The NASA Marshall Space Flight Center Earth Global Reference Atmospheric Model-2010 Version

NASA Technical Reports Server (NTRS)

Leslie, F. W.; Justus, C. G.

2011-01-01

Reference or standard atmospheric models have long been used for design and mission planning of various aerospace systems. The NASA Marshall Space Flight Center Global Reference Atmospheric Model was developed in response to the need for a design reference atmosphere that provides complete global geographical variability and complete altitude coverage (surface to orbital altitudes), as well as complete seasonal and monthly variability of the thermodynamic variables and wind components. In addition to providing the geographical, height, and monthly variation of the mean atmospheric state, it includes the ability to simulate spatial and temporal perturbations.

Modeling the complete Otto cycle: Preliminary version. [computer programming

NASA Technical Reports Server (NTRS)

Zeleznik, F. J.; Mcbride, B. J.

1977-01-01

A description is given of the equations and the computer program being developed to model the complete Otto cycle. The program incorporates such important features as: (1) heat transfer, (2) finite combustion rates, (3) complete chemical kinetics in the burned gas, (4) exhaust gas recirculation, and (5) manifold vacuum or supercharging. Changes in thermodynamic, kinetic and transport data as well as model parameters can be made without reprogramming. Preliminary calculations indicate that: (1) chemistry and heat transfer significantly affect composition and performance, (2) there seems to be a strong interaction among model parameters, and (3) a number of cycles must be calculated in order to obtain steady-state conditions.

Pi-CO₂ aqueous post-combustion CO₂ capture: Proof of concept through thermodynamic, hydrodynamic, and gas-lift pump modeling

DOE PAGES

Blount, G.; Gorensek, M.; Hamm, L.; ...

2014-12-31

Partnering in Innovation, Inc. (Pi-Innovation) introduces an aqueous post-combustion carbon dioxide (CO₂) capture system (Pi-CO₂) that offers high market value by directly addressing the primary constraints limiting beneficial re-use markets (lowering parasitic energy costs, reducing delivered cost of capture, eliminating the need for special solvents, etc.). A highly experienced team has completed initial design, modeling, manufacturing verification, and financial analysis for commercial market entry. Coupled thermodynamic and thermal-hydraulic mass transfer modeling results fully support proof of concept. Pi-CO₂ has the potential to lower total cost and risk to levels sufficient to stimulate global demand for CO₂ from local industrial sources.

Important aspects in the formulation of solid-fluid debris-flow models. Part I. Thermodynamic implications

NASA Astrophysics Data System (ADS)

Hutter, Kolumban; Schneider, Lukas

2010-06-01

This article points at some critical issues which are connected with the theoretical formulation of the thermodynamics of solid-fluid mixtures of frictional materials. It is our view that a complete thermodynamic exploitation of the second law of thermodynamics is necessary to obtain the proper parameterizations of the constitutive quantities in such theories. These issues are explained in detail in a recently published book by Schneider and Hutter (Solid-Fluid Mixtures of Frictional Materials in Geophysical and Geotechnical Context, 2009), which we wish to advertize with these notes. The model is a saturated mixture of an arbitrary number of solid and fluid constituents which may be compressible or density preserving, which exhibit visco-frictional (visco-hypoplastic) behavior, but are all subject to the same temperature. Mass exchange between the constituents may account for particle size separation and phase changes due to fragmentation and abrasion. Destabilization of a saturated soil mass from the pre- and the post-critical phases of a catastrophic motion from initiation to deposition is modeled by symmetric tensorial variables which are related to the rate independent parts of the constituent stress tensors.

Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

PubMed

Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

2015-05-07

Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

Developpement de techniques numeriques pour l'estimation, la modelisation et la prediction de proprietes thermodynamiques et structurales de systems metalliques a fort ordonnancement chimique

NASA Astrophysics Data System (ADS)

Harvey, Jean-Philippe

In this work, the possibility to calculate and evaluate with a high degree of precision the Gibbs energy of complex multiphase equilibria for which chemical ordering is explicitly and simultaneously considered in the thermodynamic description of solid (short range order and long range order) and liquid (short range order) metallic phases is studied. The cluster site approximation (CSA) and the cluster variation method (CVM) are implemented in a new minimization technique of the Gibbs energy of multicomponent and multiphase systems to describe the thermodynamic behaviour of metallic solid solutions showing strong chemical ordering. The modified quasichemical model in the pair approximation (MQMPA) is also implemented in the new minimization algorithm presented in this work to describe the thermodynamic behaviour of metallic liquid solutions. The constrained minimization technique implemented in this work consists of a sequential quadratic programming technique based on an exact Newton’s method (i.e. the use of exact second derivatives in the determination of the Hessian of the objective function) combined to a line search method to identify a direction of sufficient decrease of the merit function. The implementation of a new algorithm to perform the constrained minimization of the Gibbs energy is justified by the difficulty to identify, in specific cases, the correct multiphase assemblage of a system where the thermodynamic behaviour of the equilibrium phases is described by one of the previously quoted models using the FactSage software (ex.: solid_CSA+liquid_MQMPA; solid1_CSA+solid2_CSA). After a rigorous validation of the constrained Gibbs energy minimization algorithm using several assessed binary and ternary systems found in the literature, the CVM and the CSA models used to describe the energetic behaviour of metallic solid solutions present in systems with key industrial applications such as the Cu-Zr and the Al-Zr systems are parameterized using fully consistent thermodynamic an structural data generated from a Monte Carlo (MC) simulator also implemented in the framework of this project. In this MC simulator, the modified embedded atom model in the second nearest neighbour formalism (MEAM-2NN) is used to describe the cohesive energy of each studied structure. A new Al-Zr MEAM-2NN interatomic potential needed to evaluate the cohesive energy of the condensed phases of this system is presented in this work. The thermodynamic integration (TI) method implemented in the MC simulator allows the evaluation of the absolute Gibbs energy of the considered solid or liquid structures. The original implementation of the TI method allowed us to evaluate theoretically for the first time all the thermodynamic mixing contributions (i.e., mixing enthalpy and mixing entropy contributions) of a metallic liquid (Cu-Zr and Al-Zr) and of a solid solution (face-centered cubic (FCC) Al-Zr solid solution) described by the MEAM-2NN. Thermodynamic and structural data obtained from MC and molecular dynamic simulations are then used to parameterize the CVM for the Al-Zr FCC solid solution and the MQMPA for the Al-Zr and the Cu-Zr liquid phase respectively. The extended thermodynamic study of these systems allow the introduction of a new type of configuration-dependent excess parameters in the definition of the thermodynamic function of solid solutions described by the CVM or the CSA. These parameters greatly improve the precision of these thermodynamic models based on experimental evidences found in the literature. A new parameterization approach of the MQMPA model of metallic liquid solutions is presented throughout this work. In this new approach, calculated pair fractions obtained from MC/MD simulations are taken into account as well as configuration-independent volumetric relaxation effects (regular like excess parameters) in order to parameterize precisely the Gibbs energy function of metallic melts. The generation of a complete set of fully consistent thermodynamic, physical and structural data for solid, liquid, and stoichiometric compounds and the subsequent parameterization of their respective thermodynamic model lead to the first description of the complete Al-Zr phase diagram in the range of composition [0 ≤ XZr ≤ 5 / 9] based on theoretical and fully consistent thermodynamic properties. MC and MD simulations are performed for the Al-Zr system to define for the first time the precise thermodynamic behaviour of the amorphous phase for its entire range of composition. Finally, all the thermodynamic models for the liquid phase, the FCC solid solution and the amorphous phase are used to define conditions based on thermodynamic and volumetric considerations that favor the amorphization of Al-Zr alloys.

Enthalpies of formation of Cd–Pr intermetallic compounds and thermodynamic assessment of the Cd–Pr system

PubMed Central

Reichmann, Thomas L.; Richter, Klaus W.; Delsante, Simona; Borzone, Gabriella; Ipser, Herbert

2014-01-01

In the present study standard enthalpies of formation were measured by reaction and solution calorimetry at stoichiometric compositions of Cd2Pr, Cd3Pr, Cd58Pr13 and Cd6Pr. The corresponding values were determined to be −46.0, −38.8, −35.2 and −24.7 kJ/mol(at), respectively. These data together with thermodynamic data and phase diagram information from literature served as input data for a CALPHAD-type optimization of the Cd–Pr phase diagram. The complete composition range could be described precisely with the present models, both with respect to phase equilibria as well as to thermodynamic input data. The thermodynamic parameters of all intermetallic compounds were modelled following Neumann–Kopp rule. Temperature dependent contributions to the individual Gibbs energies were used for all compounds. Extended solid solubilities are well described for the low- and high-temperature modifications of Pr and also for the intermetallic compound CdPr. A quite good agreement with all viable data available from literature was found and is presented. PMID:25540475

An Interface Damage Model for the Simulation of Delamination Under Variable-Mode Ratio in Composite Materials

NASA Technical Reports Server (NTRS)

Turon, Albert; Camanho, Pedro P.; Costa, Josep; Davila, Carlos G.

2004-01-01

A thermodynamically consistent damage model for the simulation of progressive delamination under variable mode ratio is presented. The model is formulated in the context of the Damage Mechanics (DM). The constitutive equations that result from the variation of the free energy with damage are used to model the initiation and propagation of delamination. A new delamination initiation criterion is developed to assure that the formulation can account for changes in the loading mode in a thermodynamically consistent way. Interfacial penetration of two adjacent layers after complete decohesion is prevented by the formulation of the free energy. The model is implemented into the commercial finite element code ABAQUS by means of a user-written decohesion element. Finally, the numerical predictions given by the model are compared with experimental results.

Thermodynamic Evaluation and Optimization of the MnO-B2O3 and MnO-B2O3-SiO2 Systems and Its Application to Oxidation of High-Strength Steels Containing Boron

NASA Astrophysics Data System (ADS)

Kim, Young-Min; Jung, In-Ho

2015-06-01

A complete literature review, critical evaluation, and thermodynamic optimization of phase equilibrium and thermodynamic properties of all available oxide phases in the MnO-B2O3 and MnO-B2O3-SiO2 systems at 1 bar pressure are presented. Due to the lack of the experimental data in these systems, the systematic trend of CaO- and MgO-containing systems were taken into account in the optimization. The molten oxide phase is described by the Modified Quasichemical Model. A set of optimized model parameters of all phases is obtained which reproduces all available and reliable thermodynamic and phase equilibrium data. The unexplored binary and ternary phase diagrams of the MnO-B2O3 and MnO-B2O3-SiO2 systems have been predicted for the first time. The thermodynamic calculations relevant to the oxidation of advanced high-strength steels containing boron were performed to find that B can form liquid B2O3-SiO2-rich phase in the annealing furnace under reducing N2-H2 atmosphere, which can significantly influence the wetting behavior of liquid Zn in Zn galvanizing process.

Penetrable square-well fluids: exact results in one dimension.

PubMed

Santos, Andrés; Fantoni, Riccardo; Giacometti, Achille

2008-05-01

We introduce a model of attractive penetrable spheres by adding a short-range attractive square well outside a penetrable core, and we provide a detailed analysis of structural and thermodynamical properties in one dimension using the exact impenetrable counterpart as a starting point. The model is expected to describe star polymers in regimes of good and moderate solvent under dilute conditions. We derive the exact coefficients of a low-density expansion up to second order for the radial distribution function and up to fourth order in the virial expansion. These exact results are used as a benchmark to test the reliability of approximate theories (Percus-Yevick and hypernetted chain). Notwithstanding the lack of an exact solution for arbitrary densities, our results are expected to be rather precise within a wide range of temperatures and densities. A detailed analysis of some limiting cases is carried out. In particular, we provide a complete solution of the sticky penetrable-sphere model in one dimension up to the same order in density. The issue of Ruelle's thermodynamics stability is analyzed and the region of a well-defined thermodynamic limit is identified.

Thermodynamic analysis of a new conception of supplementary firing in a combined cycle

NASA Astrophysics Data System (ADS)

Kotowicz, Janusz; Bartela, Łukasz; Balicki, Adrian

2010-10-01

The paper analyzes a new concept of integration of combined cycle with the installation of supplementary firing. The whole system was enclosed by thermodynamic analysis, which consists of a gas-steam unit with triple-pressure heat recovery steam generator. The system uses a determined model of the gas turbine and the assumptions relating to the construction features of steam-water part were made. The proposed conception involves building of supplementary firing installation only on part of the exhaust stream leaving the gas turbine. In the proposed solution superheater was divided into two sections, one of which was located on the exhaust gases leaving the installation of supplementary firing. The paper presents the results of the analyses of which the main aim was to demonstrate the superiority of the new thermodynamic concept of the supplementary firing over the classical one. For this purpose a model of a system was built, in which it was possible to carry out simulations of the gradual transition from a classically understood supplementary firing to the supplementary firing completely modified. For building of a model the GateCycle™ software was used.

Structure and thermodynamics of a mixture of patchy and spherical colloids: A multi-body association theory with complete reference fluid information

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

Bansal, Artee; Asthagiri, D.; Cox, Kenneth R.

A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures. Because of multi-body correlations, predicting the structure and thermodynamics of such systems remains a challenge. Earlier Marshall and Chapman [J. Chem. Phys. 139, 104904 (2013)] developed a theory wherein association effects due to interactions multiply the partition function for clustering of particles in a reference hard-sphere system. The multi-body effects are incorporated in the clustering process, which in their work was obtained in the absence of the bulk medium.more » The bulk solvent effects were then modeled approximately within a second order perturbation approach. However, their approach is inadequate at high densities and for large association strengths. Based on the idea that the clustering of solvent in a defined coordination volume around the solute is related to occupancy statistics in that defined coordination volume, we develop an approach to incorporate the complete information about hard-sphere clustering in a bulk solvent at the density of interest. The occupancy probabilities are obtained from enhanced sampling simulations but we also develop a concise parametric form to model these probabilities using the quasichemical theory of solutions. We show that incorporating the complete reference information results in an approach that can predict the bonding state and thermodynamics of the colloidal solute for a wide range of system conditions.« less

NASA Astrophysics Data System (ADS)

Bechetti, Daniel H.; DuPont, John N.; deBarbadillo, John J.; Baker, Brian A.

2014-06-01

Thermodynamic and kinetic modeling were used to determine appropriate heat treatment schedules for homogenization and second phase dissolution in INCONEL® alloy 740H® (INCONEL and 740H are registered trademarks of Special Metals Corporation) fusion welds. Following these simulations, a two-step heat treatment process was applied to specimens from a single pass gas tungsten arc weld (GTAW). Scanning electron microscopy (SEM) has been used to assess the changes in the distribution of alloying elements as well as changes in the fraction of second phase particles within the fusion zone. Experimental results demonstrate that adequate homogenization of alloy 740H weld metal can be achieved by a 1373 K/4 h (1100 °C/4 h) treatment. Complete dissolution of second phase particles could not be completely achieved, even at exposure to temperatures near the alloy's solidus temperature. These results are in good agreement with thermodynamic and kinetic predictions.

Isotherm-Based Thermodynamic Model for Solute Activities of Asymmetric Electrolyte Aqueous Solutions.

PubMed

Nandy, Lucy; Dutcher, Cari S

2017-09-21

Adsorption isotherm-based statistical thermodynamic models can be used to determine solute concentration and solute and solvent activities in aqueous solutions. Recently, the number of adjustable parameters in the isotherm model of Dutcher et al. J. Phys. Chem. A/C 2011, 2012, 2013 were reduced for neutral solutes as well as symmetric 1:1 electrolytes by using a Coulombic model to describe the solute-solvent energy interactions (Ohm et al. J. Phys. Chem. A 2015, Nandy et al. J. Phys. Chem. A 2016). Here, the Coulombic treatment for symmetric electrolytes is extended to establish improved isotherm model equations for asymmetric 1-2 and 1-3 electrolyte systems. The Coulombic model developed here results in prediction of activities and other thermodynamic properties in multicomponent systems containing ions of arbitrary charge. The model is found to accurately calculate the osmotic coefficient over the entire solute concentration range with two model parameters, related to intermolecular solute-solute and solute-solvent spacing. The inorganic salts and acids treated here are generally considered to be fully dissociated. However, there are certain weak acids that do not dissociate completely, such as the bisulfate ion. In this work, partial dissociation of the bisulfate ion from sulfuric acid is treated as a mixture, with an additional model parameter that accounts for the dissociation ratio of the dissociated ions to nondissociated ions.

Dissipative open systems theory as a foundation for the thermodynamics of linear systems.

PubMed

Delvenne, Jean-Charles; Sandberg, Henrik

2017-03-06

In this paper, we advocate the use of open dynamical systems, i.e. systems sharing input and output variables with their environment, and the dissipativity theory initiated by Jan Willems as models of thermodynamical systems, at the microscopic and macroscopic level alike. We take linear systems as a study case, where we show how to derive a global Lyapunov function to analyse networks of interconnected systems. We define a suitable notion of dynamic non-equilibrium temperature that allows us to derive a discrete Fourier law ruling the exchange of heat between lumped, discrete-space systems, enriched with the Maxwell-Cattaneo correction. We complete these results by a brief recall of the steps that allow complete derivation of the dissipation and fluctuation in macroscopic systems (i.e. at the level of probability distributions) from lossless and deterministic systems.This article is part of the themed issue 'Horizons of cybernetical physics'. © 2017 The Author(s).

Protonation linked equilibria and apparent affinity constants: the thermodynamic profile of the alpha-chymotrypsin-proflavin interaction.

PubMed

Bruylants, Gilles; Wintjens, René; Looze, Yvan; Redfield, Christina; Bartik, Kristin

2007-12-01

Protonation/deprotonation equilibria are frequently linked to binding processes involving proteins. The presence of these thermodynamically linked equilibria affects the observable thermodynamic parameters of the interaction (K(obs), DeltaH(obs)(0) ). In order to try and elucidate the energetic factors that govern these binding processes, a complete thermodynamic characterisation of each intrinsic equilibrium linked to the complexation event is needed and should furthermore be correlated to structural information. We present here a detailed study, using NMR and ITC, of the interaction between alpha-chymotrypsin and one of its competitive inhibitors, proflavin. By performing proflavin titrations of the enzyme, at different pH values, we were able to highlight by NMR the effect of the complexation of the inhibitor on the ionisable residues of the catalytic triad of the enzyme. Using ITC we determined the intrinsic thermodynamic parameters of the different equilibria linked to the binding process. The possible driving forces of the interaction between alpha-chymotrypsin and proflavin are discussed in the light of the experimental data and on the basis of a model of the complex. This study emphasises the complementarities between ITC and NMR for the study of binding processes involving protonation/deprotonation equilibria.

Mixed Spin-1/2 and Spin-5/2 Model by Renormalization Group Theory: Recursion Equations and Thermodynamic Study

NASA Astrophysics Data System (ADS)

Antari, A. El; Zahir, H.; Hasnaoui, A.; Hachem, N.; Alrajhi, A.; Madani, M.; Bouziani, M. El

2018-04-01

Using the renormalization group approximation, specifically the Migdal-Kadanoff technique, we investigate the Blume-Capel model with mixed spins S = 1/2 and S = 5/2 on d-dimensional hypercubic lattice. The flow in the parameter space of the Hamiltonian and the thermodynamic functions are determined. The phase diagram of this model is plotted in the (anisotropy, temperature) plane for both cases d = 2 and d = 3 in which the system exhibits the first and second order phase transitions and critical end-points. The associated fixed points are drawn up in a table, and by linearizing the transformation at the vicinity of these points, we determine the critical exponents for d = 2 and d = 3. We have also presented a variation of the free energy derivative at the vicinity of the first and second order transitions. Finally, this work is completed by a discussion and comparison with other approximation.

Coevolving complex networks in the model of social interactions

NASA Astrophysics Data System (ADS)

Raducha, Tomasz; Gubiec, Tomasz

2017-04-01

We analyze Axelrod's model of social interactions on coevolving complex networks. We introduce four extensions with different mechanisms of edge rewiring. The models are intended to catch two kinds of interactions-preferential attachment, which can be observed in scientists or actors collaborations, and local rewiring, which can be observed in friendship formation in everyday relations. Numerical simulations show that proposed dynamics can lead to the power-law distribution of nodes' degree and high value of the clustering coefficient, while still retaining the small-world effect in three models. All models are characterized by two phase transitions of a different nature. In case of local rewiring we obtain order-disorder discontinuous phase transition even in the thermodynamic limit, while in case of long-distance switching discontinuity disappears in the thermodynamic limit, leaving one continuous phase transition. In addition, we discover a new and universal characteristic of the second transition point-an abrupt increase of the clustering coefficient, due to formation of many small complete subgraphs inside the network.

Long-range interacting systems in the unconstrained ensemble.

PubMed

Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

2017-01-01

Completely open systems can exchange heat, work, and matter with the environment. While energy, volume, and number of particles fluctuate under completely open conditions, the equilibrium states of the system, if they exist, can be specified using the temperature, pressure, and chemical potential as control parameters. The unconstrained ensemble is the statistical ensemble describing completely open systems and the replica energy is the appropriate free energy for these control parameters from which the thermodynamics must be derived. It turns out that macroscopic systems with short-range interactions cannot attain equilibrium configurations in the unconstrained ensemble, since temperature, pressure, and chemical potential cannot be taken as a set of independent variables in this case. In contrast, we show that systems with long-range interactions can reach states of thermodynamic equilibrium in the unconstrained ensemble. To illustrate this fact, we consider a modification of the Thirring model and compare the unconstrained ensemble with the canonical and grand-canonical ones: The more the ensemble is constrained by fixing the volume or number of particles, the larger the space of parameters defining the equilibrium configurations.

Association effects in the {methanol + inert solvent} system via Monte Carlo simulations. II. Thermodynamics

NASA Astrophysics Data System (ADS)

Gómez-Álvarez, Paula; Romaní, Luis; González-Salgado, Diego

2013-05-01

Mixtures containing associated substances show a singular thermodynamic behaviour that has attracted to scientific community during the last century. Particularly, binary systems composed of an associating fluid and an inert solvent, where association occurs only between molecules of the same kind, have been extensively studied. A number of theoretical approaches were used in order to gain insights into the effect of the association on the macroscopic behaviour, especially on the second-order thermodynamic derivatives (or response functions). Curiously, to our knowledge, molecular simulations have not been used to that end despite describing the molecules and their interactions in a more complete and realistic way than theoretical models. With this in mind, a simple methodology developed in the framework of Monte Carlo molecular simulation is used in this work to quantify the association contribution to a wide set of thermodynamic properties for the {methanol + Lennard Jones} specific system under room conditions and throughout the composition range. Special attention was paid to the response functions and their respective excess properties, for which a detailed comparison with selected previous works in the field has been established.

A new general model for predicting melting thermodynamics of complementary and mismatched B-form duplexes containing locked nucleic acids: application to probe design for digital PCR detection of somatic mutations.

PubMed

Hughesman, Curtis; Fakhfakh, Kareem; Bidshahri, Roza; Lund, H Louise; Haynes, Charles

2015-02-17

Advances in real-time polymerase chain reaction (PCR), as well as the emergence of digital PCR (dPCR) and useful modified nucleotide chemistries, including locked nucleic acids (LNAs), have created the potential to improve and expand clinical applications of PCR through their ability to better quantify and differentiate amplification products, but fully realizing this potential will require robust methods for designing dual-labeled hydrolysis probes and predicting their hybridization thermodynamics as a function of their sequence, chemistry, and template complementarity. We present here a nearest-neighbor thermodynamic model that accurately predicts the melting thermodynamics of a short oligonucleotide duplexed either to its perfect complement or to a template containing mismatched base pairs. The model may be applied to pure-DNA duplexes or to duplexes for which one strand contains any number and pattern of LNA substitutions. Perturbations to duplex stability arising from mismatched DNA:DNA or LNA:DNA base pairs are treated at the Gibbs energy level to maintain statistical significance in the regressed model parameters. This approach, when combined with the model's accounting of the temperature dependencies of the melting enthalpy and entropy, permits accurate prediction of T(m) values for pure-DNA homoduplexes or LNA-substituted heteroduplexes containing one or two independent mismatched base pairs. Terms accounting for changes in solution conditions and terminal addition of fluorescent dyes and quenchers are then introduced so that the model may be used to accurately predict and thereby tailor the T(m) of a pure-DNA or LNA-substituted hydrolysis probe when duplexed either to its perfect-match template or to a template harboring a noncomplementary base. The model, which builds on classic nearest-neighbor thermodynamics, should therefore be of use to clinicians and biologists who require probes that distinguish and quantify two closely related alleles in either a quantitative PCR or dPCR assay. This potential is demonstrated by using the model to design allele-specific probes that completely discriminate and quantify clinically relevant mutant alleles (BRAF V600E and KIT D816V) in a dPCR assay.

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.

Protein thin film machines

NASA Astrophysics Data System (ADS)

Federici, Stefania; Oliviero, Giulio; Hamad-Schifferli, Kimberly; Bergese, Paolo

2010-12-01

We report the first example of microcantilever beams that are reversibly driven by protein thin film machines fuelled by cycling the salt concentration of the surrounding solution. We also show that upon the same salinity stimulus the drive can be completely reversed in its direction by introducing a surface coating ligand. Experimental results are throughout discussed within a general yet simple thermodynamic model.

A model for the latent heat of melting in free standing metal nanoparticles

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

Shin, Jeong-Heon; Deinert, Mark R., E-mail: mdeinert@mail.utexas.edu

2014-04-28

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

A model for the latent heat of melting in free standing metal nanoparticles

NASA Astrophysics Data System (ADS)

Shin, Jeong-Heon; Deinert, Mark R.

2014-04-01

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

A model for the latent heat of melting in free standing metal nanoparticles.

PubMed

Shin, Jeong-Heon; Deinert, Mark R

2014-04-28

Nanoparticles of many metals are known to exhibit scale dependent latent heats of melting. Analytical models for this phenomenon have so far failed to completely capture the observed phenomena. Here we present a thermodynamic analysis for the melting of metal nanoparticles in terms of their internal energy and a scale dependent surface tension proposed by Tolman. The resulting model predicts the scale dependence of the latent heat of melting and is confirmed using published data for tin and aluminum.

AntiJen: a quantitative immunology database integrating functional, thermodynamic, kinetic, biophysical, and cellular data

PubMed Central

Toseland, Christopher P; Clayton, Debra J; McSparron, Helen; Hemsley, Shelley L; Blythe, Martin J; Paine, Kelly; Doytchinova, Irini A; Guan, Pingping; Hattotuwagama, Channa K; Flower, Darren R

2005-01-01

AntiJen is a database system focused on the integration of kinetic, thermodynamic, functional, and cellular data within the context of immunology and vaccinology. Compared to its progenitor JenPep, the interface has been completely rewritten and redesigned and now offers a wider variety of search methods, including a nucleotide and a peptide BLAST search. In terms of data archived, AntiJen has a richer and more complete breadth, depth, and scope, and this has seen the database increase to over 31,000 entries. AntiJen provides the most complete and up-to-date dataset of its kind. While AntiJen v2.0 retains a focus on both T cell and B cell epitopes, its greatest novelty is the archiving of continuous quantitative data on a variety of immunological molecular interactions. This includes thermodynamic and kinetic measures of peptide binding to TAP and the Major Histocompatibility Complex (MHC), peptide-MHC complexes binding to T cell receptors, antibodies binding to protein antigens and general immunological protein-protein interactions. The database also contains quantitative specificity data from position-specific peptide libraries and biophysical data, in the form of diffusion co-efficients and cell surface copy numbers, on MHCs and other immunological molecules. The uses of AntiJen include the design of vaccines and diagnostics, such as tetramers, and other laboratory reagents, as well as helping parameterize the bioinformatic or mathematical in silico modeling of the immune system. The database is accessible from the URL: . PMID:16305757

Modeling of Shock Waves with Multiple Phase Transitions in Condensed Materials

NASA Astrophysics Data System (ADS)

Missonnier, Marc; Heuzé, Olivier

2006-07-01

When a shock wave crosses a solid material and subjects it to solid-solid or solid-liquid phase transition, related phenomena occur: shock splitting, and the corresponding released shock wave after reflection. Modelling of these phenomena raises physical and numerical issues. After shock loading, such materials can reach different kinds of states: single-phase states, binary-phase states, and triple points. The thermodynamic path can be studied and easily understood in the (V,E) or (V,S) planes. In the case of 3 phase tin (β,γ, and liquid) submitted to shock waves, seven states can occur: β,γ, liquid, β-γ, β-liquid, γ-liquid, and β-γ-liquid. After studying the thermodynamic properties with a complete 3-phase Equation of State, we show the existence of these seven states with a hydrodynamic simulation.

Thermodynamically consistent model calibration in chemical kinetics

PubMed Central

2011-01-01

Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC) method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints) into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new models. Furthermore, TCMC can provide dimensionality reduction, better estimation performance, and lower computational complexity, and can help to alleviate the problem of data overfitting. PMID:21548948

Analysis of the thermodynamics of binding of an SH3 domain to proline-rich peptides using a chimeric fusion protein.

PubMed

Candel, Adela M; van Nuland, Nico A J; Martin-Sierra, Francisco M; Martinez, Jose C; Conejero-Lara, Francisco

2008-03-14

A complete understanding of the thermodynamic determinants of binding between SH3 domains and proline-rich peptides is crucial to the development of rational strategies for designing ligands for these important domains. Recently we engineered a single-chain chimeric protein by fusing the alpha-spectrin Src homology region 3 (SH3) domain to the decapeptide APSYSPPPPP (p41). This chimera mimics the structural and energetic features of the interaction between SH3 domains and proline-rich peptides. Here we show that analysing the unfolding thermodynamics of single-point mutants of this chimeric fusion protein constitutes a very useful approach to deciphering the thermodynamics of SH3-ligand interactions. To this end, we investigated the contribution of each proline residue of the ligand sequence to the SH3-peptide interaction by producing six single Pro-Ala mutants of the chimeric protein and analysing their unfolding thermodynamics by differential scanning calorimetry (DSC). Structural analyses of the mutant chimeras by circular dichroism, fluorescence and NMR together with NMR-relaxation measurements indicate conformational flexibility at the binding interface, which is strongly affected by the different Pro-Ala mutations. An analysis of the DSC thermograms on the basis of a three-state unfolding model has allowed us to distinguish and separate the thermodynamic magnitudes of the interaction at the binding interface. The model assumes equilibrium between the "unbound" and "bound" states at the SH3-peptide binding interface. The resulting thermodynamic magnitudes classify the different proline residues according to their importance in the interaction as P2 approximately P7 approximately P10>P9 approximately P6>P8, which agrees well with Lim's model for the interaction between SH3 domains and proline-rich peptides. In addition, the thermodynamic signature of the interaction is the same as that usually found for this type of binding, with a strong enthalpy-entropy compensation for all the mutants. This compensation appears to derive from an increase in conformational flexibility concomitant to the weakening of the interactions at the binding interface. We conclude that our approach, based on DSC and site-directed mutagenesis analysis of chimeric fusion proteins, may serve as a suitable tool to analyse the energetics of weak biomolecular interactions such as those involving SH3 domains.

Solvation Thermodynamics of Oligoglycine with Respect to Chain Length and Flexibility.

PubMed

Drake, Justin A; Harris, Robert C; Pettitt, B Montgomery

2016-08-23

Oligoglycine is a backbone mimic for all proteins and is prevalent in the sequences of intrinsically disordered proteins. We have computed the absolute chemical potential of glycine oligomers at infinite dilution by simulation with the CHARMM36 and Amber ff12SB force fields. We performed a thermodynamic decomposition of the solvation free energy (ΔG(sol)) of Gly2-5 into enthalpic (ΔH(sol)) and entropic (ΔS(sol)) components as well as their van der Waals and electrostatic contributions. Gly2-5 was either constrained to a rigid/extended conformation or allowed to be completely flexible during simulations to assess the effects of flexibility on these thermodynamic quantities. For both rigid and flexible oligoglycine models, the decrease in ΔG(sol) with chain length is enthalpically driven with only weak entropic compensation. However, the apparent rates of decrease of ΔG(sol), ΔH(sol), ΔS(sol), and their elec and vdw components differ for the rigid and flexible models. Thus, we find solvation entropy does not drive aggregation for this system and may not explain the collapse of long oligoglycines. Additionally, both force fields yield very similar thermodynamic scaling relationships with respect to chain length despite both force fields generating different conformational ensembles of various oligoglycine chains. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Thermodynamic Parameterization of Subduction-Zone Devolatilization and Application to Quantify Carbon Fluxes from Slab

NASA Astrophysics Data System (ADS)

Tian, M.; Katz, R. F.; Rees Jones, D. W.; May, D.

2017-12-01

Compared with other plate-tectonic boundaries, subduction zones (SZ) host the most drastic mechanical, thermal, and chemical changes. The transport of carbon through this complex environment is crucial to mantle carbon budget but remains the subject of active debate. Synthesis of field studies suggests that carbon subducted with the incoming slab is almost completely returned to the surface environment [Kelemen and Manning, 2015], whereas thermodynamic modelling indicates that a significant portion of carbon is retained in the slab and descends into the deep mantle [Gorman et al., 2006]. To address this controversy and quantify the carbon fluxes within SZs, it is necessary to treat the chemistry of fluid/volatile-rock interaction and the mechanics of porous fluid/volatile migration in a consistent modelling framework. This requirement is met by coupling a thermodynamic parameterization of de/re-volatilization with a two-phase flow model of subduction zones. The two-phase system is assumed to comprise three chemical components: rock containing only non-volatile oxides, H2O and CO2; the fluid phase includes only the latter two. Perple_X is used to map out the binary subsystems rock+H2O and rock+CO2; the results are parameterised in terms of volatile partition coefficients as a function of pressure and temperature. In synthesising the binary subsystems to describe phase equilibria that incorporate all three components, a Margules coefficient is introduced to account for non-ideal mixing of CO2/H2O in the fluid, such that the partition coefficients depend further on bulk composition. This procedure is applied to representative compositions of sediment, MORB, and gabbro for the slab, and peridotite for the mantle. The derived parameterization of each rock type serves as a lightweight thermodynamic module interfaceable with two-phase flow models of SZs. We demonstrate the application of this thermodynamic module through a simple model of carbon flux with a prescribed flow direction through (and out of) the slab. This model allows us to evaluate the effects of flow path and lithology on carbon storage within the slab.

The 2017 Release Cloudy

NASA Astrophysics Data System (ADS)

Ferland, G. J.; Chatzikos, M.; Guzmán, F.; Lykins, M. L.; van Hoof, P. A. M.; Williams, R. J. R.; Abel, N. P.; Badnell, N. R.; Keenan, F. P.; Porter, R. L.; Stancil, P. C.

2017-10-01

We describe the 2017 release of the spectral synthesis code Cloudy, summarizing the many improvements to the scope and accuracy of the physics which have been made since the previous release. Exporting the atomic data into external data files has enabled many new large datasets to be incorporated into the code. The use of the complete datasets is not realistic for most calculations, so we describe the limited subset of data used by default, which predicts significantly more lines than the previous release of Cloudy. This version is nevertheless faster than the previous release, as a result of code optimizations. We give examples of the accuracy limits using small models, and the performance requirements of large complete models. We summarize several advances in the H- and He-like iso-electronic sequences and use our complete collisional-radiative models to establish the densities where the coronal and local thermodynamic equilibrium approximations work.

Simulating the Generalized Gibbs Ensemble (GGE): A Hilbert space Monte Carlo approach

NASA Astrophysics Data System (ADS)

Alba, Vincenzo

By combining classical Monte Carlo and Bethe ansatz techniques we devise a numerical method to construct the Truncated Generalized Gibbs Ensemble (TGGE) for the spin-1/2 isotropic Heisenberg (XXX) chain. The key idea is to sample the Hilbert space of the model with the appropriate GGE probability measure. The method can be extended to other integrable systems, such as the Lieb-Liniger model. We benchmark the approach focusing on GGE expectation values of several local observables. As finite-size effects decay exponentially with system size, moderately large chains are sufficient to extract thermodynamic quantities. The Monte Carlo results are in agreement with both the Thermodynamic Bethe Ansatz (TBA) and the Quantum Transfer Matrix approach (QTM). Remarkably, it is possible to extract in a simple way the steady-state Bethe-Gaudin-Takahashi (BGT) roots distributions, which encode complete information about the GGE expectation values in the thermodynamic limit. Finally, it is straightforward to simulate extensions of the GGE, in which, besides the local integral of motion (local charges), one includes arbitrary functions of the BGT roots. As an example, we include in the GGE the first non-trivial quasi-local integral of motion.

Thermodynamic origin of surface melting on ice crystals

PubMed Central

Murata, Ken-ichiro; Asakawa, Harutoshi; Nagashima, Ken; Furukawa, Yoshinori; Sazaki, Gen

2016-01-01

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice–vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs. PMID:27791107

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.

Large deviation approach to the generalized random energy model

NASA Astrophysics Data System (ADS)

Dorlas, T. C.; Dukes, W. M. B.

2002-05-01

The generalized random energy model is a generalization of the random energy model introduced by Derrida to mimic the ultrametric structure of the Parisi solution of the Sherrington-Kirkpatrick model of a spin glass. It was solved exactly in two special cases by Derrida and Gardner. A complete solution for the thermodynamics in the general case was given by Capocaccia et al. Here we use large deviation theory to analyse the model in a very straightforward way. We also show that the variational expression for the free energy can be evaluated easily using the Cauchy-Schwarz inequality.

Lost in folding space? Comparing four variants of the thermodynamic model for RNA secondary structure prediction.

PubMed

Janssen, Stefan; Schudoma, Christian; Steger, Gerhard; Giegerich, Robert

2011-11-03

Many bioinformatics tools for RNA secondary structure analysis are based on a thermodynamic model of RNA folding. They predict a single, "optimal" structure by free energy minimization, they enumerate near-optimal structures, they compute base pair probabilities and dot plots, representative structures of different abstract shapes, or Boltzmann probabilities of structures and shapes. Although all programs refer to the same physical model, they implement it with considerable variation for different tasks, and little is known about the effects of heuristic assumptions and model simplifications used by the programs on the outcome of the analysis. We extract four different models of the thermodynamic folding space which underlie the programs RNAFOLD, RNASHAPES, and RNASUBOPT. Their differences lie within the details of the energy model and the granularity of the folding space. We implement probabilistic shape analysis for all models, and introduce the shape probability shift as a robust measure of model similarity. Using four data sets derived from experimentally solved structures, we provide a quantitative evaluation of the model differences. We find that search space granularity affects the computed shape probabilities less than the over- or underapproximation of free energy by a simplified energy model. Still, the approximations perform similar enough to implementations of the full model to justify their continued use in settings where computational constraints call for simpler algorithms. On the side, we observe that the rarely used level 2 shapes, which predict the complete arrangement of helices, multiloops, internal loops and bulges, include the "true" shape in a rather small number of predicted high probability shapes. This calls for an investigation of new strategies to extract high probability members from the (very large) level 2 shape space of an RNA sequence. We provide implementations of all four models, written in a declarative style that makes them easy to be modified. Based on our study, future work on thermodynamic RNA folding may make a choice of model based on our empirical data. It can take our implementations as a starting point for further program development.

Limits of predictions in thermodynamic systems: a review

NASA Astrophysics Data System (ADS)

Marsland, Robert, III; England, Jeremy

2018-01-01

The past twenty years have seen a resurgence of interest in nonequilibrium thermodynamics, thanks to advances in the theory of stochastic processes and in their thermodynamic interpretation. Fluctuation theorems provide fundamental constraints on the dynamics of systems arbitrarily far from thermal equilibrium. Thermodynamic uncertainty relations bound the dissipative cost of precision in a wide variety of processes. Concepts of excess work and excess heat provide the basis for a complete thermodynamics of nonequilibrium steady states, including generalized Clausius relations and thermodynamic potentials. But these general results carry their own limitations: fluctuation theorems involve exponential averages that can depend sensitively on unobservably rare trajectories; steady-state thermodynamics makes use of a dual dynamics that lacks any direct physical interpretation. This review aims to present these central results of contemporary nonequilibrium thermodynamics in such a way that the power of each claim for making physical predictions can be clearly assessed, using examples from current topics in soft matter and biophysics.

Thermodynamic assessment of the LiF-ThF4-PuF3-UF4 system

NASA Astrophysics Data System (ADS)

Capelli, E.; Beneš, O.; Konings, R. J. M.

2015-07-01

The LiF-ThF4-PuF3-UF4 system is the reference salt mixture considered for the Molten Salt Fast Reactor (MSFR) concept started with PuF3. In order to obtain the complete thermodynamic description of this quaternary system, two binary systems (ThF4-PuF3 and UF4-PuF3) and two ternary systems (LiF-ThF4-PuF3 and LiF-UF4-PuF3) have been assessed for the first time. The similarities between CeF3/PuF3 and ThF4/UF4 compounds have been taken into account for the presented optimization as well as in the experimental measurements performed, which have confirmed the temperatures predicted by the model. Moreover, the experimental results and the thermodynamic database developed have been used to identify potential compositions for the MSFR fuel and to evaluate the influence of partial substitution of ThF4 by UF4 in the salt.

Thermodynamics of mixtures of patchy and spherical colloids of different sizes: A multi-body association theory with complete reference fluid information.

PubMed

Bansal, Artee; Valiya Parambathu, Arjun; Asthagiri, D; Cox, Kenneth R; Chapman, Walter G

2017-04-28

We present a theory to predict the structure and thermodynamics of mixtures of colloids of different diameters, building on our earlier work [A. Bansal et al., J. Chem. Phys. 145, 074904 (2016)] that considered mixtures with all particles constrained to have the same size. The patchy, solvent particles have short-range directional interactions, while the solute particles have short-range isotropic interactions. The hard-sphere mixture without any association site forms the reference fluid. An important ingredient within the multi-body association theory is the description of clustering of the reference solvent around the reference solute. Here we account for the physical, multi-body clusters of the reference solvent around the reference solute in terms of occupancy statistics in a defined observation volume. These occupancy probabilities are obtained from enhanced sampling simulations, but we also present statistical mechanical models to estimate these probabilities with limited simulation data. Relative to an approach that describes only up to three-body correlations in the reference, incorporating the complete reference information better predicts the bonding state and thermodynamics of the physical solute for a wide range of system conditions. Importantly, analysis of the residual chemical potential of the infinitely dilute solute from molecular simulation and theory shows that whereas the chemical potential is somewhat insensitive to the description of the structure of the reference fluid, the energetic and entropic contributions are not, with the results from the complete reference approach being in better agreement with particle simulations.

Thermodynamics of mixtures of patchy and spherical colloids of different sizes: A multi-body association theory with complete reference fluid information

NASA Astrophysics Data System (ADS)

Bansal, Artee; Valiya Parambathu, Arjun; Asthagiri, D.; Cox, Kenneth R.; Chapman, Walter G.

2017-04-01

We present a theory to predict the structure and thermodynamics of mixtures of colloids of different diameters, building on our earlier work [A. Bansal et al., J. Chem. Phys. 145, 074904 (2016)] that considered mixtures with all particles constrained to have the same size. The patchy, solvent particles have short-range directional interactions, while the solute particles have short-range isotropic interactions. The hard-sphere mixture without any association site forms the reference fluid. An important ingredient within the multi-body association theory is the description of clustering of the reference solvent around the reference solute. Here we account for the physical, multi-body clusters of the reference solvent around the reference solute in terms of occupancy statistics in a defined observation volume. These occupancy probabilities are obtained from enhanced sampling simulations, but we also present statistical mechanical models to estimate these probabilities with limited simulation data. Relative to an approach that describes only up to three-body correlations in the reference, incorporating the complete reference information better predicts the bonding state and thermodynamics of the physical solute for a wide range of system conditions. Importantly, analysis of the residual chemical potential of the infinitely dilute solute from molecular simulation and theory shows that whereas the chemical potential is somewhat insensitive to the description of the structure of the reference fluid, the energetic and entropic contributions are not, with the results from the complete reference approach being in better agreement with particle simulations.

3D RISM theory with fast reciprocal-space electrostatics.

PubMed

Heil, Jochen; Kast, Stefan M

2015-03-21

The calculation of electrostatic solute-solvent interactions in 3D RISM ("three-dimensional reference interaction site model") integral equation theory is recast in a form that allows for a computational treatment analogous to the "particle-mesh Ewald" formalism as used for molecular simulations. In addition, relations that connect 3D RISM correlation functions and interaction potentials with thermodynamic quantities such as the chemical potential and average solute-solvent interaction energy are reformulated in a way that calculations of expensive real-space electrostatic terms on the 3D grid are completely avoided. These methodical enhancements allow for both, a significant speedup particularly for large solute systems and a smoother convergence of predicted thermodynamic quantities with respect to box size, as illustrated for several benchmark systems.

A Hamiltonian approach for the Thermodynamics of AdS black holes

NASA Astrophysics Data System (ADS)

Baldiotti, M. C.; Fresneda, R.; Molina, C.

2017-07-01

In this work we study the Thermodynamics of D-dimensional Schwarzschild-anti de Sitter (SAdS) black holes. The minimal Thermodynamics of the SAdS spacetime is briefly discussed, highlighting some of its strong points and shortcomings. The minimal SAdS Thermodynamics is extended within a Hamiltonian approach, by means of the introduction of an additional degree of freedom. We demonstrate that the cosmological constant can be introduced in the thermodynamic description of the SAdS black hole with a canonical transformation of the Schwarzschild problem, closely related to the introduction of an anti-de Sitter thermodynamic volume. The treatment presented is consistent, in the sense that it is compatible with the introduction of new thermodynamic potentials, and respects the laws of black hole Thermodynamics. By demanding homogeneity of the thermodynamic variables, we are able to construct a new equation of state that completely characterizes the Thermodynamics of SAdS black holes. The treatment naturally generates phenomenological constants that can be associated with different boundary conditions in underlying microscopic theories. A whole new set of phenomena can be expected from the proposed generalization of SAdS Thermodynamics.

Development and Integration of an Advanced Stirling Convertor Linear Alternator Model for a Tool Simulating Convertor Performance and Creating Phasor Diagrams

NASA Technical Reports Server (NTRS)

Metscher, Jonathan F.; Lewandowski, Edward J.

2013-01-01

A simple model of the Advanced Stirling Convertors (ASC) linear alternator and an AC bus controller has been developed and combined with a previously developed thermodynamic model of the convertor for a more complete simulation and analysis of the system performance. The model was developed using Sage, a 1-D thermodynamic modeling program that now includes electro-magnetic components. The convertor, consisting of a free-piston Stirling engine combined with a linear alternator, has sufficiently sinusoidal steady-state behavior to allow for phasor analysis of the forces and voltages acting in the system. A MATLAB graphical user interface (GUI) has been developed to interface with the Sage software for simplified use of the ASC model, calculation of forces, and automated creation of phasor diagrams. The GUI allows the user to vary convertor parameters while fixing different input or output parameters and observe the effect on the phasor diagrams or system performance. The new ASC model and GUI help create a better understanding of the relationship between the electrical component voltages and mechanical forces. This allows better insight into the overall convertor dynamics and performance.

Thermodynamic resource theories, non-commutativity and maximum entropy principles

NASA Astrophysics Data System (ADS)

Lostaglio, Matteo; Jennings, David; Rudolph, Terry

2017-04-01

We discuss some features of thermodynamics in the presence of multiple conserved quantities. We prove a generalisation of Landauer principle illustrating tradeoffs between the erasure costs paid in different ‘currencies’. We then show how the maximum entropy and complete passivity approaches give different answers in the presence of multiple observables. We discuss how this seems to prevent current resource theories from fully capturing thermodynamic aspects of non-commutativity.

Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

NASA Astrophysics Data System (ADS)

Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane

2011-10-01

The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges. Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System (T-MATS)

NASA Technical Reports Server (NTRS)

Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei (OA)

2014-01-01

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This presentation describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this presentation is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture.

Thermodynamic and fluid mechanic analysis of rapid pressurization in a dead-end tube

NASA Technical Reports Server (NTRS)

Leslie, Ian H.

1989-01-01

Three models have been applied to very rapid compression of oxygen in a dead-ended tube. Pressures as high as 41 MPa (6000 psi) leading to peak temperatures of 1400 K are predicted. These temperatures are well in excess of the autoignition temperature (750 K) of teflon, a frequently used material for lining hoses employed in oxygen service. These findings are in accord with experiments that have resulted in ignition and combustion of the teflon, leading to the combustion of the stainless steel braiding and catastrophic failure. The system analyzed was representative of a capped off-high-pressure oxygen line, which could be part of a larger system. Pressurization of the larger system would lead to compression in the dead-end line, and possible ignition of the teflon liner. The model consists of a large plenum containing oxygen at the desired pressure (500 to 6000 psi). The plenum is connected via a fast acting valve to a stainless steel tube 2 cm inside diameter. Opening times are on the order of 15 ms. Downstream of the valve is an orifice sized to increase filling times to around 100 ms. The total length from the valve to the dead-end is 150 cm. The distance from the valve to the orifice is 95 cm. The models describe the fluid mechanics and thermodynamics of the flow, and do not include any combustion phenomena. A purely thermodynamic model assumes filling to be complete upstream of the orifice before any gas passes through the orifice. This simplification is reasonable based on experiment and computer modeling. Results show that peak temperatures as high as 4800 K can result from recompression of the gas after expanding through the orifice. An approximate transient model without an orifice was developed assuming an isentropic compression process. An analytical solution was obtained. Results indicated that fill times can be considerably shorter than valve opening times. The third model was a finite difference, 1-D transient compressible flow model. Results from the code show the recompression effect but predict much lower peak temperatures than the thermodynamic model.

Thermodynamic and fluid mechanic analysis of rapid pressurization in a dead-end tube

NASA Astrophysics Data System (ADS)

Leslie, Ian H.

1989-12-01

Three models have been applied to very rapid compression of oxygen in a dead-ended tube. Pressures as high as 41 MPa (6000 psi) leading to peak temperatures of 1400 K are predicted. These temperatures are well in excess of the autoignition temperature (750 K) of teflon, a frequently used material for lining hoses employed in oxygen service. These findings are in accord with experiments that have resulted in ignition and combustion of the teflon, leading to the combustion of the stainless steel braiding and catastrophic failure. The system analyzed was representative of a capped off-high-pressure oxygen line, which could be part of a larger system. Pressurization of the larger system would lead to compression in the dead-end line, and possible ignition of the teflon liner. The model consists of a large plenum containing oxygen at the desired pressure (500 to 6000 psi). The plenum is connected via a fast acting valve to a stainless steel tube 2 cm inside diameter. Opening times are on the order of 15 ms. Downstream of the valve is an orifice sized to increase filling times to around 100 ms. The total length from the valve to the dead-end is 150 cm. The distance from the valve to the orifice is 95 cm. The models describe the fluid mechanics and thermodynamics of the flow, and do not include any combustion phenomena. A purely thermodynamic model assumes filling to be complete upstream of the orifice before any gas passes through the orifice. This simplification is reasonable based on experiment and computer modeling. Results show that peak temperatures as high as 4800 K can result from recompression of the gas after expanding through the orifice. An approximate transient model without an orifice was developed assuming an isentropic compression process. An analytical solution was obtained.

The Operational Equations of State, 3: Recovery of the EOS for Hydrocode From the Measured Heat Capacity, Isentrope, and Hugoniot Adiabat

DTIC Science & Technology

2012-07-01

hydrocode from experimental data. It is assumed that the substance in question possesses only two thermodynamic degrees of freedom – the specific volume V...excludes the possibility of phase transformations). 15. SUBJECT TERMS thermodynamics , EOS, hydrocode 16. SECURITY CLASSIFICATION OF: 17. LIMITATION...we gave several examples of generating complete thermodynamically consistent equations of state (EOS). The methodology used there was based on

Quantum Rényi relative entropies affirm universality of thermodynamics.

PubMed

Misra, Avijit; Singh, Uttam; Bera, Manabendra Nath; Rajagopal, A K

2015-10-01

We formulate a complete theory of quantum thermodynamics in the Rényi entropic formalism exploiting the Rényi relative entropies, starting from the maximum entropy principle. In establishing the first and second laws of quantum thermodynamics, we have correctly identified accessible work and heat exchange in both equilibrium and nonequilibrium cases. The free energy (internal energy minus temperature times entropy) remains unaltered, when all the entities entering this relation are suitably defined. Exploiting Rényi relative entropies we have shown that this "form invariance" holds even beyond equilibrium and has profound operational significance in isothermal process. These results reduce to the Gibbs-von Neumann results when the Rényi entropic parameter α approaches 1. Moreover, it is shown that the universality of the Carnot statement of the second law is the consequence of the form invariance of the free energy, which is in turn the consequence of maximum entropy principle. Further, the Clausius inequality, which is the precursor to the Carnot statement, is also shown to hold based on the data processing inequalities for the traditional and sandwiched Rényi relative entropies. Thus, we find that the thermodynamics of nonequilibrium state and its deviation from equilibrium together determine the thermodynamic laws. This is another important manifestation of the concepts of information theory in thermodynamics when they are extended to the quantum realm. Our work is a substantial step towards formulating a complete theory of quantum thermodynamics and corresponding resource theory.

Sensitivity study of a dynamic thermodynamic sea ice model

NASA Astrophysics Data System (ADS)

Holland, David M.; Mysak, Lawrence A.; Manak, Davinder K.; Oberhuber, Josef M.

1993-02-01

A numerical simulation of the seasonal sea ice cover in the Arctic Ocean and the Greenland, Iceland, and Norwegian seas is presented. The sea ice model is extracted from Oberhuber's (1990) coupled sea ice-mixed layer-isopycnal general circulation model and is written in spherical coordinates. The advantage of such a model over previous sea ice models is that it can be easily coupled to either global atmospheric or ocean general circulation models written in spherical coordinates. In this model, the thermodynamics are a modification of that of Parkinson and Washington (1979), while the dynamics use the full Hibler (1979) viscous-plastic rheology. Monthly thermodynamic and dynamic forcing fields for the atmosphere and ocean are specified. The simulations of the seasonal cycle of ice thickness, compactness, and velocity, for a control set of parameters, compare favorably with the known seasonal characteristics of these fields. A sensitivity study of the control simulation of the seasonal sea ice cover is presented. The sensitivity runs are carried out under three different themes, namely, numerical conditions, parameter values, and physical processes. This last theme refers to experiments in which physical processes are either newly added or completely removed from the model. Approximately 80 sensitivity runs have been performed in which a change from the control run environment has been implemented. Comparisons have been made between the control run and a particular sensitivity run based on time series of the seasonal cycle of the domain-averaged ice thickness, compactness, areal coverage, and kinetic energy. In addition, spatially varying fields of ice thickness, compactness, velocity, and surface temperature for each season are presented for selected experiments. A brief description and discussion of the more interesting experiments are presented. The simulation of the seasonal cycle of Arctic sea ice cover is shown to be robust.

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.

Predicting RNA folding thermodynamics with a reduced chain representation model

PubMed Central

CAO, SONG; CHEN, SHI-JIE

2005-01-01

Based on the virtual bond representation for the nucleotide backbone, we develop a reduced conformational model for RNA. We use the experimentally measured atomic coordinates to model the helices and use the self-avoiding walks in a diamond lattice to model the loop conformations. The atomic coordinates of the helices and the lattice representation for the loops are matched at the loop–helix junction, where steric viability is accounted for. Unlike the previous simplified lattice-based models, the present virtual bond model can account for the atomic details of realistic three-dimensional RNA structures. Based on the model, we develop a statistical mechanical theory for RNA folding energy landscapes and folding thermodynamics. Tests against experiments show that the theory can give much more improved predictions for the native structures, the thermal denaturation curves, and the equilibrium folding/unfolding pathways than the previous models. The application of the model to the P5abc region of Tetrahymena group I ribozyme reveals the misfolded intermediates as well as the native-like intermediates in the equilibrium folding process. Moreover, based on the free energy landscape analysis for each and every loop mutation, the model predicts five lethal mutations that can completely alter the free energy landscape and the folding stability of the molecule. PMID:16251382

On Thermodynamic Constraints upon Turbulence Modeling

NASA Astrophysics Data System (ADS)

Huang, Yu-Ning; Durst, Franz

2000-11-01

Turbulence is a continuum phenomenon which can be described within the framework of continuum mechanics. Such foundation has the potential for improving turbulence modeling, making it less heuristic and more rational. In the present research, we consider the compatibility of turbulence modeling with the second law of thermodynamics. We show that the Clausius-Planck inequality, as an expression of the principle of entropy growth, places a thermodynamic restriction upon the turbulence modeling of an incompressible Navier-Stokes fluid in an isothermal temperature field. This thermodynamic restriction is given in the form of an inequality, which ensures non-negativeness of the mean internal dissipation. As an illustration, we show the thermodynamic constraints on the modeling of a few typical homogeneous turbulent flows.

Thermodynamics of protein folding using a modified Wako-Saitô-Muñoz-Eaton model.

PubMed

Tsai, Min-Yeh; Yuan, Jian-Min; Teranishi, Yoshiaki; Lin, Sheng Hsien

2012-09-01

Herein, we propose a modified version of the Wako-Saitô-Muñoz-Eaton (WSME) model. The proposed model introduces an empirical temperature parameter for the hypothetical structural units (i.e., foldons) in proteins to include site-dependent thermodynamic behavior. The thermodynamics for both our proposed model and the original WSME model were investigated. For a system with beta-hairpin topology, a mathematical treatment (contact-pair treatment) to facilitate the calculation of its partition function was developed. The results show that the proposed model provides better insight into the site-dependent thermodynamic behavior of the system, compared with the original WSME model. From this site-dependent point of view, the relationship between probe-dependent experimental results and model's thermodynamic predictions can be explained. The model allows for suggesting a general principle to identify foldon behavior. We also find that the backbone hydrogen bonds may play a role of structural constraints in modulating the cooperative system. Thus, our study may contribute to the understanding of the fundamental principles for the thermodynamics of protein folding.

Computing Critical Properties with Yang-Yang Anomalies

NASA Astrophysics Data System (ADS)

Orkoulas, Gerassimos; Cerdeirina, Claudio; Fisher, Michael

2017-01-01

Computation of the thermodynamics of fluids in the critical region is a challenging task owing to divergence of the correlation length and lack of particle-hole symmetries found in Ising or lattice-gas models. In addition, analysis of experiments and simulations reveals a Yang-Yang (YY) anomaly which entails sharing of the specific heat singularity between the pressure and the chemical potential. The size of the YY anomaly is measured by the YY ratio Rμ =C μ /CV of the amplitudes of C μ = - T d2 μ /dT2 and of the total specific heat CV. A ``complete scaling'' theory, in which the pressure mixes into the scaling fields, accounts for the YY anomaly. In Phys. Rev. Lett. 116, 040601 (2016), compressible cell gas (CCG) models which exhibit YY and singular diameter anomalies, have been advanced for near-critical fluids. In such models, the individual cell volumes are allowed to fluctuate. The thermodynamics of CCGs can be computed through mapping onto the Ising model via the seldom-used great grand canonical ensemble. The computations indicate that local free volume fluctuations are the origins of the YY effects. Furthermore, local energy-volume coupling (to model water) is another crucial factor underlying the phenomena.

The Effect of Learning Based on Technology Model and Assessment Technique toward Thermodynamic Learning Achievement

NASA Astrophysics Data System (ADS)

Makahinda, T.

2018-02-01

The purpose of this research is to find out the effect of learning model based on technology and assessment technique toward thermodynamic achievement by controlling students intelligence. This research is an experimental research. The sample is taken through cluster random sampling with the total respondent of 80 students. The result of the research shows that the result of learning of thermodynamics of students who taught the learning model of environmental utilization is higher than the learning result of student thermodynamics taught by simulation animation, after controlling student intelligence. There is influence of student interaction, and the subject between models of technology-based learning with assessment technique to student learning result of Thermodynamics, after controlling student intelligence. Based on the finding in the lecture then should be used a thermodynamic model of the learning environment with the use of project assessment technique.

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.

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.

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System T-MATS

NASA Technical Reports Server (NTRS)

Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

2014-01-01

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS)

NASA Technical Reports Server (NTRS)

Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

2014-01-01

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

Some Considerations about Thermodynamic Cycles

ERIC Educational Resources Information Center

da Silva, M. F. Ferreira

2012-01-01

After completing their introductory studies on thermodynamics at the university level, typically in a second-year university course, most students show a number of misconceptions. In this work, we identify some of those erroneous ideas and try to explain their origins. We also give a suggestion to attack the problem through a systematic and…

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.

Amino acid substitutions affecting protein dynamics in eglin C do not affect heat capacity change upon unfolding.

PubMed

Gribenko, Alexey V; Keiffer, Timothy R; Makhatadze, George I

2006-08-01

The heat capacity change upon unfolding (deltaC(p)) is a thermodynamic parameter that defines the temperature dependence of the thermodynamic stability of proteins; however, physical basis of the heat capacity change is not completely understood. Although empirical surface area-based calculations can predict heat capacity changes reasonably well, accumulating evidence suggests that changes in hydration of those surfaces is not the only parameter contributing to the observed heat capacity changes upon unfolding. Because packing density in the protein interior is similar to that observed in organic crystals, we hypothesized that changes in protein dynamics resulting in increased rigidity of the protein structure might contribute to the observed heat capacity change upon unfolding. Using differential scanning calorimetry we characterized the thermodynamic behavior of a serine protease inhibitor eglin C and two eglin C variants with altered native state dynamics, as determined by NMR. We found no evidence of changes in deltaC(p) in either of the variants, suggesting that changes in rigidity do not contribute to the heat capacity change upon unfolding in this model system. Copyright 2006 Wiley-Liss, Inc.

Modeling of Surface Thermodynamics and Damage Thresholds in the IR and THz Regime

DTIC Science & Technology

2007-01-01

Conference on Optical Interactions with Tissue and Cells [18th] Held in San Jose, California on January 22-24, 2007 To order the complete compilation report...United States; c Air Force Reasearch Lab, Human Effectivness Directorate Optical Branch, 2624 Louis Bauer Drive, San Antonio, TX, United States...equation (radial and axial) in a biological system construct. Tissues are represented as multi-layer structures, with optical and thermal properties

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

PubMed

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

Nonequilibrium thermodynamics of restricted Boltzmann machines.

PubMed

Salazar, Domingos S P

2017-08-01

In this work, we analyze the nonequilibrium thermodynamics of a class of neural networks known as restricted Boltzmann machines (RBMs) in the context of unsupervised learning. We show how the network is described as a discrete Markov process and how the detailed balance condition and the Maxwell-Boltzmann equilibrium distribution are sufficient conditions for a complete thermodynamics description, including nonequilibrium fluctuation theorems. Numerical simulations in a fully trained RBM are performed and the heat exchange fluctuation theorem is verified with excellent agreement to the theory. We observe how the contrastive divergence functional, mostly used in unsupervised learning of RBMs, is closely related to nonequilibrium thermodynamic quantities. We also use the framework to interpret the estimation of the partition function of RBMs with the annealed importance sampling method from a thermodynamics standpoint. Finally, we argue that unsupervised learning of RBMs is equivalent to a work protocol in a system driven by the laws of thermodynamics in the absence of labeled data.

Complete spectrum of long operators in Script N = 4 SYM at one loop

NASA Astrophysics Data System (ADS)

Beisert, Niklas; Kazakov, Vladimir A.; Sakai, Kazuhiro; Zarembo, Konstantin

2005-07-01

We construct the complete spectral curve for an arbitrary local operator, including fermions and covariant derivatives, of one-loop Script N = 4 gauge theory in the thermodynamic limit. This curve perfectly reproduces the Frolov-Tseytlin limit of the full spectral curve of classical strings on AdS5 × S5 derived in [64]. To complete the comparison we introduce stacks, novel bound states of roots of different flavors which arise in the thermodynamic limit of the corresponding Bethe ansatz equations. We furthermore show the equivalence of various types of Bethe equations for the underlying fraktur sfraktur u(2,2|4) superalgebra, in particular of the type ``Beauty'' and ``Beast''.

Steepest entropy ascent model for far-nonequilibrium thermodynamics: Unified implementation of the maximum entropy production principle

NASA Astrophysics Data System (ADS)

Beretta, Gian Paolo

2014-10-01

By suitable reformulations, we cast the mathematical frameworks of several well-known different approaches to the description of nonequilibrium dynamics into a unified formulation valid in all these contexts, which extends to such frameworks the concept of steepest entropy ascent (SEA) dynamics introduced by the present author in previous works on quantum thermodynamics. Actually, the present formulation constitutes a generalization also for the quantum thermodynamics framework. The analysis emphasizes that in the SEA modeling principle a key role is played by the geometrical metric with respect to which to measure the length of a trajectory in state space. In the near-thermodynamic-equilibrium limit, the metric tensor is directly related to the Onsager's generalized resistivity tensor. Therefore, through the identification of a suitable metric field which generalizes the Onsager generalized resistance to the arbitrarily far-nonequilibrium domain, most of the existing theories of nonequilibrium thermodynamics can be cast in such a way that the state exhibits the spontaneous tendency to evolve in state space along the path of SEA compatible with the conservation constraints and the boundary conditions. The resulting unified family of SEA dynamical models is intrinsically and strongly consistent with the second law of thermodynamics. The non-negativity of the entropy production is a general and readily proved feature of SEA dynamics. In several of the different approaches to nonequilibrium description we consider here, the SEA concept has not been investigated before. We believe it defines the precise meaning and the domain of general validity of the so-called maximum entropy production principle. Therefore, it is hoped that the present unifying approach may prove useful in providing a fresh basis for effective, thermodynamically consistent, numerical models and theoretical treatments of irreversible conservative relaxation towards equilibrium from far nonequilibrium states. The mathematical frameworks we consider are the following: (A) statistical or information-theoretic models of relaxation; (B) small-scale and rarefied gas dynamics (i.e., kinetic models for the Boltzmann equation); (C) rational extended thermodynamics, macroscopic nonequilibrium thermodynamics, and chemical kinetics; (D) mesoscopic nonequilibrium thermodynamics, continuum mechanics with fluctuations; and (E) quantum statistical mechanics, quantum thermodynamics, mesoscopic nonequilibrium quantum thermodynamics, and intrinsic quantum thermodynamics.

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.

Thermodynamical stability of FRW models with quintessence

NASA Astrophysics Data System (ADS)

Sharif, M.; Ashraf, Sara

2018-03-01

In this paper, we study the thermodynamic stability of quintessence in the background of homogeneous and isotropic universe model. For the evolutionary picture, we consider two different forms of potentials and investigate the behavior of different physical parameters. We conclude that the quintessence model expands adiabatically and this expansion is thermodynamically stable for both potentials with suitable model parameters.

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

2017-01-01

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

Quantum thermodynamics of general quantum processes.

PubMed

Binder, Felix; Vinjanampathy, Sai; Modi, Kavan; Goold, John

2015-03-01

Accurately describing work extraction from a quantum system is a central objective for the extension of thermodynamics to individual quantum systems. The concepts of work and heat are surprisingly subtle when generalizations are made to arbitrary quantum states. We formulate an operational thermodynamics suitable for application to an open quantum system undergoing quantum evolution under a general quantum process by which we mean a completely positive and trace-preserving map. We derive an operational first law of thermodynamics for such processes and show consistency with the second law. We show that heat, from the first law, is positive when the input state of the map majorizes the output state. Moreover, the change in entropy is also positive for the same majorization condition. This makes a strong connection between the two operational laws of thermodynamics.

Thermodynamic stability of RNA structures formed by CNG trinucleotide repeats. Implication for prediction of RNA structure.

PubMed

Broda, Magdalena; Kierzek, Elzbieta; Gdaniec, Zofia; Kulinski, Tadeusz; Kierzek, Ryszard

2005-08-16

Trinucleotide repeat expansion diseases (TREDs) are correlated with elongation of CNG DNA and RNA repeats to pathological level. This paper shows, for the first time, complete data concerning thermodynamic stabilities of RNA with CNG trinucleotide repeats. Our studies include the stability of oligoribonucleotides composed of two to seven of CAG, CCG, CGG, and CUG repeats. The thermodynamic parameters of helix propagation correlated with the presence of multiple N-N mismatches within CNG RNA duplexes were also determined. Moreover, the total stability of CNG RNA hairpins, as well as the contribution of trinucleotide repeats placed only in the stem or loop regions, was evaluated. The improved thermodynamic parameters allow to predict much more accurately the thermodynamic stabilities and structures of CNG RNAs.

Thermodynamics of various F420 coenzyme models as sources of electrons, hydride ions, hydrogen atoms and protons in acetonitrile.

PubMed

Xia, Ke; Shen, Guang-Bin; Zhu, Xiao-Qing

2015-06-14

32 F420 coenzyme models with alkylation of the three different N atoms (N1, N3 and N10) in the core structure (XFH(-)) were designed and synthesized and the thermodynamic driving forces (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the 32 XFH(-) releasing hydride ions, hydrogen atoms and electrons, the thermodynamic driving forces of the 32 XFH˙ releasing protons and hydrogen atoms and the thermodynamic driving forces of XF(-)˙ releasing electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The effects of the methyl group at N1, N3 and N10 and a negative charge on N1 and N10 atoms on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were examined; the results show that seating arrangements of the methyl group and the negative charge have remarkably different effects on the thermodynamic properties of the F420 coenzyme models and their related reaction intermediates. The effects of the substituents at C7 and C8 on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were also examined; the results show that the substituents at C7 and C8 have good Hammett linear free energy relationships with the six thermodynamic parameters. Meanwhile, a reasonable determination of possible reactions between members of the F420 family and NADH family in vivo was given according to a thermodynamic analysis platform constructed using the elementary step thermodynamic parameter of F420 coenzyme model 2FH(-) and NADH model MNAH releasing hydride ions in acetonitrile. The information disclosed in this work can not only fill a gap in the chemical thermodynamics of F420 coenzyme models as a class of very important organic sources of electrons, hydride ions, hydrogen atoms and protons, but also strongly promote the fast development of the chemistry and applications of F420 coenzyme.

First-principles study of elastic and thermodynamic properties of orthorhombic OsB4 under high pressure

NASA Astrophysics Data System (ADS)

Yan, Hai-Yan; Zhang, Mei-Guang; Huang, Duo-Hui; Wei, Qun

2013-04-01

The first-principles study on the elastic properties, elastic anisotropy and thermodynamic properties of the orthorhombic OsB4 is reported using density functional theory method with the ultrasoft pseudopotential scheme in the frame of the generalized gradient approximation. The calculated equilibrium parameters are in good agreement with the available theoretical data. A complete elastic tensor and crystal anisotropies of the ultra-incompressible OsB4 are determined in the pressure range of 0-50 GPa. By the elastic stability criteria, it is predicted that the orthorhombic OsB4 is stable below 50 GPa. By using the quasi-harmonic Debye model, the heat capacity, the coefficient of thermal expansion, and the Grüneisen parameter of OsB4 are also successfully obtained in the present work.

Physics and Chemistry of Earth Materials

NASA Astrophysics Data System (ADS)

Navrotsky, Alexandra

1994-11-01

Stressing the fundamental solid state behavior of minerals, and emphasizing both theory and experiment, this text surveys the physics and chemistry of earth materials. The author begins with a systematic tour of crystal chemistry of both simple and complex structures (with completely new structural drawings) and discusses how to obtain structural and thermodynamic information experimentally. Dr. Navrotsky also reviews the quantitative concepts of chemical bonding--band theory, molecular orbit and ionic models. She then covers physical properties and relates microscopic features to macroscopic thermodynamic behavior and treats high pressure phase transitions, amorphous materials and solid state reactions. The author concludes with a look at the interface between mineral physics and materials science. Highly illustrated throughout, this book fills the gap between undergraduate texts and specialized review volumes and is appropriate for students and researchers in earth science and materials science.

Mayer-cluster expansion of instanton partition functions and thermodynamic bethe ansatz

NASA Astrophysics Data System (ADS)

Meneghelli, Carlo; Yang, Gang

2014-05-01

In [19] Nekrasov and Shatashvili pointed out that the = 2 instanton partition function in a special limit of the Ω-deformation parameters is characterized by certain thermodynamic Bethe ansatz (TBA) like equations. In this work we present an explicit derivation of this fact as well as generalizations to quiver gauge theories. To do so we combine various techniques like the iterated Mayer expansion, the method of expansion by regions, and the path integral tricks for non-perturbative summation. The TBA equations derived entirely within gauge theory have been proposed to encode the spectrum of a large class of quantum integrable systems. We hope that the derivation presented in this paper elucidates further this completely new point of view on the origin, as well as on the structure, of TBA equations in integrable models.

Thermodynamic Inefficiency of Conversion of Solar Energy to Work.

ERIC Educational Resources Information Center

Adamson, Arthur W.; And Others

1984-01-01

Considers the thermodynamic limitation to the efficiency with which light energy can be converted into work, indicating that no single chemical system converting solar energy into useful work can be very efficient. Also indicates that if solar energy is absorbed as heat for heating purposes, it is almost completely used. (JN)

A constitutive model for magnetostriction based on thermodynamic framework

NASA Astrophysics Data System (ADS)

Ho, Kwangsoo

2016-08-01

This work presents a general framework for the continuum-based formulation of dissipative materials with magneto-mechanical coupling in the viewpoint of irreversible thermodynamics. The thermodynamically consistent model developed for the magnetic hysteresis is extended to include the magnetostrictive effect. The dissipative and hysteretic response of magnetostrictive materials is captured through the introduction of internal state variables. The evolution rate of magnetostrictive strain as well as magnetization is derived from thermodynamic and dissipative potentials in accordance with the general principles of thermodynamics. It is then demonstrated that the constitutive model is competent to describe the magneto-mechanical behavior by comparing simulation results with the experimental data reported in the literature.

Universalities of thermodynamic signatures in topological phases

PubMed Central

Kempkes, S. N.; Quelle, A.; Smith, C. Morais

2016-01-01

Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this challenge has been overcome: by using Hill thermodynamics to describe the Bernevig-Hughes-Zhang model in two dimensions, it was shown that at the topological phase transition the thermodynamic potential does not scale extensively due to boundary effects. Here, we extend this approach to different topological models in various dimensions (the Kitaev chain and Su-Schrieffer-Heeger model in one dimension, the Kane-Mele model in two dimensions and the Bernevig-Hughes-Zhang model in three dimensions) at zero temperature. Surprisingly, all models exhibit the same universal behavior in the order of the topological-phase transition, depending on the dimension. Moreover, we derive the topological phase diagram at finite temperature using this thermodynamic description, and show that it displays a good agreement with the one calculated from the Uhlmann phase. Our work reveals unexpected universalities and opens the path to a thermodynamic description of systems with a non-local order parameter. PMID:27929041

Universalities of thermodynamic signatures in topological phases.

PubMed

Kempkes, S N; Quelle, A; Smith, C Morais

2016-12-08

Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this challenge has been overcome: by using Hill thermodynamics to describe the Bernevig-Hughes-Zhang model in two dimensions, it was shown that at the topological phase transition the thermodynamic potential does not scale extensively due to boundary effects. Here, we extend this approach to different topological models in various dimensions (the Kitaev chain and Su-Schrieffer-Heeger model in one dimension, the Kane-Mele model in two dimensions and the Bernevig-Hughes-Zhang model in three dimensions) at zero temperature. Surprisingly, all models exhibit the same universal behavior in the order of the topological-phase transition, depending on the dimension. Moreover, we derive the topological phase diagram at finite temperature using this thermodynamic description, and show that it displays a good agreement with the one calculated from the Uhlmann phase. Our work reveals unexpected universalities and opens the path to a thermodynamic description of systems with a non-local order parameter.

Hard sphere perturbation theory for thermodynamics of soft-sphere model liquid

NASA Astrophysics Data System (ADS)

Mon, K. K.

2001-09-01

It is a long-standing consensus in the literature that hard sphere perturbation theory (HSPT) is not accurate for dense soft sphere model liquids, interacting with repulsive r-n pair potentials for small n. In this paper, we show that if the intrinsic error of HSPT for soft sphere model liquids is accounted for, then this is not completely true. We present results for n=4, 6, 9, 12 which indicate that, even first order variational HSPT can provide free energy upper bounds to within a few percent at densities near freezing when corrected for the intrinsic error of the HSPT.

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.

Comparisons between thermodynamic and one-dimensional combustion models of spark-ignition engines

NASA Technical Reports Server (NTRS)

Ramos, J. I.

1986-01-01

Results from a one-dimensional combustion model employing a constant eddy diffusivity and a one-step chemical reaction are compared with those of one-zone and two-zone thermodynamic models to study the flame propagation in a spark-ignition engine. One-dimensional model predictions are found to be very sensitive to the eddy diffusivity and reaction rate data. The average mixing temperature found using the one-zone thermodynamic model is higher than those of the two-zone and one-dimensional models during the compression stroke, and that of the one-dimensional model is higher than those predicted by both thermodynamic models during the expansion stroke. The one-dimensional model is shown to predict an accelerating flame even when the front approaches the cold cylinder wall.

Thermodynamically Feasible Kinetic Models of Reaction Networks

PubMed Central

Ederer, Michael; Gilles, Ernst Dieter

2007-01-01

The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilibrium all fluxes vanish. We introduce a thermodynamic-kinetic modeling (TKM) formalism that adapts the concepts of potentials and forces from irreversible thermodynamics to kinetic modeling. In the proposed formalism, the thermokinetic potential of a compound is proportional to its concentration. The proportionality factor is a compound-specific parameter called capacity. The thermokinetic force of a reaction is a function of the potentials. Every reaction has a resistance that is the ratio of thermokinetic force and reaction rate. For mass-action type kinetics, the resistances are constant. Since it relies on the thermodynamic concept of potentials and forces, the TKM formalism structurally observes detailed balance for all values of capacities and resistances. Thus, it provides an easy way to formulate physically feasible, kinetic models of biological reaction networks. The TKM formalism is useful for modeling large biological networks that are subject to many detailed balance relations. PMID:17208985

Decoherence-induced conductivity in the one-dimensional Anderson model

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

Stegmann, Thomas; Wolf, Dietrich E.; Ujsághy, Orsolya

We study the effect of decoherence on the electron transport in the one-dimensional Anderson model by means of a statistical model [1, 2, 3, 4, 5]. In this model decoherence bonds are randomly distributed within the system, at which the electron phase is randomized completely. Afterwards, the transport quantity of interest (e.g. resistance or conductance) is ensemble averaged over the decoherence configurations. Averaging the resistance of the sample, the calculation can be performed analytically. In the thermodynamic limit, we find a decoherence-driven transition from the quantum-coherent localized regime to the Ohmic regime at a critical decoherence density, which is determinedmore » by the second-order generalized Lyapunov exponent (GLE) [4].« less

Irreversible thermodynamics of Poisson processes with reaction.

PubMed

Méndez, V; Fort, J

1999-11-01

A kinetic model is derived to study the successive movements of particles, described by a Poisson process, as well as their generation. The irreversible thermodynamics of this system is also studied from the kinetic model. This makes it possible to evaluate the differences between thermodynamical quantities computed exactly and up to second-order. Such differences determine the range of validity of the second-order approximation to extended irreversible thermodynamics.

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.

Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) User's Guide

NASA Technical Reports Server (NTRS)

Chapman, Jeffryes W.; Lavelle, Thomas M.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

2014-01-01

The Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) software package is an open source, MATLABSimulink toolbox (plug in) that can be used by industry professionals and academics for the development of thermodynamic and controls simulations.

A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

PubMed

Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

2015-03-28

Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

Thermodynamic Modeling of Hydrogen Storage Capacity in Mg-Na Alloys

PubMed Central

Abdessameud, S.; Mezbahul-Islam, M.; Medraj, M.

2014-01-01

Thermodynamic modeling of the H-Mg-Na system is performed for the first time in this work in order to understand the phase relationships in this system. A new thermodynamic description of the stable NaMgH3 hydride is performed and the thermodynamic models for the H-Mg, Mg-Na, and H-Na systems are reassessed using the modified quasichemical model for the liquid phase. The thermodynamic properties of the ternary system are estimated from the models of the binary systems and the ternary compound using CALPHAD technique. The constructed database is successfully used to reproduce the pressure-composition isotherms for MgH2 + 10 wt.% NaH mixtures. Also, the pressure-temperature equilibrium diagram and reaction paths for the same composition are predicted at different temperatures and pressures. Even though it is proved that H-Mg-Na does not meet the DOE hydrogen storage requirements for onboard applications, the best working temperatures and pressures to benefit from its full catalytic role are given. Also, the present database can be used for thermodynamic assessments of higher order systems. PMID:25383361

Thermodynamic modeling of hydrogen storage capacity in Mg-Na alloys.

PubMed

Abdessameud, S; Mezbahul-Islam, M; Medraj, M

2014-01-01

Thermodynamic modeling of the H-Mg-Na system is performed for the first time in this work in order to understand the phase relationships in this system. A new thermodynamic description of the stable NaMgH3 hydride is performed and the thermodynamic models for the H-Mg, Mg-Na, and H-Na systems are reassessed using the modified quasichemical model for the liquid phase. The thermodynamic properties of the ternary system are estimated from the models of the binary systems and the ternary compound using CALPHAD technique. The constructed database is successfully used to reproduce the pressure-composition isotherms for MgH2 + 10 wt.% NaH mixtures. Also, the pressure-temperature equilibrium diagram and reaction paths for the same composition are predicted at different temperatures and pressures. Even though it is proved that H-Mg-Na does not meet the DOE hydrogen storage requirements for onboard applications, the best working temperatures and pressures to benefit from its full catalytic role are given. Also, the present database can be used for thermodynamic assessments of higher order systems.

Strong Helioseismic Constraints on Weakly-Coupled Plasmas

NASA Astrophysics Data System (ADS)

Nayfonov, Alan

The extraordinary accuracy of helioseismic data allows detailed theoretical studies of solar plasmas. The necessity to produce solar models matching the experimental results in accuracy imposes strong constrains on the equations of state of solar plasmas. Several discrepancies between the experimental data and models have been successfully identified as the signatures of various non-ideal phenomena. Of a particular interest are questions of the position of the energy levels and the continuum edge and of the effect of the excited states in the solar plasma. Calculations of energy level and continuum shifts, based on the Green function formalism, appeared recently in the literature. These results have been used to examine effects of the shifts on the thermodynamic quantities. A comparison with helioseismic data has shown that the calculations based on lower-level approximations, such as the static screening in the effective two-particle wave equation, agree very well with the experimental data. However, the case of full dynamic screening produces thermodynamic quantities inconsistent with observations. The study of the effect of different internal partition functions on a complete set of thermodynamic quantities has revealed the signature of the excited states in the MHD (Mihalas, Hummer, Dappen) equation of state. The presence of exited states causes a characteristic 'wiggle' in the thermodynamic quantities due to the density-dependent occupation probabilities. This effect is absent if the ACTEX (ACTivity EXpansion) equation of state is used. The wiggle has been found to be most prominent in the quantities sensitive to density. The size of this excited states effect is well within the observational power of helioseismology, and very recent inversion analyses of helioseismic data seem to indicate the presence of the wiggle in the sun. This has a potential importance for the helioseismic determination of the helium abundance of the sun.

Thermodynamics of adaptive molecular resolution

NASA Astrophysics Data System (ADS)

Delgado-Buscalioni, R.

2016-11-01

A relatively general thermodynamic formalism for adaptive molecular resolution (AMR) is presented. The description is based on the approximation of local thermodynamic equilibrium and considers the alchemic parameter λ as the conjugate variable of the potential energy difference between the atomistic and coarse-grained model Φ=U(1)-U(0). The thermodynamic formalism recovers the relations obtained from statistical mechanics of H-AdResS (Español et al., J. Chem. Phys. 142, 064115, 2015 (doi:10.1063/1.4907006)) and provides relations between the free energy compensation and thermodynamic potentials. Inspired by this thermodynamic analogy, several generalizations of AMR are proposed, such as the exploration of new Maxwell relations and how to treat λ and Φ as `real' thermodynamic variables. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

Research into the rationality and the application scopes of different melting models of nanoparticles

NASA Astrophysics Data System (ADS)

Fu, Qingshan; Xue, Yongqiang; Cui, Zixiang; Duan, Huijuan

2017-07-01

A rational melting model is indispensable to address the fundamental issue regarding the melting of nanoparticles. To ascertain the rationality and the application scopes of the three classical thermodynamic models, namely Pawlow, Rie, and Reiss melting models, corresponding accurate equations for size-dependent melting temperature of nanoparticles were derived. Comparison of the melting temperatures of Au, Al, and Sn nanoparticles calculated by the accurate equations with available experimental results demonstrates that both Reiss and Rie melting models are rational and capable of accurately describing the melting behaviors of nanoparticles at different melting stages. The former (surface pre-melting) is applicable to the stage from initial melting to critical thickness of liquid shell, while the latter (solid particles surrounded by a great deal of liquid) from the critical thickness to complete melting. The melting temperatures calculated by the accurate equation based on Reiss melting model are in good agreement with experimental results within the whole size range of calculation compared with those by other theoretical models. In addition, the critical thickness of liquid shell is found to decrease with particle size decreasing and presents a linear variation with particle size. The accurate thermodynamic equations based on Reiss and Rie melting models enable us to quantitatively and conveniently predict and explain the melting behaviors of nanoparticles at all size range in the whole melting process. [Figure not available: see fulltext.

Application of thermodynamics to silicate crystalline solutions

NASA Technical Reports Server (NTRS)

Saxena, S. K.

1972-01-01

A review of thermodynamic relations is presented, describing Guggenheim's regular solution models, the simple mixture, the zeroth approximation, and the quasi-chemical model. The possibilities of retrieving useful thermodynamic quantities from phase equilibrium studies are discussed. Such quantities include the activity-composition relations and the free energy of mixing in crystalline solutions. Theory and results of the study of partitioning of elements in coexisting minerals are briefly reviewed. A thermodynamic study of the intercrystalline and intracrystalline ion exchange relations gives useful information on the thermodynamic behavior of the crystalline solutions involved. Such information is necessary for the solution of most petrogenic problems and for geothermometry. Thermodynamic quantities for tungstates (CaWO4-SrWO4) are calculated.

Cantera Integration with the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)

NASA Technical Reports Server (NTRS)

Lavelle, Thomas M.; Chapman, Jeffryes W.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

2014-01-01

NASA Glenn Research Center (GRC) has recently developed a software package for modeling generic thermodynamic systems called the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS). T-MATS is a library of building blocks that can be assembled to represent any thermodynamic system in the Simulink(Registered TradeMark) (The MathWorks, Inc.) environment. These elements, along with a Newton Raphson solver (also provided as part of the T-MATS package), enable users to create models of a wide variety of systems. The current version of T-MATS (v1.0.1) uses tabular data for providing information about a specific mixture of air, water (humidity), and hydrocarbon fuel in calculations of thermodynamic properties. The capabilities of T-MATS can be expanded by integrating it with the Cantera thermodynamic package. Cantera is an object-oriented analysis package that calculates thermodynamic solutions for any mixture defined by the user. Integration of Cantera with T-MATS extends the range of systems that may be modeled using the toolbox. In addition, the library of elements released with Cantera were developed using MATLAB native M-files, allowing for quicker prototyping of elements. This paper discusses how the new Cantera-based elements are created and provides examples for using T-MATS integrated with Cantera.

Cantera Integration with the Toolbox for Modeling and Analysis of Thermodynamic Systems (T-MATS)

NASA Technical Reports Server (NTRS)

Lavelle, Thomas M.; Chapman, Jeffryes W.; May, Ryan D.; Litt, Jonathan S.; Guo, Ten-Huei

2014-01-01

NASA Glenn Research Center (GRC) has recently developed a software package for modeling generic thermodynamic systems called the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS). T-MATS is a library of building blocks that can be assembled to represent any thermodynamic system in the Simulink (The MathWorks, Inc.) environment. These elements, along with a Newton Raphson solver (also provided as part of the T-MATS package), enable users to create models of a wide variety of systems. The current version of T-MATS (v1.0.1) uses tabular data for providing information about a specific mixture of air, water (humidity), and hydrocarbon fuel in calculations of thermodynamic properties. The capabilities of T-MATS can be expanded by integrating it with the Cantera thermodynamic package. Cantera is an object-oriented analysis package that calculates thermodynamic solutions for any mixture defined by the user. Integration of Cantera with T-MATS extends the range of systems that may be modeled using the toolbox. In addition, the library of elements released with Cantera were developed using MATLAB native M-files, allowing for quicker prototyping of elements. This paper discusses how the new Cantera-based elements are created and provides examples for using T-MATS integrated with Cantera.

T-MATS Toolbox for the Modeling and Analysis of Thermodynamic Systems

NASA Technical Reports Server (NTRS)

Chapman, Jeffryes W.

2014-01-01

The Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS) is a MATLABSimulink (The MathWorks Inc.) plug-in for creating and simulating thermodynamic systems and controls. The package contains generic parameterized components that can be combined with a variable input iterative solver and optimization algorithm to create complex system models, such as gas turbines.

Design, implementation and evaluation of a practical pseudoknot folding algorithm based on thermodynamics

PubMed Central

Reeder, Jens; Giegerich, Robert

2004-01-01

Background The general problem of RNA secondary structure prediction under the widely used thermodynamic model is known to be NP-complete when the structures considered include arbitrary pseudoknots. For restricted classes of pseudoknots, several polynomial time algorithms have been designed, where the O(n6)time and O(n4) space algorithm by Rivas and Eddy is currently the best available program. Results We introduce the class of canonical simple recursive pseudoknots and present an algorithm that requires O(n4) time and O(n2) space to predict the energetically optimal structure of an RNA sequence, possible containing such pseudoknots. Evaluation against a large collection of known pseudoknotted structures shows the adequacy of the canonization approach and our algorithm. Conclusions RNA pseudoknots of medium size can now be predicted reliably as well as efficiently by the new algorithm. PMID:15294028

Probing the General Time Scale Question of Boronic Acid Binding with Sugars in Aqueous Solution at Physiological pH

PubMed Central

Ni, Nanting; Laughlin, Sarah; Wang, Yingji; Feng, You; Zheng, Yujun

2012-01-01

The boronic acid group is widely used in chemosensor design due to its ability to reversibly bind diol-containing compounds. The thermodynamic properties of the boronic acid-diol binding process have been investigated extensively. However, there are few studies of the kinetic properties of such binding processes. In this report, stopped-flow method was used for the first time to study the kinetic properties of the binding between three model arylboronic acids, 4-, 5-, and 8-isoquinolinylboronic acids, and various sugars. With all the boronic acid-diol pair sexamined, reactions were complete within seconds. The kon values with various sugars follow the order of D-fructose >D-tagatose>D-mannose >D-glucose. This trend tracks the thermodynamic binding affinities for these sugars and demonstrates that the “on” rate is the key factor determining the binding constant. PMID:22464680

The reactants equation of state for the tri-amino-tri-nitro-benzene (TATB) based explosive PBX 9502

NASA Astrophysics Data System (ADS)

Aslam, Tariq D.

2017-07-01

The response of high explosives (HEs), due to mechanical and/or thermal insults, is of great importance for both safety and performance. A major component of how an HE responds to these stimuli stems from its reactant equation of state (EOS). Here, the tri-amino-tri-nitro-benzene based explosive PBX 9502 is investigated by examining recent experiments. Furthermore, a complete thermal EOS is calibrated based on the functional form devised by Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. It is found, by comparing to earlier calibrations, that a variety of thermodynamic data are needed to sufficiently constrain the EOS response over a wide range of thermodynamic state space. Included in the calibration presented here is the specific heat as a function of temperature, isobaric thermal expansion, and shock Hugoniot response. As validation of the resulting model, isothermal compression and isentropic compression are compared with recent experiments.

Comparison of the exact thermodynamics of the AF Blume-Emery-Grifiths and of the spin-1 ferromagnetic Ising models

NASA Astrophysics Data System (ADS)

Corrêa Silva, E. V.; Thomaz, M. T.

2016-11-01

We study in detail the thermodynamics of the anti-ferromagnetic Blume-Emery-Griffiths (AF BEG) model in the presence of a longitudinal magnetic field. Its thermodynamics is derived from the exact Helmholtz free energy (HFE) of the model, valid for T > 0. Numerical simulations of this model on a periodic space chain with 10 sites (N=10) yield the energy spectra of the model at K/J = 2 for D/J = 1 and D/J = 2, thus helping us compare, for a broad range of temperature, how some (per site) thermodynamic functions with the same value of K/J but distinct values of D/J behave, namely: the z-component of the magnetization, the specific heat and the entropy. These thermodynamic functions of the AF BEG model at K/|J| = 2 are compared to those of the spin-1 ferromagnetic Ising model with D/|J| > 1.5, for which the T=0 phase diagrams of both models are identical. This comparison is done in a large interval of temperature.

Temperature of maximum density and excess thermodynamics of aqueous mixtures of methanol

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

González-Salgado, D.; Zemánková, K.; Noya, E. G.

In this work, we present a study of representative excess thermodynamic properties of aqueous mixtures of methanol over the complete concentration range, based on extensive computer simulation calculations. In addition to test various existing united atom model potentials, we have developed a new force-field which accurately reproduces the excess thermodynamics of this system. Moreover, we have paid particular attention to the behavior of the temperature of maximum density (TMD) in dilute methanol mixtures. The presence of a temperature of maximum density is one of the essential anomalies exhibited by water. This anomalous behavior is modified in a non-monotonous fashion bymore » the presence of fully miscible solutes that partly disrupt the hydrogen bond network of water, such as methanol (and other short chain alcohols). In order to obtain a better insight into the phenomenology of the changes in the TMD of water induced by small amounts of methanol, we have performed a new series of experimental measurements and computer simulations using various force fields. We observe that none of the force-fields tested capture the non-monotonous concentration dependence of the TMD for highly diluted methanol solutions.« less

Thermodynamics of single polyethylene and polybutylene glycols with hydrogen-bonding ends: A transition from looped to open conformations

NASA Astrophysics Data System (ADS)

Lee, Eunsang; Paul, Wolfgang

2018-02-01

A variety of linear polymer precursors with hydrogen bonding motifs at both ends enable us to design supramolecular polymer systems with tailored macroscopic properties including self-healing. In this study, we investigate thermodynamic properties of single polyethylene and polybutylene glycols with hydrogen bonding motifs. In this context, we first build a coarse-grained model of building blocks of the supramolecular polymer system based on all-atom molecular structures. The density of states of the single precursor is obtained using the stochastic approximation Monte Carlo method. Constructing canonical partition functions from the density of states, we find the transition from looped to open conformations at transition temperatures which are non-monotonously changing with an increasing degree of polymerization due to the competition between chain stiffness and loop-forming entropy penalty. In the complete range of chain length under investigation, a coexistence of the looped and open morphologies at the transition temperature is shown regardless of whether the transition is first-order-like or continuous. Polyethylene and polybutylene glycols show similar behavior in all the thermodynamic properties but the transition temperature of the more flexible polybutylene glycol is shown to change more gradually.

The Statistical Interpretation of Classical Thermodynamic Heating and Expansion Processes

ERIC Educational Resources Information Center

Cartier, Stephen F.

2011-01-01

A statistical model has been developed and applied to interpret thermodynamic processes typically presented from the macroscopic, classical perspective. Through this model, students learn and apply the concepts of statistical mechanics, quantum mechanics, and classical thermodynamics in the analysis of the (i) constant volume heating, (ii)…

Quantum work and the thermodynamic cost of quantum measurements

DOE PAGES

Deffner, Sebastian; Paz, Juan Pablo; Zurek, Wojciech H.

2016-07-07

Quantum work is usually determined from two projective measurements of the energy at the beginning and at the end of a thermodynamic process. However, this paradigm cannot be considered thermodynamically consistent as it does not account for the thermodynamic cost of these measurements. To remedy this conceptual inconsistency we introduce a paradigm that relies only on the expected change of the average energy given the initial energy eigenbasis. In particular, we completely omit quantum measurements in the definition of quantum work, and hence quantum work is identified as a thermodynamic quantity of only the system. As main results we derivemore » a modified quantum Jarzynski equality and a sharpened maximum work theorem in terms of the information free energy. Lastly, a comparison of our results with the standard approach allows one to quantify the informational cost of projective measurements.« less

An Easy and Effective Demonstration of Enzyme Stereospecificity and Equilibrium Thermodynamics

ERIC Educational Resources Information Center

Herdman, Chelsea; Dickman, Michael

2011-01-01

Enzyme stereospecificity and equilibrium thermodynamics can be demonstrated using the coupling of two amino acid derivatives by Thermoase C160. This protease will catalyze peptide bond formation between Z-L-AspOH and L-PheOMe to form the Aspartame precursor Z-L-Asp-L-PheOMe. Reaction completion manifests itself by precipitation of the product. As…

Thermodynamics of adaptive molecular resolution.

PubMed

Delgado-Buscalioni, R

2016-11-13

A relatively general thermodynamic formalism for adaptive molecular resolution (AMR) is presented. The description is based on the approximation of local thermodynamic equilibrium and considers the alchemic parameter λ as the conjugate variable of the potential energy difference between the atomistic and coarse-grained model Φ=U (1) -U (0) The thermodynamic formalism recovers the relations obtained from statistical mechanics of H-AdResS (Español et al, J. Chem. Phys. 142, 064115, 2015 (doi:10.1063/1.4907006)) and provides relations between the free energy compensation and thermodynamic potentials. Inspired by this thermodynamic analogy, several generalizations of AMR are proposed, such as the exploration of new Maxwell relations and how to treat λ and Φ as 'real' thermodynamic variablesThis article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

Chirality Switching by Martensitic Transformation in Protein Cylindrical Crystals: Application to Bacterial Flagella

NASA Astrophysics Data System (ADS)

Komai, Ricardo Kiyohiro

Martensitic transformations provide unique engineering properties that, when designed properly, become important parts of new technology. Martensitic transformations have been studied for many years in traditional alloys (iron, steel, titanium, etc.), however there is still much to be learned in regards to these transformations in biological materials. Olson and Hartman showed in 1982 that these transformations are also observed in bacterial flagella and T4 bacteriophage viral sheaths, allowing for propulsion of bacteria in a fluid environment and, for the virus, is responsible for the infection mechanism. This work demonstrates, using the bacterial flagella as an example, that these transformations can be modelled using thermodynamic methods that are also used to model the transformations in alloys. This thesis work attempts to explain the transformations that occur in bacterial flagella, which are capable of small strain, highly reversible martensitic transformations. The first stress/temperature phase diagrams of these flagella were created by adding the mechanical energy of the transformation of the flagella to limited chemical thermodynamics information of the transformation. Mechanical energy is critical to the transformation process because the bacterial body applies a torque to the radius of the flagella. Finally, work has begun and will be completed in regards to understanding the kinetics of the transformation of the flagella. The motion of the transformation interface can be predicted by using a Landau-Ginzburg model. The crystallography of the transformation in bacterial flagella is also being computed to determine the invariant lines of transformation that occur within this cylindrical crystal. This work has shown that it is possible to treat proteins in a similar manner that alloys are treated when using thermodynamic modelling. Much can be learned from translating what is known regarding phase transformations in hard material systems to soft, organic systems.

Evaluating marginal likelihood with thermodynamic integration method and comparison with several other numerical methods

DOE PAGES

Liu, Peigui; Elshall, Ahmed S.; Ye, Ming; ...

2016-02-05

Evaluating marginal likelihood is the most critical and computationally expensive task, when conducting Bayesian model averaging to quantify parametric and model uncertainties. The evaluation is commonly done by using Laplace approximations to evaluate semianalytical expressions of the marginal likelihood or by using Monte Carlo (MC) methods to evaluate arithmetic or harmonic mean of a joint likelihood function. This study introduces a new MC method, i.e., thermodynamic integration, which has not been attempted in environmental modeling. Instead of using samples only from prior parameter space (as in arithmetic mean evaluation) or posterior parameter space (as in harmonic mean evaluation), the thermodynamicmore » integration method uses samples generated gradually from the prior to posterior parameter space. This is done through a path sampling that conducts Markov chain Monte Carlo simulation with different power coefficient values applied to the joint likelihood function. The thermodynamic integration method is evaluated using three analytical functions by comparing the method with two variants of the Laplace approximation method and three MC methods, including the nested sampling method that is recently introduced into environmental modeling. The thermodynamic integration method outperforms the other methods in terms of their accuracy, convergence, and consistency. The thermodynamic integration method is also applied to a synthetic case of groundwater modeling with four alternative models. The application shows that model probabilities obtained using the thermodynamic integration method improves predictive performance of Bayesian model averaging. As a result, the thermodynamic integration method is mathematically rigorous, and its MC implementation is computationally general for a wide range of environmental problems.« less

Metronidazole removal in powder-activated carbon and concrete-containing graphene adsorption systems: Estimation of kinetic, equilibrium and thermodynamic parameters and optimization of adsorption by a central composite design.

PubMed

Manjunath, S V; Kumar, S Mathava; Ngo, Huu Hao; Guo, Wenshan

2017-12-06

Metronidazole (MNZ) removal by two adsorbents, i.e., concrete-containing graphene (CG) and powder-activated carbon (PAC), was investigated via batch-mode experiments and the outcomes were used to analyze the kinetics, equilibrium and thermodynamics of MNZ adsorption. MNZ sorption on CG and PAC has followed the pseudo-second-order kinetic model, and the thermodynamic parameters revealed that MNZ adsorption was spontaneous on PAC and non-spontaneous on CG. Subsequently, two-parameter isotherm models, i.e., Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Elovich models, were applied to evaluate the MNZ adsorption capacity. The maximum MNZ adsorption capacities ([Formula: see text]) of PAC and CG were found to be between 25.5-32.8 mg/g and 0.41-0.002 mg/g, respectively. Subsequently, the effects of pH, temperature and adsorbent dosage on MNZ adsorption were evaluated by a central composite design (CCD) approach. The CCD experiments have pointed out the complete removal of MNZ at a much lower PAC dosage by increasing the system temperature (i.e., from 20°C to 40°C). On the other hand, a desorption experiment has shown 3.5% and 1.7% MNZ removal from the surface of PAC and CG, respectively, which was insignificant compared to the sorbed MNZ on the surface by adsorption. The overall findings indicate that PAC and CG with higher graphene content could be useful in MNZ removal from aqueous systems.

MnFe2O4-graphene oxide magnetic nanoparticles as a high-performance adsorbent for rare earth elements: Synthesis, isotherms, kinetics, thermodynamics and desorption.

PubMed

Ghobadi, Misagh; Gharabaghi, Mahdi; Abdollahi, Hadi; Boroumand, Zohreh; Moradian, Marzieh

2018-06-05

In recent decades, considerable amounts of rare earth elements have been used and then released into industrial wastewater, which caused serious environmental problems. In this work, in order to recycle rare earth cations (La 3+ and Ce 3+ ) from aqueous solutions, MnFe 2 O 4 -Graphene oxide magnetic nanoparticles were synthesized and after characterization studies, their adsorption isotherms, kinetics, thermodynamics and desorption were comprehensively investigated. Characterized was performed using XRD, FE-SEM, FT-IR, Raman spectroscopy, VSM, BET and DLS. REE adsorption on MnFe 2 O 4 -GO was studied for the first time in the present work and the maximum adsorption capacity at the optimum condition (room temperature and pH = 7) for La 3+ and Ce 3+ were 1001 and 982 mg/g respectively, and the reactions were completed within 20 min. In addition, the adsorption data were well matched with the Langmuir model and the adsorption kinetics were fitted with the pseudo-second order model. The thermodynamic parameters were calculated and the reactions were found to be endothermic and spontaneous. Moreover, the Dubinin-Radushkevich model predicted chemical ion-exchange adsorption. Desorption studies also demonstrated that MnFe 2 O 4 -GO can be regenerated for multiple reuses. Overall, high adsorption capacity, chemical stability, reusability, fast kinetics, easy magnetic separation, and simple synthesis method indicated that MnFe 2 O 4 -GO is a high-performance adsorbent for REE. Copyright © 2018. Published by Elsevier B.V.

A non-equilibrium thermodynamics model of reconstituted Ca(2+)-ATPase.

PubMed

Waldeck, A R; van Dam, K; Berden, J; Kuchel, P W

1998-01-01

A non-equilibrium thermodynamics (NET) model describing the action of completely coupled or 'slipping' reconstituted Ca(2+)-ATPase is presented. Variation of the coupling stoichiometries with the magnitude of the electrochemical gradients, as the ATPase hydrolyzes ATP, is an indication of molecular slip. However, the Ca2+ and H+ membrane-leak conductances may also be a function of their respective gradients. Such non-ohmic leak typically yields 'flow-force' relationships that are similar to those that are obtained when the pump slips; hence, caution needs to be exercised when interpreting data of Ca(2+)-ATPase-mediated fluxes that display a non-linear dependence on the electrochemical proton (delta mu H) and/or calcium gradients (delta mu Ca). To address this issue, three experimentally verifiable relationships differentiating between membrane leak and enzymic slip were derived. First, by measuring delta mu H as a function of the rate of ATP hydrolysis by the enzyme. Second, by measuring the overall 'efficiency' of the pump as a function of delta mu H. Third, by measuring the proton ejection rate by the pump as a function of its ATP hydrolysis rate.

Autonomous Quantum Clocks: Does Thermodynamics Limit Our Ability to Measure Time?

NASA Astrophysics Data System (ADS)

Erker, Paul; Mitchison, Mark T.; Silva, Ralph; Woods, Mischa P.; Brunner, Nicolas; Huber, Marcus

2017-07-01

Time remains one of the least well-understood concepts in physics, most notably in quantum mechanics. A central goal is to find the fundamental limits of measuring time. One of the main obstacles is the fact that time is not an observable and thus has to be measured indirectly. Here, we explore these questions by introducing a model of time measurements that is complete and autonomous. Specifically, our autonomous quantum clock consists of a system out of thermal equilibrium—a prerequisite for any system to function as a clock—powered by minimal resources, namely, two thermal baths at different temperatures. Through a detailed analysis of this specific clock model, we find that the laws of thermodynamics dictate a trade-off between the amount of dissipated heat and the clock's performance in terms of its accuracy and resolution. Our results furthermore imply that a fundamental entropy production is associated with the operation of any autonomous quantum clock, assuming that quantum machines cannot achieve perfect efficiency at finite power. More generally, autonomous clocks provide a natural framework for the exploration of fundamental questions about time in quantum theory and beyond.

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.

Beyond heat baths II: framework for generalized thermodynamic resource theories

NASA Astrophysics Data System (ADS)

Yunger Halpern, Nicole

2018-03-01

Thermodynamics, which describes vast systems, has been reconciled with small scales, relevant to single-molecule experiments, in resource theories. Resource theories have been used to model exchanges of energy and information. Recently, particle exchanges were modeled; and an umbrella family of thermodynamic resource theories was proposed to model diverse baths, interactions, and free energies. This paper motivates and details the family’s structure and prospective applications. How to model electrochemical, gravitational, magnetic, and other thermodynamic systems is explained. Szilárd’s engine and Landauer’s Principle are generalized, as resourcefulness is shown to be convertible not only between information and gravitational energy, but also among diverse degrees of freedom. Extensive variables are associated with quantum operators that might fail to commute, introducing extra nonclassicality into thermodynamic resource theories. An early version of this paper partially motivated the later development of noncommutative thermalization. This generalization expands the theories’ potential for modeling realistic systems with which small-scale statistical mechanics might be tested experimentally.

Thermodynamic assessment of the magmatic history of Blue Rock shield volcano, Jackson Co., Oregon: application of a new DNi (olivine-melt) geothermometer and other models

NASA Astrophysics Data System (ADS)

Crabtree, Stephen M.; Huber, Abigail; Beck, Karl

2017-05-01

Blue Rock is a basaltic shield volcano in the southern Oregon Cascades, north of Mt. McLoughlin, showing bulk phenocryst abundances ranging from 5 to 28 vol%, and a variety of groundmass textures. Compositional analyses of olivine and plagioclase phenocrysts and glomerocrysts allowed for the sequential application of a new {D}_{Ni}^{olivine-melt} thermometer, a plagioclase-melt hygrometer, and a viscosity model to define olivine-in conditions for a suite of lavas erupted from this edifice. Calculated olivine-in temperatures were compared to results from the anhydrous MELTS model, and the D (Mg) model of Beattie (1993). Model results were consistent with experimental data for hydrous arc basalts with respect to temperature (1053-1146 °C), dissolved-H2O contents (0.9-2.4 wt% H2O), and viscosity (1.9-2.2 log10 Pa s), confirming the utility of these models in assessing the thermodynamic properties of mafic, hydrous arc lavas over a broad range in crystallinity, requiring only the completion of bulk geochemical and microprobe analyses. These studies also reinforced the significant and predictable role of water, affecting the compositions of crystals grown during magmatic ascent, and allowed the definition of a reasonable multi-stage eruptive sequence consistent with the degassing of magmas on ascent in the formation of this small-scale basaltic edifice.

Systematic assignment of thermodynamic constraints in metabolic network models

PubMed Central

Kümmel, Anne; Panke, Sven; Heinemann, Matthias

2006-01-01

Background The availability of genome sequences for many organisms enabled the reconstruction of several genome-scale metabolic network models. Currently, significant efforts are put into the automated reconstruction of such models. For this, several computational tools have been developed that particularly assist in identifying and compiling the organism-specific lists of metabolic reactions. In contrast, the last step of the model reconstruction process, which is the definition of the thermodynamic constraints in terms of reaction directionalities, still needs to be done manually. No computational method exists that allows for an automated and systematic assignment of reaction directions in genome-scale models. Results We present an algorithm that – based on thermodynamics, network topology and heuristic rules – automatically assigns reaction directions in metabolic models such that the reaction network is thermodynamically feasible with respect to the production of energy equivalents. It first exploits all available experimentally derived Gibbs energies of formation to identify irreversible reactions. As these thermodynamic data are not available for all metabolites, in a next step, further reaction directions are assigned on the basis of network topology considerations and thermodynamics-based heuristic rules. Briefly, the algorithm identifies reaction subsets from the metabolic network that are able to convert low-energy co-substrates into their high-energy counterparts and thus net produce energy. Our algorithm aims at disabling such thermodynamically infeasible cyclic operation of reaction subnetworks by assigning reaction directions based on a set of thermodynamics-derived heuristic rules. We demonstrate our algorithm on a genome-scale metabolic model of E. coli. The introduced systematic direction assignment yielded 130 irreversible reactions (out of 920 total reactions), which corresponds to about 70% of all irreversible reactions that are required to disable thermodynamically infeasible energy production. Conclusion Although not being fully comprehensive, our algorithm for systematic reaction direction assignment could define a significant number of irreversible reactions automatically with low computational effort. We envision that the presented algorithm is a valuable part of a computational framework that assists the automated reconstruction of genome-scale metabolic models. PMID:17123434

Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

NASA Astrophysics Data System (ADS)

Qorbani, Khadijeh; Kvamme, Bjørn

2016-04-01

Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated as non-equilibrium processes under local constraint of mass and heat fluxes. In this work, we have extended RCB by adding another route for dissociation or reformation of CH4-hydrate towards CH4 into the aqueous phase and water. CH4-hydrate formation and dissociation is resolved by looking at supersaturation and undersaturation with respect to thermodynamics variables. Hydrate instability due to undersaturation of CH4 in the contacting water phase is also considered. A complete non-equilibrium thermodynamic package, developed in-house, was combined with RCB to account for competing phase transitions by considering the minimization of Gibb's free energy. The energy differences were calculated from variations in chemical potentials of hydrate and hydrate formers. Mass transport, heat transport and non-equilibrium thermodynamic effects were implemented through classical nucleation theory to model the kinetic rate of hydrate phase transitions. To illustrate our implementations we ran simulations covering time-spans in the order of hundred years. CH4 production was modelled using the depressurization method, where we employed the Messoyakha field data. We discuss our implementations, as well as results obtained from simulations utilizing our modifications.

Coupling Fluid Dynamics and Multiphase Disequilibria: Applications to Eutectic and Peritectic Systems

NASA Astrophysics Data System (ADS)

Tweed, L. E. L.; Spiegelman, M. W.; Kelemen, P. B.

2017-12-01

Computational thermodynamics has yielded great insights into petrological processes. However, on its own it cannot capture the inherently dynamic nature of many of these processes which depend on the interaction between time-dependent processes including advection, diffusion and chemical reaction. To understand this interplay, and to move away from a purely equilibrium view, requires the integration of computational thermodynamics and fluid mechanics. A key aspect of doing this is the treatment of chemical reactions as time-dependent, irreversible processes. Such a development is integral to understanding a host of petrological questions from the open system evolution of magma chambers to the dynamics of melt migration beneath mid-ocean ridges and flux melting of the mantle wedge in subduction zones. A simple thermodynamically consistent reactive model is developed that can be integrated with conservation equations for mass, momentum and energy. The model rests on the thermodynamic characterization of an independent set of reactions and has the advantage of being completely general and easily extensible to systems comprising multiple solid and liquid phases. The underlying theory is described in detail in another contribution in this session. Here we apply the framework to experimentally constrained simple systems of petrological interest including the fo-qz binary and the fo-qz-k2o ternary. These systems contain a variety of phase topologies including eutectic and peritectic reactions. As the model allows for the seamless exhaustion and stabilization of phases, we can explore the effect that these discontinuous changes have on the compositional and dynamic evolution of the system. To do this we track how the systems respond to sudden changes in intensive variables that perturb them from equilibrium. Such changes are rife in crustal magmatic systems. Simulations for decompression melting are also run to explore the interplay between reactive and advective fluxes. Buffering between the multiple reactions can result in surprising reaction paths highlighting that micro-mechanics could play a significant role in magmatic evolution. By building up the complexity of the problems gradually, we develop an intuition for the effect of model choices including the kinetic law and the set of reactions used.

Direct Thermodynamic Measurements of the Energetics of Information Processing

DTIC Science & Technology

2017-08-08

Report: Direct thermodynamic measurements of the energetics of information processing The views, opinions and/or findings contained in this report are... information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and...maintaining the data needed, and completing and reviewing the collection of information . Send comments regarding this burden estimate or any other

Workshop on Information Engines at the Frontiers of Nanoscale Thermodynamics

DTIC Science & Technology

2017-11-01

Report: Workshop on Information Engines at the Frontiers of Nanoscale Thermodynamics The views, opinions and/or findings contained in this report are... information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and...maintaining the data needed, and completing and reviewing the collection of information . Send comments regarding this burden estimate or any other

Thermodynamics of Inozemtsev's elliptic spin chain

NASA Astrophysics Data System (ADS)

Klabbers, Rob

2016-06-01

We study the thermodynamic behaviour of Inozemtsev's long-range elliptic spin chain using the Bethe ansatz equations describing the spectrum of the model in the infinite-length limit. We classify all solutions of these equations in that limit and argue which of these solutions determine the spectrum in the thermodynamic limit. Interestingly, some of the solutions are not selfconjugate, which puts the model in sharp contrast to one of the model's limiting cases, the Heisenberg XXX spin chain. Invoking the string hypothesis we derive the thermodynamic Bethe ansatz equations (TBA-equations) from which we determine the Helmholtz free energy in thermodynamic equilibrium and derive the associated Y-system. We corroborate our results by comparing numerical solutions of the TBA-equations to a direct computation of the free energy for the finite-length hamiltonian. In addition we confirm numerically the interesting conjecture put forward by Finkel and González-López that the original and supersymmetric versions of Inozemtsev's elliptic spin chain are equivalent in the thermodynamic limit.

Performance of a Kilowatt-Class Stirling Power Conversion System in a Thermodynamically Coupled Configuration

NASA Technical Reports Server (NTRS)

Geng, Steven M.; Briggs, Maxwell H.; Hervol, David S.

2011-01-01

A pair of 1-kWe free-piston Stirling power convertors has been modified into a thermodynamically coupled configuration, and performance map testing has been completed. This is the same configuration planned for the full-scale 12-kWe power conversion unit (PCU) that will be used in the Fission Power System Technology Demonstration Unit (TDU). The 1-kWe convertors were operated over a range of conditions to evaluate the effects of thermodynamic coupling on convertor performance and to identify any possible control challenges. The thermodynamically coupled convertor showed no measureable difference in performance from the baseline data collected when the engines were separate, and no major control issues were encountered during operation. The results of this test are guiding controller development and instrumentation selection for the TDU.

Performance of a Kilowatt-Class Stirling Power Conversion System in a Thermodynamically-Coupled Configuration

NASA Astrophysics Data System (ADS)

Geng, S. M.; Briggs, M. H.; Hervol, D. S.

A pair of 1kWe free-piston Stirling power convertors has been modified into a thermodynamically coupled configuration, and performance map testing has been completed. This is the same configuration planned for the full-scale 12 kWe power conversion unit (PCU) that will be used in the Fission Power System Technology Demonstration Unit (TDU). The 1-kWe convertors were operated over a range of conditions to evaluate the effects of thermodynamic coupling on convertor performance and to identify any possible control challenges. The thermodynamically coupled convertor showed no measurable difference in performance from the baseline data collected when the engines were separate and no major control issues were encountered during operation. The results of this test are guiding controller development and instrumentation selection for the TDU.

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.

Subgrid-scale Condensation Modeling for Entropy-based Large Eddy Simulations of Clouds

NASA Astrophysics Data System (ADS)

Kaul, C. M.; Schneider, T.; Pressel, K. G.; Tan, Z.

2015-12-01

An entropy- and total water-based formulation of LES thermodynamics, such as that used by the recently developed code PyCLES, is advantageous from physical and numerical perspectives. However, existing closures for subgrid-scale thermodynamic fluctuations assume more traditional choices for prognostic thermodynamic variables, such as liquid potential temperature, and are not directly applicable to entropy-based modeling. Since entropy and total water are generally nonlinearly related to diagnosed quantities like temperature and condensate amounts, neglecting their small-scale variability can lead to bias in simulation results. Here we present the development of a subgrid-scale condensation model suitable for use with entropy-based thermodynamic formulations.

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

Exploring dynamic events in the solar corona

NASA Astrophysics Data System (ADS)

Downs, Cooper James

With the advent of modern computational technology it is now becoming the norm to employ detailed 3D computer models as empirical tools that directly account for the inhomogeneous nature of the Sun-Heliosphere environment. The key advantage of this approach lies in the ability to compare model results directly to observational data and to use a successful comparison (or lack thereof) to glean information on the underlying physical processes. Using extreme ultraviolet waves (EUV waves) as the overarching scientific driver, we apply this observation modeling approach to study the complex dynamics of the magnetic and thermodynamic structures that are observed in the low solar corona. Representing a highly non-trivial effort, this work includes three main scientific thrusts: an initial modeling effort and two EUV wave case-studies. First we document the development of the new Low Corona (LC) model, a 3D time-dependent thermodynamic magnetohydrodynamic (MHD) model implemented within the Space Weather Modeling Framework (SWMF). Observation synthesis methods are integrated within the LC model, which provides the ability to compare model results directly to EUV imaging observations taken by spacecraft. The new model is then used to explore the dynamic interplay between magnetic structures and thermodynamic energy balance in the corona that is caused by coronal heating mechanisms. With the model development complete, we investigate the nature of EUV waves in detail through two case-studies. Starting with the 2008 March 25 event, we conduct a series of numerical simulations that independently vary fundamental parameters thought to govern the physical mechanisms behind EUV waves. Through the subsequent analysis of the 3D data and comparison to observations we find evidence for both wave and non-wave mechanisms contributing to the EUV wave signal. We conclude with a comprehensive observation and modeling analysis of the 2010 June 13 EUV wave event, which was observed by the recently launched Solar Dynamics Observatory. We use a high resolution simulation of the transient to unambiguously characterize the globally propagating front of EUV wave as a fast-mode magnetosonic wave, and use the rich set of observations to place the many other facets of the EUV transient within a unified scenario involving wave and non-wave components.

New predictive model for monitoring bone remodeling.

PubMed

Bougherara, Habiba; Klika, Václav; Marsík, Frantisek; Marík, Ivo A; Yahia, L'hocine

2010-10-01

The aim of this article was to present a new thermodynamic-based model for bone remodeling which is able to predict the functional adaptation of bone in response to changes in both mechanical and biochemical environments. The model was based on chemical kinetics and irreversible thermodynamic principles, in which bone is considered as a self-organizing system that exchanges matter, energy and entropy with its surroundings. The governing equations of the mathematical model have been numerically solved using Matlab software and implemented in ANSYS software using the Finite Element Method. With the aid of this model, the whole inner structure of bone was elucidated. The current model suggested that bone remodeling was a dynamic process which was driven by mechanical loading, metabolic factors and other external contributions. The model clearly indicated that in the absence of mechanical stimulus, the bone was not completely resorbed and reaches a new steady state after about 50% of bone loss. This finding agreed with previous clinical studies. Furthermore, results of virtual computations of bone density in a composite femur showed the development of a dense cortical bone around the medullary canal and a dense trabeculae bone between the femoral head and the calcar region of the medial cortex due to compressive stresses. The comparison of the predicted bone density with the structure of the proximal femur obtained from X-rays and using strain energy density gave credibility to the current model. Copyright 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010.

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)

Some comments on thermodynamic consistency for equilibrium mixture equations of state

DOE PAGES

Grove, John W.

2018-03-28

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

Thermodynamic modeling of melts in the system Na 2O-NaAlO 2-SiO 2-F 2O -1

NASA Astrophysics Data System (ADS)

Dolejš, David; Baker, Don R.

2005-12-01

Fluorine is a common volatile element in magmatic-hydrothermal systems, but its solution mechanisms and thermodynamic description in highly polymerized silicate melts are poorly known. We have developed a thermodynamic model for fluorosilicate liquids that links experimentally determined phase equilibria and spectroscopic information on melt structure. The model is applicable to crystallization of fluoride minerals, fluoride-silicate immiscibility in natural felsic melts, and metallurgical processes. Configurational properties of fluorosilicate melts are described by mixing on three site levels (sublattices): (1) alkali fluoride, polyhedral aluminofluoride and silicofluoride species and nonbridging terminations of the aluminosilicate network, (2) alkali-aluminate and silicate tetrahedra within the network and (3) bridging oxygen, nonbridging oxygen and terminal fluorine atoms on tetrahedral apices of the network. Abundances of individual chemical species are described by a homogeneous equilibrium representing melt depolymerization: F - (free) + O 0 (bridging) = F 0 (terminal) + O - (nonbridging) which corresponds to a replacement of an oxygen bridging two tetrahedra by a pair of terminations, one with F and the other with an O and a charge-balancing Na. In cryolite-bearing systems two additional interaction mechanisms occur: (1) the self-dissociation of octahedral aluminofluoride complexes: [AlF 6] = [AlF 4] + 2 [F], and (2) the short-range order between (O,F)-corners and (Si,NaAl)-centers of tetrahedra: Si-O-Si + 2 [NaAl]-F = [NaAl]-O-[NaAl] + 2 Si-F. Portrayal of these equilibria in ternary Thompson reaction space allows for the decrease in the number of interaction mechanisms by linearly combining melt depolymerization with tetrahedral short-range order. In this formulation, the nonideal thermodynamic properties are represented by reaction energies of homogeneous equilibria, thus defining directly individual chemical species concentrations and configurational properties. Thermodynamic expressions for the activity-composition relationships are simplified if all entities are expressed using symbolic molecular notation (e.g., SiO 2, SiF 4, [NaAl]O 2, [NaAl]F 4, NaF etc.) with corresponding nonfractional site multiplicities (1, 2 or 4). The model has been applied to three subsystems of the Na 2O-NaAlO 2-SiO 2-F 2O -1 compositional space. Activity-composition relationships in the villiaumite-sodium silicate binaries require clustering of silicate tetrahedra and only negligible interaction between fluoride species and silicate polymer. Phase equilibria in the cryolite-albite system with a large depression of albite liquidus are interpreted via complete substitution of O 0 by O - and F 0 in the silicate framework. With increasing fluorine content, initial Al-F and Si-O short-range order evolves into the partial O-F disorder. The present model provides a useful relationship between experimental equilibria, macroscopic thermodynamics and melt speciation, thus it facilitates comparisons with, and interpretations of, spectroscopic and molecular simulation data.

Steepest entropy ascent quantum thermodynamic model of electron and phonon transport

NASA Astrophysics Data System (ADS)

Li, Guanchen; von Spakovsky, Michael R.; Hin, Celine

2018-01-01

An advanced nonequilibrium thermodynamic model for electron and phonon transport is formulated based on the steepest-entropy-ascent quantum thermodynamics framework. This framework, based on the principle of steepest entropy ascent (or the equivalent maximum entropy production principle), inherently satisfies the laws of thermodynamics and mechanics and is applicable at all temporal and spatial scales even in the far-from-equilibrium realm. Specifically, the model is proven to recover the Boltzmann transport equations in the near-equilibrium limit and the two-temperature model of electron-phonon coupling when no dispersion is assumed. The heat and mass transport at a temperature discontinuity across a homogeneous interface where the dispersion and coupling of electron and phonon transport are both considered are then modeled. Local nonequilibrium system evolution and nonquasiequilibrium interactions are predicted and the results discussed.

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.

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.

Thermodynamic limit and boundary energy of the su(3) spin chain with non-diagonal boundary fields

NASA Astrophysics Data System (ADS)

Wen, Fakai; Yang, Tao; Yang, Zhanying; Cao, Junpeng; Hao, Kun; Yang, Wen-Li

2017-02-01

We investigate the thermodynamic limit of the su (n)-invariant spin chain models with unparallel boundary fields. It is found that the contribution of the inhomogeneous term in the associated T-Q relation to the ground state energy does vanish in the thermodynamic limit. This fact allows us to calculate the boundary energy of the system. Taking the su (2) (or the XXX) spin chain and the su (3) spin chain as concrete examples, we have studied the corresponding boundary energies of the models. The method used in this paper can be generalized to study the thermodynamic properties and boundary energy of other high rank models with non-diagonal boundary fields.

Quantum thermodynamics of the resonant-level model with driven system-bath coupling

NASA Astrophysics Data System (ADS)

Haughian, Patrick; Esposito, Massimiliano; Schmidt, Thomas L.

2018-02-01

We study nonequilibrium thermodynamics in a fermionic resonant-level model with arbitrary coupling strength to a fermionic bath, taking the wide-band limit. In contrast to previous theories, we consider a system where both the level energy and the coupling strength depend explicitly on time. We find that, even in this generalized model, consistent thermodynamic laws can be obtained, up to the second order in the drive speed, by splitting the coupling energy symmetrically between system and bath. We define observables for the system energy, work, heat, and entropy, and calculate them using nonequilibrium Green's functions. We find that the observables fulfill the laws of thermodynamics, and connect smoothly to the known equilibrium results.

The As-Cu-Ni System: A Chemical Thermodynamic Model for Ancient Recycling

NASA Astrophysics Data System (ADS)

Sabatini, Benjamin J.

2015-12-01

This article is the first thermodynamically reasoned ancient metal system assessment intended for use by archaeologists and archaeometallurgists to aid in the interpretation of remelted/recycled copper alloys composed of arsenic and copper, and arsenic, copper, and nickel. These models are meant to fulfill two main purposes: first, to be applied toward the identification of progressive and regressive temporal changes in artifact chemistry that would have occurred due to recycling, and second, to provide thermodynamic insight into why such metal combinations existed in antiquity. Built on well-established thermodynamics, these models were created using a combination of custom-written software and published binary thermodynamic systems data adjusted to within the boundary conditions of 1200°C and 1 atm. Using these parameters, the behavior of each element and their likelihood of loss in the binaries As-Cu, As-Ni, Cu-Ni, and ternary As-Cu-Ni, systems, under assumed ancient furnace conditions, was determined.

Connecting thermodynamics and economics: well-lit roads and burned bridges.

PubMed

Glucina, Mark David; Mayumi, Kozo

2010-01-01

Almost 40 years have passed since Georgescu-Roegen's seminal work, The Entropy Law and the Economic Process. During this time there has been much debate on the relevance of thermodynamics to economics, and many attempts to build bridges between the two. There has also been much confusion as to what the laws of thermodynamics actually say. This article clearly explains heat, work, and the thermodynamic laws, the meaning of entropy, and the importance of kinetics as a barrier to thermodynamically favorable processes. The two most important misunderstandings in the literature, namely entropy as disorder, and entropy as a measure of information, are highlighted. Reviewing the literature shows that thermodynamics is most relevant for building a descriptive model, or preanalytic vision of economics, because it implies physical constraints on production and consumption. Similarly, it suggests that there may be serious flaws with neoclassical economic models, and in particular the primacy of sustained growth. However, thermodynamics does not seem to aid mathematical modeling in economics, nor does it provide normative insights. As an aid to energy policy, thermodynamics is useful for assessing the feasibility of technology options--those that have the potential to meet our goals, and should be counted as options, and those that should not. But it does not provide a prescription outside of this technical realm. Factors, such as environmental impact, cost, and social acceptability, will ultimately determine which technically feasible options are most desirable.

NASA Glenn Coefficients for Calculating Thermodynamic Properties of Individual Species

NASA Technical Reports Server (NTRS)

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

2002-01-01

This report documents the library of thermodynamic data used with the NASA Glenn computer program CEA (Chemical Equilibrium with Applications). This library, containing data for over 2000 solid, liquid, and gaseous chemical species for temperatures ranging from 200 to 20,000 K, is available for use with other computer codes as well. The data are expressed as least-squares coefficients to a seven-term functional form for C((sup o)(sub p)) (T) / R with integration constants for H (sup o) (T) / RT and S(sup o) (T) / R. The NASA Glenn computer program PAC (Properties and Coefficients) was used to calculate thermodynamic functions and to generate the least-squares coefficients. PAC input was taken from a variety of sources. A complete listing of the database is given along with a summary of thermodynamic properties at 0 and 298.15 K.

Thermodynamic forces in coarse-grained simulations

NASA Astrophysics Data System (ADS)

Noid, William

Atomically detailed molecular dynamics simulations have profoundly advanced our understanding of the structure and interactions in soft condensed phases. Nevertheless, despite dramatic advances in the methodology and resources for simulating atomically detailed models, low-resolution coarse-grained (CG) models play a central and rapidly growing role in science. CG models not only empower researchers to investigate phenomena beyond the scope of atomically detailed simulations, but also to precisely tailor models for specific phenomena. However, in contrast to atomically detailed simulations, which evolve on a potential energy surface, CG simulations should evolve on a free energy surface. Therefore, the forces in CG models should reflect the thermodynamic information that has been eliminated from the CG configuration space. As a consequence of these thermodynamic forces, CG models often demonstrate limited transferability and, moreover, rarely provide an accurate description of both structural and thermodynamic properties. In this talk, I will present a framework that clarifies the origin and impact of these thermodynamic forces. Additionally, I will present computational methods for quantifying these forces and incorporating their effects into CG MD simulations. As time allows, I will demonstrate applications of this framework for liquids, polymers, and interfaces. We gratefully acknowledge the support of the National Science Foundation via CHE 1565631.

From coupled elementary units to the complexity of the glass transition.

PubMed

Rehwald, Christian; Rubner, Oliver; Heuer, Andreas

2010-09-10

Supercooled liquids display fascinating properties upon cooling such as the emergence of dynamic length scales. Different models strongly vary with respect to the choice of the elementary subsystems as well as their mutual coupling. Here we show via computer simulations of a glass former that both ingredients can be identified via analysis of finite-size effects within the continuous-time random walk framework. The subsystems already contain complete information about thermodynamics and diffusivity, whereas the coupling determines structural relaxation and the emergence of dynamic length scales.

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.

A note on the relations between thermodynamics, energy definitions and Friedmann equations

NASA Astrophysics Data System (ADS)

Moradpour, H.; Nunes, Rafael C.; Abreu, Everton M. C.; Neto, Jorge Ananias

2017-04-01

We investigate the relation between the Friedmann and thermodynamic pressure equations, through solving the Friedmann and thermodynamic pressure equations simultaneously. Our investigation shows that a perfect fluid, as a suitable solution for the Friedmann equations leading to the standard modeling of the universe expansion history, cannot simultaneously satisfy the thermodynamic pressure equation and those of Friedmann. Moreover, we consider various energy definitions, such as the Komar mass, and solve the Friedmann and thermodynamic pressure equations simultaneously to get some models for dark energy fluids. The cosmological consequences of obtained solutions are also addressed. Our results indicate that some of obtained solutions may unify the dominated fluid in both the primary inflationary and current accelerating eras into one model. In addition, by taking into account a cosmic fluid of a known equation of state (EoS), and combining it with the Friedmann and thermodynamic pressure equations, we obtain the corresponding energy of these cosmic fluids and face their limitations. Finally, we point out the cosmological features of this cosmic fluid and also study its observational constraints.

Development of a Stirling System Dynamic Model With Enhanced Thermodynamics

NASA Technical Reports Server (NTRS)

Regan, Timothy F.; Lewandowski, Edward J.

2005-01-01

The Stirling Convertor System Dynamic Model developed at NASA Glenn Research Center is a software model developed from first principles that includes the mechanical and mounting dynamics, the thermodynamics, the linear alternator, and the controller of a free-piston Stirling power convertor, along with the end user load. As such it represents the first detailed modeling tool for fully integrated Stirling convertor-based power systems. The thermodynamics of the model were originally a form of the isothermal Stirling cycle. In some situations it may be desirable to improve the accuracy of the Stirling cycle portion of the model. An option under consideration is to enhance the SDM thermodynamics by coupling the model with Gedeon Associates Sage simulation code. The result will be a model that gives a more accurate prediction of the performance and dynamics of the free-piston Stirling convertor. A method of integrating the Sage simulation code with the System Dynamic Model is described. Results of SDM and Sage simulation are compared to test data. Model parameter estimation and model validation are discussed.

Development of a Stirling System Dynamic Model with Enhanced Thermodynamics

NASA Astrophysics Data System (ADS)

Regan, Timothy F.; Lewandowski, Edward J.

2005-02-01

The Stirling Convertor System Dynamic Model developed at NASA Glenn Research Center is a software model developed from first principles that includes the mechanical and mounting dynamics, the thermodynamics, the linear alternator, and the controller of a free-piston Stirling power convertor, along with the end user load. As such it represents the first detailed modeling tool for fully integrated Stirling convertor-based power systems. The thermodynamics of the model were originally a form of the isothermal Stirling cycle. In some situations it may be desirable to improve the accuracy of the Stirling cycle portion of the model. An option under consideration is to enhance the SDM thermodynamics by coupling the model with Gedeon Associates' Sage simulation code. The result will be a model that gives a more accurate prediction of the performance and dynamics of the free-piston Stirling convertor. A method of integrating the Sage simulation code with the System Dynamic Model is described. Results of SDM and Sage simulation are compared to test data. Model parameter estimation and model validation are discussed.

Modelisation 0D/1D des emissions de particules de suie dans les turbines a gaz aeronautiques

NASA Astrophysics Data System (ADS)

Bisson, Jeremie

Because of more stringent regulations of aircraft particle emissions as well as strong uncertainties about their formation and their effects on the atmosphere, a better understanding of particle microphysical mechanisms and their interactions with the engine components is required. This thesis focuses on the development of a 0D/1D combustion model with soot production in an aeronautical gas turbine. A major objective of this study is to assess the quality of soot particle emission predictions for different flight configurations. The model should eventually allow performing parametric studies on current or future engines with a minimal computation time. The model represents the combustor as well as turbines and nozzle with a chemical reactor network (CRN) that is coupled with a detailed combustion chemistry for kerosene (Jet A-1) and a soot particle dynamics model using the method of moments. The CRN was applied to the CFM56-2C1 engine during flight configurations of the LTO cycle (Landing-Take-Off) as in the APEX-1 study on aircraft particle emissions. The model was mainly validated on gas turbine thermodynamic data and pollutant concentrations (H2O, COX, NOx, SOX) which were measured in the same study. Once the first validation completed, the model was subsequently used for the computation of mass and number-based emissions indices of the soot particulate population and average diameter. Overall, the model is representative of the thermodynamic conditions and succeeds in predicting the emissions of major pollutants, particularly at high power. Concerning soot particulate emissions, the model's ability to predict simultaneously the emission indices as well as mean diameter has been partially validated. Indeed, the mass emission indices have remained higher than experimental results particularly at high power. These differences on particulate emission index may be the result of uncertainties on thermodynamic parameters of the CRN and mass air flow distribution in the combustion chamber. The analysis of the number-based emission index profile along the CRN also highlights the need to review the nucleation model that has been used and to consider in the future the implementation of a particle aggregation mechanism.

Entropy in universes evolving from initial to final de Sitter eras

NASA Astrophysics Data System (ADS)

Mimoso, José P.; Pavón, Diego

2014-05-01

This work studies the behavior of entropy in recent cosmological models that start with an initial de Sitter expansion phase, go through the conventional radiation and matter dominated eras to be followed by a final de Sitter epoch. In spite of their seemingly similarities (observationally they are close to the Λ-CDM model), different models deeply differ in their physics. The second law of thermodynamics encapsulates the underlying microscopic, statistical description, and hence we investigate it in the present work. Our study reveals that the entropy of the apparent horizon plus that of matter and radiation inside it, increases and is a concave function of the scale factor. Thus thermodynamic equilibrium is approached in the last de Sitter era, and this class of models is thermodynamically correct. Cosmological models that do not approach equilibrium appear in conflict with the second law of thermodynamics. (Based on Mimoso & Pavon 2013)

Ternary Free-Energy Entropic Lattice Boltzmann Model with a High Density Ratio

NASA Astrophysics Data System (ADS)

Wöhrwag, M.; Semprebon, C.; Mazloomi Moqaddam, A.; Karlin, I.; Kusumaatmaja, H.

2018-06-01

A thermodynamically consistent free energy model for fluid flows comprised of one gas and two liquid components is presented and implemented using the entropic lattice Boltzmann scheme. The model allows a high density ratio, up to the order of O (103), between the liquid and gas phases, and a broad range of surface tension ratios, covering partial wetting states where Neumann triangles are formed, and full wetting states where complete encapsulation of one of the fluid components is observed. We further demonstrate that we can capture the bouncing, adhesive, and insertive regimes for the binary collisions between immiscible droplets suspended in air. Our approach opens up a vast range of multiphase flow applications involving one gas and several liquid components.

Exact low-temperature series expansion for the partition function of the zero-field Ising model on the infinite square lattice.

PubMed

Siudem, Grzegorz; Fronczak, Agata; Fronczak, Piotr

2016-10-10

In this paper, we provide the exact expression for the coefficients in the low-temperature series expansion of the partition function of the two-dimensional Ising model on the infinite square lattice. This is equivalent to exact determination of the number of spin configurations at a given energy. With these coefficients, we show that the ferromagnetic-to-paramagnetic phase transition in the square lattice Ising model can be explained through equivalence between the model and the perfect gas of energy clusters model, in which the passage through the critical point is related to the complete change in the thermodynamic preferences on the size of clusters. The combinatorial approach reported in this article is very general and can be easily applied to other lattice models.

Exact low-temperature series expansion for the partition function of the zero-field Ising model on the infinite square lattice

PubMed Central

Siudem, Grzegorz; Fronczak, Agata; Fronczak, Piotr

2016-01-01

In this paper, we provide the exact expression for the coefficients in the low-temperature series expansion of the partition function of the two-dimensional Ising model on the infinite square lattice. This is equivalent to exact determination of the number of spin configurations at a given energy. With these coefficients, we show that the ferromagnetic–to–paramagnetic phase transition in the square lattice Ising model can be explained through equivalence between the model and the perfect gas of energy clusters model, in which the passage through the critical point is related to the complete change in the thermodynamic preferences on the size of clusters. The combinatorial approach reported in this article is very general and can be easily applied to other lattice models. PMID:27721435

The role of sea ice dynamics in global climate change

NASA Technical Reports Server (NTRS)

Hibler, William D., III

1992-01-01

The topics covered include the following: general characteristics of sea ice drift; sea ice rheology; ice thickness distribution; sea ice thermodynamic models; equilibrium thermodynamic models; effect of internal brine pockets and snow cover; model simulations of Arctic Sea ice; and sensitivity of sea ice models to climate change.

Fluctuation relation based continuum model for thermoviscoplasticity in metals

NASA Astrophysics Data System (ADS)

Roy Chowdhury, Shubhankar; Roy, Debasish; Reddy, J. N.; Srinivasa, Arun

2016-11-01

A continuum plasticity model for metals is presented from considerations of non-equilibrium thermodynamics. Of specific interest is the application of a fluctuation relation that subsumes the second law of thermodynamics en route to deriving the evolution equations for the internal state variables. The modelling itself is accomplished in a two-temperature framework that appears naturally by considering the thermodynamic system to be composed of two weakly interacting subsystems, viz. a kinetic vibrational subsystem corresponding to the atomic lattice vibrations and a configurational subsystem of the slower degrees of freedom describing the motion of defects in a plastically deforming metal. An apparently physical nature of the present model derives upon considering the dislocation density, which characterizes the configurational subsystem, as a state variable. Unlike the usual constitutive modelling aided by the second law of thermodynamics that merely provides a guideline to select the admissible (though possibly non-unique) processes, the present formalism strictly determines the process or the evolution equations for the thermodynamic states while including the effect of fluctuations. The continuum model accommodates finite deformation and describes plastic deformation in a yield-free setup. The theory here is essentially limited to face-centered cubic metals modelled with a single dislocation density as the internal variable. Limited numerical simulations are presented with validation against relevant experimental data.

He I lines in B stars - Comparison of non-local thermodynamic equilibrium models with observations

NASA Technical Reports Server (NTRS)

Heasley, J. N.; Timothy, J. G.; Wolff, S. C.

1982-01-01

Profiles of He gamma-gamma 4026, 4387, 4471, 4713, 5876, and 6678 have been obtained in 17 stars of spectral type B0-B5. Parameters of the nonlocal thermodynamic equilibrium models appropriate to each star are determined from the Stromgren index and fits to H-alpha line profiles. These parameters yield generally good fits to the observed He I line profiles, with the best fits being found for the blue He I lines where departures from local thermodynamic equilibrium are relatively small. For the two red lines it is found that, in the early B stars and in stars with log g less than 3.5, both lines are systematically stronger than predicted by the nonlocal thermodynamic equilibrium models.

Examples for Non-Ideal Solution Thermodynamics Study

ERIC Educational Resources Information Center

David, Carl W.

2004-01-01

A mathematical model of a non-ideal solution is presented, where it is shown how and where the non-ideality manifests itself in the standard thermodynamics tableau. Examples related to the non-ideal solution thermodynamics study are also included.

Numerical model for thermodynamical behaviors of unsaturated soil

NASA Astrophysics Data System (ADS)

Miyamoto, Yuji; Yamada, Mitsuhide; Sako, Kazunari; Araki, Kohei; Kitamura, Ryosuke

Kitamura et al. have proposed the numerical models to establish the unsaturated soil mechanics aided by probability theory and statistics, and to apply the unsaturated soil mechanics to the geo-simulator, where the numerical model for the thermodynamical behaviors of unsaturated soil are essential. In this paper the thermodynamics is introduced to investigate the heat transfer through unsaturated soil and the evaporation of pore water in soil based on the first and second laws of thermodynamics, i.e., the conservation of energy, and increasing entropy. On the other hand the lysimeter equipment is used to obtain the data for the evaporation of pore water during fine days and seepage of rain water during rainy days. The numerical simulation is carried out by using the proposed numerical model and the results are compared with those obtained from the lysimeter test.

Thermodynamics of the variable modified Chaplygin gas

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

Panigrahi, D.; Chatterjee, S., E-mail: dibyendupanigrahi@yahoo.co.in, E-mail: chat_sujit1@yahoo.com

A cosmological model with a new variant of Chaplygin gas obeying an equation of state (EoS), P = A ρ − B /ρ{sup α} where B = B {sub 0} a {sup n} is investigated in the context of its thermodynamical behaviour. Here B {sub 0} and n are constants and a is the scale factor. We show that the equation of state of this 'Variable Modified Chaplygin gas' (VMCG) can describe the current accelerated expansion of the universe. Following standard thermodynamical criteria we mainly discuss the classical thermodynamical stability of the model and find that the new parameter, nmore » introduced in VMCG plays a crucial role in determining the stability considerations and should always be negative. We further observe that although the earlier model of Lu explains many of the current observational findings of different probes it fails the desirable tests of thermodynamical stability. We also note that for 0 n < our model points to a phantom type of expansion which, however, is found to be compatible with current SNe Ia observations and CMB anisotropy measurements. Further the third law of thermodynamics is obeyed in our case. Our model is very general in the sense that many of earlier works in this field may be obtained as a special case of our solution. An interesting point to note is that the model also apparently suggests a smooth transition from the big bang to the big rip in its whole evaluation process.« less

Untangling the Diverse Interior and Multiple Exterior Guest Interactions of a Supramolecular Host by the Simultaneous Analysis of Complementary Observables.

PubMed

Sgarlata, Carmelo; Raymond, Kenneth N

2016-07-05

The entropic and enthalpic driving forces for encapsulation versus sequential exterior guest binding to the [Ga4L6](12-) supramolecular host in solution are very different, which significantly complicates the determination of these thermodynamic parameters. The simultaneous use of complementary techniques, such as NMR, UV-vis, and isothermal titration calorimetry, enables the disentanglement of such multiple host-guest interactions. Indeed, data collected by each technique measure different components of the host-guest equilibria and together provide a complete picture of the solution thermodynamics. Unfortunately, commercially available programs do not allow for global analysis of different physical observables. We thus resorted to a novel procedure for the simultaneous refinement of multiple parameters (ΔG°, ΔH°, and ΔS°) by treating different observables through a weighted nonlinear least-squares analysis of a constrained model. The refinement procedure is discussed for the multiple binding of the Et4N(+) guest, but it is broadly applicable to the deconvolution of other intricate host-guest equilibria.

Roles of water in protein structure and function studied by molecular liquid theory.

PubMed

Imai, Takashi

2009-01-01

The roles of water in the structure and function of proteins have not been completely elucidated. Although molecular simulation has been widely used for the investigation of protein structure and function, it is not always useful for elucidating the roles of water because the effect of water ranges from atomic to thermodynamic level. The three-dimensional reference interaction site model (3D-RISM) theory, which is a statistical-mechanical theory of molecular liquids, can yield the solvation structure at the atomic level and calculate the thermodynamic quantities from the intermolecular potentials. In the last few years, the author and coworkers have succeeded in applying the 3D-RISM theory to protein aqueous solution systems and demonstrated that the theory is useful for investigating the roles of water. This article reviews some of the recent applications and findings, which are concerned with molecular recognition by protein, protein folding, and the partial molar volume of protein which is related to the pressure effect on protein.

Thermodynamic metrics for measuring the ``sustainability'' of design for recycling

NASA Astrophysics Data System (ADS)

Reuter, Markus; van Schaik, Antoinette

2008-08-01

In this article, exergy is applied as a parameter to measure the “sustainability” of a recycling system in addition to the fundamental prediction of material recycling and energy recovery, summarizing a development of over 20 years by the principal author supported by various co-workers, Ph.D., and M.Sc. students. In order to achieve this, recyclate qualities and particle size distributions throughout the system must be predicted as a function of product design, liberation during shredding, process dynamics, physical separation physics, and metallurgical thermodynamics. This crucial development enables the estimation of the true exergy of a recycling system from its inputs and outputs including all its realistic industrial traits. These models have among others been linked to computer aided design tools of the automotive industry and have been used to evaluate the performance of waste electric and electronic equipment recycling systems in The Netherlands. This paper also suggests that the complete system must be optimized to find a “truer” optimum of the material production system linked to the consumer market.

Microcanonical and resource-theoretic derivations of the thermal state of a quantum system with noncommuting charges

PubMed Central

Yunger Halpern, Nicole; Faist, Philippe; Oppenheim, Jonathan; Winter, Andreas

2016-01-01

The grand canonical ensemble lies at the core of quantum and classical statistical mechanics. A small system thermalizes to this ensemble while exchanging heat and particles with a bath. A quantum system may exchange quantities represented by operators that fail to commute. Whether such a system thermalizes and what form the thermal state has are questions about truly quantum thermodynamics. Here we investigate this thermal state from three perspectives. First, we introduce an approximate microcanonical ensemble. If this ensemble characterizes the system-and-bath composite, tracing out the bath yields the system's thermal state. This state is expected to be the equilibrium point, we argue, of typical dynamics. Finally, we define a resource-theory model for thermodynamic exchanges of noncommuting observables. Complete passivity—the inability to extract work from equilibrium states—implies the thermal state's form, too. Our work opens new avenues into equilibrium in the presence of quantum noncommutation. PMID:27384494

A Tightly Coupled Non-Equilibrium Magneto-Hydrodynamic Model for Inductively Coupled RF Plasmas

DTIC Science & Technology

2016-02-29

development a tightly coupled magneto-hydrodynamic model for Inductively Coupled Radio- Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE...for Inductively Coupled Radio-Frequency (RF) Plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State... thermodynamic variable. This choice allows one to hide the non-linearity of the gas (total) thermal conductivity κ and can partially alle- 2 viate numerical

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.

Conditioning and Robustness of RNA Boltzmann Sampling under Thermodynamic Parameter Perturbations.

PubMed

Rogers, Emily; Murrugarra, David; Heitsch, Christine

2017-07-25

Understanding how RNA secondary structure prediction methods depend on the underlying nearest-neighbor thermodynamic model remains a fundamental challenge in the field. Minimum free energy (MFE) predictions are known to be "ill conditioned" in that small changes to the thermodynamic model can result in significantly different optimal structures. Hence, the best practice is now to sample from the Boltzmann distribution, which generates a set of suboptimal structures. Although the structural signal of this Boltzmann sample is known to be robust to stochastic noise, the conditioning and robustness under thermodynamic perturbations have yet to be addressed. We present here a mathematically rigorous model for conditioning inspired by numerical analysis, and also a biologically inspired definition for robustness under thermodynamic perturbation. We demonstrate the strong correlation between conditioning and robustness and use its tight relationship to define quantitative thresholds for well versus ill conditioning. These resulting thresholds demonstrate that the majority of the sequences are at least sample robust, which verifies the assumption of sampling's improved conditioning over the MFE prediction. Furthermore, because we find no correlation between conditioning and MFE accuracy, the presence of both well- and ill-conditioned sequences indicates the continued need for both thermodynamic model refinements and alternate RNA structure prediction methods beyond the physics-based ones. Copyright © 2017. Published by Elsevier Inc.

Ab initio relaxation times and time-dependent Hamiltonians within the steepest-entropy-ascent quantum thermodynamic framework

NASA Astrophysics Data System (ADS)

Kim, Ilki; von Spakovsky, Michael R.

2017-08-01

Quantum systems driven by time-dependent Hamiltonians are considered here within the framework of steepest-entropy-ascent quantum thermodynamics (SEAQT) and used to study the thermodynamic characteristics of such systems. In doing so, a generalization of the SEAQT framework valid for all such systems is provided, leading to the development of an ab initio physically relevant expression for the intrarelaxation time, an important element of this framework and one that had as of yet not been uniquely determined as an integral part of the theory. The resulting expression for the relaxation time is valid as well for time-independent Hamiltonians as a special case and makes the description provided by the SEAQT framework more robust at the fundamental level. In addition, the SEAQT framework is used to help resolve a fundamental issue of thermodynamics in the quantum domain, namely, that concerning the unique definition of process-dependent work and heat functions. The developments presented lead to the conclusion that this framework is not just an alternative approach to thermodynamics in the quantum domain but instead one that uniquely sheds new light on various fundamental but as of yet not completely resolved questions of thermodynamics.

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.

Thermodynamic Analysis of Chemically Reacting Mixtures-Comparison of First and Second Order Models.

PubMed

Pekař, Miloslav

2018-01-01

Recently, a method based on non-equilibrium continuum thermodynamics which derives thermodynamically consistent reaction rate models together with thermodynamic constraints on their parameters was analyzed using a triangular reaction scheme. The scheme was kinetically of the first order. Here, the analysis is further developed for several first and second order schemes to gain a deeper insight into the thermodynamic consistency of rate equations and relationships between chemical thermodynamic and kinetics. It is shown that the thermodynamic constraints on the so-called proper rate coefficient are usually simple sign restrictions consistent with the supposed reaction directions. Constraints on the so-called coupling rate coefficients are more complex and weaker. This means more freedom in kinetic coupling between reaction steps in a scheme, i.e., in the kinetic effects of other reactions on the rate of some reaction in a reacting system. When compared with traditional mass-action rate equations, the method allows a reduction in the number of traditional rate constants to be evaluated from data, i.e., a reduction in the dimensionality of the parameter estimation problem. This is due to identifying relationships between mass-action rate constants (relationships which also include thermodynamic equilibrium constants) which have so far been unknown.

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.

Heading in the right direction: thermodynamics-based network analysis and pathway engineering.

PubMed

Ataman, Meric; Hatzimanikatis, Vassily

2015-12-01

Thermodynamics-based network analysis through the introduction of thermodynamic constraints in metabolic models allows a deeper analysis of metabolism and guides pathway engineering. The number and the areas of applications of thermodynamics-based network analysis methods have been increasing in the last ten years. We review recent applications of these methods and we identify the areas that such analysis can contribute significantly, and the needs for future developments. We find that organisms with multiple compartments and extremophiles present challenges for modeling and thermodynamics-based flux analysis. The evolution of current and new methods must also address the issues of the multiple alternatives in flux directionalities and the uncertainties and partial information from analytical methods. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Evolution of a terrestrial magma ocean: Thermodynamics, kinetics, rheology, convection, differentiation

NASA Technical Reports Server (NTRS)

Solomatov, V. S.; Stevenson, D. J.

1992-01-01

The evolution of an initially totally molten magma ocean is constrained on the basis of analysis of various physical problems in the magma ocean. First of all an equilibrium thermodynamics of the magma ocean is developed in the melting temperature range. The equilibrium thermodynamical parameters are found as functions only of temperature and pressure and are used in the subsequent models of kinetics and convection. Kinematic processes determine the crystal size and also determine a non-equilibrium thermodynamics of the system. Rheology controls all dynamical regimes of the magma ocean. The thermal convection models for different rheological laws are developed for both the laminar convection and for turbulent convection in the case of equilibrium thermodynamics of the multiphase system. The evolution is estimated on the basis of all the above analysis.

Insight into the microscopic structure of an AdS black hole from a thermodynamical phase transition.

PubMed

Wei, Shao-Wen; Liu, Yu-Xiao

2015-09-11

Comparing with an ordinary thermodynamic system, we investigate the possible microscopic structure of a charged anti-de Sitter black hole completely from the thermodynamic viewpoint. The number density of the black hole molecules is introduced to measure the microscopic degrees of freedom of the black hole. We found that the number density suffers a sudden change accompanied by a latent heat when the black hole system crosses the small-large black hole coexistence curve, while when the system passes the critical point, it encounters a second-order phase transition with a vanishing latent heat due to the continuous change of the number density. Moreover, the thermodynamic scalar curvature suggests that there is a weak attractive interaction between two black hole molecules. These phenomena might cast new insight into the underlying microscopic structure of a charged anti-de Sitter black hole.

Thermodynamic signature of secondary nano-emulsion formation by isothermal titration calorimetry.

PubMed

Fotticchia, Iolanda; Fotticchia, Teresa; Mattia, Carlo Andrea; Netti, Paolo Antonio; Vecchione, Raffaele; Giancola, Concetta

2014-12-09

The stabilization of oil in water nano-emulsions by means of a polymer coating is extremely important; it prolongs the shelf life of the product and makes it suitable for a variety of applications ranging from nutraceutics to cosmetics and pharmaceutics. To date, an effective methodology to assess the best formulations in terms of thermodynamic stability has yet to be designed. Here, we perform a complete physicochemical characterization based on isothermal titration calorimetry (ITC) compared to conventional dynamic light scattering (DLS) to identify polymer concentration domains that are thermodynamically stable and to define the degree of stability through thermodynamic functions depending upon any relevant parameter affecting the stability itself, such as type of polymer coating, droplet distance, etc. For instance, the method was proven by measuring the energetics in the case of two different biopolymers, chitosan and poly-L-lysine, and for different concentrations of the emulsion coated with poly-L-lysine.

Nanostructured Fe-Cr Alloys for Advanced Nuclear Energy Applications

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

Scattergood, Ronald O.

2016-04-26

We have completed research on the grain-size stabilization of model nanostructured Fe14Cr base alloys at high temperatures by the addition of non-equilibrium solutes. Fe14Cr base alloys are representative for nuclear reactor applications. The neutron flux in a nuclear reactor will generate He atoms that coalesce to form He bubbles. These can lead to premature failure of the reactor components, limiting their lifetime and increasing the cost and capacity for power generation. In order to mitigate such failures, Fe14Cr base alloys have been processed to contain very small nano-size oxide particles (less than 10 nm in size) that trap He atomsmore » and reduce bubble formation. Theoretical and experimental results indicate that the grain boundaries can also be very effective traps for He atoms and bubble formation. An optimum grain size will be less than 100 nm, ie., nanocrystalline alloys must be used. Powder metallurgy methods based on high-energy ball milling can produce Fe-Cr base nanocrystalline alloys that are suitable for nuclear energy applications. The problem with nanocrystalline alloys is that excess grain-boundary energy will cause grains to grow at higher temperatures and their propensity for He trapping will be lost. The nano-size oxide particles in current generation nuclear alloys provide some grain size stabilization by reducing grain-boundary mobility (Zener pinning – a kinetic effect). However the current mitigation strategy minimizing bubble formation is based primarily on He trapping by nano-size oxide particles. An alternate approach to nanoscale grain size stabilization has been proposed. This is based on the addition of small amounts of atoms that are large compared to the base alloy. At higher temperatures these will diffuse to the grain boundaries and will produce an equilibrium state for the grain size at higher temperatures (thermodynamic stabilization – an equilibrium effect). This would be preferred compared to a kinetic effect, which is not based on an equilibrium state. The PI and coworkers have developed thermodynamic-based models that can be used to select appropriate solute additions to Fe14Cr base alloys to achieve a contribution to grain-size stabilization and He bubble mitigation by the thermodynamic effect. All such models require approximations and the proposed research was aimed at alloy selection, processing and detailed atomic-level microstructure evaluations to establish the efficacy of the thermodynamic effect. The outcome of this research shows that appropriate alloy additions can produce a contribution from the thermodynamic stabilization effect. Furthermore, due to the oxygen typically present in nominally high purity elemental powders used for powder metallurgy processing, the optimum results obtained appeared as a synergistic combination of nano-size oxide particle pinning kinetic effect and the grain-boundary segregation thermodynamic effect.« less

Geometrothermodynamic model for the evolution of the Universe

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

Gruber, Christine; Quevedo, Hernando, E-mail: christine.gruber@correo.nucleares.unam.mx, E-mail: quevedo@nucleares.unam.mx

Using the formalism of geometrothermodynamics to derive a fundamental thermodynamic equation, we construct a cosmological model in the framework of relativistic cosmology. In a first step, we describe a system without thermodynamic interaction, and show it to be equivalent to the standard ΛCDM paradigm. The second step includes thermodynamic interaction and produces a model consistent with the main features of inflation. With the proposed fundamental equation we are thus able to describe all the known epochs in the evolution of our Universe, starting from the inflationary phase.

On the dynamical vs. thermodynamical performance of a β-type Stirling engine

NASA Astrophysics Data System (ADS)

Reséndiz-Antonio, Margarita; Santillán, Moisés

2014-09-01

In this work we present a simple mathematical model for a β-type Stirling engine. Despite its simplicity, the model considers all the engine’s relevant thermodynamic and mechanical aspects. The dynamic behavior of the model equation of motion is analyzed in order to obtain the sufficient conditions for engine cycling and to study the stability of the stationary regime. The performance of the engine’s thermodynamic part is also investigated. As a matter of fact, we found that it corresponds to a Carnot engine.

Modeling the Hydrogen Solubility in Liquid Aluminum Alloys

NASA Astrophysics Data System (ADS)

Harvey, Jean-Philippe; Chartrand, Patrice

2010-08-01

The modeling of hydrogen solubility in multicomponent Al-(Li, Mg, Cu, and Si) liquid phase has been performed with a thermodynamic approach using the modified quasichemical model with the pair approximation (MQMPA). All hydrogen solubility data available in literature was assessed critically to obtain the binary parameters of the MQMPA model for the Al-H, Li-H, Mg-H, Cu-H, Zn-H, and Si-H melts. For the Li-H system, a new thermodynamic description of the stable solid lithium hydride was determined based on the c p found in literature. The thermodynamic model for the Al-Li system also was reassessed in this work to take into account the short-range ordering observed for this system. Built-in interpolation techniques allow the model to estimate the thermodynamic properties of the multicomponent liquid solution from the liquid model parameters of the lower order subsystems. A comparison of the calculated hydrogen solubility performed at various equilibrium conditions of temperature, pressure, and composition with the available experimental data found in the literature is presented in this work, as well as a comparison with some results from previous modeling.

Film and membrane-model thermodynamics of free thin liquid films.

PubMed

Radke, C J

2015-07-01

In spite of over 7 decades of effort, the thermodynamics of thin free liquid films (as in emulsions and foams) lacks clarity. Following a brief review of the meaning and measurement of thin-film forces (i.e., conjoining/disjoining pressures), we offer a consistent analysis of thin-film thermodynamics. By carefully defining film reversible work, two distinct thermodynamic formalisms emerge: a film model with two zero-volume membranes each of film tension γ(f) and a membrane model with a single zero-volume membrane of membrane tension 2γ(m). In both models, detailed thermodynamic analysis gives rise to thin-film Gibbs adsorption equations that allow calculation of film and membrane tensions from measurements of disjoining-pressure isotherms. A modified Young-Laplace equation arises in the film model to calculate film-thickness profiles from the film center to the surrounding bulk meniscus. No corresponding relation exists in the membrane model. Illustrative calculations of disjoining-pressure isotherms for water are presented using square-gradient theory. We report considerable deviations from Hamaker theory for films less than about 3 nm in thickness. Such thin films are considerably more attractive than in classical Hamaker theory. Available molecular simulations reinforce this finding. Copyright © 2014 Elsevier Inc. All rights reserved.

Modelling grain growth in the framework of Rational Extended Thermodynamics

NASA Astrophysics Data System (ADS)

Kertsch, Lukas; Helm, Dirk

2016-05-01

Grain growth is a significant phenomenon for the thermomechanical processing of metals. Since the mobility of the grain boundaries is thermally activated and energy stored in the grain boundaries is released during their motion, a mutual interaction with the process conditions occurs. To model such phenomena, a thermodynamic framework for the representation of thermomechanical coupling phenomena in metals including a microstructure description is required. For this purpose, Rational Extended Thermodynamics appears to be a useful tool. We apply an entropy principle to derive a thermodynamically consistent model for grain coarsening due to the growth and shrinkage of individual grains. Despite the rather different approaches applied, we obtain a grain growth model which is similar to existing ones and can be regarded as a thermodynamic extension of that by Hillert (1965) to more general systems. To demonstrate the applicability of the model, we compare our simulation results to grain growth experiments in pure copper by different authors, which we are able to reproduce very accurately. Finally, we study the implications of the energy release due to grain growth on the energy balance. The present unified approach combining a microstructure description and continuum mechanics is ready to be further used to develop more elaborate material models for complex thermo-chemo-mechanical coupling phenomena.

Thermodynamic characterization of tandem mismatches found in naturally occurring RNA

PubMed Central

Christiansen, Martha E.; Znosko, Brent M.

2009-01-01

Although all sequence symmetric tandem mismatches and some sequence asymmetric tandem mismatches have been thermodynamically characterized and a model has been proposed to predict the stability of previously unmeasured sequence asymmetric tandem mismatches [Christiansen,M.E. and Znosko,B.M. (2008) Biochemistry, 47, 4329–4336], experimental thermodynamic data for frequently occurring tandem mismatches is lacking. Since experimental data is preferred over a predictive model, the thermodynamic parameters for 25 frequently occurring tandem mismatches were determined. These new experimental values, on average, are 1.0 kcal/mol different from the values predicted for these mismatches using the previous model. The data for the sequence asymmetric tandem mismatches reported here were then combined with the data for 72 sequence asymmetric tandem mismatches that were published previously, and the parameters used to predict the thermodynamics of previously unmeasured sequence asymmetric tandem mismatches were updated. The average absolute difference between the measured values and the values predicted using these updated parameters is 0.5 kcal/mol. This updated model improves the prediction for tandem mismatches that were predicted rather poorly by the previous model. This new experimental data and updated predictive model allow for more accurate calculations of the free energy of RNA duplexes containing tandem mismatches, and, furthermore, should allow for improved prediction of secondary structure from sequence. PMID:19509311

Thermodynamics of the interaction of sweeteners and lactisole with fullerenols as an artificial sweet taste receptor model.

PubMed

Chen, Zhong-Xiu; Wu, Wen; Zhang, Wei-Bin; Deng, Shao-Ping

2011-09-01

The thermodynamics of the mimetic interaction of lactisole and sweeteners with fullerenols as a synthetic sweet receptor model was elucidated by Isothermal Titration Calorimetry (ITC) technique. The presence of lactisole resulted in great differences in thermodynamics of the sweeteners binding with fullerenols in which lactisole led to much more entropy contribution to the free energy compared with the interaction of sweeteners with fullerenols. Two interaction equilibrium states were found in ITC titration profiles and competitive binding of lactisole and sweeteners with fullerenols was disclosed. Our results indicated that the larger value of the ratio of two equilibrium constant K1/K2, the more effectively lactisole inhibited the sweetness of the sweetener. The combined results of sensory evaluation and ITC thermodynamics revealed that introducing a synthetic receptor model to interact with the sweeteners and inhibitors helps to understand the inhibition mechanism and the thermodynamic basis for the initiation of sweetness inhibition. Copyright © 2011 Elsevier Ltd. All rights reserved.

The structure of evaporating and combusting sprays: Measurements and predictions

NASA Technical Reports Server (NTRS)

Shuen, J. S.; Solomon, A. S. P.; Faeth, F. M.

1983-01-01

The structure of particle-laden jets and nonevaporating and evaporating sprays was measured in order to evaluate models of these processes. Three models are being evaluated: (1) a locally homogeneous flow model, where slip between the phases is neglected and the flow is assumed to be in local thermodynamic equilibrium; (2) a deterministic separated flow model, where slip and finite interphase transport rates are considered but effects of particle/drop dispersion by turbulence and effects of turbulence on interphase transport rates are ignored; and (3) a stochastic separated flow model, where effects of interphase slip, turbulent dispersion and turbulent fluctuations are considered using random sampling for turbulence properties in conjunction with random-walk computations for particle motion. All three models use a k-e-g turbulence model. All testing and data reduction are completed for the particle laden jets. Mean and fluctuating velocities of the continuous phase and mean mixture fraction were measured in the evaporating sprays.

Estimating Model Probabilities using Thermodynamic Markov Chain Monte Carlo Methods

NASA Astrophysics Data System (ADS)

Ye, M.; Liu, P.; Beerli, P.; Lu, D.; Hill, M. C.

2014-12-01

Markov chain Monte Carlo (MCMC) methods are widely used to evaluate model probability for quantifying model uncertainty. In a general procedure, MCMC simulations are first conducted for each individual model, and MCMC parameter samples are then used to approximate marginal likelihood of the model by calculating the geometric mean of the joint likelihood of the model and its parameters. It has been found the method of evaluating geometric mean suffers from the numerical problem of low convergence rate. A simple test case shows that even millions of MCMC samples are insufficient to yield accurate estimation of the marginal likelihood. To resolve this problem, a thermodynamic method is used to have multiple MCMC runs with different values of a heating coefficient between zero and one. When the heating coefficient is zero, the MCMC run is equivalent to a random walk MC in the prior parameter space; when the heating coefficient is one, the MCMC run is the conventional one. For a simple case with analytical form of the marginal likelihood, the thermodynamic method yields more accurate estimate than the method of using geometric mean. This is also demonstrated for a case of groundwater modeling with consideration of four alternative models postulated based on different conceptualization of a confining layer. This groundwater example shows that model probabilities estimated using the thermodynamic method are more reasonable than those obtained using the geometric method. The thermodynamic method is general, and can be used for a wide range of environmental problem for model uncertainty quantification.

Integrating Thermodynamic Models in Geodynamic Simulations: The Example of the Community Software ASPECT

NASA Astrophysics Data System (ADS)

Dannberg, J.; Heister, T.; Grove, R. R.; Gassmoeller, R.; Spiegelman, M. W.; Bangerth, W.

2017-12-01

Earth's surface shows many features whose genesis can only be understood through the interplay of geodynamic and thermodynamic models. This is particularly important in the context of melt generation and transport: Mantle convection determines the distribution of temperature and chemical composition, the melting process itself is then controlled by the thermodynamic relations and in turn influences the properties and the transport of melt. Here, we present our extension of the community geodynamics code ASPECT, which solves the equations of coupled magma/mantle dynamics, and allows to integrate different parametrizations of reactions and phase transitions: They may alternatively be implemented as simple analytical expressions, look-up tables, or computed by a thermodynamics software. As ASPECT uses a variety of numerical methods and solvers, this also gives us the opportunity to compare different approaches of modelling the melting process. In particular, we will elaborate on the spatial and temporal resolution that is required to accurately model phase transitions, and show the potential of adaptive mesh refinement when applied to melt generation and transport. We will assess the advantages and disadvantages of iterating between fluid dynamics and chemical reactions derived from thermodynamic models within each time step, or decoupling them, allowing for different time step sizes. Beyond that, we will expand on the functionality required for an interface between computational thermodynamics and fluid dynamics models from the geodynamics side. Finally, using a simple example of melting of a two-phase, two-component system, we compare different time-stepping and solver schemes in terms of accuracy and efficiency, in dependence of the time scales of fluid flow and chemical reactions relative to each other. Our software provides a framework to integrate thermodynamic models in high resolution, 3d simulations of coupled magma/mantle dynamics, and can be used as a tool to study links between physical processes and geochemical signals in the Earth.

Thermodynamics-based models of transcriptional regulation with gene sequence.

PubMed

Wang, Shuqiang; Shen, Yanyan; Hu, Jinxing

2015-12-01

Quantitative models of gene regulatory activity have the potential to improve our mechanistic understanding of transcriptional regulation. However, the few models available today have been based on simplistic assumptions about the sequences being modeled or heuristic approximations of the underlying regulatory mechanisms. In this work, we have developed a thermodynamics-based model to predict gene expression driven by any DNA sequence. The proposed model relies on a continuous time, differential equation description of transcriptional dynamics. The sequence features of the promoter are exploited to derive the binding affinity which is derived based on statistical molecular thermodynamics. Experimental results show that the proposed model can effectively identify the activity levels of transcription factors and the regulatory parameters. Comparing with the previous models, the proposed model can reveal more biological sense.

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…

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.

Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

DOE PAGES

Duong, Thien C.; Hackenberg, Robert E.; Landa, Alex; ...

2016-09-20

In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibriamore » data at the γ 2/α+γ 2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.« less

Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems.

PubMed

Liu, Baoshun; Zhao, Xiujian; Terashima, Chiaki; Fujishima, Akira; Nakata, Kazuya

2014-05-21

Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ˙OH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.

Mathematical and information-geometrical entropy for phenomenological Fourier and non-Fourier heat conduction

NASA Astrophysics Data System (ADS)

Li, Shu-Nan; Cao, Bing-Yang

2017-09-01

The second law of thermodynamics governs the direction of heat transport, which provides the foundational definition of thermodynamic Clausius entropy. The definitions of entropy are further generalized for the phenomenological heat transport models in the frameworks of classical irreversible thermodynamics and extended irreversible thermodynamics (EIT). In this work, entropic functions from mathematics are combined with phenomenological heat conduction models and connected to several information-geometrical conceptions. The long-time behaviors of these mathematical entropies exhibit a wide diversity and physical pictures in phenomenological heat conductions, including the tendency to thermal equilibrium, and exponential decay of nonequilibrium and asymptotics, which build a bridge between the macroscopic and microscopic modelings. In contrast with the EIT entropies, the mathematical entropies expressed in terms of the internal energy function can avoid singularity paired with nonpositive local absolute temperature caused by non-Fourier heat conduction models.

Magnetically charged regular black hole in a model of nonlinear electrodynamics

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

Ma, Meng-Sen, E-mail: mengsenma@gmail.com

2015-11-15

We obtain a magnetically charged regular black hole in general relativity. The source to the Einstein field equations is nonlinear electrodynamic field in a physically reasonable model of nonlinear electrodynamics (NED). “Physically” here means the NED model is constructed on the basis of three conditions: the Maxwell asymptotic in the weak electromagnetic field limit; the presence of vacuum birefringence phenomenon; and satisfying the weak energy condition (WEC). In addition, we analyze the thermodynamic properties of the regular black hole in two ways. According to the usual black hole thermodynamics, we calculate the heat capacity at constant charge, from which wemore » know the smaller black hole is more stable. We also employ the horizon thermodynamics to discuss the thermodynamic quantities, especially the heat capacity at constant pressure.« less

Key issues, observations and goals for coupled, thermodynamic/geodynamic models

NASA Astrophysics Data System (ADS)

Kelemen, P. B.

2017-12-01

In coupled, thermodynamic/geodynamic models, focus should be on processes involving major rock forming minerals and simple fluid compositions, and parameters with first-order effects on likely dynamic processes: In a given setting, will fluid mass increase or decrease? How about solid density? Will flow become localized or diffuse? Will rocks flow or break? How do reactions affect global processes such as formation and evolution of the plates, plate boundary deformation, metamorphism, weathering, climate and geochemical cycles. Important reaction feedbacks in geodynamics include formation of dissolution channels and armored channels; divergence of flow and formation of permeability barriers due to crystallization in pore space; localization of fluid transport and ductile deformation in shear zones; reaction-driven cracking; mechanical channels granular media; shear heating; density instabilities; viscous fluid-weakening; fluid-induced frictional failure; and hydraulic fracture. Density instabilities often lead to melting, and there is an interesting dialectic between porous flow and diapirs. The best models provide a simple but comprehensive framework that can account for the general features in many or most of these phenomena. Ideally, calculations based on thermodynamic data and rheological observations alone should delineate the regimes in which each of these processes will occur and the boundaries between them. These often start with "toy models" and lab experiments on analog systems, with highly approximate scaling to simplified geological conditions and materials. Geologic observations provide the best constraints where `frozen' fluid transport pathways or deformation processes are preserved. Inferences about completed processes based on fluid or solid products alone is more challenging and less unique. Not all important processes have good examples in outcrop, so directed searches for specific phenomena may fail. A highly generalized approach provides a way forward, allowing serendipitous discoveries of iconic examples wherever they are best developed. These then constrain and inspire the overall "phase diagram" of geodynamic processes.

Integrating Computational Chemistry into a Course in Classical Thermodynamics

ERIC Educational Resources Information Center

Martini, Sheridan R.; Hartzell, Cynthia J.

2015-01-01

Computational chemistry is commonly addressed in the quantum mechanics course of undergraduate physical chemistry curricula. Since quantum mechanics traditionally follows the thermodynamics course, there is a lack of curricula relating computational chemistry to thermodynamics. A method integrating molecular modeling software into a semester long…

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.

Theoretical and experimental investigations on the dynamic and thermodynamic characteristics of the linear compressor for the pulse tube cryocooler

NASA Astrophysics Data System (ADS)

Zhang, L.; Dang, H. Z.; Tan, J.; Bao, D.; Zhao, Y. B.; Qian, G. Z.

2015-12-01

Theoretical and experimental investigations on the dynamic and thermodynamic characteristics of a linear compressor incorporating the thermodynamic characteristics of the inertance tube pulse tube cold finger have been made. Both the compressor and cold finger are assumed as a one-dimensional thermodynamic model. The governing equations of the thermodynamic characteristics of the working gas are summarized, and the effects of the cooling performance on the working gas in the compression space are discussed. Based on the analysis of the working gas, the governing equations of the dynamic and thermodynamic characteristics of the compressor are deduced, and then the principles of achieving the optimal performance of the compressor are discussed in detail. Systematic experimental investigations are conducted on a developed moving-coil linear compressor which drives a pulse tube cold finger, which indicate the general agreement with the simulated results, and thus verify the rationality of the theoretical model and analyses.

Thermodynamic and themoeconomic optimization of isothermal endoreversible chemical engine models

NASA Astrophysics Data System (ADS)

Ocampo-García, A.; Barranco-Jiménez, M. A.; Angulo-Brown, F.

2017-12-01

A branch of finite-time thermodynamics (FTT) is the thermoeconomical analysis of simplified power plant models. The most studied models are those of the Curzon-Ahlborn (CA) and Novikov-Chambadal types. In the decade of 90's of the past century, the FTT analysis of thermal engines was extended to chemical engines. In the present paper we made a thermoeconomical analysis of heat engines and chemical engines of the CA and Novikov types. This study is carried out for isothermal endoreversible chemical engine models with a linear mass transfer law and under three different modes of thermodynamic performance (maximum power, maximum ecological function and maximum efficient power).

Study Task for Determining the Effects of Boost-Phase Environments on Densified Propellants Thermal Conditions for Expendable Launch Vehicles

NASA Technical Reports Server (NTRS)

Haberbusch, Mark S.; Meyer, Michael L. (Technical Monitor)

2002-01-01

A thermodynamic study has been conducted that investigated the effects of the boost-phase environment on densified propellant thermal conditions for expendable launch vehicles. Two thermodynamic models were developed and utilized to bound the expected thermodynamic conditions inside the cryogenic liquid hydrogen and oxygen propellant tanks of an Atlas IIAS/Centaur launch vehicle during the initial phases of flight. The ideal isentropic compression model was developed to predict minimum pressurant gas requirements. The thermal equilibrium model was developed to predict the maximum pressurant gas requirements. The models were modified to simulate the required flight tank pressure profiles through ramp pressurization, liquid expulsion, and tank venting. The transient parameters investigated were: liquid temperature, liquid level, and pressurant gas consumption. Several mission scenarios were analyzed using the thermodynamic models, and the results indicate that flying an Atlas IIAS launch vehicle with densified propellants is feasible and beneficial but may require some minor changes to the vehicle.

Thermodynamic Model of Spatial Memory

NASA Astrophysics Data System (ADS)

Kaufman, Miron; Allen, P.

1998-03-01

We develop and test a thermodynamic model of spatial memory. Our model is an application of statistical thermodynamics to cognitive science. It is related to applications of the statistical mechanics framework in parallel distributed processes research. Our macroscopic model allows us to evaluate an entropy associated with spatial memory tasks. We find that older adults exhibit higher levels of entropy than younger adults. Thurstone's Law of Categorical Judgment, according to which the discriminal processes along the psychological continuum produced by presentations of a single stimulus are normally distributed, is explained by using a Hooke spring model of spatial memory. We have also analyzed a nonlinear modification of the ideal spring model of spatial memory. This work is supported by NIH/NIA grant AG09282-06.

Thermodynamic analysis and subscale modeling of space-based orbit transfer vehicle cryogenic propellant resupply

NASA Technical Reports Server (NTRS)

Defelice, David M.; Aydelott, John C.

1987-01-01

The resupply of the cryogenic propellants is an enabling technology for spacebased orbit transfer vehicles. As part of the NASA Lewis ongoing efforts in microgravity fluid management, thermodynamic analysis and subscale modeling techniques were developed to support an on-orbit test bed for cryogenic fluid management technologies. Analytical results have shown that subscale experimental modeling of liquid resupply can be used to validate analytical models when the appropriate target temperature is selected to relate the model to its prototype system. Further analyses were used to develop a thermodynamic model of the tank chilldown process which is required prior to the no-vent fill operation. These efforts were incorporated into two FORTRAN programs which were used to present preliminary analyticl results.

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.

Thermodynamic modeling of Cl(-), NO3(-) and SO4(2-) removal by an anion exchange resin and comparison with Dubinin-Astakhov isotherms.

PubMed

Dron, Julien; Dodi, Alain

2011-03-15

The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.

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.

Thermodynamic equilibrium-air correlations for flowfield applications

NASA Technical Reports Server (NTRS)

Zoby, E. V.; Moss, J. N.

1981-01-01

Equilibrium-air thermodynamic correlations have been developed for flowfield calculation procedures. A comparison between the postshock results computed by the correlation equations and detailed chemistry calculations is very good. The thermodynamic correlations are incorporated in an approximate inviscid flowfield code with a convective heating capability for the purpose of defining the thermodynamic environment through the shock layer. Comparisons of heating rates computed by the approximate code and a viscous-shock-layer method are good. In addition to presenting the thermodynamic correlations, the impact of several viscosity models on the convective heat transfer is demonstrated.

Specific Hardening Function Definition and Characterization of a Multimechanism Generalized Potential-based Viscoelastoplasticity Model

NASA Technical Reports Server (NTRS)

Arnold, S. M.; Saleeb, A. F.

2003-01-01

Given the previous complete-potential structure framework together with the notion of strain- and stress-partitioning in terms of separate contributions of several submechanisms (viscoelastic and viscoplastic) to the thermodynamic functions (stored energy and dissipation) a detailed viscoelastoplastic multimechanism characterization of a specific hardening functional form of the model is presented and discussed. TIMETAL 21S is the material of choice as a comprehensive test matrix, including creep, relaxation, constant strain-rate tension tests, etc. are available at various temperatures. Discussion of these correlations tests, together with comparisons to several other experimental results, are given to assess the performance and predictive capabilities of the present model particularly with regard to the notion of hardening saturation as well as the interaction of multiplicity of dissipative (reversible/irreversible) mechanisms.

Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

NASA Technical Reports Server (NTRS)

Thompson, W. R.; Zollweg, John A.; Gabis, David H.

1992-01-01

A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

Coupled electromagnetic-thermodynamic simulations of microwave heating problems using the FDTD algorithm.

PubMed

Kopyt, Paweł; Celuch, Małgorzata

2007-01-01

A practical implementation of a hybrid simulation system capable of modeling coupled electromagnetic-thermodynamic problems typical in microwave heating is described. The paper presents two approaches to modeling such problems. Both are based on an FDTD-based commercial electromagnetic solver coupled to an external thermodynamic analysis tool required for calculations of heat diffusion. The first approach utilizes a simple FDTD-based thermal solver while in the second it is replaced by a universal commercial CFD solver. The accuracy of the two modeling systems is verified against the original experimental data as well as the measurement results available in literature.

Quantitative thermodynamic predication of interactions between nucleic acid and non-nucleic acid species using Microsoft excel.

PubMed

Zou, Jiaqi; Li, Na

2013-09-01

Proper design of nucleic acid sequences is crucial for many applications. We have previously established a thermodynamics-based quantitative model to help design aptamer-based nucleic acid probes by predicting equilibrium concentrations of all interacting species. To facilitate customization of this thermodynamic model for different applications, here we present a generic and easy-to-use platform to implement the algorithm of the model with Microsoft(®) Excel formulas and VBA (Visual Basic for Applications) macros. Two Excel spreadsheets have been developed: one for the applications involving only nucleic acid species, the other for the applications involving both nucleic acid and non-nucleic acid species. The spreadsheets take the nucleic acid sequences and the initial concentrations of all species as input, guide the user to retrieve the necessary thermodynamic constants, and finally calculate equilibrium concentrations for all species in various bound and unbound conformations. The validity of both spreadsheets has been verified by comparing the modeling results with the experimental results on nucleic acid sequences reported in the literature. This Excel-based platform described here will allow biomedical researchers to rationalize the sequence design of nucleic acid probes using the thermodynamics-based modeling even without relevant theoretical and computational skills. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

A thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts.

PubMed

Wang, Kun; Chartrand, Patrice

2018-06-15

This paper presents a quantitative thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts, which is of technological importance to the Hall-Héroult electrolytic aluminum extraction cell. The Modified Quasichemical Model in the Quadruplet Approximation (MQMQA), as used to treat a large variety of molten salt systems, was adopted to thermodynamically describe the present liquid phase; all solid solutions were modeled using the Compound Energy Formalism (CEF); the gas phase was thermodynamically treated as an ideal mixture of all possible species. The model parameters were mainly obtained by critical evaluations and optimizations of thermodynamic and phase equilibrium data available from relative experimental measurements and theoretical predictions (first-principles calculations and empirical estimations) for the lower-order subsystems. These optimized model parameters were thereafter merged within the Kohler/Toop interpolation scheme, facilitating the prediction of gas solubility (H2O, HF and H2) in multicomponent cryolite-base molten salts using the FactSage thermochemical software. Several interesting diagrams were finally obtained in order to provide useful information for the industrial partners dedicated to the Hall-Héroult electrolytic aluminum production or other molten-salt technologies (the purification process and electroslag refining).

Exact Large-Deviation Statistics for a Nonequilibrium Quantum Spin Chain

NASA Astrophysics Data System (ADS)

Žnidarič, Marko

2014-01-01

We consider a one-dimensional XX spin chain in a nonequilibrium setting with a Lindblad-type boundary driving. By calculating large-deviation rate function in the thermodynamic limit, a generalization of free energy to a nonequilibrium setting, we obtain a complete distribution of current, including closed expressions for lower-order cumulants. We also identify two phase-transition-like behaviors in either the thermodynamic limit, at which the current probability distribution becomes discontinuous, or at maximal driving, when the range of possible current values changes discontinuously. In the thermodynamic limit the current has a finite upper and lower bound. We also explicitly confirm nonequilibrium fluctuation relation and show that the current distribution is the same under mapping of the coupling strength Γ→1/Γ.

Contribution to the thermodynamic description of the corium - The U-Zr-O system

NASA Astrophysics Data System (ADS)

Quaini, A.; Guéneau, C.; Gossé, S.; Dupin, N.; Sundman, B.; Brackx, E.; Domenger, R.; Kurata, M.; Hodaj, F.

2018-04-01

In order to understand the stratification process that may occur in the late phase of the fuel degradation during a severe accident in a PWR, the thermodynamic knowledge of the U-Zr-O system is crucial. The presence of a miscibility gap in the U-Zr-O liquid phase may lead to a stratified configuration, which will impact the accidental scenario management. The aim of this work was to obtain new experimental data in the U-Zr-O liquid miscibility gap. New tie-line data were provided at 2567 ± 25 K. The related thermodynamic models were reassessed using present data and literature values. The reassessed model will be implemented in the TAF-ID international database. The composition and density of phases potentially formed during stratification will be predicted by coupling current thermodynamic model with thermal-hydraulics codes.

A CFD-Based Study of the Feasibility of Adapting an Erosion Burner Rig for Examining the Effect of CMAS Deposition Corrosion on Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Miller, Robert A.; Kuczmarski, Maria A.

2015-01-01

Thermodynamic and computational fluid dynamics modeling has been conducted to examine the feasibility of adapting the NASA-Glenn erosion burner rigs for use in studies of corrosion of environmental barrier coatings by the deposition of molten CMAS. The effect of burner temperature, Mach number, particle preheat, duct heating, particle size, and particle phase (crystalline vs. glass) were analyzed. Detailed strategies for achieving complete melting of CMAS particles were developed, thereby greatly improving the probability of future successful experimental outcomes.

Effect of temperature on microbial growth rate - thermodynamic analysis, the arrhenius and eyring-polanyi connection

USDA-ARS?s Scientific Manuscript database

The objective of this work is to develop a new thermodynamic mathematical model for evaluating the effect of temperature on the rate of microbial growth. The new mathematical model is derived by combining the Arrhenius equation and the Eyring-Polanyi transition theory. The new model, suitable for ...

Introduction to the thermodynamic Bethe ansatz

NASA Astrophysics Data System (ADS)

van Tongeren, Stijn J.

2016-08-01

We give a pedagogical introduction to the thermodynamic Bethe ansatz, a method that allows us to describe the thermodynamics of integrable models whose spectrum is found via the (asymptotic) Bethe ansatz. We set the stage by deriving the Fermi-Dirac distribution and associated free energy of free electrons, and then in a similar though technically more complicated fashion treat the thermodynamics of integrable models, focusing first on the one-dimensional Bose gas with delta function interaction as a clean pedagogical example, secondly the XXX spin chain as an elementary (lattice) model with prototypical complicating features in the form of bound states, and finally the {SU}(2) chiral Gross-Neveu model as a field theory example. Throughout this discussion we emphasize the central role of particle and hole densities, whose relations determine the model under consideration. We then discuss tricks that allow us to use the same methods to describe the exact spectra of integrable field theories on a circle, in particular the chiral Gross-Neveu model. We moreover discuss the simplification of TBA equations to Y systems, including the transition back to integral equations given sufficient analyticity data, in simple examples.

Constitutive equations for an electroactive polymer

NASA Astrophysics Data System (ADS)

Tixier, Mireille; Pouget, Joël

2016-07-01

Ionic electroactive polymers can be used as sensors or actuators. For this purpose, a thin film of polyelectrolyte is saturated with a solvent and sandwiched between two platinum electrodes. The solvent causes a complete dissociation of the polymer and the release of small cations. The application of an electric field across the thickness results in the bending of the strip and vice versa. The material is modeled by a two-phase continuous medium. The solid phase, constituted by the polymer backbone inlaid with anions, is depicted as a deformable porous media. The liquid phase is composed of the free cations and the solvent (usually water). We used a coarse grain model. The conservation laws of this system have been established in a previous work. The entropy balance law and the thermodynamic relations are first written for each phase and then for the complete material using a statistical average technique and the material derivative concept. One deduces the entropy production. Identifying generalized forces and fluxes provides the constitutive equations of the whole system: the stress-strain relations which satisfy a Kelvin-Voigt model, generalized Fourier's and Darcy's laws and the Nernst-Planck equation.

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

Grove, John W.

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

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.

Ventless pressure control of two-phase propellant tanks in microgravity.

PubMed

Kassemi, Mohammad; Panzarella, Charles H

2004-11-01

This work studies pressurization and pressure control of a large liquid hydrogen storage tank. A finite element model is developed that couples a lumped thermodynamic formulation for the vapor region with a complete solution of the Navier-Stokes and energy equations for the flow and temperature fields in the liquid. Numerical results show that buoyancy effects are strong, even in microgravity, and can reposition a vapor bubble that is initially at the center of the tank to a region near the tank wall in a relatively short time. Long-term tank pressurization with the vapor bubble at the tank wall shows that after an initial transient lasting about a week, the final rate of pressure increase agrees with a purely thermodynamic analysis of the entire tank. However, the final pressure levels are quite different from thermodynamic predictions. Numerical results also show that there is significant thermal stratification in the liquid due to the effects of natural convection. A subcooled jet is used to provide simultaneous cooling and mixing in order to bring the tank pressure back down to its initial value. Three different jet speeds are examined. Although the lowest jet speed is ineffective at controlling the pressure because of insufficient penetration into the liquid region, the highest jet speed is shown to be quite effective at disrupting thermal stratification and reducing the tank pressure in reasonable time.

Ventless pressure control of two-phase propellant tanks in microgravity

NASA Technical Reports Server (NTRS)

Kassemi, Mohammad; Panzarella, Charles H.

2004-01-01

This work studies pressurization and pressure control of a large liquid hydrogen storage tank. A finite element model is developed that couples a lumped thermodynamic formulation for the vapor region with a complete solution of the Navier-Stokes and energy equations for the flow and temperature fields in the liquid. Numerical results show that buoyancy effects are strong, even in microgravity, and can reposition a vapor bubble that is initially at the center of the tank to a region near the tank wall in a relatively short time. Long-term tank pressurization with the vapor bubble at the tank wall shows that after an initial transient lasting about a week, the final rate of pressure increase agrees with a purely thermodynamic analysis of the entire tank. However, the final pressure levels are quite different from thermodynamic predictions. Numerical results also show that there is significant thermal stratification in the liquid due to the effects of natural convection. A subcooled jet is used to provide simultaneous cooling and mixing in order to bring the tank pressure back down to its initial value. Three different jet speeds are examined. Although the lowest jet speed is ineffective at controlling the pressure because of insufficient penetration into the liquid region, the highest jet speed is shown to be quite effective at disrupting thermal stratification and reducing the tank pressure in reasonable time.

Comparative thermodynamic and experimental study of some heavy metal behaviors during automotive shredder residues incineration

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

Trouve, G.; Kauffmann, A.; Delfosse, L.

1998-12-31

Experimental and theoretical studies of the behavior of some heavy metals were undertaken during Automotive Shredder Residues (ASR) incineration. A thermodynamic study at equilibrium was performed using a software minimizing the free Gibbs energy. The metals studied were barium, copper, lead and zinc. The studies were performed mostly at two temperatures: 1123 and 1373 K. The thermodynamic study showed that the chlorine content is the most important parameter influencing the volatility of the studied metals. It also showed that in default of chlorine in a system containing several metals, barium chloride in its condensed form is the most easily formed.more » Other metals remained in their metallic form or in the form of oxides. The presence of hydrogen in the system has a general limiting influence on the metal volatility because, especially at high temperatures, hydrogen chloride is more likely to be formed. In the experimental field, the behaviors of metals were studied using commercial polymers as waste models: a PVC mastic, a polyurethane mastic and a rubber powder. Copper and barium presented a non volatile behavior during the incineration of waste matrixes as ASR, being present also in residual ash. On the other hand, lead was completely formed in the gas phase and zinc showed an equal partitioning between the two principal phases of the treatment.« less

Thermodynamic properties of gaseous ruthenium species.

PubMed

Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

2015-05-21

The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

Reaction cycle and thermodynamics in bacteriorhodopsin

NASA Technical Reports Server (NTRS)

Lanyi, J. K.

1992-01-01

Light causes the all-trans to 13-cis isomerization of the retinal in bacteriorhodopsin; the thermal relaxation leading back to the initial state drives proton transport first via proton transfer between the retinal Schiff base and D85 and then between the Schiff base and D96. The reaction sequence and thermodynamics of this photocycle are described by measuring time-resolved absorption changes with a gated multichannel analyzer between 100 ns and 100 ms, at six temperatures between 5 degrees C and 30 degrees C. Analysis of the energetics of the chromophore reaction sequence is on the basis of a recently proposed model (Varo & Lanyi, Biochemistry 30, 5016-5022, 1991) which consists of a single cycle and many reversible reactions: BR -hv-->K<==>L<==>M1-->M2<==>N<==>O-->BR. The existence of the M1-->M2 reaction, which functions as the switch in the proton transfer, is confirmed by spectroscopic evidence. The calculated thermodynamic parameters indicate that the exchange of free energy between the protein and the protons is at the switch step. Further, a large entropy decrease at this reaction suggests a protein conformation change which will conserve delta G for driving the completion of the reaction cycle. The results provide insights to mechanism and energy coupling in this system, with possible relevance to the general question of how ion pumps function.

Mechanical approach to chemical transport

PubMed Central

Kocherginsky, Nikolai; Gruebele, Martin

2016-01-01

Nonequilibrium thermodynamics describes the rates of transport phenomena with the aid of various thermodynamic forces, but often the phenomenological transport coefficients are not known, and the description is not easily connected with equilibrium relations. We present a simple and intuitive model to address these issues. Our model is based on Lagrangian dynamics for chemical systems with dissipation, so one may think of the model as physicochemical mechanics. Using one main equation, the model allows a systematic derivation of all transport and equilibrium equations, subject to the limitation that heat generated or absorbed in the system must be small for the model to be valid. A table with all major examples of transport and equilibrium processes described using physicochemical mechanics is given. In equilibrium, physicochemical mechanics reduces to standard thermodynamics and the Gibbs–Duhem relation, and we show that the First and Second Laws of thermodynamics are satisfied for our system plus bath model. Out of equilibrium, our model provides relationships between transport coefficients and describes system evolution in the presence of several simultaneous external fields. The model also leads to an extension of the Onsager–Casimir reciprocal relations for properties simultaneously transported by many components. PMID:27647899

A Chemically Relevant Model for Teaching the Second Law of Thermodynamics.

ERIC Educational Resources Information Center

Williamson, Bryce E.; Morikawa, Tetsuo

2002-01-01

Introduces a chemical model illustrating the aspects of the second law of thermodynamics which explains concepts such as reversibility, path dependence, and extrapolation in terms of electrochemistry and calorimetry. Presents a thought experiment using an ideal galvanic electrochemical cell. (YDS)

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.

Miscibility and Thermodynamics of Mixing of Different Models of Formamide and Water in Computer Simulation.

PubMed

Kiss, Bálint; Fábián, Balázs; Idrissi, Abdenacer; Szőri, Milán; Jedlovszky, Pál

2017-07-27

The thermodynamic changes that occur upon mixing five models of formamide and three models of water, including the miscibility of these model combinations itself, is studied by performing Monte Carlo computer simulations using an appropriately chosen thermodynamic cycle and the method of thermodynamic integration. The results show that the mixing of these two components is close to the ideal mixing, as both the energy and entropy of mixing turn out to be rather close to the ideal term in the entire composition range. Concerning the energy of mixing, the OPLS/AA_mod model of formamide behaves in a qualitatively different way than the other models considered. Thus, this model results in negative, while the other ones in positive energy of mixing values in combination with all three water models considered. Experimental data supports this latter behavior. Although the Helmholtz free energy of mixing always turns out to be negative in the entire composition range, the majority of the model combinations tested either show limited miscibility, or, at least, approach the miscibility limit very closely in certain compositions. Concerning both the miscibility and the energy of mixing of these model combinations, we recommend the use of the combination of the CHARMM formamide and TIP4P water models in simulations of water-formamide mixtures.

Nonequilibrium thermodynamics of the shear-transformation-zone model

NASA Astrophysics Data System (ADS)

Luo, Alan M.; Ã-ttinger, Hans Christian

2014-02-01

The shear-transformation-zone (STZ) model has been applied numerous times to describe the plastic deformation of different types of amorphous systems. We formulate this model within the general equation for nonequilibrium reversible-irreversible coupling (GENERIC) framework, thereby clarifying the thermodynamic structure of the constitutive equations and guaranteeing thermodynamic consistency. We propose natural, physically motivated forms for the building blocks of the GENERIC, which combine to produce a closed set of time evolution equations for the state variables, valid for any choice of free energy. We demonstrate an application of the new GENERIC-based model by choosing a simple form of the free energy. In addition, we present some numerical results and contrast those with the original STZ equations.

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

Simulating Metabolism with Statistical Thermodynamics

PubMed Central

Cannon, William R.

2014-01-01

New methods are needed for large scale modeling of metabolism that predict metabolite levels and characterize the thermodynamics of individual reactions and pathways. Current approaches use either kinetic simulations, which are difficult to extend to large networks of reactions because of the need for rate constants, or flux-based methods, which have a large number of feasible solutions because they are unconstrained by the law of mass action. This report presents an alternative modeling approach based on statistical thermodynamics. The principles of this approach are demonstrated using a simple set of coupled reactions, and then the system is characterized with respect to the changes in energy, entropy, free energy, and entropy production. Finally, the physical and biochemical insights that this approach can provide for metabolism are demonstrated by application to the tricarboxylic acid (TCA) cycle of Escherichia coli. The reaction and pathway thermodynamics are evaluated and predictions are made regarding changes in concentration of TCA cycle intermediates due to 10- and 100-fold changes in the ratio of NAD+:NADH concentrations. Finally, the assumptions and caveats regarding the use of statistical thermodynamics to model non-equilibrium reactions are discussed. PMID:25089525

Simulating metabolism with statistical thermodynamics.

PubMed

Cannon, William R

2014-01-01

New methods are needed for large scale modeling of metabolism that predict metabolite levels and characterize the thermodynamics of individual reactions and pathways. Current approaches use either kinetic simulations, which are difficult to extend to large networks of reactions because of the need for rate constants, or flux-based methods, which have a large number of feasible solutions because they are unconstrained by the law of mass action. This report presents an alternative modeling approach based on statistical thermodynamics. The principles of this approach are demonstrated using a simple set of coupled reactions, and then the system is characterized with respect to the changes in energy, entropy, free energy, and entropy production. Finally, the physical and biochemical insights that this approach can provide for metabolism are demonstrated by application to the tricarboxylic acid (TCA) cycle of Escherichia coli. The reaction and pathway thermodynamics are evaluated and predictions are made regarding changes in concentration of TCA cycle intermediates due to 10- and 100-fold changes in the ratio of NAD+:NADH concentrations. Finally, the assumptions and caveats regarding the use of statistical thermodynamics to model non-equilibrium reactions are discussed.

The 2006 Cape Canaveral Air Force Station Range Reference Atmosphere Model Validation Study and Sensitivity Analysis to the National Aeronautics and Space Administration's Space Shuttle

NASA Technical Reports Server (NTRS)

Burns, Lee; Merry, Carl; Decker, Ryan; Harrington, Brian

2008-01-01

The 2006 Cape Canaveral Air Force Station (CCAFS) Range Reference Atmosphere (RRA) is a statistical model summarizing the wind and thermodynamic atmospheric variability from surface to 70 kin. Launches of the National Aeronautics and Space Administration's (NASA) Space Shuttle from Kennedy Space Center utilize CCAFS RRA data to evaluate environmental constraints on various aspects of the vehicle during ascent. An update to the CCAFS RRA was recently completed. As part of the update, a validation study on the 2006 version was conducted as well as a comparison analysis of the 2006 version to the existing CCAFS RRA database version 1983. Assessments to the Space Shuttle vehicle ascent profile characteristics were performed to determine impacts of the updated model to the vehicle performance. Details on the model updates and the vehicle sensitivity analyses with the update model are presented.

Thermophysics Characterization of Kerosene Combustion

NASA Technical Reports Server (NTRS)

Wang, Ten-See

2001-01-01

A one-formula surrogate fuel formulation and its quasi-global combustion kinetics model are developed to support the design of injectors and thrust chambers of kerosene-fueled rocket engines. This surrogate fuel model depicts a fuel blend that properly represents the general physical and chemical properties of kerosene. The accompanying gaseous-phase thermodynamics of the surrogate fuel is anchored with the heat of formation of kerosene and verified by comparing a series of one-dimensional rocket thrust chamber calculations. The quasi-global combustion kinetics model consists of several global steps for parent fuel decomposition, soot formation, and soot oxidation and a detailed wet-CO mechanism to complete the combustion process. The final thermophysics formulations are incorporated with a computational fluid dynamics model for prediction of the combustion efficiency of an unielement, tripropellant combustor and the radiation of a kerosene-fueled thruster plume. The model predictions agreed reasonably well with those of the tests.

A primer on thermodynamic-based models for deciphering transcriptional regulatory logic.

PubMed

Dresch, Jacqueline M; Richards, Megan; Ay, Ahmet

2013-09-01

A rigorous analysis of transcriptional regulation at the DNA level is crucial to the understanding of many biological systems. Mathematical modeling has offered researchers a new approach to understanding this central process. In particular, thermodynamic-based modeling represents the most biophysically informed approach aimed at connecting DNA level regulatory sequences to the expression of specific genes. The goal of this review is to give biologists a thorough description of the steps involved in building, analyzing, and implementing a thermodynamic-based model of transcriptional regulation. The data requirements for this modeling approach are described, the derivation for a specific regulatory region is shown, and the challenges and future directions for the quantitative modeling of gene regulation are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Theoretical Analysis of Thermodynamic Measurements near a Liquid-Gas Critical Point

NASA Technical Reports Server (NTRS)

Barmatz, M.; Zhong, Fang; Hahn, Inseob

2003-01-01

Over the years, many ground-based studies have been performed near liquid-gas critical points to elucidate the expected divergences in thermodynamic quantities. The unambiguous interpretation of these studies very near the critical point is hindered by a gravity-induced density stratification. However, these ground-based measurements can give insight into the crossover behavior between the asymptotic critical region near the transition and the mean field region farther away. We have completed a detailed analysis of heat capacity, susceptibility and coexistence curve measurements near the He-3 liquid-gas critical point using the minimal-subtraction renormalization (MSR) scheme within the phi(exp 4) model. This MSR scheme, using only two adjustable parameters, provides a reasonable global fit to all of these experimental measurements in the gravity-free region out to a reduced temperature of |t| approx. 2x10(exp -2). Recently this approach has also been applied to the earlier microgravity measurements of Haupt and Straub in SF(sub 6) with surprising results. The conclusions drawn from the MSR analyses will be presented. Measurements in the gravity-affected region closer to the He-3 critical point have also been analyzed using the recent crossover parametric model (CPM) of the equation-of-state. The results of fitting heat capacity measurements to the CPM model along the He-3 critical isochore in the gravity-affected region will also be presented.

The thermodynamics of bipolarity: a bifurcation model of bipolar illness and bipolar character and its psychotherapeutic applications.

PubMed

Sabelli, H C; Carlson-Sabelli, L; Javaid, J I

1990-11-01

Two models dominate current formulations of bipolar illness: the homeostatic model implicit in Freud's psychodynamics and most neuroamine deficit/excess theories; and the oscillatory model of exaggerated biological rhythms. The homeostatic model is based on the closed systems approach of classic thermodynamics, while the oscillatory model requires the open systems approach of modern thermodynamics. Here we present a thermodynamic model of bipolarity that includes both homeostatic and oscillatory features and adds the most important feature of open systems thermodynamics: the creation of novel structures in bifurcation processes. According to the proposed model, bipolarity is the result of exaggerated biological energy that augments homeostatic, oscillatory and creative psychological processes. Only low-energy closed systems tend to rest ("point attractor") and entropic disorder. Open processes containing and exchanging energy fluctuate between opposite states ("periodic attractors"); they are characteristic of most physiological rhythms and are exaggerated in bipolar subjects. At higher energies, their strong fluctuations destroy pre-existing patterns and structures, produce turbulence ("chaotic attractors"), which sudden switches between opposite states, and create new and more complex structures. Likewise, high-energy bipolars develop high spontaneity, great fluctuations between opposite moods, internal and interpersonal chaos, and enhanced creativity (personal, artistic, professional) as well as psychopathology (personality deviations, psychotic delusions). Offered here is a theoretical explanation of the dual--creative and destructive--nature of bipolarity in terms of the new enantiodromic concept of entropy generalized by process theory. Clinically, this article offers an integrative model of bipolarity that accounts for many clinical features and contributes to a definition of the bipolar personality.

Thermodynamic description of multicomponent nickel-base superalloys containing aluminum, chromium, ruthenium and platinum: A computational thermodynamic approach coupled with experiments

NASA Astrophysics Data System (ADS)

Zhu, Jun

Ru and Pt are candidate additional component for improving the high temperature properties of Ni-base superalloys. A thermodynamic description of the Ni-Al-Cr-Ru-Pt system, serving as an essential knowledge base for better alloy design and processing control, was developed in the present study by means of thermodynamic modeling coupled with experimental investigations of phase equilibria. To deal with the order/disorder transition occurring in the Ni-base superalloys, a physical sound model, Cluster/Site Approximation (CSA) was used to describe the fcc phases. The CSA offers computational advantages, without loss of accuracy, over the Cluster Variation Method (CVM) in the calculation of multicomponent phase diagrams. It has been successfully applied to fcc phases in calculating technologically important Ni-Al-Cr phase diagrams. Our effort in this study focused on the two key ternary systems: Ni-Al-Ru and Ni-Al-Pt. The CSA calculated Ni-Al-Ru ternary phase diagrams are in good agreement with the experimental results in the literature and from the current study. A thermodynamic description of quaternary Ni-Al-Cr-Ru was obtained based on the descriptions of the lower order systems and the calculated results agree with experimental data available in literature and in the current study. The Ni-Al-Pt system was thermodynamically modeled based on the limited experimental data available in the literature and obtained from the current study. With the help of the preliminary description, a number of alloy compositions were selected for further investigation. The information obtained was used to improve the current modeling. A thermodynamic description of the Ni-Al-Cr-Pt quaternary was then obtained via extrapolation from its constituent lower order systems. The thermodynamic description for Ni-base superalloy containing Al, Cr, Ru and Pt was obtained via extrapolation. It is believed to be reliable and useful to guide the alloy design and further experimental investigation.

A sub-grid, mixture-fraction-based thermodynamic equilibrium model for gas phase combustion in FIRETEC: development and results

Treesearch

M. M. Clark; T. H. Fletcher; R. R. Linn

2010-01-01

The chemical processes of gas phase combustion in wildland fires are complex and occur at length-scales that are not resolved in computational fluid dynamics (CFD) models of landscape-scale wildland fire. A new approach for modelling fire chemistry in HIGRAD/FIRETEC (a landscape-scale CFD wildfire model) applies a mixture– fraction model relying on thermodynamic...

Gas solubility in dilute solutions: A novel molecular thermodynamic perspective

NASA Astrophysics Data System (ADS)

Chialvo, Ariel A.

2018-05-01

We present an explicit molecular-based interpretation of the thermodynamic phase equilibrium underlying gas solubility in liquids, through rigorous links between the microstructure of the dilute systems and the relevant macroscopic quantities that characterize their solution thermodynamics. We apply the formal analysis to unravel and highlight the molecular-level nature of the approximations behind the widely used Krichevsky-Kasarnovsky [J. Am. Chem. Soc. 57, 2168 (1935)] and Krichevsky-Ilinskaya [Acta Physicochim. 20, 327 (1945)] equations for the modeling of gas solubility. Then, we implement a general molecular-based approach to gas solubility and illustrate it by studying Lennard-Jones binary systems whose microstructure and thermodynamic properties were consistently generated via integral equation calculations. Furthermore, guided by the molecular-based analysis, we propose a novel macroscopic modeling approach to gas solubility, emphasize some usually overlook modeling subtleties, and identify novel interdependences among relevant solubility quantities that can be used as either handy modeling constraints or tools for consistency tests.

Hamiltonian and Thermodynamic Modeling of Quantum Turbulence

NASA Astrophysics Data System (ADS)

Grmela, Miroslav

2010-10-01

The state variables in the novel model introduced in this paper are the fields playing this role in the classical Landau-Tisza model and additional fields of mass, entropy (or temperature), superfluid velocity, and gradient of the superfluid velocity, all depending on the position vector and another tree dimensional vector labeling the scale, describing the small-scale structure developed in 4He superfluid experiencing turbulent motion. The fluxes of mass, momentum, energy, and entropy in the position space as well as the fluxes of energy and entropy in scales, appear in the time evolution equations as explicit functions of the state variables and of their conjugates. The fundamental thermodynamic relation relating the fields to their conjugates is left in this paper undetermined. The GENERIC structure of the equations serves two purposes: (i) it guarantees that solutions to the governing equations, independently of the choice of the fundamental thermodynamic relation, agree with the observed compatibility with thermodynamics, and (ii) it is used as a guide in the construction of the novel model.

Gas solubility in dilute solutions: A novel molecular thermodynamic perspective.

PubMed

Chialvo, Ariel A

2018-05-07

We present an explicit molecular-based interpretation of the thermodynamic phase equilibrium underlying gas solubility in liquids, through rigorous links between the microstructure of the dilute systems and the relevant macroscopic quantities that characterize their solution thermodynamics. We apply the formal analysis to unravel and highlight the molecular-level nature of the approximations behind the widely used Krichevsky-Kasarnovsky [J. Am. Chem. Soc. 57, 2168 (1935)] and Krichevsky-Ilinskaya [Acta Physicochim. 20, 327 (1945)] equations for the modeling of gas solubility. Then, we implement a general molecular-based approach to gas solubility and illustrate it by studying Lennard-Jones binary systems whose microstructure and thermodynamic properties were consistently generated via integral equation calculations. Furthermore, guided by the molecular-based analysis, we propose a novel macroscopic modeling approach to gas solubility, emphasize some usually overlook modeling subtleties, and identify novel interdependences among relevant solubility quantities that can be used as either handy modeling constraints or tools for consistency tests.

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

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.

AN ASSESSMENT OF THE ABILITY OF 3-D AIR QUALITY MODELS WITH CURRENT THERMODYNAMIC EQUILIBRIUM MODELS TO PREDICT AEROSOL NO3

EPA Science Inventory

The partitioning of total nitrate (TNO3) and total ammonium (TNH4) between gas and aerosol phases is studied with two thermodynamic equilibrium models, ISORROPIA and AIM, and three datasets: high time-resolution measurement data from the 1999 Atlanta SuperSite Experiment and from...

Enhancing the Effectiveness of Carbon Dioxide Flooding by Managing Asphaltene Precipitation

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

Deo, Milind D.

2002-02-21

This project was undertaken to understand fundamental aspects of carbon dioxide (CO2) induced asphaltene precipitation. Oil and asphaltene samples from the Rangely field in Colorado were used for most of the project. The project consisted of pure component and high-pressure, thermodynamic experiments, thermodynamic modeling, kinetic experiments and modeling, targeted corefloods and compositional modeling.

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

Sea-town interactions over Marseille: 3D urban boundary layer and thermodynamic fields near the surface

NASA Astrophysics Data System (ADS)

Lemonsu, A.; Pigeon, G.; Masson, V.; Moppert, C.

2006-02-01

3D numerical simulations with the Meso-NH atmospheric model including the Town Energy Balance urban parameterization, are conducted over the south-east of France and the one million inhabitants city of Marseille in the frameworks of the ESCOMPTE-UBL program. The geographic situation of the area is relatively complex, because of the proximity of the Mediterranean Sea and the presence of numerous massifs, inducing complex meteorological flows. The present work is focused on six days of the campaign, characterized by the development of strong summer sea-breeze circulations. A complete evaluation of the model is initially realized at both regional- and city-scales, by using the large available database. The regional evaluation shows a good behavior of the model, during the six days of simulation, either for the parameters near the surface or for the vertical profiles describing the structure of the atmosphere. The urban-scale evaluation indicates that the fine structure of the horizontal fields of air temperature above the city is correctly simulated by the model. A specific attention is then pointed to the 250-m horizontal resolution outputs, focused on the Marseille area, for two days of the campaign. From the study of the vertical structure of the Urban Boundary Layer and the thermodynamic fields near the surface, one underscores the important differences due to the regional and local flows, and the complex interactions that occur between the urban effects and the effects of sea breezes.

A thermodynamic definition of protein domains.

PubMed

Porter, Lauren L; Rose, George D

2012-06-12

Protein domains are conspicuous structural units in globular proteins, and their identification has been a topic of intense biochemical interest dating back to the earliest crystal structures. Numerous disparate domain identification algorithms have been proposed, all involving some combination of visual intuition and/or structure-based decomposition. Instead, we present a rigorous, thermodynamically-based approach that redefines domains as cooperative chain segments. In greater detail, most small proteins fold with high cooperativity, meaning that the equilibrium population is dominated by completely folded and completely unfolded molecules, with a negligible subpopulation of partially folded intermediates. Here, we redefine structural domains in thermodynamic terms as cooperative folding units, based on m-values, which measure the cooperativity of a protein or its substructures. In our analysis, a domain is equated to a contiguous segment of the folded protein whose m-value is largely unaffected when that segment is excised from its parent structure. Defined in this way, a domain is a self-contained cooperative unit; i.e., its cooperativity depends primarily upon intrasegment interactions, not intersegment interactions. Implementing this concept computationally, the domains in a large representative set of proteins were identified; all exhibit consistency with experimental findings. Specifically, our domain divisions correspond to the experimentally determined equilibrium folding intermediates in a set of nine proteins. The approach was also proofed against a representative set of 71 additional proteins, again with confirmatory results. Our reframed interpretation of a protein domain transforms an indeterminate structural phenomenon into a quantifiable molecular property grounded in solution thermodynamics.

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.

Predicting RNA pseudoknot folding thermodynamics

PubMed Central

Cao, Song; Chen, Shi-Jie

2006-01-01

Based on the experimentally determined atomic coordinates for RNA helices and the self-avoiding walks of the P (phosphate) and C4 (carbon) atoms in the diamond lattice for the polynucleotide loop conformations, we derive a set of conformational entropy parameters for RNA pseudoknots. Based on the entropy parameters, we develop a folding thermodynamics model that enables us to compute the sequence-specific RNA pseudoknot folding free energy landscape and thermodynamics. The model is validated through extensive experimental tests both for the native structures and for the folding thermodynamics. The model predicts strong sequence-dependent helix-loop competitions in the pseudoknot stability and the resultant conformational switches between different hairpin and pseudoknot structures. For instance, for the pseudoknot domain of human telomerase RNA, a native-like and a misfolded hairpin intermediates are found to coexist on the (equilibrium) folding pathways, and the interplay between the stabilities of these intermediates causes the conformational switch that may underlie a human telomerase disease. PMID:16709732

Cloud characteristics, thermodynamic controls and radiative impacts during the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) experiment

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

Giangrande, Scott E.; Feng, Zhe; Jensen, Michael P.

Routine cloud, precipitation and thermodynamic observations collected by the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) and Aerial Facility (AAF) during the 2-year US Department of Energy (DOE) ARM Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign are summarized. These observations quantify the diurnal to large-scale thermodynamic regime controls on the clouds and precipitation over the undersampled, climatically important Amazon basin region. The extended ground deployment of cloud-profiling instrumentation enabled a unique look at multiple cloud regimes at high temporal and vertical resolution. This longer-term ground deployment, coupled with two short-term aircraft intensive observing periods, allowed new opportunitiesmore » to better characterize cloud and thermodynamic observational constraints as well as cloud radiative impacts for modeling efforts within typical Amazon wet and dry seasons.« less

Cloud characteristics, thermodynamic controls and radiative impacts during the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) experiment

DOE PAGES

Giangrande, Scott E.; Feng, Zhe; Jensen, Michael P.; ...

2017-12-06

Routine cloud, precipitation and thermodynamic observations collected by the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) and Aerial Facility (AAF) during the 2-year US Department of Energy (DOE) ARM Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign are summarized. These observations quantify the diurnal to large-scale thermodynamic regime controls on the clouds and precipitation over the undersampled, climatically important Amazon basin region. The extended ground deployment of cloud-profiling instrumentation enabled a unique look at multiple cloud regimes at high temporal and vertical resolution. This longer-term ground deployment, coupled with two short-term aircraft intensive observing periods, allowed new opportunitiesmore » to better characterize cloud and thermodynamic observational constraints as well as cloud radiative impacts for modeling efforts within typical Amazon wet and dry seasons.« less

Internal stress-induced melting below melting temperature at high-rate laser heating

NASA Astrophysics Data System (ADS)

Hwang, Yong Seok; Levitas, Valery I.

2014-06-01

In this Letter, continuum thermodynamic and phase field approaches (PFAs) predicted internal stress-induced reduction in melting temperature for laser-irradiated heating of a nanolayer. Internal stresses appear due to thermal strain under constrained conditions and completely relax during melting, producing an additional thermodynamic driving force for melting. Thermodynamic melting temperature for Al reduces from 933.67 K for a stress-free condition down to 898.1 K for uniaxial strain and to 920.8 K for plane strain. Our PFA simulations demonstrated barrierless surface-induced melt nucleation below these temperatures and propagation of two solid-melt interfaces toward each other at the temperatures very close to the corresponding predicted thermodynamic equilibrium temperatures for the heating rate Q ≤1.51×1010K/s. At higher heating rates, kinetic superheating competes with a reduction in melting temperature and melting under uniaxial strain occurs at 902.1 K for Q = 1.51 × 1011 K/s and 936.9 K for Q = 1.46 × 1012 K/s.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

NASA Astrophysics Data System (ADS)

Perron, A.; Turchi, P. E. A.; Landa, A.; Oudot, B.; Ravat, B.; Delaunay, F.

2016-12-01

A newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U is presented. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. The previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) is also included in the database and is briefly described in the present work. Finally, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

DOE PAGES

Perron, A.; Turchi, P. E. A.; Landa, A.; ...

2016-12-01

We present a newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. We includedmore » the previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) in the database and is briefly described in the present work. In conclusion, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.« less

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.

A phase-field approach to nonequilibrium phase transformations in elastic solids via an intermediate phase (melt) allowing for interface stresses.

PubMed

Momeni, Kasra; Levitas, Valery I

2016-04-28

A phase-field approach for phase transformations (PTs) between three different phases at nonequilibrium temperatures is developed. It includes advanced mechanics, thermodynamically consistent interfacial stresses, and interface interactions. A thermodynamic Landau-Ginzburg potential developed in terms of polar order parameters satisfies the desired instability and equilibrium conditions for homogeneous phases. The interfacial stresses were introduced with some terms from large-strain formulation even though the small-strain assumption was utilized. The developed model is applied to study the PTs between two solid phases via a highly disordered intermediate phase (IP) or an intermediate melt (IM) hundreds of degrees below the melting temperature. In particular, the β ↔ δ PTs in HMX energetic crystals via IM are analyzed. The effects of various parameters (temperature, ratios of widths and energies of solid-solid (SS) to solid-melt (SM) interfaces, elastic energy, and interfacial stresses) on the formation, stability, and structure of the IM within a propagating SS interface are studied. Interfacial and elastic stresses within a SS interphase and their relaxation and redistribution with the appearance of a partial or complete IM are analyzed. The energy and structure of the critical nucleus (CN) of the IM are studied as well. In particular, the interfacial stresses increase the aspect-ratio of the CN. Although including elastic energy can drastically reduce the energy of the CN of the IM, the activation energy of the CN of the IM within the SS interface increases when interfacial tension is taken into account. The developed thermodynamic potential can also be modified to model other multiphase physical phenomena, such as multi-variant martensitic PTs, grain boundary and surface-induced pre-melting and PTs, as well as developing phase diagrams for IPs.

Grain boundary premelting and activated sintering in binary refractory alloys

NASA Astrophysics Data System (ADS)

Shi, Xiaomeng

Quasi-liquid intergranular film (IGF) which has been widely observed in ceramic systems can persist into sub-solidus region whereby an analogy to Grain boundary (GB) premelting can be made. In this work, a grain boundary (GB) premelting/prewetting model in a metallic system was firstly built based on the Benedictus' model and computational thermodynamics, predicting that GB disordering can start at 60-85% of the bulk solidus temperatures in selected systems. This model quantitatively explains the long-standing mystery of subsolidus activated sintering in W-Pd, W-Ni, W-Co, W-Fe and W-Cu, and it has broad applications for understanding GB-controlled transport kinetics and physical properties. Furthermore, this study demonstrates the necessity of developing GB phase diagrams as a tool for materials design. Subsequently, Grain boundary (GB) wetting and prewetting in Ni-doped Mo are systematically evaluated via characterizing well-quenched specimens and thermodynamic modeling. In contrast to prior reports, the delta-NiMo phase does not wet Mo GBs in the solid state. In the solid-liquid two-phase region, the Ni-rich liquid wets Mo GBs completely. Furthermore, high-resolution transmission electron microscopy demonstrates that nanometer-thick quasi-liquid IGFs persist at GBs into the single-phase region where the bulk liquid phase is no longer stable; this is interpreted as a case of GB prewetting. An analytical thermodynamic model is developed and validated, and this model can be extended to other systems. Furthermore, the analytical model was refined based upon Beneditus' model with correction in determining interaction contribution of interfacial energy. A calculation-based GB phase diagram for Ni-Mo binary system was created and validated by comparing with GB diffusivities determined through a series of controlled sintering experiments. The dependence of GB diffusivity on doping level and temperature was examined and compared with model-predicted GB phase diagram. The consistency between GB phase diagram and GB diffusivity was evidently observed. This study revealed the existence of quasi-liquid IGF in Ni-Mo and re-confirmed our prior hypothesis proposed through work in Ni-W system. It also demonstrated further the necessity of a GB phase diagram as a new tool to guide the materials processing or design, such as selection of sintering aid and heat-treatment.

From in silica to in silico: retention thermodynamics at solid-liquid interfaces.

PubMed

El Hage, Krystel; Bemish, Raymond J; Meuwly, Markus

2018-06-28

The dynamics of solvated molecules at the solid/liquid interface is essential for a molecular-level understanding for the solution thermodynamics in reversed phase liquid chromatography (RPLC). The heterogeneous nature of the systems and the competing intermolecular interactions makes solute retention in RPLC a surprisingly challenging problem which benefits greatly from modelling at atomistic resolution. However, the quality of the underlying computational model needs to be sufficiently accurate to provide a realistic description of the energetics and dynamics of systems, especially for solution-phase simulations. Here, the retention thermodynamics and the retention mechanism of a range of benzene-derivatives in C18 stationary-phase chains in contact with water/methanol mixtures is studied using point charge (PC) and multipole (MTP) electrostatic models. The results demonstrate that free energy simulations with a faithful MTP representation of the computational model provide quantitative and molecular level insight into the thermodynamics of adsorption/desorption in chromatographic systems while a conventional PC representation fails in doing so. This provides a rational basis to develop more quantitative and validated models for the optimization of separation systems.

Magma Energy Research, 79-1. Semiannual report, October 1, 1978-March 31, 1979

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

Traeger, R.K.; Colp, J.L.; Neel, R.R.

1979-07-01

A major effort in evaluating Kilauea Iki lava lake has been completed. The physical model based on FY 76 geophysical experiments is not correct in that a low viscosity, liquid lens of appreciable thickness does not exist. Mathematical models of the cooling of the lava lake and the state of solidification of the liquid lens were verified by thermal profile and permeability measurements. New jet-augmented drilling concepts successfully penetrated the viscous, multi-phase molten rock region in some locations where conventional drilling failed. Heat transfer studies in the lake suggest injection of fluids to enhance convection may be useful to extractmore » energy from magma chamber margins. Other activities resulted in the completion and successful testing of a 800 cc simulation facility for evaluating simulated magma properties at temperatures to 1500/sup 0/C and pressures to 4 kbar. In materials compatibility studies, thermodynamic stability diagrams were developed for 15 pure metals in basaltic magma systems and compatibility tests completed. Results are being used to define simple alloy systems which may be compatible with magmas and to identify other superalloy materials candidates.« less

Complete Mie-Gruneisen Equation of State

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

Menikoff, Ralph

2012-06-28

The Mie-Gruneisen equation of state (EOS) is frequently used in hydro simulations to model solids at high pressure (up to a few Mb). It is an incomplete EOS characterized by a Gruneisen coefficient, {Lambda} = -V({partial_derivative}{sub e}P){sub V}, that is a function of only V. Expressions are derived for isentropes and isotherms. This enables the extension to a complete EOS. Thermodynamic consistency requires that the specific heat is a function of a single scaled temperature. A complete extension is uniquely determined by the temperature dependence of the specific heat at a fixed reference density. In addition we show that ifmore » the domain of the EOS extends to T = 0 and the specific heat vanishes on the zero isotherm then {Lambda} a function of only V is equivalent to a specific heat with a single temperature scale. If the EOS domain does not include the zero isotherm, then a specific heat with a single temperature scale leads to a generalization of the Mie-Gruneisen EOS in which the pressure is linear in both the specific energy and the temperature. Such an EOS has previously been used to model liquid nitromethane.« less

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lewis, J. S.

1980-01-01

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

The Finite Strain Johnson Cook Plasticity and Damage Constitutive Model in ALEGRA.

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

Sanchez, Jason James

A finite strain formulation of the Johnson Cook plasticity and damage model and it's numerical implementation into the ALEGRA code is presented. The goal of this work is to improve the predictive material failure capability of the Johnson Cook model. The new implementation consists of a coupling of damage and the stored elastic energy as well as the minimum failure strain criteria for spall included in the original model development. This effort establishes the necessary foundation for a thermodynamically consistent and complete continuum solid material model, for which all intensive properties derive from a common energy. The motivation for developingmore » such a model is to improve upon ALEGRA's present combined model framework. Several applications of the new Johnson Cook implementation are presented. Deformation driven loading paths demonstrate the basic features of the new model formulation. Use of the model produces good comparisons with experimental Taylor impact data. Localized deformation leading to fragmentation is produced for expanding ring and exploding cylinder applications.« less

Ab initio atomistic thermodynamics study on the oxidation mechanism of binary and ternary alloy surfaces

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

Liu, Shi-Yu, E-mail: buaasyliu@gmail.com; Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon, Hong Kong; Liu, Shiyang

Utilizing a combination of ab initio density-functional theory and thermodynamics formalism, we have established the microscopic mechanisms for oxidation of the binary and ternary alloy surfaces and provided a clear explanation for the experimental results of the oxidation. We construct three-dimensional surface phase diagrams (SPDs) for oxygen adsorption on three different Nb-X(110) (X = Ti, Al or Si) binary alloy surfaces. On the basis of the obtained SPDs, we conclude a general microscopic mechanism for the thermodynamic oxidation, that is, under O-rich conditions, a uniform single-phase SPD (type I) and a nonuniform double-phase SPD (type II) correspond to the sustainedmore » complete selective oxidation and the non-sustained partial selective oxidation by adding the X element, respectively. Furthermore, by revealing the framework of thermodynamics for the oxidation mechanism of ternary alloys through the comparison of the surface energies of two separated binary alloys, we provide an understanding for the selective oxidation behavior of the Nb ternary alloy surfaces. Using these general microscopic mechanisms, one could predict the oxidation behavior of any binary and multi-component alloy surfaces based on thermodynamics considerations.« less

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.

Modular rate laws for enzymatic reactions: thermodynamics, elasticities and implementation.

PubMed

Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

2010-06-15

Standard rate laws are a key requisite for systematically turning metabolic networks into kinetic models. They should provide simple, general and biochemically plausible formulae for reaction velocities and reaction elasticities. At the same time, they need to respect thermodynamic relations between the kinetic constants and the metabolic fluxes and concentrations. We present a family of reversible rate laws for reactions with arbitrary stoichiometries and various types of regulation, including mass-action, Michaelis-Menten and uni-uni reversible Hill kinetics as special cases. With a thermodynamically safe parameterization of these rate laws, parameter sets obtained by model fitting, sampling or optimization are guaranteed to lead to consistent chemical equilibrium states. A reformulation using saturation values yields simple formulae for rates and elasticities, which can be easily adjusted to the given stationary flux distributions. Furthermore, this formulation highlights the role of chemical potential differences as thermodynamic driving forces. We compare the modular rate laws to the thermodynamic-kinetic modelling formalism and discuss a simplified rate law in which the reaction rate directly depends on the reaction affinity. For automatic handling of modular rate laws, we propose a standard syntax and semantic annotations for the Systems Biology Markup Language. An online tool for inserting the rate laws into SBML models is freely available at www.semanticsbml.org. Supplementary data are available at Bioinformatics online.

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)

Thermodynamics of RNA structures by Wang–Landau sampling

PubMed Central

Lou, Feng; Clote, Peter

2010-01-01

Motivation: Thermodynamics-based dynamic programming RNA secondary structure algorithms have been of immense importance in molecular biology, where applications range from the detection of novel selenoproteins using expressed sequence tag (EST) data, to the determination of microRNA genes and their targets. Dynamic programming algorithms have been developed to compute the minimum free energy secondary structure and partition function of a given RNA sequence, the minimum free-energy and partition function for the hybridization of two RNA molecules, etc. However, the applicability of dynamic programming methods depends on disallowing certain types of interactions (pseudoknots, zig-zags, etc.), as their inclusion renders structure prediction an nondeterministic polynomial time (NP)-complete problem. Nevertheless, such interactions have been observed in X-ray structures. Results: A non-Boltzmannian Monte Carlo algorithm was designed by Wang and Landau to estimate the density of states for complex systems, such as the Ising model, that exhibit a phase transition. In this article, we apply the Wang-Landau (WL) method to compute the density of states for secondary structures of a given RNA sequence, and for hybridizations of two RNA sequences. Our method is shown to be much faster than existent software, such as RNAsubopt. From density of states, we compute the partition function over all secondary structures and over all pseudoknot-free hybridizations. The advantage of the WL method is that by adding a function to evaluate the free energy of arbitary pseudoknotted structures and of arbitrary hybridizations, we can estimate thermodynamic parameters for situations known to be NP-complete. This extension to pseudoknots will be made in the sequel to this article; in contrast, the current article describes the WL algorithm applied to pseudoknot-free secondary structures and hybridizations. Availability: The WL RNA hybridization web server is under construction at http://bioinformatics.bc.edu/clotelab/. Contact: clote@bc.edu PMID:20529917

Prediction of heat capacity of amine solutions using artificial neural network and thermodynamic models for CO2 capture processes

NASA Astrophysics Data System (ADS)

Afkhamipour, Morteza; Mofarahi, Masoud; Borhani, Tohid Nejad Ghaffar; Zanganeh, Masoud

2018-03-01

In this study, artificial neural network (ANN) and thermodynamic models were developed for prediction of the heat capacity ( C P ) of amine-based solvents. For ANN model, independent variables such as concentration, temperature, molecular weight and CO2 loading of amine were selected as the inputs of the model. The significance of the input variables of the ANN model on the C P values was investigated statistically by analyzing of correlation matrix. A thermodynamic model based on the Redlich-Kister equation was used to correlate the excess molar heat capacity ({C}_P^E) data as function of temperature. In addition, the effects of temperature and CO2 loading at different concentrations of conventional amines on the C P values were investigated. Both models were validated against experimental data and very good results were obtained between two mentioned models and experimental data of C P collected from various literatures. The AARD between ANN model results and experimental data of C P for 47 systems of amine-based solvents studied was 4.3%. For conventional amines, the AARD for ANN model and thermodynamic model in comparison with experimental data were 0.59% and 0.57%, respectively. The results showed that both ANN and Redlich-Kister models can be used as a practical tool for simulation and designing of CO2 removal processes by using amine solutions.

Thermodynamic Model of Aluminum Combustion in SDF Explosions

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

Kuhl, . L

2006-06-19

Thermodynamic states encountered during combustion of Aluminum powder in Shock-Dispersed-Fuel (SDF) explosions were analyzed with the Cheetah code. Results are displayed in the Le Chatelier diagram: the locus of states of specific internal energy versus temperature. Accuracy of the results was confirmed by comparing the fuel and products curves with the heats of detonation and combustion, and species composition as measured in bomb calorimeter experiments. Results were fit with analytic functions u = f(T) suitable for specifying the thermodynamic properties required for gas-dynamic models of combustion in explosions.

Progress of Stirling cycle analysis and loss mechanism characterization

NASA Technical Reports Server (NTRS)

Tew, R. C., Jr.

1986-01-01

An assessment of Stirling engine thermodynamic modeling and design codes shows a general deficiency; this deficiency is due to poor understanding of the fluid flow and heat transfer phenomena that occur in the oscillating flow and pressure level environment within the engines. Stirling engine thermodynamic loss mechanisms are listed. Several experimental and computational research efforts now underway to characterize various loss mechanisms are reviewed. The need for additional experimental rigs and rig upgrades is discussed. Recent developments and current efforts in Stirling engine thermodynamic modeling are also reviewed.

Thermodynamic Model of Afterburning in Explosions

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

Kuhl, A L; Howard, M; Fried, L

2003-04-23

Thermodynamic states encountered during afterburning of explosion products gases in air were analyzed with the Cheetah code. Results are displayed in the form of Le Chatelier diagrams: the locus of states of specific internal energy versus temperature, for six different condensed explosives charges. Accuracy of the results was confirmed by comparing the fuel and products curves with the heats of detonation and combustion, and species composition as measured in bomb calorimeter experiments. Results were fit with analytic functions u = f ( T ) suitable for specifying the thermodynamic properties required for gas-dynamic models of afterburning in explosions.

Kinetics versus thermodynamics in materials modeling: The case of the di-vacancy in iron

NASA Astrophysics Data System (ADS)

Djurabekova, F.; Malerba, L.; Pasianot, R. C.; Olsson, P.; Nordlund, K.

2010-07-01

Monte Carlo models are widely used for the study of microstructural and microchemical evolution of materials under irradiation. However, they often link explicitly the relevant activation energies to the energy difference between local equilibrium states. We provide a simple example (di-vacancy migration in iron) in which a rigorous activation energy calculation, by means of both empirical interatomic potentials and density functional theory methods, clearly shows that such a link is not granted, revealing a migration mechanism that a thermodynamics-linked activation energy model cannot predict. Such a mechanism is, however, fully consistent with thermodynamics. This example emphasizes the importance of basing Monte Carlo methods on models where the activation energies are rigorously calculated, rather than deduced from widespread heuristic equations.

Deformability of adsorbents during adsorption and principles of the thermodynamics of solid-phase systems

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2017-09-01

A microscopic theory of adsorption, based on a discrete continuum lattice gas model for noninert (including deformable) adsorbents that change their lattice parameters during adsorption, is presented. Cases of the complete and partial equilibrium states of the adsorbent are considered. In the former, the adsorbent consists of coexisting solid and vapor phases of adsorbent components, and the adsorbate is a mobile component of the vapor phase with an arbitrary density (up to that of the liquid adsorbate phase). The adsorptive transitioning to the bound state changes the state of the near-surface region of the adsorbent. In the latter, there are no equilibrium components of the adsorbent between the solid and vapor phases. The adsorbent state is shown to be determined by its prehistory, rather than set by chemical potentials of vapor of its components. Relations between the microscopic theory and thermodynamic interpretations are discussed: (1) adsorption on an open surface, (2) two-dimensional stratification of the adsorbate mobile phase on an open homogeneous surface, (3) small microcrystals in vacuum and the gas phase, and (4) adsorption in porous systems.

Thermodynamic model of Ak-Tuz deposit surface water formation

NASA Astrophysics Data System (ADS)

Alekhina, V. M.; Tokaver, I. V.; Ryzhenko, B. N.; Cherkasova, E. V.

2016-03-01

In Ak-Tuz deposit surface water macro and micro components concentrations are measured. Thermodynamic model is developed for aqueous composition prognosis at variation of water exchange. The concentration of n×10-8 mg Th / kg H2O and more testifies about Th containing colloid species in aqueous solution.

A phenomenological continuum model for force-driven nano-channel liquid flows

NASA Astrophysics Data System (ADS)

Ghorbanian, Jafar; Celebi, Alper T.; Beskok, Ali

2016-11-01

A phenomenological continuum model is developed using systematic molecular dynamics (MD) simulations of force-driven liquid argon flows confined in gold nano-channels at a fixed thermodynamic state. Well known density layering near the walls leads to the definition of an effective channel height and a density deficit parameter. While the former defines the slip-plane, the latter parameter relates channel averaged density with the desired thermodynamic state value. Definitions of these new parameters require a single MD simulation performed for a specific liquid-solid pair at the desired thermodynamic state and used for calibration of model parameters. Combined with our observations of constant slip-length and kinematic viscosity, the model accurately predicts the velocity distribution and volumetric and mass flow rates for force-driven liquid flows in different height nano-channels. Model is verified for liquid argon flow at distinct thermodynamic states and using various argon-gold interaction strengths. Further verification is performed for water flow in silica and gold nano-channels, exhibiting slip lengths of 1.2 nm and 15.5 nm, respectively. Excellent agreements between the model and the MD simulations are reported for channel heights as small as 3 nm for various liquid-solid pairs.

Perspectives on continuum flow models for force-driven nano-channel liquid flows

NASA Astrophysics Data System (ADS)

Beskok, Ali; Ghorbanian, Jafar; Celebi, Alper

2017-11-01

A phenomenological continuum model is developed using systematic molecular dynamics (MD) simulations of force-driven liquid argon flows confined in gold nano-channels at a fixed thermodynamic state. Well known density layering near the walls leads to the definition of an effective channel height and a density deficit parameter. While the former defines the slip-plane, the latter parameter relates channel averaged density with the desired thermodynamic state value. Definitions of these new parameters require a single MD simulation performed for a specific liquid-solid pair at the desired thermodynamic state and used for calibration of model parameters. Combined with our observations of constant slip-length and kinematic viscosity, the model accurately predicts the velocity distribution and volumetric and mass flow rates for force-driven liquid flows in different height nano-channels. Model is verified for liquid argon flow at distinct thermodynamic states and using various argon-gold interaction strengths. Further verification is performed for water flow in silica and gold nano-channels, exhibiting slip lengths of 1.2 nm and 15.5 nm, respectively. Excellent agreements between the model and the MD simulations are reported for channel heights as small as 3 nm for various liquid-solid pairs.

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.

Mathematical model of an air-filled alpha stirling refrigerator

NASA Astrophysics Data System (ADS)

McFarlane, Patrick; Semperlotti, Fabio; Sen, Mihir

2013-10-01

This work develops a mathematical model for an alpha Stirling refrigerator with air as the working fluid and will be useful in optimizing the mechanical design of these machines. Two pistons cyclically compress and expand air while moving sinusoidally in separate chambers connected by a regenerator, thus creating a temperature difference across the system. A complete non-linear mathematical model of the machine, including air thermodynamics, and heat transfer from the walls, as well as heat transfer and fluid resistance in the regenerator, is developed. Non-dimensional groups are derived, and the mathematical model is numerically solved. The heat transfer and work are found for both chambers, and the coefficient of performance of each chamber is calculated. Important design parameters are varied and their effect on refrigerator performance determined. This sensitivity analysis, which shows what the significant parameters are, is a useful tool for the design of practical Stirling refrigeration systems.

Evaluation of innovative rocket engines for single-stage earth-to-orbit vehicles

NASA Astrophysics Data System (ADS)

Manski, Detlef; Martin, James A.

1988-07-01

Computer models of rocket engines and single-stage-to-orbit vehicles that were developed by the authors at DFVLR and NASA have been combined. The resulting code consists of engine mass, performance, trajectory and vehicle sizing models. The engine mass model includes equations for each subsystem and describes their dependences on various propulsion parameters. The engine performance model consists of multidimensional sets of theoretical propulsion properties and a complete thermodynamic analysis of the engine cycle. The vehicle analyses include an optimized trajectory analysis, mass estimation, and vehicle sizing. A vertical-takeoff, horizontal-landing, single-stage, winged, manned, fully reusable vehicle with a payload capability of 13.6 Mg (30,000 lb) to low earth orbit was selected. Hydrogen, methane, propane, and dual-fuel engines were studied with staged-combustion, gas-generator, dual bell, and the dual-expander cycles. Mixture ratio, chamber pressure, nozzle exit pressure liftoff acceleration, and dual fuel propulsive parameters were optimized.

Evaluation of innovative rocket engines for single-stage earth-to-orbit vehicles

NASA Technical Reports Server (NTRS)

Manski, Detlef; Martin, James A.

1988-01-01

Computer models of rocket engines and single-stage-to-orbit vehicles that were developed by the authors at DFVLR and NASA have been combined. The resulting code consists of engine mass, performance, trajectory and vehicle sizing models. The engine mass model includes equations for each subsystem and describes their dependences on various propulsion parameters. The engine performance model consists of multidimensional sets of theoretical propulsion properties and a complete thermodynamic analysis of the engine cycle. The vehicle analyses include an optimized trajectory analysis, mass estimation, and vehicle sizing. A vertical-takeoff, horizontal-landing, single-stage, winged, manned, fully reusable vehicle with a payload capability of 13.6 Mg (30,000 lb) to low earth orbit was selected. Hydrogen, methane, propane, and dual-fuel engines were studied with staged-combustion, gas-generator, dual bell, and the dual-expander cycles. Mixture ratio, chamber pressure, nozzle exit pressure liftoff acceleration, and dual fuel propulsive parameters were optimized.

Comparison of Boltzmann and Gibbs entropies for the analysis of single-chain phase transitions

NASA Astrophysics Data System (ADS)

Shakirov, T.; Zablotskiy, S.; Böker, A.; Ivanov, V.; Paul, W.

2017-03-01

In the last 10 years, flat histogram Monte Carlo simulations have contributed strongly to our understanding of the phase behavior of simple generic models of polymers. These simulations result in an estimate for the density of states of a model system. To connect this result with thermodynamics, one has to relate the density of states to the microcanonical entropy. In a series of publications, Dunkel, Hilbert and Hänggi argued that it would lead to a more consistent thermodynamic description of small systems, when one uses the Gibbs definition of entropy instead of the Boltzmann one. The latter is the logarithm of the density of states at a certain energy, the former is the logarithm of the integral of the density of states over all energies smaller than or equal to this energy. We will compare the predictions using these two definitions for two polymer models, a coarse-grained model of a flexible-semiflexible multiblock copolymer and a coarse-grained model of the protein poly-alanine. Additionally, it is important to note that while Monte Carlo techniques are normally concerned with the configurational energy only, the microcanonical ensemble is defined for the complete energy. We will show how taking the kinetic energy into account alters the predictions from the analysis. Finally, the microcanonical ensemble is supposed to represent a closed mechanical N-particle system. But due to Galilei invariance such a system has two additional conservation laws, in general: momentum and angular momentum. We will also show, how taking these conservation laws into account alters the results.

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

Protein folding thermodynamics applied to the photocycle of the photoactive yellow protein.

PubMed Central

Van Brederode, M E; Hoff, W D; Van Stokkum, I H; Groot, M L; Hellingwerf, K J

1996-01-01

Two complementary aspects of the thermodynamics of the photoactive yellow protein (PYP), a new type of photoreceptor that has been isolated from Ectothiorhodospira halophila, have been investigated. First, the thermal denaturation of PYP at pH 3.4 has been examined by global analysis of the temperature-induced changes in the UV-VIS absorbance spectrum of this chromophoric protein. Subsequently, a thermodynamic model for protein (un)folding processes, incorporating heat capacity changes, has been applied to these data. The second aspect of PYP that has been studied is the temperature dependence of its photocycle kinetics, which have been reported to display an unexplained deviation from normal Arrhenius behavior. We have extended these measurements in two solvents with different hydrophobicities and have analyzed the number of rate constants needed to describe these data. Here we show that the resulting temperature dependence of the rate constants can be quantitatively explained by the application of a thermodynamic model which assumes that heat capacity changes are associated with the two transitions in the photocycle of PYP. This result is the first example of an enzyme catalytic cycle being described by a thermodynamic model including heat capacity changes. It is proposed that a strong link exists between the processes occurring during the photocycle of PYP and protein (un)folding processes. This permits a thermodynamic analysis of the light-induced, physiologically relevant, conformational changes occurring in this photoreceptor protein. PMID:8804619

An efficient and general approach for implementing thermodynamic phase equilibria information in geophysical and geodynamic studies

NASA Astrophysics Data System (ADS)

Afonso, Juan Carlos; Zlotnik, Sergio; Díez, Pedro

2015-10-01

We present a flexible, general, and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on Tensor Rank Decomposition methods, which transform the original multidimensional discrete information into a separated representation that contains significantly fewer terms, thus drastically reducing the amount of information to be stored in memory during a numerical simulation or geophysical inversion. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore, it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g., preliminary runs versus full resolution runs). We illustrate the benefits, generality, and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies. MATLAB implementations of the method and examples are provided as supporting information and can be downloaded from the journal's website.

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.

The third law of thermodynamics and the fractional entropies

NASA Astrophysics Data System (ADS)

Baris Bagci, G.

2016-08-01

We consider the fractal calculus based Ubriaco and Machado entropies and investigate whether they conform to the third law of thermodynamics. The Ubriaco entropy satisfies the third law of thermodynamics in the interval 0 < q ≤ 1 exactly where it is also thermodynamically stable. The Machado entropy, on the other hand, yields diverging inverse temperature in the region 0 < q ≤ 1, albeit with non-vanishing negative entropy values. Therefore, despite the divergent inverse temperature behavior, the Machado entropy fails the third law of thermodynamics. We also show that the aforementioned results are also supported by the one-dimensional Ising model with no external field.

Generalized Stefan-Boltzmann Law

NASA Astrophysics Data System (ADS)

Montambaux, Gilles

2018-03-01

We reconsider the thermodynamic derivation by L. Boltzmann of the Stefan law and we generalize it for various different physical systems whose chemical potential vanishes. Being only based on classical arguments, therefore independent of the quantum statistics, this derivation applies as well to the saturated Bose gas in various geometries as to "compensated" Fermi gas near a neutrality point, such as a gas of Weyl Fermions. It unifies in the same framework the thermodynamics of many different bosonic or fermionic non-interacting gases which were until now described in completely different contexts.

Let's Catch a (Heat) Wave

NASA Astrophysics Data System (ADS)

Herman, Rhett; Ballowe, Abigail; Ashley, Joe

2017-11-01

Two students in a recent thermodynamics/statistical mechanics course needed to complete a course-related project to receive honors credit for the class. Such courses are typically theoretical, without an accompanying laboratory, although there are existing related hands-on exercises. The choice of the project was influenced by one student's desire to become a mechanical engineer after graduating while the other wanted a project that was "fun" without "just doing more calculations." The choice of this particular project was further refined by the future engineer's interest in the thermodynamics of car engines.

Non-LTE line-blanketed model atmospheres of hot stars. 1: Hybrid complete linearization/accelerated lambda iteration method

NASA Technical Reports Server (NTRS)

Hubeny, I.; Lanz, T.

1995-01-01

A new munerical method for computing non-Local Thermodynamic Equilibrium (non-LTE) model stellar atmospheres is presented. The method, called the hybird complete linearization/accelerated lambda iretation (CL/ALI) method, combines advantages of both its constituents. Its rate of convergence is virtually as high as for the standard CL method, while the computer time per iteration is almost as low as for the standard ALI method. The method is formulated as the standard complete lineariation, the only difference being that the radiation intensity at selected frequency points is not explicity linearized; instead, it is treated by means of the ALI approach. The scheme offers a wide spectrum of options, ranging from the full CL to the full ALI method. We deonstrate that the method works optimally if the majority of frequency points are treated in the ALI mode, while the radiation intensity at a few (typically two to 30) frequency points is explicity linearized. We show how this method can be applied to calculate metal line-blanketed non-LTE model atmospheres, by using the idea of 'superlevels' and 'superlines' introduced originally by Anderson (1989). We calculate several illustrative models taking into accont several tens of thosands of lines of Fe III to Fe IV and show that the hybrid CL/ALI method provides a robust method for calculating non-LTE line-blanketed model atmospheres for a wide range of stellar parameters. The results for individual stellar types will be presented in subsequent papers in this series.

Rapid determination of thermodynamic parameters from one-dimensional programmed-temperature gas chromatography for use in retention time prediction in comprehensive multidimensional chromatography.

PubMed

McGinitie, Teague M; Ebrahimi-Najafabadi, Heshmatollah; Harynuk, James J

2014-01-17

A new method for estimating the thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for use in thermodynamic modeling of GC×GC separations has been developed. The method is an alternative to the traditional isothermal separations required to fit a three-parameter thermodynamic model to retention data. Herein, a non-linear optimization technique is used to estimate the parameters from a series of temperature-programmed separations using the Nelder-Mead simplex algorithm. With this method, the time required to obtain estimates of thermodynamic parameters a series of analytes is significantly reduced. This new method allows for precise predictions of retention time with the average error being only 0.2s for 1D separations. Predictions for GC×GC separations were also in agreement with experimental measurements; having an average relative error of 0.37% for (1)tr and 2.1% for (2)tr. Copyright © 2013 Elsevier B.V. All rights reserved.

High-Throughput Thermodynamic Modeling and Uncertainty Quantification for ICME

NASA Astrophysics Data System (ADS)

Otis, Richard A.; Liu, Zi-Kui

2017-05-01

One foundational component of the integrated computational materials engineering (ICME) and Materials Genome Initiative is the computational thermodynamics based on the calculation of phase diagrams (CALPHAD) method. The CALPHAD method pioneered by Kaufman has enabled the development of thermodynamic, atomic mobility, and molar volume databases of individual phases in the full space of temperature, composition, and sometimes pressure for technologically important multicomponent engineering materials, along with sophisticated computational tools for using the databases. In this article, our recent efforts will be presented in terms of developing new computational tools for high-throughput modeling and uncertainty quantification based on high-throughput, first-principles calculations and the CALPHAD method along with their potential propagations to downstream ICME modeling and simulations.

Thermodynamic and kinetic anisotropies in octane thin films.

PubMed

Haji-Akbari, Amir; Debenedetti, Pablo G

2015-12-07

Confinement breaks the translational symmetry of materials, making all thermodynamic and kinetic quantities functions of position. Such symmetry breaking can be used to obtain configurations that are not otherwise accessible in the bulk. Here, we use computer simulations to explore the effect of substrate-liquid interactions on thermodynamic and kinetic anisotropies induced by a solid substrate. We consider n-octane nano-films that are in contact with substrates with varying degrees of attraction, parameterized by an interaction parameter ϵS. Complete freezing of octane nano-films is observed at low temperatures, irrespective of ϵS, while at intermediate temperatures, a frozen monolayer emerges at solid-liquid and vapor-liquid interfaces. By carefully inspecting the profiles of translational and orientational relaxation times, we confirm that the translational and orientational degrees of freedom are decoupled at these frozen monolayers. At sufficiently high temperatures, however, free interfaces and solid-liquid interfaces close to loose (low-ϵS) substrates undergo "pre-freezing," characterized by mild peaks in several thermodynamic quantities. Two distinct dynamic regimes are observed at solid-liquid interfaces. The dynamics is accelerated in the vicinity of loose substrates, while sticky (high-ϵS) substrates decelerate dynamics, sometimes by as much as two orders of magnitude. These two distinct dynamical regimes have been previously reported by Haji-Akbari and Debenedetti [J. Chem. Phys. 141, 024506 (2014)] for a model atomic glass-forming liquid. We also confirm the existence of two correlations-proposed in the above-mentioned work-in solid-liquid subsurface regions of octane thin films, i.e., a correlation between atomic density and normal stress, and between atomic translational relaxation time and lateral stress. Finally, we inspect the ability of different regions of an octane film to explore the potential energy landscape by performing inherent structure calculations, and observe no noticeable difference between the free surface and the bulk in efficiently exploring the potential energy landscape. This is unlike the films of model atomic glass formers that tend to sample their respective landscape more efficiently at free surfaces. We discuss the implications of this finding to the ability of octane-and other n-alkanes-to form ultrastable glasses.

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.

Gradient and size effects on spinodal and miscibility gaps

NASA Astrophysics Data System (ADS)

Tsagrakis, Ioannis; Aifantis, Elias C.

2018-05-01

A thermodynamically consistent model of strain gradient elastodiffusion is developed. Its formulation is based on the enhancement of a robust theory of gradient elasticity, known as GRADELA, to account for a Cahn-Hilliard type of diffusion. Linear stability analysis is employed to determine the influence of concentration and strain gradients on the spinodal decomposition. For finite domains, spherically symmetric conditions are considered, and size effects on spinodal and miscibility gaps are discussed. The theoretical predictions are in agreement with the experimental trends, i.e., both gaps shrink as the grain diameter decreases and they are completely eliminated for crystals smaller than a critical size.

Water and hydrogen are immiscible in Earth's mantle.

PubMed

Bali, Enikő; Audétat, Andreas; Keppler, Hans

2013-03-14

In the deep, chemically reducing parts of Earth's mantle, hydrous fluids contain significant amounts of molecular hydrogen (H2). Thermodynamic models of fluids in Earth's mantle so far have always assumed that molecular hydrogen and water are completely miscible. Here we show experimental evidence that water and hydrogen can coexist as two separate, immiscible phases. Immiscibility between water and hydrogen may be the cause of the formation of enigmatic, ultra-reducing domains in the mantle that contain moissanite (SiC) and other phases indicative of extremely reducing conditions. Moreover, the immiscibility between water and hydrogen may provide a mechanism for the rapid oxidation of Earth's upper mantle immediately following core formation.

Thermodynamics of information processing based on enzyme kinetics: An exactly solvable model of an information pump.

PubMed

Cao, Yuansheng; Gong, Zongping; Quan, H T

2015-06-01

Motivated by the recent proposed models of the information engine [Proc. Natl. Acad. Sci. USA 109, 11641 (2012)] and the information refrigerator [Phys. Rev. Lett. 111, 030602 (2013)], we propose a minimal model of the information pump and the information eraser based on enzyme kinetics. This device can either pump molecules against the chemical potential gradient by consuming the information to be encoded in the bit stream or (partially) erase the information initially encoded in the bit stream by consuming the Gibbs free energy. The dynamics of this model is solved exactly, and the "phase diagram" of the operation regimes is determined. The efficiency and the power of the information machine is analyzed. The validity of the second law of thermodynamics within our model is clarified. Our model offers a simple paradigm for the investigating of the thermodynamics of information processing involving the chemical potential in small systems.

XSEOS: An Open Software for Chemical Engineering Thermodynamics

ERIC Educational Resources Information Center

Castier, Marcelo

2008-01-01

An Excel add-in--XSEOS--that implements several excess Gibbs free energy models and equations of state has been developed for educational use. Several traditional and modern thermodynamic models are available in the package with a user-friendly interface. XSEOS has open code, is freely available, and should be useful for instructors and students…

First-principles calculations, experimental study, and thermodynamic modeling of the Al-Co-Cr system.

PubMed

Liu, Xuan L; Gheno, Thomas; Lindahl, Bonnie B; Lindwall, Greta; Gleeson, Brian; Liu, Zi-Kui

2015-01-01

The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT) and phase-equilibria experiments that led to X-ray diffraction (XRD) and electron probe micro-analysis (EPMA) measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD) method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-γ, and tetragonal-σ phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-γ phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS) calculations predict a large bcc-A2 (disordered)/B2 (ordered) miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings.

New t-gap insertion-deletion-like metrics for DNA hybridization thermodynamic modeling.

PubMed

D'yachkov, Arkadii G; Macula, Anthony J; Pogozelski, Wendy K; Renz, Thomas E; Rykov, Vyacheslav V; Torney, David C

2006-05-01

We discuss the concept of t-gap block isomorphic subsequences and use it to describe new abstract string metrics that are similar to the Levenshtein insertion-deletion metric. Some of the metrics that we define can be used to model a thermodynamic distance function on single-stranded DNA sequences. Our model captures a key aspect of the nearest neighbor thermodynamic model for hybridized DNA duplexes. One version of our metric gives the maximum number of stacked pairs of hydrogen bonded nucleotide base pairs that can be present in any secondary structure in a hybridized DNA duplex without pseudoknots. Thermodynamic distance functions are important components in the construction of DNA codes, and DNA codes are important components in biomolecular computing, nanotechnology, and other biotechnical applications that employ DNA hybridization assays. We show how our new distances can be calculated by using a dynamic programming method, and we derive a Varshamov-Gilbert-like lower bound on the size of some of codes using these distance functions as constraints. We also discuss software implementation of our DNA code design methods.

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.

Thermodynamics of viscoelastic rate-type fluids with stress diffusion

NASA Astrophysics Data System (ADS)

Málek, Josef; Průša, Vít; Skřivan, Tomáš; Süli, Endre

2018-02-01

We propose thermodynamically consistent models for viscoelastic fluids with a stress diffusion term. In particular, we derive variants of compressible/incompressible Maxwell/Oldroyd-B models with a stress diffusion term in the evolution equation for the extra stress tensor. It is shown that the stress diffusion term can be interpreted either as a consequence of a nonlocal energy storage mechanism or as a consequence of a nonlocal entropy production mechanism, while different interpretations of the stress diffusion mechanism lead to different evolution equations for the temperature. The benefits of the knowledge of the thermodynamical background of the derived models are documented in the study of nonlinear stability of equilibrium rest states. The derived models open up the possibility to study fully coupled thermomechanical problems involving viscoelastic rate-type fluids with stress diffusion.

Simultaneous calibration of end-member thermodynamic data and solution properties with correlated uncertainties

NASA Astrophysics Data System (ADS)

Antoshechkina, P. M.; Wolf, A. S.; Hamecher, E. A.; Asimow, P. D.; Ghiorso, M. S.

2013-12-01

Community databases such as EarthChem, LEPR, and AMCSD both increase demand for quantitative petrological tools, including thermodynamic models like the MELTS family of algorithms, and are invaluable in development of such tools. The need to extend existing solid solution models to include minor components such as Cr and Na has been evident for years but as the number of components increases it becomes impossible to completely separate derivation of end-member thermodynamic data from calibration of solution properties. In Hamecher et al. (2012; 2013) we developed a calibration scheme that directly interfaces with a MySQL database based on LEPR, with volume data from AMCSD and elsewhere. Here we combine that scheme with a Bayesian approach, where independent constraints on parameter values (e.g. existence of miscibility gaps) are combined with uncertainty propagation to give a more reliable best-fit along with associated model uncertainties. We illustrate the scheme with a new model of molar volume for (Ca,Fe,Mg,Mn,Na)3(Al,Cr,Fe3+,Fe2+,Mg,Mn,Si,Ti)2Si3O12 cubic garnets. For a garnet in this chemical system, the model molar volume is obtained by adding excess volume terms to a linear combination of nine independent end-member volumes. The model calibration is broken into three main stages: (1) estimation of individual end-member thermodynamic properties; (2) calibration of standard state volumes for all available independent and dependent end members; (3) fitting of binary and mixed composition data. For each calibration step, the goodness-of-fit includes weighted residuals as well as χ2-like penalty terms representing the (not necessarily Gaussian) prior constraints on parameter values. Using the Bayesian approach, uncertainties are correctly propagated forward to subsequent steps, allowing determination of final parameter values and correlated uncertainties that account for the entire calibration process. For the aluminosilicate garnets, optimal values of the bulk modulus and its pressure derivative are obtained by fitting published compression data using the Vinet equation of state, with the Mie-Grüneisen-Debye thermal pressure formalism to model thermal expansion. End-member thermal parameters are obtained by fitting volume data while ensuring that the heat capacity is consistent with the thermodynamic database of Berman and co-workers. For other end members, data for related compositions are used where such data exist; otherwise ultrasonic data or density functional theory results are taken or, for thermal parameters, systematics in cation radii are used. In stages (2) and (3) the remaining data at ambient conditions are fit. Using this step-wise calibration scheme, most parameters are modified little by subsequent calibration steps but some, such as the standard state volume of the Ti-bearing end member, can vary within calculated uncertainties. The final model satisfies desired criteria and fits almost all the data (more than 1000 points); only excess parameters that are justified by the data are activated. The scheme can be easily extended to calibration of end-member and solution properties from experimental phase equilibria. As a first step we obtain the internally consistent standard state entropy and enthalpy of formation for knorringite and discuss differences between our results and those of Klemme and co-workers.

Theoretical analysis of Lumry-Eyring models in differential scanning calorimetry

PubMed Central

Sanchez-Ruiz, Jose M.

1992-01-01

A theoretical analysis of several protein denaturation models (Lumry-Eyring models) that include a rate-limited step leading to an irreversibly denatured state of the protein (the final state) has been carried out. The differential scanning calorimetry transitions predicted for these models can be broadly classified into four groups: situations A, B, C, and C′. (A) The transition is calorimetrically irreversible but the rate-limited, irreversible step takes place with significant rate only at temperatures slightly above those corresponding to the transition. Equilibrium thermodynamics analysis is permissible. (B) The transition is distorted by the occurrence of the rate-limited step; nevertheless, it contains thermodynamic information about the reversible unfolding of the protein, which could be obtained upon the appropriate data treatment. (C) The heat absorption is entirely determined by the kinetics of formation of the final state and no thermodynamic information can be extracted from the calorimetric transition; the rate-determining step is the irreversible process itself. (C′) same as C, but, in this case, the rate-determining step is a previous step in the unfolding pathway. It is shown that ligand and protein concentration effects on transitions corresponding to situation C (strongly rate-limited transitions) are similar to those predicted by equilibrium thermodynamics for simple reversible unfolding models. It has been widely held in recent literature that experimentally observed ligand and protein concentration effects support the applicability of equilibrium thermodynamics to irreversible protein denaturation. The theoretical analysis reported here disfavors this claim. PMID:19431826

Network Thermodynamic Curation of Human and Yeast Genome-Scale Metabolic Models

PubMed Central

Martínez, Verónica S.; Quek, Lake-Ee; Nielsen, Lars K.

2014-01-01

Genome-scale models are used for an ever-widening range of applications. Although there has been much focus on specifying the stoichiometric matrix, the predictive power of genome-scale models equally depends on reaction directions. Two-thirds of reactions in the two eukaryotic reconstructions Homo sapiens Recon 1 and Yeast 5 are specified as irreversible. However, these specifications are mainly based on biochemical textbooks or on their similarity to other organisms and are rarely underpinned by detailed thermodynamic analysis. In this study, a to our knowledge new workflow combining network-embedded thermodynamic and flux variability analysis was used to evaluate existing irreversibility constraints in Recon 1 and Yeast 5 and to identify new ones. A total of 27 and 16 new irreversible reactions were identified in Recon 1 and Yeast 5, respectively, whereas only four reactions were found with directions incorrectly specified against thermodynamics (three in Yeast 5 and one in Recon 1). The workflow further identified for both models several isolated internal loops that require further curation. The framework also highlighted the need for substrate channeling (in human) and ATP hydrolysis (in yeast) for the essential reaction catalyzed by phosphoribosylaminoimidazole carboxylase in purine metabolism. Finally, the framework highlighted differences in proline metabolism between yeast (cytosolic anabolism and mitochondrial catabolism) and humans (exclusively mitochondrial metabolism). We conclude that network-embedded thermodynamics facilitates the specification and validation of irreversibility constraints in compartmentalized metabolic models, at the same time providing further insight into network properties. PMID:25028891

A fast multipole method combined with a reaction field for long-range electrostatics in molecular dynamics simulations: The effects of truncation on the properties of water

NASA Astrophysics Data System (ADS)

Mathias, Gerald; Egwolf, Bernhard; Nonella, Marco; Tavan, Paul

2003-06-01

We present a combination of the structure adapted multipole method with a reaction field (RF) correction for the efficient evaluation of electrostatic interactions in molecular dynamics simulations under periodic boundary conditions. The algorithm switches from an explicit electrostatics evaluation to a continuum description at the maximal distance that is consistent with the minimum image convention, and, thus, avoids the use of a periodic electrostatic potential. A physically motivated switching function enables charge clusters interacting with a given charge to smoothly move into the solvent continuum by passing through the spherical dielectric boundary surrounding this charge. This transition is complete as soon as the cluster has reached the so-called truncation radius Rc. The algorithm is used to examine the dependence of thermodynamic properties and correlation functions on Rc in the three point transferable intermolecular potential water model. Our test simulations on pure liquid water used either the RF correction or a straight cutoff and values of Rc ranging from 14 Å to 40 Å. In the RF setting, the thermodynamic properties and the correlation functions show convergence for Rc increasing towards 40 Å. In the straight cutoff case no such convergence is found. Here, in particular, the dipole-dipole correlation functions become completely artificial. The RF description of the long-range electrostatics is verified by comparison with the results of a particle-mesh Ewald simulation at identical conditions.

Thermodynamic assessment and binary nucleation modeling of Sn-seeded InGaAs nanowires

NASA Astrophysics Data System (ADS)

Ghasemi, Masoomeh; Selleby, Malin; Johansson, Jonas

2017-11-01

We have performed a thermodynamic assessment of the As-Ga-In-Sn system based on the CALculation of PHAse Diagram (CALPHAD) method. This system is part of a comprehensive thermodynamic database that we are developing for nanowire materials. Specifically, the As-Ga-In-Sn can be used in modeling the growth of GaAs, InAs, and InxGa1-xAs nanowires assisted by Sn liquid seeds. In this work, the As-Sn binary, the As-Ga-Sn, As-In-Sn, and Ga-In-Sn ternary systems have been thermodynamically assessed using the CALPHAD method. We show the relevant phase diagrams and property diagrams. They all show good agreement with experimental data. Using our optimized description we have modeled the nucleation of InxGa1-xAs in the zinc blende phase from a Sn-based quaternary liquid alloy using binary nucleation modeling. We have linked the composition of the solid nucleus to the composition of the liquid phase. Eventually, we have predicted the critical size of the nucleus that forms from InAs and GaAs pairs under various conditions. We believe that our modeling can guide future experimental realization of Sn-seeded InxGa1-xAs nanowires.

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 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.

Thermodynamic Description of the Quaternary Ag-Bi-Cu-Sn System

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech

2018-01-01

Lead-free soldering is an important part of electronic devices production. New lead-free solders that replace classical Sn-37Pb solder are still under development. Thermodynamic modeling makes the development process faster, cheaper and more environmentally friendly due to predictions of phases stabilities and phases transformations. In this work, the thermodynamic description of quaternary Ag-Bi-Cu-Sn system is presented. The thermodynamic assessment of promising lead-free quaternary solder was prepared using the Calphad approach. A good agreement between available experimental data and calculation was found.

Data Science Innovations That Streamline Development, Documentation, Reproducibility, and Dissemination of Models in Computational Thermodynamics: An Application of Image Processing Techniques for Rapid Computation, Parameterization and Modeling of Phase Diagrams

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2014-12-01

Computational thermodynamics (CT) represents a collection of numerical techniques that are used to calculate quantitative results from thermodynamic theory. In the Earth sciences, CT is most often applied to estimate the equilibrium properties of solutions, to calculate phase equilibria from models of the thermodynamic properties of materials, and to approximate irreversible reaction pathways by modeling these as a series of local equilibrium steps. The thermodynamic models that underlie CT calculations relate the energy of a phase to temperature, pressure and composition. These relationships are not intuitive and they are seldom well constrained by experimental data; often, intuition must be applied to generate a robust model that satisfies the expectations of use. As a consequence of this situation, the models and databases the support CT applications in geochemistry and petrology are tedious to maintain as new data and observations arise. What is required to make the process more streamlined and responsive is a computational framework that permits the rapid generation of observable outcomes from the underlying data/model collections, and importantly, the ability to update and re-parameterize the constitutive models through direct manipulation of those outcomes. CT procedures that take models/data to the experiential reference frame of phase equilibria involve function minimization, gradient evaluation, the calculation of implicit lines, curves and surfaces, contour extraction, and other related geometrical measures. All these procedures are the mainstay of image processing analysis. Since the commercial escalation of video game technology, open source image processing libraries have emerged (e.g., VTK) that permit real time manipulation and analysis of images. These tools find immediate application to CT calculations of phase equilibria by permitting rapid calculation and real time feedback between model outcome and the underlying model parameters.

STATEQ: a nonlinear least-squares code for obtaining Martin thermodynamic representations of fluids in the gaseous and dense gaseous regions

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

Milora, S. L.

1976-02-01

The use of the code NLIN (IBM Share Program No. 1428) to obtain empirical thermodynamic pressure-volume-temperature (P-V-T) relationships for substances in the gaseous and dense gaseous states is described. When sufficient experimental data exist, the code STATEQ will provide least-squares estimates for the 21 parameters of the Martin model. Another code, APPROX, is described which also obtains parameter estimates for the model by making use of the approximate generalized behavior of fluids. Use of the codes is illustrated in obtaining thermodynamic representations for isobutane. (auth)

Thermodynamics of organisms in the context of dynamic energy budget theory.

PubMed

Sousa, Tânia; Mota, Rui; Domingos, Tiago; Kooijman, S A L M

2006-11-01

We carry out a thermodynamic analysis to an organism. It is applicable to any type of organism because (1) it is based on a thermodynamic formalism applicable to all open thermodynamic systems and (2) uses a general model to describe the internal structure of the organism--the dynamic energy budget (DEB) model. Our results on the thermodynamics of DEB organisms are the following. (1) Thermodynamic constraints for the following types of organisms: (a) aerobic and exothermic, (b) anaerobic and exothermic, and (c) anaerobic and endothermic; showing that anaerobic organisms have a higher thermodynamic flexibility. (2) A way to compute the changes in the enthalpy and in the entropy of living biomass that accompany changes in growth rate solving the problem of evaluating the thermodynamic properties of biomass as a function of the amount of reserves. (3) Two expressions for Thornton's coefficient that explain its experimental variability and theoretically underpin its use in metabolic studies. (4) A mechanism that organisms in non-steady-state use to rid themselves of internal entropy production: "dilution of entropy production by growth." To demonstrate the practical applicability of DEB theory to quantify thermodynamic changes in organisms we use published data on Klebsiella aerogenes growing aerobically in a continuous culture. We obtain different values for molar entropies of the reserve and the structure of Klebsiella aerogenes proving that the reserve density concept of DEB theory is essential in discussions concerning (a) the relationship between organization and entropy and (b) the mechanism of storing entropy in new biomass. Additionally, our results suggest that the entropy of dead biomass is significantly different from the entropy of living biomass.

Crystallization in melts of short, semiflexible hard polymer chains: An interplay of entropies and dimensions

NASA Astrophysics Data System (ADS)

Shakirov, T.; Paul, W.

2018-04-01

What is the thermodynamic driving force for the crystallization of melts of semiflexible polymers? We try to answer this question by employing stochastic approximation Monte Carlo simulations to obtain the complete thermodynamic equilibrium information for a melt of short, semiflexible polymer chains with purely repulsive nonbonded interactions. The thermodynamics is obtained based on the density of states of our coarse-grained model, which varies by up to 5600 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density. This crystallization can be understood by the interplay of the maximization of different entropy contributions in different spatial dimensions. At sufficient stiffness and density, the three-dimensional orientational interactions drive the orientational ordering transition, which is accompanied by a two-dimensional translational ordering transition in the plane perpendicular to the chains resulting in a hexagonal crystal structure. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition can be understood in terms of the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. Based on this physical understanding, orientational ordering and translational ordering should be separable for polymer melts. A phenomenological theory based on this understanding predicts a qualitative phase diagram as a function of volume fraction and stiffness in good agreement with results from the literature.

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.

Thermodynamic potential of free energy for thermo-elastic-plastic body

NASA Astrophysics Data System (ADS)

Śloderbach, Z.; Pająk, J.

2018-01-01

The procedure of derivation of thermodynamic potential of free energy (Helmholtz free energy) for a thermo-elastic-plastic body is presented. This procedure concerns a special thermodynamic model of a thermo-elastic-plastic body with isotropic hardening characteristics. The classical thermodynamics of irreversible processes for material characterized by macroscopic internal parameters is used in the derivation. Thermodynamic potential of free energy may be used for practical determination of the level of stored energy accumulated in material during plastic processing applied, e.g., for industry components and other machinery parts received by plastic deformation processing. In this paper the stored energy for the simple stretching of austenitic steel will be presented.

Thermodynamic Investigation of the Reduction-Distillation Process for Rare Earth Metals Production

NASA Astrophysics Data System (ADS)

Judge, W. D.; Azimi, G.

2017-10-01

Owing to their high vapor pressure, the four rare earth metals samarium, europium, thulium, and ytterbium are produced by reduction-distillation whereby their oxides are reduced with metallic lanthanum in vacuo, and the produced metal is subsequently vaporized off. Here, we performed a thorough thermodynamic investigation to establish a fundamental understanding of the reduction-distillation process. Thermodynamic functions including vapor pressures, Gibbs free energies, and enthalpies of reaction were calculated and compared with available experimental data. Furthermore, the kinetics of the process was explored and theoretical evaporation rates were calculated from thermodynamic data. The thermodynamic model developed in this work can help optimize processing conditions to maximize the yield and improve the overall process.

Stirling Laboratory Research Engine: Preprototype configuration report

NASA Technical Reports Server (NTRS)

Hoehn, F. W.

1982-01-01

The concept of a simple Stirling research engine that could be used by industrial, university, and government laboratories was studied. The conceptual and final designs, hardware fabrication and the experimental validation of a preprototype stirling laboratory research engine (SLRE) were completed. Also completed was a task to identify the potential markets for research engines of this type. An analytical effort was conducted to provide a stirling cycle computer model. The versatile engine is a horizontally opposed, two piston, single acting stirling engine with a split crankshaft drive mechanism; special instrumentation is installed at all component interfaces. Results of a thermodynamic energy balance for the system are reported. Also included are the engine performance results obtained over a range of speeds, working pressures, phase angles and gas temperatures. The potential for a stirling research engine to support the laboratory requirements of educators and researchers was demonstrated.

Thermodynamics of the adsorption of flexible polymers on nanowires

NASA Astrophysics Data System (ADS)

Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

2015-03-01

Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

Thermodynamics of the adsorption of flexible polymers on nanowires.

PubMed

Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

2015-03-14

Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

Using Model Helicopters for Meteorological Observations in Support of Tornado Forecasting

NASA Astrophysics Data System (ADS)

Harrison, William; Roscoe, Bryan; Schafer, David; Bluestein, Howard; Lary, David

2012-10-01

In order to gain a better understanding of the physical factors involved in tornadogenesis, a complete 3-D profile of winds, temperature, and humidity in the forward-flank and rear-flank gust front regions in supercells is required. Conventional methods of making comparative measurements in and around storms are very limited. Measurements that comprehensively profile the boundary layer winds and thermodynamics are valuable but rare. A better understanding of the physical properties in these boundary layers will improve forecasts and increase warning times in affected areas. Remote-controlled model helicopters are a uniquely qualified platform for this application, allowing us to fully profile these boundary layers. Our system will consist of a swarm of autonomous acrobatic helicopters, each outfitted with temperature, pressure, humidity, and wind speed sensors.

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.

Landau's statistical mechanics for quasi-particle models

NASA Astrophysics Data System (ADS)

Bannur, Vishnu M.

2014-04-01

Landau's formalism of statistical mechanics [following L. D. Landau and E. M. Lifshitz, Statistical Physics (Pergamon Press, Oxford, 1980)] is applied to the quasi-particle model of quark-gluon plasma. Here, one starts from the expression for pressure and develop all thermodynamics. It is a general formalism and consistent with our earlier studies [V. M. Bannur, Phys. Lett. B647, 271 (2007)] based on Pathria's formalism [following R. K. Pathria, Statistical Mechanics (Butterworth-Heinemann, Oxford, 1977)]. In Pathria's formalism, one starts from the expression for energy density and develop thermodynamics. Both the formalisms are consistent with thermodynamics and statistical mechanics. Under certain conditions, which are wrongly called thermodynamic consistent relation, we recover other formalism of quasi-particle system, like in M. I. Gorenstein and S. N. Yang, Phys. Rev. D52, 5206 (1995), widely studied in quark-gluon plasma.

Path Integral Computation of Quantum Free Energy Differences Due to Alchemical Transformations Involving Mass and Potential.

PubMed

Pérez, Alejandro; von Lilienfeld, O Anatole

2011-08-09

Thermodynamic integration, perturbation theory, and λ-dynamics methods were applied to path integral molecular dynamics calculations to investigate free energy differences due to "alchemical" transformations. Several estimators were formulated to compute free energy differences in solvable model systems undergoing changes in mass and/or potential. Linear and nonlinear alchemical interpolations were used for the thermodynamic integration. We find improved convergence for the virial estimators, as well as for the thermodynamic integration over nonlinear interpolation paths. Numerical results for the perturbative treatment of changes in mass and electric field strength in model systems are presented. We used thermodynamic integration in ab initio path integral molecular dynamics to compute the quantum free energy difference of the isotope transformation in the Zundel cation. The performance of different free energy methods is discussed.

Thermodynamic model of natural, medieval and nuclear waste glass durability

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

Jantzen, C.M.; Plodinec, M.J.

1983-01-01

A thermodynamic model of glass durability based on hydration of structural units has been applied to natural glass, medieval window glasses, and glasses containing nuclear waste. The relative durability predicted from the calculated thermodynamics correlates directly with the experimentally observed release of structural silicon in the leaching solution in short-term laboratory tests. By choosing natural glasses and ancient glasses whose long-term performance is known, and which bracket the durability of waste glasses, the long-term stability of nuclear waste glasses can be interpolated among these materials. The current Savannah River defense waste glass formulation is as durable as natural basalt frommore » the Hanford Reservation (10/sup 6/ years old). The thermodynamic hydration energy is shown to be related to the bond energetics of the glass. 69 references, 2 figures, 1 table.« less

A reduced basis approach for implementing thermodynamic phase-equilibria information in geophysical and geodynamic studies

NASA Astrophysics Data System (ADS)

Afonso, J. C.; Zlotnik, S.; Diez, P.

2015-12-01

We present a flexible, general and efficient approach for implementing thermodynamic phase equilibria information (in the form of sets of physical parameters) into geophysical and geodynamic studies. The approach is based on multi-dimensional decomposition methods, which transform the original multi-dimensional discrete information into a dimensional-separated representation. This representation has the property of increasing the number of coefficients to be stored linearly with the number of dimensions (opposite to a full multi-dimensional cube requiring exponential storage depending on the number of dimensions). Thus, the amount of information to be stored in memory during a numerical simulation or geophysical inversion is drastically reduced. Accordingly, the amount and resolution of the thermodynamic information that can be used in a simulation or inversion increases substantially. In addition, the method is independent of the actual software used to obtain the primary thermodynamic information, and therefore it can be used in conjunction with any thermodynamic modeling program and/or database. Also, the errors associated with the decomposition procedure are readily controlled by the user, depending on her/his actual needs (e.g. preliminary runs vs full resolution runs). We illustrate the benefits, generality and applicability of our approach with several examples of practical interest for both geodynamic modeling and geophysical inversion/modeling. Our results demonstrate that the proposed method is a competitive and attractive candidate for implementing thermodynamic constraints into a broad range of geophysical and geodynamic studies.

Unified framework to evaluate panmixia and migration direction among multiple sampling locations.

PubMed

Beerli, Peter; Palczewski, Michal

2010-05-01

For many biological investigations, groups of individuals are genetically sampled from several geographic locations. These sampling locations often do not reflect the genetic population structure. We describe a framework using marginal likelihoods to compare and order structured population models, such as testing whether the sampling locations belong to the same randomly mating population or comparing unidirectional and multidirectional gene flow models. In the context of inferences employing Markov chain Monte Carlo methods, the accuracy of the marginal likelihoods depends heavily on the approximation method used to calculate the marginal likelihood. Two methods, modified thermodynamic integration and a stabilized harmonic mean estimator, are compared. With finite Markov chain Monte Carlo run lengths, the harmonic mean estimator may not be consistent. Thermodynamic integration, in contrast, delivers considerably better estimates of the marginal likelihood. The choice of prior distributions does not influence the order and choice of the better models when the marginal likelihood is estimated using thermodynamic integration, whereas with the harmonic mean estimator the influence of the prior is pronounced and the order of the models changes. The approximation of marginal likelihood using thermodynamic integration in MIGRATE allows the evaluation of complex population genetic models, not only of whether sampling locations belong to a single panmictic population, but also of competing complex structured population models.

Thermodynamics of charged Lovelock: AdS black holes

NASA Astrophysics Data System (ADS)

Prasobh, C. B.; Suresh, Jishnu; Kuriakose, V. C.

2016-04-01

We investigate the thermodynamic behavior of maximally symmetric charged, asymptotically AdS black hole solutions of Lovelock gravity. We explore the thermodynamic stability of such solutions by the ordinary method of calculating the specific heat of the black holes and investigating its divergences which signal second-order phase transitions between black hole states. We then utilize the methods of thermodynamic geometry of black hole spacetimes in order to explain the origin of these points of divergence. We calculate the curvature scalar corresponding to a Legendre-invariant thermodynamic metric of these spacetimes and find that the divergences in the black hole specific heat correspond to singularities in the thermodynamic phase space. We also calculate the area spectrum for large black holes in the model by applying the Bohr-Sommerfeld quantization to the adiabatic invariant calculated for the spacetime.

A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model

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

González, Miguel A.; Department of Chemistry, Imperial College London, London SW7 2AZ; Valeriani, Chantal

2016-08-07

The striking behavior of water has deserved it to be referred to as an “anomalous” liquid. The water anomalies are greatly amplified in metastable (supercooled and/or stretched) regions. This makes difficult a complete experimental description since, beyond certain limits, the metastable phase necessarily transforms into the stable one. Theoretical interpretation of the water anomalies could then be based on simulation results of well validated water models. But the analysis of the simulations has not yet reached a consensus. In particular, one of the most popular theoretical scenarios—involving the existence of a liquid-liquid critical point (LLCP)—is disputed by several authors. Inmore » this work, we propose to use a number of exact thermodynamic relations which may shed light on this issue. Interestingly, these relations may be tested in a region of the phase diagram which is outside the LLCP thus avoiding the problems associated to the coexistence region. The central property connected to other water anomalies is the locus of temperatures at which the density along isobars attain a maximum (TMD line) or a minimum (TmD). We have performed computer simulations to evaluate the TMD and TmD for a successful water model, namely, TIP4P/2005. We have also evaluated the vapor-liquid (VL) spinodal in the region of large negative pressures. The shape of these curves and their connection to the extrema of some response functions, in particular the isothermal compressibility and heat capacity at constant pressure, provides very useful information which may help to elucidate the validity of the theoretical proposals. In this way, we are able to present for the first time a comprehensive scenario of the thermodynamic water anomalies for TIP4P/2005 and their relation to the vapor-liquid spinodal. The overall picture shows a remarkable similarity with the corresponding one for the ST2 water model, for which the existence of a LLCP has been demonstrated in recent years. It also provides a hint as to where the long-sought for extrema in response functions might become accessible to experiments.« less

A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model.

PubMed

González, Miguel A; Valeriani, Chantal; Caupin, Frédéric; Abascal, José L F

2016-08-07

The striking behavior of water has deserved it to be referred to as an "anomalous" liquid. The water anomalies are greatly amplified in metastable (supercooled and/or stretched) regions. This makes difficult a complete experimental description since, beyond certain limits, the metastable phase necessarily transforms into the stable one. Theoretical interpretation of the water anomalies could then be based on simulation results of well validated water models. But the analysis of the simulations has not yet reached a consensus. In particular, one of the most popular theoretical scenarios-involving the existence of a liquid-liquid critical point (LLCP)-is disputed by several authors. In this work, we propose to use a number of exact thermodynamic relations which may shed light on this issue. Interestingly, these relations may be tested in a region of the phase diagram which is outside the LLCP thus avoiding the problems associated to the coexistence region. The central property connected to other water anomalies is the locus of temperatures at which the density along isobars attain a maximum (TMD line) or a minimum (TmD). We have performed computer simulations to evaluate the TMD and TmD for a successful water model, namely, TIP4P/2005. We have also evaluated the vapor-liquid (VL) spinodal in the region of large negative pressures. The shape of these curves and their connection to the extrema of some response functions, in particular the isothermal compressibility and heat capacity at constant pressure, provides very useful information which may help to elucidate the validity of the theoretical proposals. In this way, we are able to present for the first time a comprehensive scenario of the thermodynamic water anomalies for TIP4P/2005 and their relation to the vapor-liquid spinodal. The overall picture shows a remarkable similarity with the corresponding one for the ST2 water model, for which the existence of a LLCP has been demonstrated in recent years. It also provides a hint as to where the long-sought for extrema in response functions might become accessible to experiments.

Simulating Molecular Mechanisms of the MDM2-Mediated Regulatory Interactions: A Conformational Selection Model of the MDM2 Lid Dynamics

PubMed Central

Verkhivker, Gennady M.

2012-01-01

Diversity and complexity of MDM2 mechanisms govern its principal function as the cellular antagonist of the p53 tumor suppressor. Structural and biophysical studies have demonstrated that MDM2 binding could be regulated by the dynamics of a pseudo-substrate lid motif. However, these experiments and subsequent computational studies have produced conflicting mechanistic models of MDM2 function and dynamics. We propose a unifying conformational selection model that can reconcile experimental findings and reveal a fundamental role of the lid as a dynamic regulator of MDM2-mediated binding. In this work, structure, dynamics and energetics of apo-MDM2 are studied as a function of posttranslational modifications and length of the lid. We found that the dynamic equilibrium between “closed” and “semi-closed” lid forms may be a fundamental characteristic of MDM2 regulatory interactions, which can be modulated by phosphorylation, phosphomimetic mutation as well as by the lid size. Our results revealed that these factors may regulate p53-MDM2 binding by fine-tuning the thermodynamic equilibrium between preexisting conformational states of apo-MDM2. In agreement with NMR studies, the effect of phosphorylation on MDM2 interactions was more pronounced with the truncated lid variant that favored the thermodynamically dominant closed form. The phosphomimetic mutation S17D may alter the lid dynamics by shifting the thermodynamic equilibrium towards the ensemble of “semi-closed” conformations. The dominant “semi-closed” lid form and weakened dependence on the phosphorylation seen in simulations with the complete lid can provide a rationale for binding of small p53-based mimetics and inhibitors without a direct competition with the lid dynamics. The results suggested that a conformational selection model of preexisting MDM2 states may provide a robust theoretical framework for understanding MDM2 dynamics. Probing biological functions and mechanisms of MDM2 regulation would require further integration of computational and experimental studies and may help to guide drug design of novel anti-cancer therapeutics. PMID:22815859

Melting relations in the system FeCO3-MgCO3 and thermodynamic modelling of Fe-Mg carbonate melts

NASA Astrophysics Data System (ADS)

Kang, Nathan; Schmidt, Max W.; Poli, Stefano; Connolly, James A. D.; Franzolin, Ettore

2016-09-01

To constrain the thermodynamics and melting relations of the siderite-magnesite (FeCO3-MgCO3) system, 27 piston cylinder experiments were conducted at 3.5 GPa and 1170-1575 °C. Fe-rich compositions were also investigated with 13 multi-anvil experiments at 10, 13.6 and 20 GPa, 1500-1890 °C. At 3.5 GPa, the solid solution siderite-magnesite coexists with melt over a compositional range of X Mg (=Mg/(Mg + Fetot)) = 0.38-1.0, while at ≥10 GPa solid solution appears to be complete. At 3.5 GPa, the system is pseudo-binary because of the limited stability of siderite or liquid FeCO3, Fe-rich carbonates decomposing at subsolidus conditions to magnetite-magnesioferrite solid solution, graphite and CO2. Similar reactions also occur with liquid FeCO3 resulting in melt species with ferric iron components, but the decomposition of the liquid decreases in importance with pressure. At 3.5 GPa, the metastable melting temperature of pure siderite is located at 1264 °C, whereas pure magnesite melts at 1629 °C. The melting loop is non-ideal on the Fe side where the dissociation reaction resulting in Fe3+ in the melt depresses melting temperatures and causes a minimum. Over the pressure range of 3.5-20 GPa, this minimum is 20-35 °C lower than the (metastable) siderite melting temperature. By merging all present and previous experimental data, standard state (298.15 K, 1 bar) thermodynamic properties of the magnesite melt (MgCO3L) end member are calculated and the properties of (Fe,Mg)CO3 melt fit by a regular solution model with an interaction parameter of -7600 J/mol. The solution model reproduces the asymmetric melting loop and predicts the thermal minimum at 1240 °C near the siderite side at X Mg = 0.2 (3.5 GPa). The solution model is applicable to pressures reaching to the bottom of the upper mantle and allows calculation of phase relations in the FeO-MgO-O2-C system.

Equilibration of tert-alkylphenols (thermodynamic analysis of the alkylation of phenols using branched-chain olefins)

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

Nesterova, T.N.; Malova, T.N.; Pil'shchikov, V.A.

1985-09-01

The authors describe the results of a study to evaluate the thermodynamic properties of t-Alk phi. These results, combined with earlier results, have enabled the authors to complete a thermodynamic analysis of the process for preparing tertiary alkylphenols which are widely used as additives in lubricating and fuel oils. Research was conducted over a fairly wide temperature range, in which the median temperature value corresponds to the upper temperature limit for a continuous process utilizing a type KU-2 ion-exchange resin catalyst; continuous operations are currently the most widely used method for industrial preparation of alkylphenols. Experimentally determined values of themore » equilibrium constants in a table indicate that they are influenced primarily by the nature of the reaction, and do not depend on the size of the tertiary alkyl substituents. Data in another table demonstrate that the thermodynamic properties of a given reaction are determined by the reaction type and are independent of the size of the tertiary alkylphenols. It was discovered that in order to increase the yield of the desired tert-alkylphenol product, the process should be carried out at the minimum possible temperature, using catalysts which are sufficiently active to guarantee thermodynamic control.« less

On the Hayashi Effect in the Early Phases of Gravitational Contraction of the Sun

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

Faulkner, J.; Griffiths, K.; Hoyle, F.

1963-02-01

Computations are made using a program for the subphotospheric layers, including opacity effects due to the negative hydrogen ion and to Rayleigh scattering. Under thermodynamic conditions completely convective models are found to occur, displaced toward late types in the H-R (Hertzsprang-Russell) diagram. The models investigated range from the late K subclasses to about M/sub 3/. Nonthermodynamic effects are considered. It appears that free electrons produced by high-energy particles are capable of modifying the results by reducing the effective temperature and luminosity, but not by completely removing the convective structure. Nor does it seem likely that opacity effects arising from solidmore » particles can destroy the convective structure. The possibility remains, however, that convective efficiency in the subphotospheric layers could be much reduced by a magnetic field at the stage where the planetary material separated from the Sun, and during the condensation of the first planetesimals and of the parent bodies of the meteorites. Only by a suppression of the highluminosity convective models during this phase does it seem possible to explain the presence of water in meteorites, and the likely presence of any icy matrix in the first planetesimals. (auth)« less

Particle Model for Work, Heat, and the Energy of a Thermodynamic System

ERIC Educational Resources Information Center

DeVoe, Howard

2007-01-01

A model of a thermodynamic system is described in which particles (representing atoms) interact with one another, the surroundings, and the earth's gravitational field according to the principles of classical mechanics. The system's energy "E" and internal energy "U" are defined. The importance is emphasized of the dependence of energy and work on…

Space Life Support Engineering Program

NASA Technical Reports Server (NTRS)

Seagrave, Richard C.

1993-01-01

This report covers the second year of research relating to the development of closed-loop long-term life support systems. Emphasis was directed toward concentrating on the development of dynamic simulation techniques and software and on performing a thermodynamic systems analysis in an effort to begin optimizing the system needed for water purification. Four appendices are attached. The first covers the ASPEN modeling of the closed loop Environmental Control Life Support System (ECLSS) and its thermodynamic analysis. The second is a report on the dynamic model development for water regulation in humans. The third regards the development of an interactive computer-based model for determining exercise limitations. The fourth attachment is an estimate of the second law thermodynamic efficiency of the various units comprising an ECLSS.

Al-Air Batteries: Fundamental Thermodynamic Limitations from First-Principles Theory.

PubMed

Chen, Leanne D; Nørskov, Jens K; Luntz, Alan C

2015-01-02

The Al-air battery possesses high theoretical specific energy (4140 W h/kg) and is therefore an attractive candidate for vehicle propulsion. However, the experimentally observed open-circuit potential is much lower than what bulk thermodynamics predicts, and this potential loss is typically attributed to corrosion. Similarly, large Tafel slopes associated with the battery are assumed to be due to film formation. We present a detailed thermodynamic study of the Al-air battery using density functional theory. The results suggest that the maximum open-circuit potential of the Al anode is only -1.87 V versus the standard hydrogen electrode at pH 14.6 instead of the traditionally assumed -2.34 V and that large Tafel slopes are inherent in the electrochemistry. These deviations from the bulk thermodynamics are intrinsic to the electrochemical surface processes that define Al anodic dissolution. This has contributions from both asymmetry in multielectron transfers and, more importantly, a large chemical stabilization inherent to the formation of bulk Al(OH)3 from surface intermediates. These are fundamental limitations that cannot be improved even if corrosion and film effects are completely suppressed.

Transport processes in magnetically confined plasmas in the nonlinear regime.

PubMed

Sonnino, Giorgio

2006-06-01

A field theory approach to transport phenomena in magnetically confined plasmas is presented. The thermodynamic field theory (TFT), previously developed for treating the generic thermodynamic system out of equilibrium, is applied to plasmas physics. Transport phenomena are treated here as the effect of the field linking the thermodynamic forces with their conjugate flows combined with statistical mechanics. In particular, the Classical and the Pfirsch-Schluter regimes are analyzed by solving the thermodynamic field equations of the TFT in the weak-field approximation. We found that, the TFT does not correct the expressions of the ionic heat fluxes evaluated by the neoclassical theory in these two regimes. On the other hand, the fluxes of matter and electronic energy (heat flow) is further enhanced in the nonlinear Classical and Pfirsch-Schluter regimes. These results seem to be in line with the experimental observations. The complete set of the electronic and ionic transport equations in the nonlinear Banana regime, is also reported. A paper showing the comparison between our theoretic results and the experimental observations in the JET machine is currently in preparation.

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar

PubMed Central

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar.

PubMed

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.

Modeling of Density-Dependent Flow based on the Thermodynamically Constrained Averaging Theory

NASA Astrophysics Data System (ADS)

Weigand, T. M.; Schultz, P. B.; Kelley, C. T.; Miller, C. T.; Gray, W. G.

2016-12-01

The thermodynamically constrained averaging theory (TCAT) has been used to formulate general classes of porous medium models, including new models for density-dependent flow. The TCAT approach provides advantages that include a firm connection between the microscale, or pore scale, and the macroscale; a thermodynamically consistent basis; explicit inclusion of factors such as a diffusion that arises from gradients associated with pressure and activity and the ability to describe both high and low concentration displacement. The TCAT model is presented and closure relations for the TCAT model are postulated based on microscale averages and a parameter estimation is performed on a subset of the experimental data. Due to the sharpness of the fronts, an adaptive moving mesh technique was used to ensure grid independent solutions within the run time constraints. The optimized parameters are then used for forward simulations and compared to the set of experimental data not used for the parameter estimation.

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

Wu, Wei; Wang, Jin, E-mail: jin.wang.1@stonybrook.edu; State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022 Changchun, China and College of Physics, Jilin University, 130021 Changchun

We have established a general non-equilibrium thermodynamic formalism consistently applicable to both spatially homogeneous and, more importantly, spatially inhomogeneous systems, governed by the Langevin and Fokker-Planck stochastic dynamics with multiple state transition mechanisms, using the potential-flux landscape framework as a bridge connecting stochastic dynamics with non-equilibrium thermodynamics. A set of non-equilibrium thermodynamic equations, quantifying the relations of the non-equilibrium entropy, entropy flow, entropy production, and other thermodynamic quantities, together with their specific expressions, is constructed from a set of dynamical decomposition equations associated with the potential-flux landscape framework. The flux velocity plays a pivotal role on both the dynamic andmore » thermodynamic levels. On the dynamic level, it represents a dynamic force breaking detailed balance, entailing the dynamical decomposition equations. On the thermodynamic level, it represents a thermodynamic force generating entropy production, manifested in the non-equilibrium thermodynamic equations. The Ornstein-Uhlenbeck process and more specific examples, the spatial stochastic neuronal model, in particular, are studied to test and illustrate the general theory. This theoretical framework is particularly suitable to study the non-equilibrium (thermo)dynamics of spatially inhomogeneous systems abundant in nature. This paper is the second of a series.« less

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics.

PubMed

Chapman, Brian

2017-06-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis-Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis- substrate binding, cis → trans bound enzyme shuttling, trans -substrate dissociation and trans → cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive 'tuning' of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force-flux relations, with only a minority of cases having their quasi -linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically 'tuned' to its particular task, dependent on the cis- and trans- substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport.

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics

PubMed Central

2017-01-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis–Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis-substrate binding, cis→trans bound enzyme shuttling, trans-substrate dissociation and trans→cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive ‘tuning’ of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force–flux relations, with only a minority of cases having their quasi-linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically ‘tuned’ to its particular task, dependent on the cis- and trans-substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport. PMID:28680687

ARCTIC SEA ICE EXTENT AND DRIFT, MODELED AS A VISCOUS FLUID.

USGS Publications Warehouse

Ling, Chi-Hai; Parkinson, Claire L.

1986-01-01

A dynamic/thermodynamic numerical model of sea ice has been used to calculate the yearly cycle of sea ice thicknesses, concentrations, and velocities in the Arctic Ocean and surrounding seas. The model combines the formulations of two previous models, taking the thermodynamics and momentum equations from the model of Parkinson and Washington and adding the constitutive equation and equation of state from the model of Ling, Rasmussen, and Campbell. Simulated annually averaged ice drift vectors compare well with observed ice drift from the Arctic Ocean Buoy Program.

Comparison of Optimal Thermodynamic Models of the Tricarboxylic Acid Cycle from Heterotrophs, Cyanobacteria, and Green Sulfur Bacteria.

PubMed

Thomas, Dennis G; Jaramillo-Riveri, Sebastian; Baxter, Douglas J; Cannon, William R

2014-12-26

We have applied a new stochastic simulation approach to predict the metabolite levels, material flux, and thermodynamic profiles of the oxidative TCA cycles found in E. coli and Synechococcus sp. PCC 7002, and in the reductive TCA cycle typical of chemolithoautotrophs and phototrophic green sulfur bacteria such as Chlorobaculum tepidum. The simulation approach is based on modeling states using statistical thermodynamics and employs an assumption similar to that used in transition state theory. The ability to evaluate the thermodynamics of metabolic pathways allows one to understand the relationship between coupling of energy and material gradients in the environment and the self-organization of stable biological systems, and it is shown that each cycle operates in the direction expected due to its environmental niche. The simulations predict changes in metabolite levels and flux in response to changes in cofactor concentrations that would be hard to predict without an elaborate model based on the law of mass action. In fact, we show that a thermodynamically unfavorable reaction can still have flux in the forward direction when it is part of a reaction network. The ability to predict metabolite levels, energy flow, and material flux should be significant for understanding the dynamics of natural systems and for understanding principles for engineering organisms for production of specialty chemicals.

Interfacial thermodynamics of water and six other liquid solvents.

PubMed

Pascal, Tod A; Goddard, William A

2014-06-05

We examine the thermodynamics of the liquid-vapor interface by direct calculation of the surface entropy, enthalpy, and free energy from extensive molecular dynamics simulations using the two-phase thermodynamics (2PT) method. Results for water, acetonitrile, cyclohexane, dimethyl sulfoxide, hexanol, N-methyl acetamide, and toluene are presented. We validate our approach by predicting the interfacial surface tensions (IFT--excess surface free energy per unit area) in excellent agreement with the mechanical calculations using Kirkwood-Buff theory. Additionally, we evaluate the temperature dependence of the IFT of water as described by the TIP4P/2005, SPC/Ew, TIP3P, and mW classical water models. We find that the TIP4P/2005 and SPC/Ew water models do a reasonable job of describing the interfacial thermodynamics; however, the TIP3P and mW are quite poor. We find that the underprediction of the experimental IFT at 298 K by these water models results from understructured surface molecules whose binding energies are too weak. Finally, we performed depth profiles of the interfacial thermodynamics which revealed long tails that extend far into what would be considered bulk from standard Gibbs theory. In fact, we find a nonmonotonic interfacial free energy profile for water, a unique feature that could have important consequences for the absorption of ions and other small molecules.

Equilibrium, kinetic and thermodynamic studies of uranium biosorption by calcium alginate beads.

PubMed

Bai, Jing; Fan, Fangli; Wu, Xiaolei; Tian, Wei; Zhao, Liang; Yin, Xiaojie; Fan, Fuyou; Li, Zhan; Tian, Longlong; Wang, Yang; Qin, Zhi; Guo, Junsheng

2013-12-01

Calcium alginate beads are potential biosorbent for radionuclides removal as they contain carboxyl groups. However, until now limited information is available concerning the uptake behavior of uranium by this polymer gel, especially when sorption equilibrium, kinetics and thermodynamics are concerned. In present work, batch experiments were carried out to study the equilibrium, kinetics and thermodynamics of uranium sorption by calcium alginate beads. The effects of initial solution pH, sorbent amount, initial uranium concentration and temperature on uranium sorption were also investigated. The determined optimal conditions were: initial solution pH of 3.0, added sorbent amount of 40 mg, and uranium sorption capacity increased with increasing initial uranium concentration and temperature. Equilibrium data obtained under different temperatures were fitted better with Langmuir model than Freundlich model, uranium sorption was dominated by a monolayer way. The kinetic data can be well depicted by the pseudo-second-order kinetic model. The activation energy derived from Arrhenius equation was 30.0 kJ/mol and the sorption process had a chemical nature. Thermodynamic constants such as ΔH(0), ΔS(0) and ΔG(0) were also evaluated, results of thermodynamic study showed that the sorption process was endothermic and spontaneous. Copyright © 2013 Elsevier Ltd. All rights reserved.

A thermodynamically consistent model for granular-fluid mixtures considering pore pressure evolution and hypoplastic behavior

NASA Astrophysics Data System (ADS)

Hess, Julian; Wang, Yongqi

2016-11-01

A new mixture model for granular-fluid flows, which is thermodynamically consistent with the entropy principle, is presented. The extra pore pressure described by a pressure diffusion equation and the hypoplastic material behavior obeying a transport equation are taken into account. The model is applied to granular-fluid flows, using a closing assumption in conjunction with the dynamic fluid pressure to describe the pressure-like residual unknowns, hereby overcoming previous uncertainties in the modeling process. Besides the thermodynamically consistent modeling, numerical simulations are carried out and demonstrate physically reasonable results, including simple shear flow in order to investigate the vertical distribution of the physical quantities, and a mixture flow down an inclined plane by means of the depth-integrated model. Results presented give insight in the ability of the deduced model to capture the key characteristics of granular-fluid flows. We acknowledge the support of the Deutsche Forschungsgemeinschaft (DFG) for this work within the Project Number WA 2610/3-1.

Thermodynamic modeling of small scale biomass gasifiers: Development and assessment of the ''Multi-Box'' approach.

PubMed

Vakalis, Stergios; Patuzzi, Francesco; Baratieri, Marco

2016-04-01

Modeling can be a powerful tool for designing and optimizing gasification systems. Modeling applications for small scale/fixed bed biomass gasifiers have been interesting due to their increased commercial practices. Fixed bed gasifiers are characterized by a wide range of operational conditions and are multi-zoned processes. The reactants are distributed in different phases and the products from each zone influence the following process steps and thus the composition of the final products. The present study aims to improve the conventional 'Black-Box' thermodynamic modeling by means of developing multiple intermediate 'boxes' that calculate two phase (solid-vapor) equilibriums in small scale gasifiers. Therefore the model is named ''Multi-Box''. Experimental data from a small scale gasifier have been used for the validation of the model. The returned results are significantly closer with the actual case study measurements in comparison to single-stage thermodynamic modeling. Copyright © 2016 Elsevier Ltd. All rights reserved.

Integral equation and thermodynamic perturbation theory for a two-dimensional model of dimerising fluid

PubMed Central

Urbic, Tomaz

2016-01-01

In this paper we applied an analytical theory for the two dimensional dimerising fluid. We applied Wertheims thermodynamic perturbation theory (TPT) and integral equation theory (IET) for associative liquids to the dimerising model with arbitrary position of dimerising points from center of the particles. The theory was used to study thermodynamical and structural properties. To check the accuracy of the theories we compared theoretical results with corresponding results obtained by Monte Carlo computer simulations. The theories are accurate for the different positions of patches of the model at all values of the temperature and density studied. IET correctly predicts the pair correlation function of the model. Both TPT and IET are in good agreement with the Monte Carlo values of the energy, pressure, chemical potential, compressibility and ratios of free and bonded particles. PMID:28529396

Thermodynamic efficiency of learning a rule in neural networks

NASA Astrophysics Data System (ADS)

Goldt, Sebastian; Seifert, Udo

2017-11-01

Biological systems have to build models from their sensory input data that allow them to efficiently process previously unseen inputs. Here, we study a neural network learning a binary classification rule for these inputs from examples provided by a teacher. We analyse the ability of the network to apply the rule to new inputs, that is to generalise from past experience. Using stochastic thermodynamics, we show that the thermodynamic costs of the learning process provide an upper bound on the amount of information that the network is able to learn from its teacher for both batch and online learning. This allows us to introduce a thermodynamic efficiency of learning. We analytically compute the dynamics and the efficiency of a noisy neural network performing online learning in the thermodynamic limit. In particular, we analyse three popular learning algorithms, namely Hebbian, Perceptron and AdaTron learning. Our work extends the methods of stochastic thermodynamics to a new type of learning problem and might form a suitable basis for investigating the thermodynamics of decision-making.

Elucidating the effects of adsorbent flexibility on fluid adsorption using simple models and flat-histogram sampling methods

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

Shen, Vincent K., E-mail: vincent.shen@nist.gov; Siderius, Daniel W.

2014-06-28

Using flat-histogram Monte Carlo methods, we investigate the adsorptive behavior of the square-well fluid in two simple slit-pore-like models intended to capture fundamental characteristics of flexible adsorbent materials. Both models require as input thermodynamic information about the flexible adsorbent material itself. An important component of this work involves formulating the flexible pore models in the appropriate thermodynamic (statistical mechanical) ensembles, namely, the osmotic ensemble and a variant of the grand-canonical ensemble. Two-dimensional probability distributions, which are calculated using flat-histogram methods, provide the information necessary to determine adsorption thermodynamics. For example, we are able to determine precisely adsorption isotherms, (equilibrium) phasemore » transition conditions, limits of stability, and free energies for a number of different flexible adsorbent materials, distinguishable as different inputs into the models. While the models used in this work are relatively simple from a geometric perspective, they yield non-trivial adsorptive behavior, including adsorption-desorption hysteresis solely due to material flexibility and so-called “breathing” of the adsorbent. The observed effects can in turn be tied to the inherent properties of the bare adsorbent. Some of the effects are expected on physical grounds while others arise from a subtle balance of thermodynamic and mechanical driving forces. In addition, the computational strategy presented here can be easily applied to more complex models for flexible adsorbents.« less

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Elucidating the effects of adsorbent flexibility on fluid adsorption using simple models and flat-histogram sampling methods

NASA Astrophysics Data System (ADS)

Shen, Vincent K.; Siderius, Daniel W.

2014-06-01

Using flat-histogram Monte Carlo methods, we investigate the adsorptive behavior of the square-well fluid in two simple slit-pore-like models intended to capture fundamental characteristics of flexible adsorbent materials. Both models require as input thermodynamic information about the flexible adsorbent material itself. An important component of this work involves formulating the flexible pore models in the appropriate thermodynamic (statistical mechanical) ensembles, namely, the osmotic ensemble and a variant of the grand-canonical ensemble. Two-dimensional probability distributions, which are calculated using flat-histogram methods, provide the information necessary to determine adsorption thermodynamics. For example, we are able to determine precisely adsorption isotherms, (equilibrium) phase transition conditions, limits of stability, and free energies for a number of different flexible adsorbent materials, distinguishable as different inputs into the models. While the models used in this work are relatively simple from a geometric perspective, they yield non-trivial adsorptive behavior, including adsorption-desorption hysteresis solely due to material flexibility and so-called "breathing" of the adsorbent. The observed effects can in turn be tied to the inherent properties of the bare adsorbent. Some of the effects are expected on physical grounds while others arise from a subtle balance of thermodynamic and mechanical driving forces. In addition, the computational strategy presented here can be easily applied to more complex models for flexible adsorbents.

Thermodynamics, Life, the Universe and Everything

NASA Astrophysics Data System (ADS)

Neswald, Elizabeth

2015-01-01

The laws of thermodynamics were developed in the first half of the nineteenth century to describe processes governing the working of steam engines. The mechanical equivalent of heat, which quantified the relationship between heat and motion, enabled the quantification and comparison of all energy transformation processes. The energy laws and the mechanical equivalent of heat quickly moved out of the narrower field of physics to form the basis of a cosmic narrative that began with stellar evolution and continued to universal heat death. Newer physiological theories turned to the energy laws to explain life processes, energy and entropy were integrated into theories of biological evolution and degeneration, and economists and cultural theorists turned to thermodynamics to explore both the limits of natural resources and economic expansion and the contradictions of industrial modernity. This paper discusses the career of thermodynamics as an explanatory model and cultural commonplace in the late nineteenth and early twentieth centuries, and the different scientific, religious, and social perspectives that could be expressed through this model. Connected through the entropy law intimately to irreversible processes and time, thermodynamics provided an arena to debate which way the world was going.

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

Overview of heat transfer and fluid flow problem areas encountered in Stirling engine modeling

NASA Technical Reports Server (NTRS)

Tew, Roy C., Jr.

1988-01-01

NASA Lewis Research Center has been managing Stirling engine development programs for over a decade. In addition to contractual programs, this work has included in-house engine testing and development of engine computer models. Attempts to validate Stirling engine computer models with test data have demonstrated that engine thermodynamic losses need better characterization. Various Stirling engine thermodynamic losses and efforts that are underway to characterize these losses are discussed.

The application of the thermodynamic perturbation theory to study the hydrophobic hydration.

PubMed

Mohoric, Tomaz; Urbic, Tomaz; Hribar-Lee, Barbara

2013-07-14

The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures.

The application of the thermodynamic perturbation theory to study the hydrophobic hydration

NASA Astrophysics Data System (ADS)

Mohorič, Tomaž; Urbic, Tomaz; Hribar-Lee, Barbara

2013-07-01

The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures.

Analyzing Data for Systems Biology: Working at the Intersection of Thermodynamics and Data Analytics

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

Cannon, William R.; Baxter, Douglas J.

2012-08-15

Many challenges in systems biology have to do with analyzing data within the framework of molecular phenomena and cellular pathways. How does this relate to thermodynamics that we know govern the behavior of molecules? Making progress in relating data analysis to thermodynamics is essential in systems biology if we are to build predictive models that enable the field of synthetic biology. This report discusses work at the crossroads of thermodynamics and data analysis, and demonstrates that statistical mechanical free energy is a multinomial log likelihood. Applications to systems biology are presented.

Zinc complexation in chloride-rich hydrothermal fluids (25-600 °C): A thermodynamic model derived from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Mei, Yuan; Sherman, David M.; Liu, Weihua; Etschmann, Barbara; Testemale, Denis; Brugger, Joël

2015-02-01

The solubility of zinc minerals in hydrothermal fluids is enhanced by chloride complexation of Zn2+. Thermodynamic models of these complexation reactions are central to models of Zn transport and ore formation. However, existing thermodynamic models, derived from solubility measurements, are inconsistent with spectroscopic measurements of Zn speciation. Here, we used ab initio molecular dynamics simulations (with the PBE exchange-correlation functional) to predict the speciation of Zn-Cl complexes from 25 to 600 °C. We also obtained in situ XAS measurements of Zn-Cl solutions at 30-600 °C. Qualitatively, the simulations reproduced the main features derived from in situ XANES and EXAFS measurements: octahedral to tetrahedral transition with increasing temperature and salinity, stability of ZnCl42- at high chloride concentration up to ⩾500 °C, and increasing stability of the trigonal planar [ZnCl3]- complex at high temperature. Having confirmed the dominant species, we directly determined the stability constants for the Zn-Cl complexes using thermodynamic integration along constrained Zn-Cl distances in a series of MD simulations. We corrected our stability constants to infinite dilution using the b-dot model for the activity coefficients of the solute species. In order to compare the ab initio results with experiments, we need to re-model the existing solubility data using the species we identified in our MD simulations. The stability constants derived from refitting published experimental data are in reasonable agreement with those we obtained using ab initio MD simulations. Our new thermodynamic model accurately predicts the experimentally observed changes in ZnO(s) and ZnCO3(s) solubility as a function of chloride concentration from 200 (Psat) to 600 °C (2000 bar). This study demonstrates that metal speciation and geologically useful stability constants can be derived for species in hydrothermal fluids from ab initio MD simulations even at the generalized gradient approximation for exchange-correlation. We caution, however, that simulations are mostly reliable at high T where ligand exchange is fast enough to yield thermodynamic averages over the timescales of the simulations.

Application of thermodynamics and Wagner model on two problems in continuous hot-dip galvanizing

NASA Astrophysics Data System (ADS)

Liu, Huachu; He, Yanlin; Li, Lin

2009-12-01

Firstly in this paper, the influence of H 2 and water vapor content on selective oxidation occurred in continuous hot-dip galvanizing has been studied by thermodynamics and Wagner model, then, the Gibbs energy of each possible aluminothermic reducing reaction in zinc bath was calculated in order to judge the possibility of these reactions. It was found that oxides' amounts and oxidation type were greatly related to the H 2 and water content in the annealing atmosphere. And from the view of thermodynamics, surface oxides (MnO, Cr 2O 3, SiO 2 etc.) can be reduced by the effective Al in Zn bath.

Continuous information flow fluctuations

NASA Astrophysics Data System (ADS)

Rosinberg, Martin Luc; Horowitz, Jordan M.

2016-10-01

Information plays a pivotal role in the thermodynamics of nonequilibrium processes with feedback. However, much remains to be learned about the nature of information fluctuations in small-scale devices and their relation with fluctuations in other thermodynamics quantities, like heat and work. Here we derive a series of fluctuation theorems for information flow and partial entropy production in a Brownian particle model of feedback cooling and extend them to arbitrary driven diffusion processes. We then analyze the long-time behavior of the feedback-cooling model in detail. Our results provide insights into the structure and origin of large deviations of information and thermodynamic quantities in autonomous Maxwell's demons.

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 2006 Kennedy Space Center Range Reference Atmosphere Model Validation Study and Sensitivity Analysis to the Performance of the National Aeronautics and Space Administration's Space Shuttle Vehicle

NASA Technical Reports Server (NTRS)

Burns, Lee; Decker, Ryan; Harrington, Brian; Merry, Carl

2008-01-01

The Kennedy Space Center (KSC) Range Reference Atmosphere (RRA) is a statistical model that summarizes wind and thermodynamic atmospheric variability from surface to 70 km. The National Aeronautics and Space Administration's (NASA) Space Shuttle program, which launches from KSC, utilizes the KSC RRA data to evaluate environmental constraints on various aspects of the vehicle during ascent. An update to the KSC RRA was recently completed. As part of the update, the Natural Environments Branch at NASA's Marshall Space Flight Center (MSFC) conducted a validation study and a comparison analysis to the existing KSC RRA database version 1983. Assessments to the Space Shuttle vehicle ascent profile characteristics were performed by JSC/Ascent Flight Design Division to determine impacts of the updated model to the vehicle performance. Details on the model updates and the vehicle sensitivity analyses with the update model are presented.

On the thermomechanical coupling in dissipative materials: A variational approach for generalized standard materials

NASA Astrophysics Data System (ADS)

Bartels, A.; Bartel, T.; Canadija, M.; Mosler, J.

2015-09-01

This paper deals with the thermomechanical coupling in dissipative materials. The focus lies on finite strain plasticity theory and the temperature increase resulting from plastic deformation. For this type of problem, two fundamentally different modeling approaches can be found in the literature: (a) models based on thermodynamical considerations and (b) models based on the so-called Taylor-Quinney factor. While a naive straightforward implementation of thermodynamically consistent approaches usually leads to an over-prediction of the temperature increase due to plastic deformation, models relying on the Taylor-Quinney factor often violate fundamental physical principles such as the first and the second law of thermodynamics. In this paper, a thermodynamically consistent framework is elaborated which indeed allows the realistic prediction of the temperature evolution. In contrast to previously proposed frameworks, it is based on a fully three-dimensional, finite strain setting and it naturally covers coupled isotropic and kinematic hardening - also based on non-associative evolution equations. Considering a variationally consistent description based on incremental energy minimization, it is shown that the aforementioned problem (thermodynamical consistency and a realistic temperature prediction) is essentially equivalent to correctly defining the decomposition of the total energy into stored and dissipative parts. Interestingly, this decomposition shows strong analogies to the Taylor-Quinney factor. In this respect, the Taylor-Quinney factor can be well motivated from a physical point of view. Furthermore, certain intervals for this factor can be derived in order to guarantee that fundamental physically principles are fulfilled a priori. Representative examples demonstrate the predictive capabilities of the final constitutive modeling framework.

A Thermodynamic Model for Genome Packaging in Hepatitis B Virus.

PubMed

Kim, Jehoon; Wu, Jianzhong

2015-10-20

Understanding the fundamentals of genome packaging in viral capsids is important for finding effective antiviral strategies and for utilizing benign viral particles for gene therapy. While the structure of encapsidated genomic materials has been routinely characterized with experimental techniques such as cryo-electron microscopy and x-ray diffraction, much less is known about the molecular driving forces underlying genome assembly in an intracellular environment and its in vivo interactions with the capsid proteins. Here we study the thermodynamic basis of the pregenomic RNA encapsidation in human Hepatitis B virus in vivo using a coarse-grained molecular model that captures the essential components of nonspecific intermolecular interactions. The thermodynamic model is used to examine how the electrostatic interaction between the packaged RNA and the highly charged C-terminal domains (CTD) of capsid proteins regulate the nucleocapsid formation. The theoretical model predicts optimal RNA content in Hepatitis B virus nucleocapsids with different CTD lengths in good agreement with mutagenesis measurements, confirming the predominant role of electrostatic interactions and molecular excluded-volume effects in genome packaging. We find that the amount of encapsidated RNA is not linearly correlated with the net charge of CTD tails as suggested by earlier theoretical studies. Our thermodynamic analysis of the nucleocapsid structure and stability indicates that ∼10% of the CTD residues are free from complexation with RNA, resulting in partially exposed CTD tails. The thermodynamic model also predicts the free energy of complex formation between macromolecules, which corroborates experimental results for the impact of CTD truncation on the nucleocapsid stability. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Network thermodynamic curation of human and yeast genome-scale metabolic models.

PubMed

Martínez, Verónica S; Quek, Lake-Ee; Nielsen, Lars K

2014-07-15

Genome-scale models are used for an ever-widening range of applications. Although there has been much focus on specifying the stoichiometric matrix, the predictive power of genome-scale models equally depends on reaction directions. Two-thirds of reactions in the two eukaryotic reconstructions Homo sapiens Recon 1 and Yeast 5 are specified as irreversible. However, these specifications are mainly based on biochemical textbooks or on their similarity to other organisms and are rarely underpinned by detailed thermodynamic analysis. In this study, a to our knowledge new workflow combining network-embedded thermodynamic and flux variability analysis was used to evaluate existing irreversibility constraints in Recon 1 and Yeast 5 and to identify new ones. A total of 27 and 16 new irreversible reactions were identified in Recon 1 and Yeast 5, respectively, whereas only four reactions were found with directions incorrectly specified against thermodynamics (three in Yeast 5 and one in Recon 1). The workflow further identified for both models several isolated internal loops that require further curation. The framework also highlighted the need for substrate channeling (in human) and ATP hydrolysis (in yeast) for the essential reaction catalyzed by phosphoribosylaminoimidazole carboxylase in purine metabolism. Finally, the framework highlighted differences in proline metabolism between yeast (cytosolic anabolism and mitochondrial catabolism) and humans (exclusively mitochondrial metabolism). We conclude that network-embedded thermodynamics facilitates the specification and validation of irreversibility constraints in compartmentalized metabolic models, at the same time providing further insight into network properties. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Complete Mie-Gruneisen Equation of State (update)

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

Menikoff, Ralph

2016-03-14

The Mie-Gruneisen equation of state (EOS) is frequently used in hydro simulations to model solids at high pressure (up to a few Mb). It is an incomplete EOS characterized by a Gr¨uneisen coefficient, = -V (@eP)V , that is a function of only V . Expressions are derived for isentropes and isotherms. This enables the extension to a complete EOS. Thermodynamic consistency requires that the specific heat is a function of a single scaled-temperature. A complete extension is uniquely determined by the temperature dependence of the specific heat at a fixed reference density. In addition we show that if themore » domain of the EOS extends to T = 0 and the specific heat vanishes on the zero isotherm then a function of only V is equivalent to a specific heat with a single temperature scale. If the EOS domain does not include the zero isotherm, then a specific heat with a single temperature scale leads to a generalization of the Mie-Gr¨uneisen EOS in which the pressure is linear in both the specific energy and the temperature. This corresponds to the limiting case of two temperature scales with one of the scales in the high temperature limit. Such an EOS has previously been used to model liquid nitromethane.« less

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.

Investigating homology between proteins using energetic profiles.

PubMed

Wrabl, James O; Hilser, Vincent J

2010-03-26

Accumulated experimental observations demonstrate that protein stability is often preserved upon conservative point mutation. In contrast, less is known about the effects of large sequence or structure changes on the stability of a particular fold. Almost completely unknown is the degree to which stability of different regions of a protein is generally preserved throughout evolution. In this work, these questions are addressed through thermodynamic analysis of a large representative sample of protein fold space based on remote, yet accepted, homology. More than 3,000 proteins were computationally analyzed using the structural-thermodynamic algorithm COREX/BEST. Estimated position-specific stability (i.e., local Gibbs free energy of folding) and its component enthalpy and entropy were quantitatively compared between all proteins in the sample according to all-vs.-all pairwise structural alignment. It was discovered that the local stabilities of homologous pairs were significantly more correlated than those of non-homologous pairs, indicating that local stability was indeed generally conserved throughout evolution. However, the position-specific enthalpy and entropy underlying stability were less correlated, suggesting that the overall regional stability of a protein was more important than the thermodynamic mechanism utilized to achieve that stability. Finally, two different types of statistically exceptional evolutionary structure-thermodynamic relationships were noted. First, many homologous proteins contained regions of similar thermodynamics despite localized structure change, suggesting a thermodynamic mechanism enabling evolutionary fold change. Second, some homologous proteins with extremely similar structures nonetheless exhibited different local stabilities, a phenomenon previously observed experimentally in this laboratory. These two observations, in conjunction with the principal conclusion that homologous proteins generally conserved local stability, may provide guidance for a future thermodynamically informed classification of protein homology.

Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water

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

Singh, Rakesh S.; Debenedetti, Pablo G.; Biddle, John W.

Water shows intriguing thermodynamic and dynamic anomalies in the supercooled liquid state. One possible explanation of the origin of these anomalies lies in the existence of a metastable liquid-liquid phase transition (LLPT) between two (high and low density) forms of water. While the anomalies are observed in experiments on bulk and confined water and by computer simulation studies of different water-like models, the existence of a LLPT in water is still debated. Unambiguous experimental proof of the existence of a LLPT in bulk supercooled water is hampered by fast ice nucleation which is a precursor of the hypothesized LLPT. Moreover,more » the hypothesized LLPT, being metastable, in principle cannot exist in the thermodynamic limit (infinite size, infinite time). Therefore, computer simulations of water models are crucial for exploring the possibility of the metastable LLPT and the nature of the anomalies. In this work, we present new simulation results in the NVT ensemble for one of the most accurate classical molecular models of water, TIP4P/2005. To describe the computed properties and explore the possibility of a LLPT, we have applied two-structure thermodynamics, viewing water as a non-ideal mixture of two interconvertible local structures (“states”). The results suggest the presence of a liquid-liquid critical point and are consistent with the existence of a LLPT in this model for the simulated length and time scales. We have compared the behavior of TIP4P/2005 with other popular water-like models, namely, mW and ST2, and with real water, all of which are well described by two-state thermodynamics. In view of the current debate involving different studies of TIP4P/2005, we discuss consequences of metastability and finite size in observing the liquid-liquid separation. We also address the relationship between the phenomenological order parameter of two-structure thermodynamics and the microscopic nature of the low-density structure.« less

Kaluza-Klein Bulk Viscous Fluid Cosmological Models and the Validity of the Second Law of Thermodynamics in f(R, T) Gravity

NASA Astrophysics Data System (ADS)

Samanta, Gauranga Charan; Myrzakulov, Ratbay; Shah, Parth

2017-04-01

The authors considered the bulk viscous fluid in f(R, T) gravity within the framework of Kaluza-Klein space time. The bulk viscous coefficient (ξ) expressed as ξ = {ξ_0} + {ξ_1}{{\\dot a} \\over a} + {ξ_2}{{\\ddot a} \\over {\\dot a}}, where ξ0, ξ1, and ξ2 are positive constants. We take p=(γ-1)ρ, where 0≤γ≤2 as an equation of state for perfect fluid. The exact solutions to the corresponding field equations are given by assuming a particular model of the form of f(R, T)=R+2f(T), where f(T)=λT, λ is constant. We studied the cosmological model in two stages, in first stage: we studied the model with no viscosity, and in second stage: we studied the model involve with viscosity. The cosmological model involve with viscosity is studied by five possible scenarios for bulk viscous fluid coefficient (ξ). The total bulk viscous coefficient seems to be negative, when the bulk viscous coefficient is proportional to {ξ _2}{{\\ddot a} \\over {\\dot a}}, hence, the second law of thermodynamics is not valid; however, it is valid with the generalised second law of thermodynamics. The total bulk viscous coefficient seems to be positive, when the bulk viscous coefficient is proportional to ξ = {ξ _1}{{\\dot a} \\over a} + {ξ _2}{{\\ddot a} \\over {\\dot a}} and ξ = {ξ _0} + {ξ _1}{{\\dot a} \\over a} + {ξ _2}{{\\ddot a} \\over {\\dot a}}, so the second law of thermodynamics and the generalised second law of thermodynamics is satisfied throughout the evolution. We calculate statefinder parameters of the model and observed that it is different from the ∧CDM model. Finally, some physical and geometrical properties of the models are discussed.

Towards driving mantle convection by mineral physics

NASA Astrophysics Data System (ADS)

Piazzoni, A. S.; Bunge, H.; Steinle-Neumann, G.

2005-12-01

Models of mantle convection have become increasingly sophisticated over the past decade, accounting, for example, for 3 D spherical geometry, and changes in mantle rheology due to variations in temperature and stress. In light of such advances it is surprising that growing constraints on mantle structure derived from mineral physics have not yet been fully brought to bear on mantle convection models. In fact, despite much progress in our understanding of mantle mineralogy a partial description of the equation of state is often used to relate density changes to pressure and temperature alone, without taking into account compositional and mineralogical models of the mantle. Similarly, for phase transitions an incomplete description of thermodynamic constraints is often used, resulting in significant uncertainties in model behavior. While a number of thermodynamic models (some with limited scope) have been constructed recently, some lack the rigor in thermodynamics - for example with respect to the treatment of solid solution - that is needed to make predictions about mantle structure. Here we have constructed a new thermodynamic database for the mantle and have coupled the resulting density dynamically with mantle convection models. The database is build on a self-consistent Gibb's free energy minimization of the system MgO-FeO-SiO2-CaO-Al2O3 that is appropriate for standard (dry) chemical models of the Earth's mantle for relevant high pressure and temperature phases. We have interfaced the database with a high-resolution 2-D convection code (2DTERRA), dynamically coupling the thermodynamic model (density) with the conservation equations of mantle flow. The coupled model is run for different parameterizations of viscosity, initial temperature conditions, and varying the internal vs. external heating. We compare the resulting flow and temperature fields to cases with the Boussinesq approximation and other classical descriptions of the equation of state in mantle dynamics to assess the influence of realistic mineralogical density on mantle convection.

Einstein-Podolsky-Rosen paradox implies a minimum achievable temperature

NASA Astrophysics Data System (ADS)

Rogers, David M.

2017-01-01

This work examines the thermodynamic consequences of the repeated partial projection model for coupling a quantum system to an arbitrary series of environments under feedback control. This paper provides observational definitions of heat and work that can be realized in current laboratory setups. In contrast to other definitions, it uses only properties of the environment and the measurement outcomes, avoiding references to the "measurement" of the central system's state in any basis. These definitions are consistent with the usual laws of thermodynamics at all temperatures, while never requiring complete projective measurement of the entire system. It is shown that the back action of measurement must be counted as work rather than heat to satisfy the second law. Comparisons are made to quantum jump (unravelling) and transition-probability based definitions, many of which appear as particular limits of the present model. These limits show that our total entropy production is a lower bound on traditional definitions of heat that trace out the measurement device. Examining the master equation approximation to the process at finite measurement rates, we show that most interactions with the environment make the system unable to reach absolute zero. We give an explicit formula for the minimum temperature achievable in repeatedly measured quantum systems. The phenomenon of minimum temperature offers an explanation of recent experiments aimed at testing fluctuation theorems in the quantum realm and places a fundamental purity limit on quantum computers.

Complete devil's staircase and crystal-superfluid transitions in a dipolar XXZ spin chain: a trapped ion quantum simulation

NASA Astrophysics Data System (ADS)

Hauke, Philipp; Cucchietti, Fernando M.; Müller-Hermes, Alexander; Bañuls, Mari-Carmen; Cirac, J. Ignacio; Lewenstein, Maciej

2010-11-01

Systems with long-range interactions show a variety of intriguing properties: they typically accommodate many metastable states, they can give rise to spontaneous formation of supersolids, and they can lead to counterintuitive thermodynamic behavior. However, the increased complexity that comes with long-range interactions strongly hinders theoretical studies. This makes a quantum simulator for long-range models highly desirable. Here, we show that a chain of trapped ions can be used to quantum simulate a one-dimensional (1D) model of hard-core bosons with dipolar off-site interaction and tunneling, equivalent to a dipolar XXZ spin-1/2 chain. We explore the rich phase diagram of this model in detail, employing perturbative mean-field theory, exact diagonalization and quasi-exact numerical techniques (density-matrix renormalization group and infinite time-evolving block decimation). We find that the complete devil's staircase—an infinite sequence of crystal states existing at vanishing tunneling—spreads to a succession of lobes similar to the Mott lobes found in Bose-Hubbard models. Investigating the melting of these crystal states at increased tunneling, we do not find (contrary to similar 2D models) clear indications of supersolid behavior in the region around the melting transition. However, we find that inside the insulating lobes there are quasi-long-range (algebraic) correlations, as opposed to models with nearest-neighbor tunneling, that show exponential decay of correlations.

Thermodynamics of Biological Processes

PubMed Central

Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

2012-01-01

There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

On the Relationship of the Fractal Dimension of Structure with the State of Drying Drops of Crystallizing Solutions (Thermodynamic and Experimental Modeling)

NASA Astrophysics Data System (ADS)

Golovanova, O. A.; Chikanova, E. S.; Fedoseev, V. B.

2018-05-01

The processes occurring in aqueous salt solutions have been investigated based on thermodynamic and experimental modeling. The self-organization in a drying drop of dehydrated liquids is analyzed using the fractal theory, due to which the quantitative characteristics of the crystallization processes in a small volume are obtained.

Thermodynamic feature of a Brownian heat engine operating between two heat baths.

PubMed

Asfaw, Mesfin

2014-01-01

A generalized theory of nonequilibrium thermodynamics for a Brownian motor operating between two different heat baths is presented. Via a simple paradigmatic model, we not only explore the thermodynamic feature of the engine in the regime of the nonequilibrium steady state but also study the short time behavior of the system for either the isothermal case with load or, in general, the nonisothermal case with or without load. Many elegant thermodynamic theories can be checked via the present model. Furthermore the dependence of the velocity, the efficiency, and the performance of the refrigerator on time t is examined. Our study reveals a current reversal due to time t. In the early system relaxation period, the model works neither as a heat engine nor as a refrigerator and only after a certain period of time does the model start functioning as a heat engine or as a refrigerator. The performance of the engine also improves with time and at steady state the engine manifests a higher efficiency or performance as a refrigerator. Furthermore the effect of energy exchange via the kinetic energy on the performance of the heat engine is explored.

Entanglement and thermodynamics after a quantum quench in integrable systems.

PubMed

Alba, Vincenzo; Calabrese, Pasquale

2017-07-25

Entanglement and entropy are key concepts standing at the foundations of quantum and statistical mechanics. Recently, the study of quantum quenches revealed that these concepts are intricately intertwined. Although the unitary time evolution ensuing from a pure state maintains the system at zero entropy, local properties at long times are captured by a statistical ensemble with nonzero thermodynamic entropy, which is the entanglement accumulated during the dynamics. Therefore, understanding the entanglement evolution unveils how thermodynamics emerges in isolated systems. Alas, an exact computation of the entanglement dynamics was available so far only for noninteracting systems, whereas it was deemed unfeasible for interacting ones. Here, we show that the standard quasiparticle picture of the entanglement evolution, complemented with integrability-based knowledge of the steady state and its excitations, leads to a complete understanding of the entanglement dynamics in the space-time scaling limit. We thoroughly check our result for the paradigmatic Heisenberg chain.

Entanglement and thermodynamics after a quantum quench in integrable systems

NASA Astrophysics Data System (ADS)

Alba, Vincenzo; Calabrese, Pasquale

2017-07-01

Entanglement and entropy are key concepts standing at the foundations of quantum and statistical mechanics. Recently, the study of quantum quenches revealed that these concepts are intricately intertwined. Although the unitary time evolution ensuing from a pure state maintains the system at zero entropy, local properties at long times are captured by a statistical ensemble with nonzero thermodynamic entropy, which is the entanglement accumulated during the dynamics. Therefore, understanding the entanglement evolution unveils how thermodynamics emerges in isolated systems. Alas, an exact computation of the entanglement dynamics was available so far only for noninteracting systems, whereas it was deemed unfeasible for interacting ones. Here, we show that the standard quasiparticle picture of the entanglement evolution, complemented with integrability-based knowledge of the steady state and its excitations, leads to a complete understanding of the entanglement dynamics in the space-time scaling limit. We thoroughly check our result for the paradigmatic Heisenberg chain.

Progress report for the CCT-WG5 high temperature fixed point research plan

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

Machin, G.; Woolliams, E. R.; Anhalt, K.

2013-09-11

An overview of the progress in High Temperature Fixed Point (HTFP) research conducted under the auspices of the CCT-WG5 research plan is reported. In brief highlights are: Provisional long term stability of HTFPs has been demonstrated. Optimum construction methods for HTFPs have been established and high quality HTFPs of Co-C, Pt-C and Re-C have been constructed for thermodynamic temperature assignment. The major sources of uncertainty in the assignment of thermodynamic temperature have been identified and quantified. The status of absolute radiometric temperature measurement has been quantified through the circulation of a set of HTFPs. The measurement campaign to assign lowmore » uncertainty thermodynamic temperatures to a selected set of HTFPs will begin in mid-2012. It is envisaged that this will be complete by 2015 leading to HTFPs becoming routine reference standards for radiometry and high temperature metrology.« less

Entanglement and thermodynamics after a quantum quench in integrable systems

PubMed Central

Alba, Vincenzo; Calabrese, Pasquale

2017-01-01

Entanglement and entropy are key concepts standing at the foundations of quantum and statistical mechanics. Recently, the study of quantum quenches revealed that these concepts are intricately intertwined. Although the unitary time evolution ensuing from a pure state maintains the system at zero entropy, local properties at long times are captured by a statistical ensemble with nonzero thermodynamic entropy, which is the entanglement accumulated during the dynamics. Therefore, understanding the entanglement evolution unveils how thermodynamics emerges in isolated systems. Alas, an exact computation of the entanglement dynamics was available so far only for noninteracting systems, whereas it was deemed unfeasible for interacting ones. Here, we show that the standard quasiparticle picture of the entanglement evolution, complemented with integrability-based knowledge of the steady state and its excitations, leads to a complete understanding of the entanglement dynamics in the space–time scaling limit. We thoroughly check our result for the paradigmatic Heisenberg chain. PMID:28698379

Thermodynamics and H2 Transfer in a Methanogenic, Syntrophic Community

PubMed Central

Hamilton, Joshua J.; Calixto Contreras, Montserrat; Reed, Jennifer L.

2015-01-01

Microorganisms in nature do not exist in isolation but rather interact with other species in their environment. Some microbes interact via syntrophic associations, in which the metabolic by-products of one species serve as nutrients for another. These associations sustain a variety of natural communities, including those involved in methanogenesis. In anaerobic syntrophic communities, energy is transferred from one species to another, either through direct contact and exchange of electrons, or through small molecule diffusion. Thermodynamics plays an important role in governing these interactions, as the oxidation reactions carried out by the first community member are only possible because degradation products are consumed by the second community member. This work presents the development and analysis of genome-scale network reconstructions of the bacterium Syntrophobacter fumaroxidans and the methanogenic archaeon Methanospirillum hungatei. The models were used to verify proposed mechanisms of ATP production within each species. We then identified additional constraints and the cellular objective function required to match experimental observations. The thermodynamic S. fumaroxidans model could not explain why S. fumaroxidans does not produce H2 in monoculture, indicating that current methods might not adequately estimate the thermodynamics, or that other cellular processes (e.g., regulation) play a role. We also developed a thermodynamic coculture model of the association between the organisms. The coculture model correctly predicted the exchange of both H2 and formate between the two species and suggested conditions under which H2 and formate produced by S. fumaroxidans would be fully consumed by M. hungatei. PMID:26147299

Effects of Anisotropy on Scalar Field Ghost Dark Energy and the Non-Equilibrium Thermodynamics in Fractal Cosmology

NASA Astrophysics Data System (ADS)

Najafi, A.; Hossienkhani, H.

2017-10-01

Since the fractal cosmology has been created in early universe, therefore their models were mostly isotropic. The majority of previous studies had been based on FRW universe, while in the early universe, the best model for describing fractal cosmology is actually the anisotropic universe. Therefore in this work, by assuming the anisotropic universe, the cosmological implications of ghost and generalized ghost dark energy models with dark matter in fractal cosmology has been discussed. Moreover, the different kinds of dark energy models such as quintessence and tachyon field, with the generalized ghost dark energy in fractal universe has been investigated. In addition, we have reconstructed the Hubble parameter, H, the energy density, ρ, the deceleration parameter, q, the equations of state parameter, {ω }{{}D}, for both ghost and generalized ghost dark energy models. This correspondence allows us to reconstruct the potential and the dynamics of a fractal canonical scalar field according to the evolution of generalized ghost dark energy density. Eventually, thermodynamics of the cosmological apparent horizon in fractal cosmology was investigated and the validity of the Generalized second law of thermodynamics (GSLT) have been examined in an anisotropic universe. The results show the influence of the anisotropy on the GSLT of thermodynamics in a fractal cosmology.

The effect of anisotropy on the thermodynamics of the interacting holographic dark energy model

NASA Astrophysics Data System (ADS)

Hossienkhani, H.; Jafari, A.; Fayaz, V.; Ramezani, A. H.

2018-02-01

By considering a holographic model for the dark energy in an anisotropic universe, the thermodynamics of a scheme of dark matter and dark energy interaction has been investigated. The results suggest that when holographic dark energy and dark matter evolve separately, each of them remains in thermodynamic equilibrium, therefore the interaction between them may be viewed as a stable thermal fluctuation that brings a logarithmic correction to the equilibrium entropy. Also the relation between the interaction term of the dark components and this thermal fluctuation has been obtained. Additionally, for a cosmological interaction as a free function, the anisotropy effects on the generalized second law of thermodynamics have been studied. By using the latest observational data on the holographic dark energy models as the unification of dark matter and dark energy, the observational constraints have been probed. To do this, we focus on observational determinations of the Hubble expansion rate H( z). Finally, we evaluate the anisotropy effects (although low) on various topics, such as the evolution of the statefinder diagnostic, the distance modulus and the spherical collapse from the holographic dark energy model and compare them with the results of the holographic dark energy of the Friedmann-Robertson-Walker and Λ CDM models.

Thermodynamically Constrained Averaging Theory (TCAT) Two-Phase Flow Model: Derivation, Closure, and Simulation Results

NASA Astrophysics Data System (ADS)

Weigand, T. M.; Miller, C. T.; Dye, A. L.; Gray, W. G.; McClure, J. E.; Rybak, I.

2015-12-01

The thermodynamically constrained averaging theory (TCAT) has been usedto formulate general classes of porous medium models, including newmodels for two-fluid-phase flow. The TCAT approach provides advantagesthat include a firm connection between the microscale, or pore scale,and the macroscale; a thermodynamically consistent basis; explicitinclusion of factors such as interfacial areas, contact angles,interfacial tension, and curvatures; and dynamics of interface movementand relaxation to an equilibrium state. In order to render the TCATmodel solvable, certain closure relations are needed to relate fluidpressure, interfacial areas, curvatures, and relaxation rates. In thiswork, we formulate and solve a TCAT-based two-fluid-phase flow model. We detail the formulation of the model, which is a specific instancefrom a hierarchy of two-fluid-phase flow models that emerge from thetheory. We show the closure problem that must be solved. Using recentresults from high-resolution microscale simulations, we advance a set ofclosure relations that produce a closed model. Lastly, we solve the model using a locally conservative numerical scheme and compare the TCAT model to the traditional model.

Thermodynamics of information processing based on enzyme kinetics: An exactly solvable model of an information pump

NASA Astrophysics Data System (ADS)

Cao, Yuansheng; Gong, Zongping; Quan, H. T.

2015-06-01

Motivated by the recent proposed models of the information engine [Proc. Natl. Acad. Sci. USA 109, 11641 (2012), 10.1073/pnas.1204263109] and the information refrigerator [Phys. Rev. Lett. 111, 030602 (2013), 10.1103/PhysRevLett.111.030602], we propose a minimal model of the information pump and the information eraser based on enzyme kinetics. This device can either pump molecules against the chemical potential gradient by consuming the information to be encoded in the bit stream or (partially) erase the information initially encoded in the bit stream by consuming the Gibbs free energy. The dynamics of this model is solved exactly, and the "phase diagram" of the operation regimes is determined. The efficiency and the power of the information machine is analyzed. The validity of the second law of thermodynamics within our model is clarified. Our model offers a simple paradigm for the investigating of the thermodynamics of information processing involving the chemical potential in small systems.

Modelling the spreading rate of controlled communicable epidemics through an entropy-based thermodynamic model

NASA Astrophysics Data System (ADS)

Wang, WenBin; Wu, ZiNiu; Wang, ChunFeng; Hu, RuiFeng

2013-11-01

A model based on a thermodynamic approach is proposed for predicting the dynamics of communicable epidemics assumed to be governed by controlling efforts of multiple scales so that an entropy is associated with the system. All the epidemic details are factored into a single and time-dependent coefficient, the functional form of this coefficient is found through four constraints, including notably the existence of an inflexion point and a maximum. The model is solved to give a log-normal distribution for the spread rate, for which a Shannon entropy can be defined. The only parameter, that characterizes the width of the distribution function, is uniquely determined through maximizing the rate of entropy production. This entropy-based thermodynamic (EBT) model predicts the number of hospitalized cases with a reasonable accuracy for SARS in the year 2003. This EBT model can be of use for potential epidemics such as avian influenza and H7N9 in China.

Simulation of Nonisothermal Consolidation of Saturated Soils Based on a Thermodynamic Model

PubMed Central

Cheng, Xiaohui

2013-01-01

Based on the nonequilibrium thermodynamics, a thermo-hydro-mechanical coupling model for saturated soils is established, including a constitutive model without such concepts as yield surface and flow rule. An elastic potential energy density function is defined to derive a hyperelastic relation among the effective stress, the elastic strain, and the dry density. The classical linear non-equilibrium thermodynamic theory is employed to quantitatively describe the unrecoverable energy processes like the nonelastic deformation development in materials by the concepts of dissipative force and dissipative flow. In particular the granular fluctuation, which represents the kinetic energy fluctuation and elastic potential energy fluctuation at particulate scale caused by the irregular mutual movement between particles, is introduced in the model and described by the concept of granular entropy. Using this model, the nonisothermal consolidation of saturated clays under cyclic thermal loadings is simulated in this paper to validate the model. The results show that the nonisothermal consolidation is heavily OCR dependent and unrecoverable. PMID:23983623

Simulation of nonisothermal consolidation of saturated soils based on a thermodynamic model.

PubMed

Zhang, Zhichao; Cheng, Xiaohui

2013-01-01

Based on the nonequilibrium thermodynamics, a thermo-hydro-mechanical coupling model for saturated soils is established, including a constitutive model without such concepts as yield surface and flow rule. An elastic potential energy density function is defined to derive a hyperelastic relation among the effective stress, the elastic strain, and the dry density. The classical linear non-equilibrium thermodynamic theory is employed to quantitatively describe the unrecoverable energy processes like the nonelastic deformation development in materials by the concepts of dissipative force and dissipative flow. In particular the granular fluctuation, which represents the kinetic energy fluctuation and elastic potential energy fluctuation at particulate scale caused by the irregular mutual movement between particles, is introduced in the model and described by the concept of granular entropy. Using this model, the nonisothermal consolidation of saturated clays under cyclic thermal loadings is simulated in this paper to validate the model. The results show that the nonisothermal consolidation is heavily OCR dependent and unrecoverable.

Continuity and boundary conditions in thermodynamics: From Carnot's efficiency to efficiencies at maximum power

NASA Astrophysics Data System (ADS)

Ouerdane, H.; Apertet, Y.; Goupil, C.; Lecoeur, Ph.

2015-07-01

Classical equilibrium thermodynamics is a theory of principles, which was built from empirical knowledge and debates on the nature and the use of heat as a means to produce motive power. By the beginning of the 20th century, the principles of thermodynamics were summarized into the so-called four laws, which were, as it turns out, definitive negative answers to the doomed quests for perpetual motion machines. As a matter of fact, one result of Sadi Carnot's work was precisely that the heat-to-work conversion process is fundamentally limited; as such, it is considered as a first version of the second law of thermodynamics. Although it was derived from Carnot's unrealistic model, the upper bound on the thermodynamic conversion efficiency, known as the Carnot efficiency, became a paradigm as the next target after the failure of the perpetual motion ideal. In the 1950's, Jacques Yvon published a conference paper containing the necessary ingredients for a new class of models, and even a formula, not so different from that of Carnot's efficiency, which later would become the new efficiency reference. Yvon's first analysis of a model of engine producing power, connected to heat source and sink through heat exchangers, went fairly unnoticed for twenty years, until Frank Curzon and Boye Ahlborn published their pedagogical paper about the effect of finite heat transfer on output power limitation and their derivation of the efficiency at maximum power, now mostly known as the Curzon-Ahlborn (CA) efficiency. The notion of finite rate explicitly introduced time in thermodynamics, and its significance cannot be overlooked as shown by the wealth of works devoted to what is now known as finite-time thermodynamics since the end of the 1970's. The favorable comparison of the CA efficiency to actual values led many to consider it as a universal upper bound for real heat engines, but things are not so straightforward that a simple formula may account for a variety of situations. The object of the article is thus to cover some of the milestones of thermodynamics, and show through the illustrative case of thermoelectric generators, our model heat engine, that the shift from Carnot's efficiency to efficienc ies at maximum power explains itself naturally as one considers continuity and boundary conditions carefully; indeed, as an adaptation of Friedrich Nietzche's quote, we may say that the thermodynamic demon is in the details. This article is supplemented with comments by J.M.R. Parrondo and a final reply by the authors.

The modelling routes for the chemical vapour deposition process: application to Si 1- xGe x deposition

NASA Astrophysics Data System (ADS)

Pons, M.; Bernard, C.; Rouch, H.; Madar, R.

1995-10-01

The purpose of this article is to present the modelling routes for the chemical vapour deposition process with a special emphasis on mass transport models with near local thermochemical equilibrium imposed in the gas-phase and at the deposition surface. The theoretical problems arising from the linking of the two selected approaches, thermodynamics and mass transport, are shown and a solution procedure is proposed. As an illustration, selected results of thermodynamic and mass transport analysis and of the coupled approach showed that, for the deposition of Si 1- xGe x solid solution at 1300 K (system SiGeClHAr), the thermodynamic heterogeneous stability of the reactive gases and the thermal diffusion led to the germanium depletion of the deposit.

Generalized thermodynamic relations for a system experiencing heat and mass diffusion in the far-from-equilibrium realm based on steepest entropy ascent.

PubMed

Li, Guanchen; von Spakovsky, Michael R

2016-09-01

This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the nonmutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micromechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and near-equilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single-particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in the near-equilibrium realm.

Thermodynamic Modeling and Analysis of Human Stress Response

NASA Technical Reports Server (NTRS)

Boregowda, S. C.; Tiwari, S. N.

1999-01-01

A novel approach based on the second law of thermodynamics is developed to investigate the psychophysiology and quantify human stress level. Two types of stresses (thermal and mental) are examined. A Unified Stress Response Theory (USRT) is developed under the new proposed field of study called Engineering Psychophysiology. The USRT is used to investigate both thermal and mental stresses from a holistic (human body as a whole) and thermodynamic viewpoint. The original concepts and definitions are established as postulates which form the basis for thermodynamic approach to quantify human stress level. An Objective Thermal Stress Index (OTSI) is developed by applying the second law of thermodynamics to the human thermal system to quantify thermal stress or dis- comfort in the human body. The human thermal model based on finite element method is implemented. It is utilized as a "Computational Environmental Chamber" to conduct series of simulations to examine the human thermal stress responses under different environmental conditions. An innovative hybrid technique is developed to analyze human thermal behavior based on series of human-environment interaction simulations. Continuous monitoring of thermal stress is demonstrated with the help of OTSI. It is well established that the human thermal system obeys the second law of thermodynamics. Further, the OTSI is validated against the experimental data. Regarding mental stress, an Objective Mental Stress Index (OMSI) is developed by applying the Maxwell relations of thermodynamics to the combined thermal and cardiovascular system in the human body. The OMSI is utilized to demonstrate the technique of monitoring mental stress continuously and is validated with the help of series of experimental studies. Although the OMSI indicates the level of mental stress, it provides a strong thermodynamic and mathematical relationship between activities of thermal and cardiovascular systems of the human body.

Thermodynamic Behavior Research Analysis of Twin-roll Casting Lead Alloy Strip Process

NASA Astrophysics Data System (ADS)

Jiang, Chengcan; Rui, Yannian

2017-03-01

The thermodynamic behavior of twin-roll casting (TRC) lead alloy strip process directly affects the forming of the lead strip, the quality of the lead strip and the production efficiency. However, there is little research on the thermodynamics of lead alloy strip at home and abroad. The TRC lead process is studied in four parameters: the pouring temperature of molten lead, the depth of molten pool, the roll casting speed, and the rolling thickness of continuous casting. Firstly, the thermodynamic model for TRC lead process is built. Secondly, the thermodynamic behavior of the TRC process is simulated with the use of Fluent. Through the thermodynamics research and analysis, the process parameters of cast rolling lead strip can be obtained: the pouring temperature of molten lead: 360-400 °C, the depth of molten pool: 250-300 mm, the roll casting speed: 2.5-3 m/min, the rolling thickness: 8-9 mm. Based on the above process parameters, the optimal parameters(the pouring temperature of molten lead: 375-390 °C, the depth of molten pool: 285-300 mm, the roll casting speed: 2.75-3 m/min, the rolling thickness: 8.5-9 mm) can be gained with the use of the orthogonal experiment. Finally, the engineering test of TRC lead alloy strip is carried out and the test proves the thermodynamic model is scientific, necessary and correct. In this paper, a detailed study on the thermodynamic behavior of lead alloy strip is carried out and the process parameters of lead strip forming are obtained through the research, which provide an effective theoretical guide for TRC lead alloy strip process.

Chemical Thermodynamics of Aqueous Atmospheric Aerosols: Modeling and Microfluidic Measurements

NASA Astrophysics Data System (ADS)

Nandy, L.; Dutcher, C. S.

2017-12-01

Accurate predictions of gas-liquid-solid equilibrium phase partitioning of atmospheric aerosols by thermodynamic modeling and measurements is critical for determining particle composition and internal structure at conditions relevant to the atmosphere. Organic acids that originate from biomass burning, and direct biogenic emission make up a significant fraction of the organic mass in atmospheric aerosol particles. In addition, inorganic compounds like ammonium sulfate and sea salt also exist in atmospheric aerosols, that results in a mixture of single, double or triple charged ions, and non-dissociated and partially dissociated organic acids. Statistical mechanics based on a multilayer adsorption isotherm model can be applied to these complex aqueous environments for predictions of thermodynamic properties. In this work, thermodynamic analytic predictive models are developed for multicomponent aqueous solutions (consisting of partially dissociating organic and inorganic acids, fully dissociating symmetric and asymmetric electrolytes, and neutral organic compounds) over the entire relative humidity range, that represent a significant advancement towards a fully predictive model. The model is also developed at varied temperatures for electrolytes and organic compounds the data for which are available at different temperatures. In addition to the modeling approach, water loss of multicomponent aerosol particles is measured by microfluidic experiments to parameterize and validate the model. In the experimental microfluidic measurements, atmospheric aerosol droplet chemical mimics (organic acids and secondary organic aerosol (SOA) samples) are generated in microfluidic channels and stored and imaged in passive traps until dehydration to study the influence of relative humidity and water loss on phase behavior.

Modeling of dielectric properties of aqueous salt solutions with an equation of state.

PubMed

Maribo-Mogensen, Bjørn; Kontogeorgis, Georgios M; Thomsen, Kaj

2013-09-12

The static permittivity is the most important physical property for thermodynamic models that account for the electrostatic interactions between ions. The measured static permittivity in mixtures containing electrolytes is reduced due to kinetic depolarization and reorientation of the dipoles in the electrical field surrounding ions. Kinetic depolarization may explain 25-75% of the observed decrease in the permittivity of solutions containing salts, but since this is a dynamic property, this effect should not be included in the thermodynamic modeling of electrolytes. Kinetic depolarization has, however, been ignored in relation to thermodynamic modeling, and authors have either neglected the effect of salts on permittivity or used empirical correlations fitted to the measured static permittivity, leading to an overestimation of the reduction in the thermodynamic static permittivity. We present a new methodology for obtaining the static permittivity over wide ranges of temperatures, pressures, and compositions for use within an equation of state for mixed solvents containing salts. The static permittivity is calculated from a new extension of the framework developed by Onsager, Kirkwood, and Fröhlich to associating mixtures. Wertheim's association model as formulated in the statistical associating fluid theory is used to account for hydrogen-bonding molecules and ion-solvent association. Finally, we compare the Debye-Hückel Helmholtz energy obtained using an empirical model with the new physical model and show that the empirical models may introduce unphysical behavior in the equation of state.

Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

NASA Astrophysics Data System (ADS)

Li, Qingzhu; Chai, Liyuan; Yang, Zhihui; Wang, Qingwei

2009-01-01

Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy ( Ea) of Pb(II) adsorption was determined as 12.33 kJ mol -1 according to the Arrhenius equation. Various thermodynamic parameters such as Δ Gads, Δ Hads and Δ Sads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.

A thermodynamic approach to obtain materials properties for engineering applications

NASA Technical Reports Server (NTRS)

Chang, Y. Austin

1993-01-01

With the ever increases in the capabilities of computers for numerical computations, we are on the verge of using these tools to model manufacturing processes for improving the efficiency of these processes as well as the quality of the products. One such process is casting for the production of metals. However, in order to model metal casting processes in a meaningful way it is essential to have the basic properties of these materials in their molten state, solid state as well as in the mixed state of solid and liquid. Some of the properties needed may be considered as intrinsic such as the density, heat capacity or enthalpy of freezing of a pure metal, while others are not. For instance, the enthalpy of solidification of an alloy is not a defined thermodynamic quantity. Its value depends on the micro-segregation of the phases during the course of solidification. The objective of the present study is to present a thermodynamic approach to obtain some of the intrinsic properties and combining thermodynamics with kinetic models to estimate such quantities as the enthalpy of solidification of an alloy.

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

Khodam-Mohammadi, A.; Monshizadeh, M.

We give a review of the existence of Taub-NUT/bolt solutions in Einstein Gauss-Bonnet gravity with the parameter {alpha} in six dimensions. Although the spacetime with base space S{sup 2}xS{sup 2} has a curvature singularity at r=N, which does not admit NUT solutions, we may proceed with the same computations as in the CP{sup 2} case. The investigation of thermodynamics of NUT/bolt solutions in six dimensions is carried out. We compute the finite action, mass, entropy, and temperature of the black hole. Then the validity of the first law of thermodynamics is demonstrated. It is shown that in NUT solutions allmore » thermodynamic quantities for both base spaces are related to each other by substituting {alpha}{sup CP{sup k}}=[(k+1)/k]{alpha}{sup S{sup 2}}{sup xS{sup 2}}{sup x...S{sub k}{sup 2}}. So, no further information is given by investigating NUT solutions in the S{sup 2}xS{sup 2} case. This relation is not true for bolt solutions. A generalization of the thermodynamics of black holes to arbitrary even dimensions is made using a new method based on the Gibbs-Duhem relation and Gibbs free energy for NUT solutions. According to this method, the finite action in Einstein Gauss-Bonnet is obtained by considering the generalized finite action in Einstein gravity with an additional term as a function of {alpha}. Stability analysis is done by investigating the heat capacity and entropy in the allowed range of {alpha}, {lambda}, and N. For NUT solutions in d dimensions, there exists a stable phase at a narrow range of {alpha}. In six-dimensional bolt solutions, the metric is completely stable for B=S{sup 2}xS{sup 2} and is completely unstable for the B=CP{sup 2} case.« less

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

NASA Astrophysics Data System (ADS)

Blanc, Philippe; Gailhanou, Hélène; Rogez, Jacques; Mikaelian, Georges; Kawaji, Hitoshi; Warmont, Fabienne; Gaboreau, Stéphane; Grangeon, Sylvain; Grenèche, Jean-Marc; Vieillard, Philippe; Fialips, Claire I.; Giffaut, Eric; Gaucher, Eric C.; Claret, F.

2014-09-01

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al0.975FeIII0.182FeII1.422Mg0.157Li0.035Mn0.002)(Si1.332Al0.668)O5(OH)4] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si2.633Al1.367)(Al1.116FeIII0.215Mg2.952FeII1.712Mn0.012Ca0.011)O10(OH)8]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738-4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.

Thermodynamic assessment of the U–La–O system

DOE PAGES

McMurray, J. W.; Shin, D.; Besmann, T. M.

2014-10-03

The CALPHAD methodology was used to develop a thermodynamic assessment of the U-La-O system. The solid solution and liquid phases are described with the compound energy formalism and the partially ionic two-sublattice liquid model respectively. A density functional theory (DFT) calculation for the lattice stability of the fictive lanthanum oxide fluorite structure compound is used to determine the Gibbs energies for the La containing end-members in the CEF model for U 1-yLa yO 2+x. Experimental thermodynamic and phase equilibria data were then used in optimizations to develop representations of the phases in the system that can be extended to includemore » other actinide and fission products to develop multi-component models. The models that comprise this assessment very well reproduce experimentally determined oxygen potentials and the observed phase relations for the U-La-O system.« less

Numerical Predictions of Damage and Failure in Carbon Fiber Reinforced Laminates Using a Thermodynamically-Based Work Potential Theory

NASA Technical Reports Server (NTRS)

Pineda, Evan Jorge; Waas, Anthony M.

2013-01-01

A thermodynamically-based work potential theory for modeling progressive damage and failure in fiber-reinforced laminates is presented. The current, multiple-internal state variable (ISV) formulation, referred to as enhanced Schapery theory (EST), utilizes separate ISVs for modeling the effects of damage and failure. Consistent characteristic lengths are introduced into the formulation to govern the evolution of the failure ISVs. Using the stationarity of the total work potential with respect to each ISV, a set of thermodynamically consistent evolution equations for the ISVs are derived. The theory is implemented into a commercial finite element code. The model is verified against experimental results from two laminated, T800/3900-2 panels containing a central notch and different fiber-orientation stacking sequences. Global load versus displacement, global load versus local strain gage data, and macroscopic failure paths obtained from the models are compared against the experimental results.

Modeling of outgassing and matrix decomposition in carbon-phenolic composites

NASA Technical Reports Server (NTRS)

Mcmanus, Hugh L.

1994-01-01

Work done in the period Jan. - June 1994 is summarized. Two threads of research have been followed. First, the thermodynamics approach was used to model the chemical and mechanical responses of composites exposed to high temperatures. The thermodynamics approach lends itself easily to the usage of variational principles. This thermodynamic-variational approach has been applied to the transpiration cooling problem. The second thread is the development of a better algorithm to solve the governing equations resulting from the modeling. Explicit finite difference method is explored for solving the governing nonlinear, partial differential equations. The method allows detailed material models to be included and solution on massively parallel supercomputers. To demonstrate the feasibility of the explicit scheme in solving nonlinear partial differential equations, a transpiration cooling problem was solved. Some interesting transient behaviors were captured such as stress waves and small spatial oscillations of transient pressure distribution.

Use of Thermodynamic Modeling for Selection of Electrolyte for Electrorefining of Magnesium from Aluminum Alloy Melts

NASA Astrophysics Data System (ADS)

Gesing, Adam J.; Das, Subodh K.

2017-02-01

With United States Department of Energy Advanced Research Project Agency funding, experimental proof-of-concept was demonstrated for RE-12TM electrorefining process of extraction of desired amount of Mg from recycled scrap secondary Al molten alloys. The key enabling technology for this process was the selection of the suitable electrolyte composition and operating temperature. The selection was made using the FactSage thermodynamic modeling software and the light metal, molten salt, and oxide thermodynamic databases. Modeling allowed prediction of the chemical equilibria, impurity contents in both anode and cathode products, and in the electrolyte. FactSage also provided data on the physical properties of the electrolyte and the molten metal phases including electrical conductivity and density of the molten phases. Further modeling permitted selection of electrode and cell construction materials chemically compatible with the combination of molten metals and the electrolyte.

Thermodynamics and emergent universe

NASA Astrophysics Data System (ADS)

Ghosh, Saumya; Gangopadhyay, Sunandan

2017-05-01

We show that in the isentropic scenario, the first-order thermodynamical particle creation model gives an emergent universe solution even when the chemical potential is nonzero. However, there exists no emergent universe scenario in the second-order non-equilibrium theory for the particle creation model. We then point out a correspondence between the particle creation model with barotropic equation of state and the equation of state giving rise to an emergent universe without particle creation in spatially flat FRW cosmology.

Quantum information processing by a continuous Maxwell demon

NASA Astrophysics Data System (ADS)

Stevens, Josey; Deffner, Sebastian

Quantum computing is believed to be fundamentally superior to classical computing; however quantifying the specific thermodynamic advantage has been elusive. Experimentally motivated, we generalize previous minimal models of discrete demons to continuous state space. Analyzing our model allows one to quantify the thermodynamic resources necessary to process quantum information. By further invoking the semi-classical limit we compare the quantum demon with its classical analogue. Finally, this model also serves as a starting point to study open quantum systems.

Thermodynamic ocean-atmosphere Coupling and the Predictability of Nordeste rainfall

NASA Astrophysics Data System (ADS)

Chang, P.; Saravanan, R.; Giannini, A.

2003-04-01

The interannual variability of rainfall in the northeastern region of Brazil, or Nordeste, is known to be very strongly correlated with sea surface temperature (SST) variability, of Atlantic and Pacific origin. For this reason the potential predictability of Nordeste rainfall is high. The current generation of state-of-the-art atmospheric models can replicate the observed rainfall variability with high skill when forced with the observed record of SST variability. The correlation between observed and modeled indices of Nordeste rainfall, in the AMIP-style integrations with two such models (NSIPP and CCM3) analyzed here, is of the order of 0.8, i.e. the models explain about 2/3 of the observed variability. Assuming that thermodynamic, ocean-atmosphere heat exchange plays the dominant role in tropical Atlantic SST variability on the seasonal to interannual time scale, we analyze its role in Nordeste rainfall predictability using an atmospheric general circulation model coupled to a slab ocean model. Predictability experiments initialized with observed December SST show that thermodynamic coupling plays a significant role in enhancing the persistence of SST anomalies, both in the tropical Pacific and in the tropical Atlantic. We show that thermodynamic coupling is sufficient to provide fairly accurate forecasts of tropical Atlantic SST in the boreal spring that are significantly better than the persistence forecasts. The consequences for the prediction of Nordeste rainfall are analyzed.

Molecular dynamics studies of CaAl 2Si 2O 8 liquid. Part II: Equation of state and a thermodynamic model

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.; Nevins, Dean; Cutler, Ian; Spera, Frank J.

2009-11-01

A thermodynamic model and equation of state (EOS) is developed from the molecular dynamics simulation experiments of Spera et al. (2009) for CaAl 2Si 2O 8 liquid over the temperature range 3500-6000 K and pressure interval 0-125 GPa. The model is constructed utilizing the isothermal Universal EOS of Vinet et al. (1986) combined with an expression for the temperature-dependence of the internal energy derived from density functional theory ( Rosenfeld and Tarazona, 1998). It is demonstrated that this model is more successful at reproducing the data than the temperature-dependent Universal EOS ( Vinet et al., 1987) or the volume-explicit EOS of Ghiorso (2004a). Distinct parameterizations are required to model low (<20 GPa) and high (>20 GPa) pressure regimes. This result is ascribed to the affect of liquid structure on macroscopic thermodynamic properties, specifically the interdependence of average cation-oxygen coordination number on the bulk modulus. The thermodynamic transition between the high- and low-pressure parameterizations is modeled as second order, although the nature of the transition is open to question and may well be first order or lambda-like in character. Analysis of the thermodynamic model reveals a predicted region of liquid-liquid un-mixing at low-temperatures (<1624 K) and pressures (<1.257 GPa). These pressure-temperature conditions are above the glass transition temperature but within the metastable liquid region. They represent the highest temperatures yet suggested for liquid-liquid un-mixing in a silicate bulk composition. A shock wave Hugoniot curve is calculated for comparison with the experimental data of Rigden et al. (1989) and of Asimow and Ahrens (2008). The comparison suggests that the model developed in this paper underestimates the density of the liquid by roughly 10% at pressures greater than ˜20 GPa.

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.

Exact infinite-time statistics of the Loschmidt echo for a quantum quench.

PubMed

Campos Venuti, Lorenzo; Jacobson, N Tobias; Santra, Siddhartha; Zanardi, Paolo

2011-07-01

The equilibration dynamics of a closed quantum system is encoded in the long-time distribution function of generic observables. In this Letter we consider the Loschmidt echo generalized to finite temperature, and show that we can obtain an exact expression for its long-time distribution for a closed system described by a quantum XY chain following a sudden quench. In the thermodynamic limit the logarithm of the Loschmidt echo becomes normally distributed, whereas for small quenches in the opposite, quasicritical regime, the distribution function acquires a universal double-peaked form indicating poor equilibration. These findings, obtained by a central limit theorem-type result, extend to completely general models in the small-quench regime.

How to Decide on Modeling Details: Risk and Benefit Assessment.

PubMed

Özilgen, Mustafa

Mathematical models based on thermodynamic, kinetic, heat, and mass transfer analysis are central to this chapter. Microbial growth, death, enzyme inactivation models, and the modeling of material properties, including those pertinent to conduction and convection heating, mass transfer, such as diffusion and convective mass transfer, and thermodynamic properties, such as specific heat, enthalpy, and Gibbs free energy of formation and specific chemical exergy are also needed in this task. The origins, simplifying assumptions, and uses of model equations are discussed in this chapter, together with their benefits. The simplified forms of these models are sometimes referred to as "laws," such as "the first law of thermodynamics" or "Fick's second law." Starting to modeling a study with such "laws" without considering the conditions under which they are valid runs the risk of ending up with erronous conclusions. On the other hand, models started with fundamental concepts and simplified with appropriate considerations may offer explanations for the phenomena which may not be obtained just with measurements or unprocessed experimental data. The discussion presented here is strengthened with case studies and references to the literature.

Multiensemble Markov models of molecular thermodynamics and kinetics.

PubMed

Wu, Hao; Paul, Fabian; Wehmeyer, Christoph; Noé, Frank

2016-06-07

We introduce the general transition-based reweighting analysis method (TRAM), a statistically optimal approach to integrate both unbiased and biased molecular dynamics simulations, such as umbrella sampling or replica exchange. TRAM estimates a multiensemble Markov model (MEMM) with full thermodynamic and kinetic information at all ensembles. The approach combines the benefits of Markov state models-clustering of high-dimensional spaces and modeling of complex many-state systems-with those of the multistate Bennett acceptance ratio of exploiting biased or high-temperature ensembles to accelerate rare-event sampling. TRAM does not depend on any rate model in addition to the widely used Markov state model approximation, but uses only fundamental relations such as detailed balance and binless reweighting of configurations between ensembles. Previous methods, including the multistate Bennett acceptance ratio, discrete TRAM, and Markov state models are special cases and can be derived from the TRAM equations. TRAM is demonstrated by efficiently computing MEMMs in cases where other estimators break down, including the full thermodynamics and rare-event kinetics from high-dimensional simulation data of an all-atom protein-ligand binding model.

Fundamental molecules of life are pigments which arose and co-evolved as a response to the thermodynamic imperative of dissipating the prevailing solar spectrum

NASA Astrophysics Data System (ADS)

Michaelian, K.; Simeonov, A.

2015-08-01

The driving force behind the origin and evolution of life has been the thermodynamic imperative of increasing the entropy production of the biosphere through increasing the global solar photon dissipation rate. In the upper atmosphere of today, oxygen and ozone derived from life processes are performing the short-wavelength UV-C and UV-B dissipation. On Earth's surface, water and organic pigments in water facilitate the near-UV and visible photon dissipation. The first organic pigments probably formed, absorbed, and dissipated at those photochemically active wavelengths in the UV-C and UV-B that could have reached Earth's surface during the Archean. Proliferation of these pigments can be understood as an autocatalytic photochemical process obeying non-equilibrium thermodynamic directives related to increasing solar photon dissipation rate. Under these directives, organic pigments would have evolved over time to increase the global photon dissipation rate by (1) increasing the ratio of their effective photon cross sections to their physical size, (2) decreasing their electronic excited state lifetimes, (3) quenching radiative de-excitation channels (e.g., fluorescence), (4) covering ever more completely the prevailing solar spectrum, and (5) proliferating and dispersing to cover an ever greater surface area of Earth. From knowledge of the evolution of the spectrum of G-type stars, and considering the most probable history of the transparency of Earth's atmosphere, we construct the most probable Earth surface solar spectrum as a function of time and compare this with the history of molecular absorption maxima obtained from the available data in the literature. This comparison supports the conjecture that many fundamental molecules of life are pigments which arose, proliferated, and co-evolved as a response to dissipating the solar spectrum, supports the thermodynamic dissipation theory for the origin of life, constrains models for Earth's early atmosphere, and sheds some new light on the origin of photosynthesis.

A molecular dynamic investigation for shock induced phase transition of water

NASA Astrophysics Data System (ADS)

Mitra, Nilanjan; Neogi, Anupam

2015-06-01

Atomistic equilibrium molecular dynamics (EMD) was carried out to investigate shock induced phase transition of bulk liquid water. Multi-scale shock technique (MSST) was utilized to investigate low (US = 2 . 5km /s) to strong (US = 6 . 5km /s) intensity shock response on an extended flexible three point model up to 100 ns. The thermodynamic pathway of phase transition from liquid water to ice VII was investigated using temporal variation of thermodynamic state variables, power spectrum analyses of O-H bond vibration along with temporal evolution of pair correlation function between O-O, O-H and H-H atoms. Static structure factor along with pair-distribution function extended up to 20 Å was calculated and compared against the ideal ice VII to get information regarding long range ordering. Bragg reflection at different crystal planes were evaluated to investigate percentage of crystallinity of the shocked sample. Specific questions answered in this work involves: What is the exact time frame after the passage of shock at certain intensity in which nucleation of solid phase can be observed? Is it a complete or partial phase transition? Are external nucleators essential for this transformation? What is the percentage of crystallinity of the nucleated phase?

SIMPLE estimate of the free energy change due to aliphatic mutations: superior predictions based on first principles.

PubMed

Bueno, Marta; Camacho, Carlos J; Sancho, Javier

2007-09-01

The bioinformatics revolution of the last decade has been instrumental in the development of empirical potentials to quantitatively estimate protein interactions for modeling and design. Although computationally efficient, these potentials hide most of the relevant thermodynamics in 5-to-40 parameters that are fitted against a large experimental database. Here, we revisit this longstanding problem and show that a careful consideration of the change in hydrophobicity, electrostatics, and configurational entropy between the folded and unfolded state of aliphatic point mutations predicts 20-30% less false positives and yields more accurate predictions than any published empirical energy function. This significant improvement is achieved with essentially no free parameters, validating past theoretical and experimental efforts to understand the thermodynamics of protein folding. Our first principle analysis strongly suggests that both the solute-solute van der Waals interactions in the folded state and the electrostatics free energy change of exposed aliphatic mutations are almost completely compensated by similar interactions operating in the unfolded ensemble. Not surprisingly, the problem of properly accounting for the solvent contribution to the free energy of polar and charged group mutations, as well as of mutations that disrupt the protein backbone remains open. 2007 Wiley-Liss, Inc.

Thermodynamic wetness loss calculation in nozzle and turbine cascade: nucleating steam flow

NASA Astrophysics Data System (ADS)

Joseph, Joby; Subramanian, Sathyanarayanan; Vigney, K.; Prasad, B. V. S. S. S.; Biswas, D.

2017-11-01

Rapid expansion of steam in turbines and nozzles cause condensation. The formation of liquid droplets due to condensation results in wetness losses, which include aerodynamic losses (due to friction between liquid droplets and the vapour), thermodynamic losses (due to irreversible latent heat addition), and braking losses (due to the impact of liquid droplets on the turbine blade). In this study, a numerical investigation of the thermodynamic loss in a nucleating steam flow is performed. The thermodynamic loss is calculated using the change in entropy due to condensation. The effect of different operating conditions on the thermodynamic loss is estimated for a nozzle and turbine cascade in a nucleating flow. The non-equilibrium condensation in high-speed steam flows is modelled using Eulerian-Eulerian approach.

Exergy parametric study of carbon monoxide oxidation in moist air

NASA Astrophysics Data System (ADS)

Souidi, Ferhat; Benmalek, Toufik; Yesaad, Billel; Baik, Mouloud

2015-12-01

This study aims to analyze the oxidation of carbon monoxide in moist air from the second thermodynamic law aspect. A mathematical model of laminar premixed flame in a stagnation point flow has been achieved by numerical solution of the boundary layer equation using a self-made code. The chemical kinetic mechanism for flameless combustion of fuel, which is a mixture of carbon monoxide, oxygen, and water vapor, is modeled by 34 elementary reactions that incorporate (09) nine chemical species: CO, O, CO2, O2, H2O, H, H2, HO2, and OH. The salient point is that for all the parameters we considered, the exergy of the process is completely destroyed by irreversibilities. From the chemical viewpoint, the OH radical plays an essential role in CO oxidation. This latter point has already been mentioned by previous investigators.

Thermodynamics of the adsorption of flexible polymers on nanowires

DOE PAGES

Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

2015-03-09

Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached tomore » or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. In conclusion, the classification of the transitions is performed by microcanonical inflection-point analysis.« less

Growth Control and Disease Mechanisms in Computational Embryogeny

NASA Technical Reports Server (NTRS)

Shapiro, Andrew A.; Yogev, Or; Antonsson, Erik K.

2008-01-01

This paper presents novel approach to applying growth control and diseases mechanisms in computational embryogeny. Our method, which mimics fundamental processes from biology, enables individuals to reach maturity in a controlled process through a stochastic environment. Three different mechanisms were implemented; disease mechanisms, gene suppression, and thermodynamic balancing. This approach was integrated as part of a structural evolutionary model. The model evolved continuum 3-D structures which support an external load. By using these mechanisms we were able to evolve individuals that reached a fixed size limit through the growth process. The growth process was an integral part of the complete development process. The size of the individuals was determined purely by the evolutionary process where different individuals matured to different sizes. Individuals which evolved with these characteristics have been found to be very robust for supporting a wide range of external loads.

Solute Nucleation and Growth in Supercritical Fluid Mixtures

NASA Technical Reports Server (NTRS)

Smedley, Gregory T.; Wilemski, Gerald; Rawlins, W. Terry; Joshi, Prakash; Oakes, David B.; Durgin, William W.

1996-01-01

This research effort is directed toward two primary scientific objectives: (1) to determine the gravitational effect on the measurement of nucleation and growth rates near a critical point and (2) to investigate the nucleation process in supercritical fluids to aid in the evaluation and development of existing theoretical models and practical applications. A nucleation pulse method will be employed for this investigation using a rapid expansion to a supersaturated state that is maintained for approximately 1 ms followed by a rapid recompression to a less supersaturated state that effectively terminates nucleation while permitting growth to continue. Nucleation, which occurs during the initial supersaturated state, is decoupled from growth by producing rapid pressure changes. Thermodynamic analysis, condensation modeling, apparatus design, and optical diagnostic design necessary for the initiation of a theoretical and experimental investigation of naphthalene nucleation from supercritical CO2 have been completed.

Self-consistent quantum kinetic theory of diatomic molecule formation

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

Forrey, Robert C.

2015-07-14

A quantum kinetic theory of molecule formation is presented which includes three-body recombination and radiative association for a thermodynamically closed system which may or may not exchange energy with its surrounding at a constant temperature. The theory uses a Sturmian representation of a two-body continuum to achieve a steady-state solution of a governing master equation which is self-consistent in the sense that detailed balance between all bound and unbound states is rigorously enforced. The role of quasibound states in catalyzing the molecule formation is analyzed in complete detail. The theory is used to make three predictions which differ from conventionalmore » kinetic models. These predictions suggest significant modifications may be needed to phenomenological rate constants which are currently in wide use. Implications for models of low and high density systems are discussed.« less

Stability of the thermodynamic equilibrium - A test of the validity of dynamic models as applied to gyroviscous perpendicular magnetohydrodynamics

NASA Astrophysics Data System (ADS)

Faghihi, Mustafa; Scheffel, Jan; Spies, Guenther O.

1988-05-01

Stability of the thermodynamic equilibrium is put forward as a simple test of the validity of dynamic equations, and is applied to perpendicular gyroviscous magnetohydrodynamics (i.e., perpendicular magnetohydrodynamics with gyroviscosity added). This model turns out to be invalid because it predicts exponentially growing Alfven waves in a spatially homogeneous static equilibrium with scalar pressure.

COED Transactions, Vol. 8, No. 10, October 1976. The Computer Generation of Thermodynamic Phase Diagrams.

ERIC Educational Resources Information Center

Jolls, Kenneth R.; And Others

A technique is described for the generation of perspective views of three-dimensional models using computer graphics. The technique is applied to models of familiar thermodynamic phase diagrams and the results are presented for the ideal gas and van der Waals equations of state as well as the properties of liquid water and steam from the Steam…

ThermoFit: A Set of Software Tools, Protocols and Schema for the Organization of Thermodynamic Data and for the Development, Maintenance, and Distribution of Internally Consistent Thermodynamic Data/Model Collections

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2013-12-01

Internally consistent thermodynamic databases are critical resources that facilitate the calculation of heterogeneous phase equilibria and thereby support geochemical, petrological, and geodynamical modeling. These 'databases' are actually derived data/model systems that depend on a diverse suite of physical property measurements, calorimetric data, and experimental phase equilibrium brackets. In addition, such databases are calibrated with the adoption of various models for extrapolation of heat capacities and volumetric equations of state to elevated temperature and pressure conditions. Finally, these databases require specification of thermochemical models for the mixing properties of solid, liquid, and fluid solutions, which are often rooted in physical theory and, in turn, depend on additional experimental observations. The process of 'calibrating' a thermochemical database involves considerable effort and an extensive computational infrastructure. Because of these complexities, the community tends to rely on a small number of thermochemical databases, generated by a few researchers; these databases often have limited longevity and are universally difficult to maintain. ThermoFit is a software framework and user interface whose aim is to provide a modeling environment that facilitates creation, maintenance and distribution of thermodynamic data/model collections. Underlying ThermoFit are data archives of fundamental physical property, calorimetric, crystallographic, and phase equilibrium constraints that provide the essential experimental information from which thermodynamic databases are traditionally calibrated. ThermoFit standardizes schema for accessing these data archives and provides web services for data mining these collections. Beyond simple data management and interoperability, ThermoFit provides a collection of visualization and software modeling tools that streamline the model/database generation process. Most notably, ThermoFit facilitates the rapid visualization of predicted model outcomes and permits the user to modify these outcomes using tactile- or mouse-based GUI interaction, permitting real-time updates that reflect users choices, preferences, and priorities involving derived model results. This ability permits some resolution of the problem of correlated model parameters in the common situation where thermodynamic models must be calibrated from inadequate data resources. The ability also allows modeling constraints to be imposed using natural data and observations (i.e. petrologic or geochemical intuition). Once formulated, ThermoFit facilitates deployment of data/model collections by automated creation of web services. Users consume these services via web-, excel-, or desktop-clients. ThermoFit is currently under active development and not yet generally available; a limited capability prototype system has been coded for Macintosh computers and utilized to construct thermochemical models for H2O-CO2 mixed fluid saturation in silicate liquids. The longer term goal is to release ThermoFit as a web portal application client with server-based cloud computations supporting the modeling environment.

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.

Reactivity, characterization, equilibrium thermodynamics and hetero-bimetallic studies of tridentate and tetradentate complexes relevant to syngas catalysis

NASA Astrophysics Data System (ADS)

Imler, Gregory H.

The unifying objective of this work is the study of model systems that will assist in the development of new metal catalysts capable of converting carbon monoxide and hydrogen (syngas) into organic oxygenates at mild temperature and pressure. The selective catalytic transformation of carbon monoxide and hydrogen to liquid fuels and chemical feedstocks represents a major "Grand Challenge" of catalysis science. A core objective is the study of a macrocycle that is related to a porphyrin ligand in order to circumvent some of the disadvantages of utilizing porphyrins in catalysis. The rhodium complex of the macrocycle dibenzotetramethylaza[14]annulene ([(tmtaa)Rh]2]) was reacted with a series of small molecules relevant to CO reduction and hydrogenation. Several complexes were formed that demonstrated the ability to partially reduce and hydrogenate carbon monoxide, including the dirhodium ketone (Rh-C(O)-Rh) and an example of a thermodynamically favorable metal formyl complex ((tmtaa)Rh-C(O)H). An important feature of this work is the measurement of thermodynamic data to provide experimental benchmarks for obtaining key species in CO reduction and hydrogenation. A thorough study of the (tmtaa)Rh system will help in identifying structural features that assist or hinder CO hydrogenation. All reactions are monitored by 1H NMR which permits determination of solution thermodynamics from equilibrium constants obtained by NMR peak integrations. DFT calculations have supplemented experimental results by providing estimates to compare with the experimentally determined thermodynamic data. These computations also provide insight into the structures and thermodynamics of species that cannot be observed directly such as short lived intermediates and thermodynamically unfavorable products. Heterobimetallic complexes of (tmtaa)Rh• with a second metal radical have been utilized to attempt to convert CO to organic products. Reactivity with CO and H2 has been accomplished, with most of these metal systems providing (tmtaa)Rh-C(O)H and M-H as final products. These systems are now ideally set up for catalysis in which M-H can deliver hydrogen to reduce and hydrogenate the rhodium formyl unit. Performing these reactions at high pressures of CO/H2 or with a more sterically hindered analog of tmtaa may provide the conditions necessary for catalysis. Reactivity, thermodynamic and computational studies have been used to analyze and compare bond energies in this current work with previous studies accomplished in the Wayland group. These comparisons permit further understanding into the factors that control bond strength, guiding future studies and allowing tuning of bond strengths based on choice of conditions for a catalytic process. This research has resulted in a more complete understanding of the factors that control the favorability of various intermediates in CO reduction and hydrogenation and the application of these results can be used to guide the next generation of metal ligand systems that will yield organic oxygenates at mild conditions.

Thermodynamic universality of quantum Carnot engines

DOE PAGES

Gardas, Bartłomiej; Deffner, Sebastian

2015-10-12

The Carnot statement of the second law of thermodynamics poses an upper limit on the efficiency of all heat engines. Recently, it has been studied whether generic quantum features such as coherence and quantum entanglement could allow for quantum devices with efficiencies larger than the Carnot efficiency. The present study shows that this is not permitted by the laws of thermodynamic —independent of the model. We will show that rather the definition of heat has to be modified to account for the thermodynamic cost of maintaining non-Gibbsian equilibrium states. As a result, our theoretical findings are illustrated for two experimentallymore » relevant examples.« less

The application of the thermodynamic perturbation theory to study the hydrophobic hydration

PubMed Central

Mohorič, Tomaž; Urbic, Tomaz; Hribar-Lee, Barbara

2013-01-01

The thermodynamic perturbation theory was tested against newly obtained Monte Carlo computer simulations to describe the major features of the hydrophobic effect in a simple 3D-Mercedes-Benz water model: the temperature and hydrophobe size dependence on entropy, enthalpy, and free energy of transfer of a simple hydrophobic solute into water. An excellent agreement was obtained between the theoretical and simulation results. Further, the thermodynamic perturbation theory qualitatively correctly (with respect to the experimental data) describes the solvation thermodynamics under conditions where the simulation results are difficult to obtain with good enough accuracy, e.g., at high pressures. PMID:23862923

Systems Models for Transportation Problems : Volume 1. Introducing a Systems Science for Transportation Planning.

DOT National Transportation Integrated Search

1976-03-01

This introductory portion of a system science for tranportation planning, which is based on the statistical physics of ensembles, a foundations laid on how statistical mechanics, equilibrium thermodynamics, and near equilbrium thermodynamics can be u...

Chiral Symmetry Breaking and Complete Chiral Purity by Thermodynamic-Kinetic Feedback Near Equilibrium: Implications for the Origin of Biochirality

NASA Astrophysics Data System (ADS)

Viedma, Cristobal

2007-05-01

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers-left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This ``thermodynamic-kinetic feedback near equilibrium'' is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.

Experimental study of phase equilibria and thermodynamic optimization of the Fe-Zn-O system

NASA Astrophysics Data System (ADS)

Degterov, Sergei A.; Pelton, Arthur D.; Jak, Evgueni; Hayes, Peter C.

2001-08-01

The Fe-Zn-O phase diagram in air was studied over the temperature range from 900 °C to 1500 °C. The compositions of the phases in quenched samples were obtained by electron probe X-ray microanalysis (EPMA). This experimental technique is not affected by zinc losses resulting from vaporization of zinc at high temperatures. The model for the spinel solid solution was developed within the framework of the compound-energy formalism (CEF). The choice of parameters of the CEF and the sequence of their optimization can have a major influence on the predictions in multicomponent phases. These choices can only be made rationally by reference to the specific model being represented in the CEF. This is discussed for the case of the two-sublattice spinel model. In the limiting case, the proposed model reduces to the model by O’Neill and Navrotsky for spinels. When the CEF is used in combination with the equation of Hillert and Jarl to describe the magnetic contribution to thermodynamic functions of a solution, it is necessary to assign certain values of magnetic properties to all pseudocomponents and to magnetic interaction parameters to obtain the most reasonable approximation of the magnetic properties of a solution. It was shown how this can be done based on very limited experimental data. The same equations can be used when the Murnaghan or the Birch-Murnaghan equation is combined with the CEF to describe the pressure dependence of thermodynamic functions. The polynomial model was used to describe the properties of wustite and zincite, and the modified quasichemical model was used for the liquid slag. All thermodynamic and phase-equilibria data on the Fe-O and Fe-Zn-O systems were critically evaluated, and parameters of the models were optimized to give a self-consistent set of thermodynamic functions of the phases in these systems. All experimental data are reproduced within experimental error limits. These include the thermodynamic properties of phases (such as specific heat, heat content, entropy, enthalpy, and Gibbs energy); the cation distribution between octahedral and tetrahedral sites in spinel; the oxygen partial pressure over single-phase, two-phase, and three-phase regions; the phase boundaries (liquidus, solidus, and subsolidus); and the tie-lines.

Al-Air Batteries: Fundamental Thermodynamic Limitations from First Principles Theory

NASA Astrophysics Data System (ADS)

Chen, Leanne D.; Noerskov, Jens K.; Luntz, Alan C.

2015-03-01

The Al-air battery possesses high theoretical specific energy (4140 Wh/kg) and is therefore an attractive candidate for vehicle propulsion applications. However, the experimentally observed open-circuit potential is much lower than what thermodynamics predicts, and this potential loss is widely believed to be an effect of corrosion. We present a detailed study of the Al-air battery using density functional theory. The results suggest that the difference between bulk thermodynamic and surface potentials is due to both the effects of asymmetry in multi-electron transfer reactions that define the anodic dissolution of Al and, more importantly, a large chemical step inherent to the formation of bulk Al(OH)3 from surface intermediates. The former results in an energy loss of 3%, while the latter accounts for 14 -29% of the total thermodynamic energy depending on the surface site where dissolution occurs. Therefore, the maximum open-circuit potential of the Al anode is only -1.87 V vs. SHE in the absence of thermal excitations, contrary to -2.34 V predicted by bulk thermodynamics at pH 14.6. This is a fundamental limitation of the system and governs the maximum output potential, which cannot be improved even if corrosion effects were completely suppressed. Supported by the Natural Sciences and Engineering Research Council of Canada and the ReLiable Project (#11-116792) funded by the Danish Council for Strategic Research.

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.

The Markov process admits a consistent steady-state thermodynamic formalism

NASA Astrophysics Data System (ADS)

Peng, Liangrong; Zhu, Yi; Hong, Liu

2018-01-01

The search for a unified formulation for describing various non-equilibrium processes is a central task of modern non-equilibrium thermodynamics. In this paper, a novel steady-state thermodynamic formalism was established for general Markov processes described by the Chapman-Kolmogorov equation. Furthermore, corresponding formalisms of steady-state thermodynamics for the master equation and Fokker-Planck equation could be rigorously derived in mathematics. To be concrete, we proved that (1) in the limit of continuous time, the steady-state thermodynamic formalism for the Chapman-Kolmogorov equation fully agrees with that for the master equation; (2) a similar one-to-one correspondence could be established rigorously between the master equation and Fokker-Planck equation in the limit of large system size; (3) when a Markov process is restrained to one-step jump, the steady-state thermodynamic formalism for the Fokker-Planck equation with discrete state variables also goes to that for master equations, as the discretization step gets smaller and smaller. Our analysis indicated that general Markov processes admit a unified and self-consistent non-equilibrium steady-state thermodynamic formalism, regardless of underlying detailed models.

Thermodynamic assessment of the Pr-O system

DOE PAGES

McMurray, Jake W.

2015-12-24

We found that the Calphad method was used to perform a thermodynamic assessment of the Pr–O system. Compound energy formalism representations were developed for the fluorite α-PrO 2–x and bixbyite σ-Pr 3 O 5 ± x solid solutions while the two-sublattice liquid model was used to describe the binary melt. The series of phases between Pr 2 O 3 and PrO 2 were taken to be stoichiometric. Moreover, the equilibrium oxygen pressure, phase equilibria, and enthalpy data were used to optimize the adjustable parameters of the models for a self-consistent representation of the thermodynamic behavior of the Pr–O system frommore » 298 K to melting.« less

Exp6-polar thermodynamics of dense supercritical water

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

Bastea, S; Fried, L E

2007-12-13

We introduce a simple polar fluid model for the thermodynamics of dense supercritical water based on a Buckingham (exp-6) core and point dipole representation of the water molecule. The proposed exp6-polar thermodynamics, based on ideas originally applied to dipolar hard spheres, performs very well when tested against molecular dynamics simulations. Comparisons of the model predictions with experimental data available for supercritical water yield excellent agreement for the shock Hugoniot, isotherms and sound speeds, and are also quite good for the self-diffusion constant and relative dielectric constant. We expect the present approach to be also useful for other small polar moleculesmore » and their mixtures.« less

Magnetization process and low-temperature thermodynamics of a spin-1/2 Heisenberg octahedral chain

NASA Astrophysics Data System (ADS)

Strečka, Jozef; Richter, Johannes; Derzhko, Oleg; Verkholyak, Taras; Karľová, Katarína

2018-05-01

Low-temperature magnetization curves and thermodynamics of a spin-1/2 Heisenberg octahedral chain with the intra-plaquette and monomer-plaquette interactions are examined within a two-component lattice-gas model of hard-core monomers, which takes into account all low-lying energy modes in a highly frustrated parameter space involving the monomer-tetramer, localized many-magnon and fully polarized ground states. It is shown that the developed lattice-gas model satisfactorily describes all pronounced features of the low-temperature magnetization process and the magneto-thermodynamics such as abrupt changes of the isothermal magnetization curves, a double-peak structure of the specific heat or a giant magnetocaloric effect.

Statistical thermodynamics of long straight rigid rods on triangular lattices: nematic order and adsorption thermodynamic functions.

PubMed

Matoz-Fernandez, D A; Linares, D H; Ramirez-Pastor, A J

2012-09-04

The statistical thermodynamics of straight rigid rods of length k on triangular lattices was developed on a generalization in the spirit of the lattice-gas model and the classical Guggenheim-DiMarzio approximation. In this scheme, the Helmholtz free energy and its derivatives were written in terms of the order parameter, δ, which characterizes the nematic phase occurring in the system at intermediate densities. Then, using the principle of minimum free energy with δ as a parameter, the main adsorption properties were calculated. Comparisons with Monte Carlo simulations and experimental data were performed in order to evaluate the outcome and limitations of the theoretical model.

Stochastic ontogenetic growth model

NASA Astrophysics Data System (ADS)

West, B. J.; West, D.

2012-02-01

An ontogenetic growth model (OGM) for a thermodynamically closed system is generalized to satisfy both the first and second law of thermodynamics. The hypothesized stochastic ontogenetic growth model (SOGM) is shown to entail the interspecies allometry relation by explicitly averaging the basal metabolic rate and the total body mass over the steady-state probability density for the total body mass (TBM). This is the first derivation of the interspecies metabolic allometric relation from a dynamical model and the asymptotic steady-state distribution of the TBM is fit to data and shown to be inverse power law.

The flood event that affected Badajoz in November 1997

NASA Astrophysics Data System (ADS)

Lorente, P.; Hernández, E.; Queralt, S.; Ribera, P.

2008-04-01

The flooding episode of November 1997 in Badajoz was one of the most dramatic catastrophes in Spain: as a result, there were 21 fatalities and huge financial damages. The main purpose of this work is to assess the prevailing synoptic conditions as well as detailing the mesoscale effects by means of moisture sources and dynamic and thermodynamic instability analysis involved in the November 1997 Spanish severe weather episode. In order to achieve the above, this flood event is described in terms of moisture content evolution by means of individual particle simulation along 3-day back-trajectories. A Lagrangian model is applied in order to characterize the atmospheric particles involved in the focused case (localization, height and specific humidity) which give rise to sudden precipitation stream. Geopotential height and temperature fields were used to describe the synoptic situation. Thermodynamic indices, such as CAPE, SWEAT and KI, and dynamic parameters like potential vorticity anomaly at 330 K isentropic surface and Q vector divergence were also calculated in order to complete the analysis and to give a thorough weather frame taking into account the atmospheric instability. The results of this work suggest this flood event was due mainly to strong dynamic instability along with large amounts of moisture advected by a trough, while the thermodynamic instability played a secondary role. Finally, a new methodology based on a technique proposed by Tremblay (2005) has been developed in order to separate the precipitation into stratiform and convective components. It is evident that the event was associated with a predominant convective regime.

Experimental opto-mechanics with levitated nanoparticles: towards quantum control and thermodynamic cycles (Presentation Recording)

NASA Astrophysics Data System (ADS)

Kiesel, Nikolai; Blaser, Florian; Delic, Uros; Grass, David; Dechant, Andreas; Lutz, Eric; Bathaee, Marzieh; Aspelmeyer, Markus

2015-08-01

Combining optical levitation and cavity optomechanics constitutes a promising approach to prepare and control the motional quantum state of massive objects (>10^9 amu). This, in turn, would represent a completely new type of light-matter interface and has, for example, been predicted to enable experimental tests of macrorealistic models or of non-Newtonian gravity at small length scales. Such ideas have triggered significant experimental efforts to realizing such novel systems. To this end, we have recently successfully demonstrated cavity-cooling of a levitated sub-micron silica particle in a classical regime at a pressure of approximately 1mbar. Access to higher vacuum of approx. 10^-6 mbar has been demonstrated using 3D-feedback cooling in optical tweezers without cavity-coupling. Here we will illustrate our strategy towards trapping, 3D-cooling and quantum control of nanoparticles in ultra-high vacuum using cavity-based feedback cooling methods and clean particle loading with hollow-core photonic crystal fibers. We will also discuss the current experimental progress both in 3D-cavity cooling and HCPCF-based transport of nanoparticles. As yet another application of cavity-controlled levitated nanoparticles we will show how to implement a thermodynamic Sterling cycle operating in the underdamped regime. We present optimized protocols with respect to efficiency at maximum power in this little explored regime. We also show that the excellent level of control in our system will allow reproducing all relevant features of such optimized protocols. In a next step, this will enable studies of thermodynamics cycles in a regime where the quantization of the mechanical motion becomes relevant.

Thermodynamic and kinetic modeling of grain boundary equilibrium segregation of P in α-Fe

DOE PAGES

Yang, Y.; Chen, S. -L.

2017-04-18

Phosphorus is a primary contributor to interface fracture and embrittlement in steels because of its strong segregation tendency at grain boundaries (GBs). The lack of consistency in literature data imposes great difficulties in performing segregation modeling that is compatible with both the Langmuir-Mclean segregation theory and the thermodynamic description of the Bcc(Fe,P) phase. Our work carefully evaluated experimental data for phosphorus segregation at GBs in -Fe and provided a new formula for converting the auger electron spectroscopy (AES) peak height ratio to GBs. Furthermore, based on newly assessed literature data, this work proposes that the major driving force for phosphorusmore » segregation is the formation of Fe 3P-type clusters at GBs, which is supported not only by the almost equivalent Gibbs energy of _Fe using the Bcc(Fe,P) substitutional model and the Bcc(Fe,Fe 3P, P) associate model, but also by the good agreement between thermodynamic/kinetic modeling results and experimental data.« less

Connecting thermodynamic and dynamical anomalies of water-like liquid-liquid phase transition in the Fermi-Jagla model

NASA Astrophysics Data System (ADS)

Higuchi, Saki; Kato, Daiki; Awaji, Daisuke; Kim, Kang

2018-03-01

We present a study using molecular dynamics simulations based on the Fermi-Jagla potential model, which is the continuous version of the mono-atomic core-softened Jagla model [J. Y. Abraham, S. V. Buldyrev, and N. Giovambattista, J. Phys. Chem. B 115, 14229 (2011)]. This model shows the water-like liquid-liquid phase transition between high-density and low-density liquids at the liquid-liquid critical point. In particular, the slope of the coexistence line becomes weakly negative, which is expected to represent one of the anomalies of liquid polyamorphism. In this study, we examined the density, dynamic, and thermodynamic anomalies in the vicinity of the liquid-liquid critical point. The boundaries of density, self-diffusion, shear viscosity, and excess entropy anomalies were characterized. Furthermore, these anomalies are connected according to Rosenfeld's scaling relationship between the excess entropy and the transport coefficients such as diffusion and viscosity. The results demonstrate the hierarchical and nested structures regarding the thermodynamic and dynamic anomalies of the Fermi-Jagla model.

Prediction of retention times in comprehensive two-dimensional gas chromatography using thermodynamic models.

PubMed

McGinitie, Teague M; Harynuk, James J

2012-09-14

A method was developed to accurately predict both the primary and secondary retention times for a series of alkanes, ketones and alcohols in a flow-modulated GC×GC system. This was accomplished through the use of a three-parameter thermodynamic model where ΔH, ΔS, and ΔC(p) for an analyte's interaction with the stationary phases in both dimensions are known. Coupling this thermodynamic model with a time summation calculation it was possible to accurately predict both (1)t(r) and (2)t(r) for all analytes. The model was able to predict retention times regardless of the temperature ramp used, with an average error of only 0.64% for (1)t(r) and an average error of only 2.22% for (2)t(r). The model shows promise for the accurate prediction of retention times in GC×GC for a wide range of compounds and is able to utilize data collected from 1D experiments. Copyright © 2012 Elsevier B.V. All rights reserved.

ASTM Data Banks and Chemical Information Sources

ERIC Educational Resources Information Center

Batik, Albert; Hale, Eleanor

1972-01-01

Among the data described are infrared indexes, mass spectral data, chromatographic data, X-ray emmission data, odor and taste threshold data, and thermodynamics data. This paper provides the chemical documentarian a complete reference source to a wide variety of analytical data. (Author/NH)

Implications of Modern Non-Equilibrium Thermodynamics for Georgescu-Roegen's Macro-Economics: lessons from a comprehensive historical review

NASA Astrophysics Data System (ADS)

Poisson, Alexandre

2011-12-01

In the early 1970s, mathematician and economist Nicolas Georgescu-Roegen developed an alternative framework to macro-economics (his hourglass model) based on two principles of classical thermodynamics applied to the earth-system as a whole. The new model led him to the radical conclusion that "not only growth, but also a zero-growth state, nay, even a declining state which does not converge toward annihilation, cannot exist forever in a finite environment" (Georgescu-Roegen 1976, p.23). Georgescu-Roegen's novel approach long served as a devastating critique of standard neoclassical growth theories. It also helped establish the foundations for the new trans-disciplinary field of ecological economics. In recent decades however, it has remained unclear whether revolutionary developments in "modern non-equilibrium thermodynamics" (Kondepudi and Prigogine 1998) refute some of Georgescu-Roegen's initial conclusions and provide fundamentally new lessons for very long-term macro-economic analysis. Based on a broad historical review of literature from many fields (thermodynamics, cosmology, ecosystems ecology and economics), I argue that Georgescu-Roegen's hourglass model is largely based on old misconceptions and assumptions from 19th century thermodynamics (including an out-dated cosmology) which make it very misleading. Ironically, these assumptions (path independence and linearity of the entropy function in particular) replicate the non-evolutionary thinking he seemed to despise in his colleagues. In light of modern NET, I propose a different model. Contrary to Georgescu-Roegen's hourglass, I do not assume the path independence of the entropy function. In the new model, achieving critical free energy rate density thresholds can abruptly increase the level of complexity and maximum remaining lifespan of stock-based civilizations.

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 actuation of a biomimetic poly(vinyl alcohol)poly(acrylic acid) gel.

PubMed

Marra, S P; Ramesh, K T; Douglas, A S

2002-02-15

Active polymer gels expand and contract in response to certain environmental stimuli, such as the application of an electric field or a change in the pH level of the surroundings. This ability to achieve large, reversible deformations with no external mechanical loading has generated much interest in the use of these gels as biomimetic actuators and "artificial muscles". In previous work, a thermodynamically consistent finite-elastic constitutive model has been developed to describe the mechanical and actuation behaviours of active polymer gels. The mechanical properties were characterized by a free-energy function, and the model uses an evolving internal variable to describe the actuation state. In this work, an evolution law for the internal variable is determined from free actuation experiments on a poly(vinyl alcohol)poly(acrylic acid) (PVAPAA) gel. The complete finite-elastic/evolution law constitutive model is then used to predict the response of the PVA-PAA gel to isotonic and isometric loading and actuation. The model is shown to give relatively good agreement with experimental results.

Observations and modeling of cool, evolved stars: from chromospheric to wind regions

NASA Astrophysics Data System (ADS)

Rau, Gioia; Carpenter, Ken G.; Nielsen, Krister E.; Kober, Gladys V.; Josef Hron, Bernard Aringer, Kjell Eriksson, Paola Marigo, Claudia Paladini

2018-01-01

Evolved stars are fundamental contributors to the enrichment of the interstellar medium, via their mass loss, with heavy elements produced in their interior, and with the dust formed in their envelope. We present the results of the first systematic comparison (Rau et al. 2017, 2015) of multi-technique observations of a sample of C-rich Mira, semi-regular and irregular stars with the predictions from dynamic model atmospheres (Mattsson et al. 2010) and simpler models based on hydrostatic atmospheres combined with dusty envelopes. The chromosphere, located in the outer atmosphere of these stars, plays a crucial role in driving the mass loss in evolved K-M giant stars (see e.g. Carpenter et al. 2014, 1988). Despite recent efforts, details of the mass-loss scenario remain mysterious, as well as a complete understanding of the dynamic line formation regions, profiles, and structures. To solve these riddles, we present observation of flow and turbulent velocities, together with preliminary derivation of thermodynamic constraints for theoretical models (Rau, Carpenter, et al., in prep).

Helicon thruster plasma modeling: Two-dimensional fluid-dynamics and propulsive performances

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

Ahedo, Eduardo; Navarro-Cavalle, Jaume

2013-04-15

An axisymmetric macroscopic model of the magnetized plasma flow inside the helicon thruster chamber is derived, assuming that the power absorbed from the helicon antenna emission is known. Ionization, confinement, subsonic flows, and production efficiency are discussed in terms of design and operation parameters. Analytical solutions and simple scaling laws for ideal plasma conditions are obtained. The chamber model is then matched with a model of the external magnetic nozzle in order to characterize the whole plasma flow and assess thruster performances. Thermal, electric, and magnetic contributions to thrust are evaluated. The energy balance provides the power conversion between ionsmore » and electrons in chamber and nozzle, and the power distribution among beam power, ionization losses, and wall losses. Thruster efficiency is assessed, and the main causes of inefficiency are identified. The thermodynamic behavior of the collisionless electron population in the nozzle is acknowledged to be poorly known and crucial for a complete plasma expansion and good thrust efficiency.« less

Internal Flow Thermal/Fluid Modeling of STS-107 Port Wing in Support of the Columbia Accident Investigation Board

NASA Technical Reports Server (NTRS)

Sharp, John R.; Kittredge, Ken; Schunk, Richard G.

2003-01-01

As part of the aero-thermodynamics team supporting the Columbia Accident Investigation Board (CAB), the Marshall Space Flight Center was asked to perform engineering analyses of internal flows in the port wing. The aero-thermodynamics team was split into internal flow and external flow teams with the support being divided between shorter timeframe engineering methods and more complex computational fluid dynamics. In order to gain a rough order of magnitude type of knowledge of the internal flow in the port wing for various breach locations and sizes (as theorized by the CAB to have caused the Columbia re-entry failure), a bulk venting model was required to input boundary flow rates and pressures to the computational fluid dynamics (CFD) analyses. This paper summarizes the modeling that was done by MSFC in Thermal Desktop. A venting model of the entire Orbiter was constructed in FloCAD based on Rockwell International s flight substantiation analyses and the STS-107 reentry trajectory. Chemical equilibrium air thermodynamic properties were generated for SINDA/FLUINT s fluid property routines from a code provided by Langley Research Center. In parallel, a simplified thermal mathematical model of the port wing, including the Thermal Protection System (TPS), was based on more detailed Shuttle re-entry modeling previously done by the Dryden Flight Research Center. Once the venting model was coupled with the thermal model of the wing structure with chemical equilibrium air properties, various breach scenarios were assessed in support of the aero-thermodynamics team. The construction of the coupled model and results are presented herein.

H-Theorem and Thermodynamic Efficiency of the Radiation Work Inducing a Chemically Nonequilibrium State of Matter

NASA Astrophysics Data System (ADS)

Seleznev, V. D.; Buchina, O.

2015-06-01

The Sun's radiation is a source of origin and maintenance of life on Earth. The Sun-Earth system is a thermodynamic machine transforming radiation into useful work of living organisms. Despite the importance of efficiency for such a thermodynamic machine, the analysis of its efficiency coefficient (EC) available in the literature has considerable shortcomings: As is noted by the author of the classical study on this subject (Oxenius in J Quant Spectrosc Radiat Transf 6:65-91, 1996), the second law of thermodynamics is violated for the radiation beam (without direction integration). The typical thermodynamic analysis of the interaction between radiation and matter is performed assuming an equilibrium of the chemical composition thereof as opposed to the radiation work in the biosphere (photosynthesis), which usually occurs under the conditions of a significant deviation of the active substance's composition from its equilibrium values. The "black box" model (Aoki in J Phys Soc Jpn 52:1075-1078, 1983) is traditionally used to analyze the work efficiency of the Sun-Earth thermodynamic machine. It fails to explain the influence of many internal characteristics of the radiation-matter interaction on the process's EC. The present paper overcomes the above shortcomings using a relatively simple model of interaction between anisotropic radiation and two-level molecules of a rarefied component in a buffer substance.

Multiensemble Markov models of molecular thermodynamics and kinetics

PubMed Central

Wu, Hao; Paul, Fabian; Noé, Frank

2016-01-01

We introduce the general transition-based reweighting analysis method (TRAM), a statistically optimal approach to integrate both unbiased and biased molecular dynamics simulations, such as umbrella sampling or replica exchange. TRAM estimates a multiensemble Markov model (MEMM) with full thermodynamic and kinetic information at all ensembles. The approach combines the benefits of Markov state models—clustering of high-dimensional spaces and modeling of complex many-state systems—with those of the multistate Bennett acceptance ratio of exploiting biased or high-temperature ensembles to accelerate rare-event sampling. TRAM does not depend on any rate model in addition to the widely used Markov state model approximation, but uses only fundamental relations such as detailed balance and binless reweighting of configurations between ensembles. Previous methods, including the multistate Bennett acceptance ratio, discrete TRAM, and Markov state models are special cases and can be derived from the TRAM equations. TRAM is demonstrated by efficiently computing MEMMs in cases where other estimators break down, including the full thermodynamics and rare-event kinetics from high-dimensional simulation data of an all-atom protein–ligand binding model. PMID:27226302

Thermodynamic models for vapor-liquid equilibria of nitrogen + oxygen + carbon dioxide at low temperatures

NASA Astrophysics Data System (ADS)

Vrabec, Jadran; Kedia, Gaurav Kumar; Buchhauser, Ulrich; Meyer-Pittroff, Roland; Hasse, Hans

2009-02-01

For the design and optimization of CO 2 recovery from alcoholic fermentation processes by distillation, models for vapor-liquid equilibria (VLE) are needed. Two such thermodynamic models, the Peng-Robinson equation of state (EOS) and a model based on Henry's law constants, are proposed for the ternary mixture N 2 + O 2 + CO 2. Pure substance parameters of the Peng-Robinson EOS are taken from the literature, whereas the binary parameters of the Van der Waals one-fluid mixing rule are adjusted to experimental binary VLE data. The Peng-Robinson EOS describes both binary and ternary experimental data well, except at high pressures approaching the critical region. A molecular model is validated by simulation using binary and ternary experimental VLE data. On the basis of this model, the Henry's law constants of N 2 and O 2 in CO 2 are predicted by molecular simulation. An easy-to-use thermodynamic model, based on those Henry's law constants, is developed to reliably describe the VLE in the CO 2-rich region.

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.

Thermodynamic signature of Dirac electrons across a possible topological transition in ZrTe5

NASA Astrophysics Data System (ADS)

Nair, Nityan L.; Dumitrescu, Philipp T.; Channa, Sanyum; Griffin, Sinéad M.; Neaton, Jeffrey B.; Potter, Andrew C.; Analytis, James G.

2018-01-01

We combine transport, magnetization, and torque magnetometry measurements to investigate the electronic structure of ZrTe5, a system that is thought to be near a topological phase transition. At fields beyond the quantum limit, we observe a magnetization reversal from paramagnetic to diamagnetic response, which is characteristic of a Dirac semimetal. However, on increasing temperature across a corresponding transport anomaly, all signatures of this Dirac-like nature are completely suppressed, providing the first thermodynamic evidence of a possible topological phase transition in this compound. ZrTe5 may thus provide a rare, experimentally accessible example in which such phase transitions can be studied directly.

Effect of Sulfate Aerosol Geoengineering on Tropical cyclones

NASA Astrophysics Data System (ADS)

Wang, Q.; Moore, J.; Ji, D.

2017-12-01

Variation in tropical cyclone (TC) number and intensity is driven in part by changes in the thermodynamics that can be defined by ocean and atmospheric variables. Genesis Potential Index (GPI) and ventilation index (VI) are combinations of potential intensity, vertical wind shear, relative humidity, midlevel entropy deficit, and absolute vorticity that quantify thermodynamic forcing of TC activity under changed climates, and can be calculated from climate model output. Here we use five CMIP5 models running the RCP45 experiment the Geoengineering Model Intercomparison Project (GeoMIP) stratospheric aerosol injection G4 experiment to calculate the two indices over the 2020 to 2069 period. Globally, GPI under G4 is lower than under RCP45, though both have a slight increasing trend. Spatial patterns in the relative effectiveness of geoengineering show reductions in TC in all models in the North Atlantic basin, and northern Indian Ocean in all except NorESM1-M. In the North Pacific, most models also show relative reductions under G4. VI generally coincide with the GPI patterns. Most models project Potential intensity and Relative Humidity to be the dominant variable to affect genesis potential. Changes in vertical wind shear and vorticity are small with scatter across different models and ocean basins. We find that tropopause temperature maybe as important as sea surface temperature in effecting TC genesis. Thus stratospheric aerosol geoengineering impacts on potential intensity and hence TC intensity are reasonably consistent, but probably underestimated by statistical forecasts of Tropical North Atlantic hurricane activity driven by sea surface temperatures alone. However the impacts of geoengineering on other ocean basins are more difficult to assess, and require more complete understanding of their driving parameters under present day climates. Furthermore, the possible effects of stratospheric injection on chemical reactions in the stratosphere, such as ozone, are not well rendered in the models used so far.

A sharp interface model for void growth in irradiated materials

NASA Astrophysics Data System (ADS)

Hochrainer, Thomas; El-Azab, Anter

2015-03-01

A thermodynamic formalism for the interaction of point defects with free surfaces in single-component solids has been developed and applied to the problem of void growth by absorption of point defects in irradiated metals. This formalism consists of two parts, a detailed description of the dynamics of defects within the non-equilibrium thermodynamic frame, and the application of the second law of thermodynamics to provide closure relations for all kinetic equations. Enforcing the principle of non-negative entropy production showed that the description of the problem of void evolution under irradiation must include a relationship between the normal fluxes of defects into the void surface and the driving thermodynamic forces for the void surface motion; these thermodynamic forces are identified for both vacancies and interstitials and the relationships between these forces and the normal point defect fluxes are established using the concepts of transition state theory. The latter theory implies that the defect accommodation into the surface is a thermally activated process. Numerical examples are given to illustrate void growth dynamics in this new formalism and to investigate the effect of the surface energy barriers on void growth. Consequences for phase field models of void growth are discussed.

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.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-01

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Additional strange hadrons from QCD thermodynamics and strangeness freezeout in heavy ion collisions.

PubMed

Bazavov, A; Ding, H-T; Hegde, P; Kaczmarek, O; Karsch, F; Laermann, E; Maezawa, Y; Mukherjee, Swagato; Ohno, H; Petreczky, P; Schmidt, C; Sharma, S; Soeldner, W; Wagner, M

2014-08-15

We compare lattice QCD results for appropriate combinations of net strangeness fluctuations and their correlations with net baryon number fluctuations with predictions from two hadron resonance gas (HRG) models having different strange hadron content. The conventionally used HRG model based on experimentally established strange hadrons fails to describe the lattice QCD results in the hadronic phase close to the QCD crossover. Supplementing the conventional HRG with additional, experimentally uncharted strange hadrons predicted by quark model calculations and observed in lattice QCD spectrum calculations leads to good descriptions of strange hadron thermodynamics below the QCD crossover. We show that the thermodynamic presence of these additional states gets imprinted in the yields of the ground-state strange hadrons leading to a systematic 5-8 MeV decrease of the chemical freeze-out temperatures of ground-state strange baryons.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.

PubMed

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-06

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

The Law of Entropy Increase - A Lab Experiment

NASA Astrophysics Data System (ADS)

Dittrich, William; Drosd, Robert; Minkin, Leonid; Shapovalov, Alexander S.

2016-09-01

The second law of thermodynamics has various formulations. There is the "Clausius formulation," which can be stated in a very intuitive way: "No process is possible whose sole result is the transfer of heat from a cooler to a hotter body." There is also the "Kelvin-Plank principle," which states that "no cyclic process exists whose sole result is the absorption of heat from a reservoir and the conversion of all this heat into work" [emphasis added] (since this would require perfect energy conversion efficiency). Both these statements can be presented to physics students in a conceptual manner, and students' "everyday" experiences will support either statement of the second law of thermodynamics. However, when the second law of thermodynamics is expressed using the concept of entropy (ΔS ≥ 0, for a closed system), most first-year physics students lack any direct experimental experience with this parameter. This paper describes a calculation of the increase in entropy that can be performed while completing three traditional thermodynamics experiments. These simple and quick calculations help students become familiar and comfortable with the concept of entropy. This paper is complementary to prior work where classroom activities were developed to provide insight into the statistical nature of entropy.

Development of models and software for liquidus temperatures of glasses of HWVP products. Final report

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

Hrma, P.R.; Vienna, J.D.; Pelton, A.D.

In an earlier report [92 Pel] was described the development of software and thermodynamic databases for the calculation of liquidus temperatures of glasses of HWVP products containing the components SiO{sub 2}-B{sub 2}O{sub 3}-Na{sub 2}O-Li{sub 2}O-CaO-MgO-Fe{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-ZrO{sub 2}-{open_quotes}others{close_quotes}. The software package developed at that time consisted of the EQUILIB program of the F*A*C*T computer system with special input/output routines. Since then, Battelle has purchased the entire F*A*C*T computer system, and this fully replaces the earlier package. Furthermore, with the entire F*A*C*T system, additional calculations can be performed such as calculations at fixed O{sub 2}, SO{sub 2} etc. pressures,more » or graphing of output. Furthermore, the public F*A*C*T database of over 5000 gaseous species and condensed phases is now accessible. The private databases for the glass and crystalline phases were developed for Battelle by optimization of thermodynamic and phase diagram data. That is, all available data for 2- and 3-component sub-systems of the 9-component oxide system were collected, and parameters of model equations for the thermodynamic properties were found which best reproduce all the data. For representing the thermodynamic properties of the glass as a function of composition and temperature, the modified quasichemical model was used. This model was described in the earlier report [92 Pel] along with all the optimizations. With the model, it was possible to predict the thermodynamic properties of the 9-component glass, and thereby to calculate liquidus temperatures. Liquidus temperatures measured by Battelle for 123 CVS glass compositions were used to test the model and to refine the model by the addition of further parameters.« less

Standard state thermodynamic properties of completely ionized aqueous sodium sulfate using high dilution calorimetry up to 598.15 K.

PubMed

Djamali, Essmaiil; Chen, Keith; Cobble, James W

2009-08-27

Pabalan and Pitzer (Geochim. Cosmochim. Acta 1988, 52, 2393-2404) reported a comprehensive set of thermodynamic properties of aqueous solutions of sodium sulfate without using ion association or hydrolysis. However, there is now ample evidence available indicating that the ion association cannot be ignored at temperatures T>or=373 K. For example, even at the lowest concentration of their studies (m>or=0.05) and at 573.15 K, less than 20% of SO4(2-)(aq) is available as free ions. In the present study, the integral heats of solution of sodium sulfate were measured to very low concentrations (10(-4) m) up to 573.16 K. The data were analyzed correcting for the hydrolysis of SO4(2-)(aq) and the association of Na+(aq) with SO4(2-)(aq) and NaSO4-(aq) in order to obtain the final standard state thermodynamic properties of completely ionized aqueous sodium sulfate, Na2SO4(aq). From these and the available solubility data, the stoichiometric activity coefficients of saturated aqueous solutions of sodium sulfate were calculated up to 573.15 K and compared with literature data. The stoichiometric activity coefficients of aqueous solutions of sodium sulfate, as a function of temperature at all concentrations (0

Simulation of Two-Phase Flow Based on a Thermodynamically Constrained Averaging Theory Flow Model

NASA Astrophysics Data System (ADS)

Weigand, T. M.; Dye, A. L.; McClure, J. E.; Farthing, M. W.; Gray, W. G.; Miller, C. T.

2014-12-01

The thermodynamically constrained averaging theory (TCAT) has been used to formulate general classes of porous medium models, including new models for two-fluid-phase flow. The TCAT approach provides advantages that include a firm connection between the microscale, or pore scale, and the macroscale; a thermodynamically consistent basis; explicit inclusion of factors such as interfacial areas, contact angles, interfacial tension, and curvatures; and dynamics of interface movement and relaxation to an equilibrium state. In order to render the TCAT model solvable, certain closure relations are needed to relate fluid pressure, interfacial areas, curvatures, and relaxation rates. In this work, we formulate and solve a TCAT-based two-fluid-phase flow model. We detail the formulation of the model, which is a specific instance from a hierarchy of two-fluid-phase flow models that emerge from the theory. We show the closure problem that must be solved. Using recent results from high-resolution microscale simulations, we advance a set of closure relations that produce a closed model. Lastly, we use locally conservative spatial discretization and higher order temporal discretization methods to approximate the solution to this new model and compare the solution to the traditional model.

Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

PubMed

Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

2007-01-01

The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

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.

Landscape approaches for determining the ensemble of folding transition states: Success and failure hinge on the degree of frustration

NASA Astrophysics Data System (ADS)

Nymeyer, Hugh; Socci, Nicholas D.; Onuchic, José Nelson

2000-01-01

* Department of Physics, University of California at San Diego, La Jolla, CA 92093-0319; and § Center for Studies in Physics and Biology, The Rockefeller University, New York, NY 10021 Edited by R. Stephen Berry, University of Chicago, Chicago, IL, and approved November 5, 1999 (received for review July 2, 1999) We present a method for determining structural properties of the ensemble of folding transition states from protein simulations. This method relies on thermodynamic quantities (free energies as a function of global reaction coordinates, such as the percentage of native contacts) and not on "kinetic" measurements (rates, transmission coefficients, complete trajectories); consequently, it requires fewer computational resources compared with otherapproaches, making it more suited to large and complex models. We explain the theoretical framework that underlies this method and use it to clarify the connection between the experimentally determined value, a quantity determined by the ratio of rate and stability changes due to point mutations, and the average structure of the transition state ensemble. To determine the accuracy of this thermodynamic approach, we apply it to minimalist protein models and compare these results with the ones obtained by using the standard experimental procedure for determining values. We show that the accuracy of both methods depends sensitively on the amount of frustration. In particular, the results are similar when applied to models with minimal amounts of frustration, characteristic of rapid-folding, single-domain globular proteins.

Thermodynamics of a Higher Dimensional Noncommutative Inspired Anti-de Sitter-Einstein-Born-Infeld Black Hole

NASA Astrophysics Data System (ADS)

González, Angélica; Linares, Román; Maceda, Marco; Sánchez-Santos, Oscar

2018-04-01

We analyze noncommutative deformations of a higher dimensional anti-de Sitter-Einstein-Born-Infeld black hole. Two models based on noncommutative inspired distributions of mass and charge are discussed and their thermodynamical properties such as the equation of state are explicitly calculated. In the (3 + 1)-dimensional case the Gibbs energy function of each model is used to discuss the presence of phase transitions.

Thermodynamics of micellization from heat-capacity measurements.

PubMed

Šarac, Bojan; Bešter-Rogač, Marija; Lah, Jurij

2014-06-23

Differential scanning calorimetry (DSC), the most important technique for studying the thermodynamics of structural transitions of biological macromolecules, is seldom used in quantitative thermodynamic studies of surfactant micellization/demicellization. The reason for this could be ascribed to an insufficient understanding of the temperature dependence of the heat capacity of surfactant solutions (DSC data) in terms of thermodynamics, which leads to problems with the design of experiments and interpretation of the output signals. We address these issues by careful design of DSC experiments performed with solutions of ionic and nonionic surfactants at various surfactant concentrations, and individual and global mass-action model analysis of the obtained DSC data. Our approach leads to reliable thermodynamic parameters of micellization for all types of surfactants, comparable with those obtained by using isothermal titration calorimetry (ITC). In summary, we demonstrate that DSC can be successfully used as an independent method to obtain temperature-dependent thermodynamic parameters for micellization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic behavior of glassy state of structurally related compounds.

PubMed

Kaushal, Aditya Mohan; Bansal, Arvind Kumar

2008-08-01

Thermodynamic properties of amorphous pharmaceutical forms are responsible for enhanced solubility as well as poor physical stability. The present study was designed to investigate the differences in thermodynamic parameters arising out of disparate molecular structures and associations for four structurally related pharmaceutical compounds--celecoxib, valdecoxib, rofecoxib, and etoricoxib. Conventional and modulated temperature differential scanning calorimetry were employed to study glass forming ability and thermodynamic behavior of the glassy state of model compounds. Glass transition temperature of four glassy compounds was in a close range of 327.6-331.8 K, however, other thermodynamic parameters varied considerably. Kauzmann temperature, strength parameter and fragility parameter showed rofecoxib glass to be most fragile of the four compounds. Glass forming ability of the compounds fared similar in the critical cooling rate experiments, suggesting that different factors were determining the glass forming ability and subsequent behavior of the compounds in glassy state. A comprehensive understanding of such thermodynamic facets of amorphous form would help in rationalizing the approaches towards development of stable glassy pharmaceuticals.

Modeling nanostructural surface modifications in metal cutting by an approach of thermodynamic irreversibility: Derivation and experimental validation

NASA Astrophysics Data System (ADS)

Buchkremer, S.; Klocke, F.

2017-01-01

Performance and operational safety of many metal parts in engineering depend on their surface integrity. During metal cutting, large thermomechanical loads and high gradients of the loads concerning time and location act on the surfaces and may yield significant structural material modifications, which alter the surface integrity. In this work, the derivation and validation of a model of nanostructural surface modifications in metal cutting are presented. For the first time in process modeling, initiation and kinetics of these modifications are predicted using a thermodynamic potential, which considers the interdependent developments of plastic work, dissipation, heat conduction and interface energy as well as the associated productions and flows of entropy. The potential is expressed based on the free Helmholtz energy. The irreversible thermodynamic state changes in the workpiece surface are homogenized over the volume in order to bridge the gap between discrete phenomena involved with the initiation and kinetics of dynamic recrystallization and its macroscopic implications for surface integrity. The formulation of the thermodynamic potential is implemented into a finite element model of orthogonal cutting of steel AISI 4140. Close agreement is achieved between predicted nanostructures and those obtained in transmission electron microscopical investigations of specimen produced in cutting experiments.

Thermodynamical effects accompanied freezing of two water layers separated by sea ice sheet

NASA Astrophysics Data System (ADS)

Bogorodsky, Petr; Marchenko, Aleksey

2014-05-01

The process of melt pond freezing is very important for generation of sea ice cover thermodynamic and mass balance during winterperiod. However, due to significant difficulties of field measurements the available data of model estimations still have no instrumental confirmation. In May 2009 the authors carried out laboratory experiment on freezing of limited water volume in the University Centre in Svalbard ice tank. In the course of experiment fresh water layer of 27.5 cm thickness at freezing point poured on the 24 cm sea ice layer was cooled during 50 hours at the temperature -10º C and then once again during 60 hours at -20º C. For revealing process typical characteristics the data of continuous measurements of temperature and salinity in different phases were compared with data of numerical computations obtained with thermodynamic model which was formulated in the frames of 1-D equation system (infinite extension of water freezing layer) and adapted to laboratory conditions. The known surprise of the experiment became proximity of calculated and measured estimates of process dynamics that confirmed the adequacy of the problem mathematical statement (excluding probably process finale stage). This effect can be explained by formation of cracks on the upper layer of ice at sharp decreases of air temperature, which temporary compensated hydrostatic pressure growth during freezing of closed water volume. Another compensated mechanism can be migration of brine through the lower layer of ice under influence of vertical pressure gradient and also rejection of gas dissolved in water which increased its compressibility. During 110 hours cooling thickness of water layer between ice layers reduced approximately to 2 cm. According to computations this layer is not chilled completely but keeps as thin brine interlayer within ice body whose thickness (about units of mm) is determined by temperature fluctuations of cooled surface. Nevertheless, despite good coincidence of experimental and model estimates the question of existence of liquid phase under actual conditions is still open and can be clarified in a continuous laboratory experiment. This work was supported by Russian Foundation for Basic Research (Project # 14-05-00677).