Thermodynamics--A Practical Subject.

ERIC Educational Resources Information Center

Jones, Hugh G.

1984-01-01

Provides a simplified, synoptic overview of the area of thermodynamics, enumerating and explaining the four basic laws, and introducing the mathematics involved in a stepwise fashion. Discusses such basic tools of thermodynamics as enthalpy, entropy, Helmholtz free energy, and Gibbs free energy, and their uses in problem solving. (JM)

Numerical Mantle Convection Models With a Flexible Thermodynamic Interface

NASA Astrophysics Data System (ADS)

van den Berg, A. P.; Jacobs, M. H.; de Jong, B. H.

2001-12-01

Accurate material properties are needed for deep mantle (P,T) conditions in order to predict the longterm behavior of convection planetary mantles. Also the interpretation of seismological observations concerning the deep mantle in terms of mantle flow models calls for a consistent thermodynamical description of the basic physical parameters. We have interfaced a compressible convection code using the anelastic liquid approach based on finite element methods, to a database containing a full thermodynamic description of mantle silicates (Ita and King, J. Geophys. Res., 99, 15,939-15,940, 1994). The model is based on high resolution (P,T) tables of the relevant thermodynamic properties containing typically 50 million (P,T) table gridpoints to obtain resolution in (P,T) space of 1 K and an equivalent of 1 km. The resulting model is completely flexible such that numerical mantle convection experiments can be performed for any mantle composition for which the thermodynamic database is available. We present results of experiments for 2D cartesian models using a data base for magnesium-iron silicate in a pyrolitic composition (Stixrude and Bukowinski, Geoph.Monogr.Ser., 74, 131-142, 1993) and a recent thermodynamical model for magnesium silicate for the complete mantle (P,T) range, (Jacobs and Oonk, Phys. Chem. Mineral, 269, inpress 2001). Preliminary results of bulksound velocity distribution derived in a consistent way from the convection results and the thermodynamic database show a `realistic' mantle profile with bulkvelocity variations decreasing from several percent in the upper mantle to less than a percent in the deep lower mantle.

Steam tables for pure water as an ActiveX component in Visual Basic 6.0

NASA Astrophysics Data System (ADS)

Verma, Mahendra P.

2003-11-01

The IAPWS-95 formulation for the thermodynamic properties of pure water was implemented as an ActiveX component ( SteamTables) in Visual Basic 6.0. For input parameters as temperature ( T=190-2000 K) and pressure ( P=3.23×10 -8-10,000 MPa) the program SteamTables calculates the following properties: volume ( V), density ( D), compressibility factor ( Z0), internal energy ( U), enthalpy ( H), Gibbs free energy ( G), Helmholtz free energy ( A), entropy ( S), heat capacity at constant pressure ( Cp), heat capacity at constant volume ( Cv), coefficient of thermal expansion ( CTE), isothermal compressibility ( Ziso), velocity of sound ( VelS), partial derivative of P with T at constant V (d Pd T), partial derivative of T with V at constant P (d Td V), partial derivative of V with P at constant T (d Vd P), Joule-Thomson coefficient ( JTC), isothermal throttling coefficient ( IJTC), viscosity ( Vis), thermal conductivity ( ThrmCond), surface tension ( SurfTen), Prandtl number ( PrdNum) and dielectric constant ( DielCons) for the liquid and vapor phases of pure water. It also calculates T as a function of P (or P as a function of T) along the sublimation, saturation and critical isochor curves, depending on the values of P (or T). The SteamTables can be incorporated in a program in any computer language, which supports object link embedding (OLE) in the Windows environment. An application of SteamTables is illustrated in a program in Visual Basic 6.0 to tabulate the values of the thermodynamic properties of water and vapor. Similarly, four functions, Temperature(Press), Pressure(Temp), State(Temp, Press) and WtrStmTbls(Temp, Press, Nphs, Nprop), where Temp, Press, Nphs and Nprop are temperature, pressure, phase number and property number, respectively, are written in Visual Basic for Applications (VBA) to use the SteamTables in a workbook in MS-Excel.

On the time arrows, and randomness in cosmological signals

NASA Astrophysics Data System (ADS)

Gurzadyan, V. G.; Sargsyan, S.; Yegorian, G.

2013-09-01

Arrows of time - thermodynamical, cosmological, electromagnetic, quantum mechanical, psychological - are basic properties of Nature. For a quantum system-bath closed system the de-correlated initial conditions and no-memory (Markovian) dynamics are outlined as necessary conditions for the appearance of the thermodynamical arrow. The emergence of the arrow for the system evolving according to non-unitary dynamics due to the presence of the bath, then, is a result of limited observability, and we conjecture the arrow in the observable Universe as determined by the dark sector acting as a bath. The voids in the large scale matter distribution induce hyperbolicity of the null geodesics, with possible observational consequences.

Magnetic and thermodynamic properties of Ising model with borophene structure in a longitudinal magnetic field

NASA Astrophysics Data System (ADS)

Shi, Kaile; Jiang, Wei; Guo, Anbang; Wang, Kai; Wu, Chuang

2018-06-01

The magnetic and thermodynamic properties of borophene structure have been studied for the first time by Monte Carlo simulation. Two-dimensional borophene structure consisting of seven hexagonal B36 units is described by Ising model. Each B36 basic unit includes three benzene-like with spin-3/2. The general formula for the borophene structure is given. The numerical results of the magnetization, the magnetic susceptibility, the internal energy and the specific heat are studied with various parameters. The possibility to test the predicted magnetism in experiment are illustrated, for instance, the maximum on the magnetization curve. The multiple hysteresis loops and the magnetization plateaus are sensitive to the ferromagnetic or ferrimagnetic exchange coupling in borophene structure. The results show the borophene structure could have applications in spintronics, which deserves further studies in experiments.

Lattice model of linear telechelic polymer melts. II. Influence of chain stiffness on basic thermodynamic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu; Freed, Karl F., E-mail: freed@uchicago.edu; Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

2015-07-14

The lattice cluster theory (LCT) for semiflexible linear telechelic melts, developed in Paper I, is applied to examine the influence of chain stiffness on the average degree of self-assembly and the basic thermodynamic properties of linear telechelic polymer melts. Our calculations imply that chain stiffness promotes self-assembly of linear telechelic polymer melts that assemble on cooling when either polymer volume fraction ϕ or temperature T is high, but opposes self-assembly when both ϕ and T are sufficiently low. This allows us to identify a boundary line in the ϕ-T plane that separates two regions of qualitatively different influence of chainmore » stiffness on self-assembly. The enthalpy and entropy of self-assembly are usually treated as adjustable parameters in classical Flory-Huggins type theories for the equilibrium self-assembly of polymers, but they are demonstrated here to strongly depend on chain stiffness. Moreover, illustrative calculations for the dependence of the entropy density of linear telechelic polymer melts on chain stiffness demonstrate the importance of including semiflexibility within the LCT when exploring the nature of glass formation in models of linear telechelic polymer melts.« less

Atomistic modeling of high temperature uranium-zirconium alloy structure and thermodynamics

NASA Astrophysics Data System (ADS)

Moore, A. P.; Beeler, B.; Deo, C.; Baskes, M. I.; Okuniewski, M. A.

2015-12-01

A semi-empirical Modified Embedded Atom Method (MEAM) potential is developed for application to the high temperature body-centered-cubic uranium-zirconium alloy (γ-U-Zr) phase and employed with molecular dynamics (MD) simulations to investigate the high temperature thermo-physical properties of U-Zr alloys. Uranium-rich U-Zr alloys (e.g. U-10Zr) have been tested and qualified for use as metallic nuclear fuel in U.S. fast reactors such as the Integral Fast Reactor and the Experimental Breeder Reactors, and are a common sub-system of ternary metallic alloys like U-Pu-Zr and U-Zr-Nb. The potential was constructed to ensure that basic properties (e.g., elastic constants, bulk modulus, and formation energies) were in agreement with first principles calculations and experimental results. After which, slight adjustments were made to the potential to fit the known thermal properties and thermodynamics of the system. The potentials successfully reproduce the experimental melting point, enthalpy of fusion, volume change upon melting, thermal expansion, and the heat capacity of pure U and Zr. Simulations of the U-Zr system are found to be in good agreement with experimental thermal expansion values, Vegard's law for the lattice constants, and the experimental enthalpy of mixing. This is the first simulation to reproduce the experimental thermodynamics of the high temperature γ-U-Zr metallic alloy system. The MEAM potential is then used to explore thermodynamics properties of the high temperature U-Zr system including the constant volume heat capacity, isothermal compressibility, adiabatic index, and the Grüneisen parameters.

An approach to get thermodynamic properties from speed of sound

NASA Astrophysics Data System (ADS)

Núñez, M. A.; Medina, L. A.

2017-01-01

An approach for estimating thermodynamic properties of gases from the speed of sound u, is proposed. The square u2, the compression factor Z and the molar heat capacity at constant volume C V are connected by two coupled nonlinear partial differential equations. Previous approaches to solving this system differ in the conditions used on the range of temperature values [Tmin,Tmax]. In this work we propose the use of Dirichlet boundary conditions at Tmin, Tmax. The virial series of the compression factor Z = 1+Bρ+Cρ2+… and other properties leads the problem to the solution of a recursive set of linear ordinary differential equations for the B, C. Analytic solutions of the B equation for Argon are used to study the stability of our approach and previous ones under perturbation errors of the input data. The results show that the approach yields B with a relative error bounded basically by that of the boundary values and the error of other approaches can be some orders of magnitude lager.

The role of Minkowski functionals in the thermodynamics of two-phase systems

NASA Astrophysics Data System (ADS)

Eder, Gerhard

2018-01-01

Within this work quite old concepts from integral geometry are applied to classical equilibrium thermodynamics of two-phase systems. In addition to the area as basic interfacial quantity the full geometric characterization of the interface is used, which includes the two remaining Minkowski functionals, the mean curvature integral and the Euler Poincaré characteristic. The basic energetic characteristic of the interface (i.e. the interfacial tension) is extended by two additional properties: edge force as (up to a factor 4/π) the work necessary to form a right-angled edge of unit length, and item energy as the work to form an additional item in the phase morphology. Both quantities are of increasing importance, when going to micro- and nano-scales. They are subsequently used for interfaces of arbitrary shape to derive a relationship extending the classical Young-Laplace equation. The supplementary contribution is proportional to the Gaussian curvature, with the edge force as proportionality constant. Furthermore, both edge force and item energy are shown to be applicable to the description of crystal nucleation in liquids (extending the classical Becker Döring theory). It turns out, that even above the thermodynamic melting temperature stable nuclei can be present in the liquid phase. They immediately are able to grow when quenched to a temperature below a characteristic temperature. This temperature of spontaneous homogeneous nucleation is simply connected to the edge force, whereas the number of stable clusters per unit volume is dominated by the item energy. Finally, the additional energetic interfacial properties are used in a similar way to characterize the stability of emulsions.

Understanding AlN Obtaining Through Computational Thermodynamics Combined with Experimental Investigation

NASA Astrophysics Data System (ADS)

Florea, R. M.

2017-06-01

Basic material concept, technology and some results of studies on aluminum matrix composite with dispersive aluminum nitride reinforcement was shown. Studied composites were manufactured by „in situ” technique. Aluminum nitride (AlN) has attracted large interest recently, because of its high thermal conductivity, good dielectric properties, high flexural strength, thermal expansion coefficient matches that of Si and its non-toxic nature, as a suitable material for hybrid integrated circuit substrates. AlMg alloys are the best matrix for AlN obtaining. Al2O3-AlMg, AlN-Al2O3, and AlN-AlMg binary diagrams were thermodynamically modelled. The obtained Gibbs free energies of components, solution parameters and stoichiometric phases were used to build a thermodynamic database of AlN- Al2O3-AlMg system. Obtaining of AlN with Liquid-phase of AlMg as matrix has been studied and compared with the thermodynamic results. The secondary phase microstructure has a significant effect on the final thermal conductivity of the obtained AlN. Thermodynamic modelling of AlN-Al2O3-AlMg system provided an important basis for understanding the obtaining behavior and interpreting the experimental results.

Estimation of the viscosities of liquid binary alloys

NASA Astrophysics Data System (ADS)

Wu, Min; Su, Xiang-Yu

2018-01-01

As one of the most important physical and chemical properties, viscosity plays a critical role in physics and materials as a key parameter to quantitatively understanding the fluid transport process and reaction kinetics in metallurgical process design. Experimental and theoretical studies on liquid metals are problematic. Today, there are many empirical and semi-empirical models available with which to evaluate the viscosity of liquid metals and alloys. However, the parameter of mixed energy in these models is not easily determined, and most predictive models have been poorly applied. In the present study, a new thermodynamic parameter Δ G is proposed to predict liquid alloy viscosity. The prediction equation depends on basic physical and thermodynamic parameters, namely density, melting temperature, absolute atomic mass, electro-negativity, electron density, molar volume, Pauling radius, and mixing enthalpy. Our results show that the liquid alloy viscosity predicted using the proposed model is closely in line with the experimental values. In addition, if the component radius difference is greater than 0.03 nm at a certain temperature, the atomic size factor has a significant effect on the interaction of the binary liquid metal atoms. The proposed thermodynamic parameter Δ G also facilitates the study of other physical properties of liquid metals.

Physico-chemical properties of aqueous drug solutions: From the basic thermodynamics to the advanced experimental and simulation results.

PubMed

Bellich, Barbara; Gamini, Amelia; Brady, John W; Cesàro, Attilio

2018-04-05

The physical chemical properties of aqueous solutions of model compounds are illustrated in relation to hydration and solubility issues by using three perspectives: thermodynamic, spectroscopic and molecular dynamics simulations. The thermodynamic survey of the fundamental backgrounds of concentration dependence and experimental solubility results show some peculiar behavior of aqueous solutions with several types of similar solutes. Secondly, the use of a variety of experimental spectroscopic devices, operating under different experimental conditions of dimension and frequency, has produced a large amount of structural and dynamic data on aqueous solutions showing the richness of the information produced, depending on where and how the experiment is carried out. Finally, the use of molecular dynamics computational work is presented to highlight how the different types of solute functional groups and surface topologies organize adjacent water molecules differently. The highly valuable contribution of computer simulation studies in providing molecular explanations for experimental deductions, either of a thermodynamic or spectroscopic nature, is shown to have changed the current knowledge of many aqueous solution processes. While this paper is intended to provide a collective view on the latest literature results, still the presentation aims at a tutorial explanation of the potentials of the three methodologies in the field of aqueous solutions of pharmaceutical molecules. Copyright © 2018. Published by Elsevier B.V.

Available Energy via Nonequilibrium Thermodynamics.

ERIC Educational Resources Information Center

Woollett, E. L.

1979-01-01

Presents basic relations involving the concept of available energy that are derived from the local equations of nonequilibrium thermodynamics. The equations and applications of the local thermodynamic equilibrium LTD model are also presented. (HM)

Characterization of the superconducting state in hafnium hydride under high pressure

NASA Astrophysics Data System (ADS)

Duda, A. M.; Szewczyk, K. A.; Jarosik, M. W.; Szcześniak, K. M.; Sowińska, M. A.; Szcześniak, D.

2018-05-01

The hydrogen-rich compounds at high pressure may exhibit notably high superconducting transition temperatures. In the paper, we have calculated the basic thermodynamic parameters of the superconducting state in two selected phases of HfH2 hydride under high-pressure respectively at 180 GPa for Cmma and 260 GPa for P21 / m . Calculations has been conducted in the framework of the Eliashberg formalism. In particular, we have determined the values of the critical temperature (TC) to be equal to 8 K and 13 K for the Cmma and P21 / m phases, respectively. Moreover, we have estimated other thermodynamic properties such as the order parameter (Δ (T)) , the thermodynamic critical field (HC (T)) , and the specific heat for the normal (CN) and superconducting (CS) state. Finally, we have shown that the characteristic ratios: RΔ = 2 Δ (0) /kBTC and RC = ΔC (TC) /CN (TC) , which are related to the above thermodynamic functions, slightly differ from the predictions of the Bardeen-Cooper-Schrieffer theory due to the strong-coupling and retardation effects.

Size- and shape-dependent surface thermodynamic properties of nanocrystals

NASA Astrophysics Data System (ADS)

Fu, Qingshan; Xue, Yongqiang; Cui, Zixiang

2018-05-01

As the fundamental properties, the surface thermodynamic properties of nanocrystals play a key role in the physical and chemical changes. However, it remains ambiguous about the quantitative influence regularities of size and shape on the surface thermodynamic properties of nanocrystals. Thus by introducing interface variables into the Gibbs energy and combining Young-Laplace equation, relations between the surface thermodynamic properties (surface Gibbs energy, surface enthalpy, surface entropy, surface energy and surface heat capacity), respectively, and size of nanocrystals with different shapes were derived. Theoretical estimations of the orders of the surface thermodynamic properties of nanocrystals agree with available experimental values. Calculated results of the surface thermodynamic properties of Au, Bi and Al nanocrystals suggest that when r > 10 nm, the surface thermodynamic properties linearly vary with the reciprocal of particle size, and when r < 10 nm, the effect of particle size on the surface thermodynamic properties becomes greater and deviates from linear variation. For nanocrystals with identical equivalent diameter, the more the shape deviates from sphere, the larger the surface thermodynamic properties (absolute value) are.

Marine polysaccharides in microencapsulation and application to aquaculture: "from sea to sea".

PubMed

Borgogna, Massimiliano; Bellich, Barbara; Cesàro, Attilio

2011-12-01

This review's main objective is to discuss some physico-chemical features of polysaccharides as intrinsic determinants for the supramolecular structures that can efficiently provide encapsulation of drugs and other biological entities. Thus, the general characteristics of some basic polysaccharides are outlined in terms of their conformational, dynamic and thermodynamic properties. The analysis of some polysaccharide gelling properties is also provided, including the peculiarity of the charged polysaccharides. Then, the way the basic physical chemistry of polymer self-assembly is made in practice through the laboratory methods is highlighted. A description of the several literature procedures used to influence molecular interactions into the macroscopic goal of the encapsulation is given with an attempt at classification. Finally, a practical case study of specific interest, the use of marine polysaccharide matrices for encapsulation of vaccines in aquaculture, is reported.

Nanothermodynamics Applied to Thermal Processes in Heterogeneous Materials

DTIC Science & Technology

2012-08-03

models agree favorably with a wide range of measurements of local thermal and dynamic properties. Progress in understanding basic thermodynamic...Monte- Carlo (MC) simulations of the Ising model .7 The solid black lines in Fig. 4 show results using the uncorrected (Metropolis) algorithm on the...parameter g=0.5 (green, dash-dot), g=1 (black, solid ), and g=2 (blue, dash-dot-dot). Note the failure of the standard Ising model (g=0) to match

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.

Misconceptions regarding basic thermodynamics and enzyme kinetics have led to erroneous conclusions regarding the metabolic importance of lactate dehydrogenase isoenzyme expression.

PubMed

Bak, Lasse K; Schousboe, Arne

2017-11-01

Lactate dehydrogenase (LDH) catalyzes the interconversion of pyruvate and lactate involving the coenzyme NAD + . Part of the foundation for the proposed shuttling of lactate from astrocytes to neurons during brain activation is the differential distribution of LDH isoenzymes between the two cell types. In this short review, we outline the basic kinetic properties of the LDH isoenzymes expressed in neurons and astrocytes, and argue that the distribution of LDH isoenzymes does not in any way govern directional flow of lactate between the two cellular compartments. The two main points are as follows. First, in line with the general concept of chemical catalysis, enzymes do not influence the thermodynamic equilibrium of a chemical reaction but merely the speed at which equilibrium is obtained. Thus, differential distribution of LDH isoenzymes with different kinetic parameters does not predict which cells are producing and which are consuming lactate. Second, the thermodynamic equilibrium of the reaction is toward the reduced substrate (i.e., lactate), which is reflected in the concentrations measured in brain tissue, suggesting that the reaction is at near-equilibrium at steady state. To conclude, the cellular distribution of LDH isoenzymes is of little if any consequence in determining any directional flow of lactate between neurons and astrocytes. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Formation enthalpies for transition metal alloys using machine learning

NASA Astrophysics Data System (ADS)

Ubaru, Shashanka; Miedlar, Agnieszka; Saad, Yousef; Chelikowsky, James R.

2017-06-01

The enthalpy of formation is an important thermodynamic property. Developing fast and accurate methods for its prediction is of practical interest in a variety of applications. Material informatics techniques based on machine learning have recently been introduced in the literature as an inexpensive means of exploiting materials data, and can be used to examine a variety of thermodynamics properties. We investigate the use of such machine learning tools for predicting the formation enthalpies of binary intermetallic compounds that contain at least one transition metal. We consider certain easily available properties of the constituting elements complemented by some basic properties of the compounds, to predict the formation enthalpies. We show how choosing these properties (input features) based on a literature study (using prior physics knowledge) seems to outperform machine learning based feature selection methods such as sensitivity analysis and LASSO (least absolute shrinkage and selection operator) based methods. A nonlinear kernel based support vector regression method is employed to perform the predictions. The predictive ability of our model is illustrated via several experiments on a dataset containing 648 binary alloys. We train and validate the model using the formation enthalpies calculated using a model by Miedema, which is a popular semiempirical model used for the prediction of formation enthalpies of metal alloys.

On introduction of artificial intelligence elements to heat power engineering

NASA Astrophysics Data System (ADS)

Dregalin, A. F.; Nazyrova, R. R.

1993-10-01

The basic problems of 'the thermodynamic intelligence' of personal computers have been outlined. The thermodynamic intellect of personal computers as a concept has been introduced to heat processes occurring in engines of flying vehicles. In particular, the thermodynamic intellect of computers is determined by the possibility of deriving formal relationships between thermodynamic functions. In chemical thermodynamics, a concept of a characteristic function has been introduced.

Marine Polysaccharides in Microencapsulation and Application to Aquaculture: “From Sea to Sea”

PubMed Central

Borgogna, Massimiliano; Bellich, Barbara; Cesàro, Attilio

2011-01-01

This review’s main objective is to discuss some physico-chemical features of polysaccharides as intrinsic determinants for the supramolecular structures that can efficiently provide encapsulation of drugs and other biological entities. Thus, the general characteristics of some basic polysaccharides are outlined in terms of their conformational, dynamic and thermodynamic properties. The analysis of some polysaccharide gelling properties is also provided, including the peculiarity of the charged polysaccharides. Then, the way the basic physical chemistry of polymer self-assembly is made in practice through the laboratory methods is highlighted. A description of the several literature procedures used to influence molecular interactions into the macroscopic goal of the encapsulation is given with an attempt at classification. Finally, a practical case study of specific interest, the use of marine polysaccharide matrices for encapsulation of vaccines in aquaculture, is reported. PMID:22363241

Structure, thermodynamic properties, and phase diagrams of few colloids confined in a spherical pore.

PubMed

Paganini, Iván E; Pastorino, Claudio; Urrutia, Ignacio

2015-06-28

We study a system of few colloids confined in a small spherical cavity with event driven molecular dynamics simulations in the canonical ensemble. The colloidal particles interact through a short range square-well potential that takes into account the basic elements of attraction and excluded-volume repulsion of the interaction among colloids. We analyze the structural and thermodynamic properties of this few-body confined system in the framework of inhomogeneous fluids theory. Pair correlation function and density profile are used to determine the structure and the spatial characteristics of the system. Pressure on the walls, internal energy, and surface quantities such as surface tension and adsorption are also analyzed for a wide range of densities and temperatures. We have characterized systems from 2 to 6 confined particles, identifying distinctive qualitative behavior over the thermodynamic plane T - ρ, in a few-particle equivalent to phase diagrams of macroscopic systems. Applying the extended law of corresponding states, the square well interaction is mapped to the Asakura-Oosawa model for colloid-polymer mixtures. We link explicitly the temperature of the confined square-well fluid to the equivalent packing fraction of polymers in the Asakura-Oosawa model. Using this approach, we study the confined system of few colloids in a colloid-polymer mixture.

Nature of the anomalies in the supercooled liquid state of the mW model of water.

PubMed

Holten, Vincent; Limmer, David T; Molinero, Valeria; Anisimov, Mikhail A

2013-05-07

The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

Nature of the anomalies in the supercooled liquid state of the mW model of water

NASA Astrophysics Data System (ADS)

Holten, Vincent; Limmer, David T.; Molinero, Valeria; Anisimov, Mikhail A.

2013-05-01

The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

Structure, thermodynamic properties, and phase diagrams of few colloids confined in a spherical pore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paganini, Iván E.; Pastorino, Claudio, E-mail: pastor@cnea.gov.ar; Urrutia, Ignacio, E-mail: iurrutia@cnea.gov.ar

2015-06-28

We study a system of few colloids confined in a small spherical cavity with event driven molecular dynamics simulations in the canonical ensemble. The colloidal particles interact through a short range square-well potential that takes into account the basic elements of attraction and excluded-volume repulsion of the interaction among colloids. We analyze the structural and thermodynamic properties of this few-body confined system in the framework of inhomogeneous fluids theory. Pair correlation function and density profile are used to determine the structure and the spatial characteristics of the system. Pressure on the walls, internal energy, and surface quantities such as surfacemore » tension and adsorption are also analyzed for a wide range of densities and temperatures. We have characterized systems from 2 to 6 confined particles, identifying distinctive qualitative behavior over the thermodynamic plane T − ρ, in a few-particle equivalent to phase diagrams of macroscopic systems. Applying the extended law of corresponding states, the square well interaction is mapped to the Asakura-Oosawa model for colloid-polymer mixtures. We link explicitly the temperature of the confined square-well fluid to the equivalent packing fraction of polymers in the Asakura-Oosawa model. Using this approach, we study the confined system of few colloids in a colloid-polymer mixture.« less

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.

Role of basicity and tetrahedral speciation in controlling the thermodynamic properties of silicate liquids, part 1: the system CaO-MgO-Al 2O 3-SiO 2

NASA Astrophysics Data System (ADS)

Beckett, John R.

2002-01-01

Activity coefficients of oxide components in the system CaO-MgO-Al2O3-SiO2 (CMAS) were calculated with the model of Berman (Berman R. G., ;A thermodynamic model for multicomponent melts with application to the system CaO-MgO-Al2O3-SiO2,; Ph.D. dissertation, University of British Columbia, 1983) and used to explore large-scale relationships among these variables and between them and the liquid composition. On the basis of Berman's model, the natural logarithm of the activity coefficient of MgO, ln(γMgOLiq), and ln(γMgOLiq/γSiO2Liq) are nearly linear functions of ln(γCaOLiq). All three of these variables are simple functions of the optical basicity Λ with which they display minima near Λ ∼ 0.54 that are generated by liquids with low ratios of nonbridging to tetrahedral oxygens (NBO/T) (<0.3) and a mole fraction ratio, XSiO2Liq/XAl2O3Liq, in the range 4 to 20. Variations in ln(γCaOLiq) at constant Λ near the minimum are due mostly to liquids with (XCaOLiq + XMgOLiq)/XAl2O3Liq < 1. The correlations with optical basicity imply that the electron donor power is an important factor in determining the thermodynamic properties of aluminosilicate liquids. For a constant NBO/T, ln(γCaOLiq/γAl2O3Liq) and ln(γMgOLiqγAl2O3Liq) form curves in terms of XSiO2Liq/XAl2O3Liq. The same liquids that generate minima in the Λ plots are also associated with minima in ln(γCaOLiqγAl2O3Liq) and ln(γMgOLiqγAl2O3Liq) as a function of XSiO2Liq/XAl2O3Liq. In addition, there are maxima or sharp changes in slope for NBO/T > 0.3, which occur for XSiO2Liq/XAl2O3Liq ranging from ∼0 to ∼6 and increase with increasing NBO/T. The systematic variations in activity coefficients as a function of composition and optical basicity reflect underlying shifts in speciation as the composition of the liquid is changed. On the basis of correlations among the activity coefficients, it is likely that the use of CaO, an exchange component such as SiMg-1 and two of MgO, CaAl2O4, or MgAl2O4 would yield significant savings in the number of parameters required to model the excess free energy surface of liquids over large portions of CMAS relative to the use of oxide end members. Systematic behavior of thermodynamic properties extends to small amounts of other elements dissolved in otherwise CMAS liquids. For example, ln(XFe2+Liq/XFe3+Liq) at constant oxygen fugacity is linearly correlated with ln(γCaOLiq). Similarly, ln(CS), where CS is the sulfide capacity is linearly correlated at constant temperature with each of the optical basicity, ln(aCaOLiq) and ln(γCaOLiq), although the correlation for the latter breaks down for low values of Λ. The well-known systematic behavior of sulfide capacity as a function of optical basicity for systems inside as well as outside CMAS suggests that ln(γCaSLiq) is also a simple function of optical basicity and that the relationships observed among the activity coefficients in CMAS may hold for more complex systems.

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.

Laser engines operating by resonance absorption. [thermodynamic feasibility study

NASA Technical Reports Server (NTRS)

Garbuny, M.; Pechersky, M. J.

1976-01-01

Basic tutorial article on the thermodynamic feasibility of laser engines at the present state of the art. Three main options are considered: (1) laser power applied externally to a heat reservoir (boiler approach); (2) internal heating of working fluid by resonance absorption; and (3) direct conversion of selective excitation into work. Only (2) is considered practically feasible at present. Basic concepts and variants, efficiency relations, upper temperature limits of laser engines, selection of absorbing gases, engine walls, bleaching, thermodynamic cycles of optimized laser engines, laser-powered turbines, laser heat pumps are discussed. Photon engines and laser dissociation engines are also considered.

Cloud and Thermodynamic Parameters Retrieved from Satellite Ultraspectral Infrared Measurements

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Smith, William L.; Larar, Allen M.; Liu, Xu; Taylor, Jonathan P.; Schluessel, Peter; Strow, L. Larrabee; Mango, Stephen A.

2008-01-01

Atmospheric-thermodynamic parameters and surface properties are basic meteorological parameters for weather forecasting. A physical geophysical parameter retrieval scheme dealing with cloudy and cloud-free radiance observed with satellite ultraspectral infrared sounders has been developed and applied to the Infrared Atmospheric Sounding Interferometer (IASI) and the Atmospheric InfraRed Sounder (AIRS). The retrieved parameters presented herein are from radiance data gathered during the Joint Airborne IASI Validation Experiment (JAIVEx). JAIVEx provided intensive aircraft observations obtained from airborne Fourier Transform Spectrometer (FTS) systems, in-situ measurements, and dedicated dropsonde and radiosonde measurements for the validation of the IASI products. Here, IASI atmospheric profile retrievals are compared with those obtained from dedicated dropsondes, radiosondes, and the airborne FTS system. The IASI examples presented here demonstrate the ability to retrieve fine-scale horizontal features with high vertical resolution from satellite ultraspectral sounder radiance spectra.

More than Meets the Eye - Infrared Cameras in Open-Ended University Thermodynamics Labs

NASA Astrophysics Data System (ADS)

Melander, Emil; Haglund, Jesper; Weiszflog, Matthias; Andersson, Staffan

2016-12-01

Educational research has found that students have challenges understanding thermal science. Undergraduate physics students have difficulties differentiating basic thermal concepts, such as heat, temperature, and internal energy. Engineering students have been found to have difficulties grasping surface emissivity as a thermal material property. One potential source of students' challenges with thermal science is the lack of opportunity to visualize energy transfer in intuitive ways with traditional measurement equipment. Thermodynamics laboratories have typically depended on point measures of temperature by use of thermometers (detecting heat conduction) or pyrometers (detecting heat radiation). In contrast, thermal imaging by means of an infrared (IR) camera provides a real-time, holistic image. Here we provide some background on IR cameras and their uses in education, and summarize five qualitative investigations that we have used in our courses.

Partial compilation and revision of basic data in the WATEQ programs

USGS Publications Warehouse

Nordstrom, D. Kirk; Valentine, S.D.; Ball, J.W.; Plummer, Niel; Jones, B.F.

1984-01-01

Several portions of the basic data in the WATEQ series of computer programs (WATEQ, WATEQF, WATEQ2, WATEQ3, and PHREEQE) are compiled. The density and dielectric constant of water and their temperature dependence are evaluated for the purpose of updating the Debye-Huckel solvent parameters in the activity coefficient equations. The standard state thermodynamic properties of the Fe2+ and Fe3+ aqueous ions are refined. The main portion of this report is a comprehensive listing of aluminum hydrolysis constants, aluminum fluoride, aluminum sulfate, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate stability constants, solubility product constants for gibbsite and amorphous aluminum hydroxide, and the standard electrode potentials for Fe (s)/Fe2+(aq) and Fe2 +(aq)/Fe3+(aq). (USGS)

Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ke, Haochen; van der Linde, Christian; Lisy, James M.

2014-06-01

Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

The Physics of Energy

NASA Astrophysics Data System (ADS)

Jaffe, Robert L.; Taylor, Washington

2018-01-01

Part I. Basic Energy Physics and Uses: 1. Introduction; 2. Mechanical energy; 3. Electromagnetic energy; 4. Waves and light; 5. Thermodynamics I: heat and thermal energy; 6. Heat transfer; 7. Introduction to quantum physics; 8. Thermodynamics II: entropy and temperature; 9. Energy in matter; 10. Thermal energy conversion; 11. Internal combustion engines; 12. Phase-change energy conversion; 13. Thermal power and heat extraction cycles; Part II. Energy Sources: 14. The forces of nature; 15. Quantum phenomena in energy systems; 16. An overview of nuclear power; 17. Structure, properties and decays of nuclei; 18. Nuclear energy processes: fission and fusion; 19. Nuclear fission reactors and nuclear fusion experiments; 20. Ionizing radiation; 21. Energy in the universe; 22. Solar energy: solar production and radiation; 23. Solar energy: solar radiation on Earth; 24. Solar thermal energy; 25. Photovoltaic solar cells; 26. Biological energy; 27. Ocean energy flow; 28. Wind: a highly variable resource; 29. Fluids – the basics; 30. Wind turbines; 31. Energy from moving water: hydro, wave, tidal, and marine current power; 32. Geothermal energy; 33. Fossil fuels; Part III. Energy System Issues and Externalities: 34. Energy and climate; 35. Earth's climate: past, present, and future; 36. Energy efficiency, conservation, and changing energy sources; 37. Energy storage; 38. Electricity generation and transmission.

Fundamental properties of high-temperature SF6 mixed with CO2 as a replacement for SF6 in high-voltage circuit breakers

NASA Astrophysics Data System (ADS)

Wang, Weizong; Rong, Mingzhe; Wu, Yi; Yan, Joseph D.

2014-06-01

Sulfur hexafluoride (SF6) gas, used widely in high-voltage circuit breakers, can produce a remarkable greenhouse effect if released into the atmosphere. Fundamental properties of SF6 mixed with CO2 at high temperatures are presented in this paper, considering their reduction of adverse impact on the environment as a replacement for pure SF6 in high-voltage circuit breakers: to the knowledge of the authors, related data have not been reported in the literature. The species composition and thermodynamic properties (mass density, enthalpy and specific heat at constant pressure) are determined by the method of Gibbs free energy minimization, using standard thermodynamic tables. The transport properties, including viscosity, thermal conductivity and electrical conductivity, are evaluated by using the Chapman-Enskog method expanded up to the third-order approximation (second order for viscosity). Particular attention is paid to the establishment of a collision integral database related to a reacting species system containing basic elements of carbon, oxygen and sulfur as well as fluoride by the use of recent cross sections or interaction potentials available in the literature. The calculations, which assume a local thermodynamic equilibrium, are performed in the temperature range 300 to 30 000 K for different pressures between 0.01 and 1.6 MPa. The results obtained are compared to those of previously published studies, and the reasons for discrepancies are analysed. An evaluation of the current interruption performance by adding CO2 to SF6 is discussed from a microscopic point of view. The results provide reliable reference data for the simulation of switching arcs in high-voltage circuit breakers in SF6-CO2 mixtures.

An Interpolation Method for Obtaining Thermodynamic Properties Near Saturated Liquid and Saturated Vapor Lines

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.

A numerical solution of the Navier-Stokes equations for supercritical fluid thermodynamic analysis

NASA Technical Reports Server (NTRS)

Heinmiller, P. J.

1971-01-01

An explicit numerical solution of the compressible Navier-Stokes equations is applied to the thermodynamic analysis of supercritical oxygen in the Apollo cryogenic storage system. The wave character is retained in the conservation equations which are written in the basic fluid variables for a two-dimensional Cartesian coordinate system. Control-volume cells are employed to simplify imposition of boundary conditions and to ensure strict observance of local and global conservation principles. Non-linear real-gas thermodynamic properties responsible for the pressure collapse phenomonon in supercritical fluids are represented by tabular and empirical functions relating pressure and temperature to density and internal energy. Wall boundary conditions are adjusted at one cell face to emit a prescribed mass flowrate. Scaling principles are invoked to achieve acceptable computer execution times for very low Mach number convection problems. Detailed simulations of thermal stratification and fluid mixing occurring under low acceleration in the Apollo 12 supercritical oxygen tank are presented which model the pressure decay associated with de-stratification induced by an ordinary vehicle maneuver and heater cycle operation.

Numerical implementation and oceanographic application of the thermodynamic potentials of water, vapour, ice, seawater and air - Part 2: The library routines

NASA Astrophysics Data System (ADS)

Wright, D. G.; Feistel, R.; Reissmann, J. H.; Miyagawa, K.; Jackett, D. R.; Wagner, W.; Overhoff, U.; Guder, C.; Feistel, A.; Marion, G. M.

2010-03-01

The SCOR/IAPSO1 Working Group 127 on Thermodynamics and Equation of State of Seawater has prepared recommendations for new methods and algorithms for numerical estimation of the thermophysical properties of seawater. As an outcome of this work, a new International Thermodynamic Equation of Seawater (TEOS-10) was endorsed by IOC/UNESCO2 in June 2009 as the official replacement and extension of the 1980 International Equation of State, EOS-80. As part of this new standard a source code package has been prepared that is now made freely available to users via the World Wide Web. This package includes two libraries referred to as the SIA (Sea-Ice-Air) library and the GSW (Gibbs SeaWater) library. Information on the GSW library may be found on the TEOS-10 web site (http://www.TEOS-10.org). This publication provides an introduction to the SIA library which contains routines to calculate various thermodynamic properties as discussed in the companion paper. The SIA library is very comprehensive, including routines to deal with fluid water, ice, seawater and humid air as well as equilibrium states involving various combinations of these, with equivalent code developed in different languages. The code is hierachically structured in modules that support (i) almost unlimited extension with respect to additional properties or relations, (ii) an extraction of self-contained sub-libraries, (iii) separate updating of the empirical thermodynamic potentials, and (iv) code verification on different platforms and between different languages. Error trapping is implemented to identify when one or more of the primary routines are accessed significantly beyond their established range of validity. The initial version of the SIA library is available in Visual Basic and FORTRAN as a supplement to this publication and updates will be maintained on the TEOS-10 web site. 1 SCOR/IAPSO: Scientific Committee on Oceanic Research/International Association for the Physical Sciences of the Oceans 2 IOC/UNESCO: Intergovernmental Oceanographic Commission/United Nations Educational, Scientific and Cultural Organization

Numerical implementation and oceanographic application of the thermodynamic potentials of liquid water, water vapour, ice, seawater and humid air - Part 2: The library routines

NASA Astrophysics Data System (ADS)

Wright, D. G.; Feistel, R.; Reissmann, J. H.; Miyagawa, K.; Jackett, D. R.; Wagner, W.; Overhoff, U.; Guder, C.; Feistel, A.; Marion, G. M.

2010-07-01

The SCOR/IAPSO1 Working Group 127 on Thermodynamics and Equation of State of Seawater has prepared recommendations for new methods and algorithms for numerical estimation of the the thermophysical properties of seawater. As an outcome of this work, a new International Thermodynamic Equation of Seawater (TEOS-10) was endorsed by IOC/UNESCO2 in June 2009 as the official replacement and extension of the 1980 International Equation of State, EOS-80. As part of this new standard a source code package has been prepared that is now made freely available to users via the World Wide Web. This package includes two libraries referred to as the SIA (Sea-Ice-Air) library and the GSW (Gibbs SeaWater) library. Information on the GSW library may be found on the TEOS-10 web site (http://www.TEOS-10.org). This publication provides an introduction to the SIA library which contains routines to calculate various thermodynamic properties as discussed in the companion paper. The SIA library is very comprehensive, including routines to deal with fluid water, ice, seawater and humid air as well as equilibrium states involving various combinations of these, with equivalent code developed in different languages. The code is hierachically structured in modules that support (i) almost unlimited extension with respect to additional properties or relations, (ii) an extraction of self-contained sub-libraries, (iii) separate updating of the empirical thermodynamic potentials, and (iv) code verification on different platforms and between different languages. Error trapping is implemented to identify when one or more of the primary routines are accessed significantly beyond their established range of validity. The initial version of the SIA library is available in Visual Basic and FORTRAN as a supplement to this publication and updates will be maintained on the TEOS-10 web site. 1SCOR/IAPSO: Scientific Committee on Oceanic Research/International Association for the Physical Sciences of the Oceans 2IOC/UNESCO: Intergovernmental Oceanographic Commission/United Nations Educational, Scientific and Cultural Organization

Enhancement of Thermodynamic Gas-Phase Acidity and Basicity of Water by Means of Secondary Interactions.

PubMed

Montero-Campillo, M Merced; Alkorta, Ibon; Elguero, Jose

2018-06-26

A series of A···water, B···water complexes (A = acid, B =base) are studied at the G4 level of theory to show that water acidity or basicity can be modulated by non-covalent interactions. Protic and non-protic acids interacting with water form hydrogen bonds or other kind of non-covalent interactions, respectively, that may dramatically change the acidity of water up to almost 360 kJ·mol-1 in terms of enthalpy. Similarly, hydrogen bonds responsible for the interaction between typical small nitrogen-containing Lewis bases and water can enhance the proton affinity of water by almost 300 kJ·mol-1. Our results reveal that these large enhancements are linearly related with the binding energy of the charged complexes, and are determined by the Lewis acid-base properties of the molecule involved in the interaction, allowing a quite precise modulation of the corresponding acid-base properties of water. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An overview of the nonequilibrium behavior of polymer glasses

NASA Technical Reports Server (NTRS)

Tant, M. R.; Wilkes, G. L.

1981-01-01

It is pointed out that research efforts are at present being directed in two areas, one comprising experimental studies of this phenomenon in various glassy polymer systems and the other involving the development of a quantitative theory capable of satisfactorily predicting aging behavior for a variety of polymer materials under different conditions. Recent work in both these areas is surveyed. The basic principles of nonequilibrium behavior are outlined, with emphasis placed on changes in material properties with annealing below the glass transition temperature. Free volume theory and thermodynamic theory are discussed.

A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

PubMed

Lilić, Aleksandra; Wei, Tiantian; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-09-11

The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO 2 , NbP, and heteropolyanions on silica, HPA/SiO 2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases CO x production. On strong acid sites, production of acrolein and carbon oxides (CO x ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (<100 μmol g -1 ) of very strong basic sites (Q diff >150 kJ mol -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Premixed autoignition in compressible turbulence

NASA Astrophysics Data System (ADS)

Konduri, Aditya; Kolla, Hemanth; Krisman, Alexander; Chen, Jacqueline

2016-11-01

Prediction of chemical ignition delay in an autoignition process is critical in combustion systems like compression ignition engines and gas turbines. Often, ignition delay times measured in simple homogeneous experiments or homogeneous calculations are not representative of actual autoignition processes in complex turbulent flows. This is due the presence of turbulent mixing which results in fluctuations in thermodynamic properties as well as chemical composition. In the present study the effect of fluctuations of thermodynamic variables on the ignition delay is quantified with direct numerical simulations of compressible isotropic turbulence. A premixed syngas-air mixture is used to remove the effects of inhomogeneity in the chemical composition. Preliminary results show a significant spatial variation in the ignition delay time. We analyze the topology of autoignition kernels and identify the influence of extreme events resulting from compressibility and intermittency. The dependence of ignition delay time on Reynolds and turbulent Mach numbers is also quantified. Supported by Basic Energy Sciences, Dept of Energy, United States.

Quantum thermodynamics: a nonequilibrium Green's function approach.

PubMed

Esposito, Massimiliano; Ochoa, Maicol A; Galperin, Michael

2015-02-27

We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green's functions. The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit.

THERMODYNAMIC FUNDAMENTALS USED IN HAZARDOUS WASTE INCINERATION

EPA Science Inventory

Thermodynamics is the basic foundation of many engineeringpractices. nvironmental engineering is no exception, it is usingthermodynamic principles in many applications. n particular,those who are involved in the incineration of various wastes suchas hazardous and municipal wastes...

The Theory of Thermodynamic Systems with Internal Variables of State: Necessary and Sufficient Conditions for Compliance with the Second Law of Thermodynamics

NASA Astrophysics Data System (ADS)

Shnip, A. I.

2018-01-01

Based on the entropy-free thermodynamic approach, a generalized theory of thermodynamic systems with internal variables of state is being developed. For the case of nonlinear thermodynamic systems with internal variables of state and linear relaxation, the necessary and sufficient conditions have been proved for fulfillment of the second law of thermodynamics in entropy-free formulation which, according to the basic theorem of the theory, are also necessary and sufficient for the existence of a thermodynamic potential. Moreover, relations of correspondence between thermodynamic systems with memory and systems with internal variables of state have been established, as well as some useful relations in the spaces of states of both types of systems.

Thermodynamic and Transport Properties of Real Air Plasma in Wide Range of Temperature and Pressure

NASA Astrophysics Data System (ADS)

Wang, Chunlin; Wu, Yi; Chen, Zhexin; Yang, Fei; Feng, Ying; Rong, Mingzhe; Zhang, Hantian

2016-07-01

Air plasma has been widely applied in industrial manufacture. In this paper, both dry and humid air plasmas' thermodynamic and transport properties are calculated in temperature 300-100000 K and pressure 0.1-100 atm. To build a more precise model of real air plasma, over 70 species are considered for composition. Two different methods, the Gibbs free energy minimization method and the mass action law method, are used to determinate the composition of the air plasma in a different temperature range. For the transport coefficients, the simplified Chapman-Enskog method developed by Devoto has been applied using the most recent collision integrals. It is found that the presence of CO2 has almost no effect on the properties of air plasma. The influence of H2O can be ignored except in low pressure air plasma, in which the saturated vapor pressure is relatively high. The results will serve as credible inputs for computational simulation of air plasma. supported by the National Key Basic Research Program of China (973 Program)(No. 2015CB251002), National Natural Science Foundation of China (Nos. 51521065, 51577145), the Science and Technology Project Funds of the Grid State Corporation (SGTYHT/13-JS-177), the Fundamental Research Funds for the Central Universities, and State Grid Corporation Project (GY71-14-004)

Influence of volume magnetostriction on the thermodynamic properties of Ni-Mn-Ga shape memory alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kosogor, Anna; Institute of Magnetism, 36-b, Vernadsky Str., Kyiv 03142; Donetsk Institute for Physics and Engineering, Kyiv 03028

2015-10-07

In the present article, the thermodynamic properties of Ni-Mn-Ga ferromagnetic shape memory alloys exhibiting the martensitic transformations (MTs) above and below Curie temperature are compared. It is shown that when MT goes below Curie temperature, the elastic and thermal properties of alloy noticeably depend on magnetization value due to spontaneous volume magnetostriction. However, the separation of magnetic parts from the basic characteristics of MT is a difficult task, because the volume magnetostriction does not qualitatively change the transformational behaviour of alloy. This problem is solved for several Ni-Mn-Ga alloys by means of the quantitative theoretical analysis of experimental data obtainedmore » in the course of stress-strain tests. For each alloy, the entropy change and the transformation heat evolved in the course of MT are evaluated, first, from the results of stress-strain tests and, second, from differential scanning calorimetry data. For all alloys, a quantitative agreement between the values obtained in two different ways is observed. It is shown that the magnetic part of transformation heat exceeds the non-magnetic one for the Ni-Mn-Ga alloys undergoing MTs in ferromagnetic state, while the elevated values of transformation heat measured for the alloys undergoing MTs in paramagnetic state are caused by large MT strains.« less

Influence of volume magnetostriction on the thermodynamic properties of Ni-Mn-Ga shape memory alloys

NASA Astrophysics Data System (ADS)

Kosogor, Anna; L'vov, Victor A.; Cesari, Eduard

2015-10-01

In the present article, the thermodynamic properties of Ni-Mn-Ga ferromagnetic shape memory alloys exhibiting the martensitic transformations (MTs) above and below Curie temperature are compared. It is shown that when MT goes below Curie temperature, the elastic and thermal properties of alloy noticeably depend on magnetization value due to spontaneous volume magnetostriction. However, the separation of magnetic parts from the basic characteristics of MT is a difficult task, because the volume magnetostriction does not qualitatively change the transformational behaviour of alloy. This problem is solved for several Ni-Mn-Ga alloys by means of the quantitative theoretical analysis of experimental data obtained in the course of stress-strain tests. For each alloy, the entropy change and the transformation heat evolved in the course of MT are evaluated, first, from the results of stress-strain tests and, second, from differential scanning calorimetry data. For all alloys, a quantitative agreement between the values obtained in two different ways is observed. It is shown that the magnetic part of transformation heat exceeds the non-magnetic one for the Ni-Mn-Ga alloys undergoing MTs in ferromagnetic state, while the elevated values of transformation heat measured for the alloys undergoing MTs in paramagnetic state are caused by large MT strains.

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.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

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.

Nanotransition Materials (NTMs): Photocatalysis, Validated High Effective Sorbent Models Study for Organic Dye Degradation and Precise Mathematical Data’s at Standardized Level

PubMed Central

Khan, Farheen; Wahab, Rizwan; Hagar, Mohamed; Alnoman, Rua; Lutfullah; Rashid, Mohd

2018-01-01

The present work describes the synthesis of copper oxide nanoparticles (CuONPs) via a solution process with the aim of applying the nano-adsorbent for the reduction of methylene blue (MB) dye in alkaline media. These NPs were characterized via Field emission scanning electron microscopy (FE-SEM), X-ray diffraction, high-resolution Transmission electron microscopy (TEM), and ultra violet UV-visible spectroscopy to confirm their morphology and crystalline and optical properties in order to design an adsorption-degradation process. The photocatalytic CuONPs exhibited dynamic properties, great adsorption affinity during the chemisorption process, and operated at various modes with a strong interaction between the adsorbent and the adsorptive species, and equilibrium isotherm, kinetic isotherm, and thermodynamic activities in the presence of UV light. All basic quantities, such as concentration, pH, adsorbent dose, time, and temperature, were determined by an optimization process. The best-fitted adsorption Langmuir model (R2 = 0.9988) and performance, including adsorption capacity (350.87 mg/g), photocatalytic efficiency (90.74%), and degradation rate constant (Ks = 2.23 ×10−2 min−1), illustrate good feasibility with respect to sorption-reduction reactions but followed a pseudo-second-order kinetic on the adsorbent surface, reaching an equilibrium point in 80 min. The thermodynamic analysis suggests that the adsorption reaction is spontaneous and endothermic in nature. The thermodynamic parameters such as enthalpy (∆H°), entropy (∆S°), and Gibbs free energy (∆G°) give effective results to support a chemical reduction reaction at 303 K temperature. The equilibrium isotherm and kinetic and thermodynamic models with error function analysis explore the potential, acceptability, accuracy, access to adsorbents, and novelty of an unrivaled-sorption system. PMID:29495511

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.

Free energy of formation of Mo2C and the thermodynamic properties of carbon in solid molybdenum

NASA Technical Reports Server (NTRS)

Seigle, L. L.; Chang, C. L.; Sharma, T. P.

1979-01-01

As part of a study of the thermodynamical properties of interstitial elements in refractory metals, the free energy of formation of Mo2C is determined, and the thermodynamical properties of C in solution in solid Mo evaluated. The activity of C in the two-phase region Mo + Mo2C is obtained from the C content of iron rods equilibrated with metal + carbide powder mixtures. The free energy of formation of alpha-Mo2C is determined from the activity data. The thermodynamic properties of C in the terminal solid solution are calculated from available data on the solid solubility of C in Mo. Lattice distortion due to misfit of the C atoms in the interstitial sites appears to play a significant role in determining the thermodynamic properties of C in solid Mo.

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.

Models of the earth's core

NASA Technical Reports Server (NTRS)

Stevenson, D. J.

1981-01-01

Combined inferences from seismology, high-pressure experiment and theory, geomagnetism, fluid dynamics, and current views of terrestrial planetary evolution lead to models of the earth's core with five basic properties. These are that core formation was contemporaneous with earth accretion; the core is not in chemical equilibrium with the mantle; the outer core is a fluid iron alloy containing significant quantities of lighter elements and is probably almost adiabatic and compositionally uniform; the more iron-rich inner solid core is a consequence of partial freezing of the outer core, and the energy release from this process sustains the earth's magnetic field; and the thermodynamic properties of the core are well constrained by the application of liquid-state theory to seismic and labroatory data.

Exact Calculation of the Thermodynamics of Biomacromolecules on Cubic Recursive Lattice.

NASA Astrophysics Data System (ADS)

Huang, Ran

The thermodynamics of biomacromolecules featured as foldable polymer with inner-linkage of hydrogen bonds, e. g. protein, RNA and DNA, play an impressive role in either physical, biological, and polymer sciences. By treating the foldable chains to be the two-tolerate self-avoiding trails (2T polymer), abstract lattice modeling of these complex polymer systems to approach their thermodynamics and subsequent bio-functional properties have been developed for decades. Among these works, the calculations modeled on Bethe and Husimi lattice have shown the excellence of being exactly solvable. Our project extended this effort into the 3D situation, i.e. the cubic recursive lattice. The preliminary exploration basically confirmed others' previous findings on the planar structure, that we have three phases in the grand-canonical phase diagram, with a 1st order transition between non-polymerized and polymer phases, and a 2nd order transition between two distinguishable polymer phases. However the hydrogen bond energy J, stacking energy ɛ, and chain rigidity energy H play more vigorous effects on the thermal behaviors, and this is hypothesized to be due to the larger number of possible configurations provided by the complicated 3D model. By the so far progress, the calculation of biomacromolecules may be applied onto more complex recursive lattices, such as the inhomogeneous lattice to describe the cross-dimensional situations, and beside the thermal properties of the 2T polymers, we may infer some interesting insights of the mysterious folding problem itself. National Natural Science Foundation of China.

Significance of DNA bond strength in programmable nanoparticle thermodynamics and dynamics.

PubMed

Yu, Qiuyan; Hu, Jinglei; Hu, Yi; Wang, Rong

2018-04-04

Assembly of nanoparticles (NPs) coated with complementary DNA strands leads to novel crystals with nanosized basic units rather than classic atoms, ions or molecules. The assembly process is mediated by hybridization of DNA via specific base pairing interaction, and is kinetically linked to the disassociation of DNA duplexes. DNA-level physiochemical quantities, both thermodynamic and kinetic, are key to understanding this process and essential for the design of DNA-NP crystals. The melting transition properties are helpful to judge the thermostability and sensitivity of relative DNA probes or other applications. Three different cases are investigated by changing the linker length and the spacer length on which the melting properties depend using the molecular dynamics method. Melting temperature is determined by sigmoidal melting curves based on hybridization percentage versus temperature and the Lindemann melting rule simultaneously. We provide a computational strategy based on a coarse-grained model to estimate the hybridization enthalpy, entropy and free energy from percentages of hybridizations which are readily accessible in experiments. Importantly, the lifetime of DNA bond dehybridization based on temperature and the activation energy depending on DNA bond strength are also calculated. The simulation results are in good agreement with the theoretical analysis and the present experimental data. Our study provides a good strategy to predict the melting temperature which is important for the DNA-directed nanoparticle system, and bridges the dynamics and thermodynamics of DNA-directed nanoparticle systems by estimating the equilibrium constant from the hybridization of DNA bonds quantitatively.

Solubility prediction, solvate and cocrystal screening as tools for rational crystal engineering.

PubMed

Loschen, Christoph; Klamt, Andreas

2015-06-01

The fact that novel drug candidates are becoming increasingly insoluble is a major problem of current drug development. Computational tools may address this issue by screening for suitable solvents or by identifying potential novel cocrystal formers that increase bioavailability. In contrast to other more specialized methods, the fluid phase thermodynamics approach COSMO-RS (conductor-like screening model for real solvents) allows for a comprehensive treatment of drug solubility, solvate and cocrystal formation and many other thermodynamics properties in liquids. This article gives an overview of recent COSMO-RS developments that are of interest for drug development and contains several new application examples for solubility prediction and solvate/cocrystal screening. For all property predictions COSMO-RS has been used. The basic concept of COSMO-RS consists of using the screening charge density as computed from first principles calculations in combination with fast statistical thermodynamics to compute the chemical potential of a compound in solution. The fast and accurate assessment of drug solubility and the identification of suitable solvents, solvate or cocrystal formers is nowadays possible and may be used to complement modern drug development. Efficiency is increased by avoiding costly quantum-chemical computations using a database of previously computed molecular fragments. COSMO-RS theory can be applied to a range of physico-chemical properties, which are of interest in rational crystal engineering. Most notably, in combination with experimental reference data, accurate quantitative solubility predictions in any solvent or solvent mixture are possible. Additionally, COSMO-RS can be extended to the prediction of cocrystal formation, which results in considerable predictive accuracy concerning coformer screening. In a recent variant costly quantum chemical calculations are avoided resulting in a significant speed-up and ease-of-use. © 2015 Royal Pharmaceutical Society.

The calculated magnetic, electronic and thermodynamic properties of Ce{sub 3}Co{sub 29}Si{sub 4}B{sub 10} compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huo, Jin-Rong; Wang, Xiao-Xu; Cloud Computing Department, Beijing Computing Center, Beijing 100084

2016-05-15

The magnetic moment, lattice parameter and atom fraction coordinates for Ce{sub 3}Co{sub 29}Si{sub 4}B{sub 10} are calculated by the first-principles GGA+U method, and the results indicate that the calculated and experimental values are basically accordant when U=2.6 eV. We study the interaction effect and orbital hybridization between Co and Ce atoms. The projected density of states at U=2.6 eV which provided by Co-2c, Ce-2b and Ce-4d sites are contrasted with else U values. Meanwhile the electron density of states for different sites and the distance between various atoms are exhibited. In addition, the thermodynamic properties of Ce{sub 3}Co{sub 29}Si{sub 4}B{submore » 10} are evaluated by using a series of interatomic pair potentials. - Graphical abstract: Change of the total magnetic moment for Ce{sub 3}Co{sub 29}Si{sub 4}B{sub 10} along with the value of U. There is a sharply decline of the curve at U=2.6 eV and, at the moment, the total magnetic moment of the compound have a good agreement with the experimental data. - Highlights: • We research of quaternary rare earth and transition metal compounds. • We perform the calculation of magnetic moment and electronic structure by GGA+U method. • The orbital hybridization between Co and Ce atoms is displayed and analyzed. • Show the plot of projected density of states for different sites more clearly. • Calculate the thermodynamic property of rare-earth transition metal compound.« less

An Interpolation Method for Obtaining Thermodynamic Properties Near Saturated Liquid and Saturated Vapor Lines

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.

Advances in first-principles calculations of thermodynamic properties of planetary materials (Invited)

NASA Astrophysics Data System (ADS)

Wilson, H. F.

2013-12-01

First-principles atomistic simulation is a vital tool for understanding the properties of materials at the high-pressure high-temperature conditions prevalent in giant planet interiors, but properties such as solubility and phase boundaries are dependent on entropy, a quantity not directly accessible in simulation. Determining entropic properties from atomistic simulations is a difficult problem typically requiring a time-consuming integration over molecular dynamics trajectories. Here I will describe recent advances in first-principles thermodynamic calculations which substantially increase the simplicity and efficiency of thermodynamic integration and make entropic properties more readily accessible. I will also describe the use of first-principles thermodynamic calculations for understanding problems including core solubility in gas giants and superionic phase changes in ice giants, as well as future prospects for combining first-principles thermodynamics with planetary-scale models to help us understand the origin and consequences of compositional inhomogeneity in giant planet interiors.

Electrochemistry of the Zinc-Silver Oxide System. Part 1: Thermodynamic Studies Using Commercial Miniature Cells.

ERIC Educational Resources Information Center

Smith, Michael J.; Vincent, Colin A.

1989-01-01

Uses reversible electrochemical cells near equilibrium to study basic thermodynamic concepts such as maximum work and free energy. Selects sealed, miniature, commercial cells to obtain accurate measurement of enthalpy, entropy, and Gibbs free energy. (MVL)

Comparing contribution of flexural and planar modes to thermodynamic properties

NASA Astrophysics Data System (ADS)

Mann, Sarita; Rani, Pooja; Jindal, V. K.

2017-05-01

Graphene, the most studied and explored 2D structure has unusual thermal properties such as negative thermal expansion, high thermal conductivity etc. We have already studied the thermal expansion behavior and various thermodynamic properties of pure graphene like heat capacity, entropy and free energy. The results of thermal expansion and various thermodynamic properties match well with available theoretical studies. For a deeper understanding of these properties, we analyzed the contribution of each phonon branch towards the total value of the individual property. To compute these properties, the dynamical matrix was calculated using VASP code where the density functional perturbation theory (DFPT) is employed under quasi-harmonic approximation in interface with phonopy code. It is noticed that transverse mode has major contribution to negative thermal expansion and all branches have almost same contribution towards the various thermodynamic properties with the contribution of ZA mode being the highest.

Contrail Formation in Aircraft Wakes Using Large-Eddy Simulations

NASA Technical Reports Server (NTRS)

Paoli, R.; Helie, J.; Poinsot, T. J.; Ghosal, S.

2002-01-01

In this work we analyze the issue of the formation of condensation trails ("contrails") in the near-field of an aircraft wake. The basic configuration consists in an exhaust engine jet interacting with a wing-tip training vortex. The procedure adopted relies on a mixed Eulerian/Lagrangian two-phase flow approach; a simple micro-physics model for ice growth has been used to couple ice and vapor phases. Large eddy simulations have carried out at a realistic flight Reynolds number to evaluate the effects of turbulent mixing and wake vortex dynamics on ice-growth characteristics and vapor thermodynamic properties.

Cyanide and antimony thermodynamic database for the aqueous species and solids for the EPA-MINTEQ geochemical code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sehmel, G.A.

1989-05-01

Thermodynamic data for aqueous species and solids that contain cyanide and antimony were tabulated from several commonly accepted, published sources of thermodynamic data and recent journal article. The review does not include gases or organic complexes of either antimony or cyanide, nor does the review include the sulfur compounds of cyanide. The basic thermodynamic data, ..delta..G/sub f,298//sup o/, ..delta..H/sub f,298//sup o/, and S/sub f//sup o/ values, were chosen to represent each solid phase and aqueous species for which data were available in the appropriate standard state. From these data the equilibrium constants (log K/sub r,298//sup o/) and enthalpies of reactionmore » (..delta..H/sub r,298//sup o/) at 298 K (25/degree/C) were calculated for reactions involving the formation of these aqueous species and solids from the basic components. 34 refs., 14 tabs.« less

Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide.

PubMed

Domańska, Urszula; Bogel-Łukasik, Rafał

2005-06-23

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.

Biochemical Thermodynamics under near Physiological Conditions

ERIC Educational Resources Information Center

Mendez, Eduardo

2008-01-01

The recommendations for nomenclature and tables in Biochemical Thermodynamics approved by IUBMB and IUPAC in 1994 can be easily introduced after the chemical thermodynamic formalism. Substitution of the usual standard thermodynamic properties by the transformed ones in the thermodynamic equations, and the use of appropriate thermodynamic tables…

A Simple Statistical Thermodynamics Experiment

ERIC Educational Resources Information Center

LoPresto, Michael C.

2010-01-01

Comparing the predicted and actual rolls of combinations of both two and three dice can help to introduce many of the basic concepts of statistical thermodynamics, including multiplicity, probability, microstates, and macrostates, and demonstrate that entropy is indeed a measure of randomness, that disordered states (those of higher entropy) are…

Thermodynamic Properties of HCFC142b

NASA Astrophysics Data System (ADS)

Fukushima, Masato; Watanabe, Naohiro

Thermodynamic properties of HCFC142b,namely saturated densities,vapor pressures and PVT properties,were measured and the critical parameters were determined through those experimental results. The correlations for vpor 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 and etc.,could be considered to be reasonab1y estimatedby the expression reported in this paper.

A Review of the Thermodynamic, Transport, and Chemical Reaction Rate Properties of High-temperature Air

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.

On the universal behavior of some thermodynamic properties along the whole liquid-vapor coexistence curve

NASA Astrophysics Data System (ADS)

Román, F. L.; White, J. A.; Velasco, S.; Mulero, A.

2005-09-01

When thermodynamic properties of a pure substance are transformed to reduced form by using both critical- and triple-point values, the corresponding experimental data along the whole liquid-vapor coexistence curve can be correlated with a very simple analytical expression that interpolates between the behavior near the triple and the critical points. The leading terms of this expression contain only two parameters: the critical exponent and the slope at the triple point. For a given thermodynamic property, the critical exponent has a universal character but the slope at the triple point can vary significantly from one substance to another. However, for certain thermodynamic properties including the difference of coexisting densities, the enthalpy of vaporization, and the surface tension of the saturated liquid, one finds that the slope at the triple point also has a nearly universal value for a wide class of fluids. These thermodynamic properties thus show a corresponding apparently universal behavior along the whole coexistence curve.

Polarization Coupling in Ferroelectric Multilayers as a Function of Interface Charge Concentration

NASA Astrophysics Data System (ADS)

Okatan, Mahmut; Mantese, Joseph; Alpay, Pamir

2009-03-01

Intriguing properties of multilayered and graded ferroelectrics follow from the electrostatic and electromechanical interactions. The strength of the interlayer coupling depends on the concentration of interfacial defects with short-range local electrostatic fields. Defects may locally relax polarization differences and thus reduce the commensurate bound charge concentration at the interlayer interfaces. In this talk, we develop a theoretical analysis based on non-linear thermodynamics coupled with basic electrostatic relations to understand the role of charge compensation at the interlayer interfaces. The results show multilayered ferroelectrics with systematic variations in the composition may display a colossal dielectric response depending upon the interlayer electrostatic interactions. It is expected that other properties such as the pyroelectric and piezoelectric response will yield concomitant increases through the dielectric permittivity.

CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients. Revised

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

2002-01-01

For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

2001-01-01

For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

Thermodynamic Laws Applied to Economic Systems

ERIC Educational Resources Information Center

González, José Villacís

2009-01-01

Economic activity in its different manifestations--production, exchange, consumption and, particularly, information on quantities and prices--generates and transfers energy. As a result, we can apply to it the basic laws of thermodynamics. These laws are applicable within a system, i.e., in a country or between systems and countries. To these…

Thermodynamical Arguments against Evolution

ERIC Educational Resources Information Center

Rosenhouse, Jason

2017-01-01

The argument that the second law of thermodynamics contradicts the theory of evolution has recently been revived by anti-evolutionists. In its basic form, the argument asserts that whereas evolution implies that there has been an increase in biological complexity over time, the second law, a fundamental principle of physics, shows this to be…

Molecular Thermodynamics for Cell Biology as Taught with Boxes

ERIC Educational Resources Information Center

Mayorga, Luis S.; Lopez, Maria Jose; Becker, Wayne M.

2012-01-01

Thermodynamic principles are basic to an understanding of the complex fluxes of energy and information required to keep cells alive. These microscopic machines are nonequilibrium systems at the micron scale that are maintained in pseudo-steady-state conditions by very sophisticated processes. Therefore, several nonstandard concepts need to be…

Thermodynamic control of anvil cloud amount

PubMed Central

Bony, Sandrine; Stevens, Bjorn; Coppin, David; Becker, Tobias; Reed, Kevin A.; Voigt, Aiko

2016-01-01

General circulation models show that as the surface temperature increases, the convective anvil clouds shrink. By analyzing radiative–convective equilibrium simulations, we show that this behavior is rooted in basic energetic and thermodynamic properties of the atmosphere: As the climate warms, the clouds rise and remain at nearly the same temperature, but find themselves in a more stable atmosphere; this enhanced stability reduces the convective outflow in the upper troposphere and decreases the anvil cloud fraction. By warming the troposphere and increasing the upper-tropospheric stability, the clustering of deep convection also reduces the convective outflow and the anvil cloud fraction. When clouds are radiatively active, this robust coupling between temperature, high clouds, and circulation exerts a positive feedback on convective aggregation and favors the maintenance of strongly aggregated atmospheric states at high temperatures. This stability iris mechanism likely contributes to the narrowing of rainy areas as the climate warms. Whether or not it influences climate sensitivity requires further investigation. PMID:27412863

Cross-platform comparison of nucleic acid hybridization: toward quantitative reference standards.

PubMed

Halvorsen, Ken; Agris, Paul F

2014-11-15

Measuring interactions between biological molecules is vitally important to both basic and applied research as well as development of pharmaceuticals. Although a wide and growing range of techniques is available to measure various kinetic and thermodynamic properties of interacting biomolecules, it can be difficult to compare data across techniques of different laboratories and personnel or even across different instruments using the same technique. Here we evaluate relevant biological interactions based on complementary DNA and RNA oligonucleotides that could be used as reference standards for many experimental systems. We measured thermodynamics of duplex formation using isothermal titration calorimetry, differential scanning calorimetry, and ultraviolet-visible (UV-vis) monitored denaturation/renaturation. These standards can be used to validate results, compare data from disparate techniques, act as a teaching tool for laboratory classes, or potentially to calibrate instruments. The RNA and DNA standards have many attractive features, including low cost, high purity, easily measurable concentrations, and minimal handling concerns, making them ideal for use as a reference material. Copyright © 2014 Elsevier Inc. All rights reserved.

Cross-platform comparison of nucleic acid hybridization: toward quantitative reference standardsa

PubMed Central

Halvorsen, Ken; Agris, Paul F.

2014-01-01

Measuring interactions between biological molecules is vitally important to both basic and applied research, as well as development of pharmaceuticals. While a wide and growing range of techniques are available to measure various kinetic and thermodynamic properties of interacting biomolecules, it can be difficult to compare data across techniques of different laboratories and personnel, or even across different instruments using the same technique. Here we evaluate relevant biological interactions based on complementary DNA and RNA oligonucleotides that could be used as reference standards for many experimental systems. We measured thermodynamics of duplex formation using Isothermal Titration Calorimetry, Differential Scanning Calorimetry, and UV-Vis monitored denaturation/renaturation. These standards can be used to validate results, compare data from disparate techniques, act as a teaching tool for laboratory classes, or potentially to calibrate instruments. The RNA and DNA standards have many attractive features including low cost, high purity, easily measureable concentrations, and minimal handling concerns, making them ideal for use as a reference material. PMID:25124363

Thermodynamic control of anvil cloud amount

DOE PAGES

Bony, Sandrine; Stevens, Bjorn; Coppin, David; ...

2016-07-13

General circulation models show that as the surface temperature increases, the convective anvil clouds shrink. By analyzing radiative–convective equilibrium simulations, our work shows that this behavior is rooted in basic energetic and thermodynamic properties of the atmosphere: As the climate warms, the clouds rise and remain at nearly the same temperature, but find themselves in a more stable atmosphere; this enhanced stability reduces the convective outflow in the upper troposphere and decreases the anvil cloud fraction. By warming the troposphere and increasing the upper-tropospheric stability, the clustering of deep convection also reduces the convective outflow and the anvil cloud fraction.more » When clouds are radiatively active, this robust coupling between temperature, high clouds, and circulation exerts a positive feedback on convective aggregation and favors the maintenance of strongly aggregated atmospheric states at high temperatures. This stability iris mechanism likely contributes to the narrowing of rainy areas as the climate warms. Whether or not it influences climate sensitivity requires further investigation.« less

Atomistic simulation of cubic and tetragonal phases of U-Mo alloy: Structure and thermodynamic properties

NASA Astrophysics Data System (ADS)

Starikov, S. V.; Kolotova, L. N.; Kuksin, A. Yu.; Smirnova, D. E.; Tseplyaev, V. I.

2018-02-01

We studied structure and thermodynamic properties of cubic and tetragonal phases of pure uranium and U-Mo alloys using atomistic simulations: molecular dynamics and density functional theory. The main attention was paid to the metastable γ0 -phase that is formed in U-Mo alloys at low temperature. Structure of γ0 -phase is similar to body-centered tetragonal (bct) lattice with displacement of a central atom in the basic cell along [ 001 ] direction. Such displacements have opposite orientations for part of the neighbouring basic cells. In this case, such ordering of the displacements can be designated as antiferro-displacement. Formation of such complex structure may be interpreted through forming of short U-U bonds. At heating, the tetragonal structure transforms into cubic γs -phase, still showing ordering of central atom displacements. With rise in temperature, γs -phase transforms to γ-phase with a quasi body-centered cubic (q-bcc) lattice. The local positions of uranium atoms in γ-phase correspond to γs -phase, however, orientations of the central atom displacements become disordered. Transition from γ0 to γ can be considered as antiferro-to paraelastic transition of order-disorder type. This approach to the structure description of uranium alloy allows to explain a number of unusual features found in the experiments: anisotropy of lattice at low temperature; remarkably high self-diffusion mobility in γ-phase; decreasing of electrical resistivity at heating for some alloys. In addition, important part of this work is the development of new interatomic potential for U-Mo system made with taking into account details of studied structures.

Thermodynamic properties of deep eutectic solvent and ionic liquid mixtures at temperatures from 293.15 K to 343.15 K

NASA Astrophysics Data System (ADS)

Achsah, R. S.; Shyam, S.; Mayuri, N.; Anantharaj, R.

2018-04-01

Deep eutectic solvents (DES) and ionic liquids (ILs) have their applications in various fields of research and in industries due to their attractive physiochemical properties. In this study, the combined thermodynamic properties of DES (choline chloride-glycerol) + IL1 (1-butyl-3-methylimiazolium acetate) and DES(choline chloride-glycerol) + IL2 (1-ethyl-3-methylimadzolium ethyl sulphate) have been studied. The thermodynamic properties such as excess molar volume, partial molar volume, excess partial molar volume and apparent molar volume were calculated for different mole fractions ranging from 0 to 1 and varying temperatures from 293.15 K to 343.15 K. In order to know the solvent properties of DESs and ILs mixtures at different temperatures and their molecular interactions to enhance the solvent performance and process efficiency at fixed composition and temperature the thermodynamic properties were analyzed.

Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

PubMed

Bacon, Stuart L; Peterson, Eric C; Daugulis, Andrew J; Parent, J Scott

2015-01-01

Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection. © 2015 American Institute of Chemical Engineers.

Cryogenic Propellant Feed System Analytical Tool Development

NASA Technical Reports Server (NTRS)

Lusby, Brian S.; Miranda, Bruno M.; Collins, Jacob A.

2011-01-01

The Propulsion Systems Branch at NASA s Lyndon B. Johnson Space Center (JSC) has developed a parametric analytical tool to address the need to rapidly predict heat leak into propellant distribution lines based on insulation type, installation technique, line supports, penetrations, and instrumentation. The Propellant Feed System Analytical Tool (PFSAT) will also determine the optimum orifice diameter for an optional thermodynamic vent system (TVS) to counteract heat leak into the feed line and ensure temperature constraints at the end of the feed line are met. PFSAT was developed primarily using Fortran 90 code because of its number crunching power and the capability to directly access real fluid property subroutines in the Reference Fluid Thermodynamic and Transport Properties (REFPROP) Database developed by NIST. A Microsoft Excel front end user interface was implemented to provide convenient portability of PFSAT among a wide variety of potential users and its ability to utilize a user-friendly graphical user interface (GUI) developed in Visual Basic for Applications (VBA). The focus of PFSAT is on-orbit reaction control systems and orbital maneuvering systems, but it may be used to predict heat leak into ground-based transfer lines as well. PFSAT is expected to be used for rapid initial design of cryogenic propellant distribution lines and thermodynamic vent systems. Once validated, PFSAT will support concept trades for a variety of cryogenic fluid transfer systems on spacecraft, including planetary landers, transfer vehicles, and propellant depots, as well as surface-based transfer systems. The details of the development of PFSAT, its user interface, and the program structure will be presented.

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

Foundations of radiation hydrodynamics

NASA Astrophysics Data System (ADS)

Mihalas, D.; Mihalas, B. W.

This book is the result of an attempt, over the past few years, to gather the basic tools required to do research on radiating flows in astrophysics. The microphysics of gases is discussed, taking into account the equation of state of a perfect gas, the first and second law of thermodynamics, the thermal properties of a perfect gas, the distribution function and Boltzmann's equation, the collision integral, the Maxwellian velocity distribution, Boltzmann's H-theorem, the time of relaxation, and aspects of classical statistical mechanics. Other subjects explored are related to the dynamics of ideal fluids, the dynamics of viscous and heat-conducting fluids, relativistic fluid flow, waves, shocks, winds, radiation and radiative transfer, the equations of radiation hydrodynamics, and radiating flows. Attention is given to small-amplitude disturbances, nonlinear flows, the interaction of radiation and matter, the solution of the transfer equation, acoustic waves, acoustic-gravity waves, basic concepts of special relativity, and equations of motion and energy.

Thermodynamic properties of gaseous fluorocarbons and isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon

NASA Technical Reports Server (NTRS)

Talcott, N. A., Jr.

1977-01-01

Equations and computer code are given for the thermodynamic properties of gaseous fluorocarbons in chemical equilibrium. In addition, isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon are included. The computer code calculates the equilibrium thermodynamic properties and, in some cases, the transport properties for the following fluorocarbons: CCl2F, CCl2F2, CBrF3, CF4, CHCl2F, CHF3, CCL2F-CCl2F, CCLF2-CClF2, CF3-CF3, and C4F8. Equilibrium thermodynamic properties are tabulated for six of the fluorocarbons(CCl3F, CCL2F2, CBrF3, CF4, CF3-CF3, and C4F8) and pressure-enthalpy diagrams are presented for CBrF3.

Measuring the Thermodynamics of the Alloy/Scale Interface

NASA Technical Reports Server (NTRS)

Copland, Evan

2004-01-01

A method is proposed for the direct measurement of the thermodynamic properties of the alloy and oxide compound at the alloy/scale interface observed during steady-state oxidation. The thermodynamic properties of the alloy/scale interface define the driving force for solid-state transport in the alloy and oxide compound. Accurate knowledge of thermodynamic properties of the interface will advance our understanding of oxidation behavior. The method is based on the concept of local equilibrium and assumes that an alloy+scale equilibrium very closely approximates the alloy/scale interface observed during steady-state oxidation. The thermodynamics activities of this alloy+scale equilibrium are measured directly by Knudsen effusion-cell mass spectrometer (KEMS) using the vapor pressure technique. The theory and some practical considerations of this method are discussed in terms of beta-NiAl oxidation.

On the thermodynamic properties of thermal plasma in the flame kernel of hydrocarbon/air premixed gases

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.

An Outlook on Biothermodynamics: Needs, Problems, and New Developments. I. Stability and Hydration of Proteins

NASA Astrophysics Data System (ADS)

Keller, Jürgen U.

2008-12-01

The application of concepts, principles, and methods of thermodynamics of equilibria and processes to bioengineering systems has led to a new and growing field: engineering biothermodynamics. This article, which is meant as the first in a series, gives an outline of basic aspects, changes, and actual examples in this field. After a few introductory remarks, the basic concepts and laws of thermodynamics extended to systems with internal variables, which serve as models for biofluids and other biosystems, are given. The method of thermodynamics is then applied to the problem of thermal stability of aqueous protein solutions, especially to that of myoglobin solutions. After this, the phenomenon of hydration of proteins by adsorption and intrusion of water molecules is considered. Several other phenomena like the adsorption of proteins on solid surfaces or cell membranes and their temperature and pressure-related behavior represented by an equation of state, or the thermodynamics of bacterial solutions including chemical reactions like wine fermentation, etc., will be presented in Parts II and III of this article.

Thermodynamics of Bioreactions.

PubMed

Held, Christoph; Sadowski, Gabriele

2016-06-07

Thermodynamic principles have been applied to enzyme-catalyzed reactions since the beginning of the 1930s in an attempt to understand metabolic pathways. Currently, thermodynamics is also applied to the design and analysis of biotechnological processes. The key thermodynamic quantity is the Gibbs energy of reaction, which must be negative for a reaction to occur spontaneously. However, the application of thermodynamic feasibility studies sometimes yields positive Gibbs energies of reaction even for reactions that are known to occur spontaneously, such as glycolysis. This article reviews the application of thermodynamics in enzyme-catalyzed reactions. It summarizes the basic thermodynamic relationships used for describing the Gibbs energy of reaction and also refers to the nonuniform application of these relationships in the literature. The review summarizes state-of-the-art approaches that describe the influence of temperature, pH, electrolytes, solvents, and concentrations of reacting agents on the Gibbs energy of reaction and, therefore, on the feasibility and yield of biological reactions.

Thermodynamic properties of potassium chloride aqueous solutions

NASA Astrophysics Data System (ADS)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

Thermodynamics-based Metabolite Sensitivity Analysis in metabolic networks.

PubMed

Kiparissides, A; Hatzimanikatis, V

2017-01-01

The increasing availability of large metabolomics datasets enhances the need for computational methodologies that can organize the data in a way that can lead to the inference of meaningful relationships. Knowledge of the metabolic state of a cell and how it responds to various stimuli and extracellular conditions can offer significant insight in the regulatory functions and how to manipulate them. Constraint based methods, such as Flux Balance Analysis (FBA) and Thermodynamics-based flux analysis (TFA), are commonly used to estimate the flow of metabolites through genome-wide metabolic networks, making it possible to identify the ranges of flux values that are consistent with the studied physiological and thermodynamic conditions. However, unless key intracellular fluxes and metabolite concentrations are known, constraint-based models lead to underdetermined problem formulations. This lack of information propagates as uncertainty in the estimation of fluxes and basic reaction properties such as the determination of reaction directionalities. Therefore, knowledge of which metabolites, if measured, would contribute the most to reducing this uncertainty can significantly improve our ability to define the internal state of the cell. In the present work we combine constraint based modeling, Design of Experiments (DoE) and Global Sensitivity Analysis (GSA) into the Thermodynamics-based Metabolite Sensitivity Analysis (TMSA) method. TMSA ranks metabolites comprising a metabolic network based on their ability to constrain the gamut of possible solutions to a limited, thermodynamically consistent set of internal states. TMSA is modular and can be applied to a single reaction, a metabolic pathway or an entire metabolic network. This is, to our knowledge, the first attempt to use metabolic modeling in order to provide a significance ranking of metabolites to guide experimental measurements. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Free energy of steps using atomistic simulations

NASA Astrophysics Data System (ADS)

Freitas, Rodrigo; Frolov, Timofey; Asta, Mark

The properties of solid-liquid interfaces are known to play critical roles in solidification processes. Particularly special importance is given to thermodynamic quantities that describe the equilibrium state of these surfaces. For example, on the solid-liquid-vapor heteroepitaxial growth of semiconductor nanowires the crystal nucleation process on the faceted solid-liquid interface is influenced by the solid-liquid and vapor-solid interfacial free energies, and also by the free energies of associated steps at these faceted interfaces. Crystal-growth theories and mesoscale simulation methods depend on quantitative information about these properties, which are often poorly characterized from experimental measurements. In this work we propose an extension of the capillary fluctuation method for calculation of the free energy of steps on faceted crystal surfaces. From equilibrium atomistic simulations of steps on (111) surfaces of Copper we computed accurately the step free energy for different step orientations. We show that the step free energy remains finite at all temperature up to the melting point and that the results obtained agree with the more well established method of thermodynamic integration if finite size effects are taken into account. The research of RF and MA at UC Berkeley were supported by the US National Science Foundation (Grant No. DMR-1105409). TF acknowledges support through a postdoctoral fellowship from the Miller Institute for Basic Research in Science.

Firewalking: A Lesson in Physics.

ERIC Educational Resources Information Center

Taylor, John R.

1989-01-01

Emphasizes firewalking as a good illustration of basic concepts in thermodynamics. Describes the basic principles of firewalking and other factors including the cooling of the surface embers, moisture of the feet, thick skin on the feet, tolerance for pain, and other uncontrolled factors. (YP)

The heat capacities of osumilite from 298.15 to 1000 K, the thermodynamic properties of two natural chlorites to 500 K, and the thermodynamic properties of petalite to 1800 K.

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.; Kittrick, J.A.; Grew, E.S.; Nelen, J.A.; London, D.

1984-01-01

Modifications to an automated low-T, adiabatic calorimeter are described. Thermodynamic data obtained with this instrument are reported for minerals from metamorphic terrains. (U.S. Bureau of Mines Report of Investigations 8451)-J.A.Z.

The H[subscript 3]PO[subscript 4] Acid Ionization Reactions: A Capstone Multiconcept Thermodynamics General Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Nyasulu, Frazier; Barlag, Rebecca; Wise, Lindy; McMills, Lauren

2013-01-01

The thermodynamic properties of weak acid ionization reactions are determined. The thermodynamic properties are corresponding values of the absolute temperature (T), the weak acid equilibrium constant (K[subscript a]), the enthalpy of ionization (delta[subscript i]H[degrees]), and the entropy of ionization (delta[subscript i]S[degrees]). The…

Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon

NASA Astrophysics Data System (ADS)

Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J.

2016-09-01

The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

Mechanics, Waves and Thermodynamics

NASA Astrophysics Data System (ADS)

Ranjan Jain, Sudhir

2016-05-01

Figures; Preface; Acknowledgement; 1. Energy, mass, momentum; 2. Kinematics, Newton's laws of motion; 3. Circular motion; 4. The principle of least action; 5. Work and energy; 6. Mechanics of a system of particles; 7. Friction; 8. Impulse and collisions; 9. Central forces; 10. Dimensional analysis; 11. Oscillations; 12. Waves; 13. Sound of music; 14. Fluid mechanics; 15. Water waves; 16. The kinetic theory of gases; 17. Concepts and laws of thermodynamics; 18. Some applications of thermodynamics; 19. Basic ideas of statistical mechanics; Bibliography; Index.

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.

Fractional watt Vuillemier cryogenic refrigerator program engineering notebook. Volume 1: Thermal analysis

NASA Technical Reports Server (NTRS)

Miller, W. S.

1974-01-01

The cryogenic refrigerator thermal design calculations establish design approach and basic sizing of the machine's elements. After the basic design is defined, effort concentrates on matching the thermodynamic design with that of the heat transfer devices (heat exchangers and regenerators). Typically, the heat transfer device configurations and volumes are adjusted to improve their heat transfer and pressure drop characteristics. These adjustments imply that changes be made to the active displaced volumes, compensating for the influence of the heat transfer devices on the thermodynamic processes of the working fluid. Then, once the active volumes are changed, the heat transfer devices require adjustment to account for the variations in flows, pressure levels, and heat loads. This iterative process is continued until the thermodynamic cycle parameters match the design of the heat transfer devices. By examing several matched designs, a near-optimum refrigerator is selected.

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Turboexpander calculations using a generalized equation of state correlation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, M.S.; Starling, K.E.

1975-01-01

A generalized method for predicting the thermodynamic properties of natural gas fluids has been developed and tested. The results of several comparisons between thermodynamic property values predicted by the method and experimental data are presented. Comparisons of predicted and experimental vapor-liquid equilibrium are presented. These comparisons indicate that the generalized correlation can be used to predict many thermodynamic properties of natural gas and LNG. Turboexpander calculations are presented to show the utility of the generalized correlation for process design calculations.

Simple optimized Brenner potential for thermodynamic properties of diamond

NASA Astrophysics Data System (ADS)

Liu, F.; Tang, Q. H.; Shang, B. S.; Wang, T. C.

2012-02-01

We have examined the commonly used Brenner potentials in the context of the thermodynamic properties of diamond. A simple optimized Brenner potential is proposed that provides very good predictions of the thermodynamic properties of diamond. It is shown that, compared to the experimental data, the lattice wave theory of molecular dynamics (LWT) with this optimized Brenner potential can accurately predict the temperature dependence of specific heat, lattice constant, Grüneisen parameters and coefficient of thermal expansion (CTE) of diamond.

Thermodynamical properties of liquid lanthanides-A variational approach

NASA Astrophysics Data System (ADS)

Patel, H. P.; Thakor, P. B.; Sonvane, Y. A.

2015-06-01

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.

Thermodynamical properties of liquid lanthanides-A variational approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, H. P.; Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat; Thakor, P. B., E-mail: pbthakor@rediffmail.com

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.

Non-equilibrium thermodynamics in cells.

PubMed

Jülicher, Frank; Grill, Stephan W; Salbreux, Guillaume

2018-03-15

We review the general hydrodynamic theory of active soft materials that is motivated in partic- ular by biological matter. We present basic concepts of irreversible thermodynamics of spatially extended multicomponent active systems. Starting from the rate of entropy production, we iden- tify conjugate thermodynamic fluxes and forces and present generic constitutive equations of polar active fluids and active gels. We also discuss angular momentum conservation which plays a role in the the physics of active chiral gels. The irreversible thermodynamics of active gels provides a general framework to discuss the physics that underlies a wide variety of biological processes in cells and in multicellular tissues. © 2018 IOP Publishing Ltd.

[Thermodynamic analysis of water adsorption and desorption process of Chinese herbal decoction pieces].

PubMed

Cheng, Lin; Luo, Xiao-Jian; Han, Xiu-Lin; Wang, Wen-Kai; Rao, Xiao-Yong; Xu, Shao-Zhong; He, Yan

2016-09-01

Based on the basic theory of thermodynamics, the thermodynamic parameters and related equations in the process of water adsorption and desorption of Chinese herbal decoction pieces were established, and their water absorption and desorption characteristics were analyzed. The physical significance of the thermodynamic parameters, such as differential adsorption enthalpy, differential adsorption entropy, integral adsorption enthalpy, integral adsorption entropy and the free energy of adsorption, were discussed in this paper to provide theoretical basis for the research on the water adsorption and desorption mechanism, optimum drying process parameters, storage conditions and packaging methods of Chinese herbal decoction pieces. Copyright© by the Chinese Pharmaceutical Association.

Structure, processing, and properties of potatoes

NASA Astrophysics Data System (ADS)

Lloyd, Isabel K.; Kolos, Kimberly R.; Menegaux, Edmond C.; Luo, Huy; McCuen, Richard H.; Regan, Thomas M.

1992-06-01

The objective of this experiment and lesson intended for high school students in an engineering or materials science course or college freshmen is to demonstrate the relation between processing, structure, and thermodynamic and physical properties. The specific objectives are to show the effect of structure and structural changes on thermodynamic properties (specific heat) and physical properties (compressive strength); to illustrate the first law of thermodynamics; to compare boiling a potato in water with cooking it in a microwave in terms of the rate of structural change and the energy consumed to 'process' the potato; and to demonstrate compression testing.

Structure, processing, and properties of potatoes

NASA Technical Reports Server (NTRS)

Lloyd, Isabel K.; Kolos, Kimberly R.; Menegaux, Edmond C.; Luo, Huy; Mccuen, Richard H.; Regan, Thomas M.

1992-01-01

The objective of this experiment and lesson intended for high school students in an engineering or materials science course or college freshmen is to demonstrate the relation between processing, structure, and thermodynamic and physical properties. The specific objectives are to show the effect of structure and structural changes on thermodynamic properties (specific heat) and physical properties (compressive strength); to illustrate the first law of thermodynamics; to compare boiling a potato in water with cooking it in a microwave in terms of the rate of structural change and the energy consumed to 'process' the potato; and to demonstrate compression testing.

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.

Partial discharges and breakdown in C3F8

NASA Astrophysics Data System (ADS)

Koch, M.; Franck, C. M.

2014-10-01

Traditional search processes of gases or gas mixtures for replacing SF6 involve time consuming measurements of partial discharges and breakdown behaviour for several voltage waveforms and different field configurations. Recently a model for prediction of this behaviour for SF6 was described in literature. The model only requires basic properties of the gas such as the critical field strength and the effective ionization coefficient, which can be obtained by swarm parameter measurements, and thermodynamic properties, which can be calculated. In this paper, we show for the well-known and electronegative gas octafluoropropane (C3F8) that it is possible to transfer the model developed for SF6 to this gas to describe the breakdown behaviour of C3F8. Thus the model can be beneficial in the screening process of new insulation gases.

An Interactive Computer Lab of the Galvanic Cell for Students in Biochemistry

ERIC Educational Resources Information Center

Ahlstrand, Emma; Buetti-Dinh, Antoine; Friedman, Ran

2018-01-01

We describe an interactive module that can be used to teach basic concepts in electrochemistry and thermodynamics to first year natural science students. The module is used together with an experimental laboratory and improves the students' understanding of thermodynamic quantities such as ?rG, ?rH, and ?rS that are calculated but not directly…

Students' Conceptions of Basic Ideas of the Second Law of Thermodynamics.

ERIC Educational Resources Information Center

Duit, Reinders; Kesidou, Sofia

The focus of this study was to portray the ideas that students with four years experience in learning physics developed in regard to the second law of thermodynamics. Data were obtained through 34 clinical interviews with grade 10 students. An analysis of student arguments revealed deeply rooted difficulties in using concepts that were learned in…

Thermodynamics of a Block Sliding across a Frictional Surface

ERIC Educational Resources Information Center

Mungan, Carl E.

2007-01-01

The following idealized problem is intended to illustrate some basic thermodynamic concepts involved in kinetic friction. A block of mass m is sliding on top of a frictional, flat-topped table of mass M. The table is magnetically levitated, so that it can move without thermal contact and friction across a horizontal floor. The table is initially…

Quantum Feynman Ratchet

NASA Astrophysics Data System (ADS)

Goyal, Ketan; Kawai, Ryoichi

As nanotechnology advances, understanding of the thermodynamic properties of small systems becomes increasingly important. Such systems are found throughout physics, biology, and chemistry manifesting striking properties that are a direct result of their small dimensions where fluctuations become predominant. The standard theory of thermodynamics for macroscopic systems is powerless for such ever fluctuating systems. Furthermore, as small systems are inherently quantum mechanical, influence of quantum effects such as discreteness and quantum entanglement on their thermodynamic properties is of great interest. In particular, the quantum fluctuations due to quantum uncertainty principles may play a significant role. In this talk, we investigate thermodynamic properties of an autonomous quantum heat engine, resembling a quantum version of the Feynman Ratchet, in non-equilibrium condition based on the theory of open quantum systems. The heat engine consists of multiple subsystems individually contacted to different thermal environments.

Polynomial approximations of thermodynamic properties of arbitrary gas mixtures over wide pressure and density ranges

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.

Extension of Generalized Fluid System Simulation Program's Fluid Property Database

NASA Technical Reports Server (NTRS)

Patel, Kishan

2011-01-01

This internship focused on the development of additional capabilities for the General Fluid Systems Simulation Program (GFSSP). GFSSP is a thermo-fluid code used to evaluate system performance by a finite volume-based network analysis method. The program was developed primarily to analyze the complex internal flow of propulsion systems and is capable of solving many problems related to thermodynamics and fluid mechanics. GFSSP is integrated with thermodynamic programs that provide fluid properties for sub-cooled, superheated, and saturation states. For fluids that are not included in the thermodynamic property program, look-up property tables can be provided. The look-up property tables of the current release version can only handle sub-cooled and superheated states. The primary purpose of the internship was to extend the look-up tables to handle saturated states. This involves a) generation of a property table using REFPROP, a thermodynamic property program that is widely used, and b) modifications of the Fortran source code to read in an additional property table containing saturation data for both saturated liquid and saturated vapor states. Also, a method was implemented to calculate the thermodynamic properties of user-fluids within the saturation region, given values of pressure and enthalpy. These additions required new code to be written, and older code had to be adjusted to accommodate the new capabilities. Ultimately, the changes will lead to the incorporation of this new capability in future versions of GFSSP. This paper describes the development and validation of the new capability.

Thermodynamic DFT analysis of natural gas.

PubMed

Neto, Abel F G; Huda, Muhammad N; Marques, Francisco C; Borges, Rosivaldo S; Neto, Antonio M J C

2017-08-01

Density functional theory was performed for thermodynamic predictions on natural gas, whose B3LYP/6-311++G(d,p), B3LYP/6-31+G(d), CBS-QB3, G3, and G4 methods were applied. Additionally, we carried out thermodynamic predictions using G3/G4 averaged. The calculations were performed for each major component of seven kinds of natural gas and to their respective air + natural gas mixtures at a thermal equilibrium between room temperature and the initial temperature of a combustion chamber during the injection stage. The following thermodynamic properties were obtained: internal energy, enthalpy, Gibbs free energy and entropy, which enabled us to investigate the thermal resistance of fuels. Also, we estimated an important parameter, namely, the specific heat ratio of each natural gas; this allowed us to compare the results with the empirical functions of these parameters, where the B3LYP/6-311++G(d,p) and G3/G4 methods showed better agreements. In addition, relevant information on the thermal and mechanic resistance of natural gases were investigated, as well as the standard thermodynamic properties for the combustion of natural gas. Thus, we show that density functional theory can be useful for predicting the thermodynamic properties of natural gas, enabling the production of more efficient compositions for the investigated fuels. Graphical abstract Investigation of the thermodynamic properties of natural gas through the canonical ensemble model and the density functional theory.

Analysis of the Glass-Forming Ability of Fe-Er Alloys, Based on Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Arutyunyan, N. A.; Zaitsev, A. I.; Dunaev, S. F.; Kalmykov, K. B.; El'nyakov, D. D.; Shaposhnikov, N. G.

2018-05-01

The Fe-Er phase diagram and thermodynamic properties of all its phases are assessed by means of self-consistent analysis. To refine the data on phase equilibria in the Fe-Er system, an investigation is performed in the 10-40 at % range of Er concentrations. The temperature-concentration dependences of the thermodynamic properties of a melt are presented using the model of ideal associated solutions. Thermodynamic parameters of each phase are obtained, and the calculated results are in agreement with available experimental data. The correlation between the thermodynamic properties of liquid Fe-Er alloys and their tendency toward amorphization are studied. It is shown that compositions of amorphous alloys prepared by melt quenching coincide with the ranges of concentration with the predominance of Fe3Er and FeEr2 associative groups that have large negative entropies of formation.

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 lanthanum in gallium-zinc alloys

NASA Astrophysics Data System (ADS)

Dedyukhin, A. S.; Shepin, I. E.; Kharina, E. A.; Shchetinskiy, A. V.; Volkovich, V. A.; Yamshchikov, L. F.

2016-09-01

Thermodynamic properties of lanthanum were determined in gallium-zinc alloys of the eutectic and over-eutectic compositions. The electromotive force measurements were used to determine thermodynamic activity and sedimentation technique to measure solubility of lanthanum in liquid metal alloys. Temperature dependencies of lanthanum activity, solubility and activity coefficients in alloys with Ga-Zn mixtures containing 3.64, 15 and 50 wt. % zinc were obtained.

Revisit on the thermodynamic stability of Hořava-Lifshitz black hole

NASA Astrophysics Data System (ADS)

Meng, Xudong; Wang, Ruihong

We study the thermodynamic properties of the black hole derived in Hořava-Lifshitz (HL) gravity without the detailed-balance condition. The parameter Ξ = 𝜖2 in the HL black hole plays the same role as that of the electric charge in the Reissner-Nordström-anti-de Sitter (RN-AdS) black hole. By analogy, we treat the parameter Ξ as the thermodynamic variable and obtain the first law of thermodynamics for the HL black hole. Although the HL black hole and the RN-AdS black hole have the similar mass and temperature, due to their very different entropy, the two black holes have very different thermodynamic properties. By calculating the heat capacity and the free energy, we analyze the thermodynamic stability of the HL black hole.

Mean-field potential approach for thermodynamic properties of lanthanide: Europium as a prototype

NASA Astrophysics Data System (ADS)

Kumar, Priyank; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

2018-03-01

In the present paper, a simple conjunction scheme [mean-field potential (MFP) + local pseudopotential] is used to study the thermodynamic properties of divalent lanthanide europium (Eu) at extreme environment. Present study has been carried out due to the fact that divalent nature of Eu arises because of stable half-filled 4f-shell at ambient condition, which has great influence on the thermodynamic properties at extreme environment. Due to such electronic structure, it is different from remaining lanthanides having incomplete 4f-shell. The presently computed results of thermodynamic properties of Eu are in good agreement with the experimental results. Looking to such success, it seems that the concept of MFP approach is successful to account contribution due to nuclear motion to the total Helmholtz free energy at finite temperatures and pressure-induced inter-band transfer of electrons for condensed state of matter. The local pseudopotential is used to evaluate cold energy and hence MFP accounts the s-p-d-f hybridization properly. Looking to the reliability and transferability along with its computational and conceptual simplicity, we would like to extend the present scheme for the study of thermodynamic properties of remaining lanthanides and actinides at extreme environment.

An EQT-based cDFT approach for thermodynamic properties of confined fluid mixtures

NASA Astrophysics Data System (ADS)

Motevaselian, M. H.; Aluru, N. R.

2017-04-01

We present an empirical potential-based quasi-continuum theory (EQT) to predict the structure and thermodynamic properties of confined fluid mixtures. The central idea in the EQT is to construct potential energies that integrate important atomistic details into a continuum-based model such as the Nernst-Planck equation. The EQT potentials can be also used to construct the excess free energy functional, which is required for the grand potential in the classical density functional theory (cDFT). In this work, we use the EQT-based grand potential to predict various thermodynamic properties of a confined binary mixture of hydrogen and methane molecules inside graphene slit channels of different widths. We show that the EQT-cDFT predictions for the structure, surface tension, solvation force, and local pressure tensor profiles are in good agreement with the molecular dynamics simulations. Moreover, we study the effect of different bulk compositions and channel widths on the thermodynamic properties. Our results reveal that the composition of methane in the mixture can significantly affect the ordering of molecules and thermodynamic properties under confinement. In addition, we find that graphene is selective to methane molecules.

Balanced Biochemical Reactions: A New Approach to Unify Chemical and Biochemical Thermodynamics

PubMed Central

Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

2012-01-01

A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction ΔrG ′0, ΔrH ′0, ΔrS ′0 and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation ΔfG ′0, ΔfH ′0 and ΔfS ′0 hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term “conditional” is proposed in substitution of “Legendre transformed” to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G′ is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately. PMID:22247780

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thakar, Nilesh A.; Bhatt, Apoorva D.; Pandya, Tushar C., E-mail: pandyatc@gmail.com

The thermodynamic properties with the wurtzite (B4) and rocksalt (B1) phases of ZnO under high pressures and high temperatures have been investigated using Tait's Equation of state (EOS). The effects of pressures and temperatures on thermodynamic properties such as bulk modulus, thermal expansivity and thermal pressure are explored for both two structures. It is found that ZnO material gradually softens with increase of temperature while it hardens with the increment of the pressure. Our predicted results of thermodynamics properties for both the phases of ZnO are in overall agreement with the available data in the literature.

Absorption Filter Based Optical Diagnostics in High Speed Flows

NASA Technical Reports Server (NTRS)

Samimy, Mo; Elliott, Gregory; Arnette, Stephen

1996-01-01

Two major regimes where laser light scattered by molecules or particles in a flow contains significant information about the flow are Mie scattering and Rayleigh scattering. Mie scattering is used to obtain only velocity information, while Rayleigh scattering can be used to measure both the velocity and the thermodynamic properties of the flow. Now, recently introduced (1990, 1991) absorption filter based diagnostic techniques have started a new era in flow visualization, simultaneous velocity and thermodynamic measurements, and planar velocity measurements. Using a filtered planar velocimetry (FPV) technique, we have modified the optically thick iodine filter profile of Miles, et al., and used it in the pressure-broaden regime which accommodates measurements in a wide range of velocity applications. Measuring velocity and thermodynamic properties simultaneously, using absorption filtered based Rayleigh scattering, involves not only the measurement of the Doppler shift, but also the spectral profile of the Rayleigh scattering signal. Using multiple observation angles, simultaneous measurement of one component velocity and thermodynamic properties in a supersonic jet were measured. Presently, the technique is being extended for simultaneous measurements of all three components of velocity and thermodynamic properties.

The A [plus] B [double arrow] C of Chemical Thermodynamics.

ERIC Educational Resources Information Center

Gerhartl, F. J.

1994-01-01

Basic chemical thermodynamics usually treats non-p,T reactions in a stepmotherly fashion. This paper covers the main aspects of the theoretical principles of reactions (p,T; V,T; p,H; and V,U) and offers results from the ABC computer program, which was designed to show the validity of the equilibrium theory to all types of reaction modes. (PVD)

Molecular Thermodynamics for Cell Biology as Taught with Boxes

PubMed Central

Mayorga, Luis S.; López, María José; Becker, Wayne M.

2012-01-01

Thermodynamic principles are basic to an understanding of the complex fluxes of energy and information required to keep cells alive. These microscopic machines are nonequilibrium systems at the micron scale that are maintained in pseudo-steady-state conditions by very sophisticated processes. Therefore, several nonstandard concepts need to be taught to rationalize why these very ordered systems proliferate actively all over our planet in seeming contradiction to the second law of thermodynamics. We propose a model consisting of boxes with different shapes that contain small balls that are in constant motion due to a stream of air blowing from below. This is a simple macroscopic system that can be easily visualized by students and that can be understood as mimicking the behavior of a set of molecules exchanging energy. With such boxes, the basic concepts of entropy, enthalpy, and free energy can be taught while reinforcing a molecular understanding of the concepts and stressing the stochastic nature of the thermodynamic laws. In addition, time-related concepts, such as reaction rates and activation energy, can be readily visualized. Moreover, the boxes provide an intuitive way to introduce the role in cellular organization of “information” and Maxwell's demons operating under nonequilibrium conditions. PMID:22383615

Molecular thermodynamics for cell biology as taught with boxes.

PubMed

Mayorga, Luis S; López, María José; Becker, Wayne M

2012-01-01

Thermodynamic principles are basic to an understanding of the complex fluxes of energy and information required to keep cells alive. These microscopic machines are nonequilibrium systems at the micron scale that are maintained in pseudo-steady-state conditions by very sophisticated processes. Therefore, several nonstandard concepts need to be taught to rationalize why these very ordered systems proliferate actively all over our planet in seeming contradiction to the second law of thermodynamics. We propose a model consisting of boxes with different shapes that contain small balls that are in constant motion due to a stream of air blowing from below. This is a simple macroscopic system that can be easily visualized by students and that can be understood as mimicking the behavior of a set of molecules exchanging energy. With such boxes, the basic concepts of entropy, enthalpy, and free energy can be taught while reinforcing a molecular understanding of the concepts and stressing the stochastic nature of the thermodynamic laws. In addition, time-related concepts, such as reaction rates and activation energy, can be readily visualized. Moreover, the boxes provide an intuitive way to introduce the role in cellular organization of "information" and Maxwell's demons operating under nonequilibrium conditions.

Effects of physical properties on thermo-fluids cavitating flows

NASA Astrophysics Data System (ADS)

Chen, T. R.; Wang, G. Y.; Huang, B.; Li, D. Q.; Ma, X. J.; Li, X. L.

2015-12-01

The aims of this paper are to study the thermo-fluid cavitating flows and to evaluate the effects of physical properties on cavitation behaviours. The Favre-averaged Navier-Stokes equations with the energy equation are applied to numerically investigate the liquid nitrogen cavitating flows around a NASA hydrofoil. Meanwhile, the thermodynamic parameter Σ is used to assess the thermodynamic effects on cavitating flows. The results indicate that the thermodynamic effects on the thermo-fluid cavitating flows significantly affect the cavitation behaviours, including pressure and temperature distribution, the variation of physical properties, and cavity structures. The thermodynamic effects can be evaluated by physical properties under the same free-stream conditions. The global sensitivity analysis of liquid nitrogen suggests that ρv, Cl and L significantly influence temperature drop and cavity structure in the existing numerical framework, while pv plays the dominant role when these properties vary with temperature. The liquid viscosity μl slightly affects the flow structure via changing the Reynolds number Re equivalently, however, it hardly affects the temperature distribution.

Building on the Legacy of Professor Keenan. Entropy An Intrinsic Property of Matter

NASA Astrophysics Data System (ADS)

Gyftopoulos, Elias P.

2008-08-01

In the scientific and engineering literature, entropy—the distinguishing feature of thermodynamics from other branches of physics—is viewed with skepticism, and thought to be not a physical property of matter—like mass or energy—but a measure either of disorder in a system, or of lack of information about the physics of a system in a thermodynamic equilibrium state, and a plethora of expressions are proposed for its analytical representation. In this article, I present briefly two revolutionary nonstatistical expositions of thermodynamics (revolutionary in the sense of Thomas Kuhn, The Structure of Scientific Revolutions, U. Chicago Press, 1970) that apply to all systems (both macroscopic and microscopic, including one spin or a single particle), to all states (thermodynamic equilibrium, and not thermodynamic equilibrium), and that disclose entropy as an intrinsic property of matter. The first theory is presented without reference to quantum mechanics even though quantum theoretic ideas are lurking behind the exposition. The second theory is a unified quantum theory of mechanics and thermodynamics without statistical probabilities, that is, I am not presenting another version of statistical quantum mechanics.

Thermodynamic and Kinematic Flow Characteristics of Some Developing and Non-Developing Disturbances in Predict

DTIC Science & Technology

2014-12-01

normal ( 1S ) and parallel ( 2S ) strain rates squared. U and V are the zonal and meridional velocities and the x and y subscripts indicate partial...between developing and non-developing tropical disturbances appears to lie with the kinematic flow boundary structure and thermodynamic properties ...tropical disturbances appears to lie with the kinematic flow boundary structure and thermodynamic properties hypothesized in the marsupial paradigm

Thermodynamic scaling of dynamic properties of liquid crystals: Verifying the scaling parameters using a molecular model

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.

Thermodynamic properties and equations of state for Ag, Al, Au, Cu and MgO using a lattice vibrational method

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, when coupled to a thermodynamic computation program, the calculation and prediction of phase equilibria and thermo-physical properties of phase equilibrium assemblages in pressure-temperature-composition space. In Jacobs and van den Berg (2011) the vibrational method, together with a thermodynamic data base, was successfully applied to mantle convection of materials in the Earth. These works demonstrate that the vibrational method has the advantages of (1) computational speed, (2) coupling or making comparisons with ab initio methods and (3) making reliable extrapolations to extreme conditions. We present results of thermodynamic analyses, using lattice vibrational methods, of Ag, Al, Au, Cu and MgO covering the pressure and temperature regime of the Earth's interior. We show results on consistency of the pressure scales for these materials using different equations of state, under the constraint that thermodynamic properties in the low-pressure regime are accurately represented.

The effect of gyrolite additive on the hydration properties of Portland cement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisinas, A., E-mail: anatolijus.eisinas@ktu.lt; Baltakys, K.; Siauciunas, R.

2012-01-15

The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C-S-H, with higher basicity (C/S {approx} 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stagemore » II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C{sub 3}S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.« less

Stochastic thermodynamics

NASA Astrophysics Data System (ADS)

Eichhorn, Ralf; Aurell, Erik

2014-04-01

'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response theory for small deviations from equilibrium, in which a general framework is constructed from the analysis of non-equilibrium states close to equilibrium. In a next step, Prigogine and others developed linear irreversible thermodynamics, which establishes relations between transport coefficients and entropy production on a phenomenological level in terms of thermodynamic forces and fluxes. However, beyond the realm of linear response no general theoretical results were available for quite a long time. This situation has changed drastically over the last 20 years with the development of stochastic thermodynamics, revealing that the range of validity of thermodynamic statements can indeed be extended deep into the non-equilibrium regime. Early developments in that direction trace back to the observations of symmetry relations between the probabilities for entropy production and entropy annihilation in non-equilibrium steady states [5-8] (nowadays categorized in the class of so-called detailed fluctuation theorems), and the derivations of the Bochkov-Kuzovlev [9, 10] and Jarzynski relations [11] (which are now classified as so-called integral fluctuation theorems). Apart from its fundamental theoretical interest, the developments in stochastic thermodynamics have experienced an additional boost from the recent experimental progress in fabricating, manipulating, controlling and observing systems on the micro- and nano-scale. These advances are not only of formidable use for probing and monitoring biological processes on the cellular, sub-cellular and molecular level, but even include the realization of a microscopic thermodynamic heat engine [12] or the experimental verification of Landauer's principle in a colloidal system [13]. The scientific program Stochastic Thermodynamics held between 4 and 15 March 2013, and hosted by The Nordic Institute for Theoretical Physics (Nordita), was attended by more than 50 scientists from the Nordic countries and elsewhere, amongst them many leading experts in the field. During the program, the most recent developments, open questions and new ideas in stochastic thermodynamics were presented and discussed. From the talks and debates, the notion of information in stochastic thermodynamics, the fundamental properties of entropy production (rate) in non-equilibrium, the efficiency of small thermodynamic machines and the characteristics of optimal protocols for the applied (cyclic) forces were crystallizing as main themes. Surprisingly, the long-studied adiabatic piston, its peculiarities and its relation to stochastic thermodynamics were also the subject of intense discussions. The comment on the Nordita program Stochastic Thermodynamics published in this issue of Physica Scripta exploits the Jarzynski relation for determining free energy differences in the adiabatic piston. This scientific program and the contribution presented here were made possible by the financial and administrative support of The Nordic Institute for Theoretical Physics.

Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

PubMed

Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

2015-07-07

The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

Generalized Poisson-Kac Processes: Basic Properties and Implications in Extended Thermodynamics and Transport

NASA Astrophysics Data System (ADS)

Giona, Massimiliano; Brasiello, Antonio; Crescitelli, Silvestro

2016-04-01

We introduce a new class of stochastic processes in Rn,{{{mathbb R}}^n}, referred to as generalized Poisson-Kac (GPK) processes, that generalizes the Poisson-Kac telegrapher's random motion in higher dimensions. These stochastic processes possess finite propagation velocity, almost everywhere smooth trajectories, and converge in the Kac limit to Brownian motion. GPK processes are defined by coupling the selection of a bounded velocity vector from a family of N distinct ones with a Markovian dynamics controlling probabilistically this selection. This model can be used as a probabilistic tool for a stochastically consistent formulation of extended thermodynamic theories far from equilibrium.

Analytical description of concentration dependence of surface tension in multicomponent systems

NASA Astrophysics Data System (ADS)

R, Dadashev; R, Kutuev; D, Elimkhanov

2008-02-01

From the basic fundamental thermodynamic expressions the equation of isotherms of the surface tension of a ternary system is received. Various assumptions concerning the concentration dependence of molar areas are usually made when the equation is derived. The dependence of the molar areas is calculated as an additive function of the structure of a volumetric phase or the structure of a surface layer. To define the concentration dependence of the molar areas we used a stricter thermodynamic expression offered by Butler. In the received equation the dependence of molar areas on the structure of the solution is taken into account. Therefore, the equation can be applied for the calculation of surface tension over a wide concentration range of the components. Unlike the known expressions, the equation includes the surface tension properties of lateral binary systems, which makes the accuracy of the calculated values considerably higher. Thus, among the advantages of the offered equation we can point out the mathematical simplicity of the received equation and the fact that the equation includes physical parameters the experimental definition of which does not present any special difficulties.

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.

The Equations of Oceanic Motions

NASA Astrophysics Data System (ADS)

Müller, Peter

2006-10-01

Modeling and prediction of oceanographic phenomena and climate is based on the integration of dynamic equations. The Equations of Oceanic Motions derives and systematically classifies the most common dynamic equations used in physical oceanography, from large scale thermohaline circulations to those governing small scale motions and turbulence. After establishing the basic dynamical equations that describe all oceanic motions, M|ller then derives approximate equations, emphasizing the assumptions made and physical processes eliminated. He distinguishes between geometric, thermodynamic and dynamic approximations and between the acoustic, gravity, vortical and temperature-salinity modes of motion. Basic concepts and formulae of equilibrium thermodynamics, vector and tensor calculus, curvilinear coordinate systems, and the kinematics of fluid motion and wave propagation are covered in appendices. Providing the basic theoretical background for graduate students and researchers of physical oceanography and climate science, this book will serve as both a comprehensive text and an essential reference.

Computer simulation of liquid metals

NASA Astrophysics Data System (ADS)

Belashchenko, D. K.

2013-12-01

Methods for and the results of the computer simulation of liquid metals are reviewed. Two basic methods, classical molecular dynamics with known interparticle potentials and the ab initio method, are considered. Most attention is given to the simulated results obtained using the embedded atom model (EAM). The thermodynamic, structural, and diffusion properties of liquid metal models under normal and extreme (shock) pressure conditions are considered. Liquid-metal simulated results for the Groups I - IV elements, a number of transition metals, and some binary systems (Fe - C, Fe - S) are examined. Possibilities for the simulation to account for the thermal contribution of delocalized electrons to energy and pressure are considered. Solidification features of supercooled metals are also discussed.

The uniform quantized electron gas revisited

NASA Astrophysics Data System (ADS)

Lomba, Enrique; Høye, Johan S.

2017-11-01

In this article we continue and extend our recent work on the correlation energy of the quantized electron gas of uniform density at temperature T=0 . As before, we utilize the methods, properties, and results obtained by means of classical statistical mechanics. These were extended to quantized systems via the Feynman path integral formalism. The latter translates the quantum problem into a classical polymer problem in four dimensions. Again, the well known RPA (random phase approximation) is recovered as a basic result which we then modify and improve upon. Here we analyze the condition of thermodynamic self-consistency. Our numerical calculations exhibit a remarkable agreement with well known results of a standard parameterization of Monte Carlo correlation energies.

Thermodynamic properties of rare earth elements in La-RE-Ga-In alloys (RE = Nd, Y)

NASA Astrophysics Data System (ADS)

Raguzina, Ekaterina V.; Maltsev, Dmitry S.; Volkovich, Vladimir A.; Yamshchikov, Leonid F.; Chukin, Andrey V.

2017-09-01

Thermodynamic properties of La, Nd, and Y were studied in pseudo-quaternary systems La-Nd-(Ga-In)eut and La-Y-(Ga-In)eut. Temperature dependences of lanthanum, neodymium, and yttrium activity in the alloys were determined at 300-800 °C employing the e.m.f. method. Partial thermodynamic functions of lanthanum in the alloys studied were calculated on the basis of the experimental data.

Characteristics of Subcooled Liquid Methane During Passage Through a Spray-Bar Joule-Thompson Thermodynamic Vent System

NASA Technical Reports Server (NTRS)

Hastings, L. J.; Bolshinskiy, L. G.; Hedayat, A.; Schnell, A.

2011-01-01

NASA s Marshall Space Flight Center (MSFC) conducted liquid methane (LCH4) testing in November 2006 using the multipurpose hydrogen test bed (MHTB) outfitted with a spray-bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with subcooled LCH4 that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 W to 420 W at a fill level of approximately 90%. During an updated evaluation of the data, it was noted that as the fluid passed through the Joule Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This paper describes the observed thermodynamic conditions that correspond with metastability and effects on TVS performance.

Thermodynamic and related properties of parahydrogen from the triple point to 300 K at pressures to 1000 bar

NASA Technical Reports Server (NTRS)

Weber, L. A.

1975-01-01

Compressibility measurements and thermodynamic properties data for parahydrogen were extended to higher temperatures and pressures. Results of an experimental program are presented in the form of new pressure, volume and temperature data in the temperature range 23 to 300 K at pressures up to 800 bar. Also given are tables of thermodynamic properties on isobars to 1000 bar including density, internal energy, enthalpy, entropy, specific heats at constant volume and constant pressure, velocity of sound, and surface derivatives. The accuracy of the data is discussed and comparisons are made with previous data.

Phase transitions and thermodynamic properties of antiferromagnetic Ising model with next-nearest-neighbor interactions on the Kagomé lattice

NASA Astrophysics Data System (ADS)

Ramazanov, M. K.; Murtazaev, A. K.; Magomedov, M. A.; Badiev, M. K.

2018-06-01

We study phase transitions and thermodynamic properties in the two-dimensional antiferromagnetic Ising model with next-nearest-neighbor interaction on a Kagomé lattice by Monte Carlo simulations. A histogram data analysis shows that a second-order transition occurs in the model. From the analysis of obtained data, we can assume that next-nearest-neighbor ferromagnetic interactions in two-dimensional antiferromagnetic Ising model on a Kagomé lattice excite the occurrence of a second-order transition and unusual behavior of thermodynamic properties on the temperature dependence.

First-principles study on the phase transitions, crystal stabilities and thermodynamic properties of TiN under high pressure

NASA Astrophysics Data System (ADS)

Sun, Xinjun; Liu, Changdong; Guo, Yongliang; Sun, Deyan; Ke, Xuezhi

2018-03-01

The structural and thermodynamic properties of titanium nitride (TiN) have been investigated by merging first-principles calculations and particle-swarm algorithm. The three phases are identified for TiN, including the B1, the P63 / mmc, and the B2 phases. A new phase of anti-TiP structure with the space group P63 / mmc has been predicted. The calculated phase transition from the B1 to the P63 / mmc occurs at 270 GPa. The vibrational, elastic, and thermodynamic properties for the three phases have been calculated and discussed.

Hybrid biosorbents for removal of pollutants and remediation

NASA Astrophysics Data System (ADS)

Burlakovs, Juris; Klavins, Maris; Robalds, Artis; Ansone, Linda

2014-05-01

For remediation of soils and purification of polluted waters, wastewaters, biosorbents might be considered as prospective groups of materials. Amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However, peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes thereby, to expand peat application sphere, the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in understanding of biosorbent means natural, biomass based modified material, covered with another sorbent material, thus combining properties of both such as sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyappatite) and organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area and elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature as the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested.

The maximum entropy production principle: two basic questions.

PubMed

Martyushev, Leonid M

2010-05-12

The overwhelming majority of maximum entropy production applications to ecological and environmental systems are based on thermodynamics and statistical physics. Here, we discuss briefly maximum entropy production principle and raises two questions: (i) can this principle be used as the basis for non-equilibrium thermodynamics and statistical mechanics and (ii) is it possible to 'prove' the principle? We adduce one more proof which is most concise today.

Evaluation of a Liquid Amine System for Spacecraft Carbon Dioxide Control

NASA Technical Reports Server (NTRS)

Breaux, D. K.; Friedel, P.; Hwang, K. C.; Probert, G.; Ruder, J. M.; Sawamura, L.

1974-01-01

The analytical and experimental studies are described which were directed toward the acquisition of basic information on utilizing a liquid amine sorbent for in use in a CO2 removal system for manned spacecraft. Liquid amine systems are successfully used on submarines for control of CO2 generated by the crew, but liquid amines were not previously considered for spacecraft applications due to lack of development of satisfactory rotary phase separators. Developments in this area now make consideration of liquid amines practical for spacecraft system CO2 removal. The following major tasks were performed to evaluate liquid amine systems for spacecraft: (1) characterization, through testing, of the basic physical and thermodynamic properties of the amine solution; (2) determination of the dynamic characteristics of a cocurrent flow absorber; and (3) evaluation, synthesis, and selection of a liquid amine system concept oriented toward low power requirements. A low weight, low power system concept was developed. Numerical and graphical data are accompanied by pertinent observations.

The two-step assemblies of basic-amino-Acid-rich Peptide with a highly charged polyoxometalate.

PubMed

Zhang, Teng; Li, Hong-Wei; Wu, Yuqing; Wang, Yizhan; Wu, Lixin

2015-06-15

Two-step assembly of a peptide from HPV16 L1 with a highly charged europium-substituted polyoxometalate (POM) cluster, accompanying a great luminescence enhancement of the inorganic polyanions, is reported. The mechanism is discussed in detail by analyzing the thermodynamic parameters from isothermal titration calorimetry (ITC), time-resolved fluorescent and NMR spectra. By comparing the actions of the peptide analogues, a binding process and model are proposed accordingly. The driving forces in each binding step are clarified, and the initial POM aggregation, basic-sequence and hydrophobic C termini of peptide are revealed to contribute essentially to the two-step assembly. The present study demonstrates both a meaningful preparation for bioinorganic materials and a strategy using POMs to modulate the assembly of peptides and even proteins, which could be extended to other proteins and/or viruses by using peptides and POMs with similar properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical calculating the thermodynamic properties of solid sorbents for CO{sub 2} capture applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 calculatedmore » 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 to several different kinds of solid systems, we demonstrate that our methodology can predict the useful information to help developing CO{sub 2} capture Technologies.« less

Thermodynamic studies of different black holes with modifications of entropy

NASA Astrophysics Data System (ADS)

Haldar, Amritendu; Biswas, Ritabrata

2018-02-01

In recent years, the thermodynamic properties of black holes are topics of interests. We investigate the thermodynamic properties like surface gravity and Hawking temperature on event horizon of regular black holes viz. Hayward Class and asymptotically AdS (Anti-de Sitter) black holes. We also analyze the thermodynamic volume and naive geometric volume of asymptotically AdS black holes and show that the entropy of these black holes is simply the ratio of the naive geometric volume to thermodynamic volume. We plot the different graphs and interpret them physically. We derive the `cosmic-Censorship-Inequality' for both type of black holes. Moreover, we calculate the thermal heat capacity of aforesaid black holes and study their stabilities in different regimes. Finally, we compute the logarithmic correction to the entropy for both the black holes considering the quantum fluctuations around the thermal equilibrium and study the corresponding thermodynamics.

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.

THERMODYNAMIC PROPERTIES OF MC (M = V, Nb, Ta): FIRST-PRINCIPLES CALCULATIONS

NASA Astrophysics Data System (ADS)

Cao, Yong; Zhu, Jingchuan; Liu, Yong; Long, Zhishen

2013-07-01

Through the quasi-harmonic Debye model, the pressure and temperature dependences of linear expansion coefficient, bulk modulus, Debye temperature and heat capacity have been investigated. The calculated thermodynamic properties were compared with experimental data and satisfactory agreement is reached.

Hydrodynamic theory of active matter

NASA Astrophysics Data System (ADS)

Jülicher, Frank; Grill, Stephan W.; Salbreux, Guillaume

2018-07-01

We review the general hydrodynamic theory of active soft materials that is motivated in particular by biological matter. We present basic concepts of irreversible thermodynamics of spatially extended multicomponent active systems. Starting from the rate of entropy production, we identify conjugate thermodynamic fluxes and forces and present generic constitutive equations of polar active fluids and active gels. We also discuss angular momentum conservation which plays a role in the the physics of active chiral gels. The irreversible thermodynamics of active gels provides a general framework to discuss the physics that underlies a wide variety of biological processes in cells and in multicellular tissues.

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Computational Thermodynamics of Materials Zi-Kui Liu and Yi Wang

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devanathan, Ram

This authoritative volume introduces the reader to computational thermodynamics and the use of this approach to the design of material properties by tailoring the chemical composition. The text covers applications of this approach, introduces the relevant computational codes, and offers exercises at the end of each chapter. The book has nine chapters and two appendices that provide background material on computer codes. Chapter 1 covers the first and second laws of thermodynamics, introduces the spinodal as the limit of stability, and presents the Gibbs-Duhem equation. Chapter 2 focuses on the Gibbs energy function. Starting with a homogeneous system with amore » single phase, the authors proceed to phases with variable compositions, and polymer blends. The discussion includes the contributions of external electric and magnetic fields to the Gibbs energy. Chapter 3 deals with phase equilibria in heterogeneous systems, the Gibbs phase rule, and phase diagrams. Chapter 4 briefly covers experimental measurements of thermodynamic properties used as input for thermodynamic modeling by Calculation of Phase Diagrams (CALPHAD). Chapter 5 discusses the use of density functional theory to obtain thermochemical data and fill gaps where experimental data is missing. The reader is introduced to the Vienna Ab Initio Simulation Package (VASP) for density functional theory and the YPHON code for phonon calculations. Chapter 6 introduces the modeling of Gibbs energy of phases with the CALPHAD method. Chapter 7 deals with chemical reactions and the Ellingham diagram for metal-oxide systems and presents the calculation of the maximum reaction rate from equilibrium thermodynamics. Chapter 8 is devoted to electrochemical reactions and Pourbaix diagrams with application examples. Chapter 9 concludes this volume with the application of a model of multiple microstates to Ce and Fe3Pt. CALPHAD modeling is briefly discussed in the context of genomics of materials. The book introduces basic thermodynamic concepts clearly and directs readers to appropriate references for advanced concepts and details of software implementation. The list of references is quite comprehensive. The authors make liberal use of diagrams to illustrate key concepts. The two Appendices at the end discuss software requirements and the file structure, and present templates for special quasi-random structures. There is also a link to download pre-compiled binary files of the YPHON code for Linux or Microsoft Windows systems. The exercises at the end of the chapters assume that the reader has access to VASP, which is not freeware. Readers without access to this code can work on a limited number of exercises. However, results from other first principles codes can be organized in the YPHON format as explained in the Appendix. This book will serve as an excellent reference on computational thermodynamics and the exercises provided at the end of each chapter make it valuable as a graduate level textbook. Reviewer: Ram Devanathan is Acting Director of Earth Systems Science Division, Pacific Northwest National Laboratory, USA.« less

Thermodynamic data for biomass conversion and waste incineration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Domalski, E.S.; Jobe, T.L. Jr; Milne, T.A.

1986-09-01

The general purpose of this collection of thermodynamic data of selected materials is to make property information available to the engineering community on chemical mixtures, polymers, composite materials, solid wastes, biomass, and materials not easily identifiable by a single stoichiometric formula. More than 700 materials have been compiled covering properties such as specific heat, gross heat of combustion, heat of fusion, heat of vaporization, and vapor pressure. The information was obtained from the master files of the NBS Chemical Thermodynamics Data Center, the annual issues of the Bulletin of Chemical Thermodynamics, intermittent examinations of the Chemical Abstracts subject indexes, individualmore » articles by various authors, and other general reference sources. The compilation is organized into several broad categories; materials are listed alphabetically within each category. For each material, the physical state, information as to the composition or character of the material, the kind of thermodynamic property reported, the specific property values for the material, and citations to the reference list are given. In addition, appendix A gives an empirical formula that allows heats of combustion of carbonaceous materials to be predicted with surprising accuracy when the elemental composition is known. A spread sheet illustrates this predictability with examples from this report and elsewhere. Appendix B lists some reports containing heats of combustion not included in this publication. Appendix C contains symbols, units, conversion factors, and atomic weights used in evaluating and compiling the thermodynamic data.« less

Thermodynamic properties of pressurized PH3 superconductor

NASA Astrophysics Data System (ADS)

Koka, S.; Rao, G. Venugopal

2018-05-01

The paper presents the superconducting thermodynamic functions determined for pressurized phosphorus trihydride (PH3). In particular, free energy difference ΔF, thermodynamic critical field Hc, specific heat etc. have been calculated using analytical expressions. The calculations were performed in the frame work of the strong-coupling formalism. The obtained dimensionless parameters: RΔ ≡ 2Δ(0)/kBTc, RC ≡ ΔC(Tc)/CN(Tc) and RH≡TcCN(Tc)/Hc2(0) are 4.05, 1.96 and 0.156 respectively, which significantly differ from the values arising from the BCS theory of superconductivity. The thermodynamic properties strongly depend on the depairing electron correlations and retardation effects.

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.

Thermodynamics Study of Removal of Heavy Metal by TiN-Nanotubes

NASA Astrophysics Data System (ADS)

Mahdavian, Leila

2015-12-01

The ability of TiN-nanotube to remove lead (Pb(II)) and arsenic (As(III)) ions from aqueous solutions is investigated. The thermodynamics properties of Pb(II) and As(III) ions passing through TiN-nanotubes (TiN-NTs) is calculated in basis set (B3LYP/6-31G**) DFT-IR method by Gaussian program package. The results showed, Pb(II) and As(III) passing through had low potential in middle nanotubes, and are trapped in this place. The thermodynamic properties showed; the passing through are spontaneous and favorable because ΔGele (MJ/mol) is negative for them. The goal of this study is the detection of surface species of TiN-NTs for metal ions removal by using computer calculations. The structural and thermodynamic properties studied ions absorption on TiN-NTs at room temperature.

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.

Electronic structure, thermodynamic properties and hydrogenation of LaPtIn and CePtIn compounds by ab-initio methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jezierski, Andrzej, E-mail: andrzej.jezierski@ifmpan.poznan.pl; Szytuła, Andrzej

2016-02-15

The electronic structures and thermodynamic properties of LaPtIn and CePtIn are studied by means of ab-initio full-relativistic full-potential local orbital basis (FPLO) method within densities functional (DFT) methodologies. We have also examined the influence of hydrogen on the electronic structure and stability of CePtInH and LaPtInH systems. The positions of the hydrogen atoms have been found from the minimum of the total energy. Our calculations have shown that band structure and topology of the Fermi surfaces changed significantly during the hydrogenation. The thermodynamic properties (bulk modulus, Debye temperatures, constant pressure heat capacity) calculated in quasi-harmonic Debye-Grüneisen model are in amore » good agreement with the experimental data. We have applied different methods of the calculation of the equation of states (EOS) (Murnaghan, Birch-Murnaghan, Poirier–Tarantola, Vinet). The thermodynamic properties are presented for the pressure 0« less

An EQT-cDFT approach to determine thermodynamic properties of confined fluids.

PubMed

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.

Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

PubMed

Jenkins, H Donald Brooke; Glasser, Leslie

2004-12-08

We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

Thermodynamic and Kinetic Properties of Shocks in Two-Dimensional Yukawa Systems [Thermodynamic and Kinetic Properties of Shocks in 2D Yukawa Systems

DOE PAGES

Marciante, Mathieu; Murillo, Michael Sean

2017-01-10

Particle-level simulations of shocked plasmas are carried out to examine kinetic properties not captured by hydrodynamic models. In particular, molecular dynamics simulations of 2D Yukawa plasmas with variable couplings and screening lengths are used to examine shock features unique to plasmas, including the presence of dispersive shock structures for weak shocks. A phase-space analysis reveals several kinetic properties, including anisotropic velocity distributions, non-Maxwellian tails, and the presence of fast particles ahead of the shock, even for moderately low Mach numbers. As a result, we also examine the thermodynamics (Rankine-Hugoniot relations) of recent experiments and find no anomalies in their equationsmore » of state.« less

Thermodynamic and Kinetic Properties of Shocks in Two-Dimensional Yukawa Systems [Thermodynamic and Kinetic Properties of Shocks in 2D Yukawa Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marciante, Mathieu; Murillo, Michael Sean

Particle-level simulations of shocked plasmas are carried out to examine kinetic properties not captured by hydrodynamic models. In particular, molecular dynamics simulations of 2D Yukawa plasmas with variable couplings and screening lengths are used to examine shock features unique to plasmas, including the presence of dispersive shock structures for weak shocks. A phase-space analysis reveals several kinetic properties, including anisotropic velocity distributions, non-Maxwellian tails, and the presence of fast particles ahead of the shock, even for moderately low Mach numbers. As a result, we also examine the thermodynamics (Rankine-Hugoniot relations) of recent experiments and find no anomalies in their equationsmore » of state.« less

Liquid Methane Testing With a Large-Scale Spray Bar Thermodynamic Vent System

NASA Technical Reports Server (NTRS)

Hastings, L. J.; Bolshinskiy, L. G.; Hedayat, A.; Flachbart, R. H.; Sisco, J. D.; Schnell. A. R.

2014-01-01

NASA's Marshall Space Flight Center conducted liquid methane testing in November 2006 using the multipurpose hydrogen test bed outfitted with a spray bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with densified methane that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 to 420 W at a fill level of approximately 90%. It was noted that as the fluid passed through the Joule-Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This Technical Publication describes conditions that correspond with metastability and its detrimental effects on TVS performance. The observed conditions were primarily functions of methane densification and helium pressurization; therefore, assurance must be provided that metastable conditions have been circumvented in future applications of thermodynamic venting to in-space methane storage.

Method for preparing salt solutions having desired properties

DOEpatents

Ally, Moonis R.; Braunstein, Jerry

1994-01-01

The specification discloses a method for preparing salt solutions which exhibit desired thermodynamic properties. The method enables prediction of the value of the thermodynamic properties for single and multiple salt solutions over a wide range of conditions from activity data and constants which are independent of concentration and temperature. A particular application of the invention is in the control of salt solutions in a process to provide a salt solution which exhibits the desired properties.

Calibration and Propagation of Uncertainty for Independence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holland, Troy Michael; Kress, Joel David; Bhat, Kabekode Ghanasham

This document reports on progress and methods for the calibration and uncertainty quantification of the Independence model developed at UT Austin. The Independence model is an advanced thermodynamic and process model framework for piperazine solutions as a high-performance CO 2 capture solvent. Progress is presented in the framework of the CCSI standard basic data model inference framework. Recent work has largely focused on the thermodynamic submodels of Independence.

Drug-binding energetics of human α-1-acid glycoprotein assessed by isothermal titration calorimetry and molecular docking simulations

PubMed Central

Huang, Johnny X.; Cooper, Matthew A.; Baker, Mark A.; Azad, Mohammad A.K.; Nation, Roger L.; Li, Jian; Velkov, Tony

2012-01-01

This study utilizes sensitive, modern isothermal titration calorimetric (ITC) methods to characterize the microscopic thermodynamic parameters that drive the binding of basic drugs to α-1-acid glycoprotein (AGP) and thereby rationalize the thermodynamic data in relation to docking models and crystallographic structures of the drug-AGP complexes. The binding of basic compounds from the tricyclic antidepressant series, together with miaserine, chlorpromazine, disopyramide and cimetidine all displayed an exothermically driven binding interaction with AGP. The impact of protonation/deprotonation events, ionic strength, temperature and the individual selectivity of the A and F1*S AGP variants on drug-binding thermodynamics were characterized. A correlation plot of the thermodynamic parameters for all of the test compounds revealed enthalpy-entropy compensation is in effect. The exothermic binding energetics of the test compounds were driven by a combination of favorable (negative) enthalpic (ΔH°) and favorable (positive) entropic (ΔS°) contributions to the Gibbs free energy (ΔG°). Collectively, the data imply that the free energies that drive drug binding to AGP and its relationship to drug-serum residency evolve from the complex interplay of enthalpic and entropic forces from interactions with explicit combinations of hydrophobic and polar side-chain sub-domains within the multi-lobed AGP ligand binding cavity. PMID:23192962

Solution of D dimensional Dirac equation for coulombic potential using NU method and its thermodynamics properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cari, C., E-mail: cari@staff.uns.ac.id; Suparmi, A., E-mail: soeparmi@staff.uns.ac.id; Yunianto, M., E-mail: muhtaryunianto@staff.uns.ac.id

2016-02-08

The analytical solution of Ddimensional Dirac equation for Coulombic potential is investigated using Nikiforov-Uvarov method. The D dimensional relativistic energy spectra are obtained from relativistic energy eigenvalue equation by using Mat Lab software.The corresponding D dimensional radial wave functions are formulated in the form of generalized Jacobi and Laguerre Polynomials. In the non-relativistic limit, the relativistic energy equation reduces to the non-relativistic energy which will be applied to determine some thermodynamical properties of the system. The thermodynamical properties of the system are expressed in terms of error function and imaginary error function.

Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys

NASA Astrophysics Data System (ADS)

Maltsev, Dmitry S.; Volkovich, Vladimir A.; Yamshchikov, Leonid F.; Chukin, Andrey V.

2016-09-01

Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys were studied. Temperature dependences of gadolinium activity in the studied alloys were determined at 573-1073 K employing the EMF method. Solubility of gadolinium in the Ga-Sn and Ga-Zn alloys was measured at 462-1073 K using IMCs sedimentation method. Activity coefficients as well as partial and excess thermodynamic functions of gadolinium in the studied alloys were calculated on the basis of the obtained experimental data.

A second look at the second law

NASA Astrophysics Data System (ADS)

Bejan, Adrian

1988-05-01

An account is given of Bejan's (1988) reformulation of the axioms of engineering thermodynamics in terms of heat transfer, rather than mechanics. Attention is given to graphic constructions that can be used to illustrate the properties in question, such as the 'stability star' diagram summarizing various extrema reached by certain thermodynamic properties when a closed system settles into stable (unconstrained) equilibrium. Also noted are the exergy analysis and refrigeration applications to which the present reformulation of the second law of thermodynamics can be put.

Sensitivity of predicted scaling and permeability in Enhanced Geothermal Systems to Thermodynamic Data and Activity Models

NASA Astrophysics Data System (ADS)

Hingerl, Ferdinand F.; Wagner, Thomas; Kulik, Dmitrii A.; Kosakowski, Georg; Driesner, Thomas; Thomsen, Kaj

2010-05-01

A consortium of research groups from ETH Zurich, EPF Lausanne, the Paul Scherrer Institut and the University of Bonn collaborates in a comprehensive program of basic research on key aspects of the Enhanced Geothermal Systems (EGSs). As part of this GEOTHERM project (www.geotherm.ethz.ch), we concentrate on the fundamental investigation of thermodynamic models suitable for describing fluid-rock interactions at geothermal conditions. Predictions of the fluid-rock interaction in EGS still face several major challenges. Slight variations in the input thermodynamic and kinetic parameters may result in significant differences in the predicted mineral solubilities and stable assemblage. Realistic modeling of mineral precipitation in turn has implications onto our understanding of the permeability evolution of the geothermal reservoir, as well as the scaling in technical installations. In order to reasonably model an EGS, thermodynamic databases and activity models must be tailored to geothermal conditions. We therefore implemented in GEMS code the Pitzer formalism, which is the standard model used for computing thermodynamic excess properties of brines at elevated temperatures and pressures. This model, however, depends on a vast amount of interaction parameters, which are to a substantial extend unknown. Furthermore, a high order polynomial temperature interpolation makes extrapolation unreliable if not impossible. As an alternative we additionally implemented the EUNIQUAC activity model. EUNIQUAC requires fewer empirical fit parameters (only binary interaction parameters needed) and uses simpler and more stable temperature and pressure extrapolations. This results in an increase in computation speed, which is of crucial importance when performing coupled long term simulations of geothermal reservoirs. To achieve better performance under geothermal conditions, we are currently partly reformulating EUNIQUAC and refitting the existing parameter set. First results of the Pitzer-EUNIQUAC benchmark applied to relevant aqueous solutions at elevated temperature, pressure and ionic strength will be presented.

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)

Chlorination pattern effect on thermodynamic parameters and environmental degradability for C₁₀-SCCPs: Quantum chemical calculation based on virtual combinational library.

PubMed

Sun, Yuzhen; Pan, Wenxiao; Lin, Yuan; Fu, Jianjie; Zhang, Aiqian

2016-01-01

Short-chain chlorinated paraffins (SCCPs) are still controversial candidates for inclusion in the Stockholm Convention. The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors. A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed. We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations. The thermodynamic properties were acquired using the AM1 method, and frontier molecular orbital analysis was carried out to obtain the E(HOMO), E(LUMO) and E(LUMO)-E(HOMO) for degradability exploration at the same level. The influence of the chlorination degree (N(Cl)) on the relative stability and environmental degradation was elucidated. A novel structural descriptor, μ, was proposed to measure the dispersion of the chlorine atoms within a molecule. There were significant correlations between thermodynamic values and N(Cl), while the reported N(Cl)-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners. In addition, isomers with large μ showed higher relative stability than those with small μ. This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and OH attack respectively. The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack, while direct photolysis of C10-SCCP congeners cannot readily occur due to the large E(LUMO)-E(HOMO) values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations. Copyright © 2015. Published by Elsevier B.V.

Major Source of Error in QSPR Prediction of Intrinsic Thermodynamic Solubility of Drugs: Solid vs Nonsolid State Contributions?

PubMed

Abramov, Yuriy A

2015-06-01

The main purpose of this study is to define the major limiting factor in the accuracy of the quantitative structure-property relationship (QSPR) models of the thermodynamic intrinsic aqueous solubility of the drug-like compounds. For doing this, the thermodynamic intrinsic aqueous solubility property was suggested to be indirectly "measured" from the contributions of solid state, ΔGfus, and nonsolid state, ΔGmix, properties, which are estimated by the corresponding QSPR models. The QSPR models of ΔGfus and ΔGmix properties were built based on a set of drug-like compounds with available accurate measurements of fusion and thermodynamic solubility properties. For consistency ΔGfus and ΔGmix models were developed using similar algorithms and descriptor sets, and validated against the similar test compounds. Analysis of the relative performances of these two QSPR models clearly demonstrates that it is the solid state contribution which is the limiting factor in the accuracy and predictive power of the QSPR models of the thermodynamic intrinsic solubility. The performed analysis outlines a necessity of development of new descriptor sets for an accurate description of the long-range order (periodicity) phenomenon in the crystalline state. The proposed approach to the analysis of limitations and suggestions for improvement of QSPR-type models may be generalized to other applications in the pharmaceutical industry.

Real Otto and Diesel Engine Cycles.

ERIC Educational Resources Information Center

Giedd, Ronald

1983-01-01

A thermodynamic analysis of the properties of otto/diesel engines during the time they operate with open chambers illustrates applicability of thermodynamics to real systems, demonstrates how delivered power is controlled, and explains the source of air pollution in terms of thermodynamic laws. (Author/JN)

The thermodynamic properties of gaseous UO2(OH)2

NASA Astrophysics Data System (ADS)

Konings, R. J. M.; Kovács, A.; Beneš, O.

2017-12-01

Quantum chemical calculations of the molecular properties of the UO2(OH)2 molecule are presented. From the results the thermodynamic properties of this gaseous species have been calculated, and these have been used to re-evaluate the existing literature study on the volatilization of U3O8 in steam, allowing to derive the enthalpy of formation of the UO2(OH)2 molecule.

Quantum thermodynamics from the nonequilibrium dynamics of open systems: Energy, heat capacity, and the third law.

PubMed

Hsiang, J-T; Chou, C H; Subaşı, Y; Hu, B L

2018-01-01

In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system +  environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage between the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. Entropy and entanglement will be the main theme of our second paper on this subject matter.

Quantum thermodynamics from the nonequilibrium dynamics of open systems: Energy, heat capacity, and the third law

DOE PAGES

Hsiang, Jen -Tsung; Chou, Chung Hsien; Subasi, Yigit; ...

2018-01-23

In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage betweenmore » the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. As a result, entropy and entanglement will be the main theme of our second paper on this subject matter.« less

Quantum thermodynamics from the nonequilibrium dynamics of open systems: Energy, heat capacity, and the third law

NASA Astrophysics Data System (ADS)

Hsiang, J.-T.; Chou, C. H.; Subaşı, Y.; Hu, B. L.

2018-01-01

In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage between the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. Entropy and entanglement will be the main theme of our second paper on this subject matter.

Thermodynamic modelling of the C-U and B-U binary systems

NASA Astrophysics Data System (ADS)

Chevalier, P. Y.; Fischer, E.

2001-02-01

The thermodynamic modelling of the carbon-uranium (C-U) and boron-uranium (B-U) binary systems is being performed in the framework of the development of a thermodynamic database for nuclear materials, for increasing the basic knowledge of key phenomena which may occur in the event of a severe accident in a nuclear power plant. Applications are foreseen in the nuclear safety field to the physico-chemical interaction modelling, on the one hand the in-vessel core degradation producing the corium (fuel, zircaloy, steel, control rods) and on the other hand the ex-vessel molten corium-concrete interaction (MCCI). The key O-U-Zr ternary system, previously modelled, allows us to describe the first interaction of the fuel with zircaloy cladding. Then, the three binary systems Fe-U, Cr-U and Ni-U were modelled as a preliminary work for modelling the O-U-Zr-Fe-Cr-Ni multicomponent system, allowing us to introduce the steel components in the corium. In the existing database (TDBCR, thermodynamic data base for corium), Ag and In were introduced for modelling AIC (silver-indium-cadmium) control rods which are used in French pressurized water reactors (PWR). Elsewhere, B 4C is also used for control rods. That is why it was agreed to extend in the next years the database with two new components, B and C. Such a work needs the thermodynamic modelling of all the binary and pseudo-binary sub-systems resulting from the combination of B, B 2O 3 and C with the major components of TDBCR, O-U-Zr-Fe-Cr-Ni-Ag-In-Ba-La-Ru-Sr-Al-Ca-Mg-Si + Ar-H. The critical assessment of the very numerous experimental information available for the C-U and B-U binary systems was performed by using a classical optimization procedure and the Scientific Group Thermodata Europe (SGTE). New optimized Gibbs energy parameters are given, and comparisons between calculated and experimental equilibrium phase diagrams or thermodynamic properties are presented. The self-consistency obtained is quite satisfactory.

Quantum thermodynamics from the nonequilibrium dynamics of open systems: Energy, heat capacity, and the third law

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsiang, Jen -Tsung; Chou, Chung Hsien; Subasi, Yigit

In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage betweenmore » the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. As a result, entropy and entanglement will be the main theme of our second paper on this subject matter.« less

Thermodynamic properties of zeolites: low-temperature heat capacities and thermodynamic functions for phillipsite and clinoptilolite. Estimates of the thermochemical properties of zeolitic water at low temperature.

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.

1984-01-01

Measured heat capacities between 15 and 305 K and calculated heat capacities, entropies, enthalpy functions and Gibbs energy functions are reported and analysed for phillipsite and clinoptilolite. - J.A.Z.

Measuring Gas-Phase Basicities of Amino Acids Using an Ion Trap Mass Spectrometer: A Physical Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Sunderlin, Lee S.; Ryzhov, Victor; Keller, Lanea M. M.; Gaillard, Elizabeth R.

2005-01-01

An experiment is performed to measure the relative gas-phase basicities of a series of five amino acids to compare the results to literature values. The experiments use the kinetic method for deriving ion thermochemistry and allow students to perform accurate measurements of thermodynamics in a relatively short time.

Thermodynamic properties by equation of state and from Ab initio molecular dynamics of liquid potassium under pressure

NASA Astrophysics Data System (ADS)

Li, Huaming; Tian, Yanting; Sun, Yongli; Li, Mo; Nonequilibrium materials; physics Team; Computational materials science Team

In this work, we apply a general equation of state of liquid and Ab initio molecular-dynamics method to study thermodynamic properties in liquid potassium under high pressure. Isothermal bulk modulus and molar volume of molten sodium are calculated within good precision as compared with the experimental data. The calculated internal energy data and the calculated values of isobaric heat capacity of molten potassium show the minimum along the isothermal lines as the previous result obtained in liquid sodium. The expressions for acoustical parameter and nonlinearity parameter are obtained based on thermodynamic relations from the equation of state. Both parameters for liquid potassium are calculated under high pressure along the isothermal lines by using the available thermodynamic data and numeric derivations. Furthermore, Ab initio molecular-dynamics simulations are used to calculate some thermodynamic properties of liquid potassium along the isothermal lines. Scientific Research Starting Foundation from Taiyuan university of Technology, Shanxi Provincial government (``100-talents program''), China Scholarship Council and National Natural Science Foundation of China (NSFC) under Grant No. 51602213.

A Catalog of NASA Special Publications

DTIC Science & Technology

1981-01-01

Properties and Mollier Perfect Carbon Dioxide and Nitrogen Chart for Hydrogen From 300 K to Mixtures 20 000 K Wt’. P. Peterson R. F. Kubin, L. L. Presley...human per- Avail NTIS 1964 formance. NASA SP-3006 Equilibrium Thermodynamic Properties N73-15091 938 pp of Carbon Dioxide Avail GPO 1973 H. E. Bailey...N64-25017 4 27 pp Avail GPO 1964 39 Charts for Equilibrium Flow Properties Equilibrium Thermodynamic Properties of Carbon Dioxide in Hypervelocity of

Three Conceptions of Thermodynamics: Technical Matrices in Science and Engineering

NASA Astrophysics Data System (ADS)

Christiansen, Frederik V.; Rump, Camilla

2008-11-01

Introductory thermodynamics is a topic which is covered in a wide variety of science and engineering educations. However, very different teaching traditions have evolved within different scientific specialties. In this study we examine three courses in introductory thermodynamics within three different scientific specialties: physics, chemical engineering and mechanical engineering. Based on a generalization of Kuhn’s theory of disciplinary matrix, and the idea of boundary objects we analyse how basic thermodynamics theory is conceived in the different scientific specialties. The study is based on interviews with teachers and analysis of the different textbook traditions. It is concluded that teachers need to take into account how subject matter is conceived in other related scientific specialties when designing courses. Two examples demonstrating how this may be done are given.

Thermodynamic properties of diamond and wurtzite model fluids from computer simulation and thermodynamic perturbation theory

NASA Astrophysics Data System (ADS)

Zhou, S.; Solana, J. R.

2018-03-01

Monte Carlo NVT simulations have been performed to obtain the thermodynamic and structural properties and perturbation coefficients up to third order in the inverse temperature expansion of the Helmholtz free energy of fluids with potential models proposed in the literature for diamond and wurtzite lattices. These data are used to analyze performance of a coupling parameter series expansion (CPSE). The main findings are summarized as follows, (1) The CPSE provides accurate predictions of the first three coefficient in the inverse temperature expansion of Helmholtz free energy for the potential models considered and the thermodynamic properties of these fluids are predicted more accurately when the CPSE is truncated at second or third order. (2) The Barker-Henderson (BH) recipe is appropriate for determining the effective hard sphere diameter for strongly repulsive potential cores, but its performance worsens with increasing the softness of the potential core. (3) For some thermodynamic properties the first-order CPSE works better for the diamond potential, whose tail is dominated by repulsive interactions, than for the potential, whose tail is dominated by attractive interactions. However, the first-order CPSE provides unsatisfactory results for the excess internal energy and constant-volume excess heat capacity for the two potential models.

Thermodynamic properties of oxygen and nitrogen III

NASA Technical Reports Server (NTRS)

Stewart, R. B.; Jacobsen, R. T.; Myers, A. F.

1972-01-01

The final equation for nitrogen was determined. In the work on the equation of state for nitrogen, coefficients were determined by constraining the critical point to selected critical point parameters. Comparisons of this equation with all the P-density-T data were made, as well as comparisons to all other thermodynamic data reported in the literature. The extrapolation of the equation of state was studied for vapor to higher temperatures and lower temperatures, and for the liquid surface to the saturated liquid and the fusion lines. A new vapor pressure equation was also determined which was constrained to the same critical temperature, pressure, and slope (dP/dT) as the equation of state. Work on the equation of state for oxygen included studies for improving the equation at the critical point. Comparisons of velocity of sound data for oxygen were also made between values calculated with a preliminary equation of state and experimental data. Functions for the calculation of the derived thermodynamic properties using the equation of state are given, together with the derivative and integral functions for the calculation of the thermodynamic properties using the equations of state. Summary tables of the thermodynamic properties of nitrogen and oxygen are also included to serve as a check for those preparing computer programs using the equations of state.

Interpreting equilibrium-conductivity and conductivity-relaxation measurements to establish thermodynamic and transport properties for multiple charged defect conducting ceramics.

PubMed

Zhu, Huayang; Ricote, Sandrine; Coors, W Grover; Kee, Robert J

2015-01-01

A model-based interpretation of measured equilibrium conductivity and conductivity relaxation is developed to establish thermodynamic, transport, and kinetics parameters for multiple charged defect conducting (MCDC) ceramic materials. The present study focuses on 10% yttrium-doped barium zirconate (BZY10). In principle, using the Nernst-Einstein relationship, equilibrium conductivity measurements are sufficient to establish thermodynamic and transport properties. However, in practice it is difficult to establish unique sets of properties using equilibrium conductivity alone. Combining equilibrium and conductivity-relaxation measurements serves to significantly improve the quantitative fidelity of the derived material properties. The models are developed using a Nernst-Planck-Poisson (NPP) formulation, which enables the quantitative representation of conductivity relaxations caused by very large changes in oxygen partial pressure.

Structural stability, elastic and thermodynamic properties of Au-Cu alloys from first-principles calculations

NASA Astrophysics Data System (ADS)

Kong, Ge-Xing; Ma, Xiao-Juan; Liu, Qi-Jun; Li, Yong; Liu, Zheng-Tang

2018-03-01

Using first-principles calculations method based on density functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE) implementation of the generalized gradient approximation (GGA), we investigate the structural, elastic and thermodynamic properties of gold-copper intermetallic compounds (Au-Cu ICs). The calculated lattice parameters are in excellent agreement with experimental data. The elastic constants show that all the investigated Au-Cu alloys are mechanically stable. Elastic properties, including the shear modulus, Young's modulus, Poisson's ratio and Pugh's indicator, of the intermetallic compounds are evaluated and discussed, with special attention to the remarkable anisotropy displayed by Au-Cu ICs. Thermodynamic and transport properties including the Debye temperature, thermal conductivity and melting point are predicted from the averaged sound velocity and elastic moduli, using semi-empirical formulas.

Fisher Information, Entropy, and the Second and Third Laws of Thermodynamics

EPA Science Inventory

We propose Fisher Information as a new calculable thermodynamic property that can be shown to follow the Second and the Third Laws of Thermodynamics. Fisher Information is, however, qualitatively different from entropy and potentially possessing a great deal more structure. Hence...

A thermodynamic and theoretical view for enzyme regulation.

PubMed

Zhao, Qinyi

2015-01-01

Precise regulation is fundamental to the proper functioning of enzymes in a cell. Current opinions about this, such as allosteric regulation and dynamic contribution to enzyme regulation, are experimental models and substantially empirical. Here we proposed a theoretical and thermodynamic model of enzyme regulation. The main idea is that enzyme regulation is processed via the regulation of abundance of active conformation in the reaction buffer. The theoretical foundation, experimental evidence, and experimental criteria to test our model are discussed and reviewed. We conclude that basic principles of enzyme regulation are laws of protein thermodynamics and it can be analyzed using the concept of distribution curve of active conformations of enzymes.

Thermodynamical detection of entanglement by Maxwell's demons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maruyama, Koji; Vedral, Vlatko; Morikoshi, Fumiaki

2005-01-01

Quantum correlation, or entanglement, is now believed to be an indispensable physical resource for certain tasks in quantum information processing, for which classically correlated states cannot be useful. Besides information processing, what kind of physical processes can exploit entanglement? In this paper, we show that there is indeed a more basic relationship between entanglement and its usefulness in thermodynamics. We derive an inequality showing that we can extract more work out of a heat bath via entangled systems than via classically correlated ones. We also analyze the work balance of the process as a heat engine, in connection with themore » second law of thermodynamics.« less

Single molecule thermodynamics in biological motors.

PubMed

Taniguchi, Yuichi; Karagiannis, Peter; Nishiyama, Masayoshi; Ishii, Yoshiharu; Yanagida, Toshio

2007-04-01

Biological molecular machines use thermal activation energy to carry out various functions. The process of thermal activation has the stochastic nature of output events that can be described according to the laws of thermodynamics. Recently developed single molecule detection techniques have allowed each distinct enzymatic event of single biological machines to be characterized providing clues to the underlying thermodynamics. In this study, the thermodynamic properties in the stepping movement of a biological molecular motor have been examined. A single molecule detection technique was used to measure the stepping movements at various loads and temperatures and a range of thermodynamic parameters associated with the production of each forward and backward step including free energy, enthalpy, entropy and characteristic distance were obtained. The results show that an asymmetry in entropy is a primary factor that controls the direction in which the motor will step. The investigation on single molecule thermodynamics has the potential to reveal dynamic properties underlying the mechanisms of how biological molecular machines work.

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

PubMed

Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M

2014-11-07

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

Dynamic properties of interfaces in soft matter: Experiments and theory

NASA Astrophysics Data System (ADS)

Sagis, Leonard M. C.

2011-10-01

The dynamic properties of interfaces often play a crucial role in the macroscopic dynamics of multiphase soft condensed matter systems. These properties affect the dynamics of emulsions, of dispersions of vesicles, of biological fluids, of coatings, of free surface flows, of immiscible polymer blends, and of many other complex systems. The study of interfacial dynamic properties, surface rheology, is therefore a relevant discipline for many branches of physics, chemistry, engineering, and life sciences. In the past three to four decades a vast amount of literature has been produced dealing with the rheological properties of interfaces stabilized by low molecular weight surfactants, proteins, (bio)polymers, lipids, colloidal particles, and various mixtures of these surface active components. In this paper recent experiments are reviewed in the field of surface rheology, with particular emphasis on the models used to analyze surface rheological data. Most of the models currently used are straightforward generalizations of models developed for the analysis of rheological data of bulk phases. In general the limits on the validity of these generalizations are not discussed. Not much use is being made of recent advances in nonequilibrium thermodynamic formalisms for multiphase systems, to construct admissible models for the stress-deformation behavior of interfaces. These formalisms are ideally suited to construct thermodynamically admissible constitutive equations for rheological behavior that include the often relevant couplings to other fluxes in the interface (heat and mass), and couplings to the transfer of mass from the bulk phase to the interface. In this review recent advances in the application of classical irreversible thermodynamics, extended irreversible thermodynamics, rational thermodynamics, extended rational thermodynamics, and the general equation for the nonequilibrium reversible-irreversible coupling formalism to multiphase systems are also discussed, and shown how these formalisms can be used to generate a wide range of thermodynamically admissible constitutive models for the surface stress tensor. Some of the generalizations currently in use are shown to have only limited validity. The aim of this review is to stimulate new developments in the fields of experimental surface rheology and constitutive modeling of multiphase systems using nonequilibrium thermodynamic formalisms and to promote a closer integration of these disciplines.

A review of second law techniques applicable to basic thermal science research

NASA Astrophysics Data System (ADS)

Drost, M. Kevin; Zamorski, Joseph R.

1988-11-01

This paper reports the results of a review of second law analysis techniques which can contribute to basic research in the thermal sciences. The review demonstrated that second law analysis has a role in basic thermal science research. Unlike traditional techniques, second law analysis accurately identifies the sources and location of thermodynamic losses. This allows the development of innovative solutions to thermal science problems by directing research to the key technical issues. Two classes of second law techniques were identified as being particularly useful. First, system and component investigations can provide information of the source and nature of irreversibilities on a macroscopic scale. This information will help to identify new research topics and will support the evaluation of current research efforts. Second, the differential approach can provide information on the causes and spatial and temporal distribution of local irreversibilities. This information enhances the understanding of fluid mechanics, thermodynamics, and heat and mass transfer, and may suggest innovative methods for reducing irreversibilities.

First-principles calculations of the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2)

NASA Astrophysics Data System (ADS)

Wen, Xiangli; Liang, Yuxuan; Bai, Pengpeng; Luo, Bingwei; Fang, Teng; Yue, Luo; An, Teng; Song, Weiyu; Zheng, Shuqi

2017-11-01

The thermodynamic properties of Fe-S compounds with different crystal structure are very different. In this study, the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2) were investigated by first-principles calculations. Examination of the electronic density of states shows that mackinawite (FeS) is metallic and that pyrite (FeS2) is a semiconductor with a band gap of Eg = 1.02 eV. Using the stress-strain method, the elastic properties including the bulk modulus and shear modulus were derived from the elastic Cij data. Density functional perturbation theory (DFPT) calculations within the quasi-harmonic approximation (QHA) were used to calculate the thermodynamic properties, and the two Fe-S compounds are found to be dynamically stable. The isothermal bulk modulus, thermal expansion coefficient, heat capacities, Gibbs free energy and entropy of the Fe-S compounds are obtained by first-principles phonon calculations. Furthermore, the temperature of the mackinawite (FeS) ⟶ pyrite (FeS2) phase transition at 0 GPa was predicted. Based on the calculation results, the model for prediction of Fe-S compounds in the Fe-H2S-H2O system was improved.

First principles investigation of structural, mechanical, dynamical and thermodynamic properties of AgMg under pressure

NASA Astrophysics Data System (ADS)

Cui, Rong Hua; Chao Dong, Zheng; Gui Zhong, Chong

2017-12-01

The effects of pressure on the structural, mechanical, dynamical and thermodynamic properties of AgMg have been investigated using first principles based on density functional theory. The optimized lattice constants agree well with previous experimental and theoretical results. The bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and Debye temperature under pressures were calculated. The calculated results of Cauchy pressure and B/G ratio indicate that AgMg shows ductile nature. Phonon dispersion curves suggest the dynamical stability of AgMg. The pressure dependent behavior of thermodynamic properties are calculated, the Helmholtz free energy and internal energy increase with increase of pressure, while entropy and heat capacity decrease.

Thermodynamic properties of a hard/soft-magnetic bilayer model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taaev, T. A., E-mail: taaev89@mail.ru; Khizriev, K. Sh.; Murtazaev, A. K.

2016-05-15

A model for describing the thermodynamic properties of a hard/soft-magnetic bilayer is proposed and thoroughly studied using the Monte Carlo method. Temperature dependences of the heat capacity, total magnetization, magnetizations of the hard- and soft-magnetic layers, total magnetic susceptibility, and susceptibilities of the hard- and soft-magnetic layers have been calculated by this method in the framework of the proposed model. The obtained temperature dependences of the heat capacity and magnetic susceptibility display double maxima that result from the two phase transitions that take place in the system. The influence of system dimensions on the thermodynamic properties of the model hasmore » been considered.« less

Tables and charts of equilibrium thermodynamic properties of ammonia for temperatures from 500 to 50,000 K.

NASA Technical Reports Server (NTRS)

Simmonds, A. L.; Miller, C. G., III; Nealy, J. E.

1976-01-01

Equilibrium thermodynamic properties for pure ammonia were generated for a range of temperature from 500 to 50,000 K and pressure from 0.01 to 40 MN/sq m and are presented in tabulated and graphical form. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, specific heat at constant pressure, specific heat at constant volume, isentropic exponent, and species mole fractions. These properties were calculated by the method which is based on minimization of the Gibbs free energy. The data presented herein are for an 18-species ammonia model. Heats of formation and spectroscopic constants used as input data are presented. Comparison of several thermodynamic properties calculated with the present program and a second computer code is performed for a range of pressure and for temperatures up to 30,000 K.

Computational studies of physical properties of Nb-Si based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ouyang, Lizhi

2015-04-16

The overall goal is to provide physical properties data supplementing experiments for thermodynamic modeling and other simulations such as phase filed simulation for microstructure and continuum simulations for mechanical properties. These predictive computational modeling and simulations may yield insights that can be used to guide materials design, processing, and manufacture. Ultimately, they may lead to usable Nb-Si based alloy which could play an important role in current plight towards greener energy. The main objectives of the proposed projects are: (1) developing a first principles method based supercell approach for calculating thermodynamic and mechanic properties of ordered crystals and disordered latticesmore » including solid solution; (2) application of the supercell approach to Nb-Si base alloy to compute physical properties data that can be used for thermodynamic modeling and other simulations to guide the optimal design of Nb-Si based alloy.« less

Teaching Thermodynamics of Ideal Solutions: An Entropy-Based Approach to Help Students Better Understand and Appreciate the Subtleties of Solution Models

ERIC Educational Resources Information Center

Tomba, J. Pablo

2015-01-01

The thermodynamic formalism of ideal solutions is developed in most of the textbooks postulating a form for the chemical potential of a generic component, which is adapted from the thermodynamics of ideal gas mixtures. From this basis, the rest of useful thermodynamic properties can be derived straightforwardly without further hypothesis. Although…

Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: a first-principles investigation

Treesearch

ShunLi Shang; Louis G. Hector Jr.; Paul Saxe; Zi-Kui Liu; Robert J. Moon; Pablo D. Zavattieri

2014-01-01

Anisotropy and temperature dependence of structural, thermodynamic and elastic properties of crystalline cellulose Iβ were computed with first-principles density functional theory (DFT) and a semi-empirical correction for van der Waals interactions. Specifically, we report the computed temperature variation (up to 500...

Ab initio interatomic potentials and the thermodynamic properties of fluids

NASA Astrophysics Data System (ADS)

Vlasiuk, Maryna; Sadus, Richard J.

2017-07-01

Monte Carlo simulations with accurate ab initio interatomic potentials are used to investigate the key thermodynamic properties of argon and krypton in both vapor and liquid phases. Data are reported for the isochoric and isobaric heat capacities, the Joule-Thomson coefficient, and the speed of sound calculated using various two-body interatomic potentials and different combinations of two-body plus three-body terms. The results are compared to either experimental or reference data at state points between the triple and critical points. Using accurate two-body ab initio potentials, combined with three-body interaction terms such as the Axilrod-Teller-Muto and Marcelli-Wang-Sadus potentials, yields systematic improvements to the accuracy of thermodynamic predictions. The effect of three-body interactions is to lower the isochoric and isobaric heat capacities and increase both the Joule-Thomson coefficient and speed of sound. The Marcelli-Wang-Sadus potential is a computationally inexpensive way to utilize accurate two-body ab initio potentials for the prediction of thermodynamic properties. In particular, it provides a very effective way of extending two-body ab initio potentials to liquid phase properties.

Ab initio interatomic potentials and the thermodynamic properties of fluids.

PubMed

Vlasiuk, Maryna; Sadus, Richard J

2017-07-14

Monte Carlo simulations with accurate ab initio interatomic potentials are used to investigate the key thermodynamic properties of argon and krypton in both vapor and liquid phases. Data are reported for the isochoric and isobaric heat capacities, the Joule-Thomson coefficient, and the speed of sound calculated using various two-body interatomic potentials and different combinations of two-body plus three-body terms. The results are compared to either experimental or reference data at state points between the triple and critical points. Using accurate two-body ab initio potentials, combined with three-body interaction terms such as the Axilrod-Teller-Muto and Marcelli-Wang-Sadus potentials, yields systematic improvements to the accuracy of thermodynamic predictions. The effect of three-body interactions is to lower the isochoric and isobaric heat capacities and increase both the Joule-Thomson coefficient and speed of sound. The Marcelli-Wang-Sadus potential is a computationally inexpensive way to utilize accurate two-body ab initio potentials for the prediction of thermodynamic properties. In particular, it provides a very effective way of extending two-body ab initio potentials to liquid phase properties.

Scaled Particle Theory for Multicomponent Hard Sphere Fluids Confined in Random Porous Media.

PubMed

Chen, W; Zhao, S L; Holovko, M; Chen, X S; Dong, W

2016-06-23

The formulation of scaled particle theory (SPT) is presented for a quite general model of fluids confined in a random porous media, i.e., a multicomponent hard sphere (HS) fluid in a multicomponent hard sphere or a multicomponent overlapping hard sphere (OHS) matrix. The analytical expressions for pressure, Helmholtz free energy, and chemical potential are derived. The thermodynamic consistency of the proposed theory is established. Moreover, we show that there is an isomorphism between the SPT for a multicomponent system and that for a one-component system. Results from grand canonical ensemble Monte Carlo simulations are also presented for a binary HS mixture in a one-component HS or a one-component OHS matrix. The accuracy of various variants derived from the basic SPT formulation is appraised against the simulation results. Scaled particle theory, initially formulated for a bulk HS fluid, has not only provided an analytical tool for calculating thermodynamic properties of HS fluid but also helped to gain very useful insight for elaborating other theoretical approaches such as the fundamental measure theory (FMT). We expect that the general SPT for multicomponent systems developed in this work can contribute to the study of confined fluids in a similar way.

Concentration Waves in High-Entropy Alloys - a new alloy design approach

NASA Astrophysics Data System (ADS)

Singh, Prashant; Johnson, Duane D.

2015-03-01

Chemical short-range order (SRO) in solid solutions can be interpreted as a ``concentration wave'' - a Fourier decomposition of nascent order - identified experimentally via Warren-Cowley SRO parameters. We present a rigorous thermodynamic theory to predict and uniquely interpret the SRO in N -component alloys. Based on KKR-CPA electronic structure, we implemented this method using thermodynamic linear-response to include all alloying effects, e.g., band-filling, hybridization, Fermi -surface nesting and van Hove instabilities. We apply this first-principles method to high-entropy alloys (HEAs), i.e., solid solutions with N >4 that inhibit small-cell order due to large entropy competing against ordering enthalpy, as their properties are sensitive to SRO. We validated theory with comparison to experiments in A2 Nb-Al-Ti and A1 Cu-Ni-Zn . We then predict and analyze SRO and mechanical trends in Ni-Ti-Zr-Cu-Al and Co-Cr-Fe-Mn-Ni systems - showcasing this new first-principles-based alloy design method. Work was supported by the USDoE, Office of Sci., Basic Energy Sci., Materials Sci. and Eng. Division for `Materials Discovery.' Research was performed at Ames Lab, operated by Iowa State University under Contract #DE-AC02-07CH11358.

Effects of NaBF4 + NaF on the Tensile and Impact Properties of Al-Si-Mg-Fe Alloys

NASA Astrophysics Data System (ADS)

Chen, Zongning; Wang, Tongmin; Zhao, Yufei; Zheng, Yuanping; Kang, Huijun

2015-05-01

NaBF4 + NaF were found to play three roles, i.e., Fe-eliminator, grain refiner, and eutectic modifier, in treating A356 alloy with a high Fe content. The joint effects led to significant improvement in both tensile and impact properties of thus treated alloy. The multiple reactions between the NaBF4 + NaF and Al-Si-Mg-Fe system are suggested to form Fe2B, AlB2, and Na in the melt, as per thermodynamic analysis. The three are responsible for Fe removal, grain refinement, and eutectic modification, respectively. When NaBF4 and NaF are mixed in weight ratio of 1:1, an optimum addition rate is in the range between 1.0 and 2.0 wt pct for treating AlSi7Mg0.3Fe0.65 alloy, based on the results of tensile and impact tests. Excessive addition of the salt may deteriorate the mechanical properties of the alloy, basically owing to overmodification of Si and contamination of salt inclusions.

Thermodynamic Properties of Polyphenylquinoxaline in the Temperature Range of T → 0 to 570 K

NASA Astrophysics Data System (ADS)

Smirnova, N. N.; Markin, A. V.; Samosudova, Ya. S.; Bykova, T. A.; Shifrina, Z. B.; Serkova, E. S.; Kuchkina, N. V.

2018-02-01

The thermodynamic properties of amorphous polyphenylquinoxaline in the temperature range of 6 to 570 K are studied via precision adiabatic vacuum calorimetry and differential scanning calorimetry. The thermodynamic characteristics of glass transition are determined. Standard thermodynamic functions C ° p, H°( T) - H°(0), S°( T) - S°(0), and G°( T) - H°(0) in the range of T → 0 to 570 K and the standard entropy of formation at T = 298.15 K are calculated. The low-temperature ( T ≤ 50 K) heat capacity is analyzed using a multifractal model for the processing of heat capacity, fractal dimension D values are determined, and conclusions on the topological structure of the compound are drawn.

Infinitely dilute partial molar properties of proteins from computer simulation.

PubMed

Ploetz, Elizabeth A; Smith, Paul E

2014-11-13

A detailed understanding of temperature and pressure effects on an infinitely dilute protein's conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method's feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages.

A homeostatic-driven turnover remodelling constitutive model for healing in soft tissues

PubMed Central

Gasser, T. Christian; Bellomo, Facundo J.

2016-01-01

Remodelling of soft biological tissue is characterized by interacting biochemical and biomechanical events, which change the tissue's microstructure, and, consequently, its macroscopic mechanical properties. Remodelling is a well-defined stage of the healing process, and aims at recovering or repairing the injured extracellular matrix. Like other physiological processes, remodelling is thought to be driven by homeostasis, i.e. it tends to re-establish the properties of the uninjured tissue. However, homeostasis may never be reached, such that remodelling may also appear as a continuous pathological transformation of diseased tissues during aneurysm expansion, for example. A simple constitutive model for soft biological tissues that regards remodelling as homeostatic-driven turnover is developed. Specifically, the recoverable effective tissue damage, whose rate is the sum of a mechanical damage rate and a healing rate, serves as a scalar internal thermodynamic variable. In order to integrate the biochemical and biomechanical aspects of remodelling, the healing rate is, on the one hand, driven by mechanical stimuli, but, on the other hand, subjected to simple metabolic constraints. The proposed model is formulated in accordance with continuum damage mechanics within an open-system thermodynamics framework. The numerical implementation in an in-house finite-element code is described, particularized for Ogden hyperelasticity. Numerical examples illustrate the basic constitutive characteristics of the model and demonstrate its potential in representing aspects of remodelling of soft tissues. Simulation results are verified for their plausibility, but also validated against reported experimental data. PMID:27009177

A homeostatic-driven turnover remodelling constitutive model for healing in soft tissues.

PubMed

Comellas, Ester; Gasser, T Christian; Bellomo, Facundo J; Oller, Sergio

2016-03-01

Remodelling of soft biological tissue is characterized by interacting biochemical and biomechanical events, which change the tissue's microstructure, and, consequently, its macroscopic mechanical properties. Remodelling is a well-defined stage of the healing process, and aims at recovering or repairing the injured extracellular matrix. Like other physiological processes, remodelling is thought to be driven by homeostasis, i.e. it tends to re-establish the properties of the uninjured tissue. However, homeostasis may never be reached, such that remodelling may also appear as a continuous pathological transformation of diseased tissues during aneurysm expansion, for example. A simple constitutive model for soft biological tissues that regards remodelling as homeostatic-driven turnover is developed. Specifically, the recoverable effective tissue damage, whose rate is the sum of a mechanical damage rate and a healing rate, serves as a scalar internal thermodynamic variable. In order to integrate the biochemical and biomechanical aspects of remodelling, the healing rate is, on the one hand, driven by mechanical stimuli, but, on the other hand, subjected to simple metabolic constraints. The proposed model is formulated in accordance with continuum damage mechanics within an open-system thermodynamics framework. The numerical implementation in an in-house finite-element code is described, particularized for Ogden hyperelasticity. Numerical examples illustrate the basic constitutive characteristics of the model and demonstrate its potential in representing aspects of remodelling of soft tissues. Simulation results are verified for their plausibility, but also validated against reported experimental data. © 2016 The Author(s).

Electronic structure, mechanical and thermodynamic properties of BaPaO3 under pressure.

PubMed

Khandy, Shakeel Ahmad; Islam, Ishtihadah; Gupta, Dinesh C; Laref, Amel

2018-05-07

Density functional theory (DFT)-based investigations have been put forward on the elastic, mechanical, and thermo-dynamical properties of BaPaO 3 . The pressure dependence of electronic band structure and other physical properties has been carefully analyzed. The increase in Bulk modulus and decrease in lattice constant is seen on going from 0 to 30 GPa. The predicted lattice constants describe this material as anisotropic and ductile in nature at ambient conditions. Post-DFT calculations using quasi-harmonic Debye model are employed to envisage the pressure-dependent thermodynamic properties like Debye temperature, specific heat capacity, Grüneisen parameter, thermal expansion, etc. Also, the computed Debye temperature and melting temperature of BaPaO 3 at 0 K are 523 K and 1764.75 K, respectively.

Standard state thermodynamic properties of Ba2+(aq), Co2+(aq), and Cu2+(aq) up to 598.15 K, and temperature effect on ligand field.

PubMed

Djamali, Essmaiil; Chen, Keith; Murray, Richard C; Turner, Peter J; Cobble, James W

2009-02-26

Integral heat of solution measurements of barium chloride to 619.81 K, copper oxide in an excess of perrhenic acid to 585 K, and cobalt perrhenate in perrhenic acid to 573 K were measured in a high dilution calorimeter (< or =10(-3) m) at psat, from which the high temperature thermodynamic properties of aqueous barium chloride, copper perrhenate, and cobalt perrhenate were obtained. From the known differences between the corresponding properties for aqueous perrhenate and chloride ions, the thermodynamic properties of completely ionized aqueous copper and cobalt chloride were obtained from ionic additivity. The enthalpy and derived heat capacity data at higher temperatures (T > 473.15 K) suggest that the ligand field stabilization energy of Co2+(aq) may be disappearing.

A basic introduction to the thermodynamics of the Earth system far from equilibrium and maximum entropy production

PubMed Central

Kleidon, A.

2010-01-01

The Earth system is remarkably different from its planetary neighbours in that it shows pronounced, strong global cycling of matter. These global cycles result in the maintenance of a unique thermodynamic state of the Earth's atmosphere which is far from thermodynamic equilibrium (TE). Here, I provide a simple introduction of the thermodynamic basis to understand why Earth system processes operate so far away from TE. I use a simple toy model to illustrate the application of non-equilibrium thermodynamics and to classify applications of the proposed principle of maximum entropy production (MEP) to such processes into three different cases of contrasting flexibility in the boundary conditions. I then provide a brief overview of the different processes within the Earth system that produce entropy, review actual examples of MEP in environmental and ecological systems, and discuss the role of interactions among dissipative processes in making boundary conditions more flexible. I close with a brief summary and conclusion. PMID:20368248

A basic introduction to the thermodynamics of the Earth system far from equilibrium and maximum entropy production.

PubMed

Kleidon, A

2010-05-12

The Earth system is remarkably different from its planetary neighbours in that it shows pronounced, strong global cycling of matter. These global cycles result in the maintenance of a unique thermodynamic state of the Earth's atmosphere which is far from thermodynamic equilibrium (TE). Here, I provide a simple introduction of the thermodynamic basis to understand why Earth system processes operate so far away from TE. I use a simple toy model to illustrate the application of non-equilibrium thermodynamics and to classify applications of the proposed principle of maximum entropy production (MEP) to such processes into three different cases of contrasting flexibility in the boundary conditions. I then provide a brief overview of the different processes within the Earth system that produce entropy, review actual examples of MEP in environmental and ecological systems, and discuss the role of interactions among dissipative processes in making boundary conditions more flexible. I close with a brief summary and conclusion.

Multiphase flows of N immiscible incompressible fluids: A reduction-consistent and thermodynamically-consistent formulation and associated algorithm

NASA Astrophysics Data System (ADS)

Dong, S.

2018-05-01

We present a reduction-consistent and thermodynamically consistent formulation and an associated numerical algorithm for simulating the dynamics of an isothermal mixture consisting of N (N ⩾ 2) immiscible incompressible fluids with different physical properties (densities, viscosities, and pair-wise surface tensions). By reduction consistency we refer to the property that if only a set of M (1 ⩽ M ⩽ N - 1) fluids are present in the system then the N-phase governing equations and boundary conditions will exactly reduce to those for the corresponding M-phase system. By thermodynamic consistency we refer to the property that the formulation honors the thermodynamic principles. Our N-phase formulation is developed based on a more general method that allows for the systematic construction of reduction-consistent formulations, and the method suggests the existence of many possible forms of reduction-consistent and thermodynamically consistent N-phase formulations. Extensive numerical experiments have been presented for flow problems involving multiple fluid components and large density ratios and large viscosity ratios, and the simulation results are compared with the physical theories or the available physical solutions. The comparisons demonstrate that our method produces physically accurate results for this class of problems.

Electronic topological transitions in the AgPd system

NASA Astrophysics Data System (ADS)

Skorodumova, N. V.; Simak, S. I.; Smirnova, E. A.; Vekilov, Yu. Kh.

1995-02-01

“First-principles” LMTO-CPA calculations of the Fermi surfaces and thermodynamic properties of AgPd random alloys are presented. We show that there are at least four electronic topological transitions (ETT) in the system. The changes of the Fermi surface topology lead to the appearance of peculiarities in the concentration dependence of the thermodynamic (ground state) properties.

Entropy and the Shelf Model: A Quantum Physical Approach to a Physical Property

ERIC Educational Resources Information Center

Jungermann, Arnd H.

2006-01-01

In contrast to most other thermodynamic data, entropy values are not given in relation to a certain--more or less arbitrarily defined--zero level. They are listed in standard thermodynamic tables as absolute values of specific substances. Therefore these values describe a physical property of the listed substances. One of the main tasks of…

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

Thermodynamic properties of liquid Au–Cu–Sn alloys determined from electromotive force measurements

PubMed Central

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

Theoretical study of isostructural compounds MTe2 (M = Ni, Pd and Pt) on structure and thermodynamic properties under high pressures

NASA Astrophysics Data System (ADS)

Lei, Jin-Qiao; Liu, Ke; Huang, Sha; Mao, Xiao-Chun; Hou, Bao-Sen; Tan, Jiao; Zhou, Xiao-Lin

2017-11-01

The mechanical, electronic and thermodynamic properties of MTe2 (M = Ni, Pd and Pt) under high pressure were investigated via the first-principles calculations. According to our calculations of these trigonal crystals (space group of P3M1, No: 164), we found that all of them are fulfilled by the mechanical stability criteria under 31 GPa (for NiTe2), 37 GPa (for PdTe2) and 73 GPa (for PtTe2). The study on their structures revealed the elastic anisotropy of these isostructural compounds. Electronic structure calculations show that MTe2 are semi-metal. On the basis of the quasi-harmonic Debye model, we also researches their thermodynamic properties.

Temperature dependence of strain energy and thermodynamic properties of V2 O5 -based single-walled nanotubes: Zone-folding approach.

PubMed

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. © 2016 Wiley Periodicals, Inc.

An integrated computational tool for precipitation simulation

NASA Astrophysics Data System (ADS)

Cao, W.; Zhang, F.; Chen, S.-L.; Zhang, C.; Chang, Y. A.

2011-07-01

Computer aided materials design is of increasing interest because the conventional approach solely relying on experimentation is no longer viable within the constraint of available resources. Modeling of microstructure and mechanical properties during precipitation plays a critical role in understanding the behavior of materials and thus accelerating the development of materials. Nevertheless, an integrated computational tool coupling reliable thermodynamic calculation, kinetic simulation, and property prediction of multi-component systems for industrial applications is rarely available. In this regard, we are developing a software package, PanPrecipitation, under the framework of integrated computational materials engineering to simulate precipitation kinetics. It is seamlessly integrated with the thermodynamic calculation engine, PanEngine, to obtain accurate thermodynamic properties and atomic mobility data necessary for precipitation simulation.

Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

NASA Technical Reports Server (NTRS)

Carter, H. G.; Bullock, R. E.

1972-01-01

Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

Investigation of thermodynamic and mechanical properties of AlyIn1-yP alloys by statistical moment method

NASA Astrophysics Data System (ADS)

Ha, Vu Thi Thanh; Hung, Vu Van; Hanh, Pham Thi Minh; Tuyen, Nguyen Viet; Hai, Tran Thi; Hieu, Ho Khac

2018-03-01

The thermodynamic and mechanical properties of III-V zinc-blende AlP, InP semiconductors and their alloys have been studied in detail from statistical moment method taking into account the anharmonicity effects of the lattice vibrations. The nearest neighbor distance, thermal expansion coefficient, bulk moduli, specific heats at the constant volume and constant pressure of the zincblende AlP, InP and AlyIn1-yP alloys are calculated as functions of the temperature. The statistical moment method calculations are performed by using the many-body Stillinger-Weber potential. The concentration dependences of the thermodynamic quantities of zinc-blende AlyIn1-yP crystals have also been discussed and compared with those of the experimental results. Our results are reasonable agreement with earlier density functional theory calculations and can provide useful qualitative information for future experiments. The moment method then can be developed extensively for studying the atomistic structure and thermodynamic properties of nanoscale materials as well.

Investigation of oxygen self-diffusion in PuO 2 by combining molecular dynamics with thermodynamic calculations

DOE PAGES

Saltas, V.; Chroneos, A.; Cooper, Michael William D.; ...

2016-01-01

In the present work, the defect properties of oxygen self-diffusion in PuO 2 are investigated over a wide temperature (300–1900 K) and pressure (0–10 GPa) range, by combining molecular dynamics simulations and thermodynamic calculations. Based on the well-established cBΩ thermodynamic model which connects the activation Gibbs free energy of diffusion with the bulk elastic and expansion properties, various point defect parameters such as activation enthalpy, activation entropy, and activation volume were calculated as a function of T and P. Molecular dynamics calculations provided the necessary bulk properties for the proper implementation of the thermodynamic model, in the lack of anymore » relevant experimental data. The estimated compressibility and the thermal expansion coefficient of activation volume are found to be more than one order of magnitude greater than the corresponding values of the bulk plutonia. As a result, the diffusion mechanism is discussed in the context of the temperature and pressure dependence of the activation volume.« less

Third Law of Thermodynamics and The Shape of the Phase Diagram for Systems With a First-Order Quantum Phase Transition.

PubMed

Kirkpatrick, T R; Belitz, D

2015-07-10

The third law of thermodynamics constrains the phase diagram of systems with a first-order quantum phase transition. For a zero conjugate field, the coexistence curve has an infinite slope at T=0. If a tricritical point exists at T>0, then the associated tricritical wings are perpendicular to the T=0 plane, but not to the zero-field plane. These results are based on the third law and basic thermodynamics only, and are completely general. As an explicit example we consider the ferromagnetic quantum phase transition in clean metals, where a first-order quantum phase transition is commonly observed.

First principles and Debye model study of the thermodynamic, electronic and optical properties of MgO under high-temperature and pressure

NASA Astrophysics Data System (ADS)

Miao, Yurun; Li, Huayang; Wang, Hongjuan; He, Kaihua; Wang, Qingbo

2018-02-01

First principles and quasi-harmonic Debye model have been used to study the thermodynamic properties, enthalpies, electronic and optical properties of MgO up to the core-mantle boundary (CMB) condition (137 GPa and 3700 K). Thermodynamic properties calculation includes thermal expansion coefficient and capacity, which have been studied up to the CMB pressure (137 GPa) and temperature (3700 K) by the Debye model with generalized gradient approximation (GGA) and local-density approximation (LDA). First principles with hybrid functional method (PBE0) has been used to calculate the electronic and optical properties under pressure up to 137 GPa and 0 K. Our results show the Debye model with LDA and first principles with PBE0 can provide accurate thermodynamic properties, enthalpies, electronic and optical properties. Calculated enthalpies show that MgO keep NaCl (B1) structure up to 137 GPa. And MgO is a direct bandgap insulator with a 7.23 eV calculated bandgap. The bandgap increased with increasing pressure, which will induce a blue shift of optical properties. We also calculated the density of states (DOS) and discussed the relation between DOS and band, optical properties. Equations were used to fit the relations between pressure and bandgaps, absorption coefficient (α(ω)) of MgO. The equations can be used to evaluate pressure after careful calibration. Our calculations can not only be used to identify some geological processes, but also offer a reference to the applications of MgO in the future.

Identification of sequence motifs significantly associated with antisense activity.

PubMed

McQuisten, Kyle A; Peek, Andrew S

2007-06-07

Predicting the suppression activity of antisense oligonucleotide sequences is the main goal of the rational design of nucleic acids. To create an effective predictive model, it is important to know what properties of an oligonucleotide sequence associate significantly with antisense activity. Also, for the model to be efficient we must know what properties do not associate significantly and can be omitted from the model. This paper will discuss the results of a randomization procedure to find motifs that associate significantly with either high or low antisense suppression activity, analysis of their properties, as well as the results of support vector machine modelling using these significant motifs as features. We discovered 155 motifs that associate significantly with high antisense suppression activity and 202 motifs that associate significantly with low suppression activity. The motifs range in length from 2 to 5 bases, contain several motifs that have been previously discovered as associating highly with antisense activity, and have thermodynamic properties consistent with previous work associating thermodynamic properties of sequences with their antisense activity. Statistical analysis revealed no correlation between a motif's position within an antisense sequence and that sequences antisense activity. Also, many significant motifs existed as subwords of other significant motifs. Support vector regression experiments indicated that the feature set of significant motifs increased correlation compared to all possible motifs as well as several subsets of the significant motifs. The thermodynamic properties of the significantly associated motifs support existing data correlating the thermodynamic properties of the antisense oligonucleotide with antisense efficiency, reinforcing our hypothesis that antisense suppression is strongly associated with probe/target thermodynamics, as there are no enzymatic mediators to speed the process along like the RNA Induced Silencing Complex (RISC) in RNAi. The independence of motif position and antisense activity also allows us to bypass consideration of this feature in the modelling process, promoting model efficiency and reducing the chance of overfitting when predicting antisense activity. The increase in SVR correlation with significant features compared to nearest-neighbour features indicates that thermodynamics alone is likely not the only factor in determining antisense efficiency.

Reclaiming the Central Role of Equations of State in Thermodynamics

ERIC Educational Resources Information Center

Talanquer, Vicente

2006-01-01

The power of thermodynamics as a tool to derive useful information for a variety of systems is described, stressing the central role of the measurement of thermodynamics properties having experimental physical chemistry. The strategy relies on the use of "response coefficients" that can be measured experimentally and on the systematic manipulation…

Thermodynamics of Quantum Gases for the Entire Range of Temperature

ERIC Educational Resources Information Center

Biswas, Shyamal; Jana, Debnarayan

2012-01-01

We have analytically explored the thermodynamics of free Bose and Fermi gases for the entire range of temperature, and have extended the same for harmonically trapped cases. We have obtained approximate chemical potentials for the quantum gases in closed forms of temperature so that the thermodynamic properties of the quantum gases become…

A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

ERIC Educational Resources Information Center

Hanson, Robert M.

2012-01-01

During the years 1873-1879, J. Willard Gibbs published his now-famous set of articles that form the basis of the current perspective on chemical thermodynamics. The second article of this series, "A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces," published in 1873, is particularly notable…

[Dynamic study of small metallic clusters]; Estudio Dinamico de Pequenos Agregados Metalicos

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, M.J.; Jellinek, J.

1995-12-31

We present a brief introduction to computer simulation techniques (particularly to classical molecular dynamics) and their application to the study of the thermodynamic properties of a material system. The basic concepts are illustrated in the study of structural and energetic properties such as the liquid-solid transition and the fragmentation of small clusters of nickel. [Espanol] Presentamos una breve introducci{acute o}n de las t{acute e}cnicas de simulaci{acute o}n por ordenador (en particular de la Din{acute a}mica Molecular cl{acute a}sica) y de su aplicaci{acute o}n al estudio de las propiedades termodin{acute a}micas de un sistema material. Los conceptos b{acute a}sicos se ilustranmore » en el estudio de las propieades estructurales y energ{acute e}ticas, as{acute i} como de la transici{acute o}n de fase s{acute o}lido-l{acute i}quido y de las fragmentaciones de peque{tilde n}os agregados de n{acute i}quel.« less

A Bridge for Accelerating Materials by Design

DOE PAGES

Sumpter, Bobby G.; Vasudevan, Rama K.; Potok, Thomas E.; ...

2015-11-25

Recent technical advances in the area of nanoscale imaging, spectroscopy, and scattering/diffraction have led to unprecedented capabilities for investigating materials structural, dynamical and functional characteristics. In addition, recent advances in computational algorithms and computer capacities that are orders of magnitude larger/faster have enabled large-scale simulations of materials properties starting with nothing but the identity of the atomic species and the basic principles of quantum- and statistical-mechanics and thermodynamics. Along with these advances, an explosion of high-resolution data has emerged. This confluence of capabilities and rise of big data offer grand opportunities for advancing materials sciences but also introduce several challenges.more » In this editorial we identify challenges impeding progress towards advancing materials by design (e.g., the design/discovery of materials with improved properties/performance), possible solutions, and provide examples of scientific issues that can be addressed by using a tightly integrated approach where theory and experiments are linked through big-deep data.« less

Temperature dependence of thermal pressure for NaCl

NASA Astrophysics Data System (ADS)

Singh, Chandra K.; Pande, Brijesh K.; Pandey, Anjani K.

2018-05-01

Engineering applications of the materials can be explored upto the desired limit of accuracy with the better knowledge of its mechanical and thermal properties such as ductility, brittleness and Thermal Pressure. For the resistance to fracture (K) and plastic deformation (G) the ratio K/G is treated as an indication of ductile or brittle character of solids. In the present work we have tested the condition of ductility and brittleness with the calculated values of K/G for the NaCl. It is concluded that the nature of NaCl can be predicted upto high temperature simply with the knowledge of its elastic stiffness constant only. Thermoelastic properties of materials at high temperature is directly related to thermal pressure and volume expansion of the materials. An expression for the temperature dependence of thermal pressure is formulated using basic thermodynamic identities. It is observed that thermal pressure ΔPth calculated for NaCl by using Kushwah formulation is in good agreement with the experimental values also the thermal pressure increases with the increase in temperature.

Utility of charge-transfer complexation for the assessment of macrocyclic polyethers: Spectroscopic, thermal and surface morphology characteristics of two highly crown ethers complexed with acido acceptors

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Adam, Abdel Majid A.; Saad, Hosam A.

2015-04-01

The study of the complexing ability of macrocyclic compounds to organic and inorganic substances is of great interest. The aim of this work is to provide basic data that can be used to the assessment of macrocyclic crown ethers quantitatively based on charge-transfer (CT) complexation. This goal was achieved by preparing CT complexes of two interesting mixed nitrogen-oxygen crown ethers with acido acceptors (chloranilic and picric acid), which were fully structurally characterized. The crown ethers are 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (HDHC) and 1,4,10-trioxa-7,13-diaza-cyclopentadecane (TDPD). The obtained complexes were structurally characterized via elemental analysis, IR, Raman, 1H NMR, and UV-visible spectroscopy. Thermal properties of these complexes were also studied, and their kinetic thermodynamic parameters were calculated. Furthermore, the microstructure properties of these complexes have also been investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM).

Thermodynamical property of entanglement entropy for excited states.

PubMed

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.

The IVTANTHERMO-Online database for thermodynamic properties of individual substances with web interface

NASA Astrophysics Data System (ADS)

Belov, G. V.; Dyachkov, S. A.; Levashov, P. R.; Lomonosov, I. V.; Minakov, D. V.; Morozov, I. V.; Sineva, M. A.; Smirnov, V. N.

2018-01-01

The database structure, main features and user interface of an IVTANTHERMO-Online system are reviewed. This system continues the series of the IVTANTHERMO packages developed in JIHT RAS. It includes the database for thermodynamic properties of individual substances and related software for analysis of experimental results, data fitting, calculation and estimation of thermodynamical functions and thermochemistry quantities. In contrast to the previous IVTANTHERMO versions it has a new extensible database design, the client-server architecture, a user-friendly web interface with a number of new features for online and offline data processing.

Electrical conductivity of MgH2 at multiple shock compression

NASA Astrophysics Data System (ADS)

Shakhray, Denis; Molodets, Alexander; Fortov, Vladimir

2011-06-01

The electrical conductivity of MgH2 has been studied under multishock compression. Earlier we had been experimentally studied metallization possibility of alane at high pressures in conditions quasiisentropic compression up to 100 GPa. A study of thermodynamic properties of MgH2 under multishock compression has been carried out also. High pressures and temperatures were obtained with an explosive device, which accelerates the metallic impactor up to 3 km/s. Identification of the hydride in experiments was made on the basis of calculations of phase trajectories loading a material in the area of existence of polymorphic phases including high-pressure phases of magnesium hydride (α and γ MgH2, hP1 and hP2). It is shown that occurrence of magnesium hydride electrical conductivity occurs in the field of existence of high-pressure hP2 phase This work was partially supported by the Presidium of the Russian Academy of Sciences within the Program of Basic Research ``Thermal Physics and Mechanics of Extreme Energy Effects and Physics of Strongly Compressed Matter and Russian Foundation for Basic Research Grant No. 10-02-01078.''

An alternative approach to the Boltzmann distribution through the chemical potential

NASA Astrophysics Data System (ADS)

D'Anna, Michele; Job, Georg

2016-05-01

The Boltzmann distribution is one of the most significant results of classical physics. Despite its importance and its wide range of application, at high school level it is mostly presented without any derivation or link to some basic ideas. In this contribution we present an approach based on the chemical potential that allows to derive it directly from the basic idea of thermodynamical equilibrium.

Two-phase thermodynamic model for efficient and accurate absolute entropy of water from molecular dynamics simulations.

PubMed

Lin, Shiang-Tai; Maiti, Prabal K; Goddard, William A

2010-06-24

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

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 the most stable intermetallics were found to have the strongest interaction in the liquid state. Eventually, a new criteria was formulated to select electrode materials for liquid metal batteries. Systems with the most stable intermetallics, which can be evaluated by the enthalpy of formation of these systems, will yield the highest voltage when assembled as positive and negative electrodes in a liquid metal battery. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs@mit.edu)

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.

Thermodynamic and mechanical properties of TiC from ab initio calculation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang, D. Y.; Fan, J. L.; Gong, H. R., E-mail: gonghr@csu.edu.cn

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,more » 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.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holland, Troy Michael; Kress, Joel David; Bhat, Kabekode Ghanasham

Year 1 Objectives (August 2016 – December 2016) – The original Independence model is a sequentially regressed set of parameters from numerous data sets in the Aspen Plus modeling framework. The immediate goal with the basic data model is to collect and evaluate those data sets relevant to the thermodynamic submodels (pure substance heat capacity, solvent mixture heat capacity, loaded solvent heat capacities, and volatility data). These data are informative for the thermodynamic parameters involved in both vapor-liquid equilibrium, and in the chemical equilibrium of the liquid phase.

Thermodynamics of a Simple Rubber-Band Heat Engine

ERIC Educational Resources Information Center

Mullen, J. G.; And Others

1975-01-01

Outlines the basic engine design and nomenclature, develops some relations between the state parameters of the rubber-band system, defines engine efficiency, and compares the Archibald engine with the Carnot engine. (GS)

MPDATA: A positive definite solver for geophysical flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smolarkiewicz, P.K.; Margolin, L.G.

1997-12-31

This paper is a review of MPDATA, a class of methods for the numerical simulation of advection based on the sign-preserving properties of upstream differencing. MPDATA was designed originally as an inexpensive alternative to flux-limited schemes for evaluating the transport of nonnegative thermodynamic variables (such as liquid water or water vapor) in atmospheric models. During the last decade, MPDATA has evolved from a simple advection scheme to a general approach for integrating the conservation laws of geophysical fluids on micro-to-planetary scales. The purpose of this paper is to summarize the basic concepts leading to a family of MPDATA schemes, reviewmore » the existing MPDATA options, as well as to demonstrate the efficacy of the approach using diverse examples of complex geophysical flows.« less

Design Parameters Affecting the Accuracy of Isothermal Thermocouples

DTIC Science & Technology

1975-01-02

Design Parameters Lead Wire Length intekference Accuracy Askew Installation Tungsten / Rhenium Wire Diameter Trajectory Insulation Thickness Heatshield...Summary ................. 73 A-3 Thermodynamic Properties of Tungsten / Rhenium Therm ocouples ............................ 75 A-4 Thermodynamic Properties...were tungsten / rhenium , chromel/alumel, and iron/constbntan, which covered the 0 to 5000, 0 to 2200, and 0 to I-00°F temperatut- ranges, resoectively. in

Calculating phase diagrams using PANDAT and panengine

NASA Astrophysics Data System (ADS)

Chen, S.-L.; Zhang, F.; Xie, F.-Y.; Daniel, S.; Yan, X.-Y.; Chang, Y. A.; Schmid-Fetzer, R.; Oates, W. A.

2003-12-01

Knowledge of phase equilibria or phase diagrams and thermodynamic properties is important in alloy design and materials-processing simulation. In principle, stable phase equilibrium is uniquely determined by the thermodynamic properties of the system, such as the Gibbs energy functions of the phases. PANDAT, a new computer software package for multicomponent phase-diagram calculation, was developed under the guidance of this principle.

The Hydrothermal Chemistry of Gold, Arsenic, Antimony, Mercury and Silver

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bessinger, Brad; Apps, John A.

2003-03-23

A comprehensive thermodynamic database based on the Helgeson-Kirkham-Flowers (HKF) equation of state was developed for metal complexes in hydrothermal systems. Because this equation of state has been shown to accurately predict standard partial molal thermodynamic properties of aqueous species at elevated temperatures and pressures, this study provides the necessary foundation for future exploration into transport and depositional processes in polymetallic ore deposits. The HKF equation of state parameters for gold, arsenic, antimony, mercury, and silver sulfide and hydroxide complexes were derived from experimental equilibrium constants using nonlinear regression calculations. In order to ensure that the resulting parameters were internally consistent,more » those experiments utilizing incompatible thermodynamic data were re-speciated prior to regression. Because new experimental studies were used to revise the HKF parameters for H2S0 and HS-1, those metal complexes for which HKF parameters had been previously derived were also updated. It was found that predicted thermodynamic properties of metal complexes are consistent with linear correlations between standard partial molal thermodynamic properties. This result allowed assessment of several complexes for which experimental data necessary to perform regression calculations was limited. Oxygen fugacity-temperature diagrams were calculated to illustrate how thermodynamic data improves our understanding of depositional processes. Predicted thermodynamic properties were used to investigate metal transport in Carlin-type gold deposits. Assuming a linear relationship between temperature and pressure, metals are predicted to predominantly be transported as sulfide complexes at a total aqueous sulfur concentration of 0.05 m. Also, the presence of arsenic and antimony mineral phases in the deposits are shown to restrict mineralization within a limited range of chemical conditions. Finally, at a lesser aqueous sulfur concentration of 0.01 m, host rock sulfidation can explain the origin of arsenic and antimony minerals within the paragenetic sequence.« less

Direct measurement of weakly nonequilibrium system entropy is consistent with Gibbs–Shannon form

PubMed Central

2017-01-01

Stochastic thermodynamics extends classical thermodynamics to small systems in contact with one or more heat baths. It can account for the effects of thermal fluctuations and describe systems far from thermodynamic equilibrium. A basic assumption is that the expression for Shannon entropy is the appropriate description for the entropy of a nonequilibrium system in such a setting. Here we measure experimentally this function in a system that is in local but not global equilibrium. Our system is a micron-scale colloidal particle in water, in a virtual double-well potential created by a feedback trap. We measure the work to erase a fraction of a bit of information and show that it is bounded by the Shannon entropy for a two-state system. Further, by measuring directly the reversibility of slow protocols, we can distinguish unambiguously between protocols that can and cannot reach the expected thermodynamic bounds. PMID:29073017

Shear viscosity of binary mixtures: The Gay-Berne potential

NASA Astrophysics Data System (ADS)

Khordad, R.

2012-05-01

The Gay-Berne (GB) potential model is an interesting and useful model to study the real systems. Using the potential model, we intend to examine the thermodynamical properties of some anisotropic binary mixtures in two different phases, liquid and gas. For this purpose, we apply the integral equation method and solve numerically the Percus-Yevick (PY) integral equation. Then, we obtain the expansion coefficients of correlation functions to calculate the thermodynamical properties. Finally, we compare our results with the available experimental data [e.g., HFC-125 + propane, R-125/143a, methanol + toluene, benzene + methanol, cyclohexane + ethanol, benzene + ethanol, carbon tetrachloride + ethyl acetate, and methanol + ethanol]. The results show that the GB potential model is capable for predicting the thermodynamical properties of binary mixtures with acceptable accuracy.

Application of zone-folding approach to the first-principles estimation of thermodynamic properties of carbon and ZrS2 -based nanotubes.

PubMed

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. © 2015 Wiley Periodicals, Inc.

Accurate radiation temperature and chemical potential from quantitative photoluminescence analysis of hot carrier populations.

PubMed

Gibelli, François; Lombez, Laurent; Guillemoles, Jean-François

2017-02-15

In order to characterize hot carrier populations in semiconductors, photoluminescence measurement is a convenient tool, enabling us to probe the carrier thermodynamical properties in a contactless way. However, the analysis of the photoluminescence spectra is based on some assumptions which will be discussed in this work. We especially emphasize the importance of the variation of the material absorptivity that should be considered to access accurate thermodynamical properties of the carriers, especially by varying the excitation power. The proposed method enables us to obtain more accurate results of thermodynamical properties by taking into account a rigorous physical description and finds direct application in investigating hot carrier solar cells, which are an adequate concept for achieving high conversion efficiencies with a relatively simple device architecture.

A review of reaction rates and thermodynamic and transport properties for the 11-species air model for chemical and thermal nonequilibrium calculations to 30000 K

NASA Technical Reports Server (NTRS)

Gupta, Roop N.; Yos, Jerrold M.; Thompson, Richard A.

1989-01-01

Reaction rate coefficients and thermodynamic and transport properties are provided for the 11-species air model which can be used for analyzing flows in chemical and thermal nonequilibrium. Such flows will likely occur around currently planned and future hypersonic vehicles. Guidelines for determining the state of the surrounding environment are provided. Approximate and more exact formulas are provided for computing the properties of partially ionized air mixtures in such environments.

Thermophysical and radiation properties of high-temperature C4F8-CO2 mixtures to replace SF6 in high-voltage circuit breakers

NASA Astrophysics Data System (ADS)

Zhong, Linlin; Cressault, Yann; Teulet, Philippe

2018-03-01

C4F8-CO2 mixtures are one of the potential substitutes to SF6 in high-voltage circuit breakers. However, the arc quenching ability of C4F8-CO2 mixtures is still unknown. In order to provide the necessary basic data for the further investigation of arc quenching performance, the compositions, thermodynamic properties, transport coefficients, and net emission coefficients (NEC) of various C4F8-CO2 mixtures are calculated at temperatures of 300-30 000 K in this work. The thermodynamic properties are presented as the product of mass density and specific heat, i.e., ρCp. The transport coefficients include electrical conductivity, viscosity, and thermal conductivity. The atomic and molecular radiation are both taken into account in the calculation of NEC. The comparison of the properties between SF6 and C4F8-CO2 mixtures is also discussed to find their differences. The results of compositions show that C4F8-CO2 mixtures have a distinctive advantage over other alternative gases e.g., CF3I and C3F8, because the dissociative product (i.e., C4F6) of C4F8 at low temperatures has a very high dielectric strength. This is good for an arc quenching medium to endure the arc recovery phase. Compared with SF6, C4F8-CO2 mixtures present lower ρCp at temperatures below 2800 K and larger thermal conductivity above 2800 K. Based on the position of peaks in thermal conductivity, we predict that the cooling of C4F8-CO2 arc will be slowed down at higher temperatures than that of SF6 arc. It is also found that the mixing of CO2 shows slight effects on the electrical conductivity and NEC of C4F8-CO2 mixtures.

Peat hybrid sorbents for treatment of wastewaters and remediation of polluted environment

NASA Astrophysics Data System (ADS)

Klavins, Maris; Burlakovs, Juris; Robalds, Artis; Ansone-Bertina, Linda

2015-04-01

For remediation of soils and purification of polluted waters, wastewaters, sorbents might be considered as an prospective group of materials and amongst them peat have a special role due to low cost, biodegradability, high number of functional groups, well developed surface area and combination of hydrophilic/hydrophobic structural elements. Peat as sorbent have good application potential for removal of trace metals, and we have demonstrated peat sorption capacities, sorption kinetics, thermodynamics in respect to metals with different valencies - Tl(I), Cu(II), Cr(III). However peat sorption capacity in respect to nonmetallic (anionic species) elements is low. Also peat mechanical properties do not support application in large scale column processes. To expand peat application possibilities the approach of biomass based hybrid sorbents has been elaborated. The concept "hybrid sorbent" in our understanding means natural, biomass based sorbent modified, covered with another sorbent material, thus combining two types of sorbent properties, sorbent functionalities, surface properties etc. As the "covering layer" both inorganic substances, mineral phases (iron oxohydroxides, oxyapatite) both organic polymers (using graft polymerization) were used. The obtained sorbents were characterised by their spectral properties, surface area, elemental composition. The obtained hybrid sorbents were tested for sorption of compounds in anionic speciation forms, for example of arsenic, antimony, tellurium and phosphorous compounds in comparison with weakly basic anionites. The highest sorption capacity was observed when peat sorbents modified with iron compounds were used. Sorption of different arsenic speciation forms onto iron-modified peat sorbents was investigated as a function of pH and temperature. It was established that sorption capacity increases with a rise in temperature, and the calculation of sorption process thermodynamic parameters indicates the spontaneity of sorption process and its endothermic nature. The recycling options of obtained compounds after their saturation with metal or non-metallic species are suggested. Acknowledgement: Support from a project 2014/0009/1DP/1.1.1.2.0/13/APIA/VIAA/044

Water Hammer Simulations of Monomethylhydrazine Propellant

NASA Technical Reports Server (NTRS)

Burkhardt, Zachary; Ramachandran, N.; Majumdar, A.

2017-01-01

Fluid Transient analysis is important for the design of spacecraft propulsion system to ensure structural stability of the system in the event of sudden closing or opening of the valve. Generalized Fluid System Simulation Program (GFSSP), a general purpose flow network code developed at NASA/MSFC is capable of simulating pressure surge due to sudden opening or closing of valve when thermodynamic properties of real fluid are available for the entire range of simulation. Specifically GFSSP needs an accurate representation of pressure density relationship in order to predict pressure surge during a fluid transient. Unfortunately, the available thermodynamic property programs such as REFPROP, GASP or GASPAK do not provide the thermodynamic properties of Monomethylhydrazine(MMH). This work illustrates the process used for building a customized table of properties of state variables from available properties and speed of sound that is required by GFSSP for simulation. Good agreement was found between the simulations and measured data. This method can be adopted for modeling flow networks and systems with other fluids whose properties are not known in detail in order to obtain general technical insight.

Resources in the VLab Science Gateway: Online applications for thermodynamics and thermal elastic properties of mantle minerals

NASA Astrophysics Data System (ADS)

Wentzcovitch, R. M.; Da Silveira, P. R.; Wu, Z.; Yu, Y.

2013-12-01

Today first principles calculations in mineral physics play a fundamental role in understanding of the Earth. They complement experiments by expanding the pressure and temperature range for which properties can be obtained and provide access to atomic scale phenomena. Since the wealth of predictive first principles results can hardly be communicated in printed form, we have developed online applications where published results can be reproduced/verified online and extensive unpublished results can be generated in customized form. So far these applications have included thermodynamics properties of end-member phases and thermal elastic properties of end-member phases and few solid solutions. Extension of this software infrastructure to include other properties is in principle straightforward. This contribution will review the nature of results that can be generated (methods, thermodynamics domain, list of minerals, properties, etc) and nature of the software infrastructure. These applications are part of a more extensive cyber-infrastructure operating in the XSEDE - the VLab Science Gateway [1]. [1] https://www.xsede.org/web/guest/gateways-listing Research supported by NSF grants ATM-0428744 and EAR-1047629.

Infinitely Dilute Partial Molar Properties of Proteins from Computer Simulation

PubMed Central

2015-01-01

A detailed understanding of temperature and pressure effects on an infinitely dilute protein’s conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method’s feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages. PMID:25325571

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions.

PubMed

Chaudhari, Mangesh I; Muralidharan, Ajay; Pratt, Lawrence R; Rempe, Susan B

2018-02-12

Progress in understanding liquid ethylene carbonate (EC) and propylene carbonate (PC) on the basis of molecular simulation, emphasizing simple models of interatomic forces, is reviewed. Results on the bulk liquids are examined from the perspective of anticipated applications to materials for electrical energy storage devices. Preliminary results on electrochemical double-layer capacitors based on carbon nanotube forests and on model solid-electrolyte interphase (SEI) layers of lithium ion batteries are considered as examples. The basic results discussed suggest that an empirically parameterized, non-polarizable force field can reproduce experimental structural, thermodynamic, and dielectric properties of EC and PC liquids with acceptable accuracy. More sophisticated force fields might include molecular polarizability and Buckingham-model description of inter-atomic overlap repulsions as extensions to Lennard-Jones models of van der Waals interactions. Simple approaches should be similarly successful also for applications to organic molecular ions in EC/PC solutions, but the important case of Li[Formula: see text] deserves special attention because of the particularly strong interactions of that small ion with neighboring solvent molecules. To treat the Li[Formula: see text] ions in liquid EC/PC solutions, we identify interaction models defined by empirically scaled partial charges for ion-solvent interactions. The empirical adjustments use more basic inputs, electronic structure calculations and ab initio molecular dynamics simulations, and also experimental results on Li[Formula: see text] thermodynamics and transport in EC/PC solutions. Application of such models to the mechanism of Li[Formula: see text] transport in glassy SEI models emphasizes the advantage of long time-scale molecular dynamics studies of these non-equilibrium materials.

Local equilibrium and the second law of thermodynamics for irreversible systems with thermodynamic inertia.

PubMed

Glavatskiy, K S

2015-10-28

Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.

A Combustion Laboratory for Undergraduates.

ERIC Educational Resources Information Center

Peters, James E.

1985-01-01

Describes a combustion laboratory facility and experiments for a senior-level (undergraduate) course in mechanical engineering. The experiment reinforces basic thermodynamic concepts and provides many students with their first opportunity to work with a combustion system. (DH)

Thermal radiative and thermodynamic properties of solid and liquid uranium and plutonium carbides in the visible-near-infrared range

NASA Astrophysics Data System (ADS)

Fisenko, Anatoliy I.; Lemberg, Vladimir F.

2016-09-01

The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these functions have not been established for plutonium carbide. The calculated values for the normal total emissivity of uranium and plutonium carbides at their melting temperatures is in good agreement with experimental data. The obtained results allow to calculate the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides for any size of samples. Based on the model of Hagen-Rubens and the Wiedemann-Franz law, a new method to determine the thermal conductivity of metals and carbides at the melting points is proposed.

Thermodynamics of Accelerating Black Holes.

PubMed

Appels, Michael; Gregory, Ruth; Kubizňák, David

2016-09-23

We address a long-standing problem of describing the thermodynamics of an accelerating black hole. We derive a standard first law of black hole thermodynamics, with the usual identification of entropy proportional to the area of the event horizon-even though the event horizon contains a conical singularity. This result not only extends the applicability of black hole thermodynamics to realms previously not anticipated, it also opens a possibility for studying novel properties of an important class of exact radiative solutions of Einstein equations describing accelerated objects. We discuss the thermodynamic volume, stability, and phase structure of these black holes.

Nonequilibrium thermodynamics and information theory: basic concepts and relaxing dynamics

NASA Astrophysics Data System (ADS)

Altaner, Bernhard

2017-11-01

Thermodynamics is based on the notions of energy and entropy. While energy is the elementary quantity governing physical dynamics, entropy is the fundamental concept in information theory. In this work, starting from first principles, we give a detailed didactic account on the relations between energy and entropy and thus physics and information theory. We show that thermodynamic process inequalities, like the second law, are equivalent to the requirement that an effective description for physical dynamics is strongly relaxing. From the perspective of information theory, strongly relaxing dynamics govern the irreversible convergence of a statistical ensemble towards the maximally non-commital probability distribution that is compatible with thermodynamic equilibrium parameters. In particular, Markov processes that converge to a thermodynamic equilibrium state are strongly relaxing. Our framework generalizes previous results to arbitrary open and driven systems, yielding novel thermodynamic bounds for idealized and real processes. , which features invited work from the best early-career researchers working within the scope of J. Phys. A. This project is part of the Journal of Physics series’ 50th anniversary celebrations in 2017. Bernhard Altaner was selected by the Editorial Board of J. Phys. A as an Emerging Talent.

Thermodynamic Calculations for Molecules with Asymmetric Internal Rotors. II. Application to the 1,2-Dihaloethanes

PubMed Central

Wong, Bryan M.; Fadri, Maria M.; Raman, Sumathy

2012-01-01

The thermodynamic properties of three halocarbon molecules relevant in atmospheric and public health applications are presented from ab initio calculations. Our technique makes use of a reaction path-like Hamiltonian to couple all the vibrational modes to a large-amplitude torsion for 1,2-difluoroethane, 1,2-dichloroethane, and 1,2-dibromoethane, each of which possesses a heavy asymmetric rotor. Optimized ab initio energies and Hessians were calculated at the CCSD(T) and MP2 levels of theory, respectively. In addition, to investigate the contribution of electronically excited states to thermodynamic properties, several excited singlet and triplet states for each of the halocarbons were computed at the CASSCF/MRCI level. Using the resulting potentials and projected frequencies, the couplings of all the vibrational modes to the large-amplitude torsion are calculated using the new STAR-P 2.4.0 software platform that automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Utilizing the efficient parallelization scheme of STAR-P, we obtain thermodynamic properties for each of the halocarbons, with temperatures ranging from 298.15 to 1000 K. We propose that the free energies, entropies, and heat capacities obtained from our methods be used to supplement theoretical and experimental values found in current thermodynamic tables. PMID:17663439

Thermodynamic calculations for molecules with asymmetric internal rotors. II. Application to the 1,2-dihaloethanes.

PubMed

Wong, Bryan M; Fadri, Maria M; Raman, Sumathy

2008-02-01

The thermodynamic properties of three halocarbon molecules relevant in atmospheric and public health applications are presented from ab initio calculations. Our technique makes use of a reaction path-like Hamiltonian to couple all the vibrational modes to a large-amplitude torsion for 1,2-difluoroethane, 1,2-dichloroethane, and 1,2-dibromoethane, each of which possesses a heavy asymmetric rotor. Optimized ab initio energies and Hessians were calculated at the CCSD(T) and MP2 levels of theory, respectively. In addition, to investigate the contribution of electronically excited states to thermodynamic properties, several excited singlet and triplet states for each of the halocarbons were computed at the CASSCF/MRCI level. Using the resulting potentials and projected frequencies, the couplings of all the vibrational modes to the large-amplitude torsion are calculated using the new STAR-P 2.4.0 software platform that automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Utilizing the efficient parallelization scheme of STAR-P, we obtain thermodynamic properties for each of the halocarbons, with temperatures ranging from 298.15 to 1000 K. We propose that the free energies, entropies, and heat capacities obtained from our methods be used to supplement theoretical and experimental values found in current thermodynamic tables. (c) 2007 Wiley Periodicals, Inc.

Structural characterization, catalytic, kinetic and thermodynamic properties of Aspergillus oryzae tannase.

PubMed

Abdel-Naby, Mohamed A; El-Tanash, Arafat Bedier; Sherief, Abdel Daium A

2016-11-01

Tannase (EC.3.1.1.20) from Aspergillus oryzae was purified using ammonium sulphate precipitation (75%), gel filtration chromatography through Sephadex G-100, and G-200. The purified enzyme was monomeric protein with a molecular mass of 106kDa. The activation energy for tannic acid hydrolysis was 32.6kJmol -1 and its temperature quotient (Q 10 ) was 1.0. The pK a1 and pK a2 values of acidic and basic limbs of the active site residues were 4.6 and 6.4. The calculated values of thermodynamic parameters for tannic acid hydrolysis, were as follows: ΔH*=30.02kJmol -1 , ΔG*=59.75kJmol -1 ΔS*=-95.90Jmol -1 K -1 , (ΔG* E-S )=3.66kJmol -1 and ΔG* E-T -12.61kJmol -1 . The pure enzyme exhibited K m , V max and k cat of 4.13mM, 3507Umgprotein -1 and 551.4s -1 . The calculated half-life time at 40, 45, 50, 55, 60, and 70°C was 955.15, 142.0, 30.28, 17.88, 8.23 and 2.95min, respectively. The thermodynamic parameters for irreversible thermal inactivation at different temperatures (40-70°C) were determined. The enzyme was activated by Ca 2+ , and Mg 2+ while Hg 2+ , Fe 2+ , and Cu 2+ strongly inhibited it. Hydrolysis of tannic acid by the pure enzyme indicated that gallic acid was the end-product. Copyright © 2016 Elsevier B.V. All rights reserved.

The thermodynamic properties of oxygen and nitrogen

NASA Technical Reports Server (NTRS)

Stewart, R. B.; Jacobsen, R. T.; Myers, A. F.

1972-01-01

The development of a single equation of state for oxygen and nitrogen based on the thermodynamic properties of the gases is described. The coefficients of the equation of state were determined by simultaneous least squares fits to values of isochoric heat capacity and saturation density values used to define the criteria for phase equilibrium. Tables of data for the conditions of both gases are included.

Experimental investigation of thermodynamic properties of binary mixture of acetic acid + n-butanol and acetic acid + water at temperature from 293.15 K to 343.15 K

NASA Astrophysics Data System (ADS)

Paul, M. Danish John; Shruthi, N.; Anantharaj, R.

2018-04-01

The derived thermodynamic properties like excess molar volume, partial molar volume, excess partial molar volume and apparent volume of binary mixture of acetic acid + n-butanolandacetic acid + water has been investigated using measured density of mixtures at temperatures from 293.15 K to 343.15.

An investigation of nonsimultaneous laser-induced fluorescence

NASA Technical Reports Server (NTRS)

Fletcher, D. G.

1993-01-01

An alternative to simultaneous, two-line laser-induced fluorescence for thermodynamic property measurement is presented. This spectroscopic approach is similar to multiple-overheat hot-wire anemometry and is based on laser excitation of different fluorescence transitions for separate, sequential wind tunnel runs. Both fluctuating and mean thermodynamic property measurements seem to be achievable with this method without exciting the transitions during the same laser pulse.

Thermodynamics properties of lanthanide series near melting point-A pseudopotential approach

NASA Astrophysics Data System (ADS)

Suthar, P. H.; Gajjar, P. N.

2018-04-01

The present paper deals with computational study of thermodynamics properties for fifteen elements of lanthanide series. The Helmholtz free energy (F), Internal energy (E) and Entropy (S)have been computed using variational method based on the Gibbs-Bogoliubov (GB) along with Percus-Yevick hard sphere reference system and Gajjar's model potential. The local field correction function proposed by Taylor is applied to introduce the exchange and correlation effects in the study of thermodynamics of these metals. The present results in comparison with available theoretical and experimental are found to be in good agreement and confirm the ability of the model potential.

The JRC-ITU approach to the safety of advanced nuclear fuel cycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fanghaenel, T.; Rondinella, V.V.; Somers, J.

2013-07-01

The JRC-ITU safety studies of advanced fuels and cycles adopt two main axes. First the full exploitation of still available and highly relevant knowledge and samples from past fuel preparation and irradiation campaigns (complementing the limited number of ongoing programmes). Secondly, the shift of focus from simple property measurement towards the understanding of basic mechanisms determining property evolution and behaviour of fuel compounds during normal, off-normal and accident conditions. The final objective of the second axis is the determination of predictive tools applicable to systems and conditions different from those from which they were derived. State of the art experimentalmore » facilities, extensive networks of partnerships and collaboration with other organizations worldwide, and a developing programme for training and education are essential in this approach. This strategy has been implemented through various programs and projects. The SUPERFACT programme constitutes the main body of existing knowledge on the behavior in-pile of MOX fuel containing minor actinides. It encompassed all steps of a closed fuel cycle. Another international project investigating the safety of a closed cycle is METAPHIX. In this case a U-Pu19-Zr10 metal alloy containing Np, Am and Cm constitutes the fuel. 9 test pins have been prepared and irradiated. In addition to the PIE (Post Irradiation Examination), pyrometallurgical separation of the irradiated fuel has been performed, to demonstrate all the steps of a multiple recycling closed cycle and characterize their safety relevant aspects. Basic studies like thermodynamic fuel properties, fuel-cladding-coolant interactions have also been carried out at JRC-ITU.« less

Contact symmetries and Hamiltonian thermodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bravetti, A., E-mail: bravetti@correo.nucleares.unam.mx; Lopez-Monsalvo, C.S., E-mail: cesar.slm@correo.nucleares.unam.mx; Nettel, F., E-mail: Francisco.Nettel@roma1.infn.it

It has been shown that contact geometry is the proper framework underlying classical thermodynamics and that thermodynamic fluctuations are captured by an additional metric structure related to Fisher’s Information Matrix. In this work we analyse several unaddressed aspects about the application of contact and metric geometry to thermodynamics. We consider here the Thermodynamic Phase Space and start by investigating the role of gauge transformations and Legendre symmetries for metric contact manifolds and their significance in thermodynamics. Then we present a novel mathematical characterization of first order phase transitions as equilibrium processes on the Thermodynamic Phase Space for which the Legendremore » symmetry is broken. Moreover, we use contact Hamiltonian dynamics to represent thermodynamic processes in a way that resembles the classical Hamiltonian formulation of conservative mechanics and we show that the relevant Hamiltonian coincides with the irreversible entropy production along thermodynamic processes. Therefore, we use such property to give a geometric definition of thermodynamically admissible fluctuations according to the Second Law of thermodynamics. Finally, we show that the length of a curve describing a thermodynamic process measures its entropy production.« less

Predicting structural properties of fluids by thermodynamic extrapolation

NASA Astrophysics Data System (ADS)

Mahynski, Nathan A.; Jiao, Sally; Hatch, Harold W.; Blanco, Marco A.; Shen, Vincent K.

2018-05-01

We describe a methodology for extrapolating the structural properties of multicomponent fluids from one thermodynamic state to another. These properties generally include features of a system that may be computed from an individual configuration such as radial distribution functions, cluster size distributions, or a polymer's radius of gyration. This approach is based on the principle of using fluctuations in a system's extensive thermodynamic variables, such as energy, to construct an appropriate Taylor series expansion for these structural properties in terms of intensive conjugate variables, such as temperature. Thus, one may extrapolate these properties from one state to another when the series is truncated to some finite order. We demonstrate this extrapolation for simple and coarse-grained fluids in both the canonical and grand canonical ensembles, in terms of both temperatures and the chemical potentials of different components. The results show that this method is able to reasonably approximate structural properties of such fluids over a broad range of conditions. Consequently, this methodology may be employed to increase the computational efficiency of molecular simulations used to measure the structural properties of certain fluid systems, especially those used in high-throughput or data-driven investigations.

Intermolecular interactions and the thermodynamic properties of supercritical fluids.

PubMed

Yigzawe, Tesfaye M; Sadus, Richard J

2013-05-21

The role of different contributions to intermolecular interactions on the thermodynamic properties of supercritical fluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercritical fluids.

MMA-EoS: A Computational Framework for Mineralogical Thermodynamics

NASA Astrophysics Data System (ADS)

Chust, T. C.; Steinle-Neumann, G.; Dolejš, D.; Schuberth, B. S. A.; Bunge, H.-P.

2017-12-01

We present a newly developed software framework, MMA-EoS, that evaluates phase equilibria and thermodynamic properties of multicomponent systems by Gibbs energy minimization, with application to mantle petrology. The code is versatile in terms of the equation-of-state and mixing properties and allows for the computation of properties of single phases, solution phases, and multiphase aggregates. Currently, the open program distribution contains equation-of-state formulations widely used, that is, Caloric-Murnaghan, Caloric-Modified-Tait, and Birch-Murnaghan-Mie-Grüneisen-Debye models, with published databases included. Through its modular design and easily scripted database, MMA-EoS can readily be extended with new formulations of equations-of-state and changes or extensions to thermodynamic data sets. We demonstrate the application of the program by reproducing and comparing physical properties of mantle phases and assemblages with previously published work and experimental data, successively increasing complexity, up to computing phase equilibria of six-component compositions. Chemically complex systems allow us to trace the budget of minor chemical components in order to explore whether they lead to the formation of new phases or extend stability fields of existing ones. Self-consistently computed thermophysical properties for a homogeneous mantle and a mechanical mixture of slab lithologies show no discernible differences that require a heterogeneous mantle structure as has been suggested previously. Such examples illustrate how thermodynamics of mantle mineralogy can advance the study of Earth's interior.

Thermodynamics of third-order Lovelock-AdS black holes in the presence of Born-Infeld type nonlinear electrodynamics

NASA Astrophysics Data System (ADS)

Hendi, S. H.; Dehghani, A.

2015-03-01

In this paper, we obtain topological black hole solutions of third-order Lovelock gravity coupled with two classes of Born-Infeld-type nonlinear electrodynamics with anti-de Sitter asymptotic structure. We investigate geometric and thermodynamics properties of the solutions and obtain conserved quantities of the black holes. We examine the first law of thermodynamics and find that the conserved and thermodynamic quantities of the black hole solutions satisfy the first law of thermodynamics. Finally, we calculate the heat capacity and determinant of the Hessian matrix to evaluate thermal stability in both canonical and grand canonical ensembles. Moreover, we consider the extended phase space thermodynamics to obtain a generalized first law of thermodynamics as well as the extended Smarr formula.

Calculating Water Thermodynamics in the Binding Site of Proteins - Applications of WaterMap to Drug Discovery.

PubMed

Cappel, Daniel; Sherman, Woody; Beuming, Thijs

2017-01-01

The ability to accurately characterize the solvation properties (water locations and thermodynamics) of biomolecules is of great importance to drug discovery. While crystallography, NMR, and other experimental techniques can assist in determining the structure of water networks in proteins and protein-ligand complexes, most water molecules are not fully resolved and accurately placed. Furthermore, understanding the energetic effects of solvation and desolvation on binding requires an analysis of the thermodynamic properties of solvent involved in the interaction between ligands and proteins. WaterMap is a molecular dynamics-based computational method that uses statistical mechanics to describe the thermodynamic properties (entropy, enthalpy, and free energy) of water molecules at the surface of proteins. This method can be used to assess the solvent contributions to ligand binding affinity and to guide lead optimization. In this review, we provide a comprehensive summary of published uses of WaterMap, including applications to lead optimization, virtual screening, selectivity analysis, ligand pose prediction, and druggability assessment. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Thermodynamic properties of asymptotically Reissner–Nordström black holes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hendi, S.H., E-mail: hendi@shirazu.ac.ir

2014-07-15

Motivated by possible relation between Born–Infeld type nonlinear electrodynamics and an effective low-energy action of open string theory, asymptotically Reissner–Nordström black holes whose electric field is described by a nonlinear electrodynamics (NLED) are studied. We take into account a four dimensional topological static black hole ansatz and solve the field equations, exactly, in terms of the NLED as a matter field. The main goal of this paper is investigation of thermodynamic properties of the obtained black holes. Moreover, we calculate the heat capacity and find that the nonlinearity affects the minimum size of stable black holes. We also use Legendre-invariantmore » metric proposed by Quevedo to obtain scalar curvature divergences. We find that the singularities of the Ricci scalar in Geometrothermodynamics (GTD) method take place at the Davies points. -- Highlights: •We examine the thermodynamical properties of black holes in Einstein gravity with nonlinear electrodynamics. •We investigate thermodynamic stability and discuss about the size of stable black holes. •We obtain analytical solutions of higher dimensional theory.« less

Iron(III) solubility and speciation in aqueous solutions. experimental study and modelling: part 1. hematite solubility from 60 to 300°C in NaOH-NaCl solutions and thermodynamic properties of Fe(OH) 4 -(aq)

NASA Astrophysics Data System (ADS)

Diakonov, Igor I.; Schott, Jacques; Martin, Francois; Harrichourry, Jean-Claude; Escalier, Jocelyne

1999-08-01

The solubility of natural and synthetic hematite (α-Fe 2O 3) was measured in NaOH-NaCl solutions (0.007 ≤ m(NaOH) ≤ 2.0) between 60 and 300°C at saturated water vapour pressure and under excess oxygen. Solubility constants determined in the present study and by Yishan et al. (1986) at 300°C were combined with the thermodynamic properties of hematite (Hemingway, 1990) and water (SUPCRT92, Johnson et al., 1992) to generate within the framework of the revised Helgeson-Kirkham-Flowers (HKF) model the standard partial molal thermodynamic properties at 25°C and 1 bar, and the revised HKF equations of state parameters of Fe(OH) 4 -. The extrapolated value for the Gibbs energy of formation for Fe(OH) 4 - at 25°C is -201.97 kcal/mol. Thermodynamic calculations show that Fe(OH) 4 - exhibits a chemical behaviour different from that of Ga(OH) 4 - and Al(OH) 4 -.

Thermodynamics and Frozen Foods.

ERIC Educational Resources Information Center

Kerr, William L.; Reid, David S.

1993-01-01

The heat content of a food at a given temperature can be described by the thermodynamic property of enthalpy. Presents a method to construct a simple calorimeter for measuring the enthalpy changes of different foods during freezing. (MDH)

A Thermodynamically General Theory for Convective Circulations and Vortices

NASA Astrophysics Data System (ADS)

Renno, N. O.

2007-12-01

Convective circulations and vortices are common features of atmospheres that absorb low-entropy-energy at higher temperatures than they reject high-entropy-energy to space. These circulations range from small to planetary-scale and play an important role in the vertical transport of heat, momentum, and tracer species. Thus, the development of theoretical models for convective phenomena is important to our understanding of many basic features of planetary atmospheres. A thermodynamically general theory for convective circulations and vortices is proposed. The theory includes irreversible processes and quantifies the pressure drop between the environment and any point in a convective updraft. The article's main result is that the proposed theory provides an expression for the pressure drop along streamlines or streamtubes that is a generalization of Bernoulli's equation to convective circulations. We speculate that the proposed theory not only explains the intensity, but also shed light on other basic features of convective circulations and vortices.

Dynamics, thermodynamics and structure of liquids and supercritical fluids: crossover at the Frenkel line

NASA Astrophysics Data System (ADS)

Fomin, Yu D.; Ryzhov, V. N.; Tsiok, E. N.; Proctor, J. E.; Prescher, C.; Prakapenka, V. B.; Trachenko, K.; Brazhkin, V. V.

2018-04-01

We review recent work aimed at understanding dynamical and thermodynamic properties of liquids and supercritical fluids. The focus of our discussion is on solid-like transverse collective modes, whose evolution in the supercritical fluids enables one to discuss the main properties of the Frenkel line separating rigid liquid-like and non-rigid gas-like supercritical states. We subsequently present recent experimental evidence of the Frenkel line showing that structural and dynamical crossovers are seen at a pressure and temperature corresponding to the line as predicted by theory and modelling. Finally, we link dynamical and thermodynamic properties of liquids and supercritical fluids by the new calculation of liquid energy governed by the evolution of solid-like transverse modes. The disappearance of those modes at high temperature results in the observed decrease of heat capacity.

Mechanical and thermodynamic properties of AlX (X = N, P, As) compounds

NASA Astrophysics Data System (ADS)

Xu, Lifang; Bu, Wei

2017-09-01

The Vickers hardness of various AlX (X = N, P, As) compound polymorphs were calculated with the bond resistance model. Thermodynamic properties, such as vibrational entropy, constant volume specific heat and Debye temperatures, were calculated using phonon dispersion relations and phonon density of states (DOS). The calculated values are in good agreement with the previous experimental and theoretical data. For the same structure of AlX (X = N, P, As) compounds, their hardness and Debye temperatures both decrease with the X atomic number. The wurtzite (wz) and zincblende (zb) structures of the same compounds AlX share an almost identical hardness, but have different Debye temperatures. The difference between wz and zb structures increases as the atomic number of X increases. The thermodynamic properties reveal that the constant volume specific heat approaches the Dulong-Petit rule at high temperatures.

Ab-initio study of thermodynamic properties of boron nanowire at atomic scale

NASA Astrophysics Data System (ADS)

Bhuyan, Prabal D.; Gupta, Sanjeev K.; Sonvane, Y.; Gajjar, P. N.

2018-04-01

In the present work, we have optimized ribbon like zigzag structure of boron (B) nanowire (NW) and investigated vibrational and thermodynamic properties using quasi-harmonic approximations (QHA). All positive phonon in the phonon dispersive curve have confirmed dynamical stability of ribbon B-NW. The thermodynamic properties, like Debye temperature, internal energy and specific heat, are calculated as a function of temperature. The variation of specific heat is proportional to T3 Debye law at lower temperature for B-NW, while it becomes constant above room temperature at 1200K; obeys Dulong-Petit's law. The high Debye temperature of 1120K is observed at ambient temperature, which can be attributed to high thermal conductivity. Our study shows that B-NW with high thermal conductivity could be the next generation electron connector for nanoscale electronic devices.

Structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 phases from first-principles calculations

NASA Astrophysics Data System (ADS)

Li, X. D.; Li, K.; Wei, C. H.; Han, W. D.; Zhou, N. G.

2018-06-01

The structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 are systematically investigated by using first-principles calculations method based on density functional theory (DFT). The calculated formation enthalpies and cohesive energies show that CaSi2 possesses the greatest structural stability and CaSi has the strongest alloying ability. The structural stability of the three phases is compared according to electronic structures. Further analysis on electronic structures indicates that the bonding of these phases exhibits the combinations of metallic, covalent, and ionic bonds. The elastic constants are calculated, and the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and anisotropy factor of polycrystalline materials are deduced. Additionally, the thermodynamic properties were theoretically predicted and discussed.

Quantum Szilard engines with arbitrary spin.

PubMed

Zhuang, Zekun; Liang, Shi-Dong

2014-11-01

The quantum Szilard engine (QSZE) is a conceptual quantum engine for understanding the fundamental physics of quantum thermodynamics and information physics. We generalize the QSZE to an arbitrary spin case, i.e., a spin QSZE (SQSZE), and we systematically study the basic physical properties of both fermion and boson SQSZEs in a low-temperature approximation. We give the analytic formulation of the total work. For the fermion SQSZE, the work might be absorbed from the environment, and the change rate of the work with temperature exhibits periodicity and even-odd oscillation, which is a generalization of a spinless QSZE. It is interesting that the average absorbed work oscillates regularly and periodically in a large-number limit, which implies that the average absorbed work in a fermion SQSZE is neither an intensive quantity nor an extensive quantity. The phase diagrams of both fermion and boson SQSZEs give the SQSZE doing positive or negative work in the parameter space of the temperature and the particle number of the system, but they have different behaviors because the spin degrees of the fermion and the boson play different roles in their configuration states and corresponding statistical properties. The critical temperature of phase transition depends sensitively on the particle number. By using Landauer's erasure principle, we give the erasure work in a thermodynamic cycle, and we define an efficiency (we refer to it as information-work efficiency) to measure the engine's ability of utilizing information to extract work. We also give the conditions under which the maximum extracted work and highest information-work efficiencies for fermion and boson SQSZEs can be achieved.

Spontaneous ultraweak photon emission from biological systems and the endogenous light field.

PubMed

Schwabl, Herbert; Klima, Herbert

2005-04-01

Still one of the most astonishing biological electromagnetic phenomena is the ultraweak photon emission (UPE) from living systems. Organisms and tissues spontaneously emit measurable intensities of light, i.e. photons in the visible part of the electromagnetic spectrum (380-780 nm), in the range from 1 to 1,000 photons x s-1 x cm-2, depending on their condition and vitality. It is important not to confuse UPE from living systems with other biogenic light emitting processes such as bioluminescence or chemiluminescence. This article examines with basic considerations from physics on the quantum nature of photons the empirical phenomenon of UPE. This leads to the description of the non-thermal origin of this radiation. This is in good correspondence with the modern understanding of life phenomena as dissipative processes far from thermodynamic equilibrium. UPE also supports the understanding of life sustaining processes as basically driven by electromagnetic fields. The basic features of UPE, like intensity and spectral distribution, are known in principle for many experimental situations. The UPE of human leukocytes contributes to an endogenous light field of about 1011 photons x s-1 which can be influenced by certain factors. Further research is needed to reveal the statistical properties of UPE and in consequence to answer questions about the underlying mechanics of the biological system. In principle, statistical properties of UPE allow to reconstruct phase-space dynamics of the light emitting structures. Many open questions remain until a proper understanding of the electromagnetic interaction of the human organism can be achieved: which structures act as receptors and emitters for electromagnetic radiation? How is electromagnetic information received and processed within cells?

Thermodynamic Versus Surface Area Control of Microbial Fe(III) Oxide Reduction Kinetics

NASA Astrophysics Data System (ADS)

Roden, E. E.

2003-12-01

Recent experimental studies of synthetic and natural Fe(III) oxide reduction permit development of conceptual and quantitative models of enzymatic Fe(III) oxide reduction at circumneutral pH that can be compared to and contrasted with established models of abiotic mineral dissolution. The findings collectively support a model for controls on enzymatic reduction that differs fundamentally from those applied to abiotic reductive dissolution as a result of two basic phenomena: (1) the relatively minor influence of oxide mineralogical and thermodynamic properties on surface area-normalized rates of enzymatic reduction compared to abiotic reductive dissolution; and (2) the major limitation which sorption and/or surface precipitation of biogenic Fe(II) on residual oxide and Fe(III)-reducing bacterial cell surfaces poses to enzymatic electron transfer in the presence of excess electron donor. Parallel studies with two major Fe(III)-reducing bacteria genera (Shewanella and Geobacter) lead to common conclusions regarding the importance of these phenomena in regulating the rate and long-term extent of Fe(III) oxide reduction. Although the extent to which these phenomena can be traced to underlying kinetic vs. thermodynamic effects cannot be resolved with current information, models in which rates of enzymatic reduction are limited kinetically by the abundance of "available" oxide surface sites (as controlled by oxide surface area and the abundance of surface-bound Fe(II)) provide an adequate macroscopic description of controls on the initial rate and long-term extent of oxide reduction. In some instances, thermodynamic limitation posed by the accumulation of aqueous reaction end-products (i.e. Fe(II) and alkalinity) must also be invoked to explain observed long-term patterns of reduction. In addition, the abundance of Fe(III)-reducing microorganisms plays an important role in governing rates of reduction and needs to be considered in models of Fe(III) reduction in nonsteady-state systems, e.g. subsurface environments in which Fe(III) reduction is stimulated by contamination with organics or for the purposes of metal/radionuclide bioremediation.

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.

Correlations for determining thermodynamic properties of hydrogen-helium gas mixtures at temperatures from 7,000 to 35,000 K

NASA Technical Reports Server (NTRS)

Zoby, E. V.; Gnoffo, P. A.; Graves, R. A., Jr.

1976-01-01

Simple relations for determining the enthalpy and temperature of hydrogen-helium gas mixtures were developed for hydrogen volumetric compositions from 1.0 to 0.7. These relations are expressed as a function of pressure and density and are valid for a range of temperatures from 7,000 to 35,000 K and pressures from 0.10 to 3.14 MPa. The proportionality constant and exponents in the correlation equations were determined for each gas composition by applying a linear least squares curve fit to a large number of thermodynamic calculations obtained from a detailed computer code. Although these simple relations yielded thermodynamic properties suitable for many engineering applications, their accuracy was improved significantly by evaluating the proportionality constants at postshock conditions and correlating these values as a function of the gas composition and the product of freestream velocity and shock angle. The resulting equations for the proportionality constants in terms of velocity and gas composition and the corresponding simple realtions for enthalpy and temperature were incorporated into a flow field computational scheme. Comparison was good between the thermodynamic properties determined from these relations and those obtained by using a detailed computer code to determine the properties. Thus, an appreciable savings in computer time was realized with no significant loss in accuracy.

Thermodynamic properties of a liquid crystal carbosilane dendrimer

NASA Astrophysics Data System (ADS)

Samosudova, Ya. S.; Markin, A. V.; Smirnova, N. N.; Ogurtsov, T. G.; Boiko, N. I.; Shibaev, V. P.

2016-11-01

The temperature dependence of the heat capacity of a first-generation liquid crystal carbosilane dendrimer with methoxyphenyl benzoate end groups is studied for the first time in the region of 6-370 K by means of precision adiabatic vacuum calorimetry. Physical transformations are observed in this interval of temperatures, and their standard thermodynamic characteristics are determined and discussed. Standard thermodynamic functions C p ° ( T), H°( T) - H°(0), S°( T) - S°(0), and G°( T) - H°(0) are calculated from the obtained experimental data for the region of T → 0 to 370 K. The standard entropy of formation of the dendrimer in the partially crystalline state at T = 298.15 K is calculated, and the standard entropy of the hypothetic reaction of its synthesis at this temperature is estimated. The thermodynamic properties of the studied dendrimer are compared to those of second- and fourth-generation liquid crystal carbosilane dendrimers with the same end groups studied earlier.

First-principles calculations of the thermodynamic properties of transuranium elements in a molten salt medium

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.

Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics.

PubMed

Glavatskiy, K S

2015-05-28

We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such that there exists an "integral of evolution" which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium.

Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glavatskiy, K. S.

We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called “mirror-image” system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such thatmore » there exists an “integral of evolution” which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium.« less

Thermodynamic properties of water in confined environments: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Gladovic, Martin; Bren, Urban; Urbic, Tomaž

2018-05-01

Monte Carlo simulations of Mercedes-Benz water in a crowded environment were performed. The simulated systems are representative of both composite, porous or sintered materials and living cells with typical matrix packings. We studied the influence of overall temperature as well as the density and size of matrix particles on water density, particle distributions, hydrogen bond formation and thermodynamic quantities. Interestingly, temperature and space occupancy of matrix exhibit a similar effect on water properties following the competition between the kinetic and the potential energy of the system, whereby temperature increases the kinetic and matrix packing decreases the potential contribution. A novel thermodynamic decomposition approach was applied to gain insight into individual contributions of different types of inter-particle interactions. This decomposition proved to be useful and in good agreement with the total thermodynamic quantities especially at higher temperatures and matrix packings, where higher-order potential-energy mixing terms lose their importance.

Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

2009-07-01

The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

Thermodynamics of multicaloric effects in multiferroic materials: application to metamagnetic shape-memory alloys and ferrotoroidics

DOE PAGES

Planes, Antoni; Castán, Teresa; Saxena, Avadh

2016-07-11

In this paper, we develop a general thermodynamic framework to investigate multicaloric effects in multiferroic materials. This is applied to the study of both magnetostructural and magnetoelectric multiferroics. Landau models with appropriate interplay between the corresponding ferroic properties (order parameters) are proposed for metamagnetic shape-memory and ferrotoroidic materials, which, respectively, belong to the two classes of multiferroics. For each ferroic property, caloric effects are quantified by the isothermal entropy change induced by the application of the corresponding thermodynamically conjugated field. The multicaloric effect is obtained as a function of the two relevant applied fields in each class of multiferroics. Itmore » is further shown that multicaloric effects comprise the corresponding contributions from caloric effects associated with each ferroic property and the cross-contribution arising from the interplay between these ferroic properties. Finally, this article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’.« less

Variational discretization of the nonequilibrium thermodynamics of simple systems

NASA Astrophysics Data System (ADS)

Gay-Balmaz, François; Yoshimura, Hiroaki

2018-04-01

In this paper, we develop variational integrators for the nonequilibrium thermodynamics of simple closed systems. These integrators are obtained by a discretization of the Lagrangian variational formulation of nonequilibrium thermodynamics developed in (Gay-Balmaz and Yoshimura 2017a J. Geom. Phys. part I 111 169–93 Gay-Balmaz and Yoshimura 2017b J. Geom. Phys. part II 111 194–212) and thus extend the variational integrators of Lagrangian mechanics, to include irreversible processes. In the continuous setting, we derive the structure preserving property of the flow of such systems. This property is an extension of the symplectic property of the flow of the Euler–Lagrange equations. In the discrete setting, we show that the discrete flow solution of our numerical scheme verifies a discrete version of this property. We also present the regularity conditions which ensure the existence of the discrete flow. We finally illustrate our discrete variational schemes with the implementation of an example of a simple and closed system.

Thermodynamic Properties and Transport Coefficients of Nitrogen, Hydrogen and Helium Plasma Mixed with Silver Vapor

NASA Astrophysics Data System (ADS)

Zhou, Xue; Cui, Xinglei; Chen, Mo; Zhai, Guofu

2016-05-01

Species composites of Ag-N2, Ag-H2 and Ag-He plasmas in the temperature range of 3,000-20,000 K and at 1 atmospheric pressure were calculated by using the minimization of Gibbs free energy. Thermodynamic properties and transport coefficients of nitrogen, hydrogen and helium plasmas mixed with a variety of silver vapor were then calculated based on the equilibrium composites and collision integral data. The calculation procedure was verified by comparing the results obtained in this paper with the published transport coefficients on the case of pure nitrogen plasma. The influences of the silver vapor concentration on composites, thermodynamic properties and transport coefficients were finally analyzed and summarized for all the three types of plasmas. Those physical properties were important for theoretical study and numerical calculation on arc plasma generated by silver-based electrodes in those gases in sealed electromagnetic relays and contacts. supported by National Natural Science Foundation of China (Nos. 51277038 and 51307030)

Local equilibrium and the second law of thermodynamics for irreversible systems with thermodynamic inertia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glavatskiy, K. S.

Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called “mirror-image” systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can bemore » derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.« less

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.

On the radiative and thermodynamic properties of the cosmic radiations using COBE FIRAS instrument data: I. Cosmic microwave background radiation

NASA Astrophysics Data System (ADS)

Fisenko, Anatoliy I.; Lemberg, Vladimir

2014-07-01

Using the explicit form of the functions to describe the monopole and dipole spectra of the Cosmic Microwave Background (CMB) radiation, the exact expressions for the temperature dependences of the radiative and thermodynamic functions, such as the total radiation power per unit area, total energy density, number density of photons, Helmholtz free energy density, entropy density, heat capacity at constant volume, and pressure in the finite range of frequencies v 1≤ v≤ v 2 are obtained. Since the dependence of temperature upon the redshift z is known, the obtained expressions can be simply presented in z representation. Utilizing experimental data for the monopole and dipole spectra measured by the COBE FIRAS instrument in the 60-600 GHz frequency interval at the temperature T=2.72548 K, the values of the radiative and thermodynamic functions, as well as the radiation density constant a and the Stefan-Boltzmann constant σ are calculated. In the case of the dipole spectrum, the constants a and σ, and the radiative and thermodynamic properties of the CMB radiation are obtained using the mean amplitude T amp=3.358 mK. It is shown that the Doppler shift leads to a renormalization of the radiation density constant a, the Stefan-Boltzmann constant σ, and the corresponding constants for the thermodynamic functions. The expressions for new astrophysical parameters, such as the entropy density/Boltzmann constant, and number density of CMB photons are obtained. The radiative and thermodynamic properties of the Cosmic Microwave Background radiation for the monopole and dipole spectra at redshift z≈1089 are calculated.

Signatures of Solvation Thermodynamics in Spectra of Intermolecular Vibrations

PubMed Central

2017-01-01

This study explores the thermodynamic and vibrational properties of water in the three-dimensional environment of solvated ions and small molecules using molecular simulations. The spectrum of intermolecular vibrations in liquid solvents provides detailed information on the shape of the local potential energy surface, which in turn determines local thermodynamic properties such as the entropy. Here, we extract this information using a spatially resolved extension of the two-phase thermodynamics method to estimate hydration water entropies based on the local vibrational density of states (3D-2PT). Combined with an analysis of solute–water and water–water interaction energies, this allows us to resolve local contributions to the solvation enthalpy, entropy, and free energy. We use this approach to study effects of ions on their surrounding water hydrogen bond network, its spectrum of intermolecular vibrations, and resulting thermodynamic properties. In the three-dimensional environment of polar and nonpolar functional groups of molecular solutes, we identify distinct hydration water species and classify them by their characteristic vibrational density of states and molecular entropies. In each case, we are able to assign variations in local hydration water entropies to specific changes in the spectrum of intermolecular vibrations. This provides an important link for the thermodynamic interpretation of vibrational spectra that are accessible to far-infrared absorption and Raman spectroscopy experiments. Our analysis provides unique microscopic details regarding the hydration of hydrophobic and hydrophilic functional groups, which enable us to identify interactions and molecular degrees of freedom that determine relevant contributions to the solvation entropy and consequently the free energy. PMID:28783431

Introductory physics going soft

NASA Astrophysics Data System (ADS)

Langbeheim, Elon; Livne, Shelly; Safran, Samuel A.; Yerushalmi, Edit

2012-01-01

We describe an elective course on soft matter at the level of introductory physics. Soft matter physics serves as a context that motivates the presentation of basic ideas in statistical thermodynamics and their applications. It also is an example of a contemporary field that is interdisciplinary and touches on chemistry, biology, and physics. We outline a curriculum that uses the lattice gas model as a quantitative and visual tool, initially to introduce entropy, and later to facilitate the calculation of interactions. We demonstrate how free energy minimization can be used to teach students to understand the properties of soft matter systems such as the phases of fluid mixtures, wetting of interfaces, self-assembly of surfactants, and polymers. We discuss several suggested activities in the form of inquiry projects which allow students to apply the concepts they have learned to experimental systems.

Water Hammer Simulations of MMH Propellant - New Capability Demonstration of the Generalized Fluid Flow Simulation Program

NASA Technical Reports Server (NTRS)

Burkhardt, Z.; Ramachandran, N.; Majumdar, A.

2017-01-01

Fluid Transient analysis is important for the design of spacecraft propulsion system to ensure structural stability of the system in the event of sudden closing or opening of the valve. Generalized Fluid System Simulation Program (GFSSP), a general purpose flow network code developed at NASA/MSFC is capable of simulating pressure surge due to sudden opening or closing of valve when thermodynamic properties of real fluid are available for the entire range of simulation. Specifically GFSSP needs an accurate representation of pressure-density relationship in order to predict pressure surge during a fluid transient. Unfortunately, the available thermodynamic property programs such as REFPROP, GASP or GASPAK does not provide the thermodynamic properties of Monomethylhydrazine (MMH). This paper will illustrate the process used for building a customized table of properties of state variables from available properties and speed of sound that is required by GFSSP for simulation. Good agreement was found between the simulations and measured data. This method can be adopted for modeling flow networks and systems with other fluids whose properties are not known in detail in order to obtain general technical insight. Rigorous code validation of this approach will be done and reported at a future date.

A Tractable Disequilbrium Framework for Integrating Computational Thermodynamics and Geodynamics

NASA Astrophysics Data System (ADS)

Spiegelman, M. W.; Tweed, L. E. L.; Evans, O.; Kelemen, P. B.; Wilson, C. R.

2017-12-01

The consistent integration of computational thermodynamics and geodynamics is essential for exploring and understanding a wide range of processes from high-PT magma dynamics in the convecting mantle to low-PT reactive alteration of the brittle crust. Nevertheless, considerable challenges remain for coupling thermodynamics and fluid-solid mechanics within computationally tractable and insightful models. Here we report on a new effort, part of the ENKI project, that provides a roadmap for developing flexible geodynamic models of varying complexity that are thermodynamically consistent with established thermodynamic models. The basic theory is derived from the disequilibrium thermodynamics of De Groot and Mazur (1984), similar to Rudge et. al (2011, GJI), but extends that theory to include more general rheologies, multiple solid (and liquid) phases and explicit chemical reactions to describe interphase exchange. Specifying stoichiometric reactions clearly defines the compositions of reactants and products and allows the affinity of each reaction (A = -Δ/Gr) to be used as a scalar measure of disequilibrium. This approach only requires thermodynamic models to return chemical potentials of all components and phases (as well as thermodynamic quantities for each phase e.g. densities, heat capacity, entropies), but is not constrained to be in thermodynamic equilibrium. Allowing meta-stable phases mitigates some of the computational issues involved with the introduction and exhaustion of phases. Nevertheless, for closed systems, these problems are guaranteed to evolve to the same equilibria predicted by equilibrium thermodynamics. Here we illustrate the behavior of this theory for a range of simple problems (constructed with our open-source model builder TerraFERMA) that model poro-viscous behavior in the well understood Fo-Fa binary phase loop. Other contributions in this session will explore a range of models with more petrologically interesting phase diagrams as well as other rheologies.

Thermodynamic metrics and optimal paths.

PubMed

Sivak, David A; Crooks, Gavin E

2012-05-11

A fundamental problem in modern thermodynamics is how a molecular-scale machine performs useful work, while operating away from thermal equilibrium without excessive dissipation. To this end, we derive a friction tensor that induces a Riemannian manifold on the space of thermodynamic states. Within the linear-response regime, this metric structure controls the dissipation of finite-time transformations, and bestows optimal protocols with many useful properties. We discuss the connection to the existing thermodynamic length formalism, and demonstrate the utility of this metric by solving for optimal control parameter protocols in a simple nonequilibrium model.

A Variational Assimilation Method for Satellite and Conventional Data: Development of Basic Model for Diagnosis of Cyclone Systems

NASA Technical Reports Server (NTRS)

Achtemeier, Gary L.; Scott, Robert W.; Chen, J.

1991-01-01

A summary is presented of the progress toward the completion of a comprehensive diagnostic objective analysis system based upon the calculus of variations. The approach was to first develop the objective analysis subject to the constraints that the final product satisfies the five basic primitive equations for a dry inviscid atmosphere: the two nonlinear horizontal momentum equations, the continuity equation, the hydrostatic equation, and the thermodynamic equation. Then, having derived the basic model, there would be added to it the equations for moist atmospheric processes and the radiative transfer equation.

Quartz: heat capacities from 340 to 1000 K and revised values for the thermodynamic properties.

USGS Publications Warehouse

Hemingway, B.S.

1987-01-01

New heat-capacity data for quartz have been measured over the T interval 340-1000 K by differential scanning calorimetry. The data were combined with recent heat-content and heat-capacity data to provide a significantly revised set of thermodynamic properties for alpha -quartz and to resolve the problem of disparate heat-content and heat-capacity data for alpha - and beta -quartz.-J.A.Z.

Thermodynamic properties and diffusion of water + methane binary mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

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 methanemore » 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.« less

Using the Antenna Effect as a Spectroscopic Tool; Photophysics and Solution Thermodynamics of the Model Luminescent Hydroxypyridonate Complex [EuIII(3,4,3-LI(1,2-HOPO))]-

PubMed Central

Abergel, Rebecca J.; D'Aléo, Anthony; Leung, Clara Ng Pak; Shuh, David K.; Raymond, Kenneth N.

2009-01-01

While widely used in bioassays, the spectrofluorimetric method described here uses the antenna effect as a tool to probe the thermodynamic parameters of ligands that sensitize lanthanide luminescence. The Eu3+ coordination chemistry, solution thermodynamic stability and photophysical properties of the spermine-based hydroxypyridonate octadentate chelator 3,4,3-LI(1,2-HOPO) are reported. The complex [EuIII(3,4,3-LI(1,2-HOPO))]- luminesces with a long lifetime (805 μs) and a quantum yield of 7.0% in aqueous solution, at pH 7.4. These remarkable optical properties were exploited to determine the high (and proton-independent) stability of the complex (log β110 = 20.2(2)) and to define the influence of the ligand scaffold on the stability and photophysical properties. PMID:19902920

Structural, vibrational and thermodynamic properties of Mg2 FeH6 complex hydride

NASA Astrophysics Data System (ADS)

Zhou, H. L.; Yu, Y.; Zhang, H. F.; Gao, T.

2011-02-01

Mg2FeH6, which has one of the highest hydrogen storage capacities among Mg based 3d-transitional metal hydrides, is considered as an attractive material for hydrogen storage. Within density-functional perturbation theory (DFPT), we have investigated the structural, vibrational and thermodynamic properties of Mg2FeH6. The band structure calculation shows that this compound is a semiconductor with a direct X-X energy gap of 1.96 eV. The calculated phonon frequencies for the Raman-active and the infrared-active modes are assigned. The phonon dispersion curves together with the corresponding phonon density of states and longitudinal-transverse optical (LO-TO) splitting are also calculated. Findings are also presented for the temperature-dependent behaviors of some thermodynamic properties such as free energy, internal energy, entropy and heat capacity within the quasi-harmonic approximation based on the calculated phonon density of states.

First-principles study of the elastic and thermodynamic properties of CaSiO(3) perovskite.

PubMed

Liu, Z J; Sun, X W; Chen, Q F; Cai, L C; Wu, H Y; Ge, S H

2007-06-20

The thermodynamic and elastic properties of CaSiO(3) perovskite are investigated at high pressures and temperatures using the plane wave pseudopotential method within the local density approximation. The athermal elastic moduli of CaSiO(3) perovskite are calculated as a function of pressure up to 200 GPa. The calculated results are in excellent agreement with available experimental data at high pressure, and compare favourably with other pseudopotential predictions over the pressure regime studied. It is also found that the elastic anisotropy drops rapidly with the increase of pressure initially, and then decreases more slowly at higher pressures. The thermodynamic properties of CaSiO(3) perovskite are predicted using the quasi-harmonic Debye model for the first time; the heat capacity and the thermal expansion coefficient agree with the observed values at ambient conditions and the other calculations at high pressures and temperatures.

M3FT-15OR0202212: SUBMIT SUMMARY REPORT ON THERMODYNAMIC EXPERIMENT AND MODELING

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurray, Jake W.; Brese, Robert G.; Silva, Chinthaka M.

2015-09-01

Modeling the behavior of nuclear fuel with a physics-based approach uses thermodynamics for key inputs such as chemical potentials and thermal properties for phase transformation, microstructure evolution, and continuum transport simulations. Many of the lanthanide (Ln) elements and Y are high-yield fission products. The U-Y-O and U-Ln-O ternaries are therefore key subsystems of multi-component high-burnup fuel. These elements dissolve in the dominant urania fluorite phase affecting many of its properties. This work reports on an effort to assess the thermodynamics of the U-Pr-O and U-Y-O systems using the CALPHAD (CALculation of PHase Diagrams) method. The models developed within this frameworkmore » are capable of being combined and extended to include additional actinides and fission products allowing calculation of the phase equilibria, thermochemical and material properties of multicomponent fuel with burnup.« less

Thermodynamic properties and static structure factor for a Yukawa fluid in the mean spherical approximation.

PubMed

Montes-Perez, J; Cruz-Vera, A; Herrera, J N

2011-12-01

This work presents the full analytic expressions for the thermodynamic properties and the static structure factor for a hard sphere plus 1-Yukawa fluid within the mean spherical approximation. To obtain these properties of the fluid type Yukawa analytically it was necessary to solve an equation of fourth order for the scaling parameter on a large scale. The physical root of this equation was determined by imposing physical conditions. The results of this work are obtained from seminal papers of Blum and Høye. We show that is not necessary the use the series expansion to solve the equation for the scaling parameter. We applied our theoretical result to find the thermodynamic and the static structure factor for krypton. Our results are in good agreement with those obtained in an experimental form or by simulation using the Monte Carlo method.

Thermodynamic properties and transport coefficients of two-temperature helium thermal plasmas

NASA Astrophysics Data System (ADS)

Guo, Xiaoxue; Murphy, Anthony B.; Li, Xingwen

2017-03-01

Helium thermal plasmas are in widespread use in arc welding and many other industrial applications. Simulation of these processes relies on accurate plasma property data, such as plasma composition, thermodynamic properties and transport coefficients. Departures from LTE (local thermodynamic equilibrium) generally occur in some regions of helium plasmas. In this paper, properties are calculated allowing for different values of the electron temperature, T e, and heavy-species temperature, T h, at atmospheric pressure from 300 K to 30 000 K. The plasma composition is first calculated using the mass action law, and the two-temperature thermodynamic properties are then derived. The viscosity, diffusion coefficients, electrical conductivity and thermal conductivity of the two-temperature helium thermal plasma are obtained using a recently-developed method that retains coupling between electrons and heavy species by including the electron-heavy-species collision term in the heavy-species Boltzmann equation. It is shown that the viscosity and the diffusion coefficients strongly depend on non-equilibrium ratio θ (θ ={{T}\\text{e}}/{{T}\\text{h}} ), through the plasma composition and the collision integrals. The electrical conductivity, which depends on the electron number density and ordinary diffusion coefficients, and the thermal conductivity have similar dependencies. The choice of definition of the Debye length is shown to affect the electrical conductivity significantly for θ  >  1. By comparing with literature data, it is shown that the coupling between electrons and heavy species has a significant influence on the electrical conductivity, but not on the viscosity. Plasma properties are tabulated in the supplementary data.

Thermodynamic Properties of Nitrogen Including Liquid and Vapor Phases from 63K to 2000K with Pressures to 10,000 Bar

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.

Extended Thermodynamics: a Theory of Symmetric Hyperbolic Field Equations

NASA Astrophysics Data System (ADS)

Müller, Ingo

2008-12-01

Extended thermodynamics is based on a set of equations of balance which are supplemented by local and instantaneous constitutive equations so that the field equations are quasi-linear first order differential equations. If the constitutive functions are subject to the requirements of the entropy principle, one may write them in symmetric hyperbolic form by a suitable choice of fields. The kinetic theory of gases, or the moment theories based on the Boltzmann equation provide an explicit example for extended thermodynamics. The theory proves its usefulness and practicality in the successful treatment of light scattering in rarefied gases. This presentation is based upon the book [1] of which the author of this paper is a co-author. For more details about the motivation and exploitation of the basic principles the interested reader is referred to that reference. It would seem that extended thermodynamics is worthy of the attention of mathematicians. It may offer them a non-trivial field of study concerning hyperbolic equations, if ever they get tired of the Burgers equation. Physicists may prefer to appreciate the success of extended thermodynamics in light scattering and to work on the open problems concerning the modification of the Navier-Stokes-Fourier theory in rarefied gases as predicted by extended thermodynamics of 13, 14, and more moments.

Impact of Friedel oscillations on vapor-liquid equilibria and supercritical properties in two and three dimensions

NASA Astrophysics Data System (ADS)

Desgranges, Caroline; Huber, Landon; Delhommelle, Jerome

2016-07-01

We determine the impact of the Friedel oscillations on the phase behavior, critical properties, and thermodynamic contours in films [two dimensions (2 D )] and bulk phases [three dimensions (3 D )]. Using expanded Wang-Landau simulations, we calculate the grand-canonical partition function and, in turn, the thermodynamic properties of systems modeled with a linear combination of the Lennard-Jones and Dzugutov potentials, weighted by a parameter X (0

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 and transport coefficients of a two-temperature polytetrafluoroethylene vapor plasma for ablation-controlled discharge applications

NASA Astrophysics Data System (ADS)

Wang, Haiyan; Wang, Weizong; Yan, Joseph D.; Qi, Haiyang; Geng, Jinyue; Wu, Yaowu

2017-10-01

Ablation-controlled plasmas have been used in a range of technical applications where local thermodynamic equilibrium (LTE) is often violated near the wall due to the strong cooling effect caused by the ablation of wall materials. The thermodynamic and transport properties of ablated polytetrafluoroethylene (PTFE) vapor, which determine the flowing plasma behavior in such applications, are calculated based on a two-temperature model at atmospheric pressure. To our knowledge, no data for PTFE have been reported in the literature. The species composition and thermodynamic properties are numerically determined using the two-temperature Saha equation and the Guldberg-Waage equation according to van de Sanden et al’s derivation. The transport coefficients, including viscosity, thermal conductivity and electrical conductivity, are calculated with the most recent collision interaction potentials using Devoto’s electron and heavy-particle decoupling approach but expanded to the third-order approximation (second-order for viscosity) in the frame of the Chapman-Enskog method. Results are computed for different degrees of thermal non-equilibrium, i.e. the ratio of electron to heavy-particle temperatures, from 1 to 10, with electron temperature ranging from 300 to 40 000 K. Plasma transport properties in the LTE state obtained from the present work are compared with existing published results and the causes for the discrepancy analyzed. The two-temperature plasma properties calculated in the present work enable the modeling of wall ablation-controlled plasma processes.

Thermodynamic limits to the efficiency of solar energy conversion by quantum devices

NASA Technical Reports Server (NTRS)

Buoncristiani, A. M.; Byvik, C. E.; Smith, B. T.

1981-01-01

The second law of thermodynamics imposes a strict limitation to the energy converted from direct solar radiation to useful work by a quantum device. This limitation requires that the amount of energy converted to useful work (energy in any form other than heat) can be no greater than the change in free energy of the radiation fields. Futhermore, in any real energy conversion device, not all of this available free energy in the radiation field can be converted to work because of basic limitations inherent in the device itself. A thermodynamic analysis of solar energy conversion by a completely general prototypical quantum device is presented. This device is completely described by two parameters, its operating temperature T sub R and the energy threshold of its absorption spectrum. An expression for the maximum thermodynamic efficiency of a quantum solar converter was derived in terms of these two parameters and the incident radiation spectrum. Efficiency curves for assumed solar spectral irradiance corresponding to air mass zero and air mass 1.5 are presented.

The Molybdenum titanium Phase Diagram Evaluated from Ab initio Calculations

DTIC Science & Technology

2016-10-07

thermodynamic properties of this binary system are not well known and two conflicting descriptions of the β-phase stability have been presented in the...computational thermodynamics CALPHAD approach [13] and the Thermo-Calc software [14]. These studies led to two conflicting descriptions of the stability of...energy calculations, with an energy cutoff separating core and valence states of -6 Ry. 2.2. Thermodynamic modeling The formation enthalpy of a

A miniaturized technique for assessing protein thermodynamics and function using fast determination of quantitative cysteine reactivity.

PubMed

Isom, Daniel G; Marguet, Philippe R; Oas, Terrence G; Hellinga, Homme W

2011-04-01

Protein thermodynamic stability is a fundamental physical characteristic that determines biological function. Furthermore, alteration of thermodynamic stability by macromolecular interactions or biochemical modifications is a powerful tool for assessing the relationship between protein structure, stability, and biological function. High-throughput approaches for quantifying protein stability are beginning to emerge that enable thermodynamic measurements on small amounts of material, in short periods of time, and using readily accessible instrumentation. Here we present such a method, fast quantitative cysteine reactivity, which exploits the linkage between protein stability, sidechain protection by protein structure, and structural dynamics to characterize the thermodynamic and kinetic properties of proteins. In this approach, the reaction of a protected cysteine and thiol-reactive fluorogenic indicator is monitored over a gradient of temperatures after a short incubation time. These labeling data can be used to determine the midpoint of thermal unfolding, measure the temperature dependence of protein stability, quantify ligand-binding affinity, and, under certain conditions, estimate folding rate constants. Here, we demonstrate the fQCR method by characterizing these thermodynamic and kinetic properties for variants of Staphylococcal nuclease and E. coli ribose-binding protein engineered to contain single, protected cysteines. These straightforward, information-rich experiments are likely to find applications in protein engineering and functional genomics. Copyright © 2010 Wiley-Liss, Inc.

Numerical Optimization Algorithms and Software for Systems Biology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saunders, Michael

2013-02-02

The basic aims of this work are: to develop reliable algorithms for solving optimization problems involving large stoi- chiometric matrices; to investigate cyclic dependency between metabolic and macromolecular biosynthetic networks; and to quantify the significance of thermodynamic constraints on prokaryotic metabolism.

Science and Mathematics

ERIC Educational Resources Information Center

Redlich, Otto

1972-01-01

The foundation of science, and of thermodynamics in particular, can be developed cogently and without arbitrariness. The goal of science, description of nature, is externally given; it requires a set of basic concepts as indispensable tools. Mathematics has no similar externally given goal. (Author/TS)

Optimization of the thermodynamic properties and phase diagrams of P2O5-containing systems

NASA Astrophysics Data System (ADS)

Hudon, Pierre; Jung, In-Ho

2014-05-01

P2O5 is an important oxide component in the late stage products of numerous igneous rocks such as granites and pegmatites. Typically, P2O5 combines with CaO and crystallizes in the form of apatite, while in volatile-free conditions, Ca-whitlockite is formed. In spite of their interest, the thermodynamic properties and phase diagrams of P2O5-containg systems are not well known yet. In the case of the pure P2O5 for example, no experimental thermodynamic data are available for the liquid and the O and O' solid phases. As a result, we re-evaluated all the thermodynamic and phase diagram data of the P2O5 unary system [1]. Optimization of the thermodynamic properties and phase diagrams of the binary P2O5 systems was then performed including the Li2O-, Na2O-, MgO-, CaO-, BaO-, MnO-, FeO-, Fe2O3-, ZnO-, Al2O3-, and SiO2-P2O5 [2] systems. All available thermodynamic and phase equilibrium data were simultaneously reproduced in order to obtain a set of model equations for the Gibbs energies of all phases as functions of temperature and composition. In particular, the Gibbs energy of the liquid solution was described using the Modified Quasichemical Model [3-5] implemented in the FactSage software [6]. Thermodynamic modeling of the Li2O-Na2O-K2O-MgO-CaO-FeO-Fe2O3-Al2O3-SiO2 system, which include many granite-forming minerals such as nepheline, leucite, pyroxene, melilite, feldspar and spinel is currently in progress. [1] Jung, I.-H., Hudon, P. (2012) Thermodynamic assessment of P2O5. J. Am. Ceram. Soc., 95 (11), 3665-3672. [2] Rahman, M., Hudon, P. and Jung, I.-H. (2013) A coupled experimental study and thermodynamic modeling of the SiO2-P2O5 system. Metall. Mater. Trans. B, 44 (4), 837-852. [3] Pelton, A.D. and Blander, M. (1984) Computer-assisted analysis of the thermodynamic properties and phase diagrams of slags. Proc. AIME Symp. Metall. Slags Fluxes, TMS-AIME, 281-294. [4] Pelton, A.D. and Blander, M. (1986) Thermodynamic analysis of ordered liquid solutions by a modified quasichemical approach application to silicate slags. Metall. Trans. B, 17, 805-815. [5] A.D. Pelton, S.A. Decterov, G. Eriksson, C. Robelin and Y. Dessureault (2000) The modified quasichemical model - I Binary solutions. Metall. Mater. Trans. B, 31, 651-660. [6] C.W. Bale, P. Chartrand, S.A. Decterov, G. Eriksson, K. Hack, R. Ben Mahfoud, J. Melançon, A.D. Pelton and S. Petersen. (2002) FactSage Thermochemical Software and Databases. Calphad, 26, 189-228.

THERMODYNAMICS USED IN ENVIRONMENTAL ENGINEERING

EPA Science Inventory

Thermodynamics is a science in which energy transformations are studied as well as their relationships to the changes in the chemical properties of a system. It is the fundamental basis of many engineering fields. The profession of environmental engineering is no exception. In pa...

Thermodynamics of the Rhodamine B Lactone--Zwitterion Equilibrium.

ERIC Educational Resources Information Center

Hinckley, Daniel A.; Seybold, Paul G.

1987-01-01

Discusses the benefits of thermochromic transformations for studying thermodynamic properties. Describes an experiment that uses a commercially available dye, attains equilibrium rapidly, employs a simple, single-beam spectrophotometer, and is suitable for both physical chemistry and introductory chemistry laboratories. (TW)

Web Thermo Tables (WTT) - Lite Edition

National Institute of Standards and Technology Data Gateway

SRD 202 NIST/TRC Web Thermo Tables (WTT) - Lite Edition (Online Subscription)   WTT - Lite Edition, a Web version of the TRC Thermodynamic Tables, represents a collection of critically evaluated thermodynamic property data for 150 commonly-used (primarily organic) pure compounds.

Computer program for calculation of ideal gas thermodynamic data

NASA Technical Reports Server (NTRS)

Gordon, S.; Mc Bride, B. J.

1968-01-01

Computer program calculates ideal gas thermodynamic properties for any species for which molecular constant data is available. Partial functions and derivatives from formulas based on statistical mechanics are provided by the program which is written in FORTRAN 4 and MAP.

Impact of protein and ligand impurities on ITC-derived protein-ligand thermodynamics.

PubMed

Grüner, Stefan; Neeb, Manuel; Barandun, Luzi Jakob; Sielaff, Frank; Hohn, Christoph; Kojima, Shun; Steinmetzer, Torsten; Diederich, François; Klebe, Gerhard

2014-09-01

The thermodynamic characterization of protein-ligand interactions by isothermal titration calorimetry (ITC) is a powerful tool in drug design, giving valuable insight into the interaction driving forces. ITC is thought to require protein and ligand solutions of high quality, meaning both the absence of contaminants as well as accurately determined concentrations. Ligands synthesized to deviating purity and protein of different pureness were titrated by ITC. Data curation was attempted also considering information from analytical techniques to correct stoichiometry. We used trypsin and tRNA-guanine transglycosylase (TGT), together with high affinity ligands to investigate the effect of errors in protein concentration as well as the impact of ligand impurities on the apparent thermodynamics. We found that errors in protein concentration did not change the thermodynamic properties obtained significantly. However, most ligand impurities led to pronounced changes in binding enthalpy. If protein binding of the respective impurity is not expected, the actual ligand concentration was corrected for and the thus revised data compared to thermodynamic properties obtained with the respective pure ligand. Even in these cases, we observed differences in binding enthalpy of about 4kJ⋅mol(-1), which is considered significant. Our results indicate that ligand purity is the critical parameter to monitor if accurate thermodynamic data of a protein-ligand complex are to be recorded. Furthermore, artificially changing fitting parameters to obtain a sound interaction stoichiometry in the presence of uncharacterized ligand impurities may lead to thermodynamic parameters significantly deviating from the accurate thermodynamic signature. Copyright © 2014 Elsevier B.V. All rights reserved.

Exhaustive Exercise-induced Oxidative Stress Alteration of Erythrocyte Oxygen Release Capacity.

PubMed

Xiong, Yanlian; Xiong, Yanlei; Wang, Yueming; Zhao, Yajin; Li, Yaojin; Ren, Yang; Wang, Ruofeng; Zhao, Mingzi; Hao, Yitong; Liu, Haibei; Wang, Xiang

2018-05-24

The aim of the present study is to explore the effect of exhaustive running exercise (ERE) in the oxygen release capacity of rat erythrocytes. Rats were divided into sedentary control (C), moderate running exercise (MRE) and exhaustive running exercise groups. The thermodynamics and kinetics properties of the erythrocyte oxygen release process of different groups were tested. We also determined the degree of band-3 oxidative and phosphorylation, anion transport activity and carbonic anhydrase isoform II(CAII) activity. Biochemical studies suggested that exhaustive running significantly increased oxidative injury parameters in TBARS and methaemoglobin levels. Furthermore, exhaustive running significantly decreased anion transport activity and carbonic anhydrase isoform II(CAII) activity. Thermodynamic analysis indicated that erythrocytes oxygen release ability also significantly increased due to elevated 2,3-DPG level after exhaustive running. Kinetic analysis indicated that exhaustive running resulted in significantly decreased T50 value. We presented evidence that exhaustive running remarkably impacted thermodynamics and kinetics properties of RBCs oxygen release. In addition, changes in 2,3-DPG levels and band-3 oxidation and phosphorylation could be the driving force for exhaustive running induced alterations in erythrocytes oxygen release thermodynamics and kinetics properties.

Correlation between structural and thermodynamic properties of some selenium based phase-change materials

NASA Astrophysics Data System (ADS)

Chandel, Namrata; Mehta, Neeraj

2018-04-01

In this study, we prepared novel selenium rich multi-component glasses by incorporating In, Cd and Sb as foreign elements in an Sn containing Sesbnd Te system in order to study their metal-induced effects on the thermal properties of the parent ternary glass. In particular, we determined the thermodynamic parameters of Se80Te18Sn2 and Se80Te8Sn2M10 (M = Cd, In, Sb) glassy semiconductors in a non-isothermal environment using the differential scanning calorimetry. Calorimetric measurements were obtained in the glass transition regions for Se80Te18Sn2 and Se80Te8Sn2M10 (M = Cd, In, Sb) glasses to determine their thermodynamic parameters such as the specific heat, enthalpy, and entropy during glass transition. We analyzed the variation in the specific heat before and after the heat capacity jump in these alloys. The metal-induced effects of foreign elements on the thermodynamic properties of the parent glass were also investigated in terms of the influence of the elemental specific heat of the added elemental metal as well as the thermal stability and glass-forming ability of the glasses.

Comparison of Themodynamic and Transport Property Models for Computing Equilibrium High Enthalpy Flows

NASA Astrophysics Data System (ADS)

Ramasahayam, Veda Krishna Vyas; Diwakar, Anant; Bodi, Kowsik

2017-11-01

To study the flow of high temperature air in vibrational and chemical equilibrium, accurate models for thermodynamic state and transport phenomena are required. In the present work, the performance of a state equation model and two mixing rules for determining equilibrium air thermodynamic and transport properties are compared with that of curve fits. The thermodynamic state model considers 11 species which computes flow chemistry by an iterative process and the mixing rules considered for viscosity are Wilke and Armaly-Sutton. The curve fits of Srinivasan, which are based on Grabau type transition functions, are chosen for comparison. A two-dimensional Navier-Stokes solver is developed to simulate high enthalpy flows with numerical fluxes computed by AUSM+-up. The accuracy of state equation model and curve fits for thermodynamic properties is determined using hypersonic inviscid flow over a circular cylinder. The performance of mixing rules and curve fits for viscosity are compared using hypersonic laminar boundary layer prediction on a flat plate. It is observed that steady state solutions from state equation model and curve fits match with each other. Though curve fits are significantly faster the state equation model is more general and can be adapted to any flow composition.

The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems

PubMed

Yongqiang; Baojiao; Jianfeng

1997-07-01

In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.

Thermodynamics and phase transition of charged AdS black holes with a global monopole

NASA Astrophysics Data System (ADS)

Deng, Gao-Ming; Fan, Jinbo; Li, Xinfei; Huang, Yong-Chang

2018-01-01

Thermodynamical properties of charged AdS black holes with a global monopole still remain obscure. In this paper, we investigate the thermodynamics and phase transition of the black holes in the extended phase space. It is shown that thermodynamical quantities of the black holes exhibit an interesting dependence on the internal global monopole, and they perfectly satisfy both the first law of thermodynamics and Smarr relation. Furthermore, analysis of the local and the global thermodynamical stability manifests that the charged AdS black hole undergoes an elegant phase transition at critical point. Of special interest, critical behaviors of the black holes resemble a Van der Waals liquid-gas system. Our results not only reveal the effect of a global monopole on thermodynamics of AdS black holes, but also further support that Van der Waals-like behavior of the black holes is a universal phenomenon.

Analysis of the Spectroscopic Aspects of Cationic Dye Basic Orange 21.

PubMed

Eizig, Zehavit; Major, Dan T; Kasdan, Harvey L; Afrimzon, Elena; Zurgil, Naomi; Sobolev, Maria; Deutsch, Mordechai

2015-09-24

Spectroscopic properties of cationic dye basic orange 21 (BO21) in solutions, in solids, and within leukocytes were examined. Results obtained with solutions indicate that influence of variables such as pH, viscosity, salt composition, and various proteins on the absorption spectrum of BO21 is negligible. However, in the presence of heparin, a blue shift (484-465 nm) is observed, which is attributed to the aggregation of BO21 on the polyanion. Applying density functional theory demonstrates that in aqueous solutions (a) the formation of BO21 oligomers is thermodynamically favorable, they are oriented in an antiparallel dipolar arrangement, and their binding energies are lower than those of parallel dipolar arrangements, (b) association between BO21 aggregates and heparin is highly favorable, and (c) the blue shift is due to the mixing of π → π* transitions caused by BO21 molecule stacking. However, when embedded in basophils, the absorption spectra of intracellular BO21 is extremely red-shifted, with two peaks (at 505 and 550 nm) found to be attributed to BO21 and the BO21-heparin complex, respectively, which are intracellularly hosted in nonaqueous environments. Initial evidence of the ability to differentiate between leukocyte types by BO21 is presented.

Exchange interactions and magnetocaloric effects of the Heusler alloys Ni-Mn-In-R (R = Fe, Co)

NASA Astrophysics Data System (ADS)

Li, Yan-Ru; Su, Hui-Ling; Sun, Ji-Bing; Li, Ying

2018-05-01

The magnetic interactions and magnetocaloric effects in Ni2Mn1.4In0.6‑xRx (x = 0-0.2) (R = Fe, Co) Heusler alloys are investigated by the first-principles and Monte Carlo method. The ab initio calculations provide a basic understanding of the competition of ferromagnetic and antiferromagnetic interactions due to the chemical disorder of the alloy compositions. The thermodynamic properties including magnetization, specific heat and magnetic entropy change are calculated by the finite-temperature Monte Carlo simulations using the exchange couplings and magnetic moments from ab initio calculation as input parameters. The results show that the Fe or Co doping in Ni2Mn1.4In0.6 leads to an increase of magnetic moment and magnetic entropy change but a decrease of magnetic transition temperature with the increase in the Fe or Co contents. This indicates that the transition temperature and magnetocaloric properties of Ni2Mn1.4In0.6 alloy can be tuned by substituting In atom by Fe or Co with different contents.

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

NASA Astrophysics Data System (ADS)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Binary Phase Diagrams and Thermodynamic Properties of Silicon and Essential Doping Elements (Al, As, B, Bi, Ga, In, N, P, Sb and Tl)

PubMed Central

Mostafa, Ahmad; Medraj, Mamoun

2017-01-01

Fabrication of solar and electronic silicon wafers involves direct contact between solid, liquid and gas phases at near equilibrium conditions. Understanding of the phase diagrams and thermochemical properties of the Si-dopant binary systems is essential for providing processing conditions and for understanding the phase formation and transformation. In this work, ten Si-based binary phase diagrams, including Si with group IIIA elements (Al, B, Ga, In and Tl) and with group VA elements (As, Bi, N, P and Sb), have been reviewed. Each of these systems has been critically discussed on both aspects of phase diagram and thermodynamic properties. The available experimental data and thermodynamic parameters in the literature have been summarized and assessed thoroughly to provide consistent understanding of each system. Some systems were re-calculated to obtain a combination of the best evaluated phase diagram and a set of optimized thermodynamic parameters. As doping levels of solar and electronic silicon are of high technological importance, diffusion data has been presented to serve as a useful reference on the properties, behavior and quantities of metal impurities in silicon. This paper is meant to bridge the theoretical understanding of phase diagrams with the research and development of solar-grade silicon production, relying on the available information in the literature and our own analysis. PMID:28773034

Inorganic–organic hybrids presenting high basic center content: SBA-15 incorporation, toxic metals sorption and energetic behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oliveira, Fernando J.V.E.; Melo, Maurício A.; Airoldi, Claudio, E-mail: airoldi@iqm.unicamp.br

2013-03-15

Highlights: ► Mesoporous SBA-15 silicas were organofunctionalized with new silylant agents. ► Thiocarbamate was used to enhance the silylating agent chains and basic centers. ► The synthesized pendant chains contain nitrogen and sulfur basic centers. ► The new hybrids sorb toxic cations from aqueous solutions with high efficiency. ► The thermodynamic data demonstrated favorable cation/basic center interactions. - Abstract: Mesoporous SBA-15 samples were organofunctionalized with mono, di- and tri-aminosilanes that previously reacted with thiocarbamide to enhance the organic chains and attach nitrogen and sulfur basic centers to the surface of the solids. These new organosilanes were synthesized through a non-solventmore » approach to reduce both cost and hazardous wastes. The high affinities for both hard and soft Lewis acids due to the combination of nitrogen and sulfur atoms attached to the same pendant chain enabled favorable sorption capacities for Cu{sup 2+}, Cd{sup 2+} and Pb{sup 2+} cations, with maximum capacities of 1.90, 3.48 and 5.30 mmol g{sup −1}, respectively, for the most efficient mesoporous silica. Microcalorimetric investigations allowed the calculation of the thermodynamic data at the solid/liquid interface. All Gibbs energy are negative as expected for spontaneous cation/basic center interactions and the positive entropic values from 49 ± 3 to 108 ± 5 J K{sup −1} mol{sup −1}, also reinforced this favorable interactive process in heterogeneous system. The designed organosilanes covalently bonded to the inorganic siliceous skeleton can be suggested as new materials for toxic metal removal from a wastewater with high efficiency.« less

Metal-organic frameworks as selectivity regulators for hydrogenation reactions

NASA Astrophysics Data System (ADS)

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-01

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Metal-organic frameworks as selectivity regulators for hydrogenation reactions.

PubMed

Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

2016-11-03

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe 3+ , Cr 3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

The solutions and thermodynamic dark energy in the accelerating universe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demirel, E. C. Günay

Recently, Tachyonic matter expressed in terms of scalar field is suggested to be the reason of acceleration of the universe as dark energy [1]-[3]. In this study, dynamic solutions and thermodynamic properties of matters such as Tachyonic matters were investigated.

MOLECULAR THERMODYNAMICS IN THE DESIGN OF SUBSTITUTE SOLVENTS

EPA Science Inventory

The use of physical properties and fluid behavior from molecular thermodynamics can lead to better decision making in the design of substitute solvents and can greatly reduce the expense and time required to find substitutes compared to designing solvents by experiment. this pape...

Thermodynamic properties of hydrogen dissociation reaction from the small system method and reactive force field ReaxFF

NASA Astrophysics Data System (ADS)

Trinh, Thuat T.; Meling, Nora; Bedeaux, Dick; Kjelstrup, Signe

2017-03-01

We present thermodynamic properties of the H2 dissociation reaction by means of the Small System Method (SSM) using Reactive Force Field (ReaxFF) simulations. Thermodynamic correction factors, partial molar enthalpies and heat capacities of the reactant and product were obtained in the high temperature range; up to 30,000 K. The results obtained from the ReaxFF potential agree well with previous results obtained with a three body potential (TBP). This indicates that the popular reactive force field method can be combined well with the newly developed SSM in realistic simulations of chemical reactions. The approach may be useful in the study of heat and mass transport in combination with chemical reactions.

Heat capacities and thermodynamic functions for beryl, Be3Al2Si6O18, phenakite, Be2SiO4, euclase, BeAlSiO4(OH), bertrandite, Be4Si2O7(OH)2, and chrysoberyl, BeAl2O4.

USGS Publications Warehouse

Hemingway, B.S.; Barton, M.D.; Robie, R.A.; Haselton, H.T.

1986-01-01

The heat capacities of beryl, phenakite, euclase and bertrandite have been measured between approx 5 and 800 K by combined quasi-adiabatic cryogenic calorimetry and differential scanning calorimetry. The heat capacities of chrysoberyl have been measured from 340 to 800 K. The resulting data have been combined with solution and phase-equilibrium experimental data and simultaneously adjusted using the programme PHAS20 to provide an internally consistent set of thermodynamic properties for several important beryllium phases. The experimental heat capacities and tables of derived thermodynamic properties are presented.-J.A.Z.

Input guide for computer programs to generate thermodynamic data for air and Freon CF4

NASA Technical Reports Server (NTRS)

Tevepaugh, J. A.; Penny, M. M.; Baker, L. R., Jr.

1975-01-01

FORTRAN computer programs were developed to calculate the thermodynamic properties of Freon 14 and air for isentropic expansion from given plenum conditions. Thermodynamic properties for air are calculated with equations derived from the Beattie-Bridgeman nonstandard equation of state and, for Freon 14, with equations derived from the Redlich-Quang nonstandard equation of state. These two gases are used in scale model testing of model rocket nozzle flow fields which requires simulation of the prototype plume shape with a cold flow test approach. Utility of the computer programs for use in analytical prediction of flow fields is enhanced by arranging card or tape output of the data in a format compatible with a method-of-characteristics computer program.

Ab initio molecular dynamics with enhanced sampling for surface reaction kinetics at finite temperatures: CH2 ⇌ CH + H on Ni(111) as a case study

NASA Astrophysics Data System (ADS)

Sun, Geng; Jiang, Hong

2015-12-01

A comprehensive understanding of surface thermodynamics and kinetics based on first-principles approaches is crucial for rational design of novel heterogeneous catalysts, and requires combining accurate electronic structure theory and statistical mechanics modeling. In this work, ab initio molecular dynamics (AIMD) combined with the integrated tempering sampling (ITS) method has been explored to study thermodynamic and kinetic properties of elementary processes on surfaces, using a simple reaction CH 2 ⇌ CH + H on the Ni(111) surface as an example. By a careful comparison between the results from ITS-AIMD simulation and those evaluated in terms of the harmonic oscillator (HO) approximation, it is found that the reaction free energy and entropy from the HO approximation are qualitatively consistent with the results from ITS-AIMD simulation, but there are also quantitatively significant discrepancies. In particular, the HO model misses the entropy effects related to the existence of multiple adsorption configurations arising from the frustrated translation and rotation motion of adsorbed species, which are different in the reactant and product states. The rate constants are evaluated from two ITS-enhanced approaches, one using the transition state theory (TST) formulated in terms of the potential of mean force (PMF) and the other one combining ITS with the transition path sampling (TPS) technique, and are further compared to those based on harmonic TST. It is found that the rate constants from the PMF-based TST are significantly smaller than those from the harmonic TST, and that the results from PMF-TST and ITS-TPS are in a surprisingly good agreement. These findings indicate that the basic assumptions of transition state theory are valid in such elementary surface reactions, but the consideration of statistical averaging of all important adsorption configurations and reaction pathways, which are missing in the harmonic TST, are critical for accurate description of thermodynamic and kinetic properties of surface processes. This work clearly demonstrates the importance of considering temperature effects beyond the HO model, for which the AIMD simulation in combination with enhanced sampling techniques like ITS provides a feasible and general approach.

Hydrophobic Solvation: Aqueous Methane Solutions

ERIC Educational Resources Information Center

Konrod, Oliver; Lankau, Timm

2007-01-01

A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

Thermochemical Analysis of Neutralization Reactions: An Introductory Discovery Experiment

ERIC Educational Resources Information Center

Mills, Kenneth V.; Gullmette, Louise W.

2007-01-01

The article describes a new discovery experiment that uses thermodynamical analysis to study neutralization reactions based on neutralization of citric acid. The experiment would be able to reinforce students' understanding of stoichiometry and allow for the discovery of basic concepts of thermochemistry.

Information Fluxes as Concept for Categorizations of Life

NASA Astrophysics Data System (ADS)

Hildenbrand, Georg; Hausmann, M.

2012-05-01

Definitions of life are controversially discussed; however, they are mostly depending on bio- evolutionary driven arguments. Here, we propose a systematic, theoretical approach to the question what life is, by categorization and classification of different levels of life. This approach is mainly based on the analysis of information flux occurring in systems being suspicious to be alive, and on the analysis of their power of environmental control. In a first step, we show that all biological definitions of life can be derived from basic physical principles of entropy (number of possible states of a thermodynamic system) and of the energy needed for controlling entropic development. In a next step we discuss how any process where information flux is generated, regardless of its materialization is defined and related to classical definitions of life. In a third step we resume the proposed classification scheme in its most basic way, looking only for existence of data storage, its processing, and its environmental control. We join inhere a short discussion how the materialization of information fluxes can take place depending on the special properties of the four basic physical forces. Having done all this we are able to give everybody a classification catalogue at hand that one can categorize the kind of life one is talking about, thus overcoming the obstacles deriving from the simple appearing question whether something is alive or not. On its most basic level as presented here, our scheme offers a categorization for fire, crystals, prions, viruses, spores, up to cells and even tardigrada and cryostases.

Computational Modeling of Mixed Solids for CO2 CaptureSorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, Yuhua

2015-01-01

Since current technologies for capturing CO2 to fight global climate change are still too energy intensive, there is a critical need for development of new materials that can capture CO2 reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO2 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 CO2 sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculated thermodynamic properties of differentmore » classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 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 CO2 sorbent candidates were further considered for experimental validations. The ab initio thermodynamic technique has the advantage of identifying thermodynamic properties of CO2 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 apply our screening methodology to mixing solid systems to adjust the turnover temperature to help on developing CO2 capture Technologies.« less

Critical Evaluations and Thermodynamic Optimizations of the MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 Systems

NASA Astrophysics Data System (ADS)

Kang, Youn-Bae; Jung, In-Ho

2017-06-01

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-Si-O system (MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 systems) are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25°C) to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Slag (molten oxide) was modeled using the modified quasichemical model in the pair approximation. Olivine (Fe2SiO4-Mn2SiO4) was modeled using two-sublattice model in the framework of the compound energy formalism (CEF), while rhodonite (MnSiO3-FeSiO3) and braunite (Mn7SiO_{12} with excess Mn2O3) were modeled as simple Henrian solutions. It is shown that the already developed models and databases of two spinel phases (cubic- and tetragonal-(Fe, Mn)3O4) using CEF [Kang and Jung, J. Phys. Chem. Solids (2016), vol. 98, pp. 237-246] can successfully be integrated into a larger thermodynamic database to be used in practically important higher order system such as silicate. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.

Thermodynamic Modeling of the YO(l.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2003-01-01

The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

Influence of condensed species on thermo-physical properties of LTE and non-LTE SF6-Cu mixture

NASA Astrophysics Data System (ADS)

Chen, Zhexin; Wu, Yi; Yang, Fei; Sun, Hao; Rong, Mingzhe; Wang, Chunlin

2017-10-01

SF6-Cu mixture is frequently formed in high-voltage circuit breakers due to the electrode erosion and metal vapor diffusion. During the interruption process, the multiphase effect and deviation from local thermal equilibrium (non-LTE assumption) can both affect the thermo-physical of the arc plasma and further influence the performance of circuit breaker. In this paper, thermo-physical properties, namely composition, thermodynamic properties and transport coefficients are calculated for multiphase SF6-Cu mixture with and without LTE assumption. The composition is confirmed by combining classical two-temperature mass action law with phase equilibrium condition deduced from second law of thermodynamics. The thermodynamic properties and transport coefficients are calculated using the multiphase composition result. The influence of condensed species on thermo-physical properties is discussed at different temperature, pressure (0.1-10 atm), non-equilibrium degrees (1-10), and copper molar proportions (0-50%). It is found that the multiphase effect has significant influence on specific enthalpy, specific heat and heavy species thermal conductivity in both LTE and non-LTE SF6-Cu system. This paper provides a more accurate database for computational fluid dynamic calculation.

Refrigerant Performance Evaluation Including Effects of Transport Properties and Optimized Heat Exchangers.

PubMed

Brignoli, Riccardo; Brown, J Steven; Skye, H; Domanski, Piotr A

2017-08-01

Preliminary refrigerant screenings typically rely on using cycle simulation models involving thermodynamic properties alone. This approach has two shortcomings. First, it neglects transport properties, whose influence on system performance is particularly strong through their impact on the performance of the heat exchangers. Second, the refrigerant temperatures in the evaporator and condenser are specified as input, while real-life equipment operates at imposed heat sink and heat source temperatures; the temperatures in the evaporator and condensers are established based on overall heat transfer resistances of these heat exchangers and the balance of the system. The paper discusses a simulation methodology and model that addresses the above shortcomings. This model simulates the thermodynamic cycle operating at specified heat sink and heat source temperature profiles, and includes the ability to account for the effects of thermophysical properties and refrigerant mass flux on refrigerant heat transfer and pressure drop in the air-to-refrigerant evaporator and condenser. Additionally, the model can optimize the refrigerant mass flux in the heat exchangers to maximize the Coefficient of Performance. The new model is validated with experimental data and its predictions are contrasted to those of a model based on thermodynamic properties alone.

A robust and accurate numerical method for transcritical turbulent flows at supercritical pressure with an arbitrary equation of state

NASA Astrophysics Data System (ADS)

Kawai, Soshi; Terashima, Hiroshi; Negishi, Hideyo

2015-11-01

This paper addresses issues in high-fidelity numerical simulations of transcritical turbulent flows at supercritical pressure. The proposed strategy builds on a tabulated look-up table method based on REFPROP database for an accurate estimation of non-linear behaviors of thermodynamic and fluid transport properties at the transcritical conditions. Based on the look-up table method we propose a numerical method that satisfies high-order spatial accuracy, spurious-oscillation-free property, and capability of capturing the abrupt variation in thermodynamic properties across the transcritical contact surface. The method introduces artificial mass diffusivity to the continuity and momentum equations in a physically-consistent manner in order to capture the steep transcritical thermodynamic variations robustly while maintaining spurious-oscillation-free property in the velocity field. The pressure evolution equation is derived from the full compressible Navier-Stokes equations and solved instead of solving the total energy equation to achieve the spurious pressure oscillation free property with an arbitrary equation of state including the present look-up table method. Flow problems with and without physical diffusion are employed for the numerical tests to validate the robustness, accuracy, and consistency of the proposed approach.

A robust and accurate numerical method for transcritical turbulent flows at supercritical pressure with an arbitrary equation of state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawai, Soshi, E-mail: kawai@cfd.mech.tohoku.ac.jp; Terashima, Hiroshi; Negishi, Hideyo

2015-11-01

This paper addresses issues in high-fidelity numerical simulations of transcritical turbulent flows at supercritical pressure. The proposed strategy builds on a tabulated look-up table method based on REFPROP database for an accurate estimation of non-linear behaviors of thermodynamic and fluid transport properties at the transcritical conditions. Based on the look-up table method we propose a numerical method that satisfies high-order spatial accuracy, spurious-oscillation-free property, and capability of capturing the abrupt variation in thermodynamic properties across the transcritical contact surface. The method introduces artificial mass diffusivity to the continuity and momentum equations in a physically-consistent manner in order to capture themore » steep transcritical thermodynamic variations robustly while maintaining spurious-oscillation-free property in the velocity field. The pressure evolution equation is derived from the full compressible Navier–Stokes equations and solved instead of solving the total energy equation to achieve the spurious pressure oscillation free property with an arbitrary equation of state including the present look-up table method. Flow problems with and without physical diffusion are employed for the numerical tests to validate the robustness, accuracy, and consistency of the proposed approach.« less

Disulphide bond exchange inhibited by air - kinetic and thermodynamic products in a library of macrocyclic cysteine derivatives.

PubMed

Cholewiak, Agnieszka; Dobrzycki, Łukasz; Jurczak, Janusz; Ulatowski, Filip

2018-04-04

In this paper we present the synthesis and reactivity of dithiols comprising of two cysteine moieties attached to a dipicolinic acid core. Oxidation of these thiols provides oligomeric macrocycles. Monomers with 13-membered rings are kinetic products which are, however, strained and readily transform into higher oligomers under basic conditions or elevated temperature via a disulphide exchange reaction. Dimers, which are the most stable thermodynamic products, equilibrate only under inert conditions with thiolate as a catalyst. Under aerobic conditions, the thiols are oxidised before the equilibrium is reached.

Quarterly progress report for the Chemical and Energy Research Section of the Chemical Technology Division, April--June 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jubin, R.T.

The Chemical and Energy Research Section conducts basic and applied research and development in chemical engineering, applied chemistry, and bioprocessing, with an emphasis on energy-driven technologies and advanced chemical separations for nuclear and waste applications. The report describes the various tasks performed within six major areas of research: Hot Cell Operations, Process Chemistry and thermodynamics, Separations and Materials Synthesis, Solution Thermodynamics, biotechnology Research, and Molecular Studies. The name of a technical contact is included with each task described, and readers are encouraged to contact these individuals if they need additional information.

Insights into energy delivery to myocardial tissue during radiofrequency ablation through application of the first law of thermodynamics.

PubMed

Bunch, T Jared; Day, John D; Packer, Douglas L

2009-04-01

The approach to catheter-based radiofrequency ablation of atrial fibrillation has evolved, and as a consequence, more energy is delivered in the posterior left atrium, exposing neighboring tissue to untoward thermal injury. Simultaneously, catheter technology has advanced to allow more efficient energy delivery into the myocardium, which compounds the likelihood of collateral injury. This review focuses on the basic principles of thermodynamics as they apply to energy delivery during radiofrequency ablation. These principles can be used to titrate energy delivery and plan ablative approaches in an effort to minimize complications during the procedure.

Development of a critically evaluated thermodynamic database for the systems containing alkaline-earth oxides

NASA Astrophysics Data System (ADS)

Shukla, Adarsh

In a thermodynamic system which contains several elements, the phase relationships among the components are usually very complex. Especially, systems containing oxides are generally very difficult to investigate owing to the very high experimental temperatures and corrosive action of slags. Due to such difficulties, large inconsistencies are often observed among the available experimental data. In order to investigate and understand the complex phase relationships effectively, it is very useful to develop thermodynamic databases containing optimized model parameters giving the thermodynamic properties of all phases as functions of temperature and composition. In a thermodynamic optimization, adjustable model parameters are calculated using, simultaneously, all available thermodynamic and phase-equilibrium data in order to obtain one set of model equations as functions of temperature and composition. Thermodynamic data, such as activities, can aid in the evaluation of the phase diagrams, and information on phase equilibria can be used to deduce thermodynamic properties. Thus, it is frequently possible to resolve discrepancies in the available data. From the model equations, all the thermodynamic properties and phase diagrams can be back-calculated, and interpolations and extrapolations can be made in a thermodynamically correct manner. The data are thereby rendered self-consistent and consistent with thermodynamic principles, and the available data are distilled into a small set of model parameters, ideal for computer storage. As part of a broader research project at the Centre de Recherche en Calcul Thermochimique (CRCT), Ecole Polytechnique to develop a thermodynamic database for multicomponent oxide systems, this thesis deals with the addition of components SrO and BaO to the existing multicomponent database of the SiO2-B2O3-Al2O 3-CaO-MgO system. Over the years, in collaboration with many industrial companies, a thermodynamic database for the SiO2-B2O 3-Al2O3-CaO-MgO system has been built quite satisfactorily. The aim of the present work was to improve the applicability of this five component database by adding SrO and BaO to it. The databases prepared in this work will be of special importance to the glass and steel industries. In the SiO2-B2O3-Al2O 3-CaO-MgO-BaO-SrO system there are 11 binary systems and 25 ternary systems which contain either BaO or SrO or both. For most of these binary systems, and for none of these ternary systems, is there a previous thermodynamic optimization available in the literature. In this thesis, thermodynamic evaluation and optimization for the 11 binary, 17 ternary and 5 quaternary BaO- and SrO- containing systems in the SiO2-B2O3-Al 2O3-CaO-MgO-BaO-SrO system is presented. All these thermodynamic optimizations were performed based on the experimental data available in the literature, except for the SrO-B2O3-SiO2 system. This latter system was optimized on the basis of a few experimental data points generated in the present work together with the data from the literature. In the present work, all the calculations were performed using the FactSage™ thermochemical software. The Modified Quasichemical Model (MQM), which is capable of taking short-range ordering into account, was used for the liquid phase. All the binary systems were critically evaluated and optimized using available phase equilibrium and thermodynamic data. The model parameters obtained as a result of this simultaneous optimization were used to represent the Gibbs energies of all phases as functions of temperature and composition. Optimized binary model parameters were used to estimate the thermodynamic properties of phases in the ternary systems. Proper “geometric” models were used for these estimations. Ternary phase diagram were calculated and compared with available experimental data. Wherever required, ternary interaction parameters were also added. The first part of this thesis comprises a general literature review on the subject of thermodynamic modeling and experimental techniques for phase diagram determination. The next chapters include the literature review and the thermodynamic optimizations of the various systems. The last part of the thesis is the presentation of experiments performed in the present work, by quenching and EPMA, in the SrO-B2O3-SiO2 system. The experiments were designed to generate the maximum amount of information with the minimum number of experiments using the thermodynamic optimization, based only on the data available in the literature, as a guide. These newly-obtained data improved the (preceding) thermodynamic optimization, based on the experimental data in the literature, of this ternary system.

Compositions, thermodynamic properties, and transport coefficients of high-temperature C5F10O mixed with CO2 and O2 as substitutes for SF6 to reduce global warming potential

NASA Astrophysics Data System (ADS)

Zhong, Linlin; Rong, Mingzhe; Wang, Xiaohua; Wu, Junhui; Han, Guiquan; Han, Guohui; Lu, Yanhui; Yang, Aijun; Wu, Yi

2017-07-01

C5F10O has recently been found to be a very promising alternative to SF6. This paper is devoted to the investigation of compositions, thermodynamic properties, and transport coefficients of high-temperature C5F10O mixed with CO2 and O2. Firstly, the partition functions and enthalpies of formation for a few molecules (CxFy and CxFyO) which are likely to exist in the mixtures, are calculated based on the G4(MP2) theory. The isomers of the above molecules are selected according to their Gibbs energy. The compositions of C5F10O-CO2-O2 mixtures are then determined using the minimization of the Gibbs free energy. Next, the thermodynamic properties (mass density, specific enthalpy, and specific heat) are derived from the previously calculated compositions. Lastly, the transport coefficients (electrical conductivity, viscosity, and thermal conductivity) are calculated based on Chapman-Enskog method. It is found that, as an arc quenching gas, C5F10O could not recombine into itself with the temperature decreasing down to room temperature after the arc extinction. Besides, the key species at room temperature are always CF4, CO2, and C4F6 if graphite is not considered. When taken into account, graphite will replace C4F6 as one of the dominate particles. The mixing of CO2 with C5F10O plasma significantly affects the thermodynamic properties (e.g. vanishing and/or shifting of the peaks in specific heat) and transport coefficients (e.g. reducing viscosity and changing the number of peaks in thermal conductivity), while the addition of O2 with C5F10O-CO2 mixtures has no remarkable influence on both thermodynamic and transport properties.

Intermolecular potentials and the accurate prediction of the thermodynamic properties of water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

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.more » 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.« less

Equation of State for the Thermodynamic Properties of 1,1,2,2,3-Pentafluoropropane (R-245ca)

NASA Astrophysics Data System (ADS)

Zhou, Yong; Lemmon, Eric W.

2016-03-01

An equation of state for the calculation of the thermodynamic properties of 1,1,2,2,3-pentafluoropropane (R-245ca), which is a hydrofluorocarbon refrigerant, is presented. The equation of state (EOS) is expressed in terms of the Helmholtz energy as a function of temperature and density, and can calculate all thermodynamic properties through the use of derivatives of the Helmholtz energy. The equation is valid for all liquid, vapor, and supercritical states of the fluid, and is valid from the triple point to 450 K, with pressures up to 10 MPa. Comparisons to experimental data are given to verify the stated uncertainties in the EOS. The estimated uncertainty for density is 0.1 % in the liquid phase between 243 K and 373 K with pressures up to 6.5 MPa; the uncertainties increase outside this range, and are unknown. The uncertainty in vapor-phase speed of sound is 0.1 %. The uncertainty in vapor pressure is 0.2 % between 270 K and 393 K. The uncertainties in other regions and properties are unknown due to a lack of experimental data.

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

DOE PAGES

Li, Boyan; Zhang, Lei; Li, Chengliang; ...

2018-04-18

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

Amylose Phase Composition As Analyzed By FTIR In A Temperature Ramp: Influence Of Short Range Order On The Thermodynamic Properties

NASA Astrophysics Data System (ADS)

Bernazzani, Paul; Delmas, Genevieve

1998-03-01

Amylose, a major component of starch, is one of the most important biopolymers, being mainly associated with the pharmacological and food industries. Although widely studied, a complete control and understanding of the physical properties of amylose is still lacking. It is well known that structure and phase transition are important aspects of the functionality of biopolymers since they influence physical attributes such as appearance, digestibility, water holding capacity, etc. In the past, we have studied polyethylene phase composition by DSC in a very slow temperature (T) ramp (1K/h) and have demonstrated the presence and importance of short-range order on the polymer and its characteristics. In this study, we evaluated the phase composition of potato amylose and associated the thermodynamic properties with the presence of short-range order. Two methods were correlated, DSC (in a 1K/h T-ramp) and FTIR as a function of temperature, also in a 1K/h T-ramp. The effects of the various phases on thermodynamic properties such as gelation and enzyme or chemical resistance are discussed.

Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl{sup 0} and HBr{sup 0} at temperatures to 1000 C and pressures to 5 kbar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pokrovskii, V.A.

1999-04-01

Dissociation constants of aqueous ion pairs HCl{sup 0} and HBr{sup 0} derived in the literature from vapor pressure and supercritical conductance measurements (Quist and Marshall, 1968b; Frantz and Marshall, 1984) were used to calculate the standard partial molal thermodynamic properties of the species at 25 C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state (Helgeson et al., 1981; Tanger and Helgeson, 1988; Shock et al., 1989) resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties andmore » parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr{sup 0} and HCl{sup 0} given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800 C and pressures to 5 kbar.« less

A Modified Benedict-Webb-Rubin Equation of State for the Thermodynamic Properties of R152a (1,1-difluoroethane)

NASA Astrophysics Data System (ADS)

Outcalt, Stephanie L.; McLinden, Mark O.

1996-03-01

A modified Benedict-Webb-Rubin (MBWR) equation of state has been developed for R152a (1,1-difluoroethane). The correlation is based on a selection of available experimental thermodynamic property data. Single-phase pressure-volume-temperature (PVT), heat capacity, and sound speed data, as well as second virial coefficient, vapor pressure, and saturated liquid and saturated vapor density data, were used with multi-property linear least-squares fitting to determine the 32 adjustable coefficients of the MBWR equation. Ancillary equations representing the vapor pressure, saturated liquid and saturated vapor densities, and the ideal gas heat capacity were determined. Coefficients for the equation of state and the ancillary equations are given. Experimental data used in this work covered temperatures from 162 K to 453 K and pressures to 35 MPa. The MBWR equation established in this work may be used to predict thermodynamic properties of R152a from the triple-point temperature of 154.56 K to 500 K and for pressures up to 60 MPa except in the immediate vicinity of the critical point.

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Boyan; Zhang, Lei; Li, Chengliang

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

Design Optimization of Microalloyed Steels Using Thermodynamics Principles and Neural-Network-Based Modeling

NASA Astrophysics Data System (ADS)

Mohanty, Itishree; Chintha, Appa Rao; Kundu, Saurabh

2018-06-01

The optimization of process parameters and composition is essential to achieve the desired properties with minimal additions of alloying elements in microalloyed steels. In some cases, it may be possible to substitute such steels for those which are more richly alloyed. However, process control involves a larger number of parameters, making the relationship between structure and properties difficult to assess. In this work, neural network models have been developed to estimate the mechanical properties of steels containing Nb + V or Nb + Ti. The outcomes have been validated by thermodynamic calculations and plant data. It has been shown that subtle thermodynamic trends can be captured by the neural network model. Some experimental rolling data have also been used to support the model, which in addition has been applied to calculate the costs of optimizing microalloyed steel. The generated pareto fronts identify many combinations of strength and elongation, making it possible to select composition and process parameters for a range of applications. The ANN model and the optimization model are being used for prediction of properties in a running plant and for development of new alloys, respectively.

First-principles study of the phonon, mechanical and thermodynamic properties of B2-phase AlY under high pressures

NASA Astrophysics Data System (ADS)

Wang, Leini; Jian, Zhang; Ning, Wei

2017-12-01

We have investigated the phonon, mechanical and thermodynamic properties of B2-phase AlY under high pressure by performing density functional theory (DFT). The result of phonon band structure shows B2-phase AlY exhibits dynamical stability. Then, the elastic properties of AlY under high pressure have been discussed. The elastic constants of AlY increase monotonically with the increase of the pressure and all the elastic constants meet the mechanical stability standard under high pressure. By analyzing the Poisson’s ratio ν and the value of B/G of AlY, we first predicted that AlY undergoes transformation from brittleness to ductility at 30 GPa and high pressure can improve the ductility. To obtain the thermodynamic properties of B2-phase AlY, the quasi-harmonic Debye model has been employed. Debye temperature ΘD, thermal expansion coefficient α, heat capacity Cp and Grüneisen parameter γ of B2-phase AlY are systematically explored at pressure of 0-75 GPa and temperature of 0-700 K.

Pressure effect on the structural, phonon, elastic and thermodynamic properties of L12 phase RH3TA: First-principles calculations

NASA Astrophysics Data System (ADS)

Wang, Leini; Jian, Zhang; Ning, Wei

2018-06-01

The phonon, elastic and thermodynamic properties of L12 phase Rh3Ta have been investigated by the density functional theory (DFT) approach combined with the quasi-harmonic approximation model. The results of the phonon band structure show that L12 phase Rh3Ta possesses dynamical stability in the pressure range from 0-80 GPa due to the absence of imaginary frequencies. The pressure dependences with the elastic constants Cij, shear modulus G, bulk modulus B, Young’s modulus Y, Poisson’s ratio and B/G ratio have been analyzed. The results of the elastic properties studies show that L12 phase Rh3Ta compound is mechanically stable and possesses a higher hardness, improved ductility and plasticity under higher pressures. The pressure and temperature relationship of the thermodynamic properties, such as the Debye temperature ΘD, heat capacity Cp, thermal expansion coefficient α and the Grüneisen parameter γ are predicted by the quasi-harmonic Debye model in a wide pressure (0-80 GPa) and temperature (0-750 K) ranges.

Molecular machines operating on the nanoscale: from classical to quantum

PubMed Central

2016-01-01

Summary The main physical features and operating principles of isothermal nanomachines in the microworld, common to both classical and quantum machines, are reviewed. Special attention is paid to the dual, constructive role of dissipation and thermal fluctuations, the fluctuation–dissipation theorem, heat losses and free energy transduction, thermodynamic efficiency, and thermodynamic efficiency at maximum power. Several basic models are considered and discussed to highlight generic physical features. This work examines some common fallacies that continue to plague the literature. In particular, the erroneous beliefs that one should minimize friction and lower the temperature for high performance of Brownian machines, and that the thermodynamic efficiency at maximum power cannot exceed one-half are discussed. The emerging topic of anomalous molecular motors operating subdiffusively but very efficiently in the viscoelastic environment of living cells is also discussed. PMID:27335728

Thermodynamic properties of sea air

NASA Astrophysics Data System (ADS)

Feistel, R.; Wright, D. G.; Kretzschmar, H.-J.; Hagen, E.; Herrmann, S.; Span, R.

2010-02-01

Very accurate thermodynamic potential functions are available for fluid water, ice, seawater and humid air covering wide ranges of temperature and pressure conditions. They permit the consistent computation of all equilibrium properties as, for example, required for coupled atmosphere-ocean models or the analysis of observational or experimental data. With the exception of humid air, these potential functions are already formulated as international standards released by the International Association for the Properties of Water and Steam (IAPWS), and have been adopted in 2009 for oceanography by IOC/UNESCO. In this paper, we derive a collection of formulas for important quantities expressed in terms of the thermodynamic potentials, valid for typical phase transitions and composite systems of humid air and water/ice/seawater. Particular attention is given to equilibria between seawater and humid air, referred to as "sea air" here. In a related initiative, these formulas will soon be implemented in a source-code library for easy practical use. The library is primarily aimed at oceanographic applications but will be relevant to air-sea interaction and meteorology as well. The formulas provided are valid for any consistent set of suitable thermodynamic potential functions. Here we adopt potential functions from previous publications in which they are constructed from theoretical laws and empirical data; they are briefly summarized in the appendix. The formulas make use of the full accuracy of these thermodynamic potentials, without additional approximations or empirical coefficients. They are expressed in the temperature scale ITS-90 and the 2008 Reference-Composition Salinity Scale.

Thermodynamic properties of sea air

NASA Astrophysics Data System (ADS)

Feistel, R.; Kretzschmar, H.-J.; Span, R.; Hagen, E.; Wright, D. G.; Herrmann, S.

2009-10-01

Very accurate thermodynamic potential functions are available for fluid water, ice, seawater and humid air covering wide ranges of temperature and pressure conditions. They permit the consistent computation of all equilibrium properties as, for example, required for coupled atmosphere-ocean models or the analysis of observational or experimental data. With the exception of humid air, these potential functions are already formulated as international standards released by the International Association for the Properties of Water and Steam (IAPWS), and have been adopted in 2009 for oceanography by IOC/UNESCO. In this paper, we derive a collection of formulas for important quantities expressed in terms of the thermodynamic potentials, valid for typical phase transitions and composite systems of humid air and water/ice/seawater. Particular attention is given to equilibria between seawater and humid air, referred to as ''sea air'' here. In a related initiative, these formulas will soon be implemented in a source-code library for easy practical use. The library is primarily aimed at oceanographic applications but will be relevant to air-sea interaction and meteorology as well. The formulas provided are valid for any consistent set of suitable thermodynamic potential functions. Here we adopt potential functions from previous publications in which they are constructed from theoretical laws and empirical data; they are briefly summarized in the appendix. The formulas make use of the full accuracy of these thermodynamic potentials, without additional approximations or empirical coefficients. They are expressed in the temperature scale ITS-90 and the 2008 Reference-Composition Salinity Scale.

Biophysical and physicochemical methods differentiate highly ligand-efficient human D-amino acid oxidase inhibitors.

PubMed

Lange, Jos H M; Venhorst, Jennifer; van Dongen, Maria J P; Frankena, Jurjen; Bassissi, Firas; de Bruin, Natasja M W J; den Besten, Cathaline; de Beer, Stephanie B A; Oostenbrink, Chris; Markova, Natalia; Kruse, Chris G

2011-10-01

Many early drug research efforts are too reductionist thereby not delivering key parameters such as kinetics and thermodynamics of target-ligand binding. A set of human D-Amino Acid Oxidase (DAAO) inhibitors 1-6 was applied to demonstrate the impact of key biophysical techniques and physicochemical methods in the differentiation of chemical entities that cannot be adequately distinguished on the basis of their normalized potency (ligand efficiency) values. The resulting biophysical and physicochemical data were related to relevant pharmacodynamic and pharmacokinetic properties. Surface Plasmon Resonance data indicated prolonged target-ligand residence times for 5 and 6 as compared to 1-4, based on the observed k(off) values. The Isothermal Titration Calorimetry-derived thermodynamic binding profiles of 1-6 to the DAAO enzyme revealed favorable contributions of both ΔH and ΔS to their ΔG values. Surprisingly, the thermodynamic binding profile of 3 elicited a substantially higher favorable contribution of ΔH to ΔG in comparison with the structurally closely related fused bicyclic acid 4. Molecular dynamics simulations and free energy calculations of 1, 3, and 4 led to novel insights into the thermodynamic properties of the binding process at an atomic level and in the different thermodynamic signatures of 3 and 4. The presented holistic approach is anticipated to facilitate the identification of compounds with best-in-class properties at an early research stage. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Heat Transfer and Thermodynamics: a Compilation

NASA Technical Reports Server (NTRS)

1974-01-01

A compilation is presented for the dissemination of information on technological developments which have potential utility outside the aerospace and nuclear communities. Studies include theories and mechanical considerations in the transfer of heat and the thermodynamic properties of matter and the causes and effects of certain interactions.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-07-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamics of hairy black holes in Lovelock gravity

NASA Astrophysics Data System (ADS)

Hennigar, Robie A.; Tjoa, Erickson; Mann, Robert B.

2017-02-01

We perform a thorough study of the thermodynamic properties of a class of Lovelock black holes with conformal scalar hair arising from coupling of a real scalar field to the dimensionally extended Euler densities. We study the linearized equations of motion of the theory and describe constraints under which the theory is free from ghosts/tachyons. We then consider, within the context of black hole chemistry, the thermodynamics of the hairy black holes in the Gauss-Bonnet and cubic Lovelock theories. We clarify the connection between isolated critical points and thermodynamic singularities, finding a one parameter family of these critical points which occur for well-defined thermodynamic parameters. We also report on a number of novel results, including `virtual triple points' and the first example of a `λ-line' — a line of second order phase transitions — in black hole thermodynamics.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-05-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamics of reaction of praseodymium with gallium-indium eutectic alloy

NASA Astrophysics Data System (ADS)

Melchakov, S. Yu.; Ivanov, V. A.; Yamshchikov, L. F.; Volkovich, V. A.; Osipenko, A. G.; Kormilitsyn, M. V.

2013-06-01

Thermodynamic properties of Ga-In eutectic alloys saturated with praseodymium were determined for the first time employing the electromotive force method. The equilibrium potentials of the Pr-In alloys saturated with praseodymium (8.7-12.1 mol.% Pr) and Pr-Ga-In alloys (containing 0.0012-6.71 mol.% Pr) were measured between 573-1073 K. Pr-In alloy containing solid PrIn3 with known thermodynamic properties was used as the reference electrode when measuring the potentials of ternary Pr-In-Ga alloys. Activity, partial and excessive thermodynamic functions of praseodymium in alloys with indium and Ga-In eutectic were calculated. Activity (a), activity coefficients (γ) and solubility (X) of praseodymium in the studied temperature range can be expressed by the following equations: lgaα-Pr(In) = 4.425 - 11965/T ± 0.026. lgаα-Pr(Ga-In) = 5.866 - 14766/T ± 0.190. lgγα-Pr(Ga-In) = 2.351 - 9996/T ± 0.39. lgХPr(Ga-In) = 3.515 - 4770/T ± 0.20.

Development of a Knowledge Base of Ti-Alloys From First-Principles and Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Marker, Cassie

An aging population with an active lifestyle requires the development of better load-bearing implants, which have high levels of biocompatibility and a low elastic modulus. Titanium alloys, in the body centered cubic phase, are great implant candidates, due to their mechanical properties and biocompatibility. The present work aims at investigating the thermodynamic and elastic properties of bcc Tialloys, using the integrated first-principles based on Density Functional Theory (DFT) and the CALculation of PHAse Diagrams (CALPHAD) method. The use of integrated first-principles calculations based on DFT and CALPHAD modeling has greatly reduced the need for trial and error metallurgy, which is ineffective and costly. The phase stability of Ti-alloys has been shown to greatly affect their elastic properties. Traditionally, CALPHAD modeling has been used to predict the equilibrium phase formation, but in the case of Ti-alloys, predicting the formation of two metastable phases o and alpha" is of great importance as these phases also drastically effect the elastic properties. To build a knowledge base of Ti-alloys, for biomedical load-bearing implants, the Ti-Mo-Nb-Sn-Ta-Zr system was studied because of the biocompatibility and the bcc stabilizing effects of some of the elements. With the focus on bcc Ti-rich alloys, a database of thermodynamic descriptions of each phase for the pure elements, binary and Ti-rich ternary alloys was developed in the present work. Previous thermodynamic descriptions for the pure elements were adopted from the widely used SGTE database for global compatibility. The previous binary and ternary models from the literature were evaluated for accuracy and new thermodynamic descriptions were developed when necessary. The models were evaluated using available experimental data, as well as the enthalpy of formation of the bcc phase obtained from first-principles calculations based on DFT. The thermodynamic descriptions were combined into a database ensuring that the sublattice models are compatible with each other. For subsystems, such as the Sn-Ta system, where no thermodynamic description had been evaluated and minimal experimental data was available, first-principles calculations based on DFT were used. The Sn-Ta system has two intermetallic phases, TaSn2 and Ta3Sn, with three solution phases: bcc, body centered tetragonal (bct) and diamond. First-principles calculations were completed on the intermetallic and solution phases. Special quasirandom structures (SQS) were used to obtain information about the solution phases across the entire composition range. The Debye-Gruneisen approach, as well as the quasiharmonic phonon method, were used to obtain the finite-temperature data. Results from the first-principles calculations and experiments were used to complete the thermodynamic description. The resulting phase diagram reproduced the first-principles calculations and experimental data accurately. In order to determine the effect of alloying on the elastic properties, first-principles calculations based on DFT were systematically done on the pure elements, five Ti-X binary systems and Ti-X-Y ternary systems (X ≠ Y = Mo, Nb, Sn, Ta Zr) in the bcc phase. The first-principles calculations predicted the single crystal elastic stiffness constants cij 's. Correspondingly, the polycrystalline aggregate properties were also estimated from the cij's, including bulk modulus B, shear modulus G and Young's modulus E. The calculated results showed good agreement with experimental results. The CALPHAD method was then adapted to assist in the database development of the elastic properties as a function of composition. On average, the database predicted the elastic properties of higher order Ti-alloys within 5 GPa of the experimental results. Finally, the formation of the metastable phases, o and alpha" was studied in the Ti-Ta and Ti-Nb systems. The formation energy of these phases, calculated from first-principles at 0 K, showed that the phases have similar formation energies to the bcc and hcp phases. Inelastic neutron scattering was completed on four different Ti-Nb compositions to study the entropy of the phases as well as the transformations occurring when the phases form and the phase fractions. Ongoing work is being done to use the experimental information to introduce thermodynamic descriptions for these two phases in the Ti-Nb system in order to be able to predict the formation and phase fractions. DFT based first-principles were used to predict the effect these phases have on the elastic properties and a rule of mixtures was used to determine the elastic properties of multi-phase alloys. The results were compared with experiments and showed that if the ongoing modeling can predict the phase fraction, the elastic database can accurately predict the elastic properties of the o and alpha" phases. This thesis provides a knowledge base of the thermodynamic and elastic properties of Ti-alloys from computational thermodynamics. The databases created will impact research activities on Ti-alloys and specifically efforts focused on Ti-alloys for biomedical applications.

Containerless measurements on liquids at high temperatures

NASA Technical Reports Server (NTRS)

Weber, Richard

1993-01-01

The application of containerless techniques for measurements of the thermophysical properties of high temperature liquids is reviewed. Recent results obtained in the materials research laboratories at Intersonics are also presented. Work to measure high temperature liquid properties is motivated by both the need for reliable property data for modeling of industrial processes involving molten materials and generation of data form basic modeling of materials behavior. The motivation for this work and examples of variations in thermophysical property values from the literature are presented. The variations may be attributed to changes in the specimen properties caused by chemical changes in the specimen and/or to measurement errors. The two methods used to achieve containerless conditions were aeroacoustic levitation and electromagnetic levitation. Their qualities are presented. The accompanying slides show the layout of levitation equipment and present examples of levitated metallic and ceramic specimens. Containerless techniques provide a high degree of control over specimen chemistry, nucleation and allow precise control of liquid composition to be achieved. Effects of minor additions can thus be measured in a systematic way. Operation in reduced gravity enables enhanced control of liquid motion which can allow measurement of liquid transport properties. Examples of nucleation control, the thermodynamics of oxide contamination removal, and control of the chromium content of liquid aluminum oxide by high temperature containerless processes are presented. The feasibility of measuring temperature, emissivity, liquidus temperature, enthalpy, surface tension, density, viscosity, and thermal diffusivity are discussed in the final section of the paper.

Phase-field Model for Interstitial Loop Growth Kinetics and Thermodynamic and Kinetic Models of Irradiated Fe-Cr Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yulan; Hu, Shenyang Y.; Sun, Xin

2011-06-15

Microstructure evolution kinetics in irradiated materials has strongly spatial correlation. For example, void and second phases prefer to nucleate and grow at pre-existing defects such as dislocations, grain boundaries, and cracks. Inhomogeneous microstructure evolution results in inhomogeneity of microstructure and thermo-mechanical properties. Therefore, the simulation capability for predicting three dimensional (3-D) microstructure evolution kinetics and its subsequent impact on material properties and performance is crucial for scientific design of advanced nuclear materials and optimal operation conditions in order to reduce uncertainty in operational and safety margins. Very recently the meso-scale phase-field (PF) method has been used to predict gas bubblemore » evolution, void swelling, void lattice formation and void migration in irradiated materials,. Although most results of phase-field simulations are qualitative due to the lake of accurate thermodynamic and kinetic properties of defects, possible missing of important kinetic properties and processes, and the capability of current codes and computers for large time and length scale modeling, the simulations demonstrate that PF method is a promising simulation tool for predicting 3-D heterogeneous microstructure and property evolution, and providing microstructure evolution kinetics for higher scale level simulations of microstructure and property evolution such as mean field methods. This report consists of two parts. In part I, we will present a new phase-field model for predicting interstitial loop growth kinetics in irradiated materials. The effect of defect (vacancy/interstitial) generation, diffusion and recombination, sink strength, long-range elastic interaction, inhomogeneous and anisotropic mobility on microstructure evolution kinetics is taken into account in the model. The model is used to study the effect of elastic interaction on interstitial loop growth kinetics, the interstitial flux, and sink strength of interstitial loop for interstitials. In part II, we present a generic phase field model and discuss the thermodynamic and kinetic properties in phase-field models including the reaction kinetics of radiation defects and local free energy of irradiated materials. In particular, a two-sublattice thermodynamic model is suggested to describe the local free energy of alloys with irradiated defects. Fe-Cr alloy is taken as an example to explain the required thermodynamic and kinetic properties for quantitative phase-field modeling. Finally the great challenges in phase-field modeling will be discussed.« less

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 2: Compositions corresponding to Kelvin temperature schedules in part 1

NASA Technical Reports Server (NTRS)

Gordon, S.

1982-01-01

The equilibrium compositions that correspond to the thermodynamic and transport combustion properties for a wide range of conditions for the reaction of hydrocarbons with air are presented. Initially 55 gaseous species and 3 coin condensed species were considered in the calculations. Only 17 of these 55 gaseous species had equilibrium mole fractions greater than 0.000005 for any of the conditions studied and therefore these were the only ones retained in the final tables.

Thermodynamic properties of nitrogen gas derived from measurements of sound speed. [for cryogenic wind tunnels

NASA Technical Reports Server (NTRS)

Younglove, B.; Mccarty, R. D.

1979-01-01

A virial equation of state for nitrogen was determined by use of newly measured speed-of-sound data and existing pressure-density-temperature data in a multiproperty-fitting technique. The experimental data taken were chosen to optimize the equation of state for a pressure range of 0 to 10 atm and for a temperature range of 60 to 350 K. Comparisons are made for thermodynamic properties calculated both from the new equation and from existing equations of state.

New developments of the CARTE thermochemical code: A two-phase equation of state for nanocarbons

NASA Astrophysics Data System (ADS)

Dubois, Vincent; Pineau, Nicolas

2016-01-01

We developed a new equation of state (EOS) for nanocarbons in the thermodynamic range of high explosives detonation products (up to 50 GPa and 4000 K). This EOS was fitted to an extensive database of thermodynamic properties computed by molecular dynamics simulations of nanodiamonds and nano-onions with the LCBOPII potential. We reproduced the detonation properties of a variety of high explosives with the CARTE thermochemical code, including carbon-poor and carbon-rich explosives, with excellent accuracy.

Electrochemical thermodynamic measurement system

DOEpatents

Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA

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.

ThermoBuild: Online Method Made Available for Accessing NASA Glenn Thermodynamic Data

NASA Technical Reports Server (NTRS)

McBride, Bonnie; Zehe, Michael J.

2004-01-01

The new Web site program "ThermoBuild" allows users to easily access and use the NASA Glenn Thermodynamic Database of over 2000 solid, liquid, and gaseous species. A convenient periodic table allows users to "build" the molecules of interest and designate the temperature range over which thermodynamic functions are to be displayed. ThermoBuild also allows users to build custom databases for use with NASA's Chemical Equilibrium with Applications (CEA) program or other programs that require the NASA format for thermodynamic properties. The NASA Glenn Research Center has long been a leader in the compilation and dissemination of up-to-date thermodynamic data, primarily for use with the NASA CEA program, but increasingly for use with other computer programs.

Vacuum drying of apples (cv. Golden Delicious): drying characteristics, thermodynamic properties, and mass transfer parameters

NASA Astrophysics Data System (ADS)

Nadi, Fatemeh; Tzempelikos, Dimitrios

2018-01-01

In this work, apples of cv. Golden Delicious were cut into slices that were 5 and 7 mm thick and then vacuum dried at 50, 60 and 70 °C and pressure of 0.02 bar. The thin layer model drying kinetics was studied, and mass transfer properties, specifically effective moisture diffusivity and convective mass transfer coefficient, were evaluated using the Fick's equation of diffusion. Also, thermodynamic parameters of the process, i.e. enthalpy (ΔH), entropy (ΔS) and Gibbs free energy (ΔG), were determined. Colour properties were evaluated as one of the important indicators of food quality and marketability. Determination of mass transfer parameters and thermodynamic properties of vacuum dried apple slices has not been discussed much in the literature. In conclusion, the Nadi's model fitted best the observed data that represent the drying process. Thermodynamic properties were determined based on the dependence of the drying constant of the Henderson and Pabis model on temperature, and it was concluded that the variation in drying kinetics depends on the energy contribution of the surrounding environment. The enthalpy and entropy diminished, while the Gibbs free energy increased with the increase of the temperature of drying; therefore, it was possible to verify that variation in the diffusion process in the apple during drying depends on energetic contributions of the environment. The obtained results showed that diffusivity increased for 69%, while the mass transfer coefficient increase was even higher, 75%, at the variation of temperature of 20 °C. The increase in the dimensionless Biot number was 20%.

Embedded-atom-method study of structural, thermodynamic, and atomic-transport properties of liquid Ni-Al alloys

NASA Astrophysics Data System (ADS)

Asta, Mark; Morgan, Dane; Hoyt, J. J.; Sadigh, Babak; Althoff, J. D.; de Fontaine, D.; Foiles, S. M.

1999-06-01

Structural, thermodynamic, and atomic-transport properties of liquid Ni-Al alloys have been studied by Monte Carlo and molecular-dynamics simulations based upon three different embedded-atom method (EAM) interatomic potentials, namely those due to Foiles and Daw (FD) [J. Mater. Res. 2, 5 (1987)], Voter and Chen (VC) [in Characterization of Defects in Materials, edited by R. W. Siegel et al. MRS Symposia Proceedings. No. 82 (Materials Research Society, Pittsburgh, 1987), p.175] and Ludwig and Gumbsch (LG) [Model. Simul. Mater. Sci. Eng. 3, 533 (1995)]. We present detailed comparisons between calculated results and experimental data for structure factors, atomic volumes, enthalpies of mixing, activities, and viscosities. Calculated partial structure factors are found to be in semiquantitative agreement with published neutron scattering measurements for Ni20Al80 alloys, indicating that short-range order in the liquid phase is qualitatively well described. Calculated thermodynamic properties of mixing are found to agree very well with experimental data for Ni compositions greater than 75 atomic %, while for alloys richer in Al the magnitudes of the enthalpies and entropies of mixing are significantly underestimated. The VC and LG potentials give atomic densities and viscosities in good agreement with experiment for Ni-rich compositions, while FD potentials consistently underestimate both properties at all concentrations. The results of this study demonstrate that VC and LG potentials provide a realistic description of the thermodynamic and atomic transport properties for NixAl1-x liquid alloys with x>=0.75, and point to the limitations of EAM potentials for alloys richer in Al.

Vacuum drying of apples (cv. Golden Delicious): drying characteristics, thermodynamic properties, and mass transfer parameters

NASA Astrophysics Data System (ADS)

Nadi, Fatemeh; Tzempelikos, Dimitrios

2018-07-01

In this work, apples of cv. Golden Delicious were cut into slices that were 5 and 7 mm thick and then vacuum dried at 50, 60 and 70 °C and pressure of 0.02 bar. The thin layer model drying kinetics was studied, and mass transfer properties, specifically effective moisture diffusivity and convective mass transfer coefficient, were evaluated using the Fick's equation of diffusion. Also, thermodynamic parameters of the process, i.e. enthalpy ( ΔH), entropy ( ΔS) and Gibbs free energy ( ΔG), were determined. Colour properties were evaluated as one of the important indicators of food quality and marketability. Determination of mass transfer parameters and thermodynamic properties of vacuum dried apple slices has not been discussed much in the literature. In conclusion, the Nadi's model fitted best the observed data that represent the drying process. Thermodynamic properties were determined based on the dependence of the drying constant of the Henderson and Pabis model on temperature, and it was concluded that the variation in drying kinetics depends on the energy contribution of the surrounding environment. The enthalpy and entropy diminished, while the Gibbs free energy increased with the increase of the temperature of drying; therefore, it was possible to verify that variation in the diffusion process in the apple during drying depends on energetic contributions of the environment. The obtained results showed that diffusivity increased for 69%, while the mass transfer coefficient increase was even higher, 75%, at the variation of temperature of 20 °C. The increase in the dimensionless Biot number was 20%.

Thermodynamics and evolution.

PubMed

Demetrius, L

2000-09-07

The science of thermodynamics is concerned with understanding the properties of inanimate matter in so far as they are determined by changes in temperature. The Second Law asserts that in irreversible processes there is a uni-directional increase in thermodynamic entropy, a measure of the degree of uncertainty in the thermal energy state of a randomly chosen particle in the aggregate. The science of evolution is concerned with understanding the properties of populations of living matter in so far as they are regulated by changes in generation time. Directionality theory, a mathematical model of the evolutionary process, establishes that in populations subject to bounded growth constraints, there is a uni-directional increase in evolutionary entropy, a measure of the degree of uncertainty in the age of the immediate ancestor of a randomly chosen newborn. This article reviews the mathematical basis of directionality theory and analyses the relation between directionality theory and statistical thermodynamics. We exploit an analytic relation between temperature, and generation time, to show that the directionality principle for evolutionary entropy is a non-equilibrium extension of the principle of a uni-directional increase of thermodynamic entropy. The analytic relation between these directionality principles is consistent with the hypothesis of the equivalence of fundamental laws as one moves up the hierarchy, from a molecular ensemble where the thermodynamic laws apply, to a population of replicating entities (molecules, cells, higher organisms), where evolutionary principles prevail. Copyright 2000 Academic Press.

Computational Design and Discovery of Ni-Based Alloys and Coatings: Thermodynamic Approaches Validated by Experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zi-Kui; Gleeson, Brian; Shang, Shunli

This project developed computational tools that can complement and support experimental efforts in order to enable discovery and more efficient development of Ni-base structural materials and coatings. The project goal was reached through an integrated computation-predictive and experimental-validation approach, including first-principles calculations, thermodynamic CALPHAD (CALculation of PHAse Diagram), and experimental investigations on compositions relevant to Ni-base superalloys and coatings in terms of oxide layer growth and microstructure stabilities. The developed description included composition ranges typical for coating alloys and, hence, allow for prediction of thermodynamic properties for these material systems. The calculation of phase compositions, phase fraction, and phase stabilities,more » which are directly related to properties such as ductility and strength, was a valuable contribution, along with the collection of computational tools that are required to meet the increasing demands for strong, ductile and environmentally-protective coatings. Specifically, a suitable thermodynamic description for the Ni-Al-Cr-Co-Si-Hf-Y system was developed for bulk alloy and coating compositions. Experiments were performed to validate and refine the thermodynamics from the CALPHAD modeling approach. Additionally, alloys produced using predictions from the current computational models were studied in terms of their oxidation performance. Finally, results obtained from experiments aided in the development of a thermodynamic modeling automation tool called ESPEI/pycalphad - for more rapid discovery and development of new materials.« less

Ab initio thermodynamic model for magnesium carbonates and hydrates.

PubMed

Chaka, Anne M; Felmy, Andrew R

2014-09-04

An ab initio thermodynamic framework for predicting properties of hydrated magnesium carbonate minerals has been developed using density-functional theory linked to macroscopic thermodynamics through the experimental chemical potentials for MgO, water, and CO2. Including semiempirical dispersion via the Grimme method and small corrections to the generalized gradient approximation of Perdew, Burke, and Ernzerhof for the heat of formation yields a model with quantitative agreement for the benchmark minerals brucite, magnesite, nesquehonite, and hydromagnesite. The model shows how small differences in experimental conditions determine whether nesquehonite, hydromagnesite, or magnesite is the result of laboratory synthesis from carbonation of brucite, and what transformations are expected to occur on geological time scales. Because of the reliance on parameter-free first-principles methods, the model is reliably extensible to experimental conditions not readily accessible to experiment and to any mineral composition for which the structure is known or can be hypothesized, including structures containing defects, substitutions, or transitional structures during solid state transformations induced by temperature changes or processes such as water, CO2, or O2 diffusion. Demonstrated applications of the ab initio thermodynamic framework include an independent means to evaluate differences in thermodynamic data for lansfordite, predicting the properties of Mg analogues of Ca-based hydrated carbonates monohydrocalcite and ikaite, which have not been observed in nature, and an estimation of the thermodynamics of barringtonite from the stoichiometry and a single experimental observation.

Local quantum thermal susceptibility

PubMed Central

De Pasquale, Antonella; Rossini, Davide; Fazio, Rosario; Giovannetti, Vittorio

2016-01-01

Thermodynamics relies on the possibility to describe systems composed of a large number of constituents in terms of few macroscopic variables. Its foundations are rooted into the paradigm of statistical mechanics, where thermal properties originate from averaging procedures which smoothen out local details. While undoubtedly successful, elegant and formally correct, this approach carries over an operational problem, namely determining the precision at which such variables are inferred, when technical/practical limitations restrict our capabilities to local probing. Here we introduce the local quantum thermal susceptibility, a quantifier for the best achievable accuracy for temperature estimation via local measurements. Our method relies on basic concepts of quantum estimation theory, providing an operative strategy to address the local thermal response of arbitrary quantum systems at equilibrium. At low temperatures, it highlights the local distinguishability of the ground state from the excited sub-manifolds, thus providing a method to locate quantum phase transitions. PMID:27681458

Local quantum thermal susceptibility

NASA Astrophysics Data System (ADS)

de Pasquale, Antonella; Rossini, Davide; Fazio, Rosario; Giovannetti, Vittorio

2016-09-01

Thermodynamics relies on the possibility to describe systems composed of a large number of constituents in terms of few macroscopic variables. Its foundations are rooted into the paradigm of statistical mechanics, where thermal properties originate from averaging procedures which smoothen out local details. While undoubtedly successful, elegant and formally correct, this approach carries over an operational problem, namely determining the precision at which such variables are inferred, when technical/practical limitations restrict our capabilities to local probing. Here we introduce the local quantum thermal susceptibility, a quantifier for the best achievable accuracy for temperature estimation via local measurements. Our method relies on basic concepts of quantum estimation theory, providing an operative strategy to address the local thermal response of arbitrary quantum systems at equilibrium. At low temperatures, it highlights the local distinguishability of the ground state from the excited sub-manifolds, thus providing a method to locate quantum phase transitions.

Underscreening in ionic liquids: a first principles analysis.

PubMed

Rotenberg, Benjamin; Bernard, Olivier; Hansen, Jean-Pierre

2018-02-07

An attempt is made to understand the underscreening effect, observed in concentrated electrolyte solutions or melts, on the basis of simple, admittedly crude models involving charged (for the ions) and neutral (for the solvent molecules) hard spheres. The thermodynamic and structural properties of these 'primitive' and 'semi-primitive' models are calculated within mean spherical approximation, which provides the basic input required to determine the partial density response functions. The screening length [Formula: see text], which is unambiguously defined in terms of the wave-number-dependent response functions, exhibits a cross-over from a low density, Debye-like regime, to a regime where [Formula: see text] increases with density beyond a critical density at which the Debye length [Formula: see text] becomes comparable to the ion diameter. In this high density regime the ratio [Formula: see text] increases according to a power law, in qualitative agreement with experimental measurements, albeit at a much slower rate.

Underscreening in ionic liquids: a first principles analysis

NASA Astrophysics Data System (ADS)

Rotenberg, Benjamin; Bernard, Olivier; Hansen, Jean-Pierre

2018-02-01

An attempt is made to understand the underscreening effect, observed in concentrated electrolyte solutions or melts, on the basis of simple, admittedly crude models involving charged (for the ions) and neutral (for the solvent molecules) hard spheres. The thermodynamic and structural properties of these ‘primitive’ and ‘semi-primitive’ models are calculated within mean spherical approximation, which provides the basic input required to determine the partial density response functions. The screening length λS , which is unambiguously defined in terms of the wave-number-dependent response functions, exhibits a cross-over from a low density, Debye-like regime, to a regime where λS increases with density beyond a critical density at which the Debye length λD becomes comparable to the ion diameter. In this high density regime the ratio λ_S/λD increases according to a power law, in qualitative agreement with experimental measurements, albeit at a much slower rate.

Quarterly progress report for the Chemical and Energy Research Section of the Chemical Technology Division: July--September 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jubin, R.T.

This report summarizes the major activities conducted in the Chemical and Energy Research Section of the Chemical Technology Division at Oak Ridge National Laboratory (ORNL) during the period July--September 1997. The section conducts basic and applied research and development in chemical engineering, applied chemistry, and bioprocessing, with an emphasis on energy-driven technologies and advanced chemical separations for nuclear and waste applications. The report describes the various tasks performed within nine major areas of research: Hot Cell Operations, Process Chemistry and Thermodynamics, Molten Salt Reactor Experiment (MSRE) Remediation Studies, Chemistry Research, Biotechnology, Separations and Materials Synthesis, Fluid Structure and Properties, Biotechnologymore » Research, and Molecular Studies. The name of a technical contact is included with each task described, and readers are encouraged to contact these individuals if they need additional information.« less

Spray drying formulation of amorphous solid dispersions.

PubMed

Singh, Abhishek; Van den Mooter, Guy

2016-05-01

Spray drying is a well-established manufacturing technique which can be used to formulate amorphous solid dispersions (ASDs) which is an effective strategy to deliver poorly water soluble drugs (PWSDs). However, the inherently complex nature of the spray drying process coupled with specific characteristics of ASDs makes it an interesting area to explore. Numerous diverse factors interact in an inter-dependent manner to determine the final product properties. This review discusses the basic background of ASDs, various formulation and process variables influencing the critical quality attributes (CQAs) of the ASDs and aspects of downstream processing. Also various aspects of spray drying such as instrumentation, thermodynamics, drying kinetics, particle formation process and scale-up challenges are included. Recent advances in the spray-based drying techniques are mentioned along with some future avenues where major research thrust is needed. Copyright © 2015 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bony, Sandrine; Stevens, Bjorn; Coppin, David

General circulation models show that as the surface temperature increases, the convective anvil clouds shrink. By analyzing radiative–convective equilibrium simulations, our work shows that this behavior is rooted in basic energetic and thermodynamic properties of the atmosphere: As the climate warms, the clouds rise and remain at nearly the same temperature, but find themselves in a more stable atmosphere; this enhanced stability reduces the convective outflow in the upper troposphere and decreases the anvil cloud fraction. By warming the troposphere and increasing the upper-tropospheric stability, the clustering of deep convection also reduces the convective outflow and the anvil cloud fraction.more » When clouds are radiatively active, this robust coupling between temperature, high clouds, and circulation exerts a positive feedback on convective aggregation and favors the maintenance of strongly aggregated atmospheric states at high temperatures. This stability iris mechanism likely contributes to the narrowing of rainy areas as the climate warms. Whether or not it influences climate sensitivity requires further investigation.« less

Temperature effect on the acid-base behaviour of Na-montmorillonite.

PubMed

Duc, Myriam; Carteret, Cédric; Thomas, Fabien; Gaboriaud, Fabien

2008-11-15

We report a study of the acid-base properties of Na-montmorillonite suspensions at temperatures from 25 degrees C to 80 degrees C, by continuous and batch potentiometric methods, combined with analysis of the dissolved and readsorbed species. The batch titration curves reveal that the dissolution processes of Na-montmorillonite and silica-rich secondary phases are increasingly predominant, respectively at acid and basic pH, and according to the temperature. The continuous titration curves are less affected by these side reactions. In the absence of a common intersection point, the thermodynamic analysis of the curves was based on the shift of the PZNPC with the ionic strength. This shift was not significantly altered by the temperature, by comparison with the dissociation product of water in the same conditions. Therefore we concluded that protonation-deprotonation of the dissociable sites at the edges of the clay platelets is not significantly temperature dependent.

On the effect of Ti on the stability of amorphous indium zinc oxide used in thin film transistor applications

NASA Astrophysics Data System (ADS)

Lee, Sunghwan; Paine, David C.

2011-06-01

In2O3-based amorphous oxide channel materials are of increasing interest for thin film transisitor applications due, in part, to the remarkable stability of this class of materials amorphous structure and electronic properties. We report that this stability is degraded in the presence of Ti, which is widely used as a contact and/or adhesion layer. A cross-sectional transmission electron microscopy analysis, supported by glancing incident angle x-ray and selected area diffraction examination, shows that amorphous indium zinc oxide in contact with Ti undergoes crystallization to the bixbyite phase and reacts to form the rutile phase of TiO2 at a temperature of 200 °C. A basic thermodynamic analysis is presented and forms the basis of a model that describes both the crystallization and the resistivity decrease.

Structural and thermodynamic principles of viral packaging.

PubMed

Petrov, Anton S; Harvey, Stephen C

2007-01-01

Packaging of genetic material inside a capsid is one of the major processes in the lifecycle of bacteriophages. To establish the basic principles of packing double-stranded DNA into a phage, we present a low-resolution model of bacteriophage varphi29 and report simulations of DNA packaging. The simulations show excellent agreement with available experimental data, including the forces of packaging and the average structures seen in cryo-electron microscopy. The conformation of DNA inside the bacteriophage is primarily determined by the shape of the capsid and the elastic properties of DNA, but the energetics of packaging are dominated by electrostatic repulsions and the large entropic penalty associated with DNA confinement. In this slightly elongated capsid, the DNA assumes a folded toroidal conformation, rather than a coaxial spool. The model can be used to study packaging of other bacteriophages with different shapes under a range of environmental conditions.

Computer-Generated Phase Diagrams for Binary Mixtures.

ERIC Educational Resources Information Center

Jolls, Kenneth R.; And Others

1983-01-01

Computer programs that generate projections of thermodynamic phase surfaces through computer graphics were used to produce diagrams representing properties of water and steam and the pressure-volume-temperature behavior of most of the common equations of state. The program, program options emphasizing thermodynamic features of interest, and…

Hydrogen technology survey: Thermophysical properties

NASA Technical Reports Server (NTRS)

Mccarty, R. D.

1975-01-01

The thermodynamic functions, transport properties, and physical properties of both liquid and gaseous hydrogen are presented. The low temperature regime is emphasized. The tabulation of the properties of normal hydrogen in both Si and engineering units is given along with the tabulation of parahydrogen.

Properties of the two-dimensional heterogeneous Lennard-Jones dimers: An integral equation study

PubMed Central

Urbic, Tomaz

2016-01-01

Structural and thermodynamic properties of a planar heterogeneous soft dumbbell fluid are examined using Monte Carlo simulations and integral equation theory. Lennard-Jones particles of different sizes are the building blocks of the dimers. The site-site integral equation theory in two dimensions is used to calculate the site-site radial distribution functions and the thermodynamic properties. Obtained results are compared to Monte Carlo simulation data. The critical parameters for selected types of dimers were also estimated and the influence of the Lennard-Jones parameters was studied. We have also tested the correctness of the site-site integral equation theory using different closures. PMID:27875894

Microscopic approaches to liquid nitromethane detonation properties.

PubMed

Hervouët, Anaïs; Desbiens, Nicolas; Bourasseau, Emeric; Maillet, Jean-Bernard

2008-04-24

In this paper, thermodynamic and chemical properties of nitromethane are investigated using microscopic simulations. The Hugoniot curve of the inert explosive is computed using Monte Carlo simulations with a modified version of the adaptative Erpenbeck equation of state and a recently developed intermolecular potential. Molecular dynamic simulations of nitromethane decomposition have been performed using a reactive potential, allowing the calculation of kinetic rate constants and activation energies. Finally, the Crussard curve of detonation products as well as thermodynamic properties at the Chapman-Jouguet (CJ) point are computed using reactive ensemble Monte Carlo simulations. Results are in good agreement with both thermochemical calculations and experimental measurements.

Molecular dynamics simulation of the ionic liquid N-octylpyridinium tetrafluoroborate and acetonitrile: Thermodynamic and structural properties

NASA Astrophysics Data System (ADS)

Zhou, Siwen; Zhu, Guanglai; Kang, Xianqu; Li, Qiang; Sha, Maolin; Cui, Zhifeng; Xu, Xinsheng

2018-06-01

Using molecular dynamics simulation, the research obtained the thermodynamic properties and microstructures of the mixture of N-octylpyridinium tetrafluoroborate and acetonitrile, including density, self-diffusion coefficients, excess properties, radial distribution functions (RDFs) and spatial distribution functions (SDFs). Both RDFs and SDFs indicate that the local microstructure of the polar region is different from the nonpolar region with different mole fraction of ionic liquids. Acetonitrile could increase the order of the polar regions. While with acetonitrile increasing, the orderliness of the nonpolar region increases firstly and then decreases. In relatively dilute solution, ionic liquids were dispersed to form small aggregates wrapped by acetonitrile.

First-principles study on the electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites

DOE PAGES

Jia, Ting; Zeng, Zhi; Lin, H. Q.; ...

2017-08-08

The electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites are investigated using first-principles calculations. The obtained results indicate that SrCoO 3 and SrFeO 3 are metals, while LaCoO 3 and LaFeO 3 are insulators and all of them exhibit strong hybridization of the Fe/Co-3d and O-2p orbitals. By correlating the energy band structures with the peaks of the imaginary part of the dielectric function, we obtained the origin of each electron excitation to provide information about the active bands for the corresponding optical transitions observed in the experiment. Moreover, the Debye temperatures θmore » D obtained from the phonon frequencies are comparable to the available data. In conclusion, the thermodynamic properties of the Helmholtz free energy F, entropy S, and constant-volume heat capacity C v are investigated based on the phonon spectra.« less

Theoretical study of phonon dispersion, elastic, mechanical and thermodynamic properties of barium chalcogenides

NASA Astrophysics Data System (ADS)

Musari, A. A.; Orukombo, S. A.

2018-03-01

Barium chalcogenides are known for their high-technological importance and great scientific interest. Detailed studies of their elastic, mechanical, dynamical and thermodynamic properties were carried out using density functional theory and plane-wave pseudo potential method within the generalized gradient approximation. The optimized lattice constants were in good agreement when compared with experimental data. The independent elastic constants, calculated from a linear fit of the computed stress-strain function, were used to determine the Young’s modulus (E), bulk modulus (B), shear modulus (G), Poisson’s ratio (σ) and Zener’s anisotropy factor (A). Also, the Debye temperature and sound velocities for barium chalcogenides were estimated from the three independent elastic constants. The calculations of phonon dispersion showed that there are no negative frequencies throughout the Brillouin zone. Hence barium chalcogenides have dynamically stable NaCl-type crystal structure. Finally, their thermodynamic properties were calculated in the temperature range of 0-1000 K and their constant-volume specific heat capacities at room-temperature were reported.

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Atmospheric aerosols: Their Optical Properties and Effects

NASA Technical Reports Server (NTRS)

1976-01-01

Measured properties of atmospheric aerosol particles are presented. These include aerosol size frequency distribution and complex retractive index. The optical properties of aerosols are computed based on the presuppositions of thermodynamic equilibrium and of Mie-theory.

Calorimetric Determination of Thermodynamic Stability of MAX and MXene Phases

DOE PAGES

Sharma, Geetu; Naguib, Michael; Feng, Dawei; ...

2016-11-19

MXenes are layered two dimensional materials with exciting properties useful to a wide range of energy applications. They are derived from ceramics (MAX phases) by leaching and their properties reflect their resulting complex compositions which include intercalating cations and anions and water. Their thermodynamic stability is likely linked to these functional groups but has not yet been addressed by quantitative experimental measurements. We report enthalpies of formation from the elements at 25 °C measured using high temperature oxide melt solution calorimetry for a layered Ti-Al-C MAX phase, and the corresponding Ti-C based MXene. The thermodynamic stability of the Ti 3Cmore » 2T x MXene (Tx stands for anionic surface moieties, and intercalated cations) was assessed by calculating the enthalpy of reaction of the MAX phase (ideal composition Ti 3AlC 2) to form MXene, The very exothermic enthalpy of reaction confirms the stability of MXene in an aqueous environment. The surface terminations (O, OH and F) and cations (Li) chemisorbed on the surface and intercalated in the interlayers play a major role in the thermodynamic stabilization of MXene. These findings help to understand and potentially improve properties and performance by characterizing the energetics of species binding to MXene surfaces during synthesis and in energy storage, water desalination and other applications.« less

Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

PubMed

Wang, Vincent C-C

2016-08-10

Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

Computer codes for the evaluation of thermodynamic and transport properties for equilibrium air to 30000 K

NASA Technical Reports Server (NTRS)

Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

1991-01-01

The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.

Temperature Dependence of Thermodynamic Properties of Thallium Chloride and Thallium Bromide

NASA Astrophysics Data System (ADS)

Kavanoz, H. B.

2015-02-01

Thermodynamic properties as lattice parameters, thermal expansion, heat capacities Cp and Cv, bulk modulus, and Gruneisen parameter of ionic halides TlCl and TlBr in solid and liquid phases were studied using classical molecular dynamics simulation (MD) with interionic Vashistha-Rahman (VR) model potential. In addition to the static and transport properties which have been previously reported by the author [13], this study further confirms that temperature dependence of the calculated thermophysical properties of TlCl and TlBr are in agreement with the available experimental data at both solid and liquid phases in terms of providing an alternative rigid ion potential. The results give a fairly good description of TlCl and TlBr in the temperature range 10-1000 K.

Computer programs for thermodynamic and transport properties of hydrogen (tabcode-II)

NASA Technical Reports Server (NTRS)

Roder, H. M.; Mccarty, R. D.; Hall, W. J.

1972-01-01

The thermodynamic and transport properties of para and equilibrium hydrogen have been programmed into a series of computer routines. Input variables are the pair's pressure-temperature and pressure-enthalpy. The programs cover the range from 1 to 5000 psia with temperatures from the triple point to 6000 R or enthalpies from minus 130 BTU/lb to 25,000 BTU/lb. Output variables are enthalpy or temperature, density, entropy, thermal conductivity, viscosity, at constant volume, the heat capacity ratio, and a heat transfer parameter. Property values on the liquid and vapor boundaries are conveniently obtained through two small routines. The programs achieve high speed by using linear interpolation in a grid of precomputed points which define the surface of the property returned.

a Climatology of Synoptic Scale Atmospheric Structure Prior to Severe Convective Storms

NASA Astrophysics Data System (ADS)

Taylor, Gregory Eugene

1982-03-01

This investigation determines those unique properties of the thermodynamic and kinematic structure of the atmosphere in the region where tornado bearing thunderstorms develop as compared to surrounding locations. One hundred five upper air soundings from the operational rawinsonde network, hereafter called tornado proximity soundings, comprise the core of the data base. In each instance, a confirmed tornado occurred within 50 statute miles of and within 105 minutes after the release of the radiosonde. In earlier research of this nature, the thermodynamic and kinematic properties of the atmosphere in the region of tornado bearing thunderstorm development were interpolated or inferred from upper air soundings made at locations surrounding the severe storm location. These surrounding locations, however, were characterized by at most non-tornado bearing thunderstorm development. In this investigation, however, measurements of the atmospheric structure near in space and time to the subsequent tornado bearing thunderstorm development have been utilized. This fact should enhance the probability of detecting the presumably unique properties of the atmospheric structure prior to severe storm development as compared to previous investigations. Height, temperature, mixing ratio, and U and V wind component data from the tornado proximity sounding station and surrounding upper air stations were objectively analyzed to a regularly spaced three dimensional grid network centered on the tornado proximity sounding station. From the basic data, a large number of derived variables which had been previously linked to severe storms were computed. Each case was categorized into one of six different classifications based on the geographical location and date of the tornado proximity sounding. The results from the six categories indicate that the most pronounced unique properties of the pre-severe storm environment are within the lower levels of the atmosphere. In particular, the low level moisture content and the low level V-component tended to maximize near the region of subsequent severe storm development in most of the six categories. Also, a number of variables which are highly dependent upon low level moisture content and/or low level wind data such as horizontal moisture flux and stability indices delineated well the region of subsequent severe storm development.

A thermodynamic counterpart of the Axelrod model of social influence: The one-dimensional case

NASA Astrophysics Data System (ADS)

Gandica, Y.; Medina, E.; Bonalde, I.

2013-12-01

We propose a thermodynamic version of the Axelrod model of social influence. In one-dimensional (1D) lattices, the thermodynamic model becomes a coupled Potts model with a bonding interaction that increases with the site matching traits. We analytically calculate thermodynamic and critical properties for a 1D system and show that an order-disorder phase transition only occurs at T=0 independent of the number of cultural traits q and features F. The 1D thermodynamic Axelrod model belongs to the same universality class of the Ising and Potts models, notwithstanding the increase of the internal dimension of the local degree of freedom and the state-dependent bonding interaction. We suggest a unifying proposal to compare exponents across different discrete 1D models. The comparison with our Hamiltonian description reveals that in the thermodynamic limit the original out-of-equilibrium 1D Axelrod model with noise behaves like an ordinary thermodynamic 1D interacting particle system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiedemeier, Heribert, E-mail: wiedeh@rpi.edu

The observed linear (Na-, K-halides) and near-linear (Mg-, Sr-, Zn-, Cd-, and Hg-chalcogenides) dependences of Schottky constants on reciprocal interatomic distances yield the relation logK{sub S}=((s{sub s}1/T)+i{sub s})1/d{sub (A−B)}+(s{sub i}1/T)+i{sub i}, where K{sub S} is the product of metal and non-metal thermal equilibrium vacancy concentrations, and s{sub s}, i{sub s}, s{sub i} and i{sub i} are the group specific slope and intercept values obtained from an extended analysis of the above log K{sub S} versus 1/d{sub (A−B)} data. The previously reported linear dependences of log K{sub S} on the Born–Haber lattice energies [1] are the basis for combining the earliermore » results [1] with the Born–Mayer lattice energy equation to yield a new thermodynamic relationship, namely logK{sub S}=−(2.303nRT){sup −1}(c{sub (B−M)}/d{sub (A−B)}−I{sub e}), where c{sub (B−M)} is the product of the constants of the Born–Mayer equation and I{sub e} is the metal ionization energy of the above compounds. These results establish a correlation between point defect concentrations and basic thermodynamic, coulombic, and structural solid state properties for selected I–VII and II–VI semiconductor materials. - Graphical abstract: Display Omitted.« less

Methods for thermodynamic evaluation of battery state of health

DOEpatents

Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T

2013-05-21

Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination 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 battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.

Methods and systems for thermodynamic evaluation of battery state of health

DOEpatents

Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T

2014-12-02

Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination 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 battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.

Thermodynamic model of a solid with RKKY interaction and magnetoelastic coupling

NASA Astrophysics Data System (ADS)

Balcerzak, T.; Szałowski, K.; Jaščur, M.

2018-04-01

Thermodynamic description of a model system with magnetoelastic coupling is presented. The elastic, vibrational, electronic and magnetic energy contributions are taken into account. The long-range RKKY interaction is considered together with the nearest-neighbour direct exchange. The generalized Gibbs potential and the set of equations of state are derived, from which all thermodynamic functions are self-consistently obtained. Thermodynamic properties are calculated numerically for FCC structure for arbitrary external pressure, magnetic field and temperature, and widely discussed. In particular, for some parameters of interaction potential and electron concentration corresponding to antiferromagnetic phase, the existence of negative thermal expansion coefficient is predicted.

M4FT-16LL080302052-Update to Thermodynamic Database Development and Sorption Database Integration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavarin, Mavrik; Wolery, T. J.; Atkins-Duffin, C.

2016-08-16

This progress report (Level 4 Milestone Number M4FT-16LL080302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite Disposal R&D Work Package Number FT-16LL08030205. The focus of this research is the thermodynamic modeling of Engineered Barrier System (EBS) materials and properties and development of thermodynamic databases and models to evaluate the stability of EBS materials and their interactions with fluids at various physico-chemical conditions relevant to subsurface repository environments. The development and implementation of equilibrium thermodynamic models are intended to describe chemical and physical processes such as solubility, sorption, and diffusion.

Optimization of binary thermodynamic and phase diagram data

NASA Astrophysics Data System (ADS)

Bale, Christopher W.; Pelton, A. D.

1983-03-01

An optimization technique based upon least squares regression is presented to permit the simultaneous analysis of diverse experimental binary thermodynamic and phase diagram data. Coefficients of polynomial expansions for the enthalpy and excess entropy of binary solutions are obtained which can subsequently be used to calculate the thermodynamic properties or the phase diagram. In an interactive computer-assisted analysis employing this technique, one can critically analyze a large number of diverse data in a binary system rapidly, in a manner which is fully self-consistent thermodynamically. Examples of applications to the Bi-Zn, Cd-Pb, PbCl2-KCl, LiCl-FeCl2, and Au-Ni binary systems are given.

eQuilibrator--the biochemical thermodynamics calculator.

PubMed

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like 'how much Gibbs energy is released by ATP hydrolysis at pH 5?' are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use.

eQuilibrator—the biochemical thermodynamics calculator

PubMed Central

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like ‘how much Gibbs energy is released by ATP hydrolysis at pH 5?’ are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use. PMID:22064852

Leveraging the contribution of thermodynamics in drug discovery with the help of fluorescence-based thermal shift assays.

PubMed

Hau, Jean Christophe; Fontana, Patrizia; Zimmermann, Catherine; De Pover, Alain; Erdmann, Dirk; Chène, Patrick

2011-06-01

The development of new drugs with better pharmacological and safety properties mandates the optimization of several parameters. Today, potency is often used as the sole biochemical parameter to identify and select new molecules. Surprisingly, thermodynamics, which is at the core of any interaction, is rarely used in drug discovery, even though it has been suggested that the selection of scaffolds according to thermodynamic criteria may be a valuable strategy. This poor integration of thermodynamics in drug discovery might be due to difficulties in implementing calorimetry experiments despite recent technological progress in this area. In this report, the authors show that fluorescence-based thermal shift assays could be used as prescreening methods to identify compounds with different thermodynamic profiles. This approach allows a reduction in the number of compounds to be tested in calorimetry experiments, thus favoring greater integration of thermodynamics in drug discovery.

Assessment of the Potential Impact of Combustion Research on Internal Combustion Engine Emission and Fuel Consumption

DOT National Transportation Integrated Search

1979-01-01

A review of the present level of understanding of the basic thermodynamic, fluid dynamic, and chemical kinetic processes which affect the fuel economy and levels of pollutant exhaust products of Diesel, Stratified Charge, and Spark Ignition engines i...

Entropy and Information: A Multidisciplinary Overview.

ERIC Educational Resources Information Center

Shaw, Debora; Davis, Charles H.

1983-01-01

Cites representative extensions of concept of entropy (measure of the amount of energy unavailable for useful work; from the second law of thermodynamics) noting basic relationships between entropy, order, information, and meaning in such disciplines as biology, economics, information science, the arts, and religion. Seventy-eight references are…

Geometry and symmetry in non-equilibrium thermodynamic systems

NASA Astrophysics Data System (ADS)

Sonnino, Giorgio

2017-06-01

The ultimate aim of this series of works is to establish the closure equations, valid for thermodynamic systems out from the Onsager region, and to describe the geometry and symmetry in thermodynamic systems far from equilibrium. Geometry of a non-equilibrium thermodynamic system is constructed by taking into account the second law of thermodynamics and by imposing the validity of the Glansdorff-Prigogine Universal Criterion of Evolution. These two constraints allow introducing the metrics and the affine connection of the Space of the Thermodynamic Forces, respectively. The Lie group associated to the nonlinear Thermodynamic Coordinate Transformations (TCT) leaving invariant both the entropy production σ and the Glansdorff-Prigogine dissipative quantity P, is also described. The invariance under TCT leads to the formulation of the Thermodynamic Covariance Principle (TCP): The nonlinear closure equations, i.e. the flux-force relations, must be covariant under TCT. In other terms, the fundamental laws of thermodynamics should be manifestly covariant under transformations between the admissible thermodynamic forces (i.e. under TCT). The symmetry properties of a physical system are intimately related to the conservation laws characterizing the thermodynamic system. Noether's theorem gives a precise description of this relation. The macroscopic theory for closure relations, based on this geometrical description and subject to the TCP, is referred to as the Thermodynamic Field Theory (TFT). This theory ensures the validity of the fundamental theorems for systems far from equilibrium.

Property Predictions for Nitrate Salts with Nitroxy-Functionalized Cations

DTIC Science & Technology

2011-05-01

Imidazole, Indazole, and Benzimidazole . Journal of Chemical Thermodynamics, 1987, 19, 985–992. Jocelyn, P. C. Some Derivatives of 2-2...Enthalpies of Formation of Pyrazole, Imidazole, Indazole, and Benzimidazole . Journal of Chemical Thermodynamics 1987, 19, 985–992. pA B3LYP/6-31+G(d,p

Web Thermo Tables (WTT) - Professional Edition

National Institute of Standards and Technology Data Gateway

SRD 203 NIST/TRC Web Thermo Tables (WTT) - Professional Edition (Online Subscription)   WTT - Professional Edition, a Web version of the TRC Thermodynamic Tables, represents a complete collection of critically evaluated thermodynamic property data primarily for pure organic compounds. As of Nov. 2011, WTT contains information on 23999 compounds.

Computational designing and screening of solid materials for CO2capture

NASA Astrophysics Data System (ADS)

Duan, Yuhua

In this presentation, we will update our progress on computational designing and screening of solid materials for CO2 capture. 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 CO2 sorbent candidates from the vast array of possible solid materials have been proposed and validated at NETL. The advantage of this method is that it identifies the thermodynamic properties of the CO2 capture reaction as a function of temperature and pressure without any experimental input beyond crystallographic structural information of the solid phases involved. 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 CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the solids of interest, we were able to identify only those solid materials for which lower capture energy costs are expected at the desired working conditions. In addition, we present a simulation scheme to increase and decrease the turnover temperature (Tt) of solid capturing CO2 reaction by mixing other solids. Our results also show that some solid sorbents can serve as bi-functional materials: CO2 sorbent and CO oxidation catalyst. Such dual functionality could be used for removing both CO and CO2 after water-gas-shift to obtain pure H2.

Prediction of thermodynamic properties of coal derivatives. Progress report, September 1, 1981-August 31, 1982

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donohue, M.D.

It is the purpose of this research program to develop a model to predict the thermodynamic properties of coal derivatives. Unlike natural gas and petroleum, coal and its gasification and liquefaction products are predominantly aromatic and have substantial quadrupole moments. Because of these quadrupole forces, the numerous correlational techniques that have been developed for petroleum products cannot be used to predict the thermodynamic properties of coal derivatives. We are presently developing a correlation that will be useful in predicting the thermodynamic properties of coal derivatives. This theory is based on the Perturbed-Hard-Chain theory, but is different from PHCT in twomore » respects. First, PHCT uses a square-well to describe the intermolecular potential energy between two molecules. In our new theory, the Lennard-Jones potential energy function is used. The second difference is that we take into account the effect of quadrupole forces on the intermolecular potential energy. In PHCT these forces were ignored. In PHCT the contributions to the partition function (or equation of state) that arise from the attractive forces between molecules (regardless of whether these forces are treated as a square-well or by Lennard-Jones) are calculated by assuming that they are perturbations on a hard sphere. In calculating the contributions to the partition function that arise from the quadrupole-quadrupole interactions, we use a second order perturbation about the Lennard-Jones. For aromatic molecules, the effect of this additional perturbation is significant.« less

New International Skeleton Tables for the Thermodynamic Properties of Ordinary Water Substance

NASA Astrophysics Data System (ADS)

Sato, H.; Uematsu, M.; Watanabe, K.; Saul, A.; Wagner, W.

1988-10-01

The current knowledge of thermodynamic properties of ordinary water substance is summarized in a condensed form of a set of skeleton steam tables, where the most probable values with the reliabilities on specific volume and enthalpy are provided in the range of temperatures from 273 to 1073 K and pressures from 101.325 kPa to 1 GPa and at the saturation state from the triple point to the critical point. These tables have been accepted as the IAPS Skeleton Tables 1985 for the Thermodynamic Properties of Ordinary Water Substance(IST-85) by the International Association for the Properties of Steam(IAPS). The former International Skeleton Steam Tables, October 1963(IST-63), have been withdrawn by IAPS. About 17 000 experimental thermodynamic data were assessed and classified previously by Working Group 1 of IAPS. About 10 000 experimental data were collected and evaluated in detail and especially about 7000 specific-volume data among them were critically analyzed with respect to their errors using the statistical method originally developed at Keio University by the first three authors. As a result, specific-volume and enthalpy values with associated reliabilities were determined at 1455 grid points of 24 isotherms and 61 isobars in the single-fluid phase state and at 54 temperatures along the saturation curve. The background, analytical procedure, and reliability of IST-85 as well as the assessment of the existing experimental data and equations of state are also discussed in this paper.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivak, David; Crooks, Gavin

A fundamental problem in modern thermodynamics is how a molecular-scale machine performs useful work, while operating away from thermal equilibrium without excessive dissipation. To this end, we derive a friction tensor that induces a Riemannian manifold on the space of thermodynamic states. Within the linear-response regime, this metric structure controls the dissipation of finite-time transformations, and bestows optimal protocols with many useful properties. We discuss the connection to the existing thermodynamic length formalism, and demonstrate the utility of this metric by solving for optimal control parameter protocols in a simple nonequilibrium model.

Black Hole Thermodynamics and Lorentz Symmetry

NASA Astrophysics Data System (ADS)

Jacobson, Ted; Wall, Aron C.

2010-08-01

Recent developments point to a breakdown in the generalized second law of thermodynamics for theories with Lorentz symmetry violation. It appears possible to construct a perpetual motion machine of the second kind in such theories, using a black hole to catalyze the conversion of heat to work. Here we describe and extend the arguments leading to that conclusion. We suggest the inference that local Lorentz symmetry may be an emergent property of the macroscopic world with origins in a microscopic second law of causal horizon thermodynamics.

Black hole thermodynamics

NASA Astrophysics Data System (ADS)

Carlip, S.

2014-10-01

The discovery in the early 1970s that black holes radiate as black bodies has radically affected our understanding of general relativity, and offered us some early hints about the nature of quantum gravity. In this paper, will review the discovery of black hole thermodynamics and summarize the many independent ways of obtaining the thermodynamic and (perhaps) statistical mechanical properties of black holes. I will then describe some of the remaining puzzles, including the nature of the quantum microstates, the problem of universality, and the information loss paradox.

Neurobiology as Information Physics

PubMed Central

Street, Sterling

2016-01-01

This article reviews thermodynamic relationships in the brain in an attempt to consolidate current research in systems neuroscience. The present synthesis supports proposals that thermodynamic information in the brain can be quantified to an appreciable degree of objectivity, that many qualitative properties of information in systems of the brain can be inferred by observing changes in thermodynamic quantities, and that many features of the brain’s anatomy and architecture illustrate relatively simple information-energy relationships. The brain may provide a unique window into the relationship between energy and information. PMID:27895560

Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burgess, Samantha A.; Appel, Aaron M.; Linehan, John C.

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strongmore » organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

The thermodynamics of pyrochemical processes for liquid metal reactor fuel cycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, I.

1987-01-01

The thermodynamic basis for pyrochemical processes for the recovery and purification of fuel for the liquid metal reactor fuel cycle is described. These processes involve the transport of the uranium and plutonium from one liquid alloy to another through a molten salt. The processes discussed use liquid alloys of cadmium, zinc, and magnesium and molten chloride salts. The oxidation-reduction steps are done either chemically by the use of an auxiliary redox couple or electrochemically by the use of an external electrical supply. The same basic thermodynamics apply to both the salt transport and the electrotransport processes. Large deviations from idealmore » solution behavior of the actinides and lanthanides in the liquid alloys have a major influence on the solubilities and the performance of both the salt transport and electrotransport processes. Separation of plutonium and uranium from each other and decontamination from the more noble fission product elements can be achieved using both transport processes. The thermodynamic analysis is used to make process design computations for different process conditions.« less

Size-dependent pressure-induced amorphization: a thermodynamic panorama.

PubMed

Machon, Denis; Mélinon, Patrice

2015-01-14

Below a critical particle size, some pressurized compounds (e.g. TiO2, Y2O3, PbTe) undergo a crystal-to-amorphous transformation instead of a polymorphic transition. This effect reflects the greater propensity of nanomaterials for amorphization. In this work, a panorama of thermodynamic interpretations is given: first, a descriptive analysis based on the energy landscape concept gives a general comprehension of the balance between thermodynamics and kinetics to obtain an amorphous state. Then, a formal approach based on Gibbs energy to describe the thermodynamics and phase transitions in nanoparticles gives a basic explanation of size-dependent pressure-induced amorphization. The features of this transformation (amorphization occurs at pressures lower than the polymorphic transition pressure!) and the nanostructuration can be explained in an elaborated model based on the Ginzburg-Landau theory of phase transition and on percolation theory. It is shown that the crossover between polymorphic transition and amorphization is highly dependent on the defect density and interfacial energy, i.e., on the synthesis process. Their behavior at high pressure is a quality control test for the nanoparticles.

CTserver: A Computational Thermodynamics Server for the Geoscience Community

NASA Astrophysics Data System (ADS)

Kress, V. C.; Ghiorso, M. S.

2006-12-01

The CTserver platform is an Internet-based computational resource that provides on-demand services in Computational Thermodynamics (CT) to a diverse geoscience user base. This NSF-supported resource can be accessed at ctserver.ofm-research.org. The CTserver infrastructure leverages a high-quality and rigorously tested software library of routines for computing equilibrium phase assemblages and for evaluating internally consistent thermodynamic properties of materials, e.g. mineral solid solutions and a variety of geological fluids, including magmas. Thermodynamic models are currently available for 167 phases. Recent additions include Duan, Møller and Weare's model for supercritical C-O-H-S, extended to include SO2 and S2 species, and an entirely new associated solution model for O-S-Fe-Ni sulfide liquids. This software library is accessed via the CORBA Internet protocol for client-server communication. CORBA provides a standardized, object-oriented, language and platform independent, fast, low-bandwidth interface to phase property modules running on the server cluster. Network transport, language translation and resource allocation are handled by the CORBA interface. Users access server functionality in two principal ways. Clients written as browser- based Java applets may be downloaded which provide specific functionality such as retrieval of thermodynamic properties of phases, computation of phase equilibria for systems of specified composition, or modeling the evolution of these systems along some particular reaction path. This level of user interaction requires minimal programming effort and is ideal for classroom use. A more universal and flexible mode of CTserver access involves making remote procedure calls from user programs directly to the server public interface. The CTserver infrastructure relieves the user of the burden of implementing and testing the often complex thermodynamic models of real liquids and solids. A pilot application of this distributed architecture involves CFD computation of magma convection at Volcan Villarrica with magma properties and phase proportions calculated at each spatial node and at each time step via distributed function calls to MELTS-objects executing on the CTserver. Documentation and programming examples are provided at http://ctserver.ofm- research.org.

Binding thermodynamics discriminates fragments from druglike compounds: a thermodynamic description of fragment-based drug discovery.

PubMed

Williams, Glyn; Ferenczy, György G; Ulander, Johan; Keserű, György M

2017-04-01

Small is beautiful - reducing the size and complexity of chemical starting points for drug design allows better sampling of chemical space, reveals the most energetically important interactions within protein-binding sites and can lead to improvements in the physicochemical properties of the final drug. The impact of fragment-based drug discovery (FBDD) on recent drug discovery projects and our improved knowledge of the structural and thermodynamic details of ligand binding has prompted us to explore the relationships between ligand-binding thermodynamics and FBDD. Information on binding thermodynamics can give insights into the contributions to protein-ligand interactions and could therefore be used to prioritise compounds with a high degree of specificity in forming key interactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dilatonic BTZ black holes with power-law field

NASA Astrophysics Data System (ADS)

Hendi, S. H.; Eslam Panah, B.; Panahiyan, S.; Sheykhi, A.

2017-04-01

Motivated by low energy effective action of string theory and numerous applications of BTZ black holes, we will consider minimal coupling between dilaton and nonlinear electromagnetic fields in three dimensions. The main goal is studying thermodynamical structure of black holes in this set up. Temperature and heat capacity of these black holes are investigated and a picture regarding their phase transitions is given. In addition, the role and importance of studying the mass of black holes is highlighted. We will see how different parameters modify thermodynamical quantities, hence thermodynamical structure of these black holes. In addition, geometrical thermodynamics is used to investigate thermodynamical properties of these black holes. In this regard, the successful method is presented and the nature of interaction around bound and phase transition points is studied.

Critical evaluation and thermodynamic optimization of the Iron-Rare-Earth systems

NASA Astrophysics Data System (ADS)

Konar, Bikram

Rare-Earth elements by virtue of its typical magnetic, electronic and chemical properties are gaining importance in power, electronics, telecommunications and sustainable green technology related industries. The Magnets from RE-alloys are more powerful than conventional magnets which have more longevity and high temperature workability. The dis-equilibrium in the Rare-Earth element supply and demand has increased the importance of recycling and extraction of REE's from used permanent Magnets. However, lack of the thermodynamic data on RE alloys has made it difficult to design an effective extraction and recycling process. In this regard, Computational Thermodynamic calculations can serve as a cost effective and less time consuming tool to design a waste magnet recycling process. The most common RE permanent magnet is Nd magnet (Nd 2Fe14B). Various elements such as Dy, Tb, Pr, Cu, Co, Ni, etc. are also added to increase its magnetic and mechanical properties. In order to perform reliable thermodynamic calculations for the RE recycling process, accurate thermodynamic database for RE and related alloys are required. The thermodynamic database can be developed using the so-called CALPHAD method. The database development based on the CALPHAD method is essentially the critical evaluation and optimization of all available thermodynamic and phase diagram data. As a results, one set of self-consistent thermodynamic functions for all phases in the given system can be obtained, which can reproduce all reliable thermodynamic and phase diagram data. The database containing the optimized Gibbs energy functions can be used to calculate complex chemical reactions for any high temperature processes. Typically a Gibbs energy minimization routine, such as in FactSage software, can be used to obtain the accurate thermodynamic equilibrium in multicomponent systems. As part of a large thermodynamic database development for permanent magnet recycling and Mg alloy design, all thermodynamic and phase diagram data in the literature for the fourteen Fe-RE binary systems: Fe-La, Fe-Ce, Fe-Pr, Fe-Nd, Fe-Sm, Fe-Gd, Fe-Tb, Fe-Dy, Fe-Ho, Fe-Er, Fe-Tm, Fe-Lu, Fe-Sc and Fe-Y are critically evaluated and optimized to obtain thermodynamic model parameters. The model parameters can be used to calculate phase diagrams and Gibbs energies of all phases as functions of temperature and composition. This database can be incorporated with the present thermodynamic database in FactSage software to perform complex chemical reactions and phase diagram calculations for RE magnet recycling process.

Second virial coefficient of starch

NASA Astrophysics Data System (ADS)

Wohlfarth, Ch.

This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.

A study of the applicability of nucleation theory to quasi-thermodynamic transitions of second and higher Ehrenfest-order

NASA Technical Reports Server (NTRS)

Barker, R. E., Jr.; Campbell, K. W.

1985-01-01

The applicability of classical nucleation theory to second (and higher) order thermodynamic transitions in the Ehrenfest sense has been investigated and expressions have been derived upon which the qualitative and quantitative success of the basic approach must ultimately depend. The expressions describe the effect of temperature undercooling, hydrostatic pressure, and tensile stress upon the critical parameters, the critical nucleus size, and critical free energy barrier, for nucleation in a thermodynamic transition of any general order. These expressions are then specialized for the case of first and second order transitions. The expressions for the case of undercooling are then used in conjunction with literature data to estimate values for the critical quantities in a system undergoing a pseudo-second order transition (the glass transition in polystyrene). Methods of estimating the interfacial energy gamma in systems undergoing a first and second order transition are also discussed.

Entropy bounds in terms of the w parameter

NASA Astrophysics Data System (ADS)

Abreu, Gabriel; Barceló, Carlos; Visser, Matt

2011-12-01

In a pair of recent articles [PRL 105 (2010) 041302; JHEP 1103 (2011) 056] two of the current authors have developed an entropy bound for equilibrium uncollapsed matter using only classical general relativity, basic thermodynamics, and the Unruh effect. An odd feature of that bound, [InlineMediaObject not available: see fulltext.], was that the proportionality constant, 1/2 , was weaker than that expected from black hole thermodynamics, 1/4 . In the current article we strengthen the previous results by obtaining a bound involving the (suitably averaged) w parameter. Simple causality arguments restrict this averaged < w> parameter to be ≤ 1. When equality holds, the entropy bound saturates at the value expected based on black hole thermodynamics. We also add some clarifying comments regarding the (net) positivity of the chemical potential. Overall, we find that even in the absence of any black hole region, we can nevertheless get arbitrarily close to the Bekenstein entropy.

Adsorption behavior of benzenesulfonic acid by novel weakly basic anion exchange resins.

PubMed

Sun, Yue; Zuo, Peng; Luo, Junfen; Singh, Rajendra Prasad

2017-04-01

Two novel weakly basic anion exchange resins (SZ-1 and SZ-2) were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene (Cl-PS-DVB) beads with dicyclohexylamine and piperidine, respectively. The physicochemical structures of the resulting resins were characterized using Fourier Transform Infrared Spectroscopy and pore size distribution analysis. The adsorption behavior of SZ-1 and SZ-2 for benzenesulfonic acid (BA) was evaluated, and the common commercial weakly basic anion exchanger D301 was also employed for comparison purpose. Adsorption isotherms and influence of solution pH, temperature and coexisting competitive inorganic salts (Na 2 SO 4 and NaCl) on adsorption behavior were investigated and the optimum desorption agent was obtained. Adsorption isotherms of BA were found to be well represented by the Langmuir model. Thermodynamic parameters involving ΔH, ΔG and ΔS were also calculated and the results indicate that adsorption is an exothermic and spontaneous process. Enhanced selectivity of BA sorption over sulfate on the two novel resins was observed by comparison with the commercial anion exchanger D301. The fact that the tested resins loaded with BA can be efficiently regenerated by NaCl solution indicates the reversible sorption process. From a mechanistic viewpoint, this observation clearly suggests that electrostatic interaction is the predominant adsorption mechanism. Furthermore, results of column tests show that SZ-1 possesses a better adsorption property than D301, which reinforces the feasibility of SZ-1 for potential industrial application. Copyright © 2016. Published by Elsevier B.V.

First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Karl Johnson

The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. Newmore » materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.« less

Density Functional Methods for Shock Physics and High Energy Density Science

NASA Astrophysics Data System (ADS)

Desjarlais, Michael

2017-06-01

Molecular dynamics with density functional theory has emerged over the last two decades as a powerful and accurate framework for calculating thermodynamic and transport properties with broad application to dynamic compression, high energy density science, and warm dense matter. These calculations have been extensively validated against shock and ramp wave experiments, are a principal component of high-fidelity equation of state generation, and are having wide-ranging impacts on inertial confinement fusion, planetary science, and shock physics research. In addition to thermodynamic properties, phase boundaries, and the equation of state, one also has access to electrical conductivity, thermal conductivity, and lower energy optical properties. Importantly, all these properties are obtained within the same theoretical framework and are manifestly consistent. In this talk I will give a brief history and overview of molecular dynamics with density functional theory and its use in calculating a wide variety of thermodynamic and transport properties for materials ranging from ambient to extreme conditions and with comparisons to experimental data. I will also discuss some of the limitations and difficulties, as well as active research areas. Sandia is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Thermodynamic limit for coherence-limited solar power conversion

NASA Astrophysics Data System (ADS)

Mashaal, Heylal; Gordon, Jeffrey M.

2014-09-01

The spatial coherence of solar beam radiation is a key constraint in solar rectenna conversion. Here, we present a derivation of the thermodynamic limit for coherence-limited solar power conversion - an expansion of Landsberg's elegant basic bound, originally limited to incoherent converters at maximum flux concentration. First, we generalize Landsberg's work to arbitrary concentration and angular confinement. Then we derive how the values are further lowered for coherence-limited converters. The results do not depend on a particular conversion strategy. As such, they pertain to systems that span geometric to physical optics, as well as classical to quantum physics. Our findings indicate promising potential for solar rectenna conversion.

Thermodynamics of nuclear track chemical etching

NASA Astrophysics Data System (ADS)

Rana, Mukhtar Ahmed

2018-05-01

This is a brief paper with new and useful scientific information on nuclear track chemical etching. Nuclear track etching is described here by using basic concepts of thermodynamics. Enthalpy, entropy and free energy parameters are considered for the nuclear track etching. The free energy of etching is determined using etching experiments of fission fragment tracks in CR-39. Relationship between the free energy and the etching temperature is explored and is found to be approximately linear. The above relationship is discussed. A simple enthalpy-entropy model of chemical etching is presented. Experimental and computational results presented here are of fundamental interest in nuclear track detection methodology.

A Thermodynamic Theory of Solid Viscoelasticity. Part 3: Nonlinear Glassy Viscoelasticity, Stability Constraints, Specifications

NASA Technical Reports Server (NTRS)

Freed, Alan; Leonov, Arkady I.

2002-01-01

This paper, the last in the series, continues developing the nonlinear constitutive relations for non-isothermal, compressible, solid viscoelasticity. We initially discuss a single integral approach, more suitable for the glassy state of rubber-like materials, with basic functionals involved in the thermodynamic description for this type of viscoelasticity. Then we switch our attention to analyzing stability constraints, imposed on the general formulation of the nonlinear theory of solid viscoelasticity. Finally, we discuss specific (known from the literature or new) expressions for material functions that are involved in the constitutive formulations of both the rubber-like and glassy-like, complementary parts of the theory.