics Data System (ADS)
Akaogi, M.
2006-12-01
Thermodynamic properties of high-pressure minerals of geophysical interest are essential to calculate high- pressure phase relations of mantle minerals which are indispensable to clarify the mineral stability and the nature of seismic discontinuities. After Navrotsky's (1973) pioneering work on enthalpy measurement of olivine-spinel transition in Ni2SiO4, a number of calorimetric works have been carried out on high-pressure silicates and related substances. The high-temperature calorimetric techniques for high-pressure phases were developed from solution calorimetry in the initial stage to drop-solution calorimetry with gas-bubbling technique nowadays. According to the technical developments, the amount of sample used for calorimetric runs has been reduced from about hundred mg to a few mg, and it is now possible to measure enthalpies of phases synthesized at the conditions of the upper part of the lower mantle. In this paper, the technical developments are reviewed, together with current status of enthalpy measurements of high-pressure phases. We show new results on transition enthalpies among Mg2SiO4 olivine, wadsleyite and ringwoodite measured by drop-solution calorimetry with gas-bubbling technique. Determination of entropy is based on heat capacity measurement from near 0 K to room temperature. Although widely used adiabatic calorimetry is very accurate for the low-temperature heat capacity measurement, it practically cannot be applied to high-pressure minerals, because the method requires a sample of several grams. Recent development of thermal relaxation method has made it possible to measure low-temperature heat capacity of a sample of several mg. We show new data of heat capacities at 2-305 K and standard entropies of Mg2SiO4 wadsleyite and ringwoodite measured by the thermal relaxation method. Using both of the above enthalpies and entropies of transitions, we calculated olivine-wadsleyite and wadsleyite-ringwoodite transition boundaries of Mg2SiO4
A Pseudopotential Approach to Compute Thermodynamic Properties of Liquid Semiconductors
NASA Astrophysics Data System (ADS)
Prajapati, Anand; Thakor, Pankaj; Sonvane, Yogesh
2015-03-01
This paper deals with the theoretical approach for calculating the thermodynamical properties viz. Enthalpy(E),Entropy(S) and Helmholtz free energy(F) of some liquid semiconductors (Si, Ga, Ge, In, Sn, Tl, Bi, As, Se, Te and Sb). The Gibbs-Bogoliubov(GB) variational method is applied to compute the thermodynamical properties. Our well established model potential is used to define the electron-ion interaction. Charged Hard Sphere (CHS) reference system is used to describe the structural contribution to the Helmholtz free energy in the liquid phase. Local field correction function proposed by Farid et al is adopted to see the screening effect. Lastly, our newly constructed model potential is an effective one to produce the data of thermodynamical properties of some liquid semiconductor.
Thermodynamic properties of germanium/carbon microclusters
NASA Astrophysics Data System (ADS)
Wielgus, Pawel; Roszak, Szczepan; Majumdar, Devashis; Leszczynski, Jerzy
2005-12-01
Theoretical studies on the GenCm (n =1,2; m =1-3) microclusters have been performed using the state of the art calculations. Several alternative structures of these clusters were studied to locate the lowest-energy isomers. It is observed that the structures of the complexes result from the competition between ionic Ge-C, conjugated covalent C-C, and metallic Ge-Ge bonds. The ionization of the molecules enhances the ionic character of the Ge-C bond and has significant structural consequences. Using theoretically determined partition functions, thermodynamic data are computed and experimental enthalpies are enhanced. The ab initio atomization energies of germanium carbides compare well with corrected experimental functions. The experimental appearance potentials are well reproduced by the theoretical ionization potentials.
Thermodynamical properties of liquid lanthanides-A variational approach
Patel, H. P.; Thakor, P. B.; Sonvane, Y. A.
2015-06-24
Thermodynamical properties like Entropy (S), Internal energy (E) and Helmholtz free energy (F) of liquid lanthanides using a variation principle based on the Gibbs-Bogoliubuv (GB) inequality with Percus Yevick hard sphere reference system have been reported in the present investigation. To describe electron-ion interaction we have used our newly constructed parameter free model potential along with Sarkar et al. local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermodynamical properties of liquid lanthanides.
NASA Glenn Coefficients for Calculating Thermodynamic Properties of Individual Species
NASA Technical Reports Server (NTRS)
McBride, Bonnie J.; Zehe, Michael J.; Gordon, Sanford
2002-01-01
This report documents the library of thermodynamic data used with the NASA Glenn computer program CEA (Chemical Equilibrium with Applications). This library, containing data for over 2000 solid, liquid, and gaseous chemical species for temperatures ranging from 200 to 20,000 K, is available for use with other computer codes as well. The data are expressed as least-squares coefficients to a seven-term functional form for C((sup o)(sub p)) (T) / R with integration constants for H (sup o) (T) / RT and S(sup o) (T) / R. The NASA Glenn computer program PAC (Properties and Coefficients) was used to calculate thermodynamic functions and to generate the least-squares coefficients. PAC input was taken from a variety of sources. A complete listing of the database is given along with a summary of thermodynamic properties at 0 and 298.15 K.
Thermodynamic properties of bulk and confined water
Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene
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 of bulk and confined water
NASA Astrophysics Data System (ADS)
Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene
2014-11-01
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 (TL ≃ 225 K). The second, T* ˜ 315 ± 5 K, is a special locus of the isothermal compressibility KT(T, P) and the thermal expansion coefficient αP(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 (TL) and the onset of the unfolding process (T*).
Reference Fluid Thermodynamic and Transport Properties Database (REFPROP)
National Institute of Standards and Technology Data Gateway
SRD 23 NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) (PC database for purchase) NIST 23 contains revised data in a Windows version of the database, including 105 pure fluids and allowing mixtures of up to 20 components. The fluids include the environmentally acceptable HFCs, traditional HFCs and CFCs and 'natural' refrigerants like ammonia
Microcomputer Calculation of Thermodynamic Properties from Molecular Parameters of Gases.
ERIC Educational Resources Information Center
Venugopalan, Mundiyath
1990-01-01
Described in this article is a problem-solving activity which integrates the application of microcomputers with the learning of physical chemistry. Students use the program with spectroscopic data to calculate the thermodynamic properties and compare them with the values from the thermochemical tables. (Author/KR)
Computer program for calculating thermodynamic and transport properties of fluids
NASA Technical Reports Server (NTRS)
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.
Computer programs for thermodynamic and transport properties of hydrogen
NASA Technical Reports Server (NTRS)
Hall, W. J.; Mc Carty, R. D.; Roder, H. M.
1968-01-01
Computer program subroutines provide the thermodynamic and transport properties of hydrogen in tabular form. The programs provide 18 combinations of input and output variables. This program is written in FORTRAN 4 for use on the IBM 7044 or CDC 3600 computers.
Mechanical, electronic and thermodynamic properties of full Heusler compounds Fe2VX(X = Al, Ga)
NASA Astrophysics Data System (ADS)
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.
Thermodynamical properties of Strunz’s quantum dissipative models
Zen, Freddy P.; Sulaiman, A.
2015-09-30
The existence of the negative of specific heat from quantum dissipative theory is investigated. Strunz’s quantum dissipative model will be used in this studies. The thermodynamical properties will be studied starts out from the thermo-dynamic partition function of the dissipative system. The path integral technique is used to calculate the partition function under consideration. The results shows that the specific heat can be negative if the damping parameter more than a half the oscillator frequency and also occur at low temperatures. For damping factor greater than the frequency of harmonic oscillator then specific heat will oscillate at low temperatures and approaching normal conditions at a high temperature.
Thermodynamical property of entanglement entropy for excited states.
Bhattacharya, Jyotirmoy; Nozaki, Masahiro; Takayanagi, Tadashi; Ugajin, Tomonori
2013-03-01
We argue that the entanglement entropy for a very small subsystem obeys a property which is analogous to the first law of thermodynamics when we excite the system. In relativistic setups, its effective temperature is proportional to the inverse of the subsystem size. This provides a universal relationship between the energy and the amount of quantum information. We derive the results using holography and confirm them in two-dimensional field theories. We will also comment on an example with negative specific heat and suggest a connection between the second law of thermodynamics and the strong subadditivity of entanglement entropy. PMID:23496702
Thermodynamic and melting properties of RDX at elevated pressures
NASA Technical Reports Server (NTRS)
Carlson, D. W.; Nauflett, G. W.; Brasch, J. W., Sr.; Austin, T. D.
1980-01-01
The laboratory set up for determination of melting and thermodynamic properties of RDX using a diamond anvil cell apparatus capable of pressures exceeding 10 kbar and 250 C is described. The slope of the melting temperature versus applied pressure curve for RDX, as determined in the diamond cell, was found to equal 4.09 + or - 0.6 C (kbar). The density of liquid RDX at its melting point was calculated from this slope to be approximately 1.63 gm/cu cm. Practical and theoretical considerations in using the diamond anvil cell to generate thermodynamic data on RDX are discussed.
Thermodynamic and transport properties of cryogenic propellants and related fluids
NASA Technical Reports Server (NTRS)
Johnson, V. J.
1973-01-01
Significant advances have been made in recent years in the quality and range of thermophysical data for the cryogenic propellants, pressurants, and inertants. A review of recently completed and current data compilation projects for helium, hydrogen, argon, nitrogen, oxygen, fluorine, and methane is given together with recommended references for thermodynamic and transport property data tables for these fluids. Modern techniques in the plotting of thermodynamic charts from tabular data (or from functions such as the equation of state) have greatly improved their precision and value. A list of such charts is included.
Thermodynamic properties and phase transitions in CO2 molecular clusters
NASA Technical Reports Server (NTRS)
Etters, R. D.; Flurchick, K.; Pan, R. P.; Chandrasekharan, V.
1981-01-01
The thermodynamic properties of (CO2)N molecular aggregates of size N between 2 and 13 have been investigated. These crystallites exhibit well defined orientational order-disorder rotational transitions accompanied by a structural transition into a plastic crystallite phase. In addition, they exhibit melting and disassociation transitions. It is shown that the interpretation of experimental data, based upon dimer properties, depends crucially on these results. Equilibrium structures and orientations are also given.
The thermodynamic properties of organic oxygen compounds
NASA Astrophysics Data System (ADS)
Chirico, R. D.; Steele, W. V.; Hossenlopp, A.; Nguyen, A.; Archer, D. G.; Strube, M. M.
1988-01-01
The principles of group additivity are used to compare a series of cyclic hydrocarbons with the corresponding oxygen-containing analogs. The strengths and limitations of the group-additivity method are demonstrated and recommendations are made for measurements essential to the improvement of the accuracy of the predicted properties. The ideal-gas enthalpies of formation and ideal-gas entropies (which are used in combination to calculate Gibbs energies) are considered.
Predicting Thermodynamic Properties of PBXTHs with New Quantum Topological Indexes
Peng, Guowen; Yu, Limei
2016-01-01
Novel group quantitative structure-property relationship (QSPR) models on the thermodynamic properties of PBXTHs were presented, by the multiple linear regression (MLR) analysis method. Four thermodynamic properties were studied: the entropy (Sθ), the standard enthalpy of formation (ΔfHθ), the standard Gibbs energy of formation (ΔfGθ), and the relative standard Gibbs energy of formation (ΔRGθ). The results by the formula indicate that the calculated and predicted data in this study are in good agreement with those in literature and the deviation is within the experimental errors. To validate the estimation reliability for internal samples and the predictive ability for other samples, leave-one-out (LOO) cross validation (CV) and external validation were performed, and the results show that the models are satisfactory. PMID:26900689
The structural, elastic and thermodynamic properties of thorium tetraboride
NASA Astrophysics Data System (ADS)
Aydin, Sezgin; Tatar, Aynur
2011-04-01
The structural, elastic and thermodynamic properties of thorium tetraboride (ThB 4) have been investigated by using first-principles plane-wave pseudopotential density functional theory with generalized gradient approximation. The behaviors of structural parameters under 0-70 GPa hydrostatic pressure are studied by means of Broyden, Fletcher, Goldfarb, and Shanno (BFGS) geometry optimization scheme. By using the stress-strain method, single crystal elastic constants are calculated to test the mechanical stability of the crystal structure and to determine mechanical properties such as bulk modulus at each pressure. However, in order to study the thermodynamic properties of ThB 4, the quasi-harmonic Debye model is used. Then, the dependencies of bulk modulus, heat capacities, thermal expansions, Grüneisen parameters and Debye temperatures on the temperature and pressure are obtained in the whole pressure range 0-70 GPa and temperature range 0-1500 K.
Computational Models of Thermodynamic Properties of Uranium Nitride
NASA Astrophysics Data System (ADS)
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.
Thermodynamic properties by non-calorimetric methods. Final report
Steele, W.V.; Chirico, R.D.; Collier, W.B.; Strube, M.M.; Klots, T.D. |
1992-12-31
This research program provided a valuable complement to the experimental programs currently in progress at NIPER for the Advanced Research and Technology Development (AR and TD) and Advanced Exploration and Process Technology (AEPT) divisions of the Department of Energy. These experimental programs are focused on the calorimetric determination of thermodynamic properties of key polynuclear heteroatom-containing aromatic molecules. The project for the Office of Energy Research focused on the non-calorimetric determination of thermodynamic properties through the extension of existing correlation methodologies and through molecular spectroscopy with statistical mechanics. The paper discusses the following studies: Group-contribution approach for polycyclic aromatic hydrocarbons (naphthalene, phenanthrene, anthracene, pyrene, 3-methylphenanthrene, benzoquinolines, biphenyl/hydrogen system); Group-contribution approach for key monocyclic organic compounds; Molecular spectroscopy and statistical mechanics; and Thermophysical property correlations.
NASA Technical Reports Server (NTRS)
Myles, K. M.
1967-01-01
Vapor pressure data obtained by the torsion-effusion method provides the thermodynamic properties of several transition-metal alloy systems. The vapor pressure of silver over solid silver and over palladium-silver alloys was measured and the results were more accurate than those found previously by other techniques.
Tables of thermodynamic properties of helium magnet coolant. Revision A
McAshan, M.
1992-07-01
The most complete treatment of the thermodynamic properties of helium at the present time is the monograph by McCarty: ``Thermodynamic Properties of Helium 4 from 2 to 1500 K at Pressures to 10{sup 8} Pa``, Robert D. McCarty, Journal of Physical and Chemical Reference Data, Vol. 2, page 923--1040 (1973). In this work the complete range of data on helium is examined and the P-V-T surface is described by an equation of state consisting of three functions P(r,T) covering different regions together with rules for making the transition from one region to another. From this thermodynamic compilation together with correlations of the transport properties of helium was published the well-known NBS Technical Note: ``Thermophysical Properties of Helium 4 from 2 to 1500 K with pressures to 1000 Atmospheres``, Robert D. McCarty, US Department of Commerce, National Bureau of Standards Technical Note 631 (1972). This is the standard reference for helium cryogenics. The NBS 631 tables cover a wide range of temperature and pressure, and as a consequence, the number of points tabulated in the region of the single phase coolant for the SSC magnets are relatively few. The present work sets out to cover the range of interest in more detail in a way that is consistent with NBS 631. This new table is essentially identical to the older one and can be used as an auxiliary to it.
Tables of thermodynamic properties of helium magnet coolant
McAshan, M.
1992-07-01
The most complete treatment of the thermodynamic properties of helium at the present time is the monograph by McCarty: Thermodynamic Properties of Helium 4 from 2 to 1500 K at Pressures to 10{sup 8} Pa'', Robert D. McCarty, Journal of Physical and Chemical Reference Data, Vol. 2, page 923--1040 (1973). In this work the complete range of data on helium is examined and the P-V-T surface is described by an equation of state consisting of three functions P(r,T) covering different regions together with rules for making the transition from one region to another. From this thermodynamic compilation together with correlations of the transport properties of helium was published the well-known NBS Technical Note: Thermophysical Properties of Helium 4 from 2 to 1500 K with pressures to 1000 Atmospheres'', Robert D. McCarty, US Department of Commerce, National Bureau of Standards Technical Note 631 (1972). This is the standard reference for helium cryogenics. The NBS 631 tables cover a wide range of temperature and pressure, and as a consequence, the number of points tabulated in the region of the single phase coolant for the SSC magnets are relatively few. The present work sets out to cover the range of interest in more detail in a way that is consistent with NBS 631. This new table is essentially identical to the older one and can be used as an auxiliary to it.
Tables of thermodynamic properties of helium magnet coolant, revision A
NASA Astrophysics Data System (ADS)
McAshan, M.
1992-07-01
The most complete treatment of the thermodynamic properties of helium at the present time is the monograph by McCarty: 'Thermodynamic Properties of Helium 4 from 2 to 1500 K at Pressures to 10(exp 8) Pa', Robert D. McCarty, Journal of Physical and Chemical Reference Data, Vol. 2, page 923-1040 (1973). In this work the complete range of data on helium is examined and the P-V-T surface is described by an equation of state consisting of three functions P(r,T) covering different regions together with rules for making the transition from one region to another. From this thermodynamic compilation together with correlations of the transport properties of helium was published the well-known NBS Technical Note: 'Thermophysical Properties of Helium 4 from 2 to 1500 K with pressures to 1000 Atmospheres', Robert D. McCarty, US Department of Commerce, National Bureau of Standards Technical Note 631 (1972). This is the standard reference for helium cryogenics. The NBS 631 tables cover a wide range of temperature and pressure, and as a consequence, the number of points tabulated in the region of the single phase coolant for the SSC magnets are relatively few. The present work sets out to cover the range of interest in more detail in a way that is consistent with NBS 631. This new table is essentially identical to the older one and can be used as an auxiliary to it.
Thermodynamic properties of fluids from Fluctuation Solution Theory
O'Connell, J.P.
1990-01-01
Fluctuation Theory develops exact relations between integrals of molecular correlation functions and concentration derivatives of pressure and chemical potential. These quantities can be usefully correlated, particularly for mechanical and thermal properties of pure and mixed dense fluids and for activities of strongly nonideal liquid solutions. The expressions yield unique formulae for the desirable thermodynamic properties of activity and density. The molecular theory origins of the flucuation properties, their behavior for systems of technical interest and some of their successful correlations will be described. Suggestions for fruitful directions will be suggested.
Thermodynamic properties of fluids from Fluctuation Solution Theory
O`Connell, J.P.
1990-12-31
Fluctuation Theory develops exact relations between integrals of molecular correlation functions and concentration derivatives of pressure and chemical potential. These quantities can be usefully correlated, particularly for mechanical and thermal properties of pure and mixed dense fluids and for activities of strongly nonideal liquid solutions. The expressions yield unique formulae for the desirable thermodynamic properties of activity and density. The molecular theory origins of the flucuation properties, their behavior for systems of technical interest and some of their successful correlations will be described. Suggestions for fruitful directions will be suggested.
NASA Technical Reports Server (NTRS)
Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.
1990-01-01
The computer codes developed provide data to 30000 K for the thermodynamic and transport properties of individual species and reaction rates for the prominent reactions occurring in an 11-species nonequilibrium air model. These properties and the reaction-rate data are computed through the use of curve-fit relations which are functions of temperature (and number density for the equilibrium constant). The curve fits were made using the most accurate data believed available. A detailed review and discussion of the sources and accuracy of the curve-fitted data used herein are given in NASA RP 1232.
NASA Technical Reports Server (NTRS)
Thompson, R. A.
1994-01-01
Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the
Thermodynamic properties and diffusion of water + methane binary mixtures
Shvab, I.; Sadus, Richard J.
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.
Thermodynamic properties and diffusion of water + methane binary mixtures.
Shvab, I; Sadus, Richard J
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. PMID:24628180
Predictive study of thermodynamic properties of GeC
NASA Astrophysics Data System (ADS)
Sekkal, W.; Zaoui, A.
2002-03-01
We present in this paper a molecular dynamics simulation of structural and thermodynamic properties of the hypothetical IV-IV compound GeC in the zinc-blende structure. This study is performed with the use of the well-tested Tersoff potential. Various physical quantities including elastic constants, Debye temperature, thermal expansion coefficient, heat capacity, and Grüneisen parameter are predicted. The comparison with the corresponding results for SiC is also discussed.
Coefficients for calculating thermodynamic and transport properties of individual species
NASA Technical Reports Server (NTRS)
Mcbride, Bonnie J.; Gordon, Sanford; Reno, Martin A.
1993-01-01
Libraries of thermodynamic data and transport properties are given for individual species in the form of least-squares coefficients. Values of C(sup 0)(sub p)(T), H(sup 0)(T), and S(sup 0)(T) are available for 1130 solid, liquid, and gaseous species. Viscosity and thermal conductivity data are given for 155 gases. The original C(sup 0)(sub p)(T) values were fit to a fourth-order polynomial with integration constants for H(sup 0)(T) and S(sup 0)(T). For each species the integration constant for H(sup 0)(T) includes the heat of formation. Transport properties have a different functional form. The temperature range for most of the data is 300 to 5000 K, although some of the newer thermodynamic data have a range of 200 to 6000 K. Because the species are mainly possible products of reaction, the data are useful for chemical equilibrium and kinetics computer codes. Much of the data has been distributed for several years with the NASA Lewis equilibrium program CET89. The thermodynamic properties of the reference elements were updated along with about 175 species that involve the elements carbon, hydrogen, oxygen, and nitrogen. These sets of data will be distributed with the NASA Lewis personal computer program for calculating chemical equilibria, CETPC.
A thermodynamic approach to obtain materials properties for engineering applications
NASA Technical Reports Server (NTRS)
Chang, Y. Austin
1993-01-01
With the ever increases in the capabilities of computers for numerical computations, we are on the verge of using these tools to model manufacturing processes for improving the efficiency of these processes as well as the quality of the products. One such process is casting for the production of metals. However, in order to model metal casting processes in a meaningful way it is essential to have the basic properties of these materials in their molten state, solid state as well as in the mixed state of solid and liquid. Some of the properties needed may be considered as intrinsic such as the density, heat capacity or enthalpy of freezing of a pure metal, while others are not. For instance, the enthalpy of solidification of an alloy is not a defined thermodynamic quantity. Its value depends on the micro-segregation of the phases during the course of solidification. The objective of the present study is to present a thermodynamic approach to obtain some of the intrinsic properties and combining thermodynamics with kinetic models to estimate such quantities as the enthalpy of solidification of an alloy.
Mixed 2D molecular systems: Mechanic, thermodynamic and dielectric properties
NASA Astrophysics Data System (ADS)
Beňo, Juraj; Weis, Martin; Dobročka, Edmund; Haško, Daniel
2008-08-01
Study of Langmuir monolayers consisting of stearic acid (SA) and dipalmitoylphosphatidylcholine (DPPC) molecules was done by surface pressure-area isotherms ( π- A), the Maxwell displacement current (MDC) measurement, X-ray reflectivity (XRR) and atomic force microscopy (AFM) to investigate the selected mechanic, thermodynamic and dielectric properties based on orientational structure of monolayers. On the base of π- A isotherms analysis we explain the creation of stable structures and found optimal monolayer composition. The dielectric properties represented by MDC generated monolayers were analyzed in terms of excess dipole moment, proposing the effect of dipole-dipole interaction. XRR and AFM results illustrate deposited film structure and molecular ordering.
Thermodynamic properties of magnetic strings on a square lattice
NASA Astrophysics Data System (ADS)
Mol, Lucas; Oliveira, Denis Da Mata; Bachmann, Michael
2015-03-01
In the last years, spin ice systems have increasingly attracted attention by the scientific community, mainly due to the appearance of collective excitations that behave as magnetic monopole like particles. In these systems, geometrical frustration induces the appearance of degenerated ground states characterized by a local energy minimization rule, the ice rule. Violations of this rule were shown to behave like magnetic monopoles connected by a string of dipoles that carries the magnetic flux from one monopole to the other. In order to obtain a deeper knowledge about the behavior of these excitations we study the thermodynamics of a kind of magnetic polymer formed by a chain of magnetic dipoles in a square lattice. This system is expected to capture the main properties of monopole-string excitations in the artificial square spin ice. It has been found recently that in this geometry the monopoles are confined, but the effective string tension is reduced by entropic effects. To obtain the thermodynamic properties of the strings we have exactly enumerated all possible string configurations of a given length and used standard statistical mechanics analysis to calculate thermodynamic quantities. We show that the low-temperature behavior is governed by strings that satisfy ice rules. Financial support from FAPEMIG and CNPq (Brazilian agencies) are gratefully acknowledged.
The VLab repository of thermodynamics and thermoelastic properties of minerals
NASA Astrophysics Data System (ADS)
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.
Thermodynamic Properties of Eutectic Silumins Doped by Transition Metals
NASA Astrophysics Data System (ADS)
Kanibolotsky, D. S.; Stukalo, V. A.; Lisnyak, V. V.
2004-05-01
The thermodynamic properties of the liquid silumins (Al0.879Si0.121)1-xTrx, where Tr = Cu, Fe, Ni and Ti, have been measured, using the electromotive force method at 1040 K. It has been found that diluted solutions of Fe or Ni in eutectic silumins at Tr molar fractions of 0 < xFe ≤ 0.035 and 0 < xNi ≤ 0.027 are characterized by positive deviations from ideality for aluminium. However, the deviations become negative at increasing of the Tr concentration. However, molten silumins doped by Ti and Cu show negative deviations from Raoult's law for aluminium at the studied concentrations. Thermodynamic activity of Al in the silumins decreases in the sequence of Fe→Ni→Cu→Ti for the dopants.
Simplified curve fits for the thermodynamic properties of equilibrium air
NASA Technical Reports Server (NTRS)
Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.
1987-01-01
New, improved curve fits for the thermodynamic properties of equilibrium air have been developed. The curve fits are for pressure, speed of sound, temperature, entropy, enthalpy, density, and internal energy. These curve fits can be readily incorporated into new or existing computational fluid dynamics codes if real gas effects are desired. The curve fits are constructed from Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits. These improvements are due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25 000 K and densities from 10 to the -7 to 10 to the 3d power amagats.
Properties And Coefficient Program For The Calculation Of Thermodynamic Data (PAC2)
NASA Technical Reports Server (NTRS)
Mcbride, B. J.
1989-01-01
Program calculates ideal gas thermodynamic properties for any species for which molecular constant data available, and offers user choice of methodologies for performing thermodynamic calculations. PAC2 updated to PAC4. Improvements include increased user friendliness and ability to extrapolate thermodynamic properties for gases to higher temperatures using Wilhoit's formulas.
An EQT-cDFT approach to determine thermodynamic properties of confined fluids
Mashayak, S. Y.; Motevaselian, M. H.; Aluru, N. R.
2015-06-28
We present a continuum-based approach to predict the structure and thermodynamic properties of confined fluids at multiple length-scales, ranging from a few angstroms to macro-meters. The continuum approach is based on the empirical potential-based quasi-continuum theory (EQT) and classical density functional theory (cDFT). EQT is a simple and fast approach to predict inhomogeneous density and potential profiles of confined fluids. We use EQT potentials to construct a grand potential functional for cDFT. The EQT-cDFT-based grand potential can be used to predict various thermodynamic properties of confined fluids. In this work, we demonstrate the EQT-cDFT approach by simulating Lennard-Jones fluids, namely, methane and argon, confined inside slit-like channels of graphene. We show that the EQT-cDFT can accurately predict the structure and thermodynamic properties, such as density profiles, adsorption, local pressure tensor, surface tension, and solvation force, of confined fluids as compared to the molecular dynamics simulation results.
Pressure-Temperature Dependence of Thermodynamic Properties of Perovskite from First Principles
NASA Astrophysics Data System (ADS)
Abdollahi, Arash; Gholzan, Seyed Maghsoud
2015-08-01
First-principles calculations have been performed to obtain the thermodynamic properties of perovskite in a wide range of pressure (0 GPa to 30 GPa) and temperature (0 K to 1400 K). Calculations have been performed by using the pseudo-potential method within the generalized gradient approximation. Both pressure- and temperature-dependent thermodynamic properties including the bulk modulus, thermal expansion, thermal expansion coefficient, and the heat capacity at constant volume and constant pressure were calculated using three different approaches based on the quasi-harmonic Debye model: the Slater, Dugdale-MacDonald (DM), and Vaschenko-Zubarev (VZ) approaches. Also, empirical energy corrections are applied to the results of models to correct the systematic errors introduced by the functional. It is found that the VZ model provides more accurate estimates in comparison with the DM and Slater models, especially after an empirical energy correction. The results obtained from the VZ analysis on the corrected static energy show that this method can be used to determine the thermodynamic properties of compounds with reasonable accuracy.
Thermodynamics and combustion modeling
NASA Technical Reports Server (NTRS)
Zeleznik, Frank J.
1986-01-01
Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.
Chemical and Thermodynamic Properties at High Temperatures: A Symposium
NASA Technical Reports Server (NTRS)
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.
NASA Astrophysics Data System (ADS)
Li, Wenjiao; Xue, Yongqiang; Cui, Zixiang
2016-08-01
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.
Thermodynamic properties of real gases and BWR equation of state
NASA Astrophysics Data System (ADS)
Vestfálová, Magda
2015-05-01
The fundamental base for the calculation of the thermodynamic properties of materials is thermal equation of state and dependence of some of the basic specific heat capacities on temperature. The dependence of the specific thermal capacity on the second independent variable (for example on the volume) it is already possible to deduce from the thermal equation of state. The aim of this paper is to assess the compliance values of specific heat capacity which was calculated using the BWR thermal equation of the state and experimentally obtained known values of specific heat capacity for the substance, whose characteristics are available in a wide range of state space.
Spectroscopic and thermodynamic properties of L-ornithine monohydrochloride
Raja, M. Dinesh; Kumar, C. Maria Ashok; Arulmozhi, S.; Madhavan, J.
2015-06-24
L-Ornithine Monohydrochloride (LOMHCL) has been investigated with the help of B3LYP density functional theory with 6-31 G (d, p) basis set. Fourier transform infrared and Fourier transform Raman spectra is to identify the various functional groups. The theoretical frequencies showed very good agreement with experimental values. On the basis of the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H) and temperatures. Second harmonic generation (SHG) efficiency of the grown crystal has been studied.
Interaction potentials and thermodynamic properties of two component semiclassical plasma
Ramazanov, T. S.; Moldabekov, Zh. A.; Ismagambetova, T. N.; Gabdullin, M. T.
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.
NASA Technical Reports Server (NTRS)
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.
Anomalous thermodynamic properties of ice XVI and metastable hydrates
NASA Astrophysics Data System (ADS)
Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki
2016-02-01
A new ice polymorph, called ice XVI, has recently been discovered experimentally by extracting the guest molecules from Ne hydrate. The ice and its filled form (clathrate hydrate) have a unique network topology which results in several interesting properties. Here we provide a theoretical method to calculate thermodynamic properties of a semiopen system in equilibrium with guest gas and thus occupancy of the guest can be varied with temperature and pressure. Experimental observations such as the disappearance of negative thermal expansivity and contraction of the host lattice upon encaging guest molecules are well reproduced, and those behaviors are elucidated in terms of the free energy of cage occupation and its temperature and pressure dependence. We propose an application of the method for preparing ice XVI to create metastable clathrate hydrates having intriguing properties with much lower occupancy of guest molecules than that at equilibrium, which otherwise cannot form.
Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics
NASA Technical Reports Server (NTRS)
Kim, Soojin; Myerson, Allan S.
1996-01-01
The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.
NASA Astrophysics Data System (ADS)
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
Thermodynamic and kinetic properties of some diatomic gases
NASA Astrophysics Data System (ADS)
Holbrook, Robert Thomas, III
1997-11-01
In this work, the thermodynamic and kinetic properties of some diatomic gases are calculated and analyzed. In chapter 1, the partition functions of the species composing a dissociating and ionizing iodine vapor, specifically those for homonuclear diatomic 127I127I molecules, 127I atoms, 127I+ ions, and free electrons, are calculated. These partition functions are subsequently used in statistical mass action equations to determine the local thermal equilibrium dissociation degree a and the ionization degree φ of the iodine vapor over the temperature range 700 <= T/ /le 12000 K for total atomic number densities nA = 1014, 1016, 1018, and 1020 cm-3. With the equilibrium composition of the iodine vapor so specified and the partition functions, the thermodynamic properties of the iodine vapor are calculated for 700 <= T/ /le 12000 K from statistical thermodynamic equations for the four values of the total number density. In chapter 2, the statistical-mechanical treatment is extended to the more complicated cases of gas systems based on the rare earth halide molecules, DyF, HoF, and TmF. Such systems are composed of seven different species: LnF and F2 molecules (Ln≡Dy, Ho, and Tm), LnF+ molecular ions, Ln and F atoms, LnF+ atomic ions, and free electrons. Once again, the partition functions are calculated for the various species and used in statistical expressions to determine the local thermal equilibrium compositions and thermodynamic properties of the LnF-based gas mixtures for the temperature range 3000 <= T/ /le 9000 K and initial molecular number densities 1014, 1016, and 1018 cm-3. Finally, in chapter 3, the Monte Carlo trajectory method is used to study the probabilities P(Vr, b, v1, J1, v2, J2) for dissociation via collisions between two ground electronic state X1Σ(0g+) I2 molecules. The two molecules interact with an impact parameter b and a relative speed Vr. The incident molecule is in the vibrational-rotational state specified by the vibrational quantum
Thermodynamic properties of pulverized coal during rapid heating devolatilization processes
Proscia, W.M.; Freihaut, J.D.; Rastogi, S.; Klinzing, G.E.
1994-07-01
The thermodynamic properties of coal under conditions of rapid heating have been determined using a combination of UTRC facilities including a proprietary rapid heating rate differential thermal analyzer (RHR-DTA), a microbomb calorimeter (MBC), an entrained flow reactor (EFR), an elemental analyzer (EA), and a FT-IR. The total heat of devolatilization, was measured for a HVA bituminous coal (PSOC 1451D, Pittsburgh No. 8) and a LV bituminous coal (PSOC 1516D, Lower Kittaning). For the HVA coal, the contributions of each of the following components to the overall heat of devolatilization were measured: the specific heat of coal/char during devolatilization, the heat of thermal decomposition of the coal, the specific heat capacity of tars, and the heat of vaporization of tars. Morphological characterization of coal and char samples was performed at the University of Pittsburgh using a PC-based image analysis system, BET apparatus, helium pcynometer, and mercury porosimeter. The bulk density, true density, CO{sub 2} surface area, pore volume distribution, and particle size distribution as a function of extent of reaction are reported for both the HVA and LV coal. Analyses of the data were performed to obtain the fractal dimension of the particles as well as estimates for the external surface area. The morphological data together with the thermodynamic data obtained in this investigation provides a complete database for a set of common, well characterized coal and char samples. This database can be used to improve the prediction of particle temperatures in coal devolatilization models. Such models are used both to obtain kinetic rates from fundamental studies and in predicting furnace performance with comprehensive coal combustion codes. Recommendations for heat capacity functions and heats of devolatilization for the HVA and LV coals are given. Results of sample particle temperature calculations using the recommended thermodynamic properties are provided.
Improved relationships for the thermodynamic properties of carbon phases at detonation conditions
NASA Astrophysics Data System (ADS)
Stiel, L. I.; Baker, E. L.; Murphy, D. J.
2014-05-01
Accurate volumetric and heat capacity relationships have been developed for graphite and diamond carbon forms for use with the Jaguar thermochemical equilibrium program for the calculation of the detonation properties of explosives. Available experimental thermodynamic properties and Hugoniot values have been analyzed to establish the equations of state for the carbon phases. The diamond-graphite transition curve results from the equality of the chemical potentials of the phases. The resulting relationships are utilized to examine the actual phase behaviour of carbon under shock conditions. The existence of metastable carbon states is established by analyses of Hugoniot data for hydrocarbons and explosives at elevated temperatures and pressures. The accuracy of the resulting relationships is demonstrated by comparisons for several properties, including the Hugoniot behaviour of oxygen-deficient explosives at overdriven conditions.
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. PMID:25288913
Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters.
Rodríguez-López, Tonalli; del Río, Fernando
2012-01-28
In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids. PMID:22158949
Thermodynamic properties of small aggregates of rare-gas atoms
NASA Technical Reports Server (NTRS)
Etters, R. D.; Kaelberer, J.
1975-01-01
The present work reports on the equilibrium thermodynamic properties of small clusters of xenon, krypton, and argon atoms, determined from a biased random-walk Monte Carlo procedure. Cluster sizes ranged from 3 to 13 atoms. Each cluster was found to have an abrupt liquid-gas phase transition at a temperature much less than for the bulk material. An abrupt solid-liquid transition is observed for thirteen- and eleven-particle clusters. For cluster sizes smaller than 11, a gradual transition from solid to liquid occurred over a fairly broad range of temperatures. Distribution of number of bond lengths as a function of bond length was calculated for several systems at various temperatures. The effects of box boundary conditions are discussed. Results show the importance of a correct description of boundary conditions. A surprising result is the slow rate at which system properties approach bulk behavior as cluster size is increased.
Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements
NASA Astrophysics Data System (ADS)
Blanc, Philippe; Gailhanou, Hélène; Rogez, Jacques; Mikaelian, Georges; Kawaji, Hitoshi; Warmont, Fabienne; Gaboreau, Stéphane; Grangeon, Sylvain; Grenèche, Jean-Marc; Vieillard, Philippe; Fialips, Claire I.; Giffaut, Eric; Gaucher, Eric C.; Claret, F.
2014-09-01
In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al0.975FeIII0.182FeII1.422Mg0.157Li0.035Mn0.002)(Si1.332Al0.668)O5(OH)4] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si2.633Al1.367)(Al1.116FeIII0.215Mg2.952FeII1.712Mn0.012Ca0.011)O10(OH)8]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738-4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.
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.
NASA Technical Reports Server (NTRS)
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.
Simplified curve fits for the thermodynamic properties of equilibrium air
NASA Technical Reports Server (NTRS)
Srinivasan, S.; Tannehill, J. C.; Weilmuenster, K. J.
1986-01-01
New improved curve fits for the thermodynamic properties of equilibrium air were developed. The curve fits are for p = p(e,rho), a = a(e,rho), T = T(e,rho), s = s(e,rho), T = T(p,rho), h = h(p,rho), rho = rho(p,s), e = e(p,s) and a = a(p,s). These curve fits can be readily incorporated into new or existing Computational Fluid Dynamics (CFD) codes if real-gas effects are desired. The curve fits were constructed using Grabau-type transition functions to model the thermodynamic surfaces in a piecewise manner. The accuracies and continuity of these curve fits are substantially improved over those of previous curve fits appearing in NASA CR-2470. These improvements were due to the incorporation of a small number of additional terms in the approximating polynomials and careful choices of the transition functions. The ranges of validity of the new curve fits are temperatures up to 25,000 K and densities from 10 to the minus 7th to 100 amagats (rho/rho sub 0).
The thermodynamic properties of 2,3-benzothiophene
Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.; Steele, W.V.
1991-01-01
Upgrading of heavy fossil fuels is normally done by hydrotreating in the presence of catalysts at 5 to 15 MPa pressure of hydrogen and 575 to 700 K. The efficient use of expensive hydrogen in this process is essential to the economic viability of alternative fuel sources (heavy petroleum, tar sands, shale oil, and the products of the liquefaction of coal). 2,3-Benzothiophene is widely used as a model compound in catalyst-comparison and kinetic studies of the hydrodesulfurization (HDS) mechanism. To perform a thermodynamic analysis of the 2,3-benzothiophene/hydrogen reaction network at the process temperatures, Gibbs energies of reaction at those high temperatures are required for the molecules involved. Measurements leading to the calculation of the ideal-gas thermodynamic properties for 2,3-benzothiophene are reported. Experimental methods included adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c.). The critical temperature and critical density were determined with the d.s.c., and the critical pressure was derived. Entropies, enthalpies, and Gibbs energies of formation were derived for the ideal gas for selected temperatures between 260 K and 750 K. These values were derived by combining the reported measurements with values published previously for the enthalpy of combustion, the enthalpy of fusion, and the absolute entropy and enthalpy of the liquid at the triple-point temperature. Measured and derived quantities were compared with available literature values. 55 refs., 6 figs., 13 tabs.
Non-BCS thermodynamic properties of H2 S superconductor
NASA Astrophysics Data System (ADS)
Durajski, Artur P.; Szcze&şacute; niak, Radosław; Li, Yinwei
2015-08-01
The present paper determines the thermodynamic properties of the superconducting state in the H2S compound. The values of the pressure from 130 GPa to 180 GPa were taken into consideration. The calculations were performed in the framework of the Eliashberg formalism. In the first step, the experimental course of the dependence of the critical temperature on the pressure was reproduced: TC ∈ < 31, 88 > K, whereas the Coulomb pseudopotential equal to 0.15 was adopted. Next, the following quantities were calculated: the order parameter at the temperature of zero Kelvin (Δ (0)), the specific heat jump at the critical temperature (ΔC (TC) ≡CS (TC) -CN (TC)), and the thermodynamic critical field (HC (0)). It was found that the values of the dimensionless ratios: RΔ ≡ 2 Δ (0) /kBTC , RC ≡ ΔC(TC) /CN (TC) , and RH ≡TCCN (TC) / HC2(0) deviate from the predictions of the BCS theory: RΔ ∈ < 3.64, 4.16 > , RC ∈ < 1.59, 2.24 > , and RH ∈ < 0.144, 0.163 > . Generalizing the results on the whole family of the HnS -type compounds, it was shown that the maximum value of the critical temperature can be equal to ˜290 K, while RΔ,RC and RH adopt the following values: 6.53, 3.99, and 0.093, respectively.
The thermodynamic properties of hydrated -Al2O3 nanoparticles
Spencer, Elinor; Huang, Baiyu; Parker, Stewart F.; Kolesnikov, Alexander I; Ross, Dr. Nancy; Woodfield, Brian
2013-01-01
In this paper we report a combined calorimetric and inelastic neutron scattering (INS) study of hydrated -Al2O3 ( -alumina) nanoparticles. These complementary techniques have enabled a comprehensive evaluation of the thermodynamic properties of this technological and industrially important metal oxide to be achieved. The isobaric heat capacity (Cp) data presented herein provide further critical insights into the much-debated chemical composition of -alumina nanoparticles. Furthermore, the isochoric heat capacity (Cv) of the surface water, which is so essential to the stability of all metal-oxides at the nanoscale, has been extracted from the high-resolution INS data and differs significantly from that of ice Ih due to the dominating influence of strong surface-water interactions. This study also encompassed the analysis of four -alumina samples with differing pore diameters [4.5 (1), 13.8 (2), 17.9 (3), and 27.2 nm (4)], and the results obtained allow us to unambiguously conclude that the water content and pore size have no influence on the thermodynamic behaviour of hydrated -alumina nanoparticles.
NASA Astrophysics Data System (ADS)
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.
Instrumentation for Measuring Thermodynamic Properties of Rare-Earth Compounds
NASA Astrophysics Data System (ADS)
Urbina, Ulises I.; Thompson, Jonathon; Ho, Pei-Chun
2010-03-01
Current models on some Rare-Earth compounds cannot fully account for their strongly correlated electron behavior, which give rise to phenomenon such as unconventional superconductivity, heavy Fermion, and quantum critical behavior. The specific heat, thermopower, and thermal conductivity measurements give important thermodynamic properties, such as effective electronic mass, stiffness of the lattice (Debye temperature), entropy, density of states of charge carriers, and phase transitions which are crucial in characterizing these materials of interest in our laboratory. A calorimeter and a thermopower-thermal conductivity probe, which are using a modified relaxation method and standard steady-state heat flow technique, respectively, are constructed for the above purpose. Detailed schematic diagram and operating principles will be discussed in the report.
Thermodynamic properties derived from the free volume model of liquids
NASA Technical Reports Server (NTRS)
Miller, R. I.
1974-01-01
An equation of state and expressions for the isothermal compressibility, thermal expansion coefficient, heat capacity, and entropy of liquids have been derived from the free volume model partition function suggested by Turnbull. The simple definition of the free volume is used, and it is assumed that the specific volume is directly related to the cube of the intermolecular separation by a proportionality factor which is found to be a function of temperature and pressure as well as specific volume. When values of the proportionality factor are calculated from experimental data for real liquids, it is found to be approximately constant over ranges of temperature and pressure which correspond to the dense liquid phase. This result provides a single-parameter method for calculating dense liquid thermodynamic properties and is consistent with the fact that the free volume model is designed to describe liquids near the solidification point.
Thermodynamic properties of the magnetized Coulomb crystal lattices
NASA Astrophysics Data System (ADS)
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.
Thermodynamic properties of Rashba spin-orbit-coupled Fermi gas
NASA Astrophysics Data System (ADS)
Zheng, Zhen; Pu, Han; Zou, Xubo; Guo, Guangcan
2014-12-01
We investigate the thermodynamic properties of a superfluid Fermi gas subject to Rashba spin-orbit coupling and effective Zeeman field. We adopt a T -matrix scheme that takes beyond-mean-field effects, which are important for strongly interacting systems, into account. We focus on the calculation of two important quantities: the superfluid transition temperature and the isothermal compressibility. Our calculation shows very distinct influences of the out-of-plane and the in-plane Zeeman fields on the Fermi gas. We also confirm that the in-plane Zeeman field induces a Fulde-Ferrell superfluid below the critical temperature and an exotic finite-momentum pseudogap phase above the critical temperature.
Ab initio calculation of thermodynamic properties of silicon
NASA Astrophysics Data System (ADS)
Wei, Siqing; Li, Changlin; Chou, M. Y.
1994-11-01
We present a fully ab initio calculation of the thermodynamic properties for silicon within the quasiharmonic approximation, making use of volume-dependent phonon frequencies obtained from pseudopotential local-density calculations. The temperature dependence of the thermal-expansion coefficient, specific heat (at constant volume), and other related quantities are studied. We confirm that the thermal-expansion coefficient behaves differently in three temperature regions: positive for temperature below 15 K, negative between 15 and 125 K, and positive again above 125 K. This finding agrees with experiment. The abnormal (negative) thermal-expansion coefficient at low temperatures is explained through a detailed study of mode Grüneisen parameters. Both specific-heat and thermal-expansion-coefficient values calculated are in excellent agreement with experiment up to a few hundred kelvin.
Note on electrical and thermodynamic properties of isolated horizons
NASA Astrophysics Data System (ADS)
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.
ms2: A molecular simulation tool for thermodynamic properties
NASA Astrophysics Data System (ADS)
Deublein, Stephan; Eckl, Bernhard; Stoll, Jürgen; Lishchuk, Sergey V.; Guevara-Carrion, Gabriela; Glass, Colin W.; Merker, Thorsten; Bernreuther, Martin; Hasse, Hans; Vrabec, Jadran
2011-11-01
This work presents the molecular simulation program ms2 that is designed for the calculation of thermodynamic properties of bulk fluids in equilibrium consisting of small electro-neutral molecules. ms2 features the two main molecular simulation techniques, molecular dynamics (MD) and Monte-Carlo. It supports the calculation of vapor-liquid equilibria of pure fluids and multi-component mixtures described by rigid molecular models on the basis of the grand equilibrium method. Furthermore, it is capable of sampling various classical ensembles and yields numerous thermodynamic properties. To evaluate the chemical potential, Widom's test molecule method and gradual insertion are implemented. Transport properties are determined by equilibrium MD simulations following the Green-Kubo formalism. ms2 is designed to meet the requirements of academia and industry, particularly achieving short response times and straightforward handling. It is written in Fortran90 and optimized for a fast execution on a broad range of computer architectures, spanning from single processor PCs over PC-clusters and vector computers to high-end parallel machines. The standard Message Passing Interface (MPI) is used for parallelization and ms2 is therefore easily portable to different computing platforms. Feature tools facilitate the interaction with the code and the interpretation of input and output files. The accuracy and reliability of ms2 has been shown for a large variety of fluids in preceding work. Program summaryProgram title:ms2 Catalogue identifier: AEJF_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEJF_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Special Licence supplied by the authors No. of lines in distributed program, including test data, etc.: 82 794 No. of bytes in distributed program, including test data, etc.: 793 705 Distribution format: tar.gz Programming language: Fortran90 Computer: The
Thermodynamic properties of the Group 1A elements
Alcock, C.B.; Itkin, V.P.; Chase, M.W.
1994-05-01
This review describes thermodynamic properties of condensed phases of the alkali metals, excluding francium for which the amount of information is too limited. The properties considered are: heat capacities from 0 to 1600 K, temperatures and enthalpies of fusion and martensitic transformation in Li and Na; discussion of the Debye temperature and electronic heat capacity coefficient at absolute zero temperature is also included. The paper is the second part of a series. Similar to previous assessment of the IIA group [93ALC/CHA], this paper considers original studies, especially with respect to factors which influence the accuracy and reliability of results. Recommendations derived from such analyses are compared with most advanced previous reviews made at the Institute for High Temperatures (Moscow) [70SHP/YAK], [82GUR] and the National Institute of Standards and Technology (Washington) [85JAN]. The properties of individual elements of the group are compared and suggestions are made for experimental studies which should improve poorly measured quantities. The review is supplemented by an IBM PC database which contains references, assessed data, brief description of studies and has facilities for fitting and plotting of data and for adding new information.
Ideal gas thermodynamic properties for the phenyl, phenoxy, and o-biphenyl radicals
NASA Technical Reports Server (NTRS)
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.
NASA Astrophysics Data System (ADS)
Dinpajooh, Mohammadhasan; Bai, Peng; Allan, Douglas A.; Siepmann, J. Ilja
2015-09-01
Since the seminal paper by Panagiotopoulos [Mol. Phys. 61, 813 (1997)], the Gibbs ensemble Monte Carlo (GEMC) method has been the most popular particle-based simulation approach for the computation of vapor-liquid phase equilibria. However, the validity of GEMC simulations in the near-critical region has been questioned because rigorous finite-size scaling approaches cannot be applied to simulations with fluctuating volume. Valleau [Mol. Simul. 29, 627 (2003)] has argued that GEMC simulations would lead to a spurious overestimation of the critical temperature. More recently, Patel et al. [J. Chem. Phys. 134, 024101 (2011)] opined that the use of analytical tail corrections would be problematic in the near-critical region. To address these issues, we perform extensive GEMC simulations for Lennard-Jones particles in the near-critical region varying the system size, the overall system density, and the cutoff distance. For a system with N = 5500 particles, potential truncation at 8σ and analytical tail corrections, an extrapolation of GEMC simulation data at temperatures in the range from 1.27 to 1.305 yields Tc = 1.3128 ± 0.0016, ρc = 0.316 ± 0.004, and pc = 0.1274 ± 0.0013 in excellent agreement with the thermodynamic limit determined by Potoff and Panagiotopoulos [J. Chem. Phys. 109, 10914 (1998)] using grand canonical Monte Carlo simulations and finite-size scaling. Critical properties estimated using GEMC simulations with different overall system densities (0.296 ≤ ρt ≤ 0.336) agree to within the statistical uncertainties. For simulations with tail corrections, data obtained using rcut = 3.5σ yield Tc and pc that are higher by 0.2% and 1.4% than simulations with rcut = 5 and 8σ but still with overlapping 95% confidence intervals. In contrast, GEMC simulations with a truncated and shifted potential show that rcut = 8σ is insufficient to obtain accurate results. Additional GEMC simulations for hard-core square-well particles with various ranges of the
Dinpajooh, Mohammadhasan; Bai, Peng; Allan, Douglas A.; Siepmann, J. Ilja
2015-09-21
Since the seminal paper by Panagiotopoulos [Mol. Phys. 61, 813 (1997)], the Gibbs ensemble Monte Carlo (GEMC) method has been the most popular particle-based simulation approach for the computation of vapor–liquid phase equilibria. However, the validity of GEMC simulations in the near-critical region has been questioned because rigorous finite-size scaling approaches cannot be applied to simulations with fluctuating volume. Valleau [Mol. Simul. 29, 627 (2003)] has argued that GEMC simulations would lead to a spurious overestimation of the critical temperature. More recently, Patel et al. [J. Chem. Phys. 134, 024101 (2011)] opined that the use of analytical tail corrections would be problematic in the near-critical region. To address these issues, we perform extensive GEMC simulations for Lennard-Jones particles in the near-critical region varying the system size, the overall system density, and the cutoff distance. For a system with N = 5500 particles, potential truncation at 8σ and analytical tail corrections, an extrapolation of GEMC simulation data at temperatures in the range from 1.27 to 1.305 yields T{sub c} = 1.3128 ± 0.0016, ρ{sub c} = 0.316 ± 0.004, and p{sub c} = 0.1274 ± 0.0013 in excellent agreement with the thermodynamic limit determined by Potoff and Panagiotopoulos [J. Chem. Phys. 109, 10914 (1998)] using grand canonical Monte Carlo simulations and finite-size scaling. Critical properties estimated using GEMC simulations with different overall system densities (0.296 ≤ ρ{sub t} ≤ 0.336) agree to within the statistical uncertainties. For simulations with tail corrections, data obtained using r{sub cut} = 3.5σ yield T{sub c} and p{sub c} that are higher by 0.2% and 1.4% than simulations with r{sub cut} = 5 and 8σ but still with overlapping 95% confidence intervals. In contrast, GEMC simulations with a truncated and shifted potential show that r{sub cut} = 8σ is insufficient to obtain accurate results. Additional GEMC simulations for hard
NASA Astrophysics Data System (ADS)
Kawai, Soshi
2014-11-01
In this talk, we first propose a numerical strategy that is robust and high-order accurate for enabling to simulate transcritical flows at supercritical pressures under abrupt variations in thermodynamic properties due to the real fluid effects. The method is based on introducing artificial density diffusion in a physically-consistent manner in order to capture the steep variation of thermodynamic properties in transcritical conditions robustly, while solving a pressure evolution equation to achieve pressure equilibrium at the transcritical interfaces. We then discuss the direct numerical simulation (DNS) of transcritical heated turbulent boundary layers on a zero-pressure-gradient flat plate at supercritical pressures. To the best of my knowledge, the present DNS is the first DNS of zero-pressure-gradient flat-plate transcritical turbulent boundary layer. The turbulent kinetic budget indicates that the compressibility effects (especially, pressure-dilatation correlation) are not negligible at the transcritical conditions even if the flow is subsonic. The unique and interesting interactions between the real fluid effects and wall turbulence, and their turbulence statistics, which have never been seen in the ideal-fluid turbulent boundary layers, are also discussed. This work was supported in part by Japan Society for the Promotion of Science (JSPS) Grant-in-Aid for Young Scientists (A) KAKENHI 26709066 and the JAXA International Top Young Fellowship Program.
NASA Astrophysics Data System (ADS)
Jacobs, M.; Schmid-Fetzer, R.
2012-04-01
A prerequisite for the determination of pressure in static high pressure measurements, such as in diamond anvil cells is the availability of accurate equations of state for reference materials. These materials serve as luminescence gauges or as X-ray gauges and equations of state for these materials serve as secondary pressure scales. Recently, successful progress has been made in the development of consistency between static, dynamic shock-wave and ultrasonic measurements of equations of state (e.g. Dewaele et al. Phys. Rev. B70, 094112, 2004, Dorogokupets and Oganov, Doklady Earth Sciences, 410, 1091-1095, 2006, Holzapfel, High Pressure Research 30, 372-394, 2010) allowing testing models to arrive at consistent thermodynamic descriptions for X-ray gauges. Apart from applications of metallic elements in high-pressure work, thermodynamic properties of metallic elements are also of mandatory interest in the field of metallurgy for studying phase equilibria of alloys, kinetics of phase transformation and diffusion related problems, requiring accurate thermodynamic properties in the low pressure regime. Our aim is to develop a thermodynamic data base for metallic alloy systems containing Ag, Al, Au, Cu, Fe, Ni, Pt, from which volume properties in P-T space can be predicted when it is coupled to vibrational models. This mandates the description of metallic elements as a first step aiming not only at consistency in the pressure scales for the elements, but also at accurate representations of thermodynamic properties in the low pressure regime commonly addressed in metallurgical applications. In previous works (e.g. Jacobs and de Jong, Geochim. Cosmochim. Acta, 71, 3630-3655, 2007, Jacobs and van den Berg, Phys. Earth Planet. Inter., 186, 36-48, 2011) it was demonstrated that a lattice vibrational framework based on Kieffer's model for the vibrational density of states, is suitable to construct a thermodynamic database for Earth mantle materials. Such a database aims at
Electronic, mechanical, and thermodynamic properties of americium dioxide
NASA Astrophysics Data System (ADS)
Lu, Yong; Yang, Yu; Zheng, Fawei; Wang, Bao-Tian; Zhang, Ping
2013-10-01
By performing density functional theory (DFT) +U calculations, we systematically study the electronic, mechanical, tensile, and thermodynamic properties of AmO2. It is found that the chemical bonding character in AmO2 is similar to that in PuO2, with smaller charge transfer and stronger covalent interactions between americium and oxygen atoms. The stress-strain relationship of AmO2 is examined along the three low-index directions, showing that the [1 0 0] and [1 1 1] directions are the strongest and weakest tensile directions, respectively, but the theoretical tensile strengths of AmO2 are smaller than those of PuO2. The phonon dispersion curves of AmO2 are calculated and the heat capacities as well as lattice expansion curve are subsequently determined. The lattice thermal conductivity of AmO2 is further evaluated and compared with attainable experiments. Our present work integrally reveals various physical properties of AmO2 and can be referenced for technological applications of AmO2 based materials.
Thermodynamic properties and entropy scaling law for diffusivity in soft spheres
NASA Astrophysics Data System (ADS)
Pieprzyk, S.; Heyes, D. M.; Brańka, A. C.
2014-07-01
The purely repulsive soft-sphere system, where the interaction potential is inversely proportional to the pair separation raised to the power n, is considered. The Laplace transform technique is used to derive its thermodynamic properties in terms of the potential energy and its density derivative obtained from molecular dynamics simulations. The derived expressions provide an analytic framework with which to explore soft-sphere thermodynamics across the whole softness-density fluid domain. The trends in the isochoric and isobaric heat capacity, thermal expansion coefficient, isothermal and adiabatic bulk moduli, Grüneisen parameter, isothermal pressure, and the Joule-Thomson coefficient as a function of fluid density and potential softness are described using these formulas supplemented by the simulation-derived equation of state. At low densities a minimum in the isobaric heat capacity with density is found, which is a new feature for a purely repulsive pair interaction. The hard-sphere and n =3 limits are obtained, and the low density limit specified analytically for any n is discussed. The softness dependence of calculated quantities indicates freezing criteria based on features of the radial distribution function or derived functions of it are not expected to be universal. A new and accurate formula linking the self-diffusion coefficient to the excess entropy for the entire fluid softness-density domain is proposed, which incorporates the kinetic theory solution for the low density limit and an entropy-dependent function in an exponential form. The thermodynamic properties (or their derivatives), structural quantities, and diffusion coefficient indicate that three regions specified by a convex, concave, and intermediate density dependence can be expected as a function of n, with a narrow transition region within the range 5
NASA Astrophysics Data System (ADS)
Singh, Gurpreet; Sharma, Rohit; Singh, Kuldip
2015-09-01
Thermodynamic properties (compressibility coefficient Z γ , specific heat at constant volume c v , adiabatic coefficient γ a , isentropic coefficient γ i s e n , and sound speed c s ) of non-local thermodynamic equilibrium hydrogen thermal plasma have been investigated for different values of pressure and non-equilibrium parameter θ (=Te/Th) in the electron temperature range from 6000 K to 60 000 K. In order to estimate the influence of pressure derivative of partition function on thermodynamic properties, two cases have been considered: (a) in which pressure derivative of partition function is taken into account in the expressions and (b) without pressure derivative of partition function in their expressions. Here, the case (b) represents expressions already available in literature. It has been observed that the temperature from which pressure derivative of partition function starts influencing a given thermodynamic property increases with increase of pressure and non-equilibrium parameter θ. Thermodynamic property in the case (a) is always greater than its value in the case (b) for compressibility coefficient and specific heat at constant volume, whereas for adiabatic coefficient, isentropic coefficient, and sound speed, its value in the case (a) is always less than its value in the case (b). For a given value of θ, the relationship of compressibility coefficient with degree of ionization depends upon pressure in the case (a), whereas it is independent of pressure in the case (b). Relative deviation between the two cases shows that the influence of pressure derivative of partition function is significantly large and increases with the augmentation of pressure and θ for compressibility coefficient, specific heat at constant volume, and adiabatic coefficient, whereas for isentropic coefficient and sound speed, it is marginal even at high values of pressure and non-equilibrium parameter θ.
Hydrogrossular (Katoite): Vibrational, Crystal-Chemical and Thermodynamic Properties
NASA Astrophysics Data System (ADS)
Dachs, E.; Geiger, C. A.
2011-12-01
There is great current interest in understanding interactions between H2O and its components and various Earth materials. Here, questions such as the bulk water content of the mantle, and what phases can incorporate OH- and in what concentrations come immediately to mind. In this regard, the hydrogarnet substitution (i.e., O4H4↔SiO4) has received special attention, because it is a verified mechanism for allowing the incorporation of OH- in garnet and possibly in other silicates as well. At relatively low temperatures there is complete solid solution between Ca3Al2Si3O12 and Ca3Al2O12H12. The latter, pure OH-containing end-member is termed katoite/hydrogrossular. Its crystal structure has been investigated by various workers using X-ray and neutron diffraction, including at high pressures. Little is known about its vibrational properties and its thermodynamic behavior is not fully understood. Thus, we studied the low temperature IR spectra and measured the heat capacity of katoite in order to investigate its vibrational, crystal-chemical and thermophysical properties. Katoite was synthesized hydrothermally in Au capsules at 250 °C and 3 kb water pressure. X-ray powder measurements show that about 98-99% katoite was obtained. Powder IR spectra were recorded between 298 K and 10 K. The spectra are considerably different in the high wavenumber region, where O-H stretching modes occur. At room temperature the IR-active O-H band located around 3662 cm-1 is broad and it narrows and shifts to higher wavenumbers and also develops structure below about 80 K. Concomitantly, additional weak intensity O-H bands located around 3600 cm-1 begin to appear and they become sharper and increase in intensity with further decreases in temperature. The spectra indicate that the vibrational behavior of individual OH groups and their collective interactions measurably affect the lattice dynamic (i.e. thermodynamic) behavior. The low temperature heat capacity behavior was investigated
Generalizing thermodynamic properties of bulk single-walled carbon nanotubes
Rodriguez, Kenneth R.; Nanney, Warren A.; A. Maddux, Cassandra J.; Martínez, Hernán L.
2014-01-01
The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (n
Generalizing thermodynamic properties of bulk single-walled carbon nanotubes
Rodriguez, Kenneth R. Nanney, Warren A.; Maddux, Cassandra J.A.; Martínez, Hernán L.; Malone, Marvin A.; Coe, James V.
2014-12-15
The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (n
Generalizing thermodynamic properties of bulk single-walled carbon nanotubes
NASA Astrophysics Data System (ADS)
Rodriguez, Kenneth R.; Malone, Marvin A.; Nanney, Warren A.; A. Maddux, Cassandra J.; Coe, James V.; Martínez, Hernán L.
2014-12-01
The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (n
Thermodynamic properties of model CdTe/CdSe mixtures
van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; Martin, James E.
2015-02-20
We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation from ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.
Thermodynamic properties of model CdTe/CdSe mixtures
van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; Martin, James E.
2015-02-20
We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation frommore » ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.« less
Thermodynamic properties of holographic multiquark and the multiquark star
NASA Astrophysics Data System (ADS)
Burikham, P.; Hirunsirisawat, E.; Pinkanjanarod, S.
2010-06-01
We study thermodynamic properties of the multiquark nuclear matter. The dependence of the equation of state on the colour charges is explored both analytically and numerically in the limits where the baryon density is small and large at fixed temperature between the gluon deconfinement and chiral symmetry restoration. The gravitational stability of the hypothetical multiquark stars are discussed using the Tolman-Oppenheimer-Volkoff equation. Since the equations of state of the multiquarks can be well approximated by different power laws for small and large density, the content of the multiquark stars has the core and crust structure. We found that most of the mass of the star comes from the crust region where the density is relatively small. The mass limit of the multiquark star is determined as well as its relation to the star radius. For typical energy density scale of 10 GeV/fm3, the converging mass and radius of the hypothetical multiquark star in the limit of large central density are approximately 2.6 - 3.9 solar mass and 15-27 km. The adiabatic index and sound speed distributions of the multiquark matter in the star are also calculated and discussed. The sound speed never exceeds the speed of light and the multiquark matters are thus compressible even at high density and pressure.
Thermodynamic properties of liquid Au–Bi–Sn alloys
Guo, Zhongnan; Yuan, Wenxia; Hindler, Michael; Mikula, Adolf
2012-01-01
The thermodynamic properties of the liquid ternary Au–Bi–Sn alloys were determined using an electromotive force (EMF) method with an eutectic mixture of (KCl + LiCl) as liquid electrolyte. The cell arrangement was: W, Sn ( l ) / KCl – LiCl – SnCl 2 / Au – Bi – Sn ( l ) , W. The measurements were carried out over the temperature range from 723 K to 973 K. The compositions investigated were situated on three different cross-sections with a constant ratio of Au:Bi = 2:1, 1:1, and 1:2. The partial Gibbs free energies of Sn in liquid Au–Bi–Sn alloys were determined as a function of concentration and temperature. The integral Gibbs free energy and the integral enthalpy at T = 800 K were calculated by the Gibbs–Duhem integration. The ternary interaction parameters were evaluated using the Redlich–Kister–Muggianu polynomial. PMID:25550675
Molecular Dynamics Simulation of Thermodynamic Properties in Uranium Dioxide
Wang, Xiangyu; Wu, Bin; Gao, Fei; Li, Xin; Sun, Xin; Khaleel, Mohammad A.; Akinlalu, Ademola V.; Liu, L.
2014-03-01
In the present study, we investigated the thermodynamic properties of uranium dioxide (UO2) by molecular dynamics (MD) simulations. As for solid UO2, the lattice parameter, density, and enthalpy obtained by MD simulations were in good agreement with existing experimental data and previous theoretical predictions. The calculated thermal conductivities matched the experiment results at the midtemperature range but were underestimated at very low and very high temperatures. The calculation results of mean square displacement represented the stability of uranium at all temperatures and the high mobility of oxygen toward 3000 K. By fitting the diffusivity constant of oxygen with the Vogel-Fulcher-Tamman law, we noticed a secondary phase transition near 2006.4 K, which can be identified as a ‘‘strong’’ to ‘‘fragile’’ supercooled liquid or glass phase transition in UO2. By fitting the oxygen diffusion constant with the Arrhenius equation, activation energies of 2.0 and 2.7 eV that we obtained were fairly close to the recommended values of 2.3 to 2.6 eV. Xiangyu Wang, Bin Wu, Fei Gao, Xin Li, Xin Sun, Mohammed A. Khaleel, Ademola V. Akinlalu and Li Liu
Level density and thermodynamic properties of dysprosium isotopes
NASA Astrophysics Data System (ADS)
Nyhus, H. T.; Siem, S.; Guttormsen, M.; Larsen, A. C.; Bürger, A.; Syed, N. U. H.; Toft, H. K.; Tveten, G. M.; Voinov, A.
2012-01-01
163,164Dy nuclei have been measured by use of the Oslo method on data from pick-up (3He,α) and inelastic scattering (3He,3He') reactions, respectively. The level densities for these dysprosium isotopes together with previously measured 160-162Dy are extracted in the region below the neutron binding energy. Thermodynamic properties are deduced within both micro-canonical and canonical ensemble theories. A phase transition from the pair-correlated state at low energies to a less correlated or uncorrelated state is studied in both ensembles. It is investigated whether the temperature of the nucleus is constant or a varying function of excitation energy. It is found that above an excitation energy of 3 MeV the temperature of all five dysprosium nuclei have a constant value within the experimental uncertainties. The impact of a constant-temperature level density versus a Fermi gas level density is discussed with respect to the canonical heat capacity.
NASA Technical Reports Server (NTRS)
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.
SteamTablesGrid: An ActiveX control for thermodynamic properties of pure water
NASA Astrophysics Data System (ADS)
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.
Investigation of thermodynamic properties of metal-oxide catalysts
NASA Astrophysics Data System (ADS)
Shah, Parag Rasiklal
An apparatus for Coulometric Titration was developed and used to measure the redox isotherms (i.e. oxygen fugacity P(O2) vs oxygen stoichiometry) of ceria-zirconia solid solutions, mixed oxides of vanadia, and vanadia supported on ZrO2. This data was used to correlate the redox thermodynamics of these oxides to their structure and catalytic properties. From the redox isotherms measured between 873 K and 973 K, the differential enthalpies of oxidation (DeltaH) for Ce0.81Zr0.19O 2.0 and Ce0.25Zr0.75O2.0 were determined, and they were found to be independent of extent of reduction or composition of the solid solution. They were also lower than DeltaH for ceria, which explains the better redox properties of ceria-zirconia solid solutions. The oxidation was driven by entropy in the low reduction region, and a structural model was proposed to explain the observed entropy effects. Redox isotherms were also measured for a number of bulk vanadates between 823 K and 973 K. DeltaG, DeltaH and DeltaS were reported for V 2O5, Mg3(VO4)2, CeVO 4 and ZrV2O7 along with DeltaG values for AlVO 4, LaVO4, CrVO4. V2O5 and ZrV2O7, which were the only oxides having V-O-V bonds, showed a two-step transition of vanadium for V+3↔V +4 and V+4↔V+5 equilibrium in the redox isotherms. The other oxides, all of which have only M-O-V (M=cation other than V), showed a direct one-step transition, V+3↔V +5. The nature of the M-atom also influenced the P(O2) at which the V+3↔V+5 transition occurs. Redox isotherms at 748 K were measured for vanadia supported on ZrO 2; with two different vanadia loadings corresponding to isolated vanadyls and polymeric vanadyls. The isotherm for the sample with isolated vanadyls showed a single-step transition, similar to the one seen in bulk vanadates with M-O-V linkages, while no such one-step transition was observed in the isotherm of the other sample. To study the affect of the varying redox properties of the vanadium-based catalysts on oxidation rates
Thermodynamic properties and phase equilibria of selected Heusler compounds
NASA Astrophysics Data System (ADS)
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.
NASA Technical Reports Server (NTRS)
Hansen, C Frederick; Heims, Steve P
1958-01-01
Thermodynamic and transport properties of high temperature air, and the reaction rates for the important chemical processes which occur in air, are reviewed. Semiempirical, analytic expressions are presented for thermodynamic and transport properties of air. Examples are given illustrating the use of these properties to evaluate (1) equilibrium conditions following shock waves, (2) stagnation region heat flux to a blunt high-speed body, and (3) some chemical relaxation lengths in stagnation region flow.
NASA Astrophysics Data System (ADS)
Zhang, JunMin; Lu, ChunRong; Guan, YongGang; Liu, WeiDong
2015-10-01
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.
Zhang, JunMin E-mail: guanyg@tsinghua.edu.cn; Lu, ChunRong; Guan, YongGang E-mail: guanyg@tsinghua.edu.cn; Liu, WeiDong
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.
Thermodynamic properties of UF sub 6 measured with a ballistic piston compressor
NASA Technical Reports Server (NTRS)
Sterritt, D. E.; Lalos, G. T.; Schneider, R. T.
1973-01-01
From experiments performed with a ballistic piston compressor, certain thermodynamic properties of uranium hexafluoride were investigated. Difficulties presented by the nonideal processes encountered in ballistic compressors are discussed and a computer code BCCC (Ballistic Compressor Computer Code) is developed to analyze the experimental data. The BCCC unfolds the thermodynamic properties of uranium hexafluoride from the helium-uranium hexafluoride mixture used as the test gas in the ballistic compressor. The thermodynamic properties deduced include the specific heat at constant volume, the ratio of specific heats for UF6, and the viscous coupling constant of helium-uranium hexafluoride mixtures.
NASA Technical Reports Server (NTRS)
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.
Electrolytes: transport properties and non-equilibrium thermodynamics
Miller, D.G.
1980-12-01
This paper presents a review on the application of non-equilibrium thermodynamics to transport in electrolyte solutions, and some recent experimental work and results for mutual diffusion in electrolyte solutions.
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. PMID:26990664
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. PMID:27522953
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.
NASA Technical Reports Server (NTRS)
Langhoff, Stephen; Bauschlicher, Charles; Jaffe, Richard
1992-01-01
One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.
NASA Astrophysics Data System (ADS)
Langhoff, Stephen; Bauschlicher, Charles; Jaffe, Richard
1992-04-01
One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.
McKenzie, W.F.
1992-08-01
The thermodynamic properties of secondary phases observed to form during nuclear waste glass-water interactions are of particular interest as it is with the application of these properties together with the thermodynamic properties of other solid phases, fluid phases, and aqueous species that one may predict the environmental consequences of introducing radionuclides contained in the glass into groundwater at a high-level nuclear waste repository. The validation of these predicted consequences can be obtained from laboratory experiments and field observations at natural analogue sites. The purpose of this report is to update and expand the previous compilation (McKenzie, 1991) of thermodynamic data retrieved from the literature and/or estimated for secondary phases observed to form (and candidate phases from observed chemical compositions) during nuclear waste glass-water interactions. In addition, this report includes provisionally recommended thermodynamic data of secondary phases.
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.
Thermodynamic properties of uranium in gallium-aluminium based alloys
NASA Astrophysics Data System (ADS)
Volkovich, V. A.; Maltsev, D. S.; Yamshchikov, L. F.; Chukin, A. V.; Smolenski, V. V.; Novoselova, A. V.; Osipenko, A. G.
2015-10-01
Activity, activity coefficients and solubility of uranium was determined in gallium-aluminium alloys containing 1.6 (eutectic), 5 and 20 wt.% aluminium. Additionally, activity of uranium was determined in aluminium and Ga-Al alloys containing 0.014-20 wt.% Al. Experiments were performed up to 1073 K. Intermetallic compounds formed in the alloys were characterized by X-ray diffraction. Partial and excess thermodynamic functions of U in the studied alloys were calculated.
Thermodynamic properties of the itinerant-boson ferromagnet
Tao Chengjun; Wang Peilin; Qin Jihong; Gu Qiang
2008-10-01
Thermodynamics of a spin-1 Bose gas with ferromagnetic interactions is investigated via the mean-field theory. It is apparently shown in the specific-heat curve that the system undergoes two phase transitions, the ferromagnetic transition and Bose-Einstein condensation, with the Curie point above the condensation temperature. Above the Curie point, the susceptibility fits the Curie-Weiss law perfectly. At a fixed temperature, the reciprocal susceptibility is also in a good linear relationship with the ferromagnetic interaction.
Thermodynamic properties of uranium in gallium-aluminium based alloys
NASA Astrophysics Data System (ADS)
Volkovich, V. A.; Maltsev, D. S.; Yamshchikov, L. F.; Chukin, A. V.; Smolenski, V. V.; Novoselova, A. V.; Osipenko, A. G.
2015-10-01
Activity, activity coefficients and solubility of uranium was determined in gallium-aluminium alloys containing 1.6 (eutectic), 5 and 20 wt.% aluminium. Additionally, activity of uranium was determined in aluminium and Ga-Al alloys containing 0.014-20 wt.% Al. Experiments were performed up to 1073 K. Intermetallic compounds formed in the alloys were characterized by X-ray diffraction. Partial and excess thermodynamic functions of U in the studied alloys were calculated.
Thermodynamic properties of sophocarpine and oxysophocarpine alkaloids in aqueous glucose solutions
NASA Astrophysics Data System (ADS)
Li, Zongxiao; Zhao, Weiwei; Pu, Xiaohua
2012-04-01
Sophocarpine and oxysophocarpine's dissolution in aqueous glucose solutions were studied by a microcalorimetry method. The measured integral and differential heat of dissolution was used to build equations of the solute and the heat, so that dissolution thermodynamic equations, Δsol H m were achieved, which reveals the relationship between the substances structure and the thermodynamic properties. The current study provides theoretical bases for clinical applications of them.
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.
Mutelet, Fabrice; Jaubert, Jean-Noël
2006-01-13
Activity coefficients at infinite dilution of 29 organic compounds in two room temperature ionic liquids were determined using inverse gas chromatography. The measurements were carried out at different temperatures between 323.15 and 343.15K. To establish the influence of concurrent retention mechanisms on the accuracy of activity coefficients at infinite dilution for 1-butyl-3-methylimidazolium octyl sulfate and 1-ethyl-3-methylimidazolium tosylate, phase loading studies of the net retention volume per gram of packing as a function of the percent phase loading were used. It is shown that most of the solutes are retained largely by partition with a small contribution from adsorption on 1-butyl-3-methylimidazolium octyl sulfate and that the n-alkanes are retained predominantly by interfacial adsorption on 1-ethyl-3-methylimidazolium tosylate. PMID:16310203
Takesue, Shinji )
1989-08-01
This is the first part of a series devoted to the study of thermodynamic behavior of large dynamical systems with the use of a family of full-discrete and conservative models named elementary reversible cellular automata (ERCAs). In this paper, basic properties such as conservation laws and phase space structure are investigated in preparation for the later studies. ERCAs are a family of one-dimensional reversible cellular automata having two Boolean variables on each site. Reflection and Boolean conjugation symmetries divide them into 88 equivalence classes. For each rule, additive conserved quantities written in a certain form are regarded as a kind of energy, if they exist. By the aid of the discreteness of the variables, every ERCA satisfies the Liouville theorem or the preservation of phase space volume. Thus, if an energy exists in the above sense, statistical mechanics of the model can formally be constructed. If a locally defined quantity is conserved, however, it prevents the realization of statistical mechanics. The existence of such a quantity is examined for each class and a number of rules which have at least one energy but no local conservation laws are selected as hopeful candidates for the realization of thermodynamic behavior. In addition, the phase space structure of ERCAs is analyzed by enumerating cycles exactly in the phase space for systems of comparatively small sizes. As a result, it is revealed that a finite ERCA is not ergodic, that is, a large number of orbits coexist on an energy surface. It is argued that this fact does not necessarily mean the failure of thermodynamic behavior on the basis of an analogy with the ergodic nature of infinite systems.
NASA Technical Reports Server (NTRS)
Gordon, S.
1982-01-01
Thermodynamic and transport combustion properties were calculated for a wide range of conditions for the reaction of hydrocarbons with air. Three hydrogen-carbon atom ratios (H/C = 1.7, 2.0, 2.1) were selected to represent the range of aircraft fuels. For each of these H/C ratios, combustion properties were calculated for the following conditions: Equivalence ratio: 0, 0.25, 0.5, 0.75, 1.0, 1.25 Water - dry air mass ratio: 0, 0.03 Pressure, kPa: 1.01325, 10.1325, 101.325, 1013.25, 5066.25 (or in atm: 0.01, 0.1, 1, 10, 50) Temperature, K: every 10 degrees from 200 to 900 K; every 50 degrees from 900 to 3000 K Temperature, R: every 20 degrees from 360 to 1600 R; very 100 degrees from 1600 to 5400 R. The properties presented are composition, density, molecular weight, enthalphy, entropy, specific heat at constant pressure, volume derivatives, isentropic exponent, velocity of sound, viscosity, thermal conductivity, and Prandtl number. Property tables are based on composites that were calculated by assuming both: (1) chemical equilibrium (for both homogeneous and heterogeneous phases) and (2) constant compositions for all temperatures. Properties in SI units are presented in this report for the Kelvin temperature schedules.
NASA Astrophysics Data System (ADS)
Gordon, S.
1982-07-01
Thermodynamic and transport combustion properties were calculated for a wide range of conditions for the reaction of hydrocarbons with air. Three hydrogen-carbon atom ratios (H/C = 1.7, 2.0, 2.1) were selected to represent the range of aircraft fuels. For each of these H/C ratios, combustion properties were calculated for the following conditions: Equivalence ratio: 0, 0.25, 0.5, 0.75, 1.0, 1.25 Water - dry air mass ratio: 0, 0.03 Pressure, kPa: 1.01325, 10.1325, 101.325, 1013.25, 5066.25 (or in atm: 0.01, 0.1, 1, 10, 50) Temperature, K: every 10 degrees from 200 to 900 K; every 50 degrees from 900 to 3000 K Temperature, R: every 20 degrees from 360 to 1600 R; very 100 degrees from 1600 to 5400 R. The properties presented are composition, density, molecular weight, enthalphy, entropy, specific heat at constant pressure, volume derivatives, isentropic exponent, velocity of sound, viscosity, thermal conductivity, and Prandtl number. Property tables are based on composites that were calculated by assuming both: (1) chemical equilibrium (for both homogeneous and heterogeneous phases) and (2) constant compositions for all temperatures. Properties in SI units are presented in this report for the Kelvin temperature schedules.
WETAIR: A computer code for calculating thermodynamic and transport properties of air-water mixtures
NASA Technical Reports Server (NTRS)
Fessler, T. E.
1979-01-01
A computer program subroutine, WETAIR, was developed to calculate the thermodynamic and transport properties of air water mixtures. It determines the thermodynamic state from assigned values of temperature and density, pressure and density, temperature and pressure, pressure and entropy, or pressure and enthalpy. The WETAIR calculates the properties of dry air and water (steam) by interpolating to obtain values from property tables. Then it uses simple mixing laws to calculate the properties of air water mixtures. Properties of mixtures with water contents below 40 percent (by mass) can be calculated at temperatures from 273.2 to 1497 K and pressures to 450 MN/sq m. Dry air properties can be calculated at temperatures as low as 150 K. Water properties can be calculated at temperatures to 1747 K and pressures to 100 MN/sq m. The WETAIR is available in both SFTRAN and FORTRAN.
Experimental verification of the thermodynamic properties for a jet-A fuel
NASA Technical Reports Server (NTRS)
Graciasalcedo, Carmen M.; Brabbs, Theodore A.; Mcbride, Bonnie J.
1988-01-01
Thermodynamic properties for a Jet-A fuel were determined by Shell Development Company in 1970 under a contract for NASA Lewis Research Center. The polynomial fit necessary to include Jet-A fuel (liquid and gaseous phases) in the library of thermodynamic properties of the NASA Lewis Chemical Equilibrium Program is calculated. To verify the thermodynamic data, the temperatures of mixtures of liquid Jet-A injected into a hot nitrogen stream were experimentally measured and compared to those calculated by the program. Iso-octane, a fuel for which the thermodynamic properties are well known, was used as a standard to calibrate the apparatus. The measured temperatures for the iso-octane/nitrogen mixtures reproduced the calculated temperatures except for a small loss due to the non-adiabatic behavior of the apparatus. The measurements for Jet-A were corrected for this heat loss and showed excellent agreement with the calculated temperatures. These experiments show that this process can be adequately described by the thermodynamic properties fitted for the Chemical Equilibrium Program.
Molecular simulation of thermodynamic and transport properties for the H2O+NaCl system.
Orozco, Gustavo A; Moultos, Othonas A; Jiang, Hao; Economou, Ioannis G; Panagiotopoulos, Athanassios Z
2014-12-21
Molecular dynamics and Monte Carlo simulations have been carried out to obtain thermodynamic and transport properties of the binary mixture H2O+NaCl at temperatures from T = 298 to 473 K. In particular, vapor pressures, liquid densities, viscosities, and vapor-liquid interfacial tensions have been obtained as functions of pressure and salt concentration. Several previously proposed fixed-point-charge models that include either Lennard-Jones (LJ) 12-6 or exponential-6 (Exp6) functional forms to describe non-Coulombic interactions were studied. In particular, for water we used the SPC and SPC/E (LJ) models in their rigid forms, a semiflexible version of the SPC/E (LJ) model, and the Errington-Panagiotopoulos Exp6 model; for NaCl, we used the Smith-Dang and Joung-Cheatham (LJ) parameterizations as well as the Tosi-Fumi (Exp6) model. While none of the model combinations are able to reproduce simultaneously all target properties, vapor pressures are well represented using the SPC plus Joung-Cheathem model combination, and all LJ models do well for the liquid density, with the semiflexible SPC/E plus Joung-Cheatham combination being the most accurate. For viscosities, the combination of rigid SPC/E plus Smith-Dang is the best alternative. For interfacial tensions, the combination of the semiflexible SPC/E plus Smith-Dang or Joung-Cheatham gives the best results. Inclusion of water flexibility improves the mixture densities and interfacial tensions, at the cost of larger deviations for the vapor pressures and viscosities. The Exp6 water plus Tosi-Fumi salt model combination was found to perform poorly for most of the properties of interest, in particular being unable to describe the experimental trend for the vapor pressure as a function of salt concentration. PMID:25527948
Molecular simulation of thermodynamic and transport properties for the H2O+NaCl system
NASA Astrophysics Data System (ADS)
Orozco, Gustavo A.; Moultos, Othonas A.; Jiang, Hao; Economou, Ioannis G.; Panagiotopoulos, Athanassios Z.
2014-12-01
Molecular dynamics and Monte Carlo simulations have been carried out to obtain thermodynamic and transport properties of the binary mixture H2O+NaCl at temperatures from T = 298 to 473 K. In particular, vapor pressures, liquid densities, viscosities, and vapor-liquid interfacial tensions have been obtained as functions of pressure and salt concentration. Several previously proposed fixed-point-charge models that include either Lennard-Jones (LJ) 12-6 or exponential-6 (Exp6) functional forms to describe non-Coulombic interactions were studied. In particular, for water we used the SPC and SPC/E (LJ) models in their rigid forms, a semiflexible version of the SPC/E (LJ) model, and the Errington-Panagiotopoulos Exp6 model; for NaCl, we used the Smith-Dang and Joung-Cheatham (LJ) parameterizations as well as the Tosi-Fumi (Exp6) model. While none of the model combinations are able to reproduce simultaneously all target properties, vapor pressures are well represented using the SPC plus Joung-Cheathem model combination, and all LJ models do well for the liquid density, with the semiflexible SPC/E plus Joung-Cheatham combination being the most accurate. For viscosities, the combination of rigid SPC/E plus Smith-Dang is the best alternative. For interfacial tensions, the combination of the semiflexible SPC/E plus Smith-Dang or Joung-Cheatham gives the best results. Inclusion of water flexibility improves the mixture densities and interfacial tensions, at the cost of larger deviations for the vapor pressures and viscosities. The Exp6 water plus Tosi-Fumi salt model combination was found to perform poorly for most of the properties of interest, in particular being unable to describe the experimental trend for the vapor pressure as a function of salt concentration.
NASA Technical Reports Server (NTRS)
Allison, D. O.
1972-01-01
Computer programs for flow fields around planetary entry vehicles require real-gas equilibrium thermodynamic properties in a simple form which can be evaluated quickly. To fill this need, polynomial approximations were found for thermodynamic properties of air and model planetary atmospheres. A coefficient-averaging technique was used for curve fitting in lieu of the usual least-squares method. The polynomials consist of terms up to the ninth degree in each of two variables (essentially pressure and density) including all cross terms. Four of these polynomials can be joined to cover, for example, a range of about 1000 to 11000 K and 0.00001 to 1 atmosphere (1 atm = 1.0133 x 100,000 N/m sq) for a given thermodynamic property. Relative errors of less than 1 percent are found over most of the applicable range.
NASA Astrophysics Data System (ADS)
Kong, Fanjie; Hu, Yanfei; Hou, Haijun; Liu, Yanhua; Wang, Baolin; Wang, Lili
2012-12-01
The structural, electronic, thermoelectric and thermodynamic properties of ternary half-Heusler compound YPdSb are investigated using the first principle calculations. It is found that YPdSb is an indirect semiconductor. The calculated band gap is 0.161 eV with spin-orbital coupling including and 0.235 eV without spin-orbital coupling including, respectively. The electronic transport properties are obtained via Boltzman transport theory. The predicted Seebeck coefficient is 240 μV/K and the thermoelectric performance can be optimized by n-type doping at room temperature. Moreover, the lattice dynamical results regarding the phonon dispersion curves, phonon density of states and thermodynamic properties are reported. Thermodynamics (heat capacity and Debye temperature) as well as mean phonon free path and the thermal conductivity in a temperature range of 0-300 K are determined.
Thermodynamic and transport properties of air/water mixtures
NASA Technical Reports Server (NTRS)
Fessler, T. E.
1981-01-01
Subroutine WETAIR calculates properties at nearly 1,500 K and 4,500 atmospheres. Necessary inputs are assigned values of combinations of density, pressure, temperature, and entropy. Interpolation of property tables obtains dry air and water (steam) properties, and simple mixing laws calculate properties of air/water mixture. WETAIR is used to test gas turbine engines and components operating in relatively humid air. Program is written in SFTRAN and FORTRAN.
Pabalan, R.T.; Pitzer, K.S.
1988-01-01
The Pitzer ion-interaction model, which is theoretically derived but uses empirical parameters evaluated from experimental data on binary and ternary aqueous mixtures, is shown to accurately predict thermodynamic properties of aqueous eletrolytes to high temperatures and concentrations and for more complex compositions. Applications of the model include calculations of solubility equilibria, vapor pressures and boiling points of electrolyte mixtures. Examples of these calculations are given below. 32 refs., 5 figs., 2 tabs.
Thermodynamic properties of the lipid bilayer transition. Pseudocritical phenomena.
Mitaku, S; Jippo, T; Kataoka, R
1983-01-01
Ultrasonic relaxation of multilamellar liposomes formed from dipalmitoylphosphatidylcholine was measured near the gel-to-liquid crystal transition by a differential ultrasonic resonator. The relaxation time and strength increased remarkably near the transition temperature, indicating a pseudocritical phenomenon. A quantitative analysis of the relaxation in terms of thermodynamic relationships between specific heat, thermal-expansion coefficient, and compressibility showed that more than 90% of the total endothermic heat of the transition arises from the latent heat. The temperature dependence of the ultrasonic relaxation parameters was also analyzed by the Landau theory; we obtain a small but finite difference, 0.6 degree C, between the pseudocritical temperature and the transition temperature. These results provide a quantitative description of both the first-order and second-order characters of the gel-to-liquid crystal transition. PMID:6688030
Thermodynamic properties of some metal oxide-zirconia systems
NASA Technical Reports Server (NTRS)
Jacobson, Nathan S.
1989-01-01
Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.
Thermodynamic properties of mesoscale convective systems observed during BAMEX
Correia, James; Arritt, R.
2008-11-01
Dropsonde observations from the Bow-echo and Mesoscale convective vortex EXperiment (BAMEX) are used to document the spatio-temporal variability of temperature, moisture and wind within mesoscale convective systems (MCSs). Onion type sounding structures are found throughout the stratiform region of MCSs but the temperature and moisture variability is large. Composite soundings were constructed and statistics of thermodynamic variability were generated within each sub-region of the MCS. The calculated air vertical velocity helped identify subsaturated downdrafts. We found that lapse rates within the cold pool varied markedly throughout the MCS. Layered wet bulb potential temperature profiles seem to indicate that air within the lowest several km comes from a variety of source regions. We also found that lapse rate transitions across the 0 C level were more common than isothermal, melting layers. We discuss the implications these findings have and how they can be used to validate future high resolution numerical simulations of MCSs.
Thermodynamic properties of a quantum Hall anti-dot interferometer
NASA Astrophysics Data System (ADS)
Levy Schreier, Sarah; Stern, Ady; Rosenow, Bernd; Halperin, Bertrand I.
2016-02-01
We study quantum Hall interferometers in which the interference loop encircles a quantum anti-dot. We base our study on thermodynamic considerations, which we believe reflect the essential aspects of interference transport phenomena. We find that similar to the more conventional Fabry-Perot quantum Hall interferometers, in which the interference loop forms a quantum dot, the anti-dot interferometer is affected by the electro-static Coulomb interaction between the edge modes defining the loop. We show that in the Aharonov-Bohm regime, in which effects of fractional statistics should be visible, is easier to access in interferometers based on anti-dots than in those based on dots. We discuss the relevance of our results to recent measurements on anti-dots interferometers.
NASA Astrophysics Data System (ADS)
Cari, C.; Suparmi, A.; Yunianto, M.; Husein, A. S.
2016-02-01
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.
Decremps, F; Gauthier, M; Ayrinhac, S; Bove, L; Belliard, L; Perrin, B; Morand, M; Le Marchand, G; Bergame, F; Philippe, J
2015-02-01
Based on the original combination of picosecond acoustics and diamond anvils cell, recent improvements to accurately measure hypersonic sound velocities of liquids and solids under extreme conditions are described. To illustrate the capability of this technique, results are given on the pressure and temperature dependence of acoustic properties for three prototypical cases: polycrystal (iron), single-crystal (silicon) and liquid (mercury) samples. It is shown that such technique also enables the determination of the density as a function of pressure for liquids, of the complete set of elastic constants for single crystals, and of the melting curve for any kind of material. High pressure ultrafast acoustic spectroscopy technique clearly opens opportunities to measure thermodynamical properties under previously unattainable extreme conditions. Beyond physics, this state-of-the-art experiment would thus be useful in many other fields such as nonlinear acoustics, oceanography, petrology, in of view. A brief description of new developments and future directions of works conclude the article. PMID:24852260
NASA Astrophysics Data System (ADS)
Satoh, Katsuhiko
2013-08-01
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^{γ _τ }, 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 γτ 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.
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. PMID:24007031
NASA Astrophysics Data System (ADS)
Zhang, Wei; Chen, Qing Yun; Li, Bin; Zeng, Zhao Yi; Cai, Ling Cang
2015-09-01
The ground state properties of the silicon clathrate Si46 intercalated by alkali metal sodium atoms (Na8Si46) are investigated by first-principle methods. Birch-Murnaghan equation of state is fitted to two sets of the E-V data calculated by density functional theory based on the plane-wave basis set within both the local density approximation (LDA) and the generalized gradient approximation (GGA). Through quasi-harmonic Debye model, some thermodynamic properties comprise the heat capacity, the thermal expansion coefficient, Debye temperature and the Grüneisen parameter for this clathrate compounds Na8Si46 are obtained, which agree well with experimental results. Comparing the calculated heat specific in two ways with experimental results, we find that it is more accurate to describe the “rattle” modes of gust Na atoms in the cages as Einstein oscillators. Moreover, the effects of high pressure on these thermodynamic properties are also investigated which will be very helpful for a synthesis of these clathrate compounds in experiments under high pressure and high temperature condition.
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
Experimental Study of the Thermodynamic Properties of Diethyl Ether (DEE) at Saturation
NASA Astrophysics Data System (ADS)
Polikhronidi, N. G.; Abdulagatov, I. M.; Batyrova, R. G.; Stepanov, G. V.; Ustuzhanin, E. E.; Wu, J. T.
2011-03-01
The isochoric heat capacities {({C_{V1}^' ,{C_{V1}^'',{C_{V2}^',{C_{V2}^'')}, saturation densities ({ρ _S^' and ({ρ_S^'')}), vapor pressures ( P S), thermal-pressure coefficients {γ_V=left({partial P/partial T}right)_V}, and first temperature derivatives of the vapor pressure γ S = (d P S/d T) of diethyl ether (DEE) on the liquid-gas coexistence curve near the critical point have been measured with a high-temperature and high-pressure nearly constant-volume adiabatic piezo-calorimeter. The measurements of {({C_{V1}^' ,{C_{V1}^'',{C_{V2}^',{C_{V2}^'')} were made in the liquid and vapor one- and two-phase regions along the coexistence curve. The calorimeter was additionally supplied with a calibrated extensometer to accurately and simultaneously measure the PVT, C V VT, and thermal-pressure coefficient, γ V , along the saturation curve. The measurements were carried out in the temperature range from 416 K to 466.845 K (the critical temperature) for 17 liquid and vapor densities from 212.6 kg · m-3 to 534.6 kg · m-3. The quasi-static thermo- (reading of PRT, T - τ plot) and baro-gram (readings of the tensotransducer, P - τ plot) techniques were used to accurately measure the phase-transition parameters ( P S , ρ S , T S) and γ V . The total experimental uncertainty of density ( ρ S), pressure ( P S), temperature ( T S), isochoric heat capacities {({C_{V1}^' ,{C_{V1}^'',{C_{V2}^',{C_{V2}^'')}, and thermal-pressure coefficient, γ V , were estimated to be 0.02 % to 0.05 %, 0.05 %, 15 mK, 2 % to 3 %, and 0.12 % to 1.5 %, respectively. The measured values of saturated caloric {({C_{V1}^' ,{C_{V1}^'',{C_{V2}^',{C_{V2}^'')} and saturated thermal ( P S, ρ S, T S) properties were used to calculate other derived thermodynamic properties C P , C S, W, K T , P int, Δ H vap, and {left({partial V/partial T}right)_P^' of DEE near the critical point. The second temperature derivatives of the vapor pressure, (d2 P S/d T 2), and chemical potential, (d2 μ/d T 2), were
Two-temperature thermodynamic and transport properties of SF6-Cu plasmas
NASA Astrophysics Data System (ADS)
Wu, Yi; Chen, Zhexin; yang, Fei; Cressault, Yann; Murphy, Anthony B.; Guo, Anxiang; Liu, Zirui; Rong, Mingzhe; Sun, Hao
2015-10-01
SF6 and Cu are widely adopted in electrical equipment as a dielectric medium and for conductive components, respectively. SF6-Cu plasmas are frequently formed, particularly in high-voltage circuit breaker arcs and fault current arcs, due to erosion of the Cu components. In this paper, calculated values of the thermodynamic and transport properties of plasmas in SF6-Cu mixtures are presented for both thermal equilibrium and non-equilibrium conditions. The composition is determined by the two-temperature Saha equation and Guldberg-Waage equation in the form derived by van de Sanden. The composition and the thermodynamic properties are evaluated through a classical statistical mechanics approach. For the transport coefficients, the simplified Chapman-Enskog method developed by Devoto, which decouples the electrons and heavy species, has been applied using the most recent collision integrals. The thermodynamic and transport properties are calculated for different electron temperatures (300-40 000 K), ratios of electron to heavy-species temperature (1-10), pressures (0.1-10 atm) and copper molar proportions (0-50%). It is found that deviations from thermal equilibrium strongly affect the thermodynamic and transport properties of the SF6-Cu plasmas. Further, the presence of copper has different effects on some of the properties for plasmas in and out of thermal equilibrium. The main reason for these changes is that dissociation reactions are delayed for non-thermal equilibrium plasmas, which in turn influences the ionization reactions that occur.
Ritter, E R
1991-08-01
A computer package has been developed called THERM, an acronym for THermodynamic property Estimation for Radicals and Molecules. THERM is a versatile computer code designed to automate the estimation of ideal gas phase thermodynamic properties for radicals and molecules important to combustion and reaction-modeling studies. Thermodynamic properties calculated include heat of formation and entropies at 298 K and heat capacities from 300 to 1500 K. Heat capacity estimates are then extrapolated to above 5000 K, and NASA format polynomial thermodynamic property representations valid from 298 to 5000 K are generated. This code is written in Microsoft Fortran version 5.0 for use on machines running under MSDOS. THERM uses group additivity principles of Benson and current best values for bond strengths, changes in entropy, and loss of vibrational degrees of freedom to estimate properties for radical species from parent molecules. This ensemble of computer programs can be used to input literature data, estimate data when not available, and review, update, and revise entries to reflect improvements and modifications to the group contribution and bond dissociation databases. All input and output files are ASCII so that they can be easily edited, updated, or expanded. In addition, heats of reaction, entropy changes, Gibbs free-energy changes, and equilibrium constants can be calculated as functions of temperature from a NASA format polynomial database. PMID:1939398
Thermodynamic Properties of 4f- and 5f-SHELL Metals at Finite Temperatures:
NASA Astrophysics Data System (ADS)
Bhatt, N. K.; Vyas, P. R.; Jani, A. R.; Gohel, V. B.
The thermodynamic properties of 4f- and 5f-shell metals have been studied at high temperatures using mean-field potential approach. The MFP seen by the lattice ion is constructed in terms of the total energy-volume relation using local pseudopotentials due to Pandya et al. [Physica B 307, 138 (2001)]. We have calculated static compression, shock-wave compression, volume thermal expansion, isothermal and adiabatic bulk moduli (BT and BS), specific heats (CV and CP), thermodynamic Grüneisen parameter (γth), anharmonic contribution to the specific heat and temperature along shock Hugoniot for 4f (γ-Ce)- and 5f (fcc-Th)-shell metals. The results are well compared with the other theoretical and experimental findings, which ensure the use of pseudopotentials for studying thermodynamic properties at higher temperatures in case of lanthanides and actinides.
Thermodynamical properties of triangular quantum wires: entropy, specific heat, and internal energy
NASA Astrophysics Data System (ADS)
Khordad, R.
2016-07-01
In the present work, thermodynamical properties of a GaAs quantum wire with equilateral triangle cross section are studied. First, the energy levels of the system are obtained by solving the Schrödinger equation. Second, the Tsallis formalism is applied to obtain entropy, internal energy, and specific heat of the system. We have found that the specific heat and entropy have certain physically meaningful values, which mean thermodynamic properties cannot take any continuous value, unlike classical thermodynamics in which they are considered as continuous quantities. Maximum of entropy increases with increasing the wire size. The specific heat is zero at special temperatures. Specific heat decreases with increasing temperature. There are several peaks in specific heat, and these are dependent on quantum wire size.
Thermodynamical properties of Zr-based bulk metallic glasses
NASA Astrophysics Data System (ADS)
Gaur, Jitendra; Mishra, R. K.
2015-11-01
The temperature dependence of Gibb's free energy difference (ΔG), entropy difference (ΔS) and enthalpy difference (ΔH) between the undercooled melt and the corresponding equilibrium solid phases of bulk metallic glass (BMG) forming melts has been proved to be very useful in the study of their thermodynamical behavior. The present study is made by calculating ΔG, ΔS and ΔH in the entire temperature range Tm (melting temperature) to Tg (glass transition temperature) for three Zr-based samples of BMGs: Zr57Cu15.4Ni12.6Al10Nb5, Zr41.2Ti13.8Ni10Cu12.5Be22.5 and Zr58.5Cu15.6Ni12.8Al10.3Nb2.8. The study is made on the basis of Taylor's series expansion and a comparative study is also performed between the present result and the result obtained in the framework of expansions proposed by earlier workers, and also with the experimental results. An attempt has also been made to study the glass forming ability for BMGs.
Dynamics and thermodynamic properties of CXCL7 chemokine.
Herring, Charles A; Singer, Christopher M; Ermakova, Elena A; Khairutdinov, Bulat I; Zuev, Yuriy F; Jacobs, Donald J; Nesmelova, Irina V
2015-11-01
Chemokines form a family of signaling proteins mainly responsible for directing the traffic of leukocytes, where their biological activity can be modulated by their oligomerization state. We characterize the dynamics and thermodynamic stability of monomer and homodimer structures of CXCL7, one of the most abundant platelet chemokines, using experimental methods that include circular dichroism (CD) and nuclear magnetic resonance (NMR) spectroscopy, and computational methods that include the anisotropic network model (ANM), molecular dynamics (MD) simulations and the distance constraint model (DCM). A consistent picture emerges for the effects of dimerization and Cys5-Cys31 and Cys7-Cys47 disulfide bonds formation. The presence of disulfide bonds is not critical for maintaining structural stability in the monomer or dimer, but the monomer is destabilized more than the dimer upon removal of disulfide bonds. Disulfide bonds play a key role in shaping the characteristics of native state dynamics. The combined analysis shows that upon dimerization flexibly correlated motions are induced between the 30s and 50s loop within each monomer and across the dimer interface. Interestingly, the greatest gain in flexibility upon dimerization occurs when both disulfide bonds are present, and the homodimer is least stable relative to its two monomers. These results suggest that the highly conserved disulfide bonds in chemokines facilitate a structural mechanism that is tuned to optimally distinguish functional characteristics between monomer and dimer. PMID:26297927
Thermodynamic properties of lanthanide metals in liquid bismuth
NASA Astrophysics Data System (ADS)
Yamana, Hajimu; Sheng, Jiawei; Souda, Naohiko; Moriyama, Hirotake
2001-04-01
Thermodynamic quantities of La, Gd, Tb, and Dy in liquid bismuth were experimentally determined by electromotive force (EMF) measurement using a cell consisting of molten alkaline chloride and liquid bismuth. Excess Gibbs energy changes and activity coefficients were determined at varying concentrations and temperatures. Through their temperature dependence, corresponding enthalpy changes and entropy changes were determined. The excess enthalpy changes of La, Gd, Tb, and Dy in liquid bismuth in a temperature range from 850 to 1100 K were evaluated to be, -221.54±2.31, -202.25±1.80, -199.83±0.55, and -193.80±0.99 kJ/mol, respectively. The systematic variation of excess enthalpy change of lanthanides along the 4f-series was discussed. As a result, it was found that the excess enthalpy changes of La, Gd, Tb, Dy, and Er are likely to depend linearly on the 2/3 power of their metallic volume.
NASA Astrophysics Data System (ADS)
Zhuang, Houlong; Chen, Mohan; Carter, Emily A.
2016-06-01
Magnesium-aluminum (Mg-Al) alloys are important metal alloys with a wide range of engineering applications. We investigate the elastic and thermodynamic properties of Mg, Al, and four stoichiometric Mg-Al compounds including Mg17Al12 , Mg13Al14 , and Mg23Al30 , and MgAl2 with orbital-free density-functional theory (OFDFT). We first calculate the lattice constants, zero-temperature formation energy, and independent elastic constants of these six materials and compare the results to those computed via Kohn-Sham DFT (KSDFT) benchmarks. We obtain excellent agreement between these two methods. Our calculated elastic constants of hexagonal close-packed Mg and face-centered-cubic Al are also consistent with available experimental data. We next compute their phonon spectra using the force constants extracted from the very fast OFDFT calculations, because such calculations are computationally challenging using KSDFT. This is especially the case for the Mg23Al30 compound, whose 3 ×3 ×3 supercell consists of 1431 atoms. We finally employ the quasiharmonic approximation to investigate temperature-dependent thermodynamic properties, including formation energies, heat capacities, and thermal expansion of the four Mg-Al intermetallic compounds. The calculated heat capacity and thermal expansion of both Mg and Al agree well with experimental data. We additionally find that Mg13Al14 and MgAl2 are both unstable, consistent with their absence from the equilibrium Mg-Al phase diagram. Our work demonstrates that OFDFT is an efficient and accurate quantum-mechanical computational tool for predicting elastic and thermodynamic properties of complicated Mg-Al alloys and also should be applicable to many other engineering alloys.
Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium.
NASA Technical Reports Server (NTRS)
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.
The Problem of Counting the Number of Molecules and Calculating Thermodynamic Properties.
ERIC Educational Resources Information Center
Torres, Luis Alfonso; And Others
1995-01-01
Presents an experimental approach to illustrate that the thermodynamic properties of a system can be considered as the average of mechanical variables. Discusses the Knudsen effusion method to count the number of molecules, vapor pressure, the piezoelectric effect, the experimental setup, and sample experimental results. (JRH)
Iodine, bromine, and chlorine. Liquid and solid states and thermodynamic properties
Slavin, A.A.; Abramzon, A.A.; Slavina, Z.N.; Komarov, E.V.; Puchkov, A.I.
1987-10-20
The authors describe a method of determining, experimentally and mathematically, the solubility and such thermodynamic properties as sublimation heats, solution heats, and melting points among others for iodine, bromine, and chlorine. Transition temperature dependence on vapor pressure is determined and solubility in water and a number of organic solvents, including benzene, carbon disulfide, carbon tetrachloride, cyclohexane, and other alkanes. The analysis incorporated calorimetry.
Kong, Fanjie; Hu, Yanfei; Hou, Haijun; Liu, Yanhua; Wang, Baolin; Wang, Lili
2012-12-15
The structural, electronic, thermoelectric and thermodynamic properties of ternary half-Heusler compound YPdSb are investigated using the first principle calculations. It is found that YPdSb is an indirect semiconductor. The calculated band gap is 0.161 eV with spin-orbital coupling including and 0.235 eV without spin-orbital coupling including, respectively. The electronic transport properties are obtained via Boltzman transport theory. The predicted Seebeck coefficient is 240 {mu}V/K and the thermoelectric performance can be optimized by n-type doping at room temperature. Moreover, the lattice dynamical results regarding the phonon dispersion curves, phonon density of states and thermodynamic properties are reported. Thermodynamics (heat capacity and Debye temperature) as well as mean phonon free path and the thermal conductivity in a temperature range of 0-300 K are determined. - Graphical Abstract: (a) The dependence of the Seebeck coefficient on chemical potential at 300 K. (b) The dependence of the thermopower factor on chemical potential at 300 K. Highlights: Black-Right-Pointing-Pointer The Seebeck coefficient and the thermopower factor are calculated. Black-Right-Pointing-Pointer The lattice dynamics and thermodynamic properties are obtained.
Brandani, V.; Prausnitz, J. M.
1982-01-01
This paper is the second of three describing a two-fluid theory of binary liquid mixtures. The general theory presented in the preceding paper is used to derive a model for calculating thermodynamic properties of hard-sphere mixtures. Calculations indicate that desirable boundary conditions are satisfied. PMID:16593220
Defining allowable physical property variations for high accurate measurements on polymer parts
NASA Astrophysics Data System (ADS)
Mohammadi, A.; Sonne, M. R.; Madruga, D. G.; De Chiffre, L.; Hattel, J. H.
2016-06-01
Measurement conditions and material properties have a significant impact on the dimensions of a part, especially for polymers parts. Temperature variation causes part deformations that increase the uncertainty of the measurement process. Current industrial tolerances of a few micrometres demand high accurate measurements in non-controlled ambient. Most of polymer parts are manufactured by injection moulding and their inspection is carried out after stabilization, around 200 hours. The overall goal of this work is to reach ±5μm in uncertainty measurements a polymer products which is a challenge in today`s production and metrology environments. The residual deformations in polymer products at room temperature after injection molding are important when micrometer accuracy needs to be achieved. Numerical modelling can give a valuable insight to what is happening in the polymer during cooling down after injection molding. In order to obtain accurate simulations, accurate inputs to the model are crucial. In reality however, the material and physical properties will have some variations. Although these variations may be small, they can act as a source of uncertainty for the measurement. In this paper, we investigated how big the variation in material and physical properties are allowed in order to reach the 5 μm target on the uncertainty.
Fu, Q.; Sun, W.B.; Yang, P.
1998-09-01
An accurate parameterization is presented for the infrared radiative properties of cirrus clouds. For the single-scattering calculations, a composite scheme is developed for randomly oriented hexagonal ice crystals by comparing results from Mie theory, anomalous diffraction theory (ADT), the geometric optics method (GOM), and the finite-difference time domain technique. This scheme employs a linear combination of single-scattering properties from the Mie theory, ADT, and GOM, which is accurate for a wide range of size parameters. Following the approach of Q. Fu, the extinction coefficient, absorption coefficient, and asymmetry factor are parameterized as functions of the cloud ice water content and generalized effective size (D{sub ge}). The present parameterization of the single-scattering properties of cirrus clouds is validated by examining the bulk radiative properties for a wide range of atmospheric conditions. Compared with reference results, the typical relative error in emissivity due to the parameterization is {approximately}2.2%. The accuracy of this parameterization guarantees its reliability in applications to climate models. The present parameterization complements the scheme for the solar radiative properties of cirrus clouds developed by Q. Fu for use in numerical models.
Low-Temperature Thermodynamic Properties of a One-Dimensional Generalized Wigner Crystal
NASA Astrophysics Data System (ADS)
Slavin, V.
The low-temperature thermodynamic properties of a one-dimensional generalized Wigner crystal at arbitrary values of electron density and arbitrary number of interacting electrons are studied. The modified transfer-matrixes method is applied. It is shown that increasing the number of interacting electrons leads to the appearance of more and more fine "stairs" in low-temperature dependence of chemical potential against electron density. An influence of the disorder in host-lattice site positions on thermodynamic characteristics of the system is considered. It is established that the disorder destroys the "stairs".
Prediction of thermodynamic and surface properties of Pb-Hg liquid alloys at different temperatures
NASA Astrophysics Data System (ADS)
Yadav, S. K.; Jha, L. N.; Jha, I. S.; Singh, B. P.; Koirala, R. P.; Adhikari, D.
2016-06-01
The thermodynamic properties, such as free energy of mixing, heat of mixing, activity and structural properties, such as concentration fluctuation in long wavelength limit, short-range order parameter of Pb-Hg liquid alloy at 600 K have been calculated using theoretical modelling. It has then been correlated with modified Butler model to compute the surface tension of the alloys at different temperatures. The Pb-Hg system at 600 K is found to be ordering at higher concentration of Pb.
Thermodynamic model for calorimetric and phase coexistence properties of coal derived fluids
Kabadi, V.N.
1990-01-01
A model for phase equilibria of coal derived liquids is to be extended to include calorimetric properties as well. To accomplish this satisfactorily, the proposed work includes three tasks: (1) Refinement of the characterization procedure to include distribution of sulfur, oxygen, and nitrogen heteroatoms in coal liquids; (2) Measurement of high temperature (up to 400{degrees}C) and high pressure (up to 1000 psi) VLE data for binary systems of selected model compounds; and (3) Development of the thermodynamic model. The final product will include a computer program which with measurable properties of coal liquids as input, will give results for phase coexistence properties and excess enthalpies in the liquid phase. Efforts are continuing to apply the new thermodynamic model for VLE and enthalpy predictions for coal liquids by the methods of continuous thermodynamics. Recently, Thompson, Brobst and Hankinson have developed an equation of state that represents compressibilities of liquids very well. The authors have undertaken the task of combining this equation of state with their thermodynamic model to provide a comprehensive model for high pressure liquid mixtures. Calibration and preliminary set-up procedure for the VLE apparatus with the new liquid level sensor have been completed. The apparatus is currently being tested with the binary system quinoline-tetralin. Chromatographic characterization work was delayed because of complexities of the calibration procedure and tedious calculations necessary for number average and weight average molecular weights. Results on the chromatographic studies are being deferred until computer software is received.
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 CO_{2} 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. PMID:25768462
NASA Astrophysics Data System (ADS)
Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan
2014-03-01
We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.
Low-Temperature Thermodynamic Properties of Superconducting Antiperovskite CdCNi_3
NASA Astrophysics Data System (ADS)
Szczȩśniak, R.; Durajski, A. P.; Skoczylas, K. M.; Herok, Ł.
2016-06-01
We investigate the thermodynamic parameters of the superconducting antiperovskite CdCNi_3 using the Eliashberg approach which is an excellent tool to the exact characterization of the conventional superconductors. In particular, we reproduce the measured superconducting transition temperature (T_C=3.2 K) for a high value of the Coulomb pseudopotential (μ ^{star }C=0.22). Then we determine the energy gap, the thermodynamic critical field and the specific heat for the superconducting and normal state. On this basis, we show that the thermodynamic properties of CdCNi_3 differ slightly from the prediction of the Bardeen-Cooper-Schrieffer theory, which means that CdCNi_3 is a medium-coupling superconductor in contrast to related strong-coupling MgCNi_3.
Predicting the thermodynamic properties of gold nanoparticles using different force fields
NASA Astrophysics Data System (ADS)
Park, Yongjin
The objective of this research was to learn how to predict the thermodynamic properties of gold nanoparticles using computational tools. The lowest energy structures of gold nanoparticles of various sizes were determined and thermodynamic properties such as the free energy (F), internal energy (U), entropy (S), and specific heat (Cv) of the gold nanoparticles were investigated using a fully-atomistic Monte Carlo simulation method that utilizes a modified Wang-Landau algorithm. Eight well-known force fields for metallic systems were employed to model gold nanoparticles: the Lennard-Jones potential (LJ), the Lennard-Jones potential with Heinz's parameterization (LJH), the Gupta potential, the Sutton-Chen potential (SC), the Sutton-Chen potential with Pawluk's parameterization for small clusters (SCP), the Quantum Sutton-Chen potential (Q-SC), the Embedded Atom Method (EAM) by Cai and Ye, and the empirical potential for gold proposed by Olivier and coworkers (POT). Subsequently, we explored the accuracy of each force field in the description of the thermodynamic behavior of gold nanoparticles. The thermodynamic properties of gold nanoparticles were computed from the Density of States which was obtained as a result of the Monte Carlo simulation. Afterwards, the melting point of gold nanoparticles was determined from the behavior of the calculated thermodynamic properties and was compared with theory, experimental observations and other simulation results. The force fields employed predicted melting points of gold nanoparticles over a wide range of temperatures. A thorough comparison with the available experimental observations showed that the Quantum Sutton-Chen potential (Q-SC) correctly described the melting behavior of gold nanoparticles with sizes smaller than 1.3 nanometers.
Accurate transport properties for H–CO and H–CO{sub 2}
Dagdigian, Paul J.
2015-08-07
Transport properties for collisions of hydrogen atoms with CO and CO{sub 2} have been computed by means of quantum scattering calculations. The carbon oxides are important species in hydrocarbon combustion. The following potential energy surfaces (PES’s) for the interaction of the molecule fixed in its equilibrium geometry were employed: for H–CO, the PES was taken from the work of Song et al. [J. Phys. Chem. A 117, 7571 (2013)], while the PES for H–CO{sub 2} was computed in this study by a restricted coupled cluster method that included single, double, and (perturbatively) triple excitations. The computed transport properties were found to be significantly different from those computed by the conventional approach that employs isotropic Lennard-Jones (12-6) potentials. The effect of using the presently computed accurate transport properties in 1-dimensional combustion simulations of methane-air flames was investigated.
Accurate transport properties for H-CO and H-CO2
NASA Astrophysics Data System (ADS)
Dagdigian, Paul J.
2015-08-01
Transport properties for collisions of hydrogen atoms with CO and CO2 have been computed by means of quantum scattering calculations. The carbon oxides are important species in hydrocarbon combustion. The following potential energy surfaces (PES's) for the interaction of the molecule fixed in its equilibrium geometry were employed: for H-CO, the PES was taken from the work of Song et al. [J. Phys. Chem. A 117, 7571 (2013)], while the PES for H-CO2 was computed in this study by a restricted coupled cluster method that included single, double, and (perturbatively) triple excitations. The computed transport properties were found to be significantly different from those computed by the conventional approach that employs isotropic Lennard-Jones (12-6) potentials. The effect of using the presently computed accurate transport properties in 1-dimensional combustion simulations of methane-air flames was investigated.
Optical and thermodynamic properties of a plastic plasma
Kamrukov, A.S.; Kozlov, N.P.; Protasov, Yu.S.; Chuvashev, S.N.
1987-10-01
The results of calculating the properties of an equilibrium plasma of plastic at a temperature of from 1 to 100 eV are given, according to which it is possible to model the radiation-gas-dynamic processes in the multigroup approximation. The techniques for determining the radiative absorption coefficient provided for calculating the photoionized spectra in the vacuum ultraviolet while taking into account the observed similarity in cross section, individual consideration of the contributions of numerous calculations (up to 100 per ion) of the excited states, bremsstrahlung photo-processes, negative ions, etc. The results of the calculations are discussed.
Thermodynamic and mechanical properties of TiC from ab initio calculation
Dang, D. Y.; Fan, J. L.; Gong, H. R.
2014-07-21
The temperature-dependent thermodynamic and mechanical properties of TiC are systematically investigated by means of a combination of density-functional theory, quasi-harmonic approximation, and thermal electronic excitation. It is found that the quasi-harmonic Debye model should be pertinent to reflect thermodynamic properties of TiC, and the elastic properties of TiC decease almost linearly with the increase of temperature. Calculations also reveal that TiC possesses a pronounced directional pseudogap across the Fermi level, mainly due to the strong hybridization of Ti 3d and C 2p states. Moreover, the strong covalent bonding of TiC would be enhanced (reduced) with the decrease (increase) of temperature, while the change of volume (temperature) should have negligible effect on density of states at the Fermi level. The calculated results agree well with experimental observations in the literature.
An Equation of State for the Thermodynamic Properties of Cyclohexane
Zhou, Yong Liu, Jun; Penoncello, Steven G.; Lemmon, Eric W.
2014-12-15
An equation of state for cyclohexane has been developed using the Helmholtz energy as the fundamental property with independent variables of density and temperature. Multi-property fitting technology was used to fit the equation of state to data for pρT, heat capacities, sound speeds, virial coefficients, vapor pressures, and saturated densities. The equation of state was developed to conform to the Maxwell criteria for two-phase vapor-liquid equilibrium states, and is valid from the triple-point temperature to 700 K, with pressures up to 250 MPa and densities up to 10.3 mol dm{sup −3}. In general, the uncertainties (k = 2, indicating a level of confidence of 95%) in density for the equation of state are 0.1% (liquid and vapor) up to 500 K, and 0.2% above 500 K, with higher uncertainties within the critical region. Between 283 and 473 K with pressures lower than 30 MPa, the uncertainty is as low as 0.03% in density in the liquid phase. The uncertainties in the speed of sound are 0.2% between 283 and 323 K in the liquid, and 1% elsewhere. Other uncertainties are 0.05% in vapor pressure and 2% in heat capacities. The behavior of the equation of state is reasonable within the region of validity and at higher and lower temperatures and pressures. A detailed analysis has been performed in this article.
Thermodynamic properties and atomic structure of Ca-based liquid alloys
NASA Astrophysics Data System (ADS)
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
Impact of pairing on thermodynamical properties of stellar matter
NASA Astrophysics Data System (ADS)
Burrello, S.; Aymard, F.; Colonna, M.; Gulminelli, F.; Raduta, Ad. R.
2016-05-01
Superfluidity in the crust is a key ingredient for the cooling properties of proto-neutron stars. Investigations on crust superfluidity carried out so far typically assumed that the cluster component was given by a single representative nucleus and did not consider the fact that at finite temperature a wide distribution of nuclei is expected to be populated at a given crust pressure condition. We want to assess the importance of this distribution on the calculation of the heat capacity in the inner crust, in the framework of an extended NSE model. We additionally show that it is very important to consider the temperature evolution of the proton fraction, imposed by the β-equilibrium condition, for a quantitatively reliable estimation of the heat capacity.
Niu, Zhen-Wei; Zeng, Zhao-Yi; Hu, Cui-E; Cai, Ling-Cang; Chen, Xiang-Rong
2015-01-07
The thermodynamic properties of CeO{sub 2} have been reevaluated by a simple but accurate scheme. All our calculations are based on the self-consistent ab initio lattice dynamical (SCAILD) method that goes beyond the quasiharmonic approximation. Through this method, the effects of phonon-phonon interactions are included. The obtained thermodynamic properties and phonon dispersion relations are in good agreement with experimental data when considering the correction of phonon-phonon interaction. We find that the correction of phonon-phonon interaction is equally important and should not be neglected. At last, by comparing with quasiharmonic approximation, the present scheme based on SCAILD method is probably more suitable for high temperature systems.
Bandura, Andrei V; Porsev, Vitaly V; Evarestov, Robert A
2016-03-15
A zone-folding (ZF) approach is applied for the estimation of the phonon contributions to thermodynamic properties of carbon-and ZrS2 -based nanotubes (NTs) of hexagonal morphology with different chiralities. The results obtained are compared with those from the direct calculation of the thermodynamic properties of NTs using PBE0 hybrid exchange-correlation functional. The phonon contribution to the stability of NTs proved to be negligible for the internal energy and small for the Helmholtz free energy. It is found that the ZF approach allows us an accurate estimation of phonon contributions to internal energy, but slightly overestimates the phonon contributions to entropy. © 2015 Wiley Periodicals, Inc. PMID:26519863
NASA Technical Reports Server (NTRS)
Jacobsen, Richard T.; Stewart, Richard B.
1973-01-01
Tables of thermodynamic properties of nitrogen are presented for the liquid and vapor phases for temperatures from the freezing line to 2000K and pressures to 10,000 bar. The tables include values of density, internal energy, enthalpy, entropy, isochoric heat capacity, isobaric heat capacity velocity of sound, the isotherm derivative, and the isochor derivative. The thermodynamic property tables are based on an equation of state, P=P (p,T), which accurately represents liquid and gaseous nitrogen for the range of pressures and temperatures covered by the tables. Comparisons of property values calculated from the equation of state with measured values for P-p-T, heat capacity, enthalpy, latent heat, and velocity of sound are included to illustrate the agreement between the experimental data and the tables of properties presented here. The coefficients of the equation of state were determined by a weighted least squares fit to selected P-p-T data and, simultaneously, to isochoric heat capacity data determined by corresponding states analysis from oxygen data, and to data which define the phase equilibrium criteria for the saturated liquid and the saturated vapor. The vapor pressure equation, melting curve equation, and an equation to represent the ideal gas heat capacity are also presented. Estimates of the accuracy of the equation of state, the vapor pressure equation, and the ideal gas heat capacity equation are given. The equation of state, derivatives of the equation, and the integral functions for calculating derived thermodynamic properties are included.
Vibrational and thermodynamic properties of α-, β-, γ-, and 6, 6, 12-graphyne structures.
Perkgöz, Nihan Kosku; Sevik, Cem
2014-05-01
Electronic, vibrational, and thermodynamic properties of different graphyne structures, namely α-, β-, γ-, and 6, 6, 12-graphyne, are investigated through first principles-based quasi-harmonic approximation by using phonon dispersions predicted from density-functional perturbation theory. Similar to graphene, graphyne was shown to exhibit a structure with extraordinary electronic features, mechanical hardness, thermal resistance, and very high conductivity from different calculation methods. Hence, characterizing its phonon dispersions and vibrational and thermodynamic properties in a systematic way is of great importance for both understanding its fundamental molecular properties and also figuring out its phase stability issues at different temperatures. Thus, in this research work, thermodynamic stability of different graphyne allotropes is assessed by investigating vibrational properties, lattice thermal expansion coefficients, and Gibbs free energy. According to our results, although the imaginary vibrational frequencies exist for β-graphyne, there is no such a negative behavior for α-, γ-, and 6, 6, 12-graphyne structures. In general, the Grüneisen parameters and linear thermal expansion coefficients of these structures are calculated to be rather more negative when compared to those of the graphene structure. In addition, the predicted difference between the binding energies per atom for the structures of graphene and graphyne points out that graphyne networks have relatively lower phase stability in comparison with the graphene structures. PMID:24737253
Thermodynamic properties by non-calorimetric methods. Progress report, August 1, 1988--July 31, 1989
Steele, W.V.; Chirico, R.D.; Collier, W.B.; Strube, M.M. |
1989-12-31
This three year research program provides a valuable complement to the experimental programs currently in progress at NIPER for the Advanced Research and Technology Development (AR and TD) and Advanced Exploration and Process Technology (AEPT) divisions of the Department of Energy. These experimental programs are focused on the calorimetric determination of thermodynamic properties of key polynuclear heteroatom-containing aromatic molecules. This project for the Office of Energy Research focuses on the non-calorimetric determination of thermodynamic properties through the extension of existing correlation methodologies and through molecular spectroscopy with statistical mechanics. The paper discusses progress in three areas: (1) Improvement of thermochemical and thermophysical property predictions via enhancement of group-contribution methods using two approaches, namely, development and improvement of group-contribution parameters via correlations involving the expanded modern thermodynamics data base and development of group-contribution parameters via molecular spectroscopy and statistical mechanics of key monocyclic organic compounds; (2) Molecular spectroscopy and statistical mechanics: equipment development and developments in interpretation and assignment of spectra; and (3) Thermophysical property correlations.
Theoretical Investigations on the Elastic and Thermodynamic Properties of Rhenium Phosphide
NASA Astrophysics Data System (ADS)
Wei, Qun; Yan, Haiyan; Zhu, Xuanmin; Lin, Zhengzhe; Yao, Ronghui
2016-01-01
Structural, mechanical, and electronic properties of orthorhombic rhenium phosphide (Re2P) are systematically investigated by using first principles calculations. The elastic constants and anisotropy of elastic properties are obtained. The metallic character of Re2P 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 Grüneisen 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
NASA Astrophysics Data System (ADS)
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.
Elastic and thermodynamic properties of Fe3Ga from first-principles calculations
NASA Astrophysics Data System (ADS)
Lin, Ya-Ning; Li, Lin-Ling; Yan, Xiang-Hong; Zhang, Ya-Ping; Zhang, Dong-yun; Zhang, Peng
2016-03-01
First-principles calculations within the framework of density functional theory (DFT) are performed to investigate the elastic and thermodynamic properties of DO3-type Fe3Ga alloy. The obtained lattice constants and the bulk modulus are in good agreement with available experimental data. In terms of the calculated formation energy and Poisson's ratio, the Fe3Ga alloy is mechanically stable and exhibit a negative Poisson's ratio of -0.81 along the <110> direction. The thermodynamic properties such as the Gibbs free energy, thermal expansion, and the specific heat are obtained by the first-principles phonon calculations with the quasiharmonic approximation method. The predicted coefficient of linear thermal expansion and specific heat may provide a helpful reference for experimental work.
Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids
Reis, P. M.; Carvalho, P. J.; Lopes-da-Silva, J. A.; Esperança, J. M. S. S.; Araújo, J. M. M.; Rebelo, L. P. N.; Freire, M. G.; Pereiro, A. B.
2016-01-01
This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids.
Ab Initio Calculation of Structure and Thermodynamic Properties of Zintl Aluminide SrAl2
NASA Astrophysics Data System (ADS)
Fu, Zhi-Jian; Jia, Li-Jun; Xia, Ji-Hong; Tang, Ke; Li, Zhao-Hong; Sun, Xiao-Wei; Chen, Qi-Feng
2015-12-01
The structural and thermodynamic properties of the orthorhombic and cubic structure SrAl2 at pressure and temperature are investigated by using the ab initio plane-wave pseudopotential density functional theory methodwithin 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 SrAl2 are calculated by the quasi-harmonic Debye model. The pressure-volume relationship and the variations inthe thermal expansion α are obtained systematically in the pressure and temperature ranges of 0-5 GPa and 0-500 K, respectively.
Numerical prediction of the thermodynamic properties of ternary Al-Ni-Hf alloys
NASA Astrophysics Data System (ADS)
Romanowska, Jolanta; Kotowski, Sławomir; Zagula-Yavorska, Maryana
2014-10-01
Thermodynamic properties of ternary Al-Hf-Ni system, such as exG, μAl, μNi and μZr at 1373K were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting exG 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 exG on all legs of the triangle are known. exG and Lijk ternary interaction parameters in the Muggianu extension of the Redlich-Kister formalism are calculated numerically using Wolfram Mathematica 9 software.
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
NASA Astrophysics Data System (ADS)
Xing, Mengjiang; Li, Binhua; Yu, Zhengtao; Chen, Qi
2016-04-01
The structural, mechanical, electronic and thermodynamic properties of the tetragonal structure germanium carbonitride (t-GeCN) were first investigated using the density function theory with the ultrasoft psedopotential scheme in the frame of the generalized gradient approximation and the local density approximation. The elastic constants have confirmed that the t-GeCN is mechanically stable and phonon spectra have confirmed that the t-GeCN is dynamically stable. The anisotropy studies show that t-GeCN exhibits a larger anisotropy in its Poisson's ratio, Young's modulus, shear modulus, sound velocities and universal elastic anisotropy index. Electronic structure study shows that t-GeCN is an indirect semiconductor with band gap of 0.628 eV. The thermodynamic properties of t-GeCN, including Debye temperature, heat capacity, Grüneisen parameter and thermal expansion coefficient are investigated utilizing the quasi-harmonic Debye model.
Coarse-grained red blood cell model with accurate mechanical properties, rheology and dynamics.
Fedosov, Dmitry A; Caswell, Bruce; Karniadakis, George E
2009-01-01
We present a coarse-grained red blood cell (RBC) model with accurate and realistic mechanical properties, rheology and dynamics. The modeled membrane is represented by a triangular mesh which incorporates shear inplane energy, bending energy, and area and volume conservation constraints. The macroscopic membrane elastic properties are imposed through semi-analytic theory, and are matched with those obtained in optical tweezers stretching experiments. Rheological measurements characterized by time-dependent complex modulus are extracted from the membrane thermal fluctuations, and compared with those obtained from the optical magnetic twisting cytometry results. The results allow us to define a meaningful characteristic time of the membrane. The dynamics of RBCs observed in shear flow suggests that a purely elastic model for the RBC membrane is not appropriate, and therefore a viscoelastic model is required. The set of proposed analyses and numerical tests can be used as a complete model testbed in order to calibrate the modeled viscoelastic membranes to accurately represent RBCs in health and disease. PMID:19965026
Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; Pronobis, Wiktor; von Lilienfeld, O. Anatole; Müller, Klaus -Robert; Tkatchenko, Alexandre
2015-06-04
Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstratemore » prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.« less
Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; Pronobis, Wiktor; von Lilienfeld, O. Anatole; Müller, Klaus -Robert; Tkatchenko, Alexandre
2015-06-04
Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstrate prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.