Ideal thermodynamic processes of oscillatory-flow regenerative engines will go to ideal stirling cycle?

NASA Astrophysics Data System (ADS)

Luo, Ercang

2012-06-01

This paper analyzes the thermodynamic cycle of oscillating-flow regenerative machines. Unlike the classical analysis of thermodynamic textbooks, the assumptions for pistons' movement limitations are not needed and only ideal flowing and heat transfer should be maintained in our present analysis. Under such simple assumptions, the meso-scale thermodynamic cycles of each gas parcel in typical locations of a regenerator are analyzed. It is observed that the gas parcels in the regenerator undergo Lorentz cycle in different temperature levels, whereas the locus of all gas parcels inside the regenerator is the Ericson-like thermodynamic cycle. Based on this new finding, the author argued that ideal oscillating-flow machines without heat transfer and flowing losses is not the Stirling cycle. However, this new thermodynamic cycle can still achieve the same efficiency of the Carnot heat engine and can be considered a new reversible thermodynamic cycle under two constant-temperature heat sinks.

Utilization of Indonesia's Hot Spring Sources for Electricity using Kalina Cycle and Organic Rankine Cycle

NASA Astrophysics Data System (ADS)

Prabumukti, Grano; Purwanto; Widodo, Wahyu

2018-02-01

Indonesia posses 40% of the world's geothermal energy sources. The existence of hydrothermal sources is usually characterized by their surface manifestations such as hot springs, geysers and fumarole. Hot spring has a potential to be used as a heat source to generate electricity especially in a rural and isolated area. Hot springs can be converted into electricity by binary thermodynamic cycles such as Kalina cycle and ORC. The aim of this study is to obtain the best performances of cycle configuration and the potential power capacity. Simulation is conducted using UNISIM software with working fluid and its operating condition as the decision variables. The simulation result shows that R1234yf and propene with simple ORC as desired working fluid and cycle configuration. It reaches a maximum thermal efficiency up to 9.6% with a specific turbine inlet pressure. Higher temperature heat source will result a higher thermal efficiency‥ Cycle thermal efficiency varies from 4.7% to 9.6% depends on source of hot spring temperature. Power capacity that can be generated using Indonesia's hot spring is ranged from 2 kWe to 61.2 kWe. The highest capacity located in Kawah Sirung and the least located in Kaendi.

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

NASA Technical Reports Server (NTRS)

Talcott, N. A., Jr.

1977-01-01

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

Detonation Jet Engine. Part 1--Thermodynamic Cycle

ERIC Educational Resources Information Center

Bulat, Pavel V.; Volkov, Konstantin N.

2016-01-01

We present the most relevant works on jet engine design that utilize thermodynamic cycle of detonative combustion. The efficiency advantages of thermodynamic detonative combustion cycle over Humphrey combustion cycle at constant volume and Brayton combustion cycle at constant pressure were demonstrated. An ideal Ficket-Jacobs detonation cycle, and…

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.

Isobaric vapor-liquid equilibria for binary systems α-phenylethylamine + toluene and α-phenylethylamine + cyclohexane at 100 kPa

NASA Astrophysics Data System (ADS)

Wu, Xiaoru; Gao, Yingyu; Ban, Chunlan; Huang, Qiang

2016-09-01

In this paper the results of the vapor-liquid equilibria study at 100 kPa are presented for two binary systems: α-phenylethylamine(1) + toluene (2) and (α-phenylethylamine(1) + cyclohexane(2)). The binary VLE data of the two systems were correlated by the Wilson, NRTL, and UNIQUAC models. For each binary system the deviations between the results of the correlations and the experimental data have been calculated. For the both binary systems the average relative deviations in temperature for the three models were lower than 0.99%. The average absolute deviations in vapour phase composition (mole fractions) and in temperature T were lower than 0.0271 and 1.93 K, respectively. Thermodynamic consistency has been tested for all vapor-liquid equilibrium data by the Herrington method. The values calculated by Wilson and NRTL equations satisfied the thermodynamics consistency test for the both two systems, while the values calculated by UNIQUAC equation didn't.

A thermodynamic review of cryogenic refrigeration cycles for liquefaction of natural gas

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung

2015-12-01

A thermodynamic review is presented on cryogenic refrigeration cycles for the liquefaction process of natural gas. The main purpose of this review is to examine the thermodynamic structure of various cycles and provide a theoretical basis for selecting a cycle in accordance with different needs and design criteria. Based on existing or proposed liquefaction processes, sixteen ideal cycles are selected and the optimal conditions to achieve their best thermodynamic performance are investigated. The selected cycles include standard and modified versions of Joule-Thomson (JT) cycle, Brayton cycle, and their combined cycle with pure refrigerants (PR) or mixed refrigerants (MR). Full details of the cycles are presented and discussed in terms of FOM (figure of merit) and thermodynamic irreversibility. In addition, a new method of nomenclature is proposed to clearly identify the structure of cycles by abbreviation.

Chemical association in simple models of molecular and ionic fluids. III. The cavity function

NASA Astrophysics Data System (ADS)

Zhou, Yaoqi; Stell, George

1992-01-01

Exact equations which relate the cavity function to excess solvation free energies and equilibrium association constants are rederived by using a thermodynamic cycle. A zeroth-order approximation, derived previously by us as a simple interpolation scheme, is found to be very accurate if the associative bonding occurs on or near the surface of the repulsive core of the interaction potential. If the bonding radius is substantially less than the core radius, the approximation overestimates the association degree and the association constant. For binary association, the zeroth-order approximation is equivalent to the first-order thermodynamic perturbation theory (TPT) of Wertheim. For n-particle association, the combination of the zeroth-order approximation with a ``linear'' approximation (for n-particle distribution functions in terms of the two-particle function) yields the first-order TPT result. Using our exact equations to go beyond TPT, near-exact analytic results for binary hard-sphere association are obtained. Solvent effects on binary hard-sphere association and ionic association are also investigated. A new rule which generalizes Le Chatelier's principle is used to describe the three distinct forms of behaviors involving solvent effects that we find. The replacement of the dielectric-continuum solvent model by a dipolar hard-sphere model leads to improved agreement with an experimental observation. Finally, equation of state for an n-particle flexible linear-chain fluid is derived on the basis of a one-parameter approximation that interpolates between the generalized Kirkwood superposition approximation and the linear approximation. A value of the parameter that appears to be near optimal in the context of this application is obtained from comparison with computer-simulation data.

Hydration of nonelectrolytes in binary aqueous solutions

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2010-10-01

Literature data on the thermodynamic properties of binary aqueous solutions of nonelectrolytes that show negative deviations from Raoult's law due largely to the contribution of the hydration of the solute are briefly surveyed. Attention is focused on simulating the thermodynamic properties of solutions using equations of the cluster model. It is shown that the model is based on the assumption that there exists a distribution of stoichiometric hydrates over hydration numbers. In terms of the theory of ideal associated solutions, the equations for activity coefficients, osmotic coefficients, vapor pressure, and excess thermodynamic functions (volume, Gibbs energy, enthalpy, entropy) are obtained in analytical form. Basic parameters in the equations are the hydration numbers of the nonelectrolyte (the mathematical expectation of the distribution of hydrates) and the dispersions of the distribution. It is concluded that the model equations adequately describe the thermodynamic properties of a wide range of nonelectrolytes partly or completely soluble in water.

Stellivore extraterrestrials? Binary stars as living systems

NASA Astrophysics Data System (ADS)

Vidal, Clément

2016-11-01

We lack signs of extraterrestrial intelligence (ETI) despite decades of observation in the whole electromagnetic spectrum. Could evidence be buried in existing data? To recognize ETI, we first propose criteria discerning life from non-life based on thermodynamics and living systems theory. Then we extrapolate civilizational development to both external and internal growth. Taken together, these two trends lead to an argument that some existing binary stars might actually be ETI. Since these hypothetical beings feed actively on stars, we call them "stellivores". I present an independent thermodynamic argument for their existence, with a metabolic interpretation of interacting binary stars. The jury is still out, but the hypothesis is empirically testable with existing astrophysical data.

Thermodynamic cost of computation, algorithmic complexity and the information metric

NASA Technical Reports Server (NTRS)

Zurek, W. H.

1989-01-01

Algorithmic complexity is discussed as a computational counterpart to the second law of thermodynamics. It is shown that algorithmic complexity, which is a measure of randomness, sets limits on the thermodynamic cost of computations and casts a new light on the limitations of Maxwell's demon. Algorithmic complexity can also be used to define distance between binary strings.

Thermodynamic evaluation of mass diffusion in ionic mixtures

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

Kagan, Grigory; Tang, Xian-Zhu

2014-02-15

The thermodynamic technique of Landau and Lifshitz originally developed for inter-species diffusion in a binary neutral gas mixture is extended to a quasi-neutral plasma with two ion species. It is shown that, while baro- and electro-diffusion coefficients depend on the choice of the thermodynamic system, prediction for the total diffusive mass flux is invariant.

The thermodynamic cycle models for geothermal power plants by considering the working fluid characteristic

NASA Astrophysics Data System (ADS)

Mulyana, Cukup; Adiprana, Reza; Saad, Aswad H.; M. Ridwan, H.; Muhammad, Fajar

2016-02-01

The scarcity of fossil energy accelerates the development of geothermal power plant in Indonesia. The main issue is how to minimize the energy loss from the geothermal working fluid so that the power generated can be increased. In some of geothermal power plant, the hot water which is resulted from flashing is flown to injection well, and steam out from turbine is condensed in condenser, while the temperature and pressure of the working fluid is still high. The aim of this research is how the waste energy can be re-used as energy source to generate electric power. The step of the research is started by studying the characteristics of geothermal fluid out from the well head. The temperature of fluid varies from 140°C - 250°C, the pressure is more than 7 bar and the fluid phase are liquid, gas, or mixing phase. Dry steam power plant is selected for vapor dominated source, single or multiple flash power plant is used for dominated water with temperature > 225°C, while the binary power plant is used for low temperature of fluid < 160°C. Theoretically, the process in the power plant can be described by thermodynamic cycle. Utilizing the heat loss of the brine and by considering the broad range of working fluid temperature, the integrated geothermal power plant has been developed. Started with two ordinary single flash power plants named unit 1 and unit 2, with the temperature 250°C resulting power is W1'+W2'. The power is enhanced by utilizing the steam that is out from first stage of the turbine by inputting the steam to the third stage, the power of the plant increase with W1''+W2" or 10% from the original power. By using flasher, the water from unit 1 and 2 is re-flashed at 200°C, and the steam is used to drive the turbine in unit 3, while the water is re-flashed at the temperature170°C and the steam is flown to the same turbine (unit 3) resulting the power of W3+W4. Using the fluid enthalpy, the calculated power of these double and triple flash power plant are 50% of W1+W2. At the last step, the steam out from the turbine of unit 3 with the temperature 150°C is used as a heat source for binary cycle power plant named unit 4, while the hot water from the flasher is used as a heat source for the other binary cycle named unit 5 resulted power W5+W6 or 15% of W1+W2. Using this integrated model the power increased 75% from the original one.

Finite-Size Effects of Binary Mutual Diffusion Coefficients from Molecular Dynamics

PubMed Central

2018-01-01

Molecular dynamics simulations were performed for the prediction of the finite-size effects of Maxwell-Stefan diffusion coefficients of molecular mixtures and a wide variety of binary Lennard–Jones systems. A strong dependency of computed diffusivities on the system size was observed. Computed diffusivities were found to increase with the number of molecules. We propose a correction for the extrapolation of Maxwell–Stefan diffusion coefficients to the thermodynamic limit, based on the study by Yeh and Hummer (J. Phys. Chem. B, 2004, 108, 15873−15879). The proposed correction is a function of the viscosity of the system, the size of the simulation box, and the thermodynamic factor, which is a measure for the nonideality of the mixture. Verification is carried out for more than 200 distinct binary Lennard–Jones systems, as well as 9 binary systems of methanol, water, ethanol, acetone, methylamine, and carbon tetrachloride. Significant deviations between finite-size Maxwell–Stefan diffusivities and the corresponding diffusivities at the thermodynamic limit were found for mixtures close to demixing. In these cases, the finite-size correction can be even larger than the simulated (finite-size) Maxwell–Stefan diffusivity. Our results show that considering these finite-size effects is crucial and that the suggested correction allows for reliable computations. PMID:29664633

Thermodynamic study of complex formation between Ce3+ and cryptand 222 in some binary mixed nonaqueous solvents

NASA Astrophysics Data System (ADS)

Rounaghi, G. H.; Dolatshahi, S.; Tarahomi, S.

2014-12-01

The stoichiometry, stability and the thermodynamic parameters of complex formation between cerium(III) cation and cryptand 222 (4,7,13,16,21,24-hexaoxa-1,10-diazabycyclo[8.8.8]-hexacosane) were studied by conductometric titration method in some binary solvent mixtures of dimethylformamide (DMF), 1,2-dichloroethane (DCE), ethyl acetate (EtOAc) and methyl acetate (MeOAc) with methanol (MeOH), at 288, 298, 308, and 318 K. A model based on 1: 1 stoichiometry has been used to analyze the conductivity data. The data have been fitted according to a non-linear least-squares analysis that provide the stability constant, K f, for the cation-ligand inclusion complex. The results revealed that the stability order of [Ce(cryptand 222)]3+ complex changes with the nature and composition of the solvent system. A non-linear relationship was observed between the stability constant (log K f) of [Ce(cryptand 222)]3+ complex versus the composition of the binary mixed solvent. Standard thermodynamic values were obtained from temperature dependence of the stability constant of the complex, show that the studied complexation process is mainly entropy governed and are influenced by the nature and composition of the binary mixed solvent solutions.

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Silica problem in the design of geothermal power plants

NASA Astrophysics Data System (ADS)

Dipippo, R.

1985-02-01

The silica problem is examined from the perspective of the power plant designer to develop a procedure to enable a quick estimate to be made of the potential seriousness of the silica deposition problem for a wide variety of resources and for selected types of power plant. The method employs correlations for the equilibrium solubilities of quartz and amorphous silica and for the saturated liquid enthalpy and the latent heat of water substance. Single- and double-flash plants optimized for highest thermodynamic efficiency are considered. Binary-type plants are included generically without mention of cycle specifics. The results are presented both graphically and in tabular form, and the governing equations will be given in an easily-programmable form.

Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

PubMed

Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

2012-10-11

Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

Heber Binary Project. Binary Cycle Geothermal Demonstration Power Plant (RP1900-1)

NASA Astrophysics Data System (ADS)

Lacy, R. G.; Nelson, T. T.

1982-12-01

The Heber Binary Project (1) demonstrates the potential of moderate temperature (below 410 F) geothermal energy to produce economic electric power with binary cycle conversion technology; (2) allows the scaling up and evaluation of the performance of binary cycle technology in geothermal service; (3) establishes schedule, cost and equipment performance, reservoir performance, and the environmental acceptability of such plants; and (4) resolves uncertainties associated with the reservoir performance, plant operation, and economics.

A general approach to the testing of binary solubility systems for thermodynamic consistency. Consolidated Fuel Reprocessing Program

NASA Astrophysics Data System (ADS)

Hamm, L. L.; Vanbrunt, V.

1982-08-01

The numerical solution to the ordinary differential equation which describes the high-pressure vapor-liquid equilibria of a binary system where one of the components is supercritical and exists as a noncondensable gas in the pure state is considered with emphasis on the implicit Runge-Kuta and orthogonal collocation methods. Some preliminary results indicate that the implicit Runge-Kutta method is superior. Due to the extreme nonlinearity of thermodynamic properties in the region near the critical locus, and extended cubic spline fitting technique is devised for correlating the P-x data. The least-squares criterion is employed in smoothing the experimental data. The technique could easily be applied to any thermodynamic data by changing the endpoint requirements. The volumetric behavior of the systems must be given or predicted in order to perform thermodynamic consistency tests. A general procedure is developed for predicting the volumetric behavior required and some indication as to the expected limit of accuracy is given.

Experimental investigation of the phase equilibria and thermodynamic assessment in the U-Ga and U-Al-Ga systems

NASA Astrophysics Data System (ADS)

Moussa, Chantal; Berche, Alexandre; Barbosa, José; Pasturel, Mathieu; Stepnik, Bertrand; Tougait, Olivier

2018-02-01

The phase relations in the binary U-Ga and ternary U-Al-Ga systems were established as an isopleth section and two isothermal sections at 900 K and 1150 K for the whole concentration range, respectively. They were experimentally determined by means of powder and single crystal XRD, SEM-EDS analyses on both as-cast and heat-treated samples and DTA measurements. Both systems were thermodynamically assessed using the Calphad method based on the available data, i.e. phase relations and thermodynamic properties. The new description of the U-Ga phase diagram improves the composition-temperature description for most of invariant reactions. The U-Al-Ga system is characterized by large ternary extensions of the binary phases and the absence of ternary intermediate phase at both 900 K and 1150 K. These experimental results are nicely reproduced by the Calphad assessment, allowing to extract the thermodynamic parameters further used to calculate the liquidus projection and the invariant reactions along with their temperature.

The Precise Measurement of Vapor-Liquid Equilibrium Properties of the CO2/Isopentane Binary Mixture, and Fitted Parameters for a Helmholtz Energy Mixture Model

NASA Astrophysics Data System (ADS)

Miyamoto, H.; Shoji, Y.; Akasaka, R.; Lemmon, E. W.

2017-10-01

Natural working fluid mixtures, including combinations of CO2, hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor-liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm3 equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO2/ethanol and CO2/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.

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.

Computer-Generated Phase Diagrams for Binary Mixtures.

ERIC Educational Resources Information Center

Jolls, Kenneth R.; And Others

1983-01-01

Computer programs that generate projections of thermodynamic phase surfaces through computer graphics were used to produce diagrams representing properties of water and steam and the pressure-volume-temperature behavior of most of the common equations of state. The program, program options emphasizing thermodynamic features of interest, and…

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

PubMed Central

Mostafa, Ahmad; Medraj, Mamoun

2017-01-01

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

Thermodynamic scaling of the shear viscosity of Mie n-6 fluids and their binary mixtures

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

Delage-Santacreu, Stephanie; Galliero, Guillaume, E-mail: guillaume.galliero@univ-pau.fr; Hoang, Hai

2015-05-07

In this work, we have evaluated the applicability of the so-called thermodynamic scaling and the isomorph frame to describe the shear viscosity of Mie n-6 fluids of varying repulsive exponents (n = 8, 12, 18, 24, and 36). Furthermore, the effectiveness of the thermodynamic scaling to deal with binary mixtures of Mie n-6 fluids has been explored as well. To generate the viscosity database of these fluids, extensive non-equilibrium molecular dynamics simulations have been performed for various thermodynamic conditions. Then, a systematic approach has been used to determine the gamma exponent value (γ) characteristic of the thermodynamic scaling approach formore » each system. In addition, the applicability of the isomorph theory with a density dependent gamma has been confirmed in pure fluids. In both pure fluids and mixtures, it has been found that the thermodynamic scaling with a constant gamma is sufficient to correlate the viscosity data on a large range of thermodynamic conditions covering liquid and supercritical states as long as the density is not too high. Interestingly, it has been obtained that, in pure fluids, the value of γ is directly proportional to the repulsive exponent of the Mie potential. Finally, it has been found that the value of γ in mixtures can be deduced from those of the pure component using a simple logarithmic mixing rule.« less

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

pKa values of hyodeoxycholic and cholic acids in the binary mixed micelles sodium-hyodeoxycholate-Tween 40 and sodium-cholate-Tween 40: Thermodynamic stability of the micelle and the cooperative hydrogen bond formation with the steroid skeleton.

PubMed

Poša, Mihalj; Pilipović, Ana; Bećarević, Mirjana; Farkaš, Zita

2017-01-01

Due to a relatively small size of bile acid salts, their mixed micelles with nonionic surfactants are analysed. Of the special interests are real binary mixed micelles that are thermodynamically more stable than ideal mixed micelles. Thermodynamic stability is expressed with an excess Gibbs energy (G E ) or over an interaction parameter (β ij ). In this paper sodium salts of cholic (C) and hyodeoxycholic acid (HD) in their mixed micelles with Tween 40 (T40) are analysed by potentiometric titration and their pKa values are determined. Examined bile acids in mixed micelles with T40 have higher pKa values than free bile acids. The increase of ΔpKa acid constant of micellary bound C and HD is in a correlation with absolute values of an interaction parameter. According to an interaction parameter and an excess Gibbs energy, mixed micelle HD-T40 are thermodynamically more stable than mixed micelles C-T40. ΔpKa values are higher for mixed micelles with Tween 40 whose second building unit is HD, related to the building unit C. In both micellar systems, ΔpKa increases with the rise of a molar fraction of Tween 40 in binary mixtures of surfactants with sodium salts of bile acids. This suggests that, ΔpKa can be a measure of a thermodynamic stabilization of analysed binary mixed micelles as well as an interaction parameter. ΔpKa values are confirmed by determination of a distribution coefficient of HD and C in systems: water phase with Tween 40 in a micellar concentration and 1-octanol, with a change of a pH value of a water phase. Conformational analyses suggests that synergistic interactions between building units of analysed binary micelles originates from formation of hydrogen bonds between steroid OH groups and polyoxyethylene groups of the T40. Relative similarity and spatial orientation of C 3 and C 6 OH group allows cooperative formation of hydrogen bonds between T40 and HD - excess entropy in formation of mixed micelle. If a water solution of analysed binary mixtures of surfactants contains urea in concentration of 4M significant decreases of an interaction parameter value happens which confirms the importance of hydrogen bonds in synergistic interactions (urea compete in hydrogen bonds). Copyright © 2016 Elsevier Inc. All rights reserved.

Analysis and simulation of the I C engine Otto cycle using the second law of thermodynamics

NASA Astrophysics Data System (ADS)

Abdel-Rahim, Y. M.

The present investigation is an application of the second law of thermodynamics to the spark ignition engine cycle. A comprehensive thermodynamic analysis of the air standard cycle is conducted using the first and second laws of thermodynamics, the ideal gas equation of state and the perfect gas properties for air. The study investigates the effect of the cycle parameters on the cycle performance reflected by the first and second law efficiencies, the heat added, the work done, the available energy added as well as the history of the internal, available and unavailable energies along the cycle. The study shows that the second law efficiency is a function of the compression ratio, the initial temperature, the maximum temperature as well as the dead state temperature. A non-dimensional comprehensive thermodynamic simulation model for the actual Otto cycle is developed to study the effects of the design and operating parameters of the cycle on the cycle performance. The analysis takes into account engine geometry, mixture strength, heat transfer, piston motion, engine speed, mechanical friction, spark advance and combustion duration.

Study of thermodynamic properties of liquid binary alloys by a pseudopotential method

NASA Astrophysics Data System (ADS)

Vora, Aditya M.

2010-11-01

On the basis of the Percus-Yevick hard-sphere model as a reference system and the Gibbs-Bogoliubov inequality, a thermodynamic perturbation method is applied with the use of the well-known model potential. By applying a variational method, the hard-core diameters are found which correspond to a minimum free energy. With this procedure, the thermodynamic properties such as the internal energy, entropy, Helmholtz free energy, entropy of mixing, and heat of mixing are computed for liquid NaK binary systems. The influence of the local-field correction functions of Hartree, Taylor, Ichimaru-Utsumi, Farid-Heine-Engel-Robertson, and Sarkar-Sen-Haldar-Roy is also investigated. The computed excess entropy is in agreement with available experimental data in the case of liquid alloys, whereas the agreement for the heat of mixing is poor. This may be due to the sensitivity of the latter to the potential parameters and dielectric function.

Physical properties of organic fullerene cocrystals

NASA Astrophysics Data System (ADS)

Macovez, Roberto

2017-12-01

The basic facts and fundamental properties of binary fullerene cocrystals are reviewed, focusing especially on solvates and salts of Buckminsterfullerene (C60), and hydrates of hydrophilic C60 derivatives. The examined properties include the lattice structure and the presence of orientational disorder and/or rotational dynamics (of both fullerenes and cocrystallizing moieties), thermodynamic properties such as decomposition enthalpies, and charge transport properties. Both thermodynamic properties and molecular orientational disorder shed light on the extent of intermolecular interactions in these binary solid-state systems. Comparison is carried out also with pristine fullerite and with the solid phases of functionalized C60. Interesting experimental findings on binary fullerene cocrystals include the simultaneous occurrence of rotations of both constituent molecular species, crystal morphologies reminiscent of quasi-crystalline behaviour, the observation of proton conduction in hydrate solids of hydrophilic fullerene derivatives, and the production of super-hard carbon materials by application of high pressures on solvated fullerene crystals.

Quantum thermodynamic cycles and quantum heat engines. II.

PubMed

Quan, H T

2009-04-01

We study the quantum-mechanical generalization of force or pressure, and then we extend the classical thermodynamic isobaric process to quantum-mechanical systems. Based on these efforts, we are able to study the quantum version of thermodynamic cycles that consist of quantum isobaric processes, such as the quantum Brayton cycle and quantum Diesel cycle. We also consider the implementation of the quantum Brayton cycle and quantum Diesel cycle with some model systems, such as single particle in a one-dimensional box and single-mode radiation field in a cavity. These studies lay the microscopic (quantum-mechanical) foundation for Szilard-Zurek single-molecule engine.

A contact binary asteroid evolutionary cycle driven by BYORP & the classical Laplace plane

NASA Astrophysics Data System (ADS)

Rieger, Samantha; Scheeres, Daniel J.

2017-10-01

Several contact binaries have been observed to have high obliquities distributed around 90°. With this information, we explore the possibility of these high obliquities being a key characteristic that causes an evolutionary cycle of contact binary formation and separation.The contact binary cycle begins with a single asteroid that is spinning up due to the YORP effect. For the binary cycle we assume YORP will drive the obliquity to 90°. Eventually, the asteroid will reach a critical spin frequency that will cause the asteroid to fission into a binary. We assume that the mass-ratio, q, of the system is greater than 0.2. With a high q, the secondary will not escape/impact the primary but will evolve through tides into a stable circular double-synchronous orbit. The binary being synchronous will cause the forces from BYORP to have secular effects on the system. For this cycle, BYORP will need to expand the secondary away from the primary.As the system expands, we have found that the secondary will follow the classical Laplace plane. Therefore, the secondary’s orbit will increase in inclination with respect to the equator as the secondary’s orbit expands. The Laplace plane is a stable orbit to perturbations from J2 & Sun tides except for an instability region that exists for primaries with obliquities above 68.875° & a secondary orbital radius of 13.5-19.5 primary radii. Once BYORP expands the secondary into this instability region, the eccentricity of the secondary’s orbit will increase until the orbit intersects with the primary & causes an impact. This impact will create a contact binary with a new obliquity that will randomly range from 23°-150°. The cycle will begin again with YORP driving the contact binary to an obliquity of 90°.Our contribution will discuss the proposed contact binary cycle in more detail, including the mechanics of the system that drives the events given above. We will include investigations into how losing synchronous lock will disrupt the eccentricity growth in the Laplace plane instability region. We will also discuss the time scales of each event to help predict which part of the cycle we will most likely to be observing when discovering new contact binaries & binary systems.

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

Thermoelectric Properties of the Quasi-Binary MnSi1.73-FeSi2 System

NASA Astrophysics Data System (ADS)

Sadia, Yatir; Madar, Naor; Kaler, Ilan; Gelbstein, Yaniv

2015-06-01

The higher manganese silicides (HMS) are regarded as very attractive p-type thermoelectric materials for direct conversion of heat to electricity. To compete with other thermodynamic engines (e.g. the Stirling and Rankine cycles), however, the thermoelectric figure of merit of such silicides must be improved. HMS follow a complicated solidification reaction on cooling from the melt, which leads to formation of undesired secondary phases. Furthermore, the electronic carrier concentration of HMS is much higher than the optimum for thermoelectric applications and should be compensated by introduction of doping agents. In this research, the electronic donor action associated with substitution of HMS by FeSi2 was investigated. The effects of excess Si on phase distribution and thermoelectric properties are also discussed in detail.

More surprises from the violent gamma-ray binary LS 2883 /B1259-63.

NASA Astrophysics Data System (ADS)

Kargaltsev, Oleg; Hare, Jeremy; Pavlov, George G.

2018-01-01

We report the results of a Chandra X-ray Observatory (CXO) monitoring campaign of the high-mass gamma-ray binary LS 2883, which hosts the young pulsar B1259-63. The monitoring now covers two binary cycles (6.8 years) and allows us to conclude that ejections of high-velocity X-ray emitting material are common for this binary. In the first cycle we observed an extended feature which detached and moved away from the binary. The observed changes in position were consistent with a steady motion with v=(0.07+/-0.01)c and a slight hint of acceleration. Tracing the motion back in time suggested that the X-ray emitting matter was ejected close to periastron passage. In the last orbital cycle, accelerated motion (reaching (0.13+/-0.02)c) is strongly preferred over a steady motion (the latter would imply that the ejected material was launched ~400 days after the periastron passage). The moving feature is also more luminous, compared to the previous binary cycle, larger in its apparent extent, and exhibits a puzzling morphology. We will show the CXO movies from both binary cycles and discuss physical interpretation of the resolved outflow dynamics in this remarkable system, which provides unique insight into the properties of the pulsar and stellar winds and their interaction.

How important is thermodynamics for identifying elementary flux modes?

PubMed Central

Peres, Sabine; Jolicœur, Mario; Moulin, Cécile

2017-01-01

We present a method for computing thermodynamically feasible elementary flux modes (tEFMs) using equilibrium constants without need of internal metabolite concentrations. The method is compared with the method based on a binary distinction between reversible and irreversible reactions. When all reactions are reversible, adding the constraints based on equilibrium constants reduces the number of elementary flux modes (EFMs) by a factor of two. Declaring in advance some reactions as irreversible, based on reliable biochemical expertise, can in general reduce the number of EFMs by a greater factor. But, even in this case, computing tEFMs can rule out some EFMs which are biochemically irrelevant. We applied our method to two published models described with binary distinction: the monosaccharide metabolism and the central carbon metabolism of Chinese hamster ovary cells. The results show that the binary distinction is in good agreement with biochemical observations. Moreover, the suppression of the EFMs that are not consistent with the equilibrium constants appears to be biologically relevant. PMID:28222104

A thermodynamic study of complexation process between N, N'-dipyridoxylidene(1,4-butanediamine) and Cd2+ in some binary mixed solvents using conductometry

NASA Astrophysics Data System (ADS)

Ebrahimpoor, Sonia; Khoshnood, Razieh Sanavi; Beyramabadi, S. Ali

2016-12-01

Complexation of the Cd2+ ion with N, N'-dipyridoxylidene(1,4-butanediamine) Schiff base was studied in pure solvents including acetonitrile (AN), ethanol (EtOH), methanol (MeOH), tetrahydrofuran (THF), dimethylformamide (DMF), water (H2O), and various binary solvent mixtures of acetonitrile-ethanol (AN-EtOH), acetonitrile-methanol (AN-MeOH), acetonitrile-tetrahydrofuran (AN-THF), acetonitrile-dimethylformamide (AN-DMF), and acetonitrile-water (AN-H2O) systems at different temperatures using the conductometric method. The conductance data show that the stoichiometry of complex is 1: 1 [ML] in all solvent systems. A non-linear behavior was observed for changes of log K f of [Cd( N, N'-dipyridoxylidene(1,4-butanediamine)] complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions. The results show that the thermodynamics of complexation reaction is affected by the nature and composition of the mixed solvents.

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

Binding Thermodynamics of Ferredoxin:NADP+ Reductase: Two Different Protein Substrates and One Energetics

PubMed Central

Martínez-Júlvez, Marta; Medina, Milagros; Velázquez-Campoy, Adrián

2009-01-01

Abstract The thermodynamics of the formation of binary and ternary complexes between Anabaena PCC 7119 FNR and its substrates, NADP+ and Fd, or Fld, has been studied by ITC. Despite structural dissimilarities, the main difference between Fd and Fld binding to FNR relates to hydrophobicity, reflected in different binding heat capacity and number of water molecules released from the interface. At pH 8, the formation of the binary complexes is both enthalpically and entropically driven, accompanied by the protonation of at least one ionizable group. His299 FNR has been identified as the main responsible for the proton exchange observed. However, at pH 10, where no protonation occurs and intrinsic binding parameters can be obtained, the formation of the binary complexes is entropically driven, with negligible enthalpic contribution. Absence of the FMN cofactor in Fld does not alter significantly the strength of the interaction, but considerably modifies the enthalpic and entropic contributions, suggesting a different binding mode. Ternary complexes show negative cooperativity (6-fold and 11-fold reduction in binding affinity, respectively), and an increase in the enthalpic contribution (more favorable) and a decrease in the entropic contribution (less favorable), with regard to the binary complexes energetics. PMID:19527656

Theories of binary fluid mixtures: from phase-separation kinetics to active emulsions

NASA Astrophysics Data System (ADS)

Cates, Michael E.; Tjhung, Elsen

2018-02-01

Binary fluid mixtures are examples of complex fluids whose microstructure and flow are strongly coupled. For pairs of simple fluids, the microstructure consists of droplets or bicontinuous demixed domains and the physics is controlled by the interfaces between these domains. At continuum level, the structure is defined by a composition field whose gradients which are steep near interfaces drive its diffusive current. These gradients also cause thermodynamic stresses which can drive fluid flow. Fluid flow in turn advects the composition field, while thermal noise creates additional random fluxes that allow the system to explore its configuration space and move towards the Boltzmann distribution. This article introduces continuum models of binary fluids, first covering some well-studied areas such as the thermodynamics and kinetics of phase separation, and emulsion stability. We then address cases where one of the fluid components has anisotropic structure at mesoscopic scales creating nematic (or polar) liquid-crystalline order; this can be described through an additional tensor (or vector) order parameter field. We conclude by outlining a thriving area of current research, namely active emulsions, in which one of the binary components consists of living or synthetic material that is continuously converting chemical energy into mechanical work.

A global optimization method synthesizing heat transfer and thermodynamics for the power generation system with Brayton cycle

NASA Astrophysics Data System (ADS)

Fu, Rong-Huan; Zhang, Xing

2016-09-01

Supercritical carbon dioxide operated in a Brayton cycle offers a numerous of potential advantages for a power generation system, and a lot of thermodynamics analyses have been conducted to increase its efficiency. Because there are a lot of heat-absorbing and heat-lossing subprocesses in a practical thermodynamic cycle and they are implemented by heat exchangers, it will increase the gross efficiency of the whole power generation system to optimize the system combining thermodynamics and heat transfer theory. This paper analyzes the influence of the performance of heat exchangers on the actual efficiency of an ideal Brayton cycle with a simple configuration, and proposes a new method to optimize the power generation system, which aims at the minimum energy consumption. Although the method is operated only for the ideal working fluid in this paper, its merits compared to that only with thermodynamic analysis are fully shown.

Optimization of controlled processes in combined-cycle plant (new developments and researches)

NASA Astrophysics Data System (ADS)

Tverskoy, Yu S.; Muravev, I. K.

2017-11-01

All modern complex technical systems, including power units of TPP and nuclear power plants, work in the system-forming structure of multifunctional APCS. The development of the modern APCS mathematical support allows bringing the automation degree to the solution of complex optimization problems of equipment heat-mass-exchange processes in real time. The difficulty of efficient management of a binary power unit is related to the need to solve jointly at least three problems. The first problem is related to the physical issues of combined-cycle technologies. The second problem is determined by the criticality of the CCGT operation to changes in the regime and climatic factors. The third problem is related to a precise description of a vector of controlled coordinates of a complex technological object. To obtain a joint solution of this complex of interconnected problems, the methodology of generalized thermodynamic analysis, methods of the theory of automatic control and mathematical modeling are used. In the present report, results of new developments and studies are shown. These results allow improving the principles of process control and the automatic control systems structural synthesis of power units with combined-cycle plants that provide attainable technical and economic efficiency and operational reliability of equipment.

Generalized Einstein relation for the mutual diffusion coefficient of a binary fluid mixture.

PubMed

Felderhof, B U

2017-08-21

The method employed by Einstein to derive his famous relation between the diffusion coefficient and the friction coefficient of a Brownian particle is used to derive a generalized Einstein relation for the mutual diffusion coefficient of a binary fluid mixture. The expression is compared with the one derived by de Groot and Mazur from irreversible thermodynamics and later by Batchelor for a Brownian suspension. A different result was derived by several other workers in irreversible thermodynamics. For a nearly incompressible solution, the generalized Einstein relation agrees with the expression derived by de Groot and Mazur. The two expressions also agree to first order in solute density. For a Brownian suspension, the result derived from the generalized Smoluchowski equation agrees with both expressions.

Thermodynamic design of natural gas liquefaction cycles for offshore application

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung; Lim, Hye Su; Choe, Kun Hyung

2014-09-01

A thermodynamic study is carried out for natural gas liquefaction cycles applicable to offshore floating plants, as partial efforts of an ongoing governmental project in Korea. For offshore liquefaction, the most suitable cycle may be different from the on-land LNG processes under operation, because compactness and simple operation are important as well as thermodynamic efficiency. As a turbine-based cycle, closed Claude cycle is proposed to use NG (natural gas) itself as refrigerant. The optimal condition for NG Claude cycle is determined with a process simulator (Aspen HYSYS), and the results are compared with fully-developed C3-MR (propane pre-cooled mixed refrigerant) JT cycles and various N2 (nitrogen) Brayton cycles in terms of efficiency and compactness. The newly proposed NG Claude cycle could be a good candidate for offshore LNG processes.

Thermodynamics and proton activities of protic ionic liquids with quantum cluster equilibrium theory

NASA Astrophysics Data System (ADS)

Ingenmey, Johannes; von Domaros, Michael; Perlt, Eva; Verevkin, Sergey P.; Kirchner, Barbara

2018-05-01

We applied the binary Quantum Cluster Equilibrium (bQCE) method to a number of alkylammonium-based protic ionic liquids in order to predict boiling points, vaporization enthalpies, and proton activities. The theory combines statistical thermodynamics of van-der-Waals-type clusters with ab initio quantum chemistry and yields the partition functions (and associated thermodynamic potentials) of binary mixtures over a wide range of thermodynamic phase points. Unlike conventional cluster approaches that are limited to the prediction of thermodynamic properties, dissociation reactions can be effortlessly included into the bQCE formalism, giving access to ionicities, as well. The method is open to quantum chemical methods at any level of theory, but combination with low-cost composite density functional theory methods and the proposed systematic approach to generate cluster sets provides a computationally inexpensive and mostly parameter-free way to predict such properties at good-to-excellent accuracy. Boiling points can be predicted within an accuracy of 50 K, reaching excellent accuracy for ethylammonium nitrate. Vaporization enthalpies are predicted within an accuracy of 20 kJ mol-1 and can be systematically interpreted on a molecular level. We present the first theoretical approach to predict proton activities in protic ionic liquids, with results fitting well into the experimentally observed correlation. Furthermore, enthalpies of vaporization were measured experimentally for some alkylammonium nitrates and an excellent linear correlation with vaporization enthalpies of their respective parent amines is observed.

Advanced binary geothermal power plants: Limits of performance

NASA Astrophysics Data System (ADS)

Bliem, C. J.; Mines, G. L.

1991-01-01

The Heat Cycle Research Program is investigating potential improvements to power cycles utilizing moderate temperature geothermal resources to produce electrical power. Investigations have specifically examined Rankine cycle binary power systems. Binary Rankine cycles are more efficient than the flash steam cycles at moderate resource temperature, achieving a higher net brine effectiveness. At resource conditions similar to those at the Heber binary plant, it has been shown that mixtures of saturated hydrocarbons (alkanes) or halogenated hydrocarbons operating in a supercritical Rankine cycle gave improved performance over Rankine cycles with the pure working fluids executing single or dual boiling cycles or supercritical cycles. Recently, other types of cycles have been proposed for binary geothermal service. The feasible limits on efficiency of a plant given practical limits on equipment performance is explored and the methods used in these advanced concept plants to achieve the maximum possible efficiency are discussed. (Here feasible is intended to mean reasonably achievable and not cost effective.) No direct economic analysis was made because of the sensitivity of economic results to site specific input. The limit of performance of three advanced plants were considered. The performance predictions were taken from the developers of each concept. The advanced plants considered appear to be approaching the feasible limit of performance. Ultimately, the plant designer must weigh the advantages and disadvantages of the the different cycles to find the best plant for a given service. In addition, a standard is presented of comparison of the work which has been done in the Heat Cycle Research Program and in the industrial sector by Exergy, Inc. and Polythermal Technologies.

Method and apparatus for removing non-condensible gas from a working fluid in a binary power system

DOEpatents

Mohr, Charles M.; Mines, Gregory L.; Bloomfield, K. Kit

2002-01-01

Apparatus for removing non-condensible gas from a working fluid utilized in a thermodynamic system comprises a membrane having an upstream side operatively connected to the thermodynamic system so that the upstream side of the membrane receives a portion of the working fluid. The first membrane separates the non-condensible gas from the working fluid. A pump operatively associated with the membrane causes the portion of the working fluid to contact the membrane and to be returned to the thermodynamic system.

Discussion Meeting on Thermodynamics of Alloys Held in Sant Feliu de Guixols, Spain on 23-26 May 1990. Abstracts

DTIC Science & Technology

1990-05-26

OFFICE OF THE U.S. ARMY EUROPEAN RESEARCH OFFICE OF THE U.S. AIR FORCE MINISTERIO DE EDUCACION Y CIENCIA I I Wednesday, May 23 8.30 Registration 9.00... especially regarding the structural but less the thermodynamic proper- ties). The third binary system Ag-Te has been investigated in detail by our group. No

Comparison of geothermal power conversion cycles

NASA Technical Reports Server (NTRS)

Elliott, D. G.

1976-01-01

Geothermal power conversion cycles are compared with respect to recovery of the available wellhead power. The cycles compared are flash steam, in which steam turbines are driven by steam separated from one or more flash stages; binary, in which heat is transferred from the brine to an organic turbine cycle; flash binary, in which heat is transferred from flashed steam to an organic turbine cycle; and dual steam, in which two-phase expanders are driven by the flashing steam-brine mixture and steam turbines by the separated steam. Expander efficiencies assumed are 0.7 for steam turbines, 0.8 for organic turbines, and 0.6 for two-phase expanders. The fraction of available wellhead power delivered by each cycle is found to be about the same at all brine temperatures: 0.65 with one stage and 0.7 with four stages for dual stream; 0.4 with one stage and 0.6 with four stages for flash steam; 0.5 for binary; and 0.3 with one stage and 0.5 with four stages for flash binary.

On the thermal efficiency of power cycles in finite time thermodynamics

NASA Astrophysics Data System (ADS)

Momeni, Farhang; Morad, Mohammad Reza; Mahmoudi, Ashkan

2016-09-01

The Carnot, Diesel, Otto, and Brayton power cycles are reconsidered endoreversibly in finite time thermodynamics (FTT). In particular, the thermal efficiency of these standard power cycles is compared to the well-known results in classical thermodynamics. The present analysis based on FTT modelling shows that a reduction in both the maximum and minimum temperatures of the cycle causes the thermal efficiency to increase. This is antithetical to the existing trend in the classical references. Under the assumption of endoreversibility, the relation between the efficiencies is also changed to {η }{{Carnot}}\\gt {η }{{Brayton}}\\gt {η }{{Diesel}}\\gt {η }{{Otto}}, which is again very different from the corresponding classical results. The present results benefit a better understanding of the important role of irreversibility on heat engines in classical thermodynamics.

The structural, electronic, magnetic and optical properties of the half-metallic binary alloys ZCl3 (Z=Be, Mg, Ca, Sr): A first-principles study

NASA Astrophysics Data System (ADS)

Song, Jun-Tao; Zhang, Jian-Min

2018-06-01

The investigations of the electronic and magnetic properties show the binary Heusler alloys ZCl3 (Z = Be, Mg, Ca, Sr) are half-metallic (HM) ferromagnets with an integer magnetic moment (Mt) of 1 μB /f.u.. The alloy BeCl3 is thermodynamic meta-stable, while other alloys are thermodynamic stable according to their cohesive energies and formation energies. Moreover, wide HM regions for alloys ZCl3 (Z = Be, Mg, Ca, Sr) show their HM characters are robust when the lattices are expanded or compressed under uniform and tetragonal strains. Finally, some optical properties are analyzed in detail, such as the dielectric function, the absorption coefficient, the refractive index and the extinction coefficient.

Self-association of plant wax components: a thermodynamic analysis.

PubMed

Casado, C G; Heredia, A

2001-01-01

Excess specific heat, C(p)()(E), of binary mixtures of selected components of plant cuticular waxes has been determined. This thermodynamic parameter gives an explanation of the special molecular arrangement in crystalline and amorphous zones of plant waxes. C(p)()(E) values indicate that hydrogen bonding between chains results in the formation of amorphous zones. Conclusions on the self-asembly process of plant waxes have been also made.

Elastic, mechanical, and thermodynamic properties of Bi-Sb binaries: Effect of spin-orbit coupling

NASA Astrophysics Data System (ADS)

Singh, Sobhit; Valencia-Jaime, Irais; Pavlic, Olivia; Romero, Aldo H.

2018-02-01

Using first-principles calculations, we systematically study the elastic stiffness constants, mechanical properties, elastic wave velocities, Debye temperature, melting temperature, and specific heat of several thermodynamically stable crystal structures of BixSb1 -x (0

Correlation between Thermodynamic Efficiency and Ecological Cyclicity for Thermodynamic Power Cycles

PubMed Central

Layton, Astrid; Reap, John; Bras, Bert; Weissburg, Marc

2012-01-01

A sustainable global community requires the successful integration of environment and engineering. In the public and private sectors, designing cyclical (“closed loop”) resource networks increasingly appears as a strategy employed to improve resource efficiency and reduce environmental impacts. Patterning industrial networks on ecological ones has been shown to provide significant improvements at multiple levels. Here, we apply the biological metric cyclicity to 28 familiar thermodynamic power cycles of increasing complexity. These cycles, composed of turbines and the like, are scientifically very different from natural ecosystems. Despite this difference, the application results in a positive correlation between the maximum thermal efficiency and the cyclic structure of the cycles. The immediate impact of these findings results in a simple method for comparing cycles to one another, higher cyclicity values pointing to those cycles which have the potential for a higher maximum thermal efficiency. Such a strong correlation has the promise of impacting both natural ecology and engineering thermodynamics and provides a clear motivation to look for more fundamental scientific connections between natural and engineered systems. PMID:23251638

Performance assessment of an irreversible nano Brayton cycle operating with Maxwell-Boltzmann gas

NASA Astrophysics Data System (ADS)

Açıkkalp, Emin; Caner, Necmettin

2015-05-01

In the last decades, nano-technology has been developed very fast. According to this, nano-cycle thermodynamics should improve with a similar rate. In this paper, a nano-scale irreversible Brayton cycle working with helium is evaluated for different thermodynamic criteria. These are maximum work output, ecological function, ecological coefficient of performance, exergetic performance criteria and energy efficiency. Thermodynamic analysis was performed for these criteria and results were submitted numerically. In addition, these criteria are compared with each other and the most convenient methods for the optimum conditions are suggested.

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

Coker, Eric Nicholas; Rodriguez, Mark A.; Ambrosini, Andrea

Hydrogen and carbon monoxide may be produced using solar-thermal energy in two-stage reactions of water and carbon dioxide, respectively, over certain metal oxide materials. The most active materials observed experimentally for these processes are complex mixtures of ferrite and zirconia based solids, and it is not clear how far the ferrites, the zirconia, or a solid solution between the two participate in the change of oxidation state during the cycling. Identification of the key phases in the redox material that enable splitting is of paramount importance to developing a working model of the materials. A three-pronged approach was adopted here:more » computer modeling to determine thermodynamically favorable materials compositions, bench reactor testing to evaluate materials’ performance, and in-situ characterization of reactive materials to follow phase changes and identify the phases active for splitting. For the characterization and performance evaluation thrusts, cobalt ferrites were prepared by co-precipitation followed by annealing at 1400 °C. An in-situ X-ray diffraction capability was developed and tested, allowing phase monitoring in real time during thermochemical redox cycling. Key observations made for an un-supported cobalt ferrite include: 1) ferrite phases partially reduce to wustite upon heating to 1400 °C in helium; 2) exposing the material to air at 1100 °C causes immediate re-oxidation; 3) the re-oxidized material may be thermally reduced at 1400 °C under inert; 4) exposure of a reduced material to CO 2 results in gradual re-oxidation at 1100 °C, but minimization of background O 2-levels is essential; 5) even after several redox cycles, the lattice parameters of the ferrites remain constant, indicating that irreversible phase separation does not occur, at least over the first five cycles; 6) substituting chemical (hydrogen) reduction for thermal reduction resulted in formation of a CoFe metallic alloy. Materials were also evaluated for their CO 2-splitting performance in bench reactor systems utilizing chemical reduction in place of thermal reduction. These tests lead to the following general conclusions: 1) despite over-reduction of the cobalt ferrite phase to CoFe alloy on chemical reduction, splitting of CO 2 still occurs; 2) the kinetics of chemical reduction follow the sequence: un-supported < ZrO 2-supported < yttria-stabilized ZrO 2 (YSZ)-supported ferrite; 3) ferrite/YSZ re-oxidizes faster than ferrite/ZrO 2 under CO 2 in the range 400 – 700 °C. The temperature and pressure regimes in which the thermal reduction and water-splitting steps are thermodynamically favorable in terms of the enthalpy and entropy of oxide reduction, were determined. These metrics represent a useful design goal for any proposed water-splitting cycle. Applying this theoretical framework to available thermodynamic data, it was shown that none of the 105 binary oxide redox couples that were screened possess both energetically favorable reduction and oxidation steps. However, several driving forces, including low pressure and a large positive solid-state entropy of reduction of the oxide, have the potential to enable thermodynamically-favored two-step cycles.« less

Combined Brayton-JT cycles with refrigerants for natural gas liquefaction

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung; Park, Jae Hoon; Lee, Sanggyu; Choe, Kun Hyung

2012-06-01

Thermodynamic cycles for natural gas liquefaction with single-component refrigerants are investigated under a governmental project in Korea, aiming at new processes to meet the requirements on high efficiency, large capacity, and simple equipment. Based upon the optimization theory recently published by the present authors, it is proposed to replace the methane-JT cycle in conventional cascade process with a nitrogen-Brayton cycle. A variety of systems to combine nitrogen-Brayton, ethane-JT and propane-JT cycles are simulated with Aspen HYSYS and quantitatively compared in terms of thermodynamic efficiency, flow rate of refrigerants, and estimated size of heat exchangers. A specific Brayton-JT cycle is suggested with detailed thermodynamic data for further process development. The suggested cycle is expected to be more efficient and simpler than the existing cascade process, while still taking advantage of easy and robust operation with single-component refrigerants.

Phase stability in nanoscale material systems: extension from bulk phase diagrams

NASA Astrophysics Data System (ADS)

Bajaj, Saurabh; Haverty, Michael G.; Arróyave, Raymundo; Goddard Frsc, William A., III; Shankar, Sadasivan

2015-05-01

Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts. The surface energy contribution, which is the dominant factor in causing these changes, is evaluated using the spherical particle approximation. It is first validated with the Au-Si system for which experimental data on phase stability of spherical nano-sized particles is available, and then extended to calculate phase diagrams of similarly sized particles of Ge-Si and Al-Cu. Additionally, the surface energies of the associated compounds are calculated using DFT, and integrated into the thermodynamic model of the respective binary systems. In this work we found changes in miscibilities, reaction compositions of about 5 at%, and solubility temperatures ranging from 100-200 K for particles of sizes 5 nm, indicating the importance of phase equilibrium analysis at nano dimensions.Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts. The surface energy contribution, which is the dominant factor in causing these changes, is evaluated using the spherical particle approximation. It is first validated with the Au-Si system for which experimental data on phase stability of spherical nano-sized particles is available, and then extended to calculate phase diagrams of similarly sized particles of Ge-Si and Al-Cu. Additionally, the surface energies of the associated compounds are calculated using DFT, and integrated into the thermodynamic model of the respective binary systems. In this work we found changes in miscibilities, reaction compositions of about 5 at%, and solubility temperatures ranging from 100-200 K for particles of sizes 5 nm, indicating the importance of phase equilibrium analysis at nano dimensions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01535a

Application of computational thermodynamics in the study of magnsium alloys and bulk metallic glasses

NASA Astrophysics Data System (ADS)

Cao, Hongbo

In this thesis, the application of the computational thermodynamics has been explored on two subjects, the study of magnesium alloys (Chapter 1-5) and bulk metallic glasses (BMGs) (Chapter 6-9). For the former case, a strategy of experiments coupled with the CALPHAD approach was employed to establish a thermodynamic description of the quaternary system Mg-Al-Ca-Sr focusing on the Mg-rich phase equilibria. Multicomponent Mg-rich alloys based on the MgAl-Ca-Sr system are one of the most promising candidates for the high temperature applications in the transportation industry. The Mg-Al-Ca-Sr quaternary consists of four ternaries and six binaries. Thermodynamic descriptions of all constituent binaries are available in the literature. Thermodynamic descriptions of the two key ternaries, Mg-Al-Sr and Mg-Al-Ca, were obtained by an efficient and reliable methodology, combining computational thermodynamics with key experiments. The obtained thermodynamic descriptions were validated by performing extensive comparisons between the calculations and experimental information. Thermodynamic descriptions of the other two ternaries, MgCa-Sr and Al-Ca-Sr, were obtained by extrapolation. For the later case, a computational thermodynamic strategy was formulated to obtain a minor but optimum amount of additional element into a base alloy to improve its glass forming ability (GFA). This was done through thermodynamically calculating the maximum liquidus depressions caused by various alloying addition (or replacement) schemes. The success of this approach has been examined in two multicomponent systems, Zr-based Zr-Cu-Ni-Al-Ti and Cu-rich Cu-Zr-Ti-Y. For both cases, experimental results showed conclusively that the GFA increases more than 100% from the base alloy to the one with minor but optimal elemental addition. Furthermore, a thermodynamic computational approach was employed to identify the compositions of Zr-Ti-Ni-Cu-Al alloys exhibiting low-lying liquidus surfaces, which tend to favor the BMG formation. Guided by these calculations, several series of new Zr-based alloys with excellent GFA were synthesized. The approach using the thermodynamically calculated liquidus temperatures was proved to be robust in locating BMGs and can be considered as a universal method to predict novel BMGs not only of scientific interest but also potential technological applications.

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.

Metal hydrides as negative electrode materials for Ni- MH batteries

NASA Astrophysics Data System (ADS)

Yartys, V.; Noreus, D.; Latroche, M.

2016-01-01

Structural, thermodynamical and electrochemical properties of metallic hydrides belonging to the pseudo-binary family A-Mg-Ni ( A: rare earths) are reviewed and compared. Technology aspects of bipolar cells are also discussed.

Thermodynamic Cycle and CFD Analyses for Hydrogen Fueled Air-breathing Pulse Detonation Engines

NASA Technical Reports Server (NTRS)

Povinelli, Louis A.; Yungster, Shaye

2002-01-01

This paper presents the results of a thermodynamic cycle analysis of a pulse detonation engine (PDE) using a hydrogen-air mixture at static conditions. The cycle performance results, namely the specific thrust, fuel consumption and impulse are compared to a single cycle CFD analysis for a detonation tube which considers finite rate chemistry. The differences in the impulse values were indicative of the additional performance potential attainable in a PDE.

Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water.

PubMed

Reschke, Thomas; Zherikova, Kseniya V; Verevkin, Sergey P; Held, Christoph

2016-03-01

Benzoic acid is a model compound for drug substances in pharmaceutical research. Process design requires information about thermodynamic phase behavior of benzoic acid and its mixtures with water and organic solvents. This work addresses phase equilibria that determine stability and solubility. In this work, Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) was used to model the phase behavior of aqueous and organic solutions containing benzoic acid and chlorobenzoic acids. Absolute vapor pressures of benzoic acid and 2-, 3-, and 4-chlorobenzoic acid from literature and from our own measurements were used to determine pure-component PC-SAFT parameters. Two binary interaction parameters between water and/or benzoic acid were used to model vapor-liquid and liquid-liquid equilibria of water and/or benzoic acid between 280 and 413 K. The PC-SAFT parameters and 1 binary interaction parameter were used to model aqueous solubility of the chlorobenzoic acids. Additionally, solubility of benzoic acid in organic solvents was predicted without using binary parameters. All results showed that pure-component parameters for benzoic acid and for the chlorobenzoic acids allowed for satisfying modeling phase equilibria. The modeling approach established in this work is a further step to screen solubility and to predict the whole phase region of mixtures containing pharmaceuticals. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Estimation of thermodynamic acidity constants of some penicillinase-resistant penicillins.

PubMed

Demiralay, Ebru Çubuk; Üstün, Zehra; Daldal, Y Doğan

2014-03-01

In this work, thermodynamic acidity constants (pssKa) of methicillin, oxacillin, nafcillin, cloxacilin, dicloxacillin were determined with reverse phase liquid chromatographic method (RPLC) by taking into account the effect of the activity coefficients in hydro-organic water-acetonitrile binary mixtures. From these values, thermodynamic aqueous acidity constants of these drugs were calculated by different approaches. The linear relationships established between retention factors of the species and the polarity parameter of the mobile phase (ET(N)) was proved to predict accurately retention in LC as a function of the acetonitrile content (38%, 40% and 42%, v/v). Copyright © 2013 Elsevier B.V. All rights reserved.

The Thermodynamics of a Refrigeration System.

ERIC Educational Resources Information Center

Azevedo e Silva, J. F. M.

1991-01-01

An attempt to clarify the teaching of some of the concepts of thermodynamics through the observation of an experiment with an ordinary refrigeration system is presented. The cycle of operation in the refrigeration system and the individual processes in the cycle are described. (KR)

Irradiation-driven Mass Transfer Cycles in Compact Binaries

NASA Astrophysics Data System (ADS)

Büning, A.; Ritter, H.

2005-08-01

We elaborate on the analytical model of Ritter, Zhang, & Kolb (2000) which describes the basic physics of irradiation-driven mass transfer cycles in semi-detached compact binary systems. In particular, we take into account a contribution to the thermal relaxation of the donor star which is unrelated to irradiation and which was neglected in previous studies. We present results of simulations of the evolution of compact binaries undergoing mass transfer cycles, in particular also of systems with a nuclear evolved donor star. These computations have been carried out with a stellar evolution code which computes mass transfer implicitly and models irradiation of the donor star in a point source approximation, thereby allowing for much more realistic simulations than were hitherto possible. We find that low-mass X-ray binaries (LMXBs) and cataclysmic variables (CVs) with orbital periods ⪉ 6hr can undergo mass transfer cycles only for low angular momentum loss rates. CVs containing a giant donor or one near the terminal age main sequence are more stable than previously thought, but can possibly also undergo mass transfer cycles.

Phase relations in the system NaCl-KCl-H2O: IV. Differential thermal analysis of the sylvite liquidus in the KCl-H2O binary, the liquidus in the NaCl-KCl-H2O ternary, and the solidus in the NaCl-KCl binary to 2 kb pressure, and a summary of experimental data for thermodynamic-PTX analysis of solid-liquid equilibria at elevated P-T conditions

USGS Publications Warehouse

Chou, I.-Ming; Sterner, S.M.; Pitzer, Kenneth S.

1992-01-01

The sylvite liquidus in the binary system KCl-H2O and the liquidus in the ternary system NaCl-KCl-H2O were determined by using isobaric differential thermal analysis (DTA) cooling scans at pressures up to 2 kbars. Sylvite solubilities along the three-phase curve in the binary system KCl-H2O were obtained by the intersection of sylvite-liquidus isopleths with the three-phase curve in a P-T plot. These solubility data can be represented by the equation Wt.% KCl (??0.2) = 12.19 + 0.1557T - 5.4071 ?? 10-5 T2, where 400 ??? T ??? 770??C. These data are consistent with previous experimental observations. The solidus in the binary system NaCl-KCl was determined by using isobaric DTA heating scans at pressures up to 2 kbars. Using these liquidus and solidus data and other published information, a thermodynamic-PTX analysis of solid-liquid equilibria at high pressures and temperatures for the ternary system has been performed and is presented in an accompanying paper (Part V of this series). However, all experimental liquidus, solidus, and solvus data used in this analysis are summarized in this report (Part IV) and they are compared with the calculated values based on the analysis. ?? 1992.

Improving geothermal power plants with a binary cycle

NASA Astrophysics Data System (ADS)

Tomarov, G. V.; Shipkov, A. A.; Sorokina, E. V.

2015-12-01

The recent development of binary geothermal technology is analyzed. General trends in the introduction of low-temperature geothermal sources are summarized. The use of single-phase low-temperature geothermal fluids in binary power plants proves possible and expedient. The benefits of power plants with a binary cycle in comparison with traditional systems are shown. The selection of the working fluid is considered, and the influence of the fluid's physicochemical properties on the design of the binary power plant is discussed. The design of binary power plants is based on the chemical composition and energy potential of the geothermal fluids and on the landscape and climatic conditions at the intended location. Experience in developing a prototype 2.5 MW Russian binary power unit at Pauzhetka geothermal power plant (Kamchatka) is outlined. Most binary systems are designed individually for a specific location. Means of improving the technology and equipment at binary geothermal power plants are identified. One option is the development of modular systems based on several binary systems that employ the heat from the working fluid at different temperatures.

Equipment of the binary-cycle geothermal power unit at the Pauzhet geothermal power station

NASA Astrophysics Data System (ADS)

Tomarov, G. V.; Nikol'skii, A. I.; Semenov, V. N.; Shipkov, A. A.

2014-06-01

The equipment of and technological processes in the pilot industrial model of the domestically produced binary-cycle geothermal power unit operating on the discharge separate at the Pauzhet geothermal power station are considered. The development principles, the design and operational features, and the data on selecting the metal in manufacturing the main equipment of the 2.5-MW binary power unit of the geothermal power station are described.

Multinary alloy electrodes for solid state batteries I. A phase diagram approach for the selection and storage properties determination of candidate electrode materials

NASA Astrophysics Data System (ADS)

Anani, A.; Huggins, R. A.

The desire to produce high specific energy rechargeable batteries has led to the investigation of ternary alloy systems for use as negative electrode components in lithium-based cells. The addition of a third component to a binary alloy electrode could result in a significant change in the thermodynamic and/or kinetic behavior of the electrode material, depending on the relevant phase diagram and the crystal structures of the phases present. The influence of ternary phase diagram characteristics upon the thermodynamic properties and specific energies of multi-component electrodes is discussed with lithiumsilicon-based systems as an illustration. It is shown that the electrode potentials (and thus specific energies of the ensuing cell) as well as the theoretical lithium capacities of electrodes based on these ternary alloy modifications can be significantly increased with respect to their present day binary counterpart.

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Description of Adsorption in Liquid Chromatography under Nonideal Conditions.

PubMed

Ortner, Franziska; Ruppli, Chantal; Mazzotti, Marco

2018-05-15

A thermodynamically consistent description of binary adsorption in reversed-phase chromatography is presented, accounting for thermodynamic nonidealities in the liquid and adsorbed phases. The investigated system involves the adsorbent Zorbax 300SB-C18, as well as phenetole and 4- tert-butylphenol as solutes and methanol and water as inert components forming the eluent. The description is based on adsorption isotherms, which are a function of the liquid-phase activities, to account for nonidealities in the liquid phase. Liquid-phase activities are calculated with a UNIQUAC model established in this work, based on experimental phase equilibrium data. The binary interaction in the adsorbed phase is described by the adsorbed solution theory, assuming an ideal (ideal adsorbed solution theory) or real (real adsorbed solution theory) adsorbed phase. Implementation of the established adsorption model in a chromatographic code achieves a quantitative description of experimental elution profiles, with feed compositions exploiting the entire miscible region, and involving a broad range of different eluent compositions (methanol/water). The quantitative agreement of the model and experimental data serves as a confirmation of the underlying physical (thermodynamic) concepts and of their applicability to a broad range of operating conditions.

Estimation of the viscosities of liquid binary alloys

NASA Astrophysics Data System (ADS)

Wu, Min; Su, Xiang-Yu

2018-01-01

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

Thermodynamic modeling of the Ge-La binary system

NASA Astrophysics Data System (ADS)

Liu, Miao; Li, Chang-rong; Du, Zhen-min; Guo, Cui-ping; Niu, Chun-ju

2012-08-01

The Ge-La binary system was critically assessed by means of the calculation of phase diagram (CALPHAD) technique. The associate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5, and Ge1.7La. The terminal solid solution diamond-(Ge) with a small solubility of La was described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, α(Ge1.7La), β(Ge1.7La), and (GeLa), were modeled using two sublattices as α(Ge,La)1.7La, β(Ge,La)1.7La, and (Ge,La)(Ge,La), respectively. The intermediate phases with no solubility ranges, Ge4La5, Ge3La4, Ge3La5, and GeLa3, were treated as stoichiometric compounds. The three allotropic modifications of La, dhcp-La, fcc-La, and bcc-La, were kept as pure element phases since no solubility of Ge in La was reported. A set of self-consistent thermodynamic parameters of the Ge-La binary system was obtained. The calculation results agree well with the available experimental data from literatures.

Flip-flopping binary black holes.

PubMed

Lousto, Carlos O; Healy, James

2015-04-10

We study binary spinning black holes to display the long term individual spin dynamics. We perform a full numerical simulation starting at an initial proper separation of d≈25M between equal mass holes and evolve them down to merger for nearly 48 orbits, 3 precession cycles, and half of a flip-flop cycle. The simulation lasts for t=20 000M and displays a total change in the orientation of the spin of one of the black holes from an initial alignment with the orbital angular momentum to a complete antialignment after half of a flip-flop cycle. We compare this evolution with an integration of the 3.5 post-Newtonian equations of motion and spin evolution to show that this process continuously flip flops the spin during the lifetime of the binary until merger. We also provide lower order analytic expressions for the maximum flip-flop angle and frequency. We discuss the effects this dynamics may have on spin growth in accreting binaries and on the observational consequences for galactic and supermassive binary black holes.

THERMODYNAMIC EVALUATION OF FIVE ALTERNATIVE REFRIGERANTS IN VAPOR-COMPRESSION CYCLES

EPA Science Inventory

The paper gives results of a thermodynamic evaluation of five alternative refrigerants in a vapor-compression refrigeration cycle, utilizing throttling, super-heating, and combined throttling and superheating. ive alternative refrigerants (R32, R125, R134a, R143a, and R152a) were...

Investigation of waste heat recovery of binary geothermal plants using single component refrigerants

NASA Astrophysics Data System (ADS)

Unverdi, M.

2017-08-01

In this study, the availability of waste heat in a power generating capacity of 47.4 MW in Germencik Geothermal Power Plant has been investigated via binary geothermal power plant. Refrigerant fluids of 7 different single components such as R-134a, R-152a, R-227ea, R-236fa, R-600, R-143m and R-161 have been selected. The binary cycle has been modeled using the waste heat equaling to mass flow rate of 100 kg/s geothermal fluid. While the inlet temperature of the geothermal fluid into the counter flow heat exchanger has been accepted as 110°C, the outlet temperature has been accepted as 70°C. The inlet conditions have been determined for the refrigerants to be used in the binary cycle. Finally, the mass flow rate of refrigerant fluid and of cooling water and pump power consumption and power generated in the turbine have been calculated for each inlet condition of the refrigerant. Additionally, in the binary cycle, energy and exergy efficiencies have been calculated for 7 refrigerants in the availability of waste heat. In the binary geothermal cycle, it has been found out that the highest exergy destruction for all refrigerants occurs in the heat exchanger. And the highest and lowest first and second law efficiencies has been obtained for R-600 and R-161 refrigerants, respectively.

Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate.

PubMed

Florusse, Louw J; Peters, Cor J; Schoonman, Joop; Hester, Keith C; Koh, Carolyn A; Dec, Steven F; Marsh, Kenneth N; Sloan, E Dendy

2004-10-15

Thermodynamic, x-ray diffraction, and Raman and nuclear magnetic resonance spectroscopy measurements show that clusters of H2 can be stabilized and stored at low pressures in a sII binary clathrate hydrate. Clusters of H2 molecules occupy small water cages, whereas large water cages are singly occupied by tetrahydrofuran. The presence of this second guest component stabilizes the clathrate at pressures of 5 megapascals at 279.6 kelvin, versus 300 megapascals at 280 kelvin for pure H2 hydrate.

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

Performance comparison of different thermodynamic cycles for an innovative central receiver solar power plant

NASA Astrophysics Data System (ADS)

Reyes-Belmonte, Miguel A.; Sebastián, Andrés; González-Aguilar, José; Romero, Manuel

2017-06-01

The potential of using different thermodynamic cycles coupled to a solar tower central receiver that uses a novel heat transfer fluid is analyzed. The new fluid, named as DPS, is a dense suspension of solid particles aerated through a tubular receiver used to convert concentrated solar energy into thermal power. This novel fluid allows reaching high temperatures at the solar receiver what opens a wide range of possibilities for power cycle selection. This work has been focused into the assessment of power plant performance using conventional, but optimized cycles but also novel thermodynamic concepts. Cases studied are ranging from subcritical steam Rankine cycle; open regenerative Brayton air configurations at medium and high temperature; combined cycle; closed regenerative Brayton helium scheme and closed recompression supercritical carbon dioxide Brayton cycle. Power cycle diagrams and working conditions for design point are compared amongst the studied cases for a common reference thermal power of 57 MWth reaching the central cavity receiver. It has been found that Brayton air cycle working at high temperature or using supercritical carbon dioxide are the most promising solutions in terms of efficiency conversion for the power block of future generation by means of concentrated solar power plants.

Merits of full flow vs. conventional staged combustion cycles for reusable launch vehicle propulsion

NASA Astrophysics Data System (ADS)

Peery, Steven D.; Parsley, Randy C.

1996-03-01

This paper provides a comparison between full-flow and conventional staged combustion thermodynamic O2/H2 rocket engine cycles for Reusable Launch Vehicle, RLV, single-stage-to-orbit applications. The impact of the cycle thermodynamics, component configuration, and component operating parameters on engine performance and weight for the two approaches is presented. Both cycles were modeled with equivalent technology turbomachinery and chamber/nozzle RLV life requirements. The first order impact of cycle selection, pump exit pressure, and turbine temperature on the empty weight of an SSTO Reusable Launch Vehicle is presented.

Variable pressure power cycle and control system

DOEpatents

Goldsberry, Fred L.

1984-11-27

A variable pressure power cycle and control system that is adjustable to a variable heat source is disclosed. The power cycle adjusts itself to the heat source so that a minimal temperature difference is maintained between the heat source fluid and the power cycle working fluid, thereby substantially matching the thermodynamic envelope of the power cycle to the thermodynamic envelope of the heat source. Adjustments are made by sensing the inlet temperature of the heat source fluid and then setting a superheated vapor temperature and pressure to achieve a minimum temperature difference between the heat source fluid and the working fluid.

[Thermodynamic principles and physiologic criteria for the use of heat engines to drive the ventricles of an artificial heart].

PubMed

Kiselev, Iu M; Mordashev, V M; Osipov, A P; Shumakov, V I

1990-01-01

The authors review the thermodynamic bases and physiological limitations of the applicability of thermal engines for driving artificial heart ventricles. Show that the thermodynamic characteristics of Stirling and Brighton cycles do not make it possible to effectively use cycle-based engines in the artificial heart. A steam engine operating in accordance with the Rankine cycle may be regarded as an optimum type engine for that purpose. Demonstrate that according to the rules of physiology, use should be made of a separate driving of artificial heart ventricles by two independently operating steam engines. Provide the characteristics of the Soviet artificial heart "MIKRON" acceptable for implantation into the orthotopic position.

Study of thermodynamic and transport properties of binary liquid mixture of diesel with biodiesel at 298.15K

NASA Astrophysics Data System (ADS)

Suthar, Shyam Sunder; Purohit, Suresh

2018-05-01

Properties of diesel and biodiesel (produced from corn oil) are used. Densities and viscosities of binary mixture of diesel with biodiesel (produced from corn oil) have been computed by using liquid binary mixture law over the entire range of compositions at T=298.15K and atmospheric pressure. From the computed values of density and viscosities, viscosity deviation (Δη), the excess molar volume (VE) and excess Gibbs energy of activation of viscous flow (ΔG#E) have been calculated. The results of excess volume, excess Gibbs energy of activation of viscous flow and viscosity deviation have been fitted to Redlich -Kister models to estimate the binary coefficients. The results are communicated in terms of the molecular interactions and the best suited composition has been found.

On the definition of a Monte Carlo model for binary crystal growth.

PubMed

Los, J H; van Enckevort, W J P; Meekes, H; Vlieg, E

2007-02-01

We show that consistency of the transition probabilities in a lattice Monte Carlo (MC) model for binary crystal growth with the thermodynamic properties of a system does not guarantee the MC simulations near equilibrium to be in agreement with the thermodynamic equilibrium phase diagram for that system. The deviations remain small for systems with small bond energies, but they can increase significantly for systems with large melting entropy, typical for molecular systems. These deviations are attributed to the surface kinetics, which is responsible for a metastable zone below the liquidus line where no growth occurs, even in the absence of a 2D nucleation barrier. Here we propose an extension of the MC model that introduces a freedom of choice in the transition probabilities while staying within the thermodynamic constraints. This freedom can be used to eliminate the discrepancy between the MC simulations and the thermodynamic equilibrium phase diagram. Agreement is achieved for that choice of the transition probabilities yielding the fastest decrease of the free energy (i.e., largest growth rate) of the system at a temperature slightly below the equilibrium temperature. An analytical model is developed, which reproduces quite well the MC results, enabling a straightforward determination of the optimal set of transition probabilities. Application of both the MC and analytical model to conditions well away from equilibrium, giving rise to kinetic phase diagrams, shows that the effect of kinetics on segregation is even stronger than that predicted by previous models.

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.

Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

NASA Astrophysics Data System (ADS)

Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

2012-12-01

The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

Comparative thermodynamic performance of some Rankine/Brayton cycle configurations for a low-temperature energy application

NASA Technical Reports Server (NTRS)

Lansing, F. L.

1977-01-01

Various configurations combining solar-Rankine and fuel-Brayton cycles were analyzed in order to find the arrangement which has the highest thermal efficiency and the smallest fuel share. A numerical example is given to evaluate both the thermodynamic performance and the economic feasibility of each configuration. The solar-assisted regenerative Rankine cycle was found to be leading the candidates from both points of energy utilization and fuel conservation.

Thermodynamics and kinetics of binary nucleation in ideal-gas mixtures.

PubMed

Alekseechkin, Nikolay V

2015-08-07

The nonisothermal single-component theory of droplet nucleation [N. V. Alekseechkin, Physica A 412, 186 (2014)] is extended to binary case; the droplet volume V, composition x, and temperature T are the variables of the theory. An approach based on macroscopic kinetics (in contrast to the standard microscopic model of nucleation operating with the probabilities of monomer attachment and detachment) is developed for the droplet evolution and results in the derived droplet motion equations in the space (V, x, T)—equations for V̇≡dV/dt, ẋ, and Ṫ. The work W(V, x, T) of the droplet formation is obtained in the vicinity of the saddle point as a quadratic form with diagonal matrix. Also, the problem of generalizing the single-component Kelvin equation for the equilibrium vapor pressure to binary case is solved; it is presented here as a problem of integrability of a Pfaffian equation. The equation for Ṫ is shown to be the first law of thermodynamics for the droplet, which is a consequence of Onsager's reciprocal relations and the linked-fluxes concept. As an example of ideal solution for demonstrative numerical calculations, the o-xylene-m-xylene system is employed. Both nonisothermal and enrichment effects are shown to exist; the mean steady-state overheat of droplets and their mean steady-state enrichment are calculated with the help of the 3D distribution function. Some qualitative peculiarities of the nucleation thermodynamics and kinetics in the water-sulfuric acid system are considered in the model of regular solution. It is shown that there is a small kinetic parameter in the theory due to the small amount of the acid in the vapor and, as a consequence, the nucleation process is isothermal.

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.

Thermodynamics Analysis of Binary Plant Generating Power from Low-Temperature Geothermal Resource

NASA Astrophysics Data System (ADS)

Maksuwan, A.

2018-05-01

The purpose in this research was to predict tendency of increase Carnot efficiency of the binary plant generating power from low-temperature geothermal resource. Low-temperature geothermal resources or less, are usually exploited by means of binary-type energy conversion systems. The maximum efficiency is analyzed for electricity production of the binary plant generating power from low-temperature geothermal resource becomes important. By using model of the heat exchanger equivalent to a power plant together with the calculation of the combined heat and power (CHP) generation. The CHP was solved in detail with appropriate boundary originating an idea from the effect of temperature of source fluid inlet-outlet and cooling fluid supply. The Carnot efficiency from the CHP calculation was compared between condition of increase temperature of source fluid inlet-outlet and decrease temperature of cooling fluid supply. Result in this research show that the Carnot efficiency for binary plant generating power from low-temperature geothermal resource has tendency increase by decrease temperature of cooling fluid supply.

Maximum performance of solar heat engines: Discussion of thermodynamic availability and other second law considerations and their implications

NASA Astrophysics Data System (ADS)

Boehm, R. F.

1985-09-01

A review of thermodynamic principles is given in an effort to see if these concepts may indicate possibilities for improvements in solar central receiver power plants. Aspects related to rate limitations in cycles, thermodynamic availability of solar radiation, and sink temperature considerations are noted. It appears that considerably higher instantaneous plant efficiencies are possible by raising the maximum temperature and lowering the minimum temperature of the cycles. Of course, many practical engineering problems will have to be solved to realize the promised benefits.

Anatomy of particle diffusion

NASA Astrophysics Data System (ADS)

Bringuier, E.

2009-11-01

The paper analyses particle diffusion from a thermodynamic standpoint. The main goal of the paper is to highlight the conceptual connection between particle diffusion, which belongs to non-equilibrium statistical physics, and mechanics, which deals with particle motion, at the level of third-year university courses. We start out from the fact that, near equilibrium, particle transport should occur down the gradient of the chemical potential. This yields Fick's law with two additional advantages. First, splitting the chemical potential into 'mechanical' and 'chemical' contributions shows how transport and mechanics are linked through the diffusivity-mobility relationship. Second, splitting the chemical potential into entropic and energetic contributions discloses the respective roles of entropy maximization and energy minimization in driving diffusion. The paper addresses first unary diffusion, where there is only one mobile species in an immobile medium, and next turns to binary diffusion, where two species are mobile with respect to each other in a fluid medium. The interrelationship between unary and binary diffusivities is brought out and it is shown how binary diffusion reduces to unary diffusion in the limit of high dilution of one species amidst the other one. Self- and mutual diffusion are considered and contrasted within the thermodynamic framework; self-diffusion is a time-dependent manifestation of the Gibbs paradox of mixing.

Characterization of Mixtures. Part 2: QSPR Models for Prediction of Excess Molar Volume and Liquid Density Using Neural Networks.

PubMed

Ajmani, Subhash; Rogers, Stephen C; Barley, Mark H; Burgess, Andrew N; Livingstone, David J

2010-09-17

In our earlier work, we have demonstrated that it is possible to characterize binary mixtures using single component descriptors by applying various mixing rules. We also showed that these methods were successful in building predictive QSPR models to study various mixture properties of interest. Here in, we developed a QSPR model of an excess thermodynamic property of binary mixtures i.e. excess molar volume (V(E) ). In the present study, we use a set of mixture descriptors which we earlier designed to specifically account for intermolecular interactions between the components of a mixture and applied successfully to the prediction of infinite-dilution activity coefficients using neural networks (part 1 of this series). We obtain a significant QSPR model for the prediction of excess molar volume (V(E) ) using consensus neural networks and five mixture descriptors. We find that hydrogen bond and thermodynamic descriptors are the most important in determining excess molar volume (V(E) ), which is in line with the theory of intermolecular forces governing excess mixture properties. The results also suggest that the mixture descriptors utilized herein may be sufficient to model a wide variety of properties of binary and possibly even more complex mixtures. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Numerical simulation of freckle formation in directional solidification of binary alloys

NASA Technical Reports Server (NTRS)

Felicelli, Sergio D.; Heinrich, Juan C.; Poirier, David R.

1992-01-01

A mathematical model of solidification is presented which simulates the formation of segregation models known as 'freckles' during directional solidification of binary alloys. The growth of the two-phase or dendritic zone is calculated by solving the coupled equations of momentum, energy, and solute transport, as well as maintaining the thermodynamic constraints dictated by the phase diagram of the alloy. Calculations for lead-tin alloys show that the thermosolutal convection in the dendritic zone during solidification can produce heavily localized inhomogeneities in the composition of the final alloy.

Real Otto and Diesel Engine Cycles.

ERIC Educational Resources Information Center

Giedd, Ronald

1983-01-01

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

Exergy analysis of helium liquefaction systems based on modified Claude cycle with two-expanders

NASA Astrophysics Data System (ADS)

Thomas, Rijo Jacob; Ghosh, Parthasarathi; Chowdhury, Kanchan

2011-06-01

Large-scale helium liquefaction systems, being energy-intensive, demand judicious selection of process parameters. An effective tool for design and analysis of thermodynamic cycles for these systems is exergy analysis, which is used to study the behavior of a helium liquefaction system based on modified Claude cycle. Parametric evaluation using process simulator Aspen HYSYS® helps to identify the effects of cycle pressure ratio and expander flow fraction on the exergetic efficiency of the liquefaction cycle. The study computes the distribution of losses at different refrigeration stages of the cycle and helps in selecting optimum cycle pressures, operating temperature levels of expanders and mass flow rates through them. Results from the analysis may help evolving guidelines for designing appropriate thermodynamic cycles for practical helium liquefaction systems.

Thermodynamic Modeling of the Ge-Nd Binary System

NASA Astrophysics Data System (ADS)

Liu, Miao; Li, Changrong; Du, Zhenmin; Guo, Cuiping; Niu, Chunju

The Ge-Nd has been critically assessed by means of the CALculation of PHAse Diagram (CALPHAD) technique. For the liquid phase, the associate model was used with the constituent species Ge, Nd, Ge3Nd5 and Ge1.6Nd in the Ge-Nd system. The terminal solid solution diamond-(Ge), dhcp-(Nd) and bcc_A2-(Nd) in the Ge-Nd system were described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, α(Ge1.6Nd), β(Ge1.6Nd), (GeNd), (Ge4Nd5) and (Ge3Nd5) were modeled using two sublattices as α(Ge,Nd)1.6Nd, β(Ge,Nd)1.6Nd, (Ge,Nd)Nd, (Ge,Nd)4Nd5 and (Ge,Nd)3Nd5, respectively. A set of self-consistent thermodynamic parameters for each of the Ge-Nd binary systems was obtained. The calculation results agree well with the available experimental data from literatures.

Transport properties of gases and binary liquids near the critical point

NASA Technical Reports Server (NTRS)

Sengers, J. V.

1972-01-01

A status report is presented on the anomalies observed in the behavior of transport properties near the critical point of gases and binary liquids. The shear viscosity exhibits a weak singularity near the critical point. An analysis is made of the experimental data for those transport properties, thermal conductivity and thermal diffusivity near the gas-liquid critical point and binary diffusion coefficient near the critical mixing point, that determine the critical slowing down of the thermodynamic fluctuations in the order parameter. The asymptotic behavior of the thermal conductivity appears to be closely related to the asymptotic behavior of the correlation length. The experimental data for the thermal conductivity and diffusivity are shown to be in substantial agreement with current theoretical predictions.

Bioethanol production optimization: a thermodynamic analysis.

PubMed

Alvarez, Víctor H; Rivera, Elmer Ccopa; Costa, Aline C; Filho, Rubens Maciel; Wolf Maciel, Maria Regina; Aznar, Martín

2008-03-01

In this work, the phase equilibrium of binary mixtures for bioethanol production by continuous extractive process was studied. The process is composed of four interlinked units: fermentor, centrifuge, cell treatment unit, and flash vessel (ethanol-congener separation unit). A proposal for modeling the vapor-liquid equilibrium in binary mixtures found in the flash vessel has been considered. This approach uses the Predictive Soave-Redlich-Kwong equation of state, with original and modified molecular parameters. The congeners considered were acetic acid, acetaldehyde, furfural, methanol, and 1-pentanol. The results show that the introduction of new molecular parameters r and q in the UNIFAC model gives more accurate predictions for the concentration of the congener in the gas phase for binary and ternary systems.

Thermodynamic Study of Multi Pressure HRSG in Gas/Steam Combined Cycle Power Plant

NASA Astrophysics Data System (ADS)

Sharma, Meeta; Singh, Onkar

2018-01-01

Combined cycle power plants have a combination of gas based topping cycle and steam based bottoming cycle through the use of Heat Recovery Steam Generator (HRSG). These HRSG may be either of single pressure (SP) or dual pressure (DP) or multiple pressure type. Here in this study thermodynamic analysis is carried out for optimal performance of HRSG using different types of HRSG layout for combined cycle efficiency improvement. Performance of single pressure HRSG and dual pressure HRSG, utilized in gas/steam combined cycle is analyzed and presented here. In comparison to single pressure, dual pressure HRSG offers 10 to 15% higher reduction in stack temperature due to greater heat recovery and thus improved plant efficiency.

Nitrogen expander cycles for large capacity liquefaction of natural gas

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung; Park, Jae Hoon; Gwak, Kyung Hyun; Choe, Kun Hyung

2014-01-01

Thermodynamic study is performed on nitrogen expander cycles for large capacity liquefaction of natural gas. In order to substantially increase the capacity, a Brayton refrigeration cycle with nitrogen expander was recently added to the cold end of the reputable propane pre-cooled mixed-refrigerant (C3-MR) process. Similar modifications with a nitrogen expander cycle are extensively investigated on a variety of cycle configurations. The existing and modified cycles are simulated with commercial process software (Aspen HYSYS) based on selected specifications. The results are compared in terms of thermodynamic efficiency, liquefaction capacity, and estimated size of heat exchangers. The combination of C3-MR with partial regeneration and pre-cooling of nitrogen expander cycle is recommended to have a great potential for high efficiency and large capacity.

Magnetic power conversion with machines containing full or porous wheel heat exchangers

NASA Astrophysics Data System (ADS)

Egolf, Peter W.; Kitanovski, Andrej; Diebold, Marc; Gonin, Cyrill; Vuarnoz, Didier

2009-04-01

A first part of the article contains a thermodynamic theory describing the temperature distribution in a Curie wheel. The occurring nonlinear ordinary differential equation has an analytical solution. If a Curie wheel is stabilized by levitation, it is named Palmy wheel. These wheels show a full structure, and because of this reason, their uptake of heat from a flame (Curie wheel) or by (solar) light absorption (Palmy wheel) only on the periphery of a cylinder is very limited. To improve the method, a modification of the principle by introducing a convective heat transport into a porous wheel is discussed. By this the power conversion rate from a heat flux to mechanical and electric power is very much increased. The second part of the article presents results of a theoretical/numerical study on the efficiencies of magnetic power conversion plants operating with porous wheels. Furthermore, these efficiencies—which are promising—are compared with those of existing power conversion plants, as e.g. geothermal binary cycle power plants.

Geobiochemistry of metabolism: Standard state thermodynamic properties of the citric acid cycle

NASA Astrophysics Data System (ADS)

Canovas, Peter A.; Shock, Everett L.

2016-12-01

Integrating microbial metabolism into geochemical modeling allows assessments of energy and mass transfer between the geosphere and the microbial biosphere. Energy and power supplies and demands can be assessed from analytical geochemical data given thermodynamic data for compounds involved in catabolism and anabolism. Results are reported here from a critique of the available standard state thermodynamic data for organic acids and acid anions involved in the citric acid cycle (also known as the tricarboxylic acid cycle or the Krebs cycle). The development of methods for estimating standard state data unavailable from experiments is described, together with methods to predict corresponding values at elevated temperatures and pressures using the revised Helgeson-Kirkham-Flowers (HKF) equation of state for aqueous species. Internal consistency is maintained with standard state thermodynamic data for organic and inorganic aqueous species commonly used in geochemical modeling efforts. Standard state data and revised-HKF parameters are used to predict equilibrium dissociation constants for the organic acids in the citric acid cycle, and to assess standard Gibbs energies of reactions for each step in the cycle at elevated temperatures and pressures. The results presented here can be used with analytical data from natural and experimental systems to assess the energy and power demands of microorganisms throughout the habitable ranges of pressure and temperature, and to assess the consequences of abiotic organic compound alteration processes at conditions of subsurface aquifers, sedimentary basins, hydrothermal systems, meteorite parent bodies, and ocean worlds throughout the solar system.

Quantifying fluctuations in reversible enzymatic cycles and clocks

NASA Astrophysics Data System (ADS)

Wierenga, Harmen; ten Wolde, Pieter Rein; Becker, Nils B.

2018-04-01

Biochemical reactions are fundamentally noisy at a molecular scale. This limits the precision of reaction networks, but it also allows fluctuation measurements that may reveal the structure and dynamics of the underlying biochemical network. Here, we study nonequilibrium reaction cycles, such as the mechanochemical cycle of molecular motors, the phosphorylation cycle of circadian clock proteins, or the transition state cycle of enzymes. Fluctuations in such cycles may be measured using either of two classical definitions of the randomness parameter, which we show to be equivalent in general microscopically reversible cycles. We define a stochastic period for reversible cycles and present analytical solutions for its moments. Furthermore, we associate the two forms of the randomness parameter with the thermodynamic uncertainty relation, which sets limits on the timing precision of the cycle in terms of thermodynamic quantities. Our results should prove useful also for the study of temporal fluctuations in more general networks.

Alternative thermodynamic cycle for the Stirling machine

NASA Astrophysics Data System (ADS)

Romanelli, Alejandro

2017-12-01

We develop an alternative thermodynamic cycle for the Stirling machine, where the polytropic process plays a central role. Analytical expressions for pressure and temperatures of the working gas are obtained as a function of the volume and the parameter that characterizes the polytropic process. This approach achieves closer agreement with the experimental pressure-volume diagram and can be adapted to any type of Stirling engine.

Effects of hysteresis and Brayton cycle constraints on magnetocaloric refrigerant performance

NASA Astrophysics Data System (ADS)

Brown, T. D.; Buffington, T.; Shamberger, P. J.

2018-05-01

Despite promising proofs of concept, system-level implementation of magnetic refrigeration has been critically limited by history-dependent refrigerant losses that interact with governing thermodynamic cycles to adversely impact refrigeration performance. Future development demands a more detailed understanding of how hysteresis limits performance, and of how different types of cycles can mitigate these limitations, but without the extreme cost of experimental realization. Here, the utility of Brayton cycles for magnetic refrigeration is investigated via direct simulation, using a combined thermodynamic-hysteresis modeling framework to compute the path-dependent magnetization and entropy of a model alloy for a variety of feasible Brayton cycles between 0-1.5 T and 0-5 T. By simultaneously varying the model alloy's hysteresis properties and applying extensions of the thermodynamic laws to non-equilibrium systems, heat transfers and efficiencies are quantified throughout the space of hystereses and Brayton cycles and then compared with a previous investigation using Ericsson cycles. It is found that (1) hysteresis losses remain a critical obstacle to magnetic refrigeration implementation, with efficiencies >80% in the model system requiring hysteresis <0.5 K at 1.5 T; (2) optimal-efficiency Brayton cycles for given field and hysteresis constraints exist and are determined uniquely by the refrigerant transformation temperatures at the relevant fields; (3) for a given hysteresis and field constraint, Brayton and Ericsson-type cycles generate similar efficiencies; for a given temperature span, Ericsson cycles lift more heat per cycle, with the difference decreasing with the refrigerant heat capacity outside the phase transformation region.

Investment and operating costs of binary cycle geothermal power plants

NASA Technical Reports Server (NTRS)

Holt, B.; Brugman, J.

1974-01-01

Typical investment and operating costs for geothermal power plants employing binary cycle technology and utilizing the heat energy in liquid-dominated reservoirs are discussed. These costs are developed as a function of reservoir temperature. The factors involved in optimizing plant design are discussed. A relationship between the value of electrical energy and the value of the heat energy in the reservoir is suggested.

Comparative 4-E analysis of a bottoming pure NH3 and NH3-H2O mixture based power cycle for condenser waste heat recovery

NASA Astrophysics Data System (ADS)

Khankari, Goutam; Karmakar, Sujit

2017-06-01

This paper proposes a comparative performance analysis based on 4-E (Energy, Exergy, Environment, and Economic) of a bottoming pure Ammonia (NH3) based Organic Rankine Cycle (ORC) and Ammonia-water (NH3-H2O) based Kalina Cycle System 11(KCS 11) for additional power generation through condenser waste heat recovery integrated with a conventional 500MWe Subcritical coal-fired thermal power plant. A typical high-ash Indian coal is used for the analysis. The flow-sheet computer programme `Cycle Tempo' is used to simulate both the cycles for thermodynamic performance analysis at different plant operating conditions. Thermodynamic analysis is done by varying different NH3 mass fraction in KCS11 and at different turbine inlet pressure in both ORC and KCS11. Results show that the optimum operating pressure of ORC and KCS11 with NH3 mass fraction of 0.90 are about 15 bar and 11.70 bar, respectively and more than 14 bar of operating pressure, the plant performance of ORC integrated power plant is higher than the KCS11 integrated power plant and the result is observed reverse below this pressure. The energy and exergy efficiencies of ORC cycle are higher than the KCS11 by about 0.903 % point and 16.605 % points, respectively under similar saturation vapour temperature at turbine inlet for both the cycles. Similarly, plant energy and exergy efficiencies of ORC based combined cycle power plant are increased by 0.460 % point and 0.420 % point, respectively over KCS11 based combined cycle power plant. Moreover, the reduction of CO2 emission in ORC based combined cycle is about 3.23 t/hr which is about 1.5 times higher than the KCS11 based combined cycle power plant. Exergy destruction of the evaporator in ORC decreases with increase in operating pressure due to decrease in temperature difference of heat exchanging fluids. Exergy destruction rate in the evaporator of ORC is higher than KCS11 when the operating pressure of ORC reduces below 14 bar. This happens due to variable boiling temperature of NH3-H2O binary mixture in KCS11 and resulting in less irreversibility during the process of heat transfer. Levelized Cost of Electricity (LCoE) generation and the cost of implementation of ORC integrated power plant is about Rs.1.767/- per kWh and Rs. 2.187/- per kg of fuel saved, respectively whereas, the LCoE for KCS11 based combined power plant is slightly less than the ORC based combined cycle power plant and estimated as about Rs.1.734 /- per kWh. The cost of implementation of KCS11 based combined cycle power plant is about Rs. 0.332/- per kg of fuel saved. Though the energy and exergy efficiencies of ORC is better than KCS11 but considering the huge investment for developing the combined cycle power plant based on ORC in comparison with KCS11 below the operating pressure of 14 bar, KCS11 is superior than NH3 based ORC.

Thermal phase diagram of acetamide-benzoic acid and benzoic acid-phthalimide binary systems for solar thermal applications

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

Kumar, Rohitash, E-mail: dootrohit1976@gmail.com; Department of Physics & Center for Solar Energy, Indian Institute of Technology Jodhpur, Rajasthan, India 342011, +91-291-2449045; Kumar, Ravindra

2016-05-06

Thermal properties of Acetamide (AM) – Benzoic acid (BA) and Benzoic acid (BA) – Phthalimide (PM) binary eutectic systems are theoretically calculated using thermodynamic principles. We found that the binary systems of AM-BA at 67.6 : 32.4 molar ratio, BA-PM at 89.7 : 10.3 molar ratio form eutectic mixtures with melting temperatures ~ 54.5 °C and 114.3 °C respectively. Calculated latent heat of fusion for these eutectic mixtures are 191 kJ/kg and 146.5 kJ/kg respectively. These melting temperatures and heat of fusions of these eutectic mixtures make them suitable for thermal energy storage applications in solar water heating and solarmore » cooking systems.« less

Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

NASA Astrophysics Data System (ADS)

Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

2016-08-01

The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

Nonergodicity of microfine binary systems

NASA Astrophysics Data System (ADS)

Son, L. D.; Sidorov, V. E.; Popel', P. S.; Shul'gin, D. B.

2016-02-01

The correction to the equation of state that is related to the nonergodicity of diffusion dynamics is discussed for a binary solid solution with a limited solubility. It is asserted that, apart from standard thermodynamic variables (temperature, volume, concentration), this correction should be taken into account in the form of the average local chemical potential fluctuations associated with microheterogeneity in order to plot a phase diagram. It is shown that a low value of this correction lowers the miscibility gap and that this gap splits when this correction increases. This situation is discussed for eutectic systems and Ga-Pb, Fe-Cu, and Cu-Zr alloys.

Thermodynamic analysis of a new dual evaporator CO2 transcritical refrigeration cycle

NASA Astrophysics Data System (ADS)

Abdellaoui, Ezzaalouni Yathreb; Kairouani, Lakdar Kairouani

2017-03-01

In this work, a new dual-evaporator CO2 transcritical refrigeration cycle with two ejectors is proposed. In this new system, we proposed to recover the lost energy of condensation coming off the gas cooler and operate the refrigeration cycle ejector free and enhance the system performance and obtain dual-temperature refrigeration simultaneously. The effects of some key parameters on the thermodynamic performance of the modified cycle are theoretically investigated based on energetic and exergetic analysis. The simulation results for the modified cycle indicate more effective system performance improvement than the single ejector in the CO2 vapor compression cycle using ejector as an expander ranging up to 46%. The exergetic analysis for this system is made. The performance characteristics of the proposed cycle show its promise in dual-evaporator refrigeration system.

Thermodynamic analysis of steam-injected advanced gas turbine cycles

NASA Astrophysics Data System (ADS)

Pandey, Devendra; Bade, Mukund H.

2017-12-01

This paper deals with thermodynamic analysis of steam-injected gas turbine (STIGT) cycle. To analyse the thermodynamic performance of steam-injected gas turbine (STIGT) cycles, a methodology based on pinch analysis is proposed. This graphical methodology is a systematic approach proposed for a selection of gas turbine with steam injection. The developed graphs are useful for selection of steam-injected gas turbine (STIGT) for optimal operation of it and helps designer to take appropriate decision. The selection of steam-injected gas turbine (STIGT) cycle can be done either at minimum steam ratio (ratio of mass flow rate of steam to air) with maximum efficiency or at maximum steam ratio with maximum net work conditions based on the objective of plants designer. Operating the steam injection based advanced gas turbine plant at minimum steam ratio improves efficiency, resulting in reduction of pollution caused by the emission of flue gases. On the other hand, operating plant at maximum steam ratio can result in maximum work output and hence higher available power.

Theoretical Thermodynamics of Mixtures at High Pressures

NASA Technical Reports Server (NTRS)

Hubbard, W. B.

1985-01-01

The development of an understanding of the chemistry of mixtures of metallic hydrogen and abundant, higher-z material such as oxygen, carbon, etc., is important for understanding of fundamental processes of energy release, differentiation, and development of atmospheric abundances in the Jovian planets. It provides a significant theoretical base for the interpretation of atmospheric elemental abundances to be provided by atmospheric entry probes in coming years. Significant differences are found when non-perturbative approaches such as Thomas-Fermi-Dirac (TFD) theory are used. Mapping of the phase diagrams of such binary mixtures in the pressure range from approx. 10 Mbar to approx. 1000 Mbar, using results from three-dimensional TFD calculations is undertaken. Derivation of a general and flexible thermodynamic model for such binary mixtures in the relevant pressure range was facilitated by the following breakthrough: there exists an accurate nd fairly simple thermodynamic representation of a liquid two-component plasma (TCP) in which the Helmholtz free energy is represented as a suitable linear combination of terms dependent only on density and terms which depend only on the ion coupling parameter. It is found that the crystal energies of mixtures of H-He, H-C, and H-O can be satisfactorily reproduced by the same type of model, except that an effective, density-dependent ionic charge must be used in place of the actual total ionic charge.

A Comparative Study of the Coupling of Flow with Non-Fickean Thermodiffusion. Part I: Extended Irreversible Thermodynamics

NASA Astrophysics Data System (ADS)

Lebon, G.; Grmela, M.; Lhuillier, D.

2003-03-01

Our main objective is to describe non-Fickean thermodiffusion in binary fluids within the framework of three recent theories of non-equilibrium thermodynamics, namely Extended Irreversible Thermodynamics (EIT), GENERIC (General Equation for the Non-Equilibrium Reversible Irreversible Coupling) and Thermodynamics with Internal Variables (IVT). In the first part presented in this paper, we develop the EIT description. For pedagogical reasons, we start from the simplest situation to end with the most intricate one. Therefore, we first examine the simple problem of mass diffusion at uniform temperature. Then we study heat transport in a one-component fluid before considering the more complex coupled heat and mass transfer. In Part II developed in the accompanying paper, we follow the same hierarchy of situations from the point of view of GENERIC. Finally, in Part III, we present the point of view of the thermodynamic theory of internal variables. Similarities and differences between EIT, GENERIC and IVT are stressed. In the present work, we have taken advantage of the problem of heat conduction to revisit the notion of caloric.

Characterizing the information content of cloud thermodynamic phase retrievals from the notional PACE OCI shortwave reflectance measurements

NASA Astrophysics Data System (ADS)

Coddington, O. M.; Vukicevic, T.; Schmidt, K. S.; Platnick, S.

2017-08-01

We rigorously quantify the probability of liquid or ice thermodynamic phase using only shortwave spectral channels specific to the National Aeronautics and Space Administration's Moderate Resolution Imaging Spectroradiometer, Visible Infrared Imaging Radiometer Suite, and the notional future Plankton, Aerosol, Cloud, ocean Ecosystem imager. The results show that two shortwave-infrared channels (2135 and 2250 nm) provide more information on cloud thermodynamic phase than either channel alone; in one case, the probability of ice phase retrieval increases from 65 to 82% by combining 2135 and 2250 nm channels. The analysis is performed with a nonlinear statistical estimation approach, the GEneralized Nonlinear Retrieval Analysis (GENRA). The GENRA technique has previously been used to quantify the retrieval of cloud optical properties from passive shortwave observations, for an assumed thermodynamic phase. Here we present the methodology needed to extend the utility of GENRA to a binary thermodynamic phase space (i.e., liquid or ice). We apply formal information content metrics to quantify our results; two of these (mutual and conditional information) have not previously been used in the field of cloud studies.

The validity of the potential model in predicting the structural, dynamical, thermodynamic properties of the unary and binary mixture of water-alcohol: Methanol-water case

NASA Astrophysics Data System (ADS)

Obeidat, Abdalla; Abu-Ghazleh, Hind

2018-06-01

Two intermolecular potential models of methanol (TraPPE-UA and OPLS-AA) have been used in order to examine their validity in reproducing the selected structural, dynamical, and thermodynamic properties in the unary and binary systems. These two models are combined with two water models (SPC/E and TIP4P). The temperature dependence of density, surface tension, diffusion and structural properties for the unary system has been computed over specific range of temperatures (200-300K). The very good performance of the TraPPE-UA potential model in predicting surface tension, diffusion, structure, and density of the unary system led us to examine its accuracy and performance in its aqueous solution. In the binary system the same properties were examined, using different mole fractions of methanol. The TraPPE-UA model combined with TIP4P-water shows a very good agreement with the experimental results for density and surface tension properties; whereas the OPLS-AA combined with SPCE-water shows a very agreement with experimental results regarding the diffusion coefficients. Two different approaches have been used in calculating the diffusion coefficient in the mixture, namely the Einstein equation (EE) and Green-Kubo (GK) method. Our results show the advantageous of applying GK over EE in reproducing the experimental results and in saving computer time.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part III. Crystallization and phase behavior of 1-palmitoyl-2,3-stearoyl-sn-glycerol (PSS) and tristearoylglycerol (SSS) binary system.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The phase behavior of 1-palmitoyl-2,3-distearoyl-sn-glycerol (PSS)/tristearoylglycerol (SSS) binary system was investigated in terms of polymorphism, crystallization and melting behavior, microstructure and solid fat content (SFC) using widely different constant cooling rates. Kinetic phase diagrams were experimentally determined from the DSC heating thermograms and analyzed using a thermodynamic model to account for non-ideality of mixing. The kinetic phase diagram presented a typical eutectic behavior with a eutectic point at the 0.5(PSS) mixture with a probable precipitation line from 0.5(PSS) to 1.0(PSS), regardless of the rate at which the sample was cooled. The eutectic temperature decreased only slightly with increasing cooling rate. PSS has a strong effect on the physical properties of the PSS-SSS mixtures. In fact, the overall phase behavior of the PSS-SSS binary system was determined, for a very large part, by the asymmetrical TAG. Moreover, PSS is a key driver of the high stability observed in crystal growth, polymorphism and phase development. Levels as low as 10% PSS, when cooled slowly, and 30% when cooled rapidly, were found to be sufficient to suppress the effect of thermal processing. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Estimation of Solvation Quantities from Experimental Thermodynamic Data: Development of the Comprehensive CompSol Databank for Pure and Mixed Solutes

NASA Astrophysics Data System (ADS)

Moine, Edouard; Privat, Romain; Sirjean, Baptiste; Jaubert, Jean-Noël

2017-09-01

The Gibbs energy of solvation measures the affinity of a solute for its solvent and is thus a key property for the selection of an appropriate solvent for a chemical synthesis or a separation process. More fundamentally, Gibbs energies of solvation are choice data for developing and benchmarking molecular models predicting solvation effects. The Comprehensive Solvation—CompSol—database was developed with the ambition to propose very large sets of new experimental solvation chemical-potential, solvation entropy, and solvation enthalpy data of pure and mixed components, covering extended temperature ranges. For mixed compounds, the solvation quantities were generated in infinite-dilution conditions by combining experimental values of pure-component and binary-mixture thermodynamic properties. Three types of binary-mixture properties were considered: partition coefficients, activity coefficients at infinite dilution, and Henry's-law constants. A rigorous methodology was implemented with the aim to select data at appropriate conditions of temperature, pressure, and concentration for the estimation of solvation data. Finally, our comprehensive CompSol database contains 21 671 data associated with 1969 pure species and 70 062 data associated with 14 102 binary mixtures (including 760 solvation data related to the ionic-liquid class of solvents). On the basis of the very large amount of experimental data contained in the CompSol database, it is finally discussed how solvation energies are influenced by hydrogen-bonding association effects.

Viscosities of Fe Ni, Fe Co and Ni Co binary melts

NASA Astrophysics Data System (ADS)

Sato, Yuzuru; Sugisawa, Koji; Aoki, Daisuke; Yamamura, Tsutomu

2005-02-01

Viscosities of three binary molten alloys consisting of the iron group elements, Fe, Ni and Co, have been measured by using an oscillating cup viscometer over the entire composition range from liquidus temperatures up to 1600 °C with high precision and excellent reproducibility. The viscosities measured showed good Arrhenius linearity for all the compositions. The viscosities of Fe, Ni and Co as a function of temperature are as follows: \\eqalign{ & \\log \\eta={-}0.6074 + 2493/T\\qquad for\\quad Fe\\\\ & \\log \\eta={-}0.5695 + 2157/T\\qquad for\\quad Ni \\\\ & \\log \\eta={-}0.6620 + 2430/T\\qquad for\\quad Co.} The isothermal viscosities of Fe-Ni and Fe-Co binary melts increase monotonically with increasing Fe content. On the other hand, in Ni-Co binary melt, the isothermal viscosity decreases slightly and then increases with increasing Co. The activation energy of Fe-Co binary melt increased slightly on mixing, and those of Fe-Ni and Ni-Co melts decreased monotonically with increasing Ni content. The above behaviour is discussed based on the thermodynamic properties of the alloys.

Thermodynamic design of 10 kW Brayton cryocooler for HTS cable

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung; Park, C. W.; Yang, H. S.; Sohn, Song Ho; Lim, Ji Hyun; Oh, S. R.; Hwang, Si Dole

2012-06-01

Thermodynamic design of Brayton cryocooler is presented as part of an ongoing governmental project in Korea, aiming at 1 km HTS power cable in the transmission grid. The refrigeration requirement is 10 kW for continuously sub-cooling liquid nitrogen from 72 K to 65 K. An ideal Brayton cycle for this application is first investigated to examine the fundamental features. Then a practical cycle for a Brayton cryocooler is designed, taking into account the performance of compressor, expander, and heat exchangers. Commercial software (Aspen HYSYS) is used for simulating the refrigeration cycle with real fluid properties of refrigerant. Helium is selected as a refrigerant, as it is superior to neon in thermodynamic efficiency. The operating pressure and flow rate of refrigerant are decided with a constraint to avoid the freezing of liquid nitrogen

Analysis of the Properties of Working Substances for the Organic Rankine Cycle based Database "REFPROP"

NASA Astrophysics Data System (ADS)

Galashov, Nikolay; Tsibulskiy, Svyatoslav; Serova, Tatiana

2016-02-01

The object of the study are substances that are used as a working fluid in systems operating on the basis of an organic Rankine cycle. The purpose of research is to find substances with the best thermodynamic, thermal and environmental properties. Research conducted on the basis of the analysis of thermodynamic and thermal properties of substances from the base "REFPROP" and with the help of numerical simulation of combined-cycle plant utilization triple cycle, where the lower cycle is an organic Rankine cycle. Base "REFPROP" describes and allows to calculate the thermodynamic and thermophysical parameters of most of the main substances used in production processes. On the basis of scientific publications on the use of working fluids in an organic Rankine cycle analysis were selected ozone-friendly low-boiling substances: ammonia, butane, pentane and Freon: R134a, R152a, R236fa and R245fa. For these substances have been identified and tabulated molecular weight, temperature of the triple point, boiling point, at atmospheric pressure, the parameters of the critical point, the value of the derivative of the temperature on the entropy of the saturated vapor line and the potential ozone depletion and global warming. It was also identified and tabulated thermodynamic and thermophysical parameters of the steam and liquid substances in a state of saturation at a temperature of 15 °C. This temperature is adopted as the minimum temperature of heat removal in the Rankine cycle when working on the water. Studies have shown that the best thermodynamic, thermal and environmental properties of the considered substances are pentane, butane and R245fa. For a more thorough analysis based on a gas turbine plant NK-36ST it has developed a mathematical model of combined cycle gas turbine (CCGT) triple cycle, where the lower cycle is an organic Rankine cycle, and is used as the air cooler condenser. Air condenser allows stating material at a temperature below 0 °C. Calculation of the parameters of all substances in the model are based on a base "REFPROP". Numerical investigations on this model showed that the highest net efficiency will be at work on pentane. Butane and R245fa have the same net efficiency, for 0.8% lower than pentane. Ammonia has a net efficiency of 2.5% is lower than pentane. CCP net efficiency strongly depends on the condensation temperature of the substance, as for pentane at lower temperature of condensation at 10 °C it is increased by 1%.

Experimental investigation of an ammonia-based combined power and cooling cycle

NASA Astrophysics Data System (ADS)

Tamm, Gunnar Olavi

A novel ammonia-water thermodynamic cycle, capable of producing both power and refrigeration, was proposed by D. Yogi Goswami. The binary mixture exhibits variable boiling temperatures during the boiling process, which leads to a good thermal match between the heating fluid and working fluid for efficient heat source utilization. The cycle can be driven by low temperature sources such as solar, geothermal, and waste heat from a conventional power cycle, reducing the reliance on high temperature sources such as fossil fuels. A theoretical simulation of the cycle at heat source temperatures obtainable from low and mid temperature solar collectors showed that the ideal cycle could produce power and refrigeration at a maximum exergy efficiency, defined as the ratio of the net work and refrigeration output to the change in availability of the heat source, of over 60%. The exergy efficiency is a useful measure of the cycle's performance as it compares the effectiveness of different cycles in harnessing the same source. An experimental system was constructed to demonstrate the feasibility of the cycle and to compare the experimental results with the theoretical simulations. In this first phase of experimentation, the turbine expansion was simulated with a throttling valve and a heat exchanger. Results showed that the vapor generation and absorption condensation processes work experimentally. The potential for combined turbine work and refrigeration output was evidenced in operating the system. Analysis of losses led to modifications in the system design, which were implemented to yield improvements in heat exchange, vapor generation, pump performance and overall stability. The research that has been conducted verifies the potential of the power and cooling cycle as an alternative to using conventional fossil fuel technologies. The research that continues is to further demonstrate the concept and direct it towards industry. On the large scale, the cycle can be used for industrial power production or as a central power plant for a community, with refrigeration produced as required by the application. On the small scale, an affordable residential or commercial unit could allow independent electricity generation for the home or business while also cooling it.

Ligand Exchange Governs the Crystal Structures in Binary Nanocrystal Superlattices.

PubMed

Wei, Jingjing; Schaeffer, Nicolas; Pileni, Marie-Paule

2015-11-25

The surface chemistry in colloidal nanocrystals on the final crystalline structure of binary superlattices produced by self-assembly of two sets of nanocrystals is hereby demonstrated. By mixing nanocrystals having two different sizes and the same coating agent, oleylamine (OAM), the binary nanocrystal superlattices that are produced, such as NaCl, AlB2, NaZn13, and MgZn2, are well in agreement with the crystalline structures predicted by the hard-sphere model, their formation being purely driven by entropic forces. By opposition, when large and small nanocrystals are coated with two different ligands [OAM and dodecanethiol (DDT), respectively] while keeping all other experimental conditions unchanged, the final binary structures markedly change and various structures with lower packing densities, such as Cu3Au, CaB6, and quasicrystals, are observed. This effect of the nanocrystals' coating agents could also be extended to other binary systems, such as Ag-Au and CoFe2O4-Ag supracrystalline binary lattices. In order to understand this effect, a mechanism based on ligand exchange process is proposed. Ligand exchange mechanism is believed to affect the thermodynamics in the formation of binary systems composed of two sets of nanocrystals with different sizes and bearing two different coating agents. Hence, the formation of binary superlattices with lower packing densities may be favored kinetically because the required energetic penalty is smaller than that of a denser structure.

A connection between long-term luminosity variations and orbital period changes in chromospherically active binaries

NASA Technical Reports Server (NTRS)

Hall, Douglas S.

1991-01-01

The eclipsing binary CG Cyg provides observational confirmation of three predictions made by Applegate's (1991) improvement on the theory that magnetic cycles cause the quasi-periodic orbital period changes in binaries containing a convective star. The mean brightness outside eclipse and the period vary with the same cycle length of about 50 yr. The light curve and O - C curve are in phase, with maximum light and period increase occurring in early 1980. The chromospherically active star becomes bluer in phase with the brightening. Because a period increase occurs at maximum brightness, the sense of the star's differential rotation is specified: outside rotating faster.

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

PubMed Central

Kleidon, A.

2010-01-01

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

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

PubMed

Kleidon, A

2010-05-12

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

Thermodynamic Analysis of Ionic Compounds: Synthetic Applications.

ERIC Educational Resources Information Center

Yoder, Claude H.

1986-01-01

Shows how thermodynamic cycles can be used to understand trends in heats of formation and aqueous solubilities and, most importantly, how they may be used to choose synthetic routes to new ionic compounds. (JN)

Systematic Review of Life Cycle Greenhouse Gas Emissions from Geothermal Electricity

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

Eberle, Annika; Heath, Garvin A.; Carpenter Petri, Alberta C.

The primary goal of this work was to assess the magnitude and variability of published life cycle greenhouse gas (GHG) emission estimates for three types of geothermal electricity generation technologies: enhanced geothermal systems (EGS) binary, hydrothermal (HT) flash, and HT binary. These technologies were chosen to align the results of this report with technologies modeled in National Renewable Energy Laboratory's (NREL's) Regional Energy Deployment Systems (ReEDs) model. Although we did gather and screen life cycle assessment (LCA) literature on hybrid systems, dry steam, and two geothermal heating technologies, we did not analyze published GHG emission estimates for these technologies. Inmore » our systematic literature review of the LCA literature, we screened studies in two stages based on a variety of criteria adapted from NREL's Life Cycle Assessment (LCA) Harmonization study (Heath and Mann 2012). Of the more than 180 geothermal studies identified, only 29 successfully passed both screening stages and only 26 of these included estimates of life cycle GHG emissions. We found that the median estimate of life cycle GHG emissions (in grams of carbon dioxide equivalent per kilowatt-hour generated [g CO2eq/kWh]) reported by these studies are 32.0, 47.0, and 11.3 for EGS binary, HT flash, and HT binary, respectively (Figure ES-1). We also found that the total life cycle GHG emissions are dominated by different stages of the life cycle for different technologies. For example, the GHG emissions from HT flash plants are dominated by the operations phase owing to the flash cycle being open loop whereby carbon dioxide entrained in the geothermal fluids is released to the atmosphere. This is in contrast to binary plants (using either EGS or HT resources), whose GHG emissions predominantly originate in the construction phase, owing to its closed-loop process design. Finally, by comparing this review's literature-derived range of HT flash GHG emissions to data from currently operating geothermal plants, we found that emissions from operational plants exhibit more variability and the median of emissions from operational plants is twice the median of operational emissions reported by LCAs. Further investigation is warranted to better understand the cause of differences between published LCAs and estimates from operational plants and to develop LCA analytical approaches that can yield estimates closer to actual emissions.« less

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.

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

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.

Low-mass X-ray binary evolution and the origin of millisecond pulsars

NASA Technical Reports Server (NTRS)

Frank, Juhan; King, Andrew R.; Lasota, Jean-Pierre

1992-01-01

The evolution of low-mass X-ray binaries (LMXBs) is considered. It is shown that X-ray irradiation of the companion stars causes these systems to undergo episodes of rapid mass transfer followed by detached phases. The systems are visible as bright X-ray binaries only for a short part of each cycle, so that their space density must be considerably larger than previously estimated. This removes the difficulty in regarding LMXBs as the progenitors of low-mass binary pulsars. The low-accretion-rate phase of the cycle with the soft X-ray transients is identified. It is shown that 3 hr is likely to be the minimum orbital period for LMXBs with main-sequence companions and it is suggested that the evolutionary endpoint for many LMXBs may be systems which are the sites of gamma-ray bursts.

pH-dependent Differential Scanning Calorimetry and Dynamic Light Scattering Studies of 21:0 PC and 18:0 PS Lipid Binary System

NASA Astrophysics Data System (ADS)

Ali, Rejwan

2010-03-01

Large unilamallar vesicle has been a model system to study many membrane functions. High Tg lipid systems offer many potential biomedical applications in lipid-based delivery applications. While the optimized vesicle functionalities are achieved by Polyethylene Glycol (PEG) polymer, modified PEG and other functional molecule incorporation, however, the host binary lipid system plays the pivotal role in pH-dependent phase transition based lipid vehicular methods. We have investigated a lipid binary system composed of 21:0 PC (1,2-dihenarachidoyl-sn-glycero-3-phosphocholine) and 18:0 PS(1,2-distearoyl-sn-glycero-3-phospho-L-serine). Preliminary studies implementing differential scanning calorimetry shows pH plays key role in temperature shift and thermotropic phase behavior of the binary system. While dynamic light scattering study shows lipid vesicle size is almost independent of pH changes. We will also present pH-dependent thermodynamic parameters to correlate underlying molecular mechanism in relevant pH-range.

Vapor-Liquid Equilibria Using the Gibbs Energy and the Common Tangent Plane Criterion

ERIC Educational Resources Information Center

Olaya, Maria del Mar; Reyes-Labarta, Juan A.; Serrano, Maria Dolores; Marcilla, Antonio

2010-01-01

Phase thermodynamics is often perceived as a difficult subject with which many students never become fully comfortable. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based…

Development of Silica Fibers and Microstructures with Large and Thermodynamically Stable Second Order Nonlinearity

DTIC Science & Technology

2011-06-22

high degree of symmetry directly leads to a symmetry-enforced selection rule that can produce quantum entanglement [21, 22]. This report is organized...page.) Then, using a Matlab program, we converted the microscope image to a binary bitmap, from which we extract fiber radius at any given location

Ionic Liquids Database- (ILThermo)

National Institute of Standards and Technology Data Gateway

SRD 147 NIST Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

The nature of the laning transition in two dimensions

NASA Astrophysics Data System (ADS)

Glanz, T.; Löwen, H.

2012-11-01

If a binary colloidal mixture is oppositely driven by an external field, a transition towards a laned state occurs at sufficiently large drives, where particles driven alike form elongated structures (‘lanes’) characterized by a large correlation length ξ along the drive. Here we perform extensive Brownian dynamics computer simulations on a two-dimensional equimolar binary Yukawa system driven by a constant force that acts oppositely on the two species. We systematically address finite-size effects on lane formation by exploring large systems up to 262 144 particles under various boundary conditions. It is found that the correlation length ξ along the field depends exponentially on the driving force (or Peclet number). Conversely, in a finite system, ξ reaches a fraction of the system size at a driving force which is logarithmic in the system size, implying massive finite-size corrections. For a fixed finite drive, ξ does not diverge in the thermodynamic limit. Therefore, though laning has a signature as a sharp transition in a finite system, it is a smooth crossover in the thermodynamic limit.

Reports of investigations on: Derivation of an infinite-dilution activity coefficient model and application to two-component vapor/liquid equilibria data: Final report

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

Roper, V.P.; Kobayashi, R.

1988-02-01

Infinite-dilution fugacity coefficients were obtained for the system fluorene/phenanthrene at thirteen temperatures by fitting total pressure across the entire mole fraction range by a computer routine. A thermodynamically consistent routine, that allowed for both positive and negative pressure deviations from the ideal values, was used to correlate data over the full mole fraction range from 0 to 1. The four-suffix Margules activity coefficient model without modification essentially served this purpose since total pressures and total pressure derivatives with respect to mole fraction were negligible compared to pressure measurement precision. The water/ethanol system and binary systems comprised of aniline, chlorobenzene, acetonitrilemore » and other polar compounds were fit for total pressure across the entire mole fraction range for binary Vapor-Liquid-Equilbria (VLE) using the rigorous, thermodynamically consistent Gibbs-Duhem Relation derived by Ibl and Dodge. Data correlation was performed using a computer least squares procedure. Infinite-dilution fugacity coefficients were obtained using a modified Margules activity coefficient model.« less

Comment on "Not all counterclockwise thermodynamic cycles are refrigerators" [Am. J. Phys. 84, 413-418 (2016)

NASA Astrophysics Data System (ADS)

Bizarro, João P. S.

2017-11-01

Contrary to what Dickerson and Mottmann [Am. J. Phys. 84, 413-418 (2016)] state, the temperatures at which a refrigerator's working fluid absorbs heat need not always lie below those at which it expels heat; nor must a refrigerator's thermodynamic cycle have two adiabats. Moreover, what Dickerson and Mottmann call a "comparison Carnot cycle" cannot always be defined. These conclusions are illustrated here using a counter-clockwise Stirling cycle without regeneration. A refrigerator's cold reservoir can absorb some heat and its hot reservoir can expel some heat, so long as the net heat flow is still out of the cold reservoir and into the hot reservoir.

The Hydrological Sensitivity to Global Warming and Solar Geoengineering Derived from Thermodynamic Constraints

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

Kleidon, Alex; Kravitz, Benjamin S.; Renner, Maik

2015-01-16

We derive analytic expressions of the transient response of the hydrological cycle to surface warming from an extremely simple energy balance model in which turbulent heat fluxes are constrained by the thermodynamic limit of maximum power. For a given magnitude of steady-state temperature change, this approach predicts the transient response as well as the steady-state change in surface energy partitioning and the hydrologic cycle. We show that the transient behavior of the simple model as well as the steady state hydrological sensitivities to greenhouse warming and solar geoengineering are comparable to results from simulations using highly complex models. Many ofmore » the global-scale hydrological cycle changes can be understood from a surface energy balance perspective, and our thermodynamically-constrained approach provides a physically robust way of estimating global hydrological changes in response to altered radiative forcing.« less

Quasi-Periodic Oscillations in AM Herculis Binaries -- Cycle 3 Medium

NASA Astrophysics Data System (ADS)

Chanmugam, G.

1992-06-01

AM Her variables are close-binary systems in which a white dwarf with a magnetic field of 20-70 MG accretes matter from a companion star. Theoretical studies of magnetically channeled accretion flows in such systems predict that the shock formed near the white dwarf should oscillate with periods of order 0.1-1 sec. Optical high-speed photometry has indeed shown the existence of such rapid, quasi-periodic oscillations in some AM Her binaries, but not in others. We will use HST to obtain UV and optical high-speed photometry of several AM Her systems, in order to explore further the nature of the oscillations, and to extend the search into the UV. This proposal is a followup to an accepted Cycle 2 program. We are proposing it for Cycle 3 in order to complete our survey of the most suitable AM Her systems during this last opportunity for HSP observations.

Thermodynamical analysis of a quantum heat engine based on harmonic oscillators.

PubMed

Insinga, Andrea; Andresen, Bjarne; Salamon, Peter

2016-07-01

Many models of heat engines have been studied with the tools of finite-time thermodynamics and an ensemble of independent quantum systems as the working fluid. Because of their convenient analytical properties, harmonic oscillators are the most frequently used example of a quantum system. We analyze different thermodynamical aspects with the final aim of the optimization of the performance of the engine in terms of the mechanical power provided during a finite-time Otto cycle. The heat exchange mechanism between the working fluid and the thermal reservoirs is provided by the Lindblad formalism. We describe an analytical method to find the limit cycle and give conditions for a stable limit cycle to exist. We explore the power production landscape as the duration of the four branches of the cycle are varied for short times, intermediate times, and special frictionless times. For short times we find a periodic structure with atolls of purely dissipative operation surrounding islands of divergent behavior where, rather than tending to a limit cycle, the working fluid accumulates more and more energy. For frictionless times the periodic structure is gone and we come very close to the global optimal operation. The global optimum is found and interestingly comes with a particular value of the cycle time.

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.

Be discs in coplanar circular binaries: Phase-locked variations of emission lines

NASA Astrophysics Data System (ADS)

Panoglou, Despina; Faes, Daniel M.; Carciofi, Alex C.; Okazaki, Atsuo T.; Baade, Dietrich; Rivinius, Thomas; Borges Fernandes, Marcelo

2018-01-01

In this paper, we present the first results of radiative transfer calculations on decretion discs of binary Be stars. A smoothed particle hydrodynamics code computes the structure of Be discs in coplanar circular binary systems for a range of orbital and disc parameters. The resulting disc configuration consists of two spiral arms, and this can be given as input into a Monte Carlo code, which calculates the radiative transfer along the line of sight for various observational coordinates. Making use of the property of steady disc structure in coplanar circular binaries, observables are computed as functions of the orbital phase. Some orbital-phase series of line profiles are given for selected parameter sets under various viewing angles, to allow comparison with observations. Flat-topped profiles with and without superimposed multiple structures are reproduced, showing, for example, that triple-peaked profiles do not have to be necessarily associated with warped discs and misaligned binaries. It is demonstrated that binary tidal effects give rise to phase-locked variability of the violet-to-red (V/R) ratio of hydrogen emission lines. The V/R ratio exhibits two maxima per cycle; in certain cases those maxima are equal, leading to a clear new V/R cycle every half orbital period. This study opens a way to identifying binaries and to constraining the parameters of binary systems that exhibit phase-locked variations induced by tidal interaction with a companion star.

Thermodynamic Analysis and Optimization of a High Temperature Triple Absorption Heat Transformer

PubMed Central

Khamooshi, Mehrdad; Yari, Mortaza; Egelioglu, Fuat; Salati, Hana

2014-01-01

First law of thermodynamics has been used to analyze and optimize inclusively the performance of a triple absorption heat transformer operating with LiBr/H2O as the working pair. A thermodynamic model was developed in EES (engineering equation solver) to estimate the performance of the system in terms of the most essential parameters. The assumed parameters are the temperature of the main components, weak and strong solutions, economizers' efficiencies, and bypass ratios. The whole cycle is optimized by EES software from the viewpoint of maximizing the COP via applying the direct search method. The optimization results showed that the COP of 0.2491 is reachable by the proposed cycle. PMID:25136702

Thermodynamic study on the role of hydrogen during the MOVPE growth of group III nitrides

NASA Astrophysics Data System (ADS)

Koukitu, Akinori; Taki, Tetsuya; Takahashi, Naoyuki; Seki, Hisashi

1999-02-01

The role of hydrogen during the MOVPE growth of group III nitrides is investigated from a thermodynamic point of view. The effect of hydrogen is reported for the driving force for the deposition of binary nitrides as functions of growth temperature and V/III ratio. The effect of hydrogen for the InGaN growth is discussed for the vapor-solid relationship, the formation of compositional inhomogeneity and input partial pressure of the group III elements. The difference between the growth reaction of the indium containing nitrides and that of other III-V compounds is also discussed.

Thermodynamic properties of semiconductor compounds studied based on Debye-Waller factors

NASA Astrophysics Data System (ADS)

Van Hung, Nguyen; Toan, Nguyen Cong; Ba Duc, Nguyen; Vuong, Dinh Quoc

2015-08-01

Thermodynamic properties of semiconductor compounds have been studied based on Debye-Waller factors (DWFs) described by the mean square displacement (MSD) which has close relation with the mean square relative displacement (MSRD). Their analytical expressions have been derived based on the statistical moment method (SMM) and the empirical many-body Stillinger-Weber potentials. Numerical results for the MSDs of GaAs, GaP, InP, InSb, which have zinc-blende structure, are found to be in reasonable agreement with experiment and other theories. This paper shows that an elements value for MSD is dependent on the binary semiconductor compound within which it resides.

Surface tension modelling of liquid Cd-Sn-Zn alloys

NASA Astrophysics Data System (ADS)

Fima, Przemyslaw; Novakovic, Rada

2018-06-01

The thermodynamic model in conjunction with Butler equation and the geometric models were used for the surface tension calculation of Cd-Sn-Zn liquid alloys. Good agreement was found between the experimental data for limiting binaries and model calculations performed with Butler model. In the case of ternary alloys, the surface tension variation with Cd content is better reproduced in the case of alloys lying on vertical sections defined by high Sn to Zn molar fraction ratio. The calculated surface tension is in relatively good agreement with the available experimental data. In addition, the surface segregation of liquid ternary Cd-Sn-Zn and constituent binaries has also been calculated.

Enthalpies of a binary alloy during solidification

NASA Technical Reports Server (NTRS)

Poirier, D. R.; Nandapurkar, P.

1988-01-01

The purpose of the paper is to present a method of calculating the enthalpy of a dendritic alloy during solidification. The enthalpies of the dendritic solid and interdendritic liquid of alloys of the Pb-Sn system are evaluated, but the method could be applied to other binaries, as well. The enthalpies are consistent with a recent evaluation of the thermodynamics of Pb-Sn alloys and with the redistribution of solute in the same during dendritic solidification. Because of the heat of mixing in Pb-Sn alloys, the interdendritic liquid of hypoeutectic alloys (Pb-rich) of less than 50 wt pct Sn has enthalpies that increase as temperature decreases during solidification.

Formation of an amorphous phase and its crystallization in the immiscible Nb-Zr system by mechanical alloying

NASA Astrophysics Data System (ADS)

Al-Aqeeli, N.; Suryanarayana, C.; Hussein, M. A.

2013-10-01

Mechanical alloying of binary Nb-Zr powder mixtures was carried out to evaluate the formation of metastable phases in this immiscible system. The milled powders were characterized for their constitution and structure by X-ray diffraction and transmission electron microscopy methods. It was shown that an amorphous phase had formed on milling the binary powder mixture for about 10 h and that it had crystallized on subsequent milling up to 50-70 h, referred to as mechanical crystallization. Thermodynamic and structural arguments have been presented to explain the formation of the amorphous phase and its subsequent crystallization.

Absorption Refrigeration Cycles with Ammonia-Ionic Liquid Working Pairs Studied by Molecular Simulation.

PubMed

Becker, Tim M; Wang, Meng; Kabra, Abhishek; Jamali, Seyed Hossein; Ramdin, Mahinder; Dubbeldam, David; Infante Ferreira, Carlos A; Vlugt, Thijs J H

2018-04-18

For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf 2 N], and [emim][SCN]. As refrigerant NH 3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance.

Absorption Refrigeration Cycles with Ammonia–Ionic Liquid Working Pairs Studied by Molecular Simulation

PubMed Central

2018-01-01

For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf2N], and [emim][SCN]. As refrigerant NH3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance. PMID:29749996

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE PAGES

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

2017-05-12

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

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

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

Adsorption of Cr(VI) on cerium immobilized cross-linked chitosan composite in single system and coexisted with Orange II in binary system.

PubMed

Zhu, Tianyi; Huang, Wei; Zhang, Lingfan; Gao, Jie; Zhang, Wenqing

2017-10-01

In this work, cerium immobilized cross-linked chitosan (CTS-Ce) composite, employed as an efficient adsorbent for Cr(VI) in single system and coexisted with Orange II (OII) in binary system, was prepared by co-precipitation method. The as-obtained adsorbent was characterized by FTIR, SEM, EDS and XPS before and after adsorption. The adsorption behaviors of Cr(VI) in single and binary system were systematically studied. The maximum adsorption capacity of Cr(VI) on CTS-Ce (202.8mg/g) was calculated by Langmuir equation in single metal system, but it decreased to 112.9mg/g with initial concentration of 100mg/L OII in binary system at pH 2 and 293K. The adsorption data for Cr(VI) followed the Langmuir model in single system, while fitted Temkin model well in binary system. In both single and binary system, the kinetics of adsorption exhibited pseudo-second order behavior and adsorption capacity increased with increasing temperature. Moreover, the data of thermodynamic parameters (ΔG°<0, ΔH°>0) indicated that the adsorption was a spontaneous and endothermic process. Besides, |ΔG Cr |>|ΔG Cr-OII | at the same temperature further suggested that Cr(VI) was adsorbed on the CTS-Ce composite faster in binary system than in single system. Copyright © 2017 Elsevier B.V. All rights reserved.

General formalism of local thermodynamics with an example: Quantum Otto engine with a spin-1/2 coupled to an arbitrary spin.

PubMed

Altintas, Ferdi; Müstecaplıoğlu, Özgür E

2015-08-01

We investigate a quantum heat engine with a working substance of two particles, one with a spin-1/2 and the other with an arbitrary spin (spin s), coupled by Heisenberg exchange interaction, and subject to an external magnetic field. The engine operates in a quantum Otto cycle. Work harvested in the cycle and its efficiency are calculated using quantum thermodynamical definitions. It is found that the engine has higher efficiencies at higher spins and can harvest work at higher exchange interaction strengths. The role of exchange coupling and spin s on the work output and the thermal efficiency is studied in detail. In addition, the engine operation is analyzed from the perspective of local work and efficiency. We develop a general formalism to explore local thermodynamics applicable to any coupled bipartite system. Our general framework allows for examination of local thermodynamics even when global parameters of the system are varied in thermodynamic cycles. The generalized definitions of local and cooperative work are introduced by using mean field Hamiltonians. The general conditions for which the global work is not equal to the sum of the local works are given in terms of the covariance of the subsystems. Our coupled spin quantum Otto engine is used as an example of the general formalism.

General formalism of local thermodynamics with an example: Quantum Otto engine with a spin-1 /2 coupled to an arbitrary spin

NASA Astrophysics Data System (ADS)

Altintas, Ferdi; Müstecaplıoǧlu, Ã.-zgür E.

2015-08-01

We investigate a quantum heat engine with a working substance of two particles, one with a spin-1 /2 and the other with an arbitrary spin (spin s ), coupled by Heisenberg exchange interaction, and subject to an external magnetic field. The engine operates in a quantum Otto cycle. Work harvested in the cycle and its efficiency are calculated using quantum thermodynamical definitions. It is found that the engine has higher efficiencies at higher spins and can harvest work at higher exchange interaction strengths. The role of exchange coupling and spin s on the work output and the thermal efficiency is studied in detail. In addition, the engine operation is analyzed from the perspective of local work and efficiency. We develop a general formalism to explore local thermodynamics applicable to any coupled bipartite system. Our general framework allows for examination of local thermodynamics even when global parameters of the system are varied in thermodynamic cycles. The generalized definitions of local and cooperative work are introduced by using mean field Hamiltonians. The general conditions for which the global work is not equal to the sum of the local works are given in terms of the covariance of the subsystems. Our coupled spin quantum Otto engine is used as an example of the general formalism.

Composite hot subdwarf binaries - I. The spectroscopically confirmed sdB sample

NASA Astrophysics Data System (ADS)

Vos, Joris; Németh, Péter; Vučković, Maja; Østensen, Roy; Parsons, Steven

2018-01-01

Hot subdwarf-B (sdB) stars in long-period binaries are found to be on eccentric orbits, even though current binary-evolution theory predicts that these objects are circularized before the onset of Roche lobe overflow (RLOF). To increase our understanding of binary interaction processes during the RLOF phase, we started a long-term observing campaign to study wide sdB binaries. In this paper, we present a sample of composite binary sdBs, and the results of the spectral analysis of nine such systems. The grid search in stellar parameters (GSSP) code is used to derive atmospheric parameters for the cool companions. To cross-check our results and also to characterize the hot subdwarfs, we used the independent XTGRID code, which employs TLUSTY non-local thermodynamic equilibrium models to derive atmospheric parameters for the sdB component and PHOENIX synthetic spectra for the cool companions. The independent GSSP and XTGRID codes are found to show good agreement for three test systems that have atmospheric parameters available in the literature. Based on the rotational velocity of the companions, we make an estimate for the mass accreted during the RLOF phase and the minimum duration of that phase. We find that the mass transfer to the companion is minimal during the subdwarf formation.

Working fluid selection for the Organic Rankine Cycle (ORC) exhaust heat recovery of an internal combustion engine power plant

NASA Astrophysics Data System (ADS)

Douvartzides, S.; Karmalis, I.

2016-11-01

Organic Rankine cycle technology is capable to efficiently convert low-grade heat into useful mechanical power. In the present investigation such a cycle is used for the recovery of heat from the exhaust gases of a four stroke V18 MAN 51/60DF internal combustion engine power plant operating with natural gas. Design is focused on the selection of the appropriate working fluid of the Rankine cycle in terms of thermodynamic, environmental and safety criteria. 37 candidate fluids have been considered and all Rankine cycles examined were subcritical. The thermodynamic analysis of all fluids has been comparatively undertaken and the effect of key operation conditions such as the evaporation pressure and the superheating temperature was taken into account. By appropriately selecting the working fluid and the Rankine cycle operation conditions the overall plant efficiency was improved by 5.52% and fuel consumption was reduced by 12.69%.

Complexation equilibria and coordination aspects of Zn(II) complexes contain 2-aminobenzamide and some bioactive amino acid mixed ligands: pH-metric, spectroscopic and thermodynamic studies.

PubMed

Dharmaraja, Jeyaprakash; Subbaraj, Paramasivam; Esakkidurai, Thirugnanasamy; Shobana, Sutha; Raji, Saravanan

2014-01-01

Mixed ligand complexation of 2-aminobenzamide (2AB) as ligand [L] with Zn(II) in the presence of some bio-relevant amino acid constituents like glycine (gly), L-alanine (ala), L-valine (val) and L-phenylalanine (phe) as ligand [B] have been investigated using pH-metric measurements with a combined pH electrode at different temperatures (300, 310, 320 and 330 ± 0.1 K) in 50% (v/v) ethanol-water mixture containing I = 0.15 M NaClO(4) as supporting electrolyte. Computer assisted analysis of the experimental titration data showed the presence of ZnLB and ZnLB2 species as mixed ligand complexes in addition to various binary species. In ZnLB/ZnLB(2) species, both primary and secondary ligands act as bidentate to form a stable six, five membered chelate ring. The calculated stabilization parameter Deltalog K, log X, log X' and % R.S. values clearly show the mixed ligand complexes have higher stabilities than their binary. Thermodynamic parameters DeltaG, DeltaH and DeltaS have been derived from the temperature dependence of the stability constants. The complexation behavior of ZnLB species has been studied by means of electronic spectra. The percentage distribution of various binary and mixed ligand species of each type of the complexes in solution depending on pH and the ratio of Zn(II) to 2-aminobenzamide/amino acid of the systems.

Eclipse timings of the low-mass X-ray binary EXO 0748-676: Statistical arguments against orbital period changes

NASA Technical Reports Server (NTRS)

Hertz, Paul; Wood, Kent S.; Cominsky, Lynn

1995-01-01

EXO 0748-676, an eclipsing low-mass X-ray binary, is one of only about four or five low-mass X-ray binaries for which orbital period evolution has been reported. We observed a single eclipse egress with ROSAT . The time of this egress is consistent with the apparent increase in P(sub orb) previously reported on the basis of EXOSAT and Ginga observations. Standard analysis, in which O-C (observed minus calculated) timing residuals are examined for deviations from a constant period, implicitly assume that the only uncertainty in each residual is measurement error and that these errors are independent. We argue that the variable eclipse durations and profiles observed in EXO 0748-676 imply that there is an additional source of uncertainty in timing measurements, that this uncertainty is intrinsic to the binary system, and that it is correlated from observation to observation with a variance which increases as a function of the number of binary cycles between observations. This intrinsic variability gives rise to spurious trends in O-C residuals which are misinterpreted as changes in the orbital period. We describe several statistics tests which can be used to test for the presence of intrinsic variability. We apply those statistical tests which are suitable to the EXO 0748-676 observations. The apparent changes in the orbital period of EXO 0748-676 can be completely accounted for by intrinsic variability with an rms variability of approximately 0.35 s per orbital cycle. The variability appears to be correlated from cycle-to-cycle on timescales of less than 1 yr. We suggest that the intrinsic variability is related to slow changes in either the source's X-ray luminosity or the structure of the companion star's atmosphere. We note that several other X-ray binaries and cataclysmic variables have previously reported orbital period changes which may also be due to intrinsic variability rather than orbital period evolution.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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.

A Structural Molar Volume Model for Oxide Melts Part I: Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 Melts—Binary Systems

NASA Astrophysics Data System (ADS)

Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

2016-04-01

A structural molar volume model was developed to accurately reproduce the molar volume of molten oxides. As the non-linearity of molar volume is related to the change in structure of molten oxides, the silicate tetrahedral Q-species, calculated from the modified quasichemical model with an optimized thermodynamic database, were used as basic structural units in the present model. Experimental molar volume data for unary and binary melts in the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 system were critically evaluated. The molar volumes of unary oxide components and binary Q-species, which are model parameters of the present structural model, were determined to accurately reproduce the experimental data across the entire binary composition in a wide range of temperatures. The non-linear behavior of molar volume and thermal expansivity of binary melt depending on SiO2 content are well reproduced by the present model.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

Cardiorespiratory Kinetics Determined by Pseudo-Random Binary Sequences - Comparisons between Walking and Cycling.

PubMed

Koschate, J; Drescher, U; Thieschäfer, L; Heine, O; Baum, K; Hoffmann, U

2016-12-01

This study aims to compare cardiorespiratory kinetics as a response to a standardised work rate protocol with pseudo-random binary sequences between cycling and walking in young healthy subjects. Muscular and pulmonary oxygen uptake (V̇O 2 ) kinetics as well as heart rate kinetics were expected to be similar for walking and cycling. Cardiac data and V̇O 2 of 23 healthy young subjects were measured in response to pseudo-random binary sequences. Kinetics were assessed applying time series analysis. Higher maxima of cross-correlation functions between work rate and the respective parameter indicate faster kinetics responses. Muscular V̇O 2 kinetics were estimated from heart rate and pulmonary V̇O 2 using a circulatory model. Muscular (walking vs. cycling [mean±SD in arbitrary units]: 0.40±0.08 vs. 0.41±0.08) and pulmonary V̇O 2 kinetics (0.35±0.06 vs. 0.35±0.06) were not different, although the time courses of the cross-correlation functions of pulmonary V̇O 2 showed unexpected biphasic responses. Heart rate kinetics (0.50±0.14 vs. 0.40±0.14; P=0.017) was faster for walking. Regarding the biphasic cross-correlation functions of pulmonary V̇O 2 during walking, the assessment of muscular V̇O 2 kinetics via pseudo-random binary sequences requires a circulatory model to account for cardio-dynamic distortions. Faster heart rate kinetics for walking should be considered by comparing results from cycle and treadmill ergometry. © Georg Thieme Verlag KG Stuttgart · New York.

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.

Thermodynamic framework for identifying free energy inventories of enzyme catalytic cycles

PubMed Central

Fried, Stephen D.; Boxer, Steven G.

2013-01-01

Pauling’s suggestion that enzymes are complementary in structure to the activated complexes of the reactions they catalyze has provided the conceptual basis to explain how enzymes obtain their fantastic catalytic prowess, and has served as a guiding principle in drug design for over 50 y. However, this model by itself fails to predict the magnitude of enzymes’ rate accelerations. We construct a thermodynamic framework that begins with the classic concept of differential binding but invokes additional terms that are needed to account for subtle effects in the catalytic cycle’s proton inventory. Although the model presented can be applied generally, this analysis focuses on ketosteroid isomerase (KSI) as an example, where recent experiments along with a large body of kinetic and thermodynamic data have provided strong support for the noncanonical thermodynamic contribution described. The resulting analysis precisely predicts the free energy barrier of KSI’s reaction as determined from transition-state theory using only empirical thermodynamic data. This agreement is suggestive that a complete free energy inventory of the KSI catalytic cycle has been identified. PMID:23840058

Nonequilibrium thermodynamics and energy efficiency in weight loss diets.

PubMed

Feinman, Richard D; Fine, Eugene J

2007-07-30

Carbohydrate restriction as a strategy for control of obesity is based on two effects: a behavioral effect, spontaneous reduction in caloric intake and a metabolic effect, an apparent reduction in energy efficiency, greater weight loss per calorie consumed. Variable energy efficiency is established in many contexts (hormonal imbalance, weight regain and knock-out experiments in animal models), but in the area of the effect of macronutrient composition on weight loss, controversy remains. Resistance to the idea comes from a perception that variable weight loss on isocaloric diets would somehow violate the laws of thermodynamics, that is, only caloric intake is important ("a calorie is a calorie"). Previous explanations of how the phenomenon occurs, based on equilibrium thermodynamics, emphasized the inefficiencies introduced by substrate cycling and requirements for increased gluconeogenesis. Living systems, however, are maintained far from equilibrium, and metabolism is controlled by the regulation of the rates of enzymatic reactions. The principles of nonequilibrium thermodynamics which emphasize kinetic fluxes as well as thermodynamic forces should therefore also be considered. Here we review the principles of nonequilibrium thermodynamics and provide an approach to the problem of maintenance and change in body mass by recasting the problem of TAG accumulation and breakdown in the adipocyte in the language of nonequilibrium thermodynamics. We describe adipocyte physiology in terms of cycling between an efficient storage mode and a dissipative mode. Experimentally, this is measured in the rate of fatty acid flux and fatty acid oxidation. Hormonal levels controlled by changes in dietary carbohydrate regulate the relative contributions of the efficient and dissipative parts of the cycle. While no experiment exists that measures all relevant variables, the model is supported by evidence in the literature that 1) dietary carbohydrate, via its effect on hormone levels controls fatty acid flux and oxidation, 2) the rate of lipolysis is a primary target of insulin, postprandial, and 3) chronic carbohydrate-restricted diets reduce the levels of plasma TAG in response to a single meal. In summary, we propose that, in isocaloric diets of different macronutrient composition, there is variable flux of stored TAG controlled by the kinetic effects of insulin and other hormones. Because the fatty acid-TAG cycle never comes to equilibrium, net gain or loss is possible. The greater weight loss on carbohydrate restricted diets, popularly referred to as metabolic advantage can thus be understood in terms of the principles of nonequilibrium thermodynamics and is a consequence of the dynamic nature of bioenergetics where it is important to consider kinetic as well as thermodynamic variables.

Nonequilibrium thermodynamics and energy efficiency in weight loss diets

PubMed Central

Feinman, Richard D; Fine, Eugene J

2007-01-01

Carbohydrate restriction as a strategy for control of obesity is based on two effects: a behavioral effect, spontaneous reduction in caloric intake and a metabolic effect, an apparent reduction in energy efficiency, greater weight loss per calorie consumed. Variable energy efficiency is established in many contexts (hormonal imbalance, weight regain and knock-out experiments in animal models), but in the area of the effect of macronutrient composition on weight loss, controversy remains. Resistance to the idea comes from a perception that variable weight loss on isocaloric diets would somehow violate the laws of thermodynamics, that is, only caloric intake is important ("a calorie is a calorie"). Previous explanations of how the phenomenon occurs, based on equilibrium thermodynamics, emphasized the inefficiencies introduced by substrate cycling and requirements for increased gluconeogenesis. Living systems, however, are maintained far from equilibrium, and metabolism is controlled by the regulation of the rates of enzymatic reactions. The principles of nonequilibrium thermodynamics which emphasize kinetic fluxes as well as thermodynamic forces should therefore also be considered. Here we review the principles of nonequilibrium thermodynamics and provide an approach to the problem of maintenance and change in body mass by recasting the problem of TAG accumulation and breakdown in the adipocyte in the language of nonequilibrium thermodynamics. We describe adipocyte physiology in terms of cycling between an efficient storage mode and a dissipative mode. Experimentally, this is measured in the rate of fatty acid flux and fatty acid oxidation. Hormonal levels controlled by changes in dietary carbohydrate regulate the relative contributions of the efficient and dissipative parts of the cycle. While no experiment exists that measures all relevant variables, the model is supported by evidence in the literature that 1) dietary carbohydrate, via its effect on hormone levels controls fatty acid flux and oxidation, 2) the rate of lipolysis is a primary target of insulin, postprandial, and 3) chronic carbohydrate-restricted diets reduce the levels of plasma TAG in response to a single meal. In summary, we propose that, in isocaloric diets of different macronutrient composition, there is variable flux of stored TAG controlled by the kinetic effects of insulin and other hormones. Because the fatty acid-TAG cycle never comes to equilibrium, net gain or loss is possible. The greater weight loss on carbohydrate restricted diets, popularly referred to as metabolic advantage can thus be understood in terms of the principles of nonequilibrium thermodynamics and is a consequence of the dynamic nature of bioenergetics where it is important to consider kinetic as well as thermodynamic variables. PMID:17663761

Thermodynamic assessment of the LiF-NaF-BeF2-ThF4-UF4 system

NASA Astrophysics Data System (ADS)

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

2014-06-01

The present study describes the full thermodynamic assessment of the LiF-NaF-BeF2-ThF4-UF4 system which is one of the key systems considered for a molten salt reactor fuel. The work is an extension of the previously assessed LiF-NaF-ThF4-UF4 system with addition of BeF2 which is characterized by very low neutron capture cross section and a relatively low melting point. To extend the database the binary BeF2-ThF4 and BeF2-UF4 systems were optimized and the novel data were used for the thermodynamic assessment of BeF2 containing ternary systems for which experimental data exist in the literature. The obtained database is used to optimize the molten salt reactor fuel composition and to assess its properties with the emphasis on the melting behaviour.

Thermodynamic properties and diffusion of water + methane binary mixtures

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

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

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

Dark matter influence on black objects thermodynamics

NASA Astrophysics Data System (ADS)

Rogatko, Marek; Wojnar, Aneta

2018-05-01

Physical process version of the first law of black hole thermodynamics in Einstein-Maxwell dark matter gravity was derived. The dark matter sector is mimicked by the additional U(1)-gauge field coupled to the ordinary Maxwell one. By considering any cross section of the black hole event horizon to the future of the bifurcation surface, the equilibrium state version of the first law of black hole mechanics was achieved. The considerations were generalized to the case of Einstein-Yang-Mills dark matter gravity theory. The main conclusion is that the influence of dark matter is crucial in the formation process of black objects. This fact may constitute the explanation of the recent observations of the enormous mass of the super luminous quasars formed in a relatively short time after Big Bang. We also pay attention to the compact binaries thermodynamics, when dark matter sector enters the game.

Comparison of iterative inverse coarse-graining methods

NASA Astrophysics Data System (ADS)

Rosenberger, David; Hanke, Martin; van der Vegt, Nico F. A.

2016-10-01

Deriving potentials for coarse-grained Molecular Dynamics (MD) simulations is frequently done by solving an inverse problem. Methods like Iterative Boltzmann Inversion (IBI) or Inverse Monte Carlo (IMC) have been widely used to solve this problem. The solution obtained by application of these methods guarantees a match in the radial distribution function (RDF) between the underlying fine-grained system and the derived coarse-grained system. However, these methods often fail in reproducing thermodynamic properties. To overcome this deficiency, additional thermodynamic constraints such as pressure or Kirkwood-Buff integrals (KBI) may be added to these methods. In this communication we test the ability of these methods to converge to a known solution of the inverse problem. With this goal in mind we have studied a binary mixture of two simple Lennard-Jones (LJ) fluids, in which no actual coarse-graining is performed. We further discuss whether full convergence is actually needed to achieve thermodynamic representability.

A combined experimental and computational thermodynamic investigation of the U-Th-O system

DOE PAGES

McMurray, Jake Wesley; Voit, Stewart L.; Besmann, Theodore M.

2016-03-21

Here, the thermodynamics of the U–Th–O system have been assessed using the Calphad method. The compound energy formalism (CEF) and a partially ionic two-sublattice liquid model (TSLM) were used for the fluorite U 1–yTh yO 2±x, γ-(U,Th) 4O 9, and the U–Th–O melt. The O 2 activity of fluorite U 1–yTh yO 2±x with temperature and composition was determined by thermogravimetric analysis. Thermodynamic studies for the Th–O binary and U–Th–O ternary available in the open literature were critically reviewed. A self-consistent data set was selected and compiled with the equilibrium oxygen pressures determined by thermogravimetry in order to optimize themore » adjustable parameters of models selected to represent the phases in the Th–O and U–Th–O systems.« less

Thermodynamic and kinetic theory of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets on soluble particles.

PubMed

Shchekin, Alexander K; Shabaev, Ilya V; Hellmuth, Olaf

2013-02-07

Thermodynamic and kinetic peculiarities of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets formed on soluble condensation nuclei from a solvent vapor have been considered. The interplay of the effects of solubility and the size of condensation nuclei has been analyzed. Activation barriers for the deliquescence and phase transitions and for the reverse efflorescence transition have been determined as functions of the relative humidity of the vapor-gas atmosphere, initial size, and solubility of condensation nuclei. It has been demonstrated that, upon variations in the relative humidity of the atmosphere, the crossover in thermodynamically stable and unstable variables of the droplet state takes place. The physical meaning of stable and unstable variables has been clarified. The kinetic equations for establishing equilibrium and steady distributions of binary droplets have been solved. The specific times for relaxation, deliquescence and efflorescence transitions have been calculated.

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

Structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds

NASA Astrophysics Data System (ADS)

Liu, Yangzhen; Xing, Jiandong; Fu, Hanguang; Li, Yefei; Sun, Liang; Lv, Zheng

2017-08-01

The properties of sulfides are important in the design of new iron-steel materials. In this study, first-principles calculations were used to estimate the structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds. The results reveal that these XS binary compounds are thermodynamically stable, because their formation enthalpy is negative. The elastic constants, Cij, and moduli (B, G, E) were investigated using stress-strain and Voigt-Reuss-Hill approximation, respectively. The sulfide anisotropy was discussed from an anisotropic index and three-dimensional surface contours. The electronic structures reveal that the bonding characteristics of the XS compounds are a mixture of metallic and covalent bonds. Using a quasi-harmonic Debye approximation, the heat capacity at constant pressure and constant volume was estimated. NiS possesses the largest CP and CV of the sulfides.

Binary nanoparticle superlattices of soft-particle systems

DOE PAGES

Travesset, Alex

2015-08-04

The solid-phase diagram of binary systems consisting of particles of diameter σ A=σ and σ B=γσ (γ≤1) interacting with an inverse p = 12 power law is investigated as a paradigm of a soft potential. In addition to the diameter ratio γ that characterizes hard-sphere models, the phase diagram is a function of an additional parameter that controls the relative interaction strength between the different particle types. Phase diagrams are determined from extremes of thermodynamic functions by considering 15 candidate lattices. In general, it is shown that the phase diagram of a soft repulsive potential leads to the morphological diversitymore » observed in experiments with binary nanoparticles, thus providing a general framework to understand their phase diagrams. In addition, particular emphasis is shown to the two most successful crystallization strategies so far: evaporation of solvent from nanoparticles with grafted hydrocarbon ligands and DNA programmable self-assembly.« less

A Tractable Disequilbrium Framework for Integrating Computational Thermodynamics and Geodynamics

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Thermodynamic cycle in a cavity optomechanical system

NASA Astrophysics Data System (ADS)

Ian, Hou

2014-07-01

A cavity optomechanical system is initiated by the radiation pressure of a cavity field onto a mirror element acting as a quantum resonator. This radiation pressure can control the thermodynamic character of the mirror to some extent, such as by cooling its effective temperature. Here, we show that by properly engineering the spectral density of a thermal heat bath that interacts with a quantum system, the evolution of the quantum system can be effectively turned on and off. Inside a cavity optomechanical system, when the heat bath is realized by a multi-mode oscillator modelling of the mirror, this on-off effect translates to infusion or extraction of heat energy in and out of the cavity field, facilitating a four-stroke thermodynamic cycle.

Some heat engine cycles in which liquids can work.

PubMed

Allen, P C; Paulson, D N; Wheatley, J C

1981-01-01

Liquids can work in heat engine cycles that employ regeneration. Four such cycles are discussed: Stirling, Malone, Stirling-Malone, and Brayton. Both regeneration and the role of the second thermodynamic medium are treated, and the principles are verified by quantitative measurements with propylene in a Stirling-Malone cycle.

Some heat engine cycles in which liquids can work

PubMed Central

Allen, P. C.; Paulson, D. N.; Wheatley, J. C.

1981-01-01

Liquids can work in heat engine cycles that employ regeneration. Four such cycles are discussed: Stirling, Malone, Stirling-Malone, and Brayton. Both regeneration and the role of the second thermodynamic medium are treated, and the principles are verified by quantitative measurements with propylene in a Stirling-Malone cycle. PMID:16592952

Multi-objective thermodynamic optimisation of supercritical CO2 Brayton cycles integrated with solar central receivers

NASA Astrophysics Data System (ADS)

Vasquez Padilla, Ricardo; Soo Too, Yen Chean; Benito, Regano; McNaughton, Robbie; Stein, Wes

2018-01-01

In this paper, optimisation of the supercritical CO? Brayton cycles integrated with a solar receiver, which provides heat input to the cycle, was performed. Four S-CO? Brayton cycle configurations were analysed and optimum operating conditions were obtained by using a multi-objective thermodynamic optimisation. Four different sets, each including two objective parameters, were considered individually. The individual multi-objective optimisation was performed by using Non-dominated Sorting Genetic Algorithm. The effect of reheating, solar receiver pressure drop and cycle parameters on the overall exergy and cycle thermal efficiency was analysed. The results showed that, for all configurations, the overall exergy efficiency of the solarised systems achieved at maximum value between 700°C and 750°C and the optimum value is adversely affected by the solar receiver pressure drop. In addition, the optimum cycle high pressure was in the range of 24.2-25.9 MPa, depending on the configurations and reheat condition.

Dixie Valley Binary Cycle Production Data 2013 YTD

DOE Data Explorer

Lee, Vitaly

2013-10-18

Proving the technical and economic feasibility of utilizing the available unused heat to generate additional electric power from a binary power plant from the low-temperature brine at the Dixie Valley Geothermal Power Plant. Monthly data for Jan 2013-September 2013

Liquid-metal binary cycles for stationary power

NASA Technical Reports Server (NTRS)

Gutstein, M.; Furman, E. R.; Kaplan, G. M.

1975-01-01

The use of topping cycles to increase electric power plant efficiency is discussed, with particular attention to mercury and alkali metal Rankine cycle systems that could be considered for topping cycle applications. An overview of this technology, possible system applications, the required development, and possible problem areas is presented.

Binary Gene Expression Patterning of the Molt Cycle: The Case of Chitin Metabolism

PubMed Central

Abehsera, Shai; Glazer, Lilah; Tynyakov, Jenny; Plaschkes, Inbar; Chalifa-Caspi, Vered; Khalaila, Isam; Aflalo, Eliahu D.; Sagi, Amir

2015-01-01

In crustaceans, like all arthropods, growth is accompanied by a molting cycle. This cycle comprises major physiological events in which mineralized chitinous structures are built and degraded. These events are in turn governed by genes whose patterns of expression are presumably linked to the molting cycle. To study these genes we performed next generation sequencing and constructed a molt-related transcriptomic library from two exoskeletal-forming tissues of the crayfish Cherax quadricarinatus, namely the gastrolith and the mandible cuticle-forming epithelium. To simplify the study of such a complex process as molting, a novel approach, binary patterning of gene expression, was employed. This approach revealed that key genes involved in the synthesis and breakdown of chitin exhibit a molt-related pattern in the gastrolith-forming epithelium. On the other hand, the same genes in the mandible cuticle-forming epithelium showed a molt-independent pattern of expression. Genes related to the metabolism of glucosamine-6-phosphate, a chitin precursor synthesized from simple sugars, showed a molt-related pattern of expression in both tissues. The binary patterning approach unfolds typical patterns of gene expression during the molt cycle of a crustacean. The use of such a simplifying integrative tool for assessing gene patterning seems appropriate for the study of complex biological processes. PMID:25919476

Thermodynamic Analysis of Beam down Solar Gas Turbine Power Plant equipped with Concentrating Receiver System

NASA Astrophysics Data System (ADS)

Azharuddin; Santarelli, Massimo

2016-09-01

Thermodynamic analysis of a closed cycle, solar powered Brayton gas turbine power plant with Concentrating Receiver system has been studied. A Brayton cycle is simpler than a Rankine cycle and has an advantage where the water is scarce. With the normal Brayton cycle a Concentrating Receiver System has been analysed which has a dependence on field density and optical system. This study presents a method of optimization of design parameter, such as the receiver working temperature and the heliostats density. This method aims at maximizing the overall efficiency of the three major subsystem that constitute the entire plant, namely, the heliostat field and the tower, the receiver and the power block. The results of the optimization process are shown and analysed.

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.

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.

Thermodynamic assessment of the Sn-Co lead-free solder system

NASA Astrophysics Data System (ADS)

Liu, Libin; Andersson, Cristina; Liu, Johan

2004-09-01

The Sn-Co-Cu eutectic alloy can be a less expensive alternative for the Sn-Ag-Cu alloy. In order to find the eutectic solder composition of the Sn-Co-Cu system, the Sn-Co binary system has been thoroughly assessed with the calculation of phase diagram (CALPHAD) method. The liquid phase, the FCC and HCP Co-rich solid solution, and the BCT Sn-rich solid solution have been described by the Redlich-Kister model. The Hillert-Jarl-Inden model has been used to describe the magnetic contributions to Gibbs energy in FCC and HCP. The CoSn2, CoSn, Co3Sn2_β, and Co3Sn2_α phases have been treated as stoichiometric phases. A series of thermodynamic parameters have been obtained. The calculated phase diagram and thermodynamic properties are in good agreement with the experimental data. The obtained thermodynamic data was used to extrapolate the ternary Sn-Co-Cu phase diagram. The composition of the Sn-rich eutectic point of the Sn-Co-Cu system was found to be 224°C, 0.4% Co, and 0.7% Cu.

THERMODYNAMIC EVALUATION OF FLUORINATED ETHERS, ETHANES, AND PROPANES AS ALTERNATIVE REFRIGERANTS

EPA Science Inventory

The visuals, part of a thermodynamic evaluation of fluorinated ethers, ethanes, and propanes as alternative refrigerants, are a useful tool in comparing new chemicals to existing refrigerants in vapor compression cycles. hey present the required suction superheat and the performa...

C–IBI: Targeting cumulative coordination within an iterative protocol to derive coarse-grained models of (multi-component) complex fluids

DOE PAGES

de Oliveira, Tiago E.; Netz, Paulo A.; Kremer, Kurt; ...

2016-05-03

We present a coarse-graining strategy that we test for aqueous mixtures. The method uses pair-wise cumulative coordination as a target function within an iterative Boltzmann inversion (IBI) like protocol. We name this method coordination iterative Boltzmann inversion (C–IBI). While the underlying coarse-grained model is still structure based and, thus, preserves pair-wise solution structure, our method also reproduces solvation thermodynamics of binary and/or ternary mixtures. In addition, we observe much faster convergence within C–IBI compared to IBI. To validate the robustness, we apply C–IBI to study test cases of solvation thermodynamics of aqueous urea and a triglycine solvation in aqueous urea.

Phase Diagram of Kob-Andersen-Type Binary Lennard-Jones Mixtures

NASA Astrophysics Data System (ADS)

Pedersen, Ulf R.; Schrøder, Thomas B.; Dyre, Jeppe C.

2018-04-01

The binary Kob-Andersen (KA) Lennard-Jones mixture is the standard model for computational studies of viscous liquids and the glass transition. For very long simulations, the viscous KA system crystallizes, however, by phase separating into a pure A particle phase forming a fcc crystal. We present the thermodynamic phase diagram for KA-type mixtures consisting of up to 50% small (B ) particles showing, in particular, that the melting temperature of the standard KA system at liquid density 1.2 is 1.028(3) in A particle Lennard-Jones units. At large B particle concentrations, the system crystallizes into the CsCl crystal structure. The eutectic corresponding to the fcc and CsCl structures is cutoff in a narrow interval of B particle concentrations around 26% at which the bipyramidal orthorhombic PuBr3 structure is the thermodynamically stable phase. The melting temperature's variation with B particle concentration at two constant pressures, as well as at the constant density 1.2, is estimated from simulations at pressure 10.19 using isomorph theory. Our data demonstrate approximate identity between the melting temperature and the onset temperature below which viscous dynamics appears. Finally, the nature of the solid-liquid interface is briefly discussed.

Correlated Fluctuations in Strongly Coupled Binary Networks Beyond Equilibrium

NASA Astrophysics Data System (ADS)

Dahmen, David; Bos, Hannah; Helias, Moritz

2016-07-01

Randomly coupled Ising spins constitute the classical model of collective phenomena in disordered systems, with applications covering glassy magnetism and frustration, combinatorial optimization, protein folding, stock market dynamics, and social dynamics. The phase diagram of these systems is obtained in the thermodynamic limit by averaging over the quenched randomness of the couplings. However, many applications require the statistics of activity for a single realization of the possibly asymmetric couplings in finite-sized networks. Examples include reconstruction of couplings from the observed dynamics, representation of probability distributions for sampling-based inference, and learning in the central nervous system based on the dynamic and correlation-dependent modification of synaptic connections. The systematic cumulant expansion for kinetic binary (Ising) threshold units with strong, random, and asymmetric couplings presented here goes beyond mean-field theory and is applicable outside thermodynamic equilibrium; a system of approximate nonlinear equations predicts average activities and pairwise covariances in quantitative agreement with full simulations down to hundreds of units. The linearized theory yields an expansion of the correlation and response functions in collective eigenmodes, leads to an efficient algorithm solving the inverse problem, and shows that correlations are invariant under scaling of the interaction strengths.

The trigeneration cycle as a way to create multipurpose stationary power plants based on conversion of aeroderivative turbofan engines

NASA Astrophysics Data System (ADS)

Varaksin, A. Yu.; Arbekov, A. N.; Inozemtsev, A. A.

2014-10-01

A schematic cycle is considered, and thermodynamic analysis is performed to substantiate the possibility of creating multipurpose industrial power plants, operating on a trigeneration cycle, based on production-type turbofan engines.

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.

Thermodynamic design of hydrogen liquefaction systems with helium or neon Brayton refrigerator

NASA Astrophysics Data System (ADS)

Chang, Ho-Myung; Ryu, Ki Nam; Baik, Jong Hoon

2018-04-01

A thermodynamic study is carried out for the design of hydrogen liquefaction systems with helium (He) or neon (Ne) Brayton refrigerator. This effort is motivated by our immediate goal to develop a small-capacity (100 L/h) liquefier for domestic use in Korea. Eight different cycles are proposed and their thermodynamic performance is investigated in comparison with the existing liquefaction systems. The proposed cycles include the standard and modified versions of He Brayton refrigerators whose lowest temperature is below 20 K. The Brayton refrigerator is in direct thermal contact with the hydrogen flow at atmospheric pressure from ambient-temperature gas to cryogenic liquid. The Linde-Hampson system pre-cooled by a Ne Brayton refrigerator is also considered. Full cycle analysis is performed with the real properties of fluids to estimate the figure of merit (FOM) under an optimized operation condition. It is concluded that He Brayton refrigerators are feasible for this small-scale liquefaction, because a reasonably high efficiency can be achieved with simple and safe (low-pressure) operation. The complete cycles with He Brayton refrigerator are presented for the development of a prototype, including the ortho-to-para conversion.

Stirling Engine Gets Revisited

ERIC Educational Resources Information Center

Thompson, Frank

2010-01-01

One of the basic truths regarding energy conversion is that no thermodynamic cycle can be devised that is more efficient than a Carnot cycle operating between the same temperature limits. The efficiency of the Stirling cycle (patented by Rev. Robert Stirling in 1816) can approach that of the Carnot cycle and yet has not had the commercial success…

Development of a thermodynamic model for a cold cycle 3He-4He dilution refrigerator

NASA Astrophysics Data System (ADS)

Mueller, B. W.; Miller, F. K.

2016-10-01

A thermodynamic model of a 3He-4He cold cycle dilution refrigerator with no actively-driven mechanical components is developed and investigated. The refrigerator employs a reversible superfluid magnetic pump, passive check valves, a phase separation chamber, and a series of recuperative heat exchangers to continuously circulate 3He-4He and maintain a 3He concentration gradient across the mixing chamber. The model predicts cooling power and mixing chamber temperature for a range of design and operating parameters, allowing an evaluation of feasibility for potential 3He-4He cold cycle dilution refrigerator prototype designs. Model simulations for a prototype refrigerator design are presented.

Detecting Global Hydrological Cycle Intensification in Sea Surface Salinity

NASA Astrophysics Data System (ADS)

Poague, J.; Stine, A.

2016-12-01

Global warming is expected to intensify the global hydrological cycle, but significant regional differences exist in the predicted response. The proposed zonal mean thermodynamic response is enhanced horizontal moisture transport associated with increased saturation vapor pressure, which in turn drives additional net precipitation in the tropics and at high latitudes and additional net evaporation in the subtropics. Sea surface salinity (SSS) anomalies are forced from above by changes in evaporation minus precipitation (E-P) and thus will respond to changes in the global hydrological cycle, opening the possibility of using historical SSS anomalies to diagnose the response of the hydrological cycle to warming. We estimate zonal mean SSS trends in the Atlantic and Pacific ocean basins from 1955-2015 to test whether historical changes in the global hydrological cycle are consistent with a primarily thermodynamic response. Motivated by this observation, we calculate the sensitivity of basin zonal-mean SSS anomalies to sea surface temperature (SST) forcing as a function of timescale to diagnose and estimate the signal-to-noise ratio of the purely thermodynamic signal as a function of timescale. High-frequency variability in SSS anomalies is likely to be influenced by variability in atmospheric circulation, complicating the attribution of the link between basin zonal-mean SSS anomalies and global SST anomalies. We therefore estimate the basin zonal mean SSS anomaly response to the major modes of large-scale dynamic variability. We find a strong correlation between detrended zonal-mean SSS anomalies and the Pacific-North American index (R=0.71,P<0.01) in the Pacific Ocean. We interpret the relationship between zonal mean SSS anomalies and temperature in terms of the relative contribution of thermodynamic and dynamic processes.

The Carnot cycle and the teaching of thermodynamics: a historical approach

NASA Astrophysics Data System (ADS)

Laranjeiras, Cássio C.; Portela, Sebastião I. C.

2016-09-01

The Carnot cycle is a topic that is traditionally present in introductory physics courses dedicated to the teaching of thermodynamics, playing an essential role in introducing the concept of Entropy and the consequent formulation of the second Law. Its effective understanding and contribution to the development of thermodynamics is often hindered, however. Among other things, this is the result of a pragmatic approach, which usually limits itself to presenting the isotherms and adiabatic curves in a P-V diagram and is totally disconnected from the historical fundamentals of Heat Theory. The purpose of this paper is to reveal the potential of an approach to the subject that recovers the historical and social dimensions of scientific knowledge, and to promote reflections about the nature of science (NOS).

Multiplicity At Early Stages Of Star Formation, Small Clusters. Observations Overview

NASA Astrophysics Data System (ADS)

Saito, Masao

2017-07-01

The SOLA (Soul of Lupus with ALMA) project is conducting comprehensive studies of the Lupus Molecular Clouds and their star formation processes covering 10-10^4 AU scale. Our goal is to exploit ALMA and other facilities over a wide wavelength range to establish a prototypical low-mass star forming scenario based on the Lupus region. In the presentation, we will focus on angular momentum in dense cores in a filament, molecular outflows from young stars, and Class 0/I binary survey in Lupus as well as overview of our projects. Our binary survey was conducted in ALMA cycle 2 and achieved at 0.2-0.3 arcsec resolution discovering new binary systems in Lupus. At the same time, we obtained EX Lup, EXor type burst source, data in ALMA Cycle 3.

Multiplicity at Early Stages of Star Formation, Small Clusters. Observations Overview

NASA Astrophysics Data System (ADS)

Saito, Masao

2017-06-01

The SOLA (Soul of Lupus with ALMA) project is conducting comprehensive studies of the Lupus Molecular Clouds and their star formation processes covering 10-10^4 AU scale. Our goal is to exploit ALMA and other facilities over a wide wavelength range to establish a prototypical low-mass star forming scenario based on the Lupus region. In the presentation, we will focus on angular momentum in dense cores in a filament, molecular outflows from young stars, and Class 0/I binary survey in Lupus as well as overview of our projects. Our binary survey was conducted in ALMA cycle 2 and achieved at 0.2-0.3 arcsec resolution discovering new binary systems in Lupus. At the same time, we obtained EX Lup, EXor type burst source, data in ALMA Cycle 3.

Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems

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

Martin, Leigh R.

This document was prepared to meet FCR&D level 3 milestone M3FT-14IN0304022, “Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems.” This work was carried out under the auspices of the Thermodynamics and Kinetics FCR&D work package. This document reports preliminary work in support of determining the thermodynamic parameters for the ALSEP process. The ALSEP process is a mixed extractant system comprised of a cation exchanger 2-ethylhexyl-phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and a neutral solvating extractant N,N,N’,N’-tetraoctyldiglycolamide (TODGA). The extractant combination produces complex organic phase chemistry that is challenging for traditional measurement techniques. To neutralize the complexity, temperature dependent solvent extractionmore » experiments were conducted with neat TODGA and scaled down concentrations of the ALSEP formulation to determine the enthalpies of extraction for the two conditions. A full set of thermodynamic data for Eu, Am, and Cm extraction by TODGA from 3.0 M HNO3 is reported. These data are compared to previous extraction results from a 1.0 M HNO3 aqueous medium, and a short discussion of the mixed HEH[EHP]/TODGA system results is offered.« less

Liquid-Vapor Equilibrium of Multicomponent Cryogenic Systems

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Calado, Jorge C. G.; Zollweg, John A.

1990-01-01

Liquid-vapor and solid-vapor equilibria at low to moderate pressures and low temperatures are important in many solar system environments, including the surface and clouds of Titan, the clouds of Uranus and Neptune, and the surfaces of Mars and Triton. The familiar cases of ideal behavior are limiting cases of a general thermodynamic representation for the vapor pressure of each component in a homogeneous multicomponent system. The fundamental connections of laboratory measurements to thermodynamic models are through the Gibbs-Duhem relation and the Gibbs-Helmholtz relation. Using laboratory measurements of the total pressure, temperature, and compositions of the liquid and vapor phases at equilibrium, the values of these parameters can be determined. The resulting model for vapor-liquid equilibrium can then conveniently and accurately be used to calculate pressures, compositions, condensation altitudes, and their dependencies on changing climatic conditions. A specific system being investigated is CH4-C2H6-N2, at conditions relevant to Titan's surface and atmosphere. Discussed are: the modeling of existing data on CH4-N2, with applications to the composition of Titan's condensate clouds; some new measurements on the CH4-C2H6 binary, using a high-precision static/volumetric system, and on the C2H6-N2 binary, using the volumetric system and a sensitive cryogenic flow calorimeter; and describe a new cryogenic phase-equilibrium vessel with which we are beginning a detailed, systematic study of the three constituent binaries and the ternary CH4-C2H6-N2 system at temperatures ranging from 80 to 105 K and pressures from 0.1 to 7 bar.

Thermodynamic scaling of α-relaxation time and viscosity stems from the Johari-Goldstein β-relaxation or the primitive relaxation of the coupling model.

PubMed

Ngai, K L; Habasaki, J; Prevosto, D; Capaccioli, S; Paluch, Marian

2012-07-21

By now it is well established that the structural α-relaxation time, τ(α), of non-associated small molecular and polymeric glass-formers obey thermodynamic scaling. In other words, τ(α) is a function Φ of the product variable, ρ(γ)/T, where ρ is the density and T the temperature. The constant γ as well as the function, τ(α) = Φ(ρ(γ)/T), is material dependent. Actually this dependence of τ(α) on ρ(γ)/T originates from the dependence on the same product variable of the Johari-Goldstein β-relaxation time, τ(β), or the primitive relaxation time, τ(0), of the coupling model. To support this assertion, we give evidences from various sources itemized as follows. (1) The invariance of the relation between τ(α) and τ(β) or τ(0) to widely different combinations of pressure and temperature. (2) Experimental dielectric and viscosity data of glass-forming van der Waals liquids and polymer. (3) Molecular dynamics simulations of binary Lennard-Jones (LJ) models, the Lewis-Wahnström model of ortho-terphenyl, 1,4 polybutadiene, a room temperature ionic liquid, 1-ethyl-3-methylimidazolium nitrate, and a molten salt 2Ca(NO(3))(2)·3KNO(3) (CKN). (4) Both diffusivity and structural relaxation time, as well as the breakdown of Stokes-Einstein relation in CKN obey thermodynamic scaling by ρ(γ)/T with the same γ. (5) In polymers, the chain normal mode relaxation time, τ(N), is another function of ρ(γ)/T with the same γ as segmental relaxation time τ(α). (6) While the data of τ(α) from simulations for the full LJ binary mixture obey very well the thermodynamic scaling, it is strongly violated when the LJ interaction potential is truncated beyond typical inter-particle distance, although in both cases the repulsive pair potentials coincide for some distances.

Complex Autocatalysis in Simple Chemistries.

PubMed

Virgo, Nathaniel; Ikegami, Takashi; McGregor, Simon

2016-01-01

Life on Earth must originally have arisen from abiotic chemistry. Since the details of this chemistry are unknown, we wish to understand, in general, which types of chemistry can lead to complex, lifelike behavior. Here we show that even very simple chemistries in the thermodynamically reversible regime can self-organize to form complex autocatalytic cycles, with the catalytic effects emerging from the network structure. We demonstrate this with a very simple but thermodynamically reasonable artificial chemistry model. By suppressing the direct reaction from reactants to products, we obtain the simplest kind of autocatalytic cycle, resulting in exponential growth. When these simple first-order cycles are prevented from forming, the system achieves superexponential growth through more complex, higher-order autocatalytic cycles. This leads to nonlinear phenomena such as oscillations and bistability, the latter of which is of particular interest regarding the origins of life.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

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.

Model for the Prediction of the Hydriding Thermodynamics of Pd-Rh-Co Ternary Alloys

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

Teter, D.F.; Thoma, D.J.

1999-03-01

A dilute solution model (with respect to the substitutional alloying elements) has been developed, which accurately predicts the hydride formation and decomposition thermodynamics and the storage capacities of dilute ternary Pd-Rh-Co alloys. The effect of varying the rhodium and cobalt compositions on the thermodynamics of hydride formation and decomposition and hydrogen capacity of several palladium-rhodium-cobalt ternary alloys has been investigated using pressure-composition (PC) isotherms. Alloying in the dilute regime (<10 at.%) causes the enthalpy for hydride formation to linearly decrease with increasing alloying content. Cobalt has a stronger effect on the reduction in enthalpy than rhodium for equivalent alloying amounts.more » Also, cobalt reduces the hydrogen storage capacity with increasing alloying content. The plateau thermodynamics are strongly linked to the lattice parameters of the alloys. A near-linear dependence of the enthalpy of hydride formation on the lattice parameter was observed for both the binary Pd-Rh and Pd-Co alloys, as well as for the ternary Pd-Rh-Co alloys. The Pd-5Rh-3Co (at. %) alloy was found to have similar plateau thermodynamics as a Pd-10Rh alloy, however, this ternary alloy had a diminished hydrogen storage capacity relative to Pd-10Rh.« less

A generalized model for multi-marker analysis of cell cycle progression in synchrony experiments.

PubMed

Mayhew, Michael B; Robinson, Joshua W; Jung, Boyoun; Haase, Steven B; Hartemink, Alexander J

2011-07-01

To advance understanding of eukaryotic cell division, it is important to observe the process precisely. To this end, researchers monitor changes in dividing cells as they traverse the cell cycle, with the presence or absence of morphological or genetic markers indicating a cell's position in a particular interval of the cell cycle. A wide variety of marker data is available, including information-rich cellular imaging data. However, few formal statistical methods have been developed to use these valuable data sources in estimating how a population of cells progresses through the cell cycle. Furthermore, existing methods are designed to handle only a single binary marker of cell cycle progression at a time. Consequently, they cannot facilitate comparison of experiments involving different sets of markers. Here, we develop a new sampling model to accommodate an arbitrary number of different binary markers that characterize the progression of a population of dividing cells along a branching process. We engineer a strain of Saccharomyces cerevisiae with fluorescently labeled markers of cell cycle progression, and apply our new model to two image datasets we collected from the strain, as well as an independent dataset of different markers. We use our model to estimate the duration of post-cytokinetic attachment between a S.cerevisiae mother and daughter cell. The Java implementation is fast and extensible, and includes a graphical user interface. Our model provides a powerful and flexible cell cycle analysis tool, suitable to any type or combination of binary markers. The software is available from: http://www.cs.duke.edu/~amink/software/cloccs/. michael.mayhew@duke.edu; amink@cs.duke.edu.

Off-diagonal long-range order, cycle probabilities, and condensate fraction in the ideal Bose gas.

PubMed

Chevallier, Maguelonne; Krauth, Werner

2007-11-01

We discuss the relationship between the cycle probabilities in the path-integral representation of the ideal Bose gas, off-diagonal long-range order, and Bose-Einstein condensation. Starting from the Landsberg recursion relation for the canonic partition function, we use elementary considerations to show that in a box of size L3 the sum of the cycle probabilities of length k>L2 equals the off-diagonal long-range order parameter in the thermodynamic limit. For arbitrary systems of ideal bosons, the integer derivative of the cycle probabilities is related to the probability of condensing k bosons. We use this relation to derive the precise form of the pik in the thermodynamic limit. We also determine the function pik for arbitrary systems. Furthermore, we use the cycle probabilities to compute the probability distribution of the maximum-length cycles both at T=0, where the ideal Bose gas reduces to the study of random permutations, and at finite temperature. We close with comments on the cycle probabilities in interacting Bose gases.

First-principles prediction of stabilities and instabilities of compounds and alloys in the ternary B-As-P system

NASA Astrophysics Data System (ADS)

Ektarawong, A.; Simak, S. I.; Alling, B.

2017-07-01

We examine the thermodynamic stability of compounds and alloys in the ternary B-As-P system theoretically using first-principles calculations. We demonstrate that the icosahedral B12As2 is the only stable compound in the binary B-As system, while the zinc-blende BAs is thermodynamically unstable with respect to B12As2 and the pure arsenic phase at 0 K, and increasingly so at higher temperature, suggesting that BAs may merely exist as a metastable phase. On the contrary, in the binary B-P system, both zinc-blende BP and icosahedral B12P2 are predicted to be stable. As for the binary As-P system, As1 -xPx disordered alloys are predicted at elevated temperature—for example, a disordered solid solution of up to ˜75 at.% As in black phosphorus as well as a small solubility of ˜1 at.% P in gray arsenic at T =750 K, together with the presence of miscibility gaps. The calculated large solubility of As in black phosphorus explains the experimental syntheses of black-phosphorus-type As1 -xPx alloys with tunable compositions, recently reported in the literature. We investigate the phase stabilities in the ternary B-As-P system and demonstrate a high tendency for a formation of alloys in the icosahedral B12(As1 -xPx )2 structure by intermixing of As and P atoms at the diatomic chain sites. The phase diagram displays noticeable mutual solubility of the icosahedral subpnictides in each other even at room temperature as well as a closure of a pseudobinary miscibility gap around 900 K. As for pseudobinary BAs1 -xPx alloys, only a tiny amount of BAs is predicted to be able to dissolve in BP to form the BAs1 -xPx disordered alloys at elevated temperature. For example, less than 5% of BAs can dissolve in BP at T =1000 K. The small solubility limit of BAs in BP is attributed to the thermodynamic instability of BAs with respect to B12As2 and As.

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…

Teaching Thermodynamics with Physlets[R] in Introductory Physics

ERIC Educational Resources Information Center

Cox, Anne J.; Belloni, Mario; Dancy, Melissa; Christian, Wolfgang

2003-01-01

This paper describes the use of interactive, Physlet[R]-based curricular material designed to help students learn concepts of thermodynamics with a particular focus on the use of kinetic theory models. These exercises help students visualize ideal gas particle dynamics and engine cycles, make concrete connections between mechanics and…

Nonequilibrium steady state of biochemical cycle kinetics under non-isothermal conditions

NASA Astrophysics Data System (ADS)

Jin, Xiao; Ge, Hao

2018-04-01

The nonequilibrium steady state of isothermal biochemical cycle kinetics has been extensively studied, but that under non-isothermal conditions has been much less extensively investigated. When the heat exchange between subsystems is slow, the isothermal assumption of the whole system breaks down, as is true for many types of living organisms. Here, starting with a four-state model of molecular transporter across the cell membrane, we generalize the nonequilibrium steady-state theory of isothermal biochemical cycle kinetics to the circumstances with non-uniform temperatures of subsystems in terms of general master equation models. We obtain a new thermodynamic relationship between the chemical reaction rates and thermodynamic potentials in non-isothermal circumstances, based on the overdamped dynamics along the continuous reaction coordinate. We show that the entropy production can vary up to 3% in real cells, even when the temperature difference across the cell membrane is only approximately 1 K. We then decompose the total thermodynamic driving force into its thermal and chemical components and predict that the net flux of molecules transported by the molecular transporter can potentially go against the temperature gradient in the absence of a chemical driving force. Furthermore, we demonstrate that the simple application of the isothermal transition-state rate formula for each chemical reaction in terms of only the reactant’ temperature is not thermodynamically consistent. Therefore, we mathematically derive several revised reaction rate formulas that are not only consistent with the new thermodynamic relationship but also approximate the exact reaction rate better than Kramers’ rate formula under isothermal conditions.

Performance Analysis of Joule-Thomson Cooler Supplied with Gas Mixtures

NASA Astrophysics Data System (ADS)

Piotrowska, A.; Chorowski, M.; Dorosz, P.

2017-02-01

Joule-Thomson (J-T) cryo-coolers working in closed cycles and supplied with gas mixtures are the subject of intensive research in different laboratories. The replacement of pure nitrogen by nitrogen-hydrocarbon mixtures allows to improve both thermodynamic parameters and economy of the refrigerators. It is possible to avoid high pressures in the heat exchanger and to use standard refrigeration compressor instead of gas bottles or high-pressure oil free compressor. Closed cycle and mixture filled Joule-Thomson cryogenic refrigerator providing 10-20 W of cooling power at temperature range 90-100 K has been designed and manufactured. Thermodynamic analysis including the optimization of the cryo-cooler mixture has been performed with ASPEN HYSYS software. The paper describes the design of the cryo-cooler and provides thermodynamic analysis of the system. The test results are presented and discussed.

Thermodynamic assessment of Ag–Cu–In

DOE PAGES

Muzzillo, Christopher P.; Anderson, Tim

2018-01-16

The Ag-Cu-In thermodynamic material system is of interest for brazing alloys and chalcopyrite thin-film photovoltaics. To advance these applications, Ag-Cu-In was assessed and a Calphad model was developed. Binary Ag-Cu and Cu-In parameters were taken from previous assessments, while Ag-In was re-assessed. Structure-based models were employed for ..beta..-bcc(A2)-Ag 3In, ..gamma..-Ag 9In 4, and AgIn 2 to obtain good fit to enthalpy, phase boundary, and invariant reaction data for Ag-In. Ternary Ag-Cu-In parameters were optimized to achieve excellent fit to activity, enthalpy, and extensive phase equilibrium data. Relative to the previous Ag-Cu-In assessment, fit was improved while fewer parameters were used.

Thermodynamic assessment of Ag–Cu–In

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

Muzzillo, Christopher P.; Anderson, Tim

The Ag-Cu-In thermodynamic material system is of interest for brazing alloys and chalcopyrite thin-film photovoltaics. To advance these applications, Ag-Cu-In was assessed and a Calphad model was developed. Binary Ag-Cu and Cu-In parameters were taken from previous assessments, while Ag-In was re-assessed. Structure-based models were employed for ..beta..-bcc(A2)-Ag 3In, ..gamma..-Ag 9In 4, and AgIn 2 to obtain good fit to enthalpy, phase boundary, and invariant reaction data for Ag-In. Ternary Ag-Cu-In parameters were optimized to achieve excellent fit to activity, enthalpy, and extensive phase equilibrium data. Relative to the previous Ag-Cu-In assessment, fit was improved while fewer parameters were used.

Predicting Flory-Huggins χ from Simulations

NASA Astrophysics Data System (ADS)

Zhang, Wenlin; Gomez, Enrique D.; Milner, Scott T.

2017-07-01

We introduce a method, based on a novel thermodynamic integration scheme, to extract the Flory-Huggins χ parameter as small as 10-3k T for polymer blends from molecular dynamics (MD) simulations. We obtain χ for the archetypical coarse-grained model of nonpolar polymer blends: flexible bead-spring chains with different Lennard-Jones interactions between A and B monomers. Using these χ values and a lattice version of self-consistent field theory (SCFT), we predict the shape of planar interfaces for phase-separated binary blends. Our SCFT results agree with MD simulations, validating both the predicted χ values and our thermodynamic integration method. Combined with atomistic simulations, our method can be applied to predict χ for new polymers from their chemical structures.

Influence of compositional complexity on interdiffusion in Ni-containing concentrated solid-solution alloys

DOE PAGES

Jin, Ke; Zhang, Chuan; Zhang, Fan; ...

2018-03-07

To investigate the compositional effects on thermal-diffusion kinetics in concentrated solid-solution alloys, interdiffusion in seven diffusion couples with alloys from binary to quinary is systematically studied. The alloys with higher compositional complexity exhibit in general lower diffusion coefficients against homologous temperature, however, an exception is found that diffusion in NiCoFeCrPd is faster than in NiCoFeCr and NiCoCr. While the derived diffusion parameters suggest that diffusion in medium and high entropy alloys is overall more retarded than in pure metals and binary alloys, they strongly depend on specific constituents. The comparative features are captured by computational thermodynamics approaches using a self-consistentmore » database.« less

Nuclear Aircraft Feasibility Study. Volume 1

DTIC Science & Technology

1975-03-01

Cycle 6-36 6.2.2 Helium Mass Flow 6-42 6.2.3 Fan Pressure Ratio 6-42 6.2.4 Regenerative Cycle Application 6-43 6.2.5 Brayton Cycle...6-8 Engine Systems Summary 6-9 T-S Diagram of Ideal Brayton Cycle 6-13 T-S Diagram of Brayton Cycle for Turbofan Engine 6-15 Comparison of... Brayton Closed Cycle Thermodynamic Analysis 6-50 6.2.8-1 Indirect Cycle Gas Circulation System 6-53 6.2.8-2 Gas Turbine Generator — Pump Cycle

The Effect of Impurities on the Processing of Aluminum Alloys

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

Zi-Kui Liu; Shengjun Zhang; Qingyou Han

2007-04-23

For this Aluminum Industry of the Future (IOF) project, the effect of impurities on the processing of aluminum alloys was systematically investigated. The work was carried out as a collaborative effort between the Pennsylvania State University and Oak Ridge National Laboratory. Industrial support was provided by ALCOA and ThermoCalc, Inc. The achievements described below were made. A method that combines first-principles calculation and calculation of phase diagrams (CALPHAD) was used to develop the multicomponent database Al-Ca-K-Li-Mg-Na. This method was extensively used in this project for the development of a thermodynamic database. The first-principles approach provided some thermodynamic property data thatmore » are not available in the open literature. These calculated results were used in the thermodynamic modeling as experimental data. Some of the thermodynamic property data are difficult, if not impossible, to measure. The method developed and used in this project allows the estimation of these data for thermodynamic database development. The multicomponent database Al-Ca-K-Li-Mg-Na was developed. Elements such as Ca, Li, Na, and K are impurities that strongly affect the formability and corrosion behavior of aluminum alloys. However, these impurity elements are not included in the commercial aluminum alloy database. The process of thermodynamic modeling began from Al-Na, Ca-Li, Li-Na, K-Na, and Li-K sub-binary systems. Then ternary and higher systems were extrapolated because of the lack of experimental information. Databases for five binary alloy systems and two ternary systems were developed. Along with other existing binary and ternary databases, the full database of the multicomponent Al-Ca-K-Li-Mg-Na system was completed in this project. The methodology in integrating with commercial or other aluminum alloy databases can be developed. The mechanism of sodium-induced high-temperature embrittlement (HTE) of Al-Mg is now understood. Using the thermodynamic database developed in this project, thermodynamic simulations were carried out to investigate the effect of sodium on the HTE of Al-Mg alloys. The simulation results indicated that the liquid miscibility gap resulting from the dissolved sodium in the molten material plays an important role in HTE. A liquid phase forms from the solid face-centered cubic (fcc) phase (most likely at grain boundaries) during cooling, resulting in the occurrence of HTE. Comparison of the thermodynamic simulation results with experimental measurements on the high-temperature ductility of an Al-5Mg-Na alloy shows that HTE occurs in the temperature range at which the liquid phase exists. Based on this fundamental understanding of the HTE mechanism during processing of aluminum alloy, an HTE sensitive zone and a hot-rolling safe zone of the Al-Mg-Na alloys are defined as functions of processing temperature and alloy composition. The tendency of HTE was evaluated based on thermodynamic simulations of the fraction of the intergranular sodium-rich liquid phase. Methods of avoiding HTE during rolling/extrusion of Al-Mg-based alloys were suggested. Energy and environmental benefits from the results of this project could occur through a number of avenues: (1) energy benefits accruing from reduced rejection rates of the aluminum sheet and bar, (2) reduced dross formation during the remelting of the aluminum rejects, and (3) reduced CO2 emission related to the energy savings. The sheet and extruded bar quantities produced in the United States during 2000 were 10,822 and 4,546 million pounds, respectively. It is assumed that 50% of the sheet and 10% of the bar will be affected by implementing the results of this project. With the current process, the rejection rate of sheet and bar is estimated at 5%. Assuming that at least half of the 5% rejection of sheet and bar will be eliminated by using the results of this project and that 4% of the aluminum will be lost through dross (Al2O3) during remelting of the rejects, the full-scale industrial implementation of the project results would lead to energy savings in excess of 6.2 trillion Btu/year and cost savings of $42.7 million by 2020.« less

Coupling a Supercritical Carbon Dioxide Brayton Cycle to a Helium-Cooled Reactor.

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

Middleton, Bobby; Pasch, James Jay; Kruizenga, Alan Michael

2016-01-01

This report outlines the thermodynamics of a supercritical carbon dioxide (sCO 2) recompression closed Brayton cycle (RCBC) coupled to a Helium-cooled nuclear reactor. The baseline reactor design for the study is the AREVA High Temperature Gas-Cooled Reactor (HTGR). Using the AREVA HTGR nominal operating parameters, an initial thermodynamic study was performed using Sandia's deterministic RCBC analysis program. Utilizing the output of the RCBC thermodynamic analysis, preliminary values of reactor power and of Helium flow rate through the reactor were calculated in Sandia's HelCO 2 code. Some research regarding materials requirements was then conducted to determine aspects of corrosion related tomore » both Helium and to sCO 2 , as well as some mechanical considerations for pressures and temperatures that will be seen by the piping and other components. This analysis resulted in a list of materials-related research items that need to be conducted in the future. A short assessment of dry heat rejection advantages of sCO 2> Brayton cycles was also included. This assessment lists some items that should be investigated in the future to better understand how sCO 2 Brayton cycles and nuclear can maximally contribute to optimizing the water efficiency of carbon free power generation« less

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.

Interfacial tension and vapor-liquid equilibria in the critical region of mixtures

NASA Technical Reports Server (NTRS)

Moldover, Michael R.; Rainwater, James C.

1988-01-01

In the critical region, the concept of two-scale-factor universality can be used to accurately predict the surface tension between near-critical vapor and liquid phases from the singularity in the thermodynamic properties of the bulk fluid. In the present work, this idea is generalized to binary mixtures and is illustrated using the data of Hsu et al. (1985) for CO2 + n-butane. The pressure-temperature-composition-density data for coexisting, near-critical phases of the mixtures are fitted with a thermodynamic potential comprised of a sum of a singular term and nonsingular terms. The nonuniversal amplitudes characterizing the singular term for the mixtures are obtained from the amplitudes for the pure components by interpolation in a space of thermodynamic 'field' variables. The interfacial tensions predicted for the mixtures from the singular term are within 10 percent of the data on three isotherms in the pressure range (Pc - P)/Pc of less than 0.5. This difference is comparable to the combined experimental and model errors.

A thermodynamic database for tellurium-bearing systems relevant to nuclear technology

NASA Astrophysics Data System (ADS)

Chattopadhyay, G.; Juneja, J. M.

1993-06-01

A thermodynamic database for tellurium-bearing condensed phases and gaseous species which are relevant to nuclear technology is presented. It contains phase diagrams of the binary systems, PdTe, RhTe, PuTe, SmTe, CsTe, ZrTe, of the ternary systems, ZrTeO, MoTeO, AgTeO, UTeO, CsTeO, BaTeO as well as thermodynamic data for crystalline and liquid Te, for the solid phases Cs 2Te, Ag 2Te, SnTe, BaTe, CeTe, SmTe, RuTe 2, ZrTe 2, Fe 0.53Te 0.47, Mo 0.43Te 0.57, Cr 0.43Te 0.57, Ni 0.5Te 0.4, Cs 2TeO 3 and for the gaseous species, Te, Te 2, TeO, TeO 2, TeO(OH) 2, H 2Te, TeI, TeI 2, TeI 4, TeOI 2, SnTe, Sn 2Te 2, SnTe 2.

Thermodynamics of quasideterministic digital computers

NASA Astrophysics Data System (ADS)

Chu, Dominique

2018-02-01

A central result of stochastic thermodynamics is that irreversible state transitions of Markovian systems entail a cost in terms of an infinite entropy production. A corollary of this is that strictly deterministic computation is not possible. Using a thermodynamically consistent model, we show that quasideterministic computation can be achieved at finite, and indeed modest cost with accuracies that are indistinguishable from deterministic behavior for all practical purposes. Concretely, we consider the entropy production of stochastic (Markovian) systems that behave like and and a not gates. Combinations of these gates can implement any logical function. We require that these gates return the correct result with a probability that is very close to 1, and additionally, that they do so within finite time. The central component of the model is a machine that can read and write binary tapes. We find that the error probability of the computation of these gates falls with the power of the system size, whereas the cost only increases linearly with the system size.

Many-Body Effects on the Thermodynamics of Fluids, Mixtures, and Nanoconfined Fluids.

PubMed

Desgranges, Caroline; Delhommelle, Jerome

2015-11-10

Using expanded Wang-Landau simulations, we show that taking into account the many-body interactions results in sharp changes in the grand-canonical partition functions of single-component systems, binary mixtures, and nanoconfined fluids. The many-body contribution, modeled with a 3-body Axilrod-Teller-Muto term, results in shifts toward higher chemical potentials of the phase transitions from low-density phases to high-density phases and accounts for deviations of more than, e.g., 20% of the value of the partition function for a single-component liquid. Using the statistical mechanics formalism, we analyze how this contribution has a strong impact on some properties (e.g., pressure, coexisting densities, and enthalpy) and a moderate impact on others (e.g., Gibbs or Helmholtz free energies). We also characterize the effect of the 3-body terms on adsorption isotherms and adsorption thermodynamic properties, thereby providing a full picture of the effect of the 3-body contribution on the thermodynamics of nanoconfined fluids.

First-principles study on the thermal expansion of Ni-X binary alloys based on the quasi-harmonic Debye model

NASA Astrophysics Data System (ADS)

Shin, Yongjin; Jung, Woo-Sang; Lee, Young-Su

2016-11-01

In this study, we use the quasi-harmonic Debye model to predict the coefficient of thermal expansion of Ni- X binary alloys. The method bridges between the macroscopic elastic behavior and thermodynamic properties of materials without an expensive calculation of the volume dependence of the phonon density of states. Furthermore, the Grüneisen parameter is derived from the volume dependence of the Debye temperature, which is calculated from the first-principles elastic stiffness constants. The experimental coefficient of thermal expansion (CTE) of pure nickel is well reproduced, especially in the low temperature region. Among the few alloying elements tested, Al is predicted to slightly decrease the CTE whereas Mo and W are more effective in reducing the CTE. For the cases of Ni-X binary alloy systems, where the variation in the CTE is relatively small, the method used here appears to perform better than certain other formulations that rely entirely on the energy vs. volume relationship.

High-Dimensional Mutant and Modular Thermodynamic Cycles, Molecular Switching, and Free Energy Transduction

PubMed Central

Carter, Charles W.

2017-01-01

Understanding how distinct parts of proteins produce coordinated behavior has driven and continues to drive advances in protein science and enzymology. However, despite consensus about the conceptual basis for allostery, the idiosyncratic nature of allosteric mechanisms resists general approaches. Computational methods can identify conformational transition states from structural changes, revealing common switching mechanisms that impose multistate behavior. Thermodynamic cycles use factorial perturbations to measure coupling energies between side chains in molecular switches that mediate shear during domain motion. Such cycles have now been complemented by modular cycles that measure energetic coupling between separable domains. For one model system, energetic coupling between domains has been shown to be quantitatively equivalent to that between dynamic side chains. Linkages between domain motion, switching residues, and catalysis make nucleoside triphosphate hydrolysis conditional on domain movement, confirming an essential yet neglected aspect of free energy transduction and suggesting the potential generality of these studies. PMID:28375734

Theory and computer simulation of hard-core Yukawa mixtures: thermodynamical, structural and phase coexistence properties.

PubMed

Mkanya, Anele; Pellicane, Giuseppe; Pini, Davide; Caccamo, Carlo

2017-09-13

We report extensive calculations, based on the modified hypernetted chain (MHNC) theory, on the hierarchical reference theory (HRT), and on Monte Carlo simulations, of thermodynamical, structural and phase coexistence properties of symmetric binary hard-core Yukawa mixtures (HCYM) with attractive interactions at equal species concentration. The obtained results are throughout compared with those available in the literature for the same systems. It turns out that the MHNC predictions for thermodynamic and structural quantities are quite accurate in comparison with the MC data. The HRT is equally accurate for thermodynamics, and slightly less accurate for structure. Liquid-vapor (LV) and liquid-liquid (LL) consolute coexistence conditions as emerging from simulations, are also highly satisfactorily reproduced by both the MHNC and HRT for relatively long ranged potentials. When the potential range reduces, the MHNC faces problems in determining the LV binodal line; however, the LL consolute line and the critical end point (CEP) temperature and density turn out to be still satisfactorily predicted within this theory. The HRT also predicts with good accuracy the CEP position. The possibility of employing liquid state theories HCYM for the purpose of reliably determining phase equilibria in multicomponent colloidal fluids of current technological interest, is discussed.

Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides

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

Sun, Wenhao; Holder, Aaron; Orvañanos, Bernardo

Compared to oxides, the nitrides are relatively unexplored, making them a promising chemical space for novel materials discovery. Of particular interest are nitrogen-rich nitrides, which often possess useful semiconducting properties for electronic and optoelectronic applications. However, such nitrogen-rich compounds are generally metastable, and the lack of a guiding theory for their synthesis has limited their exploration. Here, we review the remarkable metastability of observed nitrides, and examine the thermodynamics of how reactive nitrogen precursors can stabilize metastable nitrogen-rich compositions during materials synthesis. We map these thermodynamic strategies onto a predictive computational search, training a data-mined ionic substitution algorithm specifically formore » nitride discovery, which we combine with grand-canonical DFT-SCAN phase stability calculations to compute stabilizing nitrogen chemical potentials. We identify several new nitrogen-rich binary nitrides for experimental investigation, notably the transition metal nitrides Mn3N4, Cr3N4, V3N4, and Nb3N5, the main group nitride SbN, and the pernitrides FeN2, CrN2, and Cu2N2. By formulating rational thermodynamic routes to metastable compounds, we expand the search space for functional technological materials beyond equilibrium phases and compositions.« less

Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides

DOE PAGES

Sun, Wenhao; Holder, Aaron; Orvañanos, Bernardo; ...

2017-07-17

Compared to oxides, the nitrides are relatively unexplored, making them a promising chemical space for novel materials discovery. Of particular interest are nitrogen-rich nitrides, which often possess useful semiconducting properties for electronic and optoelectronic applications. However, such nitrogen-rich compounds are generally metastable, and the lack of a guiding theory for their synthesis has limited their exploration. Here, we review the remarkable metastability of observed nitrides, and examine the thermodynamics of how reactive nitrogen precursors can stabilize metastable nitrogen-rich compositions during materials synthesis. We map these thermodynamic strategies onto a predictive computational search, training a data-mined ionic substitution algorithm specifically formore » nitride discovery, which we combine with grand-canonical DFT-SCAN phase stability calculations to compute stabilizing nitrogen chemical potentials. We identify several new nitrogen-rich binary nitrides for experimental investigation, notably the transition metal nitrides Mn3N4, Cr3N4, V3N4, and Nb3N5, the main group nitride SbN, and the pernitrides FeN2, CrN2, and Cu2N2. By formulating rational thermodynamic routes to metastable compounds, we expand the search space for functional technological materials beyond equilibrium phases and compositions.« less

Theory and computer simulation of hard-core Yukawa mixtures: thermodynamical, structural and phase coexistence properties

NASA Astrophysics Data System (ADS)

Mkanya, Anele; Pellicane, Giuseppe; Pini, Davide; Caccamo, Carlo

2017-09-01

We report extensive calculations, based on the modified hypernetted chain (MHNC) theory, on the hierarchical reference theory (HRT), and on Monte Carlo simulations, of thermodynamical, structural and phase coexistence properties of symmetric binary hard-core Yukawa mixtures (HCYM) with attractive interactions at equal species concentration. The obtained results are throughout compared with those available in the literature for the same systems. It turns out that the MHNC predictions for thermodynamic and structural quantities are quite accurate in comparison with the MC data. The HRT is equally accurate for thermodynamics, and slightly less accurate for structure. Liquid-vapor (LV) and liquid-liquid (LL) consolute coexistence conditions as emerging from simulations, are also highly satisfactorily reproduced by both the MHNC and HRT for relatively long ranged potentials. When the potential range reduces, the MHNC faces problems in determining the LV binodal line; however, the LL consolute line and the critical end point (CEP) temperature and density turn out to be still satisfactorily predicted within this theory. The HRT also predicts with good accuracy the CEP position. The possibility of employing liquid state theories HCYM for the purpose of reliably determining phase equilibria in multicomponent colloidal fluids of current technological interest, is discussed.

On hydrodynamic phase field models for binary fluid mixtures

NASA Astrophysics Data System (ADS)

Yang, Xiaogang; Gong, Yuezheng; Li, Jun; Zhao, Jia; Wang, Qi

2018-05-01

Two classes of thermodynamically consistent hydrodynamic phase field models have been developed for binary fluid mixtures of incompressible viscous fluids of possibly different densities and viscosities. One is quasi-incompressible, while the other is incompressible. For the same binary fluid mixture of two incompressible viscous fluid components, which one is more appropriate? To answer this question, we conduct a comparative study in this paper. First, we visit their derivation, conservation and energy dissipation properties and show that the quasi-incompressible model conserves both mass and linear momentum, while the incompressible one does not. We then show that the quasi-incompressible model is sensitive to the density deviation of the fluid components, while the incompressible model is not in a linear stability analysis. Second, we conduct a numerical investigation on coarsening or coalescent dynamics of protuberances using the two models. We find that they can predict quite different transient dynamics depending on the initial conditions and the density difference although they predict essentially the same quasi-steady results in some cases. This study thus cast a doubt on the applicability of the incompressible model to describe dynamics of binary mixtures of two incompressible viscous fluids especially when the two fluid components have a large density deviation.

Qualitative and quantitative reasoning about thermodynamics

NASA Technical Reports Server (NTRS)

Skorstad, Gordon; Forbus, Ken

1989-01-01

One goal of qualitative physics is to capture the tacit knowledge of engineers and scientists. It is shown how Qualitative Process theory can be used to express concepts of engineering thermodynamics. In particular, it is shown how to integrate qualitative and quantitative knowledge to solve textbook problems involving thermodynamic cycles, such as gas turbine plants and steam power plants. These ideas were implemented in a program called SCHISM. Its analysis of a sample textbook problem is described and plans for future work are discussed.

Thermodynamic power stations at low temperatures

NASA Astrophysics Data System (ADS)

Malherbe, J.; Ployart, R.; Alleau, T.; Bandelier, P.; Lauro, F.

The development of low-temperature thermodynamic power stations using solar energy is considered, with special attention given to the choice of the thermodynamic cycle (Rankine), working fluids (frigorific halogen compounds), and heat exchangers. Thermomechanical conversion machines, such as ac motors and rotating volumetric motors are discussed. A system is recommended for the use of solar energy for irrigation and pumping in remote areas. Other applications include the production of cold of fresh water from brackish waters, and energy recovery from hot springs.

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.

The thermodynamics of pyrochemical processes for liquid metal reactor fuel cycles

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

Johnson, I.

1987-01-01

The thermodynamic basis for pyrochemical processes for the recovery and purification of fuel for the liquid metal reactor fuel cycle is described. These processes involve the transport of the uranium and plutonium from one liquid alloy to another through a molten salt. The processes discussed use liquid alloys of cadmium, zinc, and magnesium and molten chloride salts. The oxidation-reduction steps are done either chemically by the use of an auxiliary redox couple or electrochemically by the use of an external electrical supply. The same basic thermodynamics apply to both the salt transport and the electrotransport processes. Large deviations from idealmore » solution behavior of the actinides and lanthanides in the liquid alloys have a major influence on the solubilities and the performance of both the salt transport and electrotransport processes. Separation of plutonium and uranium from each other and decontamination from the more noble fission product elements can be achieved using both transport processes. The thermodynamic analysis is used to make process design computations for different process conditions.« less

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.

Electrochemical thermodynamic measurement system

DOEpatents

Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA

2009-09-29

The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

Compressor and Turbine Models of Brayton Units for Space Nuclear Power Systems

NASA Astrophysics Data System (ADS)

Gallo, Bruno M.; El-Genk, Mohamed S.; Tournier, Jean-Michel

2007-01-01

Closed Brayton Cycles with centrifugal flow, single-shaft turbo-machines are being considered, with gas cooled nuclear reactors, to provide 10's to 100's of electrical power to support future space exploration missions and Lunar and Mars outposts. Such power system analysis is typically based on the cycle thermodynamics, for given operating pressures and temperatures and assumed polytropic efficiencies of the compressor and turbine of the Brayton energy conversion units. Thus the analysis results not suitable for modeling operation transients such as startup and changes in the electric load. To simulate these transients, accurate models of the turbine and compressor in the Brayton rotating unit, which calculate the changes in the compressor and turbine efficiencies with system operation are needed. This paper presents flow models that account for the design and dimensions of the compressor impeller and diffuser, and the turbine stator and rotor blades. These models calculate the various enthalpy losses and the polytropic efficiencies along with the pressure ratios of the turbine and compressor. The predictions of these models compare well with reported performance data of actual hardware. In addition, the results of a parametric analysis to map the operations of the compressor and turbine, as functions of the rotating shaft speed and inlet Mach number of the gas working fluid, are presented and discussed. The analysis used a binary mixture of He-Xe with a molecular weight of 40 g/mole as the working fluid.

A generalized model for multi-marker analysis of cell cycle progression in synchrony experiments

PubMed Central

Mayhew, Michael B.; Robinson, Joshua W.; Jung, Boyoun; Haase, Steven B.; Hartemink, Alexander J.

2011-01-01

Motivation: To advance understanding of eukaryotic cell division, it is important to observe the process precisely. To this end, researchers monitor changes in dividing cells as they traverse the cell cycle, with the presence or absence of morphological or genetic markers indicating a cell's position in a particular interval of the cell cycle. A wide variety of marker data is available, including information-rich cellular imaging data. However, few formal statistical methods have been developed to use these valuable data sources in estimating how a population of cells progresses through the cell cycle. Furthermore, existing methods are designed to handle only a single binary marker of cell cycle progression at a time. Consequently, they cannot facilitate comparison of experiments involving different sets of markers. Results: Here, we develop a new sampling model to accommodate an arbitrary number of different binary markers that characterize the progression of a population of dividing cells along a branching process. We engineer a strain of Saccharomyces cerevisiae with fluorescently labeled markers of cell cycle progression, and apply our new model to two image datasets we collected from the strain, as well as an independent dataset of different markers. We use our model to estimate the duration of post-cytokinetic attachment between a S.cerevisiae mother and daughter cell. The Java implementation is fast and extensible, and includes a graphical user interface. Our model provides a powerful and flexible cell cycle analysis tool, suitable to any type or combination of binary markers. Availability: The software is available from: http://www.cs.duke.edu/~amink/software/cloccs/. Contact: michael.mayhew@duke.edu; amink@cs.duke.edu PMID:21685084

Carnot's cycle for small systems: Irreversibility and cost of operations

NASA Astrophysics Data System (ADS)

Sekimoto, Ken; Takagi, Fumiko; Hondou, Tsuyoshi

2000-12-01

In the thermodynamic limit, the existence of a maximal efficiency of energy conversion attainable by a Carnot cycle consisting of quasistatic isothermal and adiabatic processes precludes the existence of a perpetual machine of the second kind, whose cycles yield positive work in an isothermal environment. We employ the recently developed framework of the energetics of stochastic processes (called ``stochastic energetics'') to reanalyze the Carnot cycle in detail, taking account of fluctuations, without taking the thermodynamic limit. We find that in this nonmacroscopic situation both processes of connection to and disconnection from heat baths and adiabatic processes that cause distortion of the energy distribution are sources of inevitable irreversibility within the cycle. Also, the so-called null-recurrence property of the cumulative efficiency of energy conversion over many cycles and the irreversible property of isolated, purely mechanical processes under external ``macroscopic'' operations are discussed in relation to the impossibility of a perpetual machine, or Maxwell's demon. This analysis may serve as the basis for the design and analysis of mesoscopic energy converters in the near future.

Statistical mechanics of unsupervised feature learning in a restricted Boltzmann machine with binary synapses

NASA Astrophysics Data System (ADS)

Huang, Haiping

2017-05-01

Revealing hidden features in unlabeled data is called unsupervised feature learning, which plays an important role in pretraining a deep neural network. Here we provide a statistical mechanics analysis of the unsupervised learning in a restricted Boltzmann machine with binary synapses. A message passing equation to infer the hidden feature is derived, and furthermore, variants of this equation are analyzed. A statistical analysis by replica theory describes the thermodynamic properties of the model. Our analysis confirms an entropy crisis preceding the non-convergence of the message passing equation, suggesting a discontinuous phase transition as a key characteristic of the restricted Boltzmann machine. Continuous phase transition is also confirmed depending on the embedded feature strength in the data. The mean-field result under the replica symmetric assumption agrees with that obtained by running message passing algorithms on single instances of finite sizes. Interestingly, in an approximate Hopfield model, the entropy crisis is absent, and a continuous phase transition is observed instead. We also develop an iterative equation to infer the hyper-parameter (temperature) hidden in the data, which in physics corresponds to iteratively imposing Nishimori condition. Our study provides insights towards understanding the thermodynamic properties of the restricted Boltzmann machine learning, and moreover important theoretical basis to build simplified deep networks.

Formation enthalpies for transition metal alloys using machine learning

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Lanthanide Al-Ni base Ericsson cycle magnetic refrigerants

DOEpatents

Gschneidner, Jr., Karl A.; Takeya, Hiroyuki

1995-10-31

A magnetic refrigerant for a magnetic refrigerator using the Ericsson thermodynamic cycle comprises DyAlNi and (Gd.sub.0.54 Er.sub.0.46)AlNi alloys having a relatively constant .DELTA.Tmc over a wide temperature range.

Nonequilibrium thermodynamics and maximum entropy production in the Earth system: applications and implications.

PubMed

Kleidon, Axel

2009-06-01

The Earth system is maintained in a unique state far from thermodynamic equilibrium, as, for instance, reflected in the high concentration of reactive oxygen in the atmosphere. The myriad of processes that transform energy, that result in the motion of mass in the atmosphere, in oceans, and on land, processes that drive the global water, carbon, and other biogeochemical cycles, all have in common that they are irreversible in their nature. Entropy production is a general consequence of these processes and measures their degree of irreversibility. The proposed principle of maximum entropy production (MEP) states that systems are driven to steady states in which they produce entropy at the maximum possible rate given the prevailing constraints. In this review, the basics of nonequilibrium thermodynamics are described, as well as how these apply to Earth system processes. Applications of the MEP principle are discussed, ranging from the strength of the atmospheric circulation, the hydrological cycle, and biogeochemical cycles to the role that life plays in these processes. Nonequilibrium thermodynamics and the MEP principle have potentially wide-ranging implications for our understanding of Earth system functioning, how it has evolved in the past, and why it is habitable. Entropy production allows us to quantify an objective direction of Earth system change (closer to vs further away from thermodynamic equilibrium, or, equivalently, towards a state of MEP). When a maximum in entropy production is reached, MEP implies that the Earth system reacts to perturbations primarily with negative feedbacks. In conclusion, this nonequilibrium thermodynamic view of the Earth system shows great promise to establish a holistic description of the Earth as one system. This perspective is likely to allow us to better understand and predict its function as one entity, how it has evolved in the past, and how it is modified by human activities in the future.

Methods for thermodynamic evaluation of battery state of health

DOEpatents

Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T

2013-05-21

Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.

Methods and systems for thermodynamic evaluation of battery state of health

DOEpatents

Yazami, Rachid; McMenamin, Joseph; Reynier, Yvan; Fultz, Brent T

2014-12-02

Described are systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and battery systems and for characterizing the state of health of electrodes and battery systems. Measurement of physical attributes of electrodes and batteries corresponding to thermodynamically stabilized electrode conditions permit determination of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and battery systems, such as energy, power density, current rate, cycle life and state of health. Also provided are systems and methods for charging a battery according to its state of health.

An Introduction to Thermodynamic Performance Analysis of Aircraft Gas Turbine Engine Cycles Using the Numerical Propulsion System Simulation Code

NASA Technical Reports Server (NTRS)

Jones, Scott M.

2007-01-01

This document is intended as an introduction to the analysis of gas turbine engine cycles using the Numerical Propulsion System Simulation (NPSS) code. It is assumed that the analyst has a firm understanding of fluid flow, gas dynamics, thermodynamics, and turbomachinery theory. The purpose of this paper is to provide for the novice the information necessary to begin cycle analysis using NPSS. This paper and the annotated example serve as a starting point and by no means cover the entire range of information and experience necessary for engine performance simulation. NPSS syntax is presented but for a more detailed explanation of the code the user is referred to the NPSS User Guide and Reference document (ref. 1).

Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

NASA Astrophysics Data System (ADS)

Grover, Valerie Ann

The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

Influence of Liquid Structure on Fickian Diffusion in Binary Mixtures of n-Hexane and Carbon Dioxide Probed by Dynamic Light Scattering, Raman Spectroscopy, and Molecular Dynamics Simulations.

PubMed

Klein, Tobias; Wu, Wenchang; Rausch, Michael Heinrich; Giraudet, Cédric; Koller, Thomas M; Fröba, Andreas Paul

2018-06-11

This study contributes to a fundamental understanding how the liquid structure in a model system consisting of weakly associative n-hexane ( n-C 6 H 14 ) and carbon dioxide (CO 2 ) influences the Fickian diffusion process. For this, the benefits of light scattering experiments and molecular dynamics (MD) simulations at macroscopic thermodynamic equilibrium were combined synergistically. Our reference Fickian diffusivities measured by dynamic light scattering (DLS) revealed an unusual trend with increasing CO 2 mole fractions up to a CO 2 concentration of about 70 mol%, which agrees with our simulation results. The molecular impacts on the Fickian diffusion were analyzed by MD simulations, where kinetic contributions related to the Maxwell-Stefan (MS) diffusivity and structural contributions quantified by the thermodynamic factor were studied separately. Both the MS diffusivity and the thermodynamic factor indicate the deceleration of Fickian diffusion compared to an ideal mixture behavior. Computed radial distribution functions as well as a significant blue-shift of the CH-stretching modes of n-C 6 H 14 identified by Raman spectroscopy show that the slowing-down of the diffusion is caused by a structural organization in the binary mixtures over a broad concentration range in the form of self-associated n-C 6 H 14 and CO 2 domains. These networks start to form close to the infinite dilution limits and seem to have their largest extent at a solute-solvent transition point at about 70 mol% of CO 2 . The current results not only improve the general understanding of mass diffusion in liquids, but also serve to develop sound prediction models for Fick diffusivities.

Calculation of phase diagrams for the FeCl2, PbCl2, and ZnCl2 binary systems by using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Seo, Won-Gap; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2006-04-01

Recently, molecular dynamics (MD) simulation has been widely employed as a very useful method for the calculation of various physicochemical properties in the molten slags and fluxes. In this study, MD simulation has been applied to calculate the structural, transport, and thermodynamic properties for the FeCl2, PbCl2, and ZnCl2 systems using the Born—Mayer—Huggins type pairwise potential with partial ionic charges. The interatomic potential parameters were determined by fitting the physicochemical properties of iron chloride, lead chloride, and zinc chloride systems with experimentally measured results. The calculated structural, transport, and thermodynamic properties of pure FeCl2, PbCl2, and ZnCl2 showed the same tendency with observed results. Especially, the calculated structural properties of molten ZnCl2 and FeCl2 show the possibility of formation of polymeric network structures based on the ionic complexes of ZnCl{4/2-}, ZnCl{3/-}, FeCl{4/2-}, and FeCl{3/-}, and these calculations have successfully reproduced the measured results. The enthalpy, entropy, and Gibbs energy of mixing for the PbCl2-ZnCl2, FeCl2-PbCl2, and FeCl2-ZnCl2 systems were calculated based on the thermodynamic and structural parameters of each binary system obtained from MD simulation. The phase diagrams of the PbCl2-ZnCl2, FeCl2-PbCl2, and FeCl2-ZnCl2 systems estimated by using the calculated Gibbs energy of mixing reproduced the experimentally measured ones reasonably well.

Repulsive particles under a general external potential: Thermodynamics by neglecting thermal noise.

PubMed

Ribeiro, Mauricio S; Nobre, Fernando D

2016-08-01

A recent proposal of an effective temperature θ, conjugated to a generalized entropy s_{q}, typical of nonextensive statistical mechanics, has led to a consistent thermodynamic framework in the case q=2. The proposal was explored for repulsively interacting vortices, currently used for modeling type-II superconductors. In these systems, the variable θ presents values much higher than those of typical room temperatures T, so that the thermal noise can be neglected (T/θ≃0). The whole procedure was developed for an equilibrium state obtained after a sufficiently long-time evolution, associated with a nonlinear Fokker-Planck equation and approached due to a confining external harmonic potential, ϕ(x)=αx^{2}/2 (α>0). Herein, the thermodynamic framework is extended to a quite general confining potential, namely ϕ(x)=α|x|^{z}/z (z>1). It is shown that the main results of the previous analyses hold for any z>1: (i) The definition of the effective temperature θ conjugated to the entropy s_{2}. (ii) The construction of a Carnot cycle, whose efficiency is shown to be η=1-(θ_{2}/θ_{1}), where θ_{1} and θ_{2} are the effective temperatures associated with two isothermal transformations, with θ_{1}>θ_{2}. The special character of the Carnot cycle is indicated by analyzing another cycle that presents an efficiency depending on z. (iii) Applying Legendre transformations for a distinct pair of variables, different thermodynamic potentials are obtained, and furthermore, Maxwell relations and response functions are derived. The present approach shows a consistent thermodynamic framework, suggesting that these results should hold for a general confining potential ϕ(x), increasing the possibility of experimental verifications.

Pulse Detonation Propulsion

DTIC Science & Technology

2010-01-01

constant-pressure ( Brayton ) cycle used in gas turbines and ramjets. The advantages of PDE for air- breathing propulsion are simplicity and easy scaling...constant-volume, and detonative combustion cycles will be referred to as Brayton , Humphrey, and PDE cycles. The efficiency of thermodynamic cycles O’ODD...efficiency of Brayton cycle, as 0G HH =′ , i.e., 0==constpχ (3) Constant-volume combustion (point E in Fig. 1) results in temperature K 2647/0E

Lanthanide Al-Ni base Ericsson cycle magnetic refrigerants

DOEpatents

Gschneidner, K.A. Jr.; Takeya, Hiroyuki

1995-10-31

A magnetic refrigerant for a magnetic refrigerator using the Ericsson thermodynamic cycle comprises DyAlNi and (Gd{sub 0.54}Er{sub 0.46})AlNi alloys having a relatively constant {Delta}Tmc over a wide temperature range. 16 figs.

A non-additive repulsive contribution in an equation of state: The development for homonuclear square well chains equation of state validated against Monte Carlo simulation

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

Trinh, Thi-Kim-Hoang; Laboratoire de Science des Procédés et des Matériaux; Passarello, Jean-Philippe, E-mail: Jean-Philippe.Passarello@lspm.cnrs.fr

This work consists of the adaptation of a non-additive hard sphere theory inspired by Malakhov and Volkov [Polym. Sci., Ser. A 49(6), 745–756 (2007)] to a square-well chain. Using the thermodynamic perturbation theory, an additional term is proposed that describes the effect of perturbing the chain of square well spheres by a non-additive parameter. In order to validate this development, NPT Monte Carlo simulations of thermodynamic and structural properties of the non-additive square well for a pure chain and a binary mixture of chains are performed. Good agreements are observed between the compressibility factors originating from the theory and thosemore » from molecular simulations.« less

Process feasibility study in support of silicon material, task 1

NASA Technical Reports Server (NTRS)

Li, K. Y.; Hansen, K. C.; Yaws, C. L.

1979-01-01

Analyses of process system properties were continued for materials involved in the alternate processes under consideration for semiconductor silicon. Primary efforts centered on physical and thermodynamic property data for dichlorosilane. The following property data are reported for dichlorosilane which is involved in processing operations for solar cell grade silicon: critical temperature, critical pressure, critical volume, critical density, acentric factor, vapor pressure, heat of vaporization, gas heat capacity, liquid heat capacity and density. Work was initiated on the assembly of a system to prepare binary gas mixtures of known proportions and to measure the thermal conductivity of these mixtures between 30 and 350 C. The binary gas mixtures include silicon source material such as silanes and halogenated silanes which are used in the production of semiconductor silicon.

Matrix isolation infrared and Raman spectra of binary and mixed group II B fluorides

NASA Astrophysics Data System (ADS)

Givan, A.; Loewenschuss, A.

1980-03-01

Infrared and Raman spectra of all MF2 and MFX molecules (M=Zn, Cd, Hg; X=Cl, Br) and the infrared spectrum of the fluoroidide HgFI isolated in solid krypton at 20 °K are reported. The MFX species were formed in a vapor mixture of the appropriate MF2 and MX2 dihalides, vaporized, at different temperatures, from separate compartments of a double-oven crucible. The spectra are the first experimental evidence for the existence of the molecular fluorohalides. All three fundamentals of the MF2 molecules and the two stretching mode frequencies of the MFX molecules are assigned. Harmonic force constants are evaluated and isotope effects are used to discuss their geometry. Thermodynamic functions are tabulated for the binary difluorides.

The disruption of multiplanet systems through resonance with a binary orbit.

PubMed

Touma, Jihad R; Sridhar, S

2015-08-27

Most exoplanetary systems in binary stars are of S-type, and consist of one or more planets orbiting a primary star with a wide binary stellar companion. Planetary eccentricities and mutual inclinations can be large, perhaps forced gravitationally by the binary companion. Earlier work on single planet systems appealed to the Kozai-Lidov instability wherein a sufficiently inclined binary orbit excites large-amplitude oscillations in the planet's eccentricity and inclination. The instability, however, can be quenched by many agents that induce fast orbital precession, including mutual gravitational forces in a multiplanet system. Here we report that orbital precession, which inhibits Kozai-Lidov cycling in a multiplanet system, can become fast enough to resonate with the orbital motion of a distant binary companion. Resonant binary forcing results in dramatic outcomes ranging from the excitation of large planetary eccentricities and mutual inclinations to total disruption. Processes such as planetary migration can bring an initially non-resonant system into resonance. As it does not require special physical or initial conditions, binary resonant driving is generic and may have altered the architecture of many multiplanet systems. It can also weaken the multiplanet occurrence rate in wide binaries, and affect planet formation in close binaries.

Unravelling the Composition Dependent Anomalies of Pair Hydrophobicity in Water-Ethanol Binary Mixtures.

PubMed

Halder, Ritaban; Jana, Biman

2018-06-05

Aqueous binary mixtures have received immense attention in recent years because of their extensive application in several biological and industrial processes. Water-ethanol binary mixture serves as a unique system because it exhibits composition dependent alteration of dynamic and thermodynamic properties. Our present work demonstrates how different compositions of water-ethanol binary mixtures affect the pair hydrophobicity of different hydrophobes. Pair hydrophobicity is measured by the depth of the first minimum (contact minima) of potential of mean force (PMF) profile between two hydrophobes. The pair hydrophobicity is found to be increased with addition of ethanol to water up to mole fraction of 0.10 and decreased with further addition of ethanol. This observation is shown to be true for three different pairs of hydrophobes. Decomposition of PMF into enthalpic and entropic contribution indicates a switch from entropic to enthalpic stabilization of the contact minimum upon addition of ethanol to water. The gain in mixing enthalpy of the binary solvent system upon association of two hydrophobes is found to be the determining factor for the stabilization of contact minimum. Several static/dynamics quantities (average composition fluctuations, diffusion coefficients, fluctuations in total dipole moment, propensity of ethyl-ethyl association, etc) of the ethanol-water binary mixture also show irregularities around xEtOH =0.10-0.15. We have also discovered that the hydrogen bonding pattern of ethanol rather than water reveals a change in trend near the similar composition range. As the anomalous behaviour of the physical/dynamical properties along with the pair hydrophobicity in aqueous binary mixture of amphiphilic solutes is common phenomena, our results may provide a general viewpoint on these aspects.

A deeper insight into an intriguing acetonitrile-water binary mixture: synergistic effect, dynamic Stokes shift, fluorescence correlation spectroscopy, and NMR studies.

PubMed

Koley, Somnath; Ghosh, Subhadip

2016-11-30

An insight study reveals the strong synergistic solvation behaviours from reporter dye molecules within the acetonitrile (ACN)-water (WT) binary mixture. Synergism of a binary mixture refers to some unique changes of the physical and thermodynamic properties of the solvent mixture, originating from the interactions among its cosolvents, which are absent within the pure cosolvents. Synergistic solvation of a binary mixture is likely to be fundamental for greater stabilization of an excited state solute dipole; at least to some extent greater as compared to one stabilized by any of its cosolvents alone. A dynamic Stokes shift due to the solvation of an excited dipole in the ACN-WT binary mixture is found to be highly relevant to the ground state physical properties of the solute molecule (polarity, hydrophilicity, acidity, etc.). Largely different solvation times in the ACN-WT mixture are observed from different dye molecules with widely varying polarities. However, earlier study shows that dye molecules, irrespective of their varying polarities, exhibit very similar solvation times within a pure solvent (J. Phys. Chem. B, 2014, 118, 7577-7785). On further study with fluorescence correlation spectroscopy (FCS) we observed that, unlike the translational diffusion coefficient (D t ) of a dye molecule within a pure solvent, which remains the same irrespective of the location of the dye molecule inside the solvent, a broad distribution among the D t values of a dye molecule is obtained from different locations within the ACN-WT binary mixture. Lastly our 1 H NMR study in the ACN-WT binary mixture shows the existence of strong hydrogen bond interactions among the cosolvents in the ACN-WT mixture.

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.

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.

THE QUASI-ROCHE LOBE OVERFLOW STATE IN THE EVOLUTION OF CLOSE BINARY SYSTEMS CONTAINING A RADIO PULSAR

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

Benvenuto, O. G.; De Vito, M. A.; Horvath, J. E., E-mail: adevito@fcaglp.unlp.edu.ar, E-mail: foton@iag.usp.br

We study the evolution of close binary systems formed by a normal (solar composition), intermediate-mass-donor star together with a neutron star. We consider models including irradiation feedback and evaporation. These nonstandard ingredients deeply modify the mass-transfer stages of these binaries. While models that neglect irradiation feedback undergo continuous, long-standing mass-transfer episodes, models including these effects suffer a number of cycles of mass transfer and detachment. During mass transfer, the systems should reveal themselves as low-mass X-ray binaries (LMXBs), whereas when they are detached they behave as binary radio pulsars. We show that at these stages irradiated models are in amore » Roche lobe overflow (RLOF) state or in a quasi-RLOF state. Quasi-RLOF stars have radii slightly smaller than their Roche lobes. Remarkably, these conditions are attained for an orbital period as well as donor mass values in the range corresponding to a family of binary radio pulsars known as ''redbacks''. Thus, redback companions should be quasi-RLOF stars. We show that the characteristics of the redback system PSR J1723-2837 are accounted for by these models. In each mass-transfer cycle these systems should switch from LMXB to binary radio pulsar states with a timescale of approximately one million years. However, there is recent and fast growing evidence of systems switching on far shorter, human timescales. This should be related to instabilities in the accretion disk surrounding the neutron star and/or radio ejection, still to be included in the model having the quasi-RLOF state as a general condition.« less

Probabilistic Analysis of Solid Oxide Fuel Cell Based Hybrid Gas Turbine System

NASA Technical Reports Server (NTRS)

Gorla, Rama S. R.; Pai, Shantaram S.; Rusick, Jeffrey J.

2003-01-01

The emergence of fuel cell systems and hybrid fuel cell systems requires the evolution of analysis strategies for evaluating thermodynamic performance. A gas turbine thermodynamic cycle integrated with a fuel cell was computationally simulated and probabilistically evaluated in view of the several uncertainties in the thermodynamic performance parameters. Cumulative distribution functions and sensitivity factors were computed for the overall thermal efficiency and net specific power output due to the uncertainties in the thermodynamic random variables. These results can be used to quickly identify the most critical design variables in order to optimize the design and make it cost effective. The analysis leads to the selection of criteria for gas turbine performance.

The Unruh quantum Otto engine

NASA Astrophysics Data System (ADS)

Arias, Enrique; de Oliveira, Thiago R.; Sarandy, M. S.

2018-02-01

We introduce a quantum heat engine performing an Otto cycle by using the thermal properties of the quantum vacuum. Since Hawking and Unruh, it has been established that the vacuum space, either near a black hole or for an accelerated observer, behaves as a bath of thermal radiation. In this work, we present a fully quantum Otto cycle, which relies on the Unruh effect for a single quantum bit (qubit) in contact with quantum vacuum fluctuations. By using the notions of quantum thermodynamics and perturbation theory we obtain that the quantum vacuum can exchange heat and produce work on the qubit. Moreover, we obtain the efficiency and derive the conditions to have both a thermodynamic and a kinematic cycle in terms of the initial populations of the excited state, which define a range of allowed accelerations for the Unruh engine.

Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies

NASA Astrophysics Data System (ADS)

Fèvre, Mathieu; Le Bouar, Yann; Finel, Alphonse

2018-05-01

The aim of this paper is to investigate the consequences of finite-size effects on the thermodynamics of nanoparticle assemblies and isolated particles. We consider a binary phase-separating alloy with a negligible atomic size mismatch, and equilibrium states are computed using off-lattice Monte Carlo simulations in several thermodynamic ensembles. First, a semi-grand-canonical ensemble is used to describe infinite assemblies of particles with the same size. When decreasing the particle size, we obtain a significant decrease of the solid/liquid transition temperatures as well as a growing asymmetry of the solid-state miscibility gap related to surface segregation effects. Second, a canonical ensemble is used to analyze the thermodynamic equilibrium of finite monodisperse particle assemblies. Using a general thermodynamic formulation, we show that a particle assembly may split into two subassemblies of identical particles. Moreover, if the overall average canonical concentration belongs to a discrete spectrum, the subassembly concentrations are equal to the semi-grand-canonical equilibrium ones. We also show that the equilibrium of a particle assembly with a prescribed size distribution combines a size effect and the fact that a given particle size assembly can adopt two configurations. Finally, we have considered the thermodynamics of an isolated particle to analyze whether a phase separation can be defined within a particle. When studying rather large nanoparticles, we found that the region in which a two-phase domain can be identified inside a particle is well below the bulk phase diagram, but the concentration of the homogeneous core remains very close to the bulk solubility limit.

Thermo-economic comparative analysis of gas turbine GT10 integrated with air and steam bottoming cycle

NASA Astrophysics Data System (ADS)

Czaja, Daniel; Chmielnak, Tadeusz; Lepszy, Sebastian

2014-12-01

A thermodynamic and economic analysis of a GT10 gas turbine integrated with the air bottoming cycle is presented. The results are compared to commercially available combined cycle power plants based on the same gas turbine. The systems under analysis have a better chance of competing with steam bottoming cycle configurations in a small range of the power output capacity. The aim of the calculations is to determine the final cost of electricity generated by the gas turbine air bottoming cycle based on a 25 MW GT10 gas turbine with the exhaust gas mass flow rate of about 80 kg/s. The article shows the results of thermodynamic optimization of the selection of the technological structure of gas turbine air bottoming cycle and of a comparative economic analysis. Quantities are determined that have a decisive impact on the considered units profitability and competitiveness compared to the popular technology based on the steam bottoming cycle. The ultimate quantity that can be compared in the calculations is the cost of 1 MWh of electricity. It should be noted that the systems analyzed herein are power plants where electricity is the only generated product. The performed calculations do not take account of any other (potential) revenues from the sale of energy origin certificates. Keywords: Gas turbine air bottoming cycle, Air bottoming cycle, Gas turbine, GT10

Black Hole Accretion Discs on a Moving Mesh

NASA Astrophysics Data System (ADS)

Ryan, Geoffrey

2017-01-01

We present multi-dimensional numerical simulations of black hole accretion disks relevant for the production of electromagnetic counterparts to gravitational wave sources. We perform these simulations with a new general relativistic version of the moving-mesh magnetohydrodynamics code DISCO which we will present. This open-source code, GR-DISCO uses an orbiting and shearing mesh which moves with the dominant flow velocity, greatly improving the numerical accuracy of the thermodynamic variables in supersonic flows while also reducing numerical viscosity and greatly increasing computational efficiency by allowing for a larger time step. We have used GR-DISCO to study black hole accretion discs subject to gravitational torques from a binary companion, relevant for both current and future supermassive binary black hole searches and also as a possible electromagnetic precursor mechanism for LIGO events. Binary torques in these discs excite spiral shockwaves which effectively transport angular momentum in the disc and propagate through the innermost stable orbit, leading to stress corresponding to an alpha-viscosity of 10-2. We also present three-dimensional GRMHD simulations of neutrino dominated accretion flows (NDAFs) occurring after a binary neutron star merger in order to elucidate the conditions for electromagnetic transient production accompanying these gravitational waves sources expected to be detected by LIGO in the near future.

Reversible Li storage for nanosize cation/anion-disordered rocksalt-type oxyfluorides: LiMoO2 - x LiF (0 ≤ x ≤ 2) binary system

NASA Astrophysics Data System (ADS)

Takeda, Nanami; Hoshino, Satoshi; Xie, Lixin; Chen, Shuo; Ikeuchi, Issei; Natsui, Ryuichi; Nakura, Kensuke; Yabuuchi, Naoaki

2017-11-01

A binary system of LiMoO2 - x LiF (0 ≤ x ≤ 2), Li1+xMoO2Fx, is systematically studied as potential positive electrode materials for rechargeable Li batteries. Single phase and nanosized samples on this binary system are successfully prepared by using a mechanical milling route. Crystal structures and Li storage properties on the binary system are also examined. Li2MoO2F (x = 1), which is classified as a cation-/anion-disordered rocksalt-type structure and is a thermodynamically metastable phase, delivers a large reversible capacity of over 300 mAh g-1 in Li cells with good reversibility. Highly reversible Li storage is realized for Li2MoO2F consisting of nanosized particles based on Mo3+/Mo5+ two-electron redox as evidenced by ex-situ X-ray absorption spectroscopy coupled with ex-situ X-ray diffractometry. Moreover, the presence of the most electronegative element in the framework structure effectively increases the electrode potential of Mo redox through an inductive effect. From these results, potential of nanosized lithium molybdenum oxyfluorides for high-capacity positive electrode materials of rechargeable Li batteries are discussed.

Modeling the [NTf2] pyridinium ionic liquids family and their mixtures with the soft statistical associating fluid theory equation of state.

PubMed

Oliveira, M B; Llovell, F; Coutinho, J A P; Vega, L F

2012-08-02

In this work, the soft statistical associating fluid theory (soft-SAFT) equation of state (EoS) has been used to provide an accurate thermodynamic characterization of the pyridinium-based family of ionic liquids (ILs) with the bis(trifluoromethylsulfonyl)imide anion [NTf(2)](-). On the basis of recent molecular simulation studies for this family, a simple molecular model was proposed within the soft-SAFT EoS framework. The chain length value was transferred from the equivalent imidazolium-based ILs family, while the dispersive energy and the molecular parameters describing the cation-anion interactions were set to constant values for all of the compounds. With these assumptions, an appropriate set of molecular parameters was found for each compound fitting to experimental temperature-density data at atmospheric pressure. Correlations for the nonconstant parameters (describing the volume of the IL) with the molecular weight were established, allowing the prediction of the parameters for other pyridiniums not included in the fitting. Then, the suitability of the proposed model and its optimized parameters were tested by predicting high-pressure densities and second-order thermodynamic derivative properties such as isothermal compressibilities of selected [NTf(2)] pyridinium ILs, in a large range of thermodynamic conditions. The surface tension was also provided using the density gradient theory coupled to the soft-SAFT equation. Finally, the soft-SAFT EoS was applied to describe the phase behavior of several binary mixtures of [NTf(2)] pyridinium ILs with carbon dioxide, sulfur dioxide, and water. In all cases, a temperature-independent binary parameter was enough to reach quantitative agreement with the experimental data. The description of the solubility of CO(2) in these ILs also allowed identification of a relation between the binary parameter and the molecular weight of the ionic liquid, allowing the prediction of the CO(2) + C(12)py[NTf(2)] mixture. The good agreement with the experimental data shows the excellent ability of the soft-SAFT EoS to describe the thermophysical properties of ILs as well as their phase behavior. Results prove that this equation of state can be a valuable tool to assist the design of ILs (in what concerns cation and anion selection) in order to obtain ILs with the desired properties and, consequently, enhancing their potential industrial applications.

Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

DOE PAGES

Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

2014-12-09

Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO 2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO 2. Despite significant losses in capacity uponmore » cycling, neither cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO 2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO 2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.« less

Natural and Artificial Satellite Dynamics and Evolution around Near-Earth Asteroids with Solar Radiation Pressure

NASA Astrophysics Data System (ADS)

Rieger, Samantha M.

Natural and artificial satellites are subject to perturbations when orbiting near-Earth asteroids. These perturbations include non-uniform gravity from the asteroid, third-body disturbances from the Sun, and solar radiation pressure. For small natural (1 cm-15 m) and artificial satellites, solar radiation pressure is the primary perturbation that will cause their orbits to go unstable. For the asteroid Bennu, the future target of the spacecraft OSIRIS-REx, the possibility of natural satellites having stable orbits around the asteroid and characterize these stable regions is investigated. It has been found that the main orbital phenomena responsible for the stability or instability of these possible natural satellites are Sun-synchronous orbits, the modified Laplace plane, and the Kozai resonance. These findings are applied to other asteroids as well as to artificial satellites. The re-emission of solar radiation pressure through BYORP is also investigated for binary asteroid systems. Specifically, the BYORP force is combined with the Laplace plane such that BYORP expands the orbit of the binary system along the Laplace surface where the secondary increases in inclination. For obliquities from 68.875° - 111.125° the binary will eventually extend into the Laplace instability region, where the eccentricity of the orbit will increase. A subset of the instability region leads to eccentricities high enough that the secondary will impact the primary. This result inspired the development of a hypothesis of a contact-binary binary cycle described briefly in the following. YORP will increase the spin rate of a contact binary while also driving the spin-pole to an obliquity of 90°. Eventually, the contact binary will fission. The binary will subsequently become double-synchronous, thus allowing the BYORP acceleration to have secular effects on the orbit. The orbit will then expand along the Laplace surface to the Laplace plane instability region eventually leading to an impact and the start of a new cycle with the YORP process.

ζ1 + ζ2 Reticuli binary system: a puzzling chromospheric activity pattern

NASA Astrophysics Data System (ADS)

Flores, M.; Saffe, C.; Buccino, A.; Jaque Arancibia, M.; González, J. F.; Nuñez, N. E.; Jofré, E.

2018-05-01

We perform, for the first time, a detailed long-term activity study of the binary system ζ Ret. We use all available HARPS spectra obtained between the years 2003 and 2016. We build a time series of the Mount Wilson S index for both stars, then we analyse these series by using Lomb-Scargle periodograms. The components ζ1 Ret and ζ2 Ret that belong to this binary system are physically very similar to each other and also similar to our Sun, which makes it a remarkable system. We detect in the solar-analogue star ζ2 Ret a long-term activity cycle with a period of ˜10 yr, similar to the solar one (˜11 yr). It is worthwhile to mention that this object satisfies previous criteria for a flat star and for a cycling star simultaneously. Another interesting feature of this binary system is a high ˜0.220 dex difference between the average log (R^' }_HK) activity levels of both stars. Our study clearly shows that ζ1 Ret is significantly more active than ζ2 Ret. In addition, ζ1 Ret shows an erratic variability in its stellar activity. In this work, we explore different scenarios trying to explain this rare behaviour in a pair of coeval stars, which could help to explain the difference in this and other binary systems. From these results, we also warn that for the development of activity-age calibrations (which commonly use binary systems and/or stellar clusters as calibrators) the whole history of activity available for the stars involved should be taken into account.

Effect of the interfacial tension and ionic strength on the thermodynamic barrier associated to the benzocaine insertion into a cell membrane.

PubMed

López Cascales, J J; Oliveira Costa, S D

2013-02-01

The insertion of local anaesthetics into a cell membrane is a key aspect for explaining their activity at a molecular level. It has been described how the potency and response time of local anaesthetics is improved (for clinical applications) when they are dissolved in a solution of sodium bicarbonate. With the aim of gaining insight into the physico-chemical principles that govern the action mechanism of these drugs at a molecular level, simulations of benzocaine in binary lipid bilayers formed by DPPC/DPPS were carried out for different ionic strengths of the aqueous solution. From these molecular dynamic simulations, we observed how the thermodynamic barrier associated with benzocaine insertion into the lipid bilayers diminished exponentially as the fraction of DPPS in the bilayer increased, especially when the ionic strength of the aqueous solution increased. In line with these results, we also observed how this thermodynamic barrier diminished exponentially with the phospholipid/water interfacial tension. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamic and kinetic modelling of fuel oxidation behaviour in operating defective fuel

NASA Astrophysics Data System (ADS)

Lewis, operating defective fuel B. J.; Thompson, W. T.; Akbari, F.; Thompson, D. M.; Thurgood, C.; Higgs, J.

2004-07-01

A theoretical treatment has been developed to predict the fuel oxidation behaviour in operating defective nuclear fuel elements. The equilibrium stoichiometry deviation in the hyper-stoichiometric fuel has been derived from thermodynamic considerations using a self-consistent set of thermodynamic properties for the U-O system, which emphasizes replication of solubilities and three-phase invariant conditions displayed in the U-O binary phase diagram. The kinetics model accounts for multi-phase transport including interstitial oxygen diffusion in the solid and gas-phase transport of hydrogen and steam in the fuel cracks. The fuel oxidation model is further coupled to a heat conduction model to account for the feedback effect of a reduced thermal conductivity in the hyper-stoichiometric fuel. A numerical solution has been developed using a finite-element technique with the FEMLAB software package. The model has been compared to available data from several in-reactor X-2 loop experiments with defective fuel conducted at the Chalk River Laboratories. The model has also been benchmarked against an O/U profile measurement for a spent defective fuel element discharged from a commercial reactor.

First-Principles Prediction of Thermodynamically Stable Two-Dimensional Electrides

DOE PAGES

Ming, Wenmei; Yoon, Mina; Univ. of Tennessee, Knoxville, TN; ...

2016-10-21

Two-dimensional (2D) electrides, emerging as a new type of layered material whose electrons are confined in interlayer spaces instead of at atomic proximities, are receiving interest for their high performance in various (opto)electronics and catalytic applications. Experimentally, however, 2D electrides have been only found in a couple of layered nitrides and carbides. We report new thermodynamically stable alkaline-earth based 2D electrides by using a first-principles global structure optimization method, phonon spectrum analysis, and molecular dynamics simulation. The method was applied to binary compounds consisting of alkaline-earth elements as cations and group VA, VIA, or VIIA nonmetal elements as anions. Wemore » also revealed that the stability of a layered 2D electride structure is closely related to the cation/anion size ratio; stable 2D electrides possess a sufficiently large cation/anion size ratio to minimize electrostatic energy among cations, anions, and anionic electrons. This work demonstrates a new avenue to the discovery of thermodynamically stable 2D electrides beyond experimental material databases and provides new insight into the principles of electride design.« less

Diffuse interface method for a compressible binary fluid.

PubMed

Liu, Jiewei; Amberg, Gustav; Do-Quang, Minh

2016-01-01

Multicomponent, multiphase, compressible flows are very important in real life, as well as in scientific research, while their modeling is in an early stage. In this paper, we propose a diffuse interface model for compressible binary mixtures, based on the balance of mass, momentum, energy, and the second law of thermodynamics. We show both analytically and numerically that this model is able to describe the phase equilibrium for a real binary mixture (CO_{2} + ethanol is considered in this paper) very well by adjusting the parameter which measures the attraction force between molecules of the two components in the model. We also show that the calculated surface tension of the CO_{2} + ethanol mixture at different concentrations match measurements in the literature when the mixing capillary coefficient is taken to be the geometric mean of the capillary coefficient of each component. Three different cases of two droplets in a shear flow, with the same or different concentration, are simulated, showing that the higher concentration of CO_{2} the smaller the surface tension and the easier the drop deforms.

Interaction between Saikosaponin D, Paeoniflorin, and Human Serum Albumin.

PubMed

Liang, Guo-Wu; Chen, Yi-Cun; Wang, Yi; Wang, Hong-Mei; Pan, Xiang-Yu; Chen, Pei-Hong; Niu, Qing-Xia

2018-01-27

Saikosaponin D (SSD) and paeoniflorin (PF) are the major active constituents of Bupleuri Radix and Paeonia lactiflora Pall , respectively, and have been widely used in China to treat liver and other diseases for many centuries. We explored the binding of SSD/PF to human serum albumin (HSA) by using fluorospectrophotometry, circular dichroism (CD) and molecular docking. Both SSD and PF produced a conformational change in HSA. Fluorescence quenching was accompanied by a blue shift in the fluorescence spectra. Co-binding of PF and SSD also induced quenching and a conformational change in HSA. The Stern-Volmer equation showed that quenching was dominated by static quenching. The binding constant for ternary interaction was below that for binary interaction. Site-competitive experiments demonstrated that SSD/PF bound to site I (subdomain IIA) and site II (subdomain IIIA) in HSA. Analysis of thermodynamic parameters indicated that hydrogen bonding and van der Waals forces were mostly responsible for the binary association. Also, there was energy transfer upon binary interaction. Molecular docking supported the experimental findings in conformation, binding sites and binding forces.

Solidification and microstructures of binary ice-I/hydrate eutectic aggregates

USGS Publications Warehouse

McCarthy, C.; Cooper, R.F.; Kirby, S.H.; Rieck, K.D.; Stern, L.A.

2007-01-01

The microstructures of two-phase binary aggregates of ice-I + salt-hydrate, prepared by eutectic solidification, have been characterized by cryogenic scanning electron microscopy (CSEM). The specific binary systems studied were H2O-Na2SO4, H2O-MgSO4, H2O-NaCl, and H2O-H2SO4; these were selected based on their potential application to the study of tectonics on the Jovian moon Europa. Homogeneous liquid solutions of eutectic compositions were undercooled modestly (??T - 1-5 ??C); similarly cooled crystalline seeds of the same composition were added to circumvent the thermodynamic barrier to nucleation and to control eutectic growth under (approximately) isothermal conditions. CSEM revealed classic eutectic solidification microstructures with the hydrate phase forming continuous lamellae, discontinuous lamellae, or forming the matrix around rods of ice-I, depending on the volume fractions of the phases and their entropy of dissolving and forming a homogeneous aqueous solution. We quantify aspects of the solidification behavior and microstructures for each system and, with these data articulate anticipated effects of the microstructure on the mechanical responses of the materials.

First-principles study of intermetallic phase stability in the ternary Ti-Al-Nb alloy system

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

Asta, M.; Ormeci, A.; Wills, J.M.

The stability of bcc-based phases in the Ti-Al-Nb alloy system has been studied from first-principles using a combination of ab-initio total energy and cluster variation method (CVM) calculations. Total energies have been computed for 18 binary and ternary bcc superstructures in order to determine low temperature ordering tendencies. From the results of these calculations a set of effective cluster interaction parameters have been derived. These interaction parameters are required input for CVM computations of alloy thermodynamic properties. The CVM has been used to study the effect of composition on finite-temperature ordering tendencies and site preferences for bcc-based phases. Strong orderingmore » tendencies are observed for binary Nb-Al and Ti-Al bcc phases as well as for ternary alloys with compositions near Ti{sub 2}AlNb. For selected superstructures we have also analyzed structural stabilities with respect to tetragonal distortions which transform the bcc into an fcc lattice. Instabilities with respect to such distortions are found to exist for binary but not ternary bcc compounds.« less

Mutual diffusion of binary liquid mixtures containing methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride

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

Guevara-Carrion, Gabriela; Janzen, Tatjana; Muñoz-Muñoz, Y. Mauricio

Mutual diffusion coefficients of all 20 binary liquid mixtures that can be formed out of methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride without a miscibility gap are studied at ambient conditions of temperature and pressure in the entire composition range. The considered mixtures show a varying mixing behavior from almost ideal to strongly non-ideal. Predictive molecular dynamics simulations employing the Green-Kubo formalism are carried out. Radial distribution functions are analyzed to gain an understanding of the liquid structure influencing the diffusion processes. It is shown that cluster formation in mixtures containing one alcoholic component has a significant impactmore » on the diffusion process. The estimation of the thermodynamic factor from experimental vapor-liquid equilibrium data is investigated, considering three excess Gibbs energy models, i.e., Wilson, NRTL, and UNIQUAC. It is found that the Wilson model yields the thermodynamic factor that best suits the simulation results for the prediction of the Fick diffusion coefficient. Four semi-empirical methods for the prediction of the self-diffusion coefficients and nine predictive equations for the Fick diffusion coefficient are assessed and it is found that methods based on local composition models are more reliable. Finally, the shear viscosity and thermal conductivity are predicted and in most cases favorably compared with experimental literature values.« less

Thermodynamic properties of model CdTe/CdSe mixtures

DOE PAGES

van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; ...

2015-02-20

We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation frommore » ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.« less

Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

PubMed

Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

2017-10-12

Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

Microwave dielectric relaxation spectroscopy study of propylene glycol/ethanol binary mixtures: Temperature dependence

NASA Astrophysics Data System (ADS)

Vishwam, T.; Shihab, Suriya; Murthy, V. R. K.; Tiong, Ha Sie; Sreehari Sastry, S.

2017-05-01

Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02 < ν/GHz < 20. The dipole moment (μ), excess dipole moment (Δμ),excess permittivity (εE), excess inverse relaxation time(1/τ)E, Bruggeman parameter (fB), excess Helmholtz energy (ΔFE) are determined using experimental data. From the minimum energy based geometry optimization, dipole moments of individual monomers of propylene glycol and ethanol and their binary system have been evaluated theoretically at gaseous state as well as alcoholic medium by using PCM and IEFPCM solvation models from the Hatree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-311G* and 6-311G** basis sets. The obtained results have been interpreted in terms of the short and long range ordering of the dipoles, Kirkwood correlation factor (geff), thermodynamic parameters, mean molecular polarizability (αM) and interaction in the mixture through hydrogen bonding. Dielectric relaxation study of propylene glycol in ethanol medium Determination of excess dielectric and thermodynamic parameters Comparison of experimental dipole moment with theoretical calculations Interpretation of the molecular interactions in the liquid through H-bonding Correlation between the evaluated dielectric parameters and theoretical results

Activity of water in aqueous systems; a frequently neglected property.

PubMed

Blandamer, Mike J; Engberts, Jan B F N; Gleeson, Peter T; Reis, Joao Carlos R

2005-05-01

In this critical review, the significance of the term 'activity' is examined in the context of the properties of aqueous solutions. The dependence of the activity of water(l) at ambient pressure and 298.15 K on solute molality is examined for aqueous solutions containing neutral solutes, mixtures of neutral solutes and salts. Addition of a solute to water(l) always lowers its thermodynamic activity. For some solutes the stabilisation of water(l) is less than and for others more than in the case where the thermodynamic properties of the aqueous solution are ideal. In one approach this pattern is accounted for in terms of hydrate formation. Alternatively the pattern is analysed in terms of the dependence of practical osmotic coefficients on the composition of the aqueous solution and then in terms of solute-solute interactions. For salt solutions the dependence of the activity of water on salt molalities is compared with that predicted by the Debye-Hückel limiting law. The analysis is extended to consideration of the activities of water in binary aqueous mixtures. The dependence on mole fraction composition of the activity of water in binary aqueous mixtures is examined. Different experimental methods for determining the activity of water in aqueous solutions are critically reviewed. The role of water activity is noted in a biochemical context, with reference to the quality, stability and safety of food and finally with regard to health science.

A facile and low-cost route for sensitive stretchable sensors by controlling kinetic and thermodynamic conductive network regulating strategies.

PubMed

Duan, Lingyan; D'hooge, Dagmar R; Spoerk, Martin; Cornillie, Pieter; Cardon, Ludwig

2018-05-29

Highly sensitive conductive polymer composites (CPCs) are designed, employing a facile and low-cost extrusion manufacturing process for both low and high strain sensing in the field of e.g. structural health/damage monitoring and human body movement tracking. Focus is on the morphology control for extrusion processed carbon black (CB)-filled CPCs, utilizing binary and ternary composites based on thermoplastic polyurethane (TPU) and olefin block copolymer (OBC). The relevance of the correct CB amount, kinetic control through a variation of the compounding sequence, and thermodynamic control induced by annealing is highlighted, considering a wide range of experimental (e.g. static and dynamic resistance/SEM/rheological measurements) and theoretical analyses. High CB mass fractions (20 m%) are needed for OBC (or TPU)-CB binary composites but only lead to an intermediate sensitivity as their conductive network is fully-packed and therefore difficult to be truly destructed. Annealing is needed to enable a monotonic increase of the relative resistance with respect to strain. With ternary composites a much higher sensitivity with a clearer monotonic increase results provided that a low CB mass fraction (10-16 m%) is used and annealing is applied. In particular, with CB first dispersed in OBC and annealing a less compact, hence, brittle conductive network (10-12 m% CB) is obtained, allowing high performance sensing.

Life cycle assessment integrated with thermodynamic analysis of bio-fuel options for solid oxide fuel cells.

PubMed

Lin, Jiefeng; Babbitt, Callie W; Trabold, Thomas A

2013-01-01

A methodology that integrates life cycle assessment (LCA) with thermodynamic analysis is developed and applied to evaluate the environmental impacts of producing biofuels from waste biomass, including biodiesel from waste cooking oil, ethanol from corn stover, and compressed natural gas from municipal solid wastes. Solid oxide fuel cell-based auxiliary power units using bio-fuel as the hydrogen precursor enable generation of auxiliary electricity for idling heavy-duty trucks. Thermodynamic analysis is applied to evaluate the fuel conversion efficiency and determine the amount of fuel feedstock needed to generate a unit of electrical power. These inputs feed into an LCA that compares energy consumption and greenhouse gas emissions of different fuel pathways. Results show that compressed natural gas from municipal solid wastes is an optimal bio-fuel option for SOFC-APU applications in New York State. However, this methodology can be regionalized within the U.S. or internationally to account for different fuel feedstock options. Copyright © 2012 Elsevier Ltd. All rights reserved.

Taub–Bolt heat engines

NASA Astrophysics Data System (ADS)

Johnson, Clifford V.

2018-02-01

It is shown that aspects of the extended thermodynamic properties of the Taub–Bolt–AdS spacetime in four dimensions are similar to those of the Schwarzschild–AdS black hole. In a high temperature expansion, the equations of state begin to deviate only at next-to-subleading orders. By analogy with what has been done for black holes, Taub–Bolt’s thermodynamic equations are used to define holographic heat engines, the first examples of gravitational heat engines defined using a spacetime that is not a black hole. As a further comparison, the Taub–Bolt engine efficiency is computed for two special kinds of engine cycle and compared to the results for analogous Schwarzschild black hole engine cycles.

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

Kagan, D. N., E-mail: d.n.kagan@mtu-net.ru; Krechetova, G. A.; Shpil'rain, E. E.

A detailed procedural analysis is given and results of implementation of the new version of the effusion method for determining the Gibbs energy (thermodynamic activity) of binary and ternary systems of alkali metals Cs-Na, K-Na, Cs-K, and Cs-K-Na are presented. The activity is determined using partial pressures of the components measured according the effusion method by the intensity of their atomic beams. The pressure range used in the experiment is intermediate between the Knudsen and hydrodynamic effusion modes. A generalized version of the effusion method involves the pressure range beyond the limits of the applicability of the Hertz-Knudsen equation. Employmentmore » of this method provides the differential equation of chemical thermodynamics; solution of this equation makes it possible to construct the Gibbs energy in the range of temperatures 400 {<=} T {<=} 1200 K and concentrations 0 {<=} x{sub i} {<=} 1.« less

Quantitative evaluation of thermodynamic parameters of Li-Sn alloys related to their use in fusion reactor

NASA Astrophysics Data System (ADS)

Krasin, V. P.; Soyustova, S. I.

2018-07-01

Along with other liquid metals liquid lithium-tin alloys can be considered as an alternative to the use of solid plasma facing components of a future fusion reactor. Therefore, parameters characterizing both the ability to retain hydrogen isotopes and those that determine the extraction of tritium from a liquid metal can be of particular importance. Theoretical correlations based on the coordination cluster model have been used to obtain Sieverts' constants for solutions of hydrogen in liquid Li-Sn alloys. The results of theoretical computations are compared with the previously published experimental values for two alloys of the Li-Sn system. The Butler equation in combination with the equations describing the thermodynamic potentials of a binary solution is used to calculate the surface composition and surface tension of liquid Li-Sn alloys.

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.

Kirkwood–Buff integrals for ideal solutions

PubMed Central

Ploetz, Elizabeth A.; Bentenitis, Nikolaos; Smith, Paul E.

2010-01-01

The Kirkwood–Buff (KB) theory of solutions is a rigorous theory of solution mixtures which relates the molecular distributions between the solution components to the thermodynamic properties of the mixture. Ideal solutions represent a useful reference for understanding the properties of real solutions. Here, we derive expressions for the KB integrals, the central components of KB theory, in ideal solutions of any number of components corresponding to the three main concentration scales. The results are illustrated by use of molecular dynamics simulations for two binary solutions mixtures, benzene with toluene, and methanethiol with dimethylsulfide, which closely approach ideal behavior, and a binary mixture of benzene and methanol which is nonideal. Simulations of a quaternary mixture containing benzene, toluene, methanethiol, and dimethylsulfide suggest this system displays ideal behavior and that ideal behavior is not limited to mixtures containing a small number of components. PMID:20441282

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

Discovery of a Superconducting Cu-Bi Intermetallic Compound by High-Pressure Synthesis

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

Clarke, Samantha M.; Walsh, James P. S.; Amsler, Maximilian

A new intermetallic compound, the first to be structurally identified in the Cu-Bi binary system, is reported. This compound is accessed by high-pressure reaction of the elements. Its detailed characterization, physical property measurements, and ab initio calculations are described. The commensurate crystal structure of Cu 11Bi 7 is a unique variation of the NiAs structure type. Temperature-dependent electrical resistivity and heat capacity measurements reveal a bulk superconducting transition at T c=1.36 K. Density functional theory calculations further demonstrate that Cu 11Bi 7 can be stabilized (relative to decomposition into the elements) at high pressure and temperature. These results highlight themore » ability of high-pressure syntheses to allow for inroads into heretofore-undiscovered intermetallic systems for which no thermodynamically stable binaries are known.« less

Estimated heats of fusion of fluoride salt mixtures suitable for thermal energy storage applications

NASA Technical Reports Server (NTRS)

Misra, A. K.; Whittenberger, J. D.

1986-01-01

The heats of fusion of several fluoride salt mixtures with melting points greater than 973 K were estimated from a coupled analysis of the available thermodynamic data and phase diagrams. Simple binary eutectic systems with and without terminal solid solutions, binary eutectics with congruent melting intermediate phases, and ternary eutectic systems were considered. Several combinations of salts were identified, most notable the eutectics LiF-22CaF2 and NaF-60MgF2 which melt at 1039 and 1273 K respectively which posses relatively high heats of fusion/gm (greater than 0.7 kJ/g). Such systems would seemingly be ideal candidates for the light weight, high energy storage media required by the thermal energy storage unit in advanced solar dynamic power systems envisioned for the future space missions.

Work extraction and thermodynamics for individual quantum systems

NASA Astrophysics Data System (ADS)

Skrzypczyk, Paul; Short, Anthony J.; Popescu, Sandu

2014-06-01

Thermodynamics is traditionally concerned with systems comprised of a large number of particles. Here we present a framework for extending thermodynamics to individual quantum systems, including explicitly a thermal bath and work-storage device (essentially a ‘weight’ that can be raised or lowered). We prove that the second law of thermodynamics holds in our framework, and gives a simple protocol to extract the optimal amount of work from the system, equal to its change in free energy. Our results apply to any quantum system in an arbitrary initial state, in particular including non-equilibrium situations. The optimal protocol is essentially reversible, similar to classical Carnot cycles, and indeed, we show that it can be used to construct a quantum Carnot engine.

Work extraction and thermodynamics for individual quantum systems.

PubMed

Skrzypczyk, Paul; Short, Anthony J; Popescu, Sandu

2014-06-27

Thermodynamics is traditionally concerned with systems comprised of a large number of particles. Here we present a framework for extending thermodynamics to individual quantum systems, including explicitly a thermal bath and work-storage device (essentially a 'weight' that can be raised or lowered). We prove that the second law of thermodynamics holds in our framework, and gives a simple protocol to extract the optimal amount of work from the system, equal to its change in free energy. Our results apply to any quantum system in an arbitrary initial state, in particular including non-equilibrium situations. The optimal protocol is essentially reversible, similar to classical Carnot cycles, and indeed, we show that it can be used to construct a quantum Carnot engine.

Consistency of Post-Newtonian Waveforms with Numerical Relativity

NASA Technical Reports Server (NTRS)

Baker, John G.; vanMeter, James R.; McWilliams, Sean T.; Centrella, Joan; Kelly, Bernard J.

2007-01-01

General relativity predicts the gravitational radiation signatures of mergers of compact binaries,such as coalescing binary black hole systems. Derivations of waveform predictions for such systems are required for optimal scientific analysis of observational gravitational wave data, and have so far been achieved primarily with the aid of the post-Newtonian (PN) approximation. The quaIity of this treatment is unclear, however, for the important late inspiral portion. We derive late-inspiral wave forms via a complementary approach, direct numerical simulation of Einstein's equations, which has recently matured sufficiently for such applications. We compare waveform phasing from simulations covering the last approximately 14 cycles of gravitational radiation from an equal-mass binary system of nonspinning black holes with corresponding 3PN and 3.5PN waveforms. We find phasing agreement consistent with internal error estimates based in either approach, at the level of one radian over approximately 10 cycles. The result suggests that PN waveforms for this system are effective roughly until the system reaches its last stable orbit just prior to the final merger.

Consistency of Post-Newtonian Waveforms with Numerical Relativity

NASA Technical Reports Server (NTRS)

Baker, John G.; vanMeter, James R.; McWilliams, Sean T.; Cewntrella, Joan; Kelly, Bernard J.

2006-01-01

General relativity predicts the gravitational radiation signatures of mergers of compact binaries, such as coalescing binary black hole systems. Derivations of waveform predictions for such systems are required for optimal scientific analysis of observational gravitational wave data, and have so far been achieved primarily with the aid of the post-Newtonian (PN) approximation. The quality of this treatment is unclear, however, for the important late inspiral portion. We derive late-inspiral waveforms via a complementary approach, direct numerical simulation of Einstein's equations, which has recently matured sufficiently for such applications. We compare waveform phasing from simulations covering the last approximately 14 cycles of gravitational radiation from an equal-mass binary system of nonspinning black holes with the corresponding 3PN and 3.5PN orbital phasing. We find agreement consistent with internal error estimates based on either approach at the level of one radian over approximately 10 cycles. The result suggests that PN waveforms for this system are effective roughly until the system reaches its last stable orbit just prior to the final merger/

Application of exergetic sustainability index to a nano-scale irreversible Brayton cycle operating with ideal Bose and Fermi gasses

NASA Astrophysics Data System (ADS)

Açıkkalp, Emin; Caner, Necmettin

2015-09-01

In this study, a nano-scale irreversible Brayton cycle operating with quantum gasses including Bose and Fermi gasses is researched. Developments in the nano-technology cause searching the nano-scale machines including thermal systems to be unavoidable. Thermodynamic analysis of a nano-scale irreversible Brayton cycle operating with Bose and Fermi gasses was performed (especially using exergetic sustainability index). In addition, thermodynamic analysis involving classical evaluation parameters such as work output, exergy output, entropy generation, energy and exergy efficiencies were conducted. Results are submitted numerically and finally some useful recommendations were conducted. Some important results are: entropy generation and exergetic sustainability index are affected mostly for Bose gas and power output and exergy output are affected mostly for the Fermi gas by x. At the high temperature conditions, work output and entropy generation have high values comparing with other degeneracy conditions.

Thermodynamic Modeling and Mechanical Design of a Liquid Nitrogen Vaporization and Pressure Building Device

NASA Astrophysics Data System (ADS)

Leege, Brian J.

The design of a liquid nitrogen vaporization and pressure building device that has zero product waste while recovering some of its stored energy is of interest for the cost reduction of nitrogen for use in industrial processes. Current devices may waste up to 30% of the gaseous nitrogen product by venting it to atmosphere. Furthermore, no attempt is made to recover the thermal energy available in the coldness of the cryogen. A seven step cycle with changing volumes and ambient heat addition is proposed, eliminating all product waste and providing the means of energy recovery from the nitrogen. This thesis discusses the new thermodynamic cycle and modeling as well as the mechanical design and testing of a prototype device. The prototype was able to achieve liquid nitrogen vaporization and pressurization up to 1000 psi, while full cycle validation is ongoing with promising initial results.

Improvements to the ejector expansion refrigeration cycle

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

Menegay, P.; Kornhauser, A.A.

1996-12-31

The ejector expansion refrigeration cycle (EERC) is a variant of the standard vapor compression cycle in which an ejector is used to recover part of the work that would otherwise be lost in the expansion valve. In initial testing EERC performance was poor, mainly due to thermodynamic non-equilibrium conditions in the ejector motive nozzle. Modifications were made to correct this problem, and significant performance improvements were found.

How Is the Freezing Point of a Binary Mixture of Liquids Related to the Composition? A Guided Inquiry Experiment

ERIC Educational Resources Information Center

Hunnicutt, Sally S.; Grushow, Alexander; Whitnell, Rob

2017-01-01

The principles of process-oriented guided inquiry learning (POGIL) are applied to a binary solid-liquid mixtures experiment. Over the course of two learning cycles, students predict, measure, and model the phase diagram of a mixture of fatty acids. The enthalpy of fusion of each fatty acid is determined from the results. This guided inquiry…

Thermal Stability of Nanocrystalline Alloys by Solute Additions and A Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Saber, Mostafa

Nanocrystalline alloys show superior properties due to their exceptional microstructure. Thermal stability of these materials is a critical aspect. It is well known that grain boundaries in nanocrystalline microstructures cause a significant increase in the total free energy of the system. A driving force provided to reduce this excess free energy can cause grain growth. The presence of a solute addition within a nanocrystalline alloy can lead to the thermal stability. Kinetic and thermodynamic stabilization are the two basic mechanisms with which stability of a nanoscale grain size can be achieved at high temperatures. The basis of this thesis is to study the effect of solute addition on thermal stability of nanocrystalline alloys. The objective is to determine the effect of Zr addition on the thermal stability of mechanically alloyed nanocrysatillne Fe-Cr and Fe-Ni alloys. In Fe-Cr-Zr alloy system, nanoscale grain size stabilization was maintained up to 900 °C by adding 2 at% Zr. Kinetic pinning by intermetallic particles in the nanoscale range was identified as a primary mechanism of thermal stabilization. In addition to the grain size strengthening, intermetallic particles also contribute to strengthening mechanisms. The analysis of microhardness, XRD data, and measured grain sizes from TEM micrographs suggested that both thermodynamic and kinetic mechanisms are possible mechanisms. It was found that alpha → gamma phase transformation in Fe-Cr-Zr system does not influence the grain size stabilization. In the Fe-Ni-Zr alloy system, it was shown that the grain growth in Fe-8Ni-1Zr alloy is much less than that of pure Fe and Fe-8Ni alloy at elevated temperatures. The microstructure of the ternary Fe-8Ni-1Zr alloy remains in the nanoscale range up to 700 °C. Using an in-situ TEM study, it was determined that drastic grain growth occurs when the alpha → gamma phase transformation occurs. Accordingly, there can be a synergistic relationship between grain growth and alpha → gamma phase transformation in Fe-Ni-Zr alloys. In addition to the experimental study of thermal stabilization of nanocrystalline Fe-Cr-Zr or Fe-Ni-Zr alloys, the thesis presented here developed a new predictive model, applicable to strongly segregating solutes, for thermodynamic stabilization of binary alloys. This model can serve as a benchmark for selecting solute and evaluating the possible contribution of stabilization. Following a regular solution model, both the chemical and elastic strain energy contributions are combined to obtain the mixing enthalpy. The total Gibbs free energy of mixing is then minimized with respect to simultaneous variations in the grain boundary volume fraction and the solute concentration in the grain boundary and the grain interior. The Lagrange multiplier method was used to obtained numerical solutions. Application are given for the temperature dependence of the grain size and the grain boundary solute excess for selected binary system where experimental results imply that thermodynamic stabilization could be operative. This thesis also extends the binary model to a new model for thermodynamic stabilization of ternary nanocrystalline alloys. It is applicable to strongly segregating size-misfit solutes and uses input data available in the literature. In a same manner as the binary model, this model is based on a regular solution approach such that the chemical and elastic strain energy contributions are incorporated into the mixing enthalpy DeltaHmix, and the mixing entropy DeltaSmix is obtained using the ideal solution approximation. The Gibbs mixing free energy Delta Gmix is then minimized with respect to simultaneous variations in grain growth and solute segregation parameters. The Lagrange multiplier method is similarly used to obtain numerical solutions for the minimum Delta Gmix. The temperature dependence of the nanocrystalline grain size and interfacial solute excess can be obtained for selected ternary systems. As an example, model predictions are compared to experimental results for Fe-Cr-Zr and Fe-Ni-Zr alloy systems. Consistency between the experimental results and the present model predictions provide a more rigorous criterion for investigating thermal stabilization. However, other possible contributions for grain growth stabilization should still be considered.

Laser engines operating by resonance absorption. [thermodynamic feasibility study

NASA Technical Reports Server (NTRS)

Garbuny, M.; Pechersky, M. J.

1976-01-01

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

Proceedings of Symposium on Energy Engineering in the 21st Century (SEE 2000). Volume Four

DTIC Science & Technology

2000-01-13

Significantly Varying Demand of Heat and Power 1347 D. Hein and K. Kwanka T2. Thermodynamic Analysis and Sensitivity Studies on Braysson cycle Using...to Volumes 1-4 T. Cycle Analysis 1346 CHENG CYCLE COGENERATION FOR A SIGNIFICANTLY VARYING DEMAND OF HEAT AND POWER Dietmar Hein, Klaus Kwanka...significantly varying demand of heat and power a Cheng Cycle gas turbine cogeneration plant was installed. By injecting steam, produced by the heat

Analysis of Pulsating Components in the Eclipsing Binary Systems LT Herculis, RZ Microscopii, LY Puppis, V632 Scorpii, and V638 Scorpii

NASA Astrophysics Data System (ADS)

Streamer, M.; Bohlsen, T.; Ogmen, Y.

2016-06-01

Eclipsing binary stars are especially valuable for studies of stellar evolution. If pulsating components are also present then the stellar interior can be studied using asteroseismology techniques. We present photometric data and the analysis of the delta Scuti pulsations that we have discovered in five eclipsing binary systems. The systems are: LT Herculis, RZ Microscopii, LY Puppis, V632 Scorpii and V638 Scorpii. The dominant pulsation frequencies range between 13 - 29 cycles per day with semi-amplitudes of 4 - 20 millimagnitudes.

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.

Irreversible thermodynamic analysis and application for molecular heat engines

NASA Astrophysics Data System (ADS)

Lucia, Umberto; Açıkkalp, Emin

2017-09-01

Is there a link between the macroscopic approach to irreversibility and microscopic behaviour of the systems? Consumption of free energy keeps the system away from a stable equilibrium. Entropy generation results from the redistribution of energy, momentum, mass and charge. This concept represents the essence of the thermodynamic approach to irreversibility. Irreversibility is the result of the interaction between systems and their environment. The aim of this paper is to determine lost works in a molecular engine and compare results with macro (classical) heat engines. Firstly, irreversible thermodynamics are reviewed for macro and molecular cycles. Secondly, irreversible thermodynamics approaches are applied for a quantum heat engine with -1/2 spin system. Finally, lost works are determined for considered system and results show that macro and molecular heat engines obey same limitations. Moreover, a quantum thermodynamic approach is suggested in order to explain the results previously obtained from an atomic viewpoint.

Irreversible thermodynamics of open chemical networks. I. Emergent cycles and broken conservation laws

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

Polettini, Matteo, E-mail: matteo.polettini@uni.lu; Esposito, Massimiliano

In this paper and Paper II, we outline a general framework for the thermodynamic description of open chemical reaction networks, with special regard to metabolic networks regulating cellular physiology and biochemical functions. We first introduce closed networks “in a box”, whose thermodynamics is subjected to strict physical constraints: the mass-action law, elementarity of processes, and detailed balance. We further digress on the role of solvents and on the seemingly unacknowledged property of network independence of free energy landscapes. We then open the system by assuming that the concentrations of certain substrate species (the chemostats) are fixed, whether because promptly regulatedmore » by the environment via contact with reservoirs, or because nearly constant in a time window. As a result, the system is driven out of equilibrium. A rich algebraic and topological structure ensues in the network of internal species: Emergent irreversible cycles are associated with nonvanishing affinities, whose symmetries are dictated by the breakage of conservation laws. These central results are resumed in the relation a + b = s{sup Y} between the number of fundamental affinities a, that of broken conservation laws b and the number of chemostats s{sup Y}. We decompose the steady state entropy production rate in terms of fundamental fluxes and affinities in the spirit of Schnakenberg's theory of network thermodynamics, paving the way for the forthcoming treatment of the linear regime, of efficiency and tight coupling, of free energy transduction, and of thermodynamic constraints for network reconstruction.« less

Irreversible thermodynamics of open chemical networks. I. Emergent cycles and broken conservation laws.

PubMed

Polettini, Matteo; Esposito, Massimiliano

2014-07-14

In this paper and Paper II, we outline a general framework for the thermodynamic description of open chemical reaction networks, with special regard to metabolic networks regulating cellular physiology and biochemical functions. We first introduce closed networks "in a box", whose thermodynamics is subjected to strict physical constraints: the mass-action law, elementarity of processes, and detailed balance. We further digress on the role of solvents and on the seemingly unacknowledged property of network independence of free energy landscapes. We then open the system by assuming that the concentrations of certain substrate species (the chemostats) are fixed, whether because promptly regulated by the environment via contact with reservoirs, or because nearly constant in a time window. As a result, the system is driven out of equilibrium. A rich algebraic and topological structure ensues in the network of internal species: Emergent irreversible cycles are associated with nonvanishing affinities, whose symmetries are dictated by the breakage of conservation laws. These central results are resumed in the relation a + b = s(Y) between the number of fundamental affinities a, that of broken conservation laws b and the number of chemostats s(Y). We decompose the steady state entropy production rate in terms of fundamental fluxes and affinities in the spirit of Schnakenberg's theory of network thermodynamics, paving the way for the forthcoming treatment of the linear regime, of efficiency and tight coupling, of free energy transduction, and of thermodynamic constraints for network reconstruction.

A non-linear irreversible thermodynamic perspective on organic pigment proliferation and biological evolution

NASA Astrophysics Data System (ADS)

Michaelian, K.

2013-12-01

The most important thermodynamic work performed by life today is the dissipation of the solar photon flux into heat through organic pigments in water. From this thermodynamic perspective, biological evolution is thus just the dispersal of organic pigments and water throughout Earth's surface, while adjusting the gases of Earth's atmosphere to allow the most intense part of the solar spectrum to penetrate the atmosphere and reach the surface to be intercepted by these pigments. The covalent bonding of atoms in organic pigments provides excited levels compatible with the energies of these photons. Internal conversion through vibrational relaxation to the ground state of these excited molecules when in water leads to rapid dissipation of the solar photons into heat, and this is the major source of entropy production on Earth. A non-linear irreversible thermodynamic analysis shows that the proliferation of organic pigments on Earth is a direct consequence of the pigments catalytic properties in dissipating the solar photon flux. A small part of the energy of the photon goes into the production of more organic pigments and supporting biomass, while most of the energy is dissipated and channeled into the hydrological cycle through the latent heat of vaporization of surface water. By dissipating the surface to atmosphere temperature gradient, the hydrological cycle further increases the entropy production of Earth. This thermodynamic perspective of solar photon dissipation by life has implications to the possibility of finding extra-terrestrial life in our solar system and the Universe.

Irreversible thermodynamics of open chemical networks. I. Emergent cycles and broken conservation laws

NASA Astrophysics Data System (ADS)

Polettini, Matteo; Esposito, Massimiliano

2014-07-01

In this paper and Paper II, we outline a general framework for the thermodynamic description of open chemical reaction networks, with special regard to metabolic networks regulating cellular physiology and biochemical functions. We first introduce closed networks "in a box", whose thermodynamics is subjected to strict physical constraints: the mass-action law, elementarity of processes, and detailed balance. We further digress on the role of solvents and on the seemingly unacknowledged property of network independence of free energy landscapes. We then open the system by assuming that the concentrations of certain substrate species (the chemostats) are fixed, whether because promptly regulated by the environment via contact with reservoirs, or because nearly constant in a time window. As a result, the system is driven out of equilibrium. A rich algebraic and topological structure ensues in the network of internal species: Emergent irreversible cycles are associated with nonvanishing affinities, whose symmetries are dictated by the breakage of conservation laws. These central results are resumed in the relation a + b = sY between the number of fundamental affinities a, that of broken conservation laws b and the number of chemostats sY. We decompose the steady state entropy production rate in terms of fundamental fluxes and affinities in the spirit of Schnakenberg's theory of network thermodynamics, paving the way for the forthcoming treatment of the linear regime, of efficiency and tight coupling, of free energy transduction, and of thermodynamic constraints for network reconstruction.

LH2 tank pressure control by thermodynamic vent system (TVS) at zero gravity

NASA Astrophysics Data System (ADS)

Wang, B.; Huang, Y. H.; Chen, Z. C.; Wu, J. Y.; Li, P.; Sun, P. J.

2017-02-01

Thermodynamic vent system (TVS) is employed for pressure control of propellant tanks at zero gravity. An analytical lumped parameter model is developed to predict pressure variation in an 18.09 m3 liquid hydrogen tank equipped with TVS. Mathematical simulations are carried out assuming tank is filled up to 75% volume (liquid mass equals to 945 kg) and is subjected to heat flux of 0.76 W/m2. Tank pressure controls at 165.5-172.4, 165.5-179.3 and 165.5-182.2 kPa are compared with reference to number of vent cycles, vent duration per cycle and loss of hydrogen. Analysis results indicate that the number of vent cycles significantly decreases from 62 to 21 when tank pressure control increases from 6.9 to 20.4 kPa. Also, duration of vent cycle increases from 63 to 152 and cycle duration decreases from 3920 to 3200 s. Further, the analysis result suggests that LH2 evaporation loss per day decreases from 0.17 to 0.14%. Based on the results of analysis, TVS is found effective in controlling the propellant tank pressure in zero gravity.

Improved Estimates of Thermodynamic Parameters

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1982-01-01

Techniques refined for estimating heat of vaporization and other parameters from molecular structure. Using parabolic equation with three adjustable parameters, heat of vaporization can be used to estimate boiling point, and vice versa. Boiling points and vapor pressures for some nonpolar liquids were estimated by improved method and compared with previously reported values. Technique for estimating thermodynamic parameters should make it easier for engineers to choose among candidate heat-exchange fluids for thermochemical cycles.

Thermodynamic Cycle Analysis of Magnetohydrodynamic-Bypass Hypersonic Airbreathing Engines

NASA Technical Reports Server (NTRS)

Litchford, R. J.; Cole, J. W.; Bityurin, V. A.; Lineberry, J. T.

2000-01-01

The prospects for realizing a magnetohydrodynamic (MHD) bypass hypersonic airbreathing engine are examined from the standpoint of fundamental thermodynamic feasibility. The MHD-bypass engine, first proposed as part of the Russian AJAX vehicle concept, is based on the idea of redistributing energy between various stages of the propulsion system flow train. The system uses an MHD generator to extract a portion of the aerodynamic heating energy from the inlet and an MHD accelerator to reintroduce this power as kinetic energy in the exhaust stream. In this way, the combustor entrance Mach number can be limited to a specified value even as the flight Mach number increases. Thus, the fuel and air can be efficiently mixed and burned within a practical combustor length, and the flight Mach number operating envelope can be extended. In this paper, we quantitatively assess the performance potential and scientific feasibility of MHD-bypass engines using a simplified thermodynamic analysis. This cycle analysis, based on a thermally and calorically perfect gas, incorporates a coupled MHD generator-accelerator system and accounts for aerodynamic losses and thermodynamic process efficiencies in the various engin components. It is found that the flight Mach number range can be significantly extended; however, overall performance is hampered by non-isentropic losses in the MHD devices.

Thermodynamics of natural selection III: Landauer's principle in computation and chemistry.

PubMed

Smith, Eric

2008-05-21

This is the third in a series of three papers devoted to energy flow and entropy changes in chemical and biological processes, and their relations to the thermodynamics of computation. The previous two papers have developed reversible chemical transformations as idealizations for studying physiology and natural selection, and derived bounds from the second law of thermodynamics, between information gain in an ensemble and the chemical work required to produce it. This paper concerns the explicit mapping of chemistry to computation, and particularly the Landauer decomposition of irreversible computations, in which reversible logical operations generating no heat are separated from heat-generating erasure steps which are logically irreversible but thermodynamically reversible. The Landauer arrangement of computation is shown to produce the same entropy-flow diagram as that of the chemical Carnot cycles used in the second paper of the series to idealize physiological cycles. The specific application of computation to data compression and error-correcting encoding also makes possible a Landauer analysis of the somewhat different problem of optimal molecular recognition, which has been considered as an information theory problem. It is shown here that bounds on maximum sequence discrimination from the enthalpy of complex formation, although derived from the same logical model as the Shannon theorem for channel capacity, arise from exactly the opposite model for erasure.

Structural properties of CuAu nanoparticles with different type. Molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Chepkasov, I. V.; Baidyshev, V. S.; Baev, A. Y.

2018-05-01

The paper is devoted to the thermal stability of a CuAu nanoparticles structure (D=5 nm) of various type (binary alloy, core-shell, "Janus" type) and of various percentage of copper atoms. The simulation was carried out with molecular dynamics, using the embedded atom potential. The authors defined the most preferable structural options from the standpoint of thermodynamics, as well as studied in detail the influence of different temperatures on the structural stability of CuAu nanoparticles.

Low temperature binary gas mixtures

NASA Astrophysics Data System (ADS)

McIntosh, Glen E.; Leonard, Kenneth R.

2017-12-01

Application of partial pressure technology to combinations of one gas above its critical temperature (helium) mixed with a two-phase liquid (nitrogen) can result in liquid temperatures down to and below the nitrogen triple point. The thermodynamics of this process is developed and an experimental apparatus is described which was used to produce a helium/nitrogen bath temperature of 59.17 K, 4 K lower than the 63.2 K nitrogen triple point and lower than any liquid nitrogen temperature reported in the literature.

The thermochemical characteristics of solution of phenol and benzoic acid in water-dimethylsulfoxide and water-acetonitrile mixtures

NASA Astrophysics Data System (ADS)

Zakharov, A. G.; Voronova, M. I.; Batov, D. V.; Smirnova, K. V.

2011-03-01

The solution of phenol and benzoic acid in water-dimethylsulfoxide (DMSO) and water-acetonitrile (AN) mixtures was studied. As distinct from benzoic acid, the thermodynamic characteristics of solution of phenol sharply change at concentrations corresponding to a change in the character of cluster formation in water-DMSO and water-AN mixtures. Differences in the solvation of phenol and benzoic acid are explained by different mechanisms of the interaction of the solutes with clusters existing in binary mixtures.

An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

NASA Technical Reports Server (NTRS)

Chao, R. E.; Cox, K. E.

1975-01-01

A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

More bang for your buck: super-adiabatic quantum engines.

PubMed

del Campo, A; Goold, J; Paternostro, M

2014-08-28

The practical untenability of the quasi-static assumption makes any realistic engine intrinsically irreversible and its operating time finite, thus implying friction effects at short cycle times. An important technological goal is thus the design of maximally efficient engines working at the maximum possible power. We show that, by utilising shortcuts to adiabaticity in a quantum engine cycle, one can engineer a thermodynamic cycle working at finite power and zero friction. Our findings are illustrated using a harmonic oscillator undergoing a quantum Otto cycle.

More bang for your buck: Super-adiabatic quantum engines

PubMed Central

Campo, A. del; Goold, J.; Paternostro, M.

2014-01-01

The practical untenability of the quasi-static assumption makes any realistic engine intrinsically irreversible and its operating time finite, thus implying friction effects at short cycle times. An important technological goal is thus the design of maximally efficient engines working at the maximum possible power. We show that, by utilising shortcuts to adiabaticity in a quantum engine cycle, one can engineer a thermodynamic cycle working at finite power and zero friction. Our findings are illustrated using a harmonic oscillator undergoing a quantum Otto cycle. PMID:25163421

How do accretion discs break?

NASA Astrophysics Data System (ADS)

Dogan, Suzan

2016-07-01

Accretion discs are common in binary systems, and they are often found to be misaligned with respect to the binary orbit. The gravitational torque from a companion induces nodal precession in misaligned disc orbits. In this study, we first calculate whether this precession is strong enough to overcome the internal disc torques communicating angular momentum. We compare the disc precession torque with the disc viscous torque to determine whether the disc should warp or break. For typical parameters precession wins: the disc breaks into distinct planes that precess effectively independently. To check our analytical findings, we perform 3D hydrodynamical numerical simulations using the PHANTOM smoothed particle hydrodynamics code, and confirm that disc breaking is widespread and enhances accretion on to the central object. For some inclinations, the disc goes through strong Kozai cycles. Disc breaking promotes markedly enhanced and variable accretion and potentially produces high-energy particles or radiation through shocks. This would have significant implications for all binary systems: e.g. accretion outbursts in X-ray binaries and fuelling supermassive black hole (SMBH) binaries. The behaviour we have discussed in this work is relevant to a variety of astrophysical systems, for example X-ray binaries, where the disc plane may be tilted by radiation warping, SMBH binaries, where accretion of misaligned gas can create effectively random inclinations and protostellar binaries, where a disc may be misaligned by a variety of effects such as binary capture/exchange, accretion after binary formation.

Computer program for determining the thermodynamic properties of Freon refrigerants

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

Riemer, D.H.; Jacobs, H.R.; Boehm, R.F.

1977-12-01

This program was written to be used as a subroutine. The program determines the thermodynamics of Freon refrigerants. The following refrigerants can be analyzed F-11, F-12, F-13, F-14, F-21, F-22, F-23, F-113, and F-114. The subroutine can evaluate a thermodynamic state for these refrigerants given any of the following pairs of state quantities: pressure and quality, pressure and entropy, pressure and enthalpy, temperature and quality, temperature and specific volume, and temperature and pressure. These six pairs of knowns allow the user to analyze any thermodynamic cycle utilizing a refrigerant as the working fluid. The Downing form of the Martin equationmore » of state was used. This report contains a brief description, flow chart and listing of all subroutines required.« less

Computer program for determining the thermodynamic properties of freon refrigerants

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

Riemer, D.H.; Jacobs, H.R.; Boehm, R.F.

1976-07-01

This program was written to be used as a subroutine. The program determines the thermodynamics of Freon refrigerants. The following refrigerants can be analyzed F-11, F-12, F-13, F-14, F-21, F-22, F-23, F-113, and F-114. The subroutine can evaluate a thermodynamic state for these refrigerants given any of the following pairs of state quantities: pressure and quality, pressure and entropy, pressure and enthalpy, temperature and quality, temperature and specific volume and temperature and pressure. These six pairs of knowns allow the user to analyze any thermodynamic cycle utilizing a refrigerant as the working fluid. The Downing form of the Martin equationmore » of state was used. A brief description, flow chart, and listing of all subroutines required are presented.« less

Using Articulate Virtual Laboratories in Teaching Energy Conversion at the U.S. Naval Academy.

ERIC Educational Resources Information Center

Wu, C.

1998-01-01

The Mechanical Engineering Department at the U.S. Naval Academy is currently evaluating a new teaching method which uses computer software. Utilizing the thermodynamic-based software CyclePad, Intelligent Computer Aided Instruction is incorporated in an advanced energy conversion course for Mechanical Engineering students. The CyclePad software…

Thermodynamic Analysis of a Mixed Refrigerant Ejector Refrigeration Cycle Operating with Two Vapor-liquid Separators

NASA Astrophysics Data System (ADS)

Tan, Yingying; Chen, Youming; Wang, Lin

2018-06-01

A mixed refrigerant ejector refrigeration cycle operating with two-stage vapor-liquid separators (MRERC2) is proposed to obtain refrigeration temperature at -40°C. The thermodynamic investigations on performance of MRERC2 using zeotropic mixture refrigerant R23/R134a are performed, and the comparisons of cycle performance between MRERC2 and MRERC1 (MRERC with one-stage vapor-liquid separator) are conducted. The results show that MRERC2 can achieve refrigeration temperature varying between -23.9°C and -42.0°C when ejector pressure ratio ranges from 1.6 to 2.3 at the generation temperature of 57.3-84.9°C. The parametric analysis indicates that increasing condensing temperature decreases coefficient of performance ( COP) of MRERC2, and increasing ejector pressure ratio and mass fraction of the low boiling point component in the mixed refrigerant can improve COP of MRERC2. The MRERC2 shows its potential in utilizing low grade thermal energy as driving power to obtain low refrigeration temperature for the ejector refrigeration cycle.

Not all counterclockwise thermodynamic cycles are refrigerators

NASA Astrophysics Data System (ADS)

Dickerson, R. H.; Mottmann, J.

2016-06-01

Clockwise cycles on PV diagrams always represent heat engines. It is therefore tempting to assume that counterclockwise cycles always represent refrigerators. This common assumption is incorrect: most counterclockwise cycles cannot be refrigerators. This surprising result is explored here for quasi-static ideal gas cycles, and the necessary conditions for refrigeration cycles are clarified. Three logically self-consistent criteria can be used to determine if a counterclockwise cycle is a refrigerator. The most fundamental test compares the counterclockwise cycle with a correctly determined corresponding Carnot cycle. Other criteria we employ include a widely accepted description of the functional behavior of refrigerators, and a corollary to the second law that limits a refrigerator's coefficient of performance.

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.

Electrical Maxwell Demon and Szilard Engine Utilizing Johnson Noise, Measurement, Logic and Control

PubMed Central

Kish, Laszlo Bela; Granqvist, Claes-Göran

2012-01-01

We introduce a purely electrical version of Maxwell's demon which does not involve mechanically moving parts such as trapdoors, etc. It consists of a capacitor, resistors, amplifiers, logic circuitry and electronically controlled switches and uses thermal noise in resistors (Johnson noise) to pump heat. The only types of energy of importance in this demon are electrical energy and heat. We also demonstrate an entirely electrical version of Szilard's engine, i.e., an information-controlled device that can produce work by employing thermal fluctuations. The only moving part is a piston that executes work, and the engine has purely electronic controls and it is free of the major weakness of the original Szilard engine in not requiring removal and repositioning the piston at the end of the cycle. For both devices, the energy dissipation in the memory and other binary informatics components are insignificant compared to the exponentially large energy dissipation in the analog part responsible for creating new information by measurement and decision. This result contradicts the view that the energy dissipation in the memory during erasure is the most essential dissipation process in a demon. Nevertheless the dissipation in the memory and information processing parts is sufficient to secure the Second Law of Thermodynamics. PMID:23077525

Electrical Maxwell demon and Szilard engine utilizing Johnson noise, measurement, logic and control.

PubMed

Kish, Laszlo Bela; Granqvist, Claes-Göran

2012-01-01

We introduce a purely electrical version of Maxwell's demon which does not involve mechanically moving parts such as trapdoors, etc. It consists of a capacitor, resistors, amplifiers, logic circuitry and electronically controlled switches and uses thermal noise in resistors (Johnson noise) to pump heat. The only types of energy of importance in this demon are electrical energy and heat. We also demonstrate an entirely electrical version of Szilard's engine, i.e., an information-controlled device that can produce work by employing thermal fluctuations. The only moving part is a piston that executes work, and the engine has purely electronic controls and it is free of the major weakness of the original Szilard engine in not requiring removal and repositioning the piston at the end of the cycle. For both devices, the energy dissipation in the memory and other binary informatics components are insignificant compared to the exponentially large energy dissipation in the analog part responsible for creating new information by measurement and decision. This result contradicts the view that the energy dissipation in the memory during erasure is the most essential dissipation process in a demon. Nevertheless the dissipation in the memory and information processing parts is sufficient to secure the Second Law of Thermodynamics.

Refractive index of liquid mixtures: theory and experiment.

PubMed

Reis, João Carlos R; Lampreia, Isabel M S; Santos, Angela F S; Moita, Maria Luísa C J; Douhéret, Gérard

2010-12-03

An innovative approach is presented to interpret the refractive index of binary liquid mixtures. The concept of refractive index "before mixing" is introduced and shown to be given by the volume-fraction mixing rule of the pure-component refractive indices (Arago-Biot formula). The refractive index of thermodynamically ideal liquid mixtures is demonstrated to be given by the volume-fraction mixing rule of the pure-component squared refractive indices (Newton formula). This theoretical formulation entails a positive change of refractive index upon ideal mixing, which is interpreted in terms of dissimilar London dispersion forces centred in the dissimilar molecules making up the mixture. For real liquid mixtures, the refractive index of mixing and the excess refractive index are introduced in a thermodynamic manner. Examples of mixtures are cited for which excess refractive indices and excess molar volumes show all of the four possible sign combinations, a fact that jeopardises the finding of a general equation linking these two excess properties. Refractive indices of 69 mixtures of water with the amphiphile (R,S)-1-propoxypropan-2-ol are reported at five temperatures in the range 283-303 K. The ideal and real refractive properties of this binary system are discussed. Pear-shaped plots of excess refractive indices against excess molar volumes show that extreme positive values of excess refractive index occur at a substantially lower mole fraction of the amphiphile than extreme negative values of excess molar volume. Analysis of these plots provides insights into the mixing schemes that occur in different composition segments. A nearly linear variation is found when Balankina's ratios between excess and ideal values of refractive indices are plotted against ratios between excess and ideal values of molar volumes. It is concluded that, when coupled with volumetric properties, the new thermodynamic functions defined for the analysis of refractive indices of liquid mixtures give important complementary information on the mixing process over the whole composition range.

Phase transformations at interfaces: Observations from atomistic modeling

DOE PAGES

Frolov, T.; Asta, M.; Mishin, Y.

2016-10-01

Here, we review the recent progress in theoretical understanding and atomistic computer simulations of phase transformations in materials interfaces, focusing on grain boundaries (GBs) in metallic systems. Recently developed simulation approaches enable the search and structural characterization of GB phases in single-component metals and binary alloys, calculation of thermodynamic properties of individual GB phases, and modeling of the effect of the GB phase transformations on GB kinetics. Atomistic simulations demonstrate that the GB transformations can be induced by varying the temperature, loading the GB with point defects, or varying the amount of solute segregation. The atomic-level understanding obtained from suchmore » simulations can provide input for further development of thermodynamics theories and continuous models of interface phase transformations while simultaneously serving as a testing ground for validation of theories and models. They can also help interpret and guide experimental work in this field.« less

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

Viscous fingering with partially miscible fluids

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2017-10-01

Viscous fingering—the fluid-mechanical instability that takes place when a low-viscosity fluid displaces a high-viscosity fluid—has traditionally been studied under either fully miscible or fully immiscible fluid systems. Here we study the impact of partial miscibility (a common occurrence in practice) on the fingering dynamics. Through a careful design of the thermodynamic free energy of a binary mixture, we develop a phase-field model of fluid-fluid displacements in a Hele-Shaw cell for the general case in which the two fluids have limited (but nonzero) solubility into one another. We show, by means of high-resolution numerical simulations, that partial miscibility exerts a powerful control on the degree of fingering: fluid dissolution hinders fingering while fluid exsolution enhances fingering. We also show that, as a result of the interplay between compositional exchange and the hydrodynamic pattern-forming process, stronger fingering promotes the system to approach thermodynamic equilibrium more quickly.

Thermodynamic evaluation of oxygen behavior in Ti powder deoxidized by Ca reductant

NASA Astrophysics Data System (ADS)

Kim, Sun-Joong; Oh, Jung-Min; Lim, Jae-Won

2016-07-01

To produce low oxygen Ti powder of less than 1000 mass ppm, commercial Ti powder was deoxidized by two types of Ca reductants: a solid Ca and a Ca vapor. Compared with the iso-oxygen partial pressure in the Ti-O binary phase diagram, the PO2 in the raw Ti powder increased with temperature compared to the reduction reaction of Ca. Therefore, the O2 content in the Ti powder decreased as the deoxidation temperature increased from 873 K, showing a local minima at 1273 K. The oxygen concentration at 1373 K was greater than that at 1273 K because the oxygen solubility of the Ti powder was increased by the equilibrium relation between Ca and CaO. On the basis of the thermodynamic assessment, the deoxidation of Ti powder can be improved by increasing the temperature and lowering the oxygen solubility with the saturation of CaO.

Solid-solution aqueous-solution equilibria: thermodynamic theory and representation

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.

1990-01-01

Thorstenson and Plummer's (1977) "stoichiometric saturation' model is reviewed, and a general relation between stoichiometric saturation Kss constants and excess free energies of mixing is derived for a binary solid-solution B1-xCxA: GE = RT[ln Kss - xln(xKCA) - (l-x)ln((l-x)KBA)]. This equation allows a suitable excess free energy function, such as Guggenheim's (1937) sub-regular function, to be fitted from experimentally determined Kss constants. Solid-phase free energies and component activity-coefficients can then be determined from one or two fitted parameters and from the endmember solubility products KBA and KCA. A general form of Lippmann's (1977,1980) "solutus equation is derived from an examination of Lippmann's (1977,1980) "total solubility product' model. Lippmann's ??II or "total solubility product' variable is used to represent graphically not only thermodynamic equilibrium states and primary saturation states but also stoichiometric saturation and pure phase saturation states. -from Authors

Scheil-Gulliver Constituent Diagrams

NASA Astrophysics Data System (ADS)

Pelton, Arthur D.; Eriksson, Gunnar; Bale, Christopher W.

2017-06-01

During solidification of alloys, conditions often approach those of Scheil-Gulliver cooling in which it is assumed that solid phases, once precipitated, remain unchanged. That is, they no longer react with the liquid or with each other. In the case of equilibrium solidification, equilibrium phase diagrams provide a valuable means of visualizing the effects of composition changes upon the final microstructure. In the present study, we propose for the first time the concept of Scheil-Gulliver constituent diagrams which play the same role as that in the case of Scheil-Gulliver cooling. It is shown how these diagrams can be calculated and plotted by the currently available thermodynamic database computing systems that combine Gibbs energy minimization software with large databases of optimized thermodynamic properties of solutions and compounds. Examples calculated using the FactSage system are presented for the Al-Li and Al-Mg-Zn systems, and for the Au-Bi-Sb-Pb system and its binary and ternary subsystems.

Computation of thermodynamic and transport properties to predict thermophoretic effects in an argon-krypton mixture

NASA Astrophysics Data System (ADS)

Miller, Nicholas A. T.; Daivis, Peter J.; Snook, Ian K.; Todd, B. D.

2013-10-01

Thermophoresis is the movement of molecules caused by a temperature gradient. Here we report the results of a study of thermophoresis using non-equilibrium molecular dynamics simulations of a confined argon-krypton fluid subject to two different temperatures at thermostated walls. The resulting temperature profile between the walls is used along with the Soret coefficient to predict the concentration profile that develops across the channel. We obtain the Soret coefficient by calculating the mutual diffusion and thermal diffusion coefficients. We report an appropriate method for calculating the transport coefficients for binary systems, using the Green-Kubo integrals and radial distribution functions obtained from equilibrium molecular dynamics simulations of the bulk fluid. Our method has the unique advantage of separating the mutual diffusion and thermal diffusion coefficients, and calculating the sign and magnitude of their individual contributions to thermophoresis in binary mixtures.

The calculation of the phase equilibrium of the multicomponent hydrocarbon systems

NASA Astrophysics Data System (ADS)

Molchanov, D. A.

2018-01-01

Hydrocarbon mixtures filtration process simulation development has resulted in use of cubic equations of state of the van der Waals type to describe the thermodynamic properties of natural fluids under real thermobaric conditions. Binary hydrocarbon systems allow to simulate the fluids of different types of reservoirs qualitatively, what makes it possible to carry out the experimental study of their filtration features. Exploitation of gas-condensate reservoirs shows the possibility of existence of various two-phase filtration regimes, including self-oscillatory one, which occurs under certain values of mixture composition, temperature and pressure drop. Plotting of the phase diagram of the model mixture is required to determine these values. A software package to calculate the vapor-liquid equilibrium of binary systems using cubic equation of state of the van der Waals type has been created. Phase diagrams of gas-condensate model mixtures have been calculated.

Thermodynamic study on competitive solubilization of cholesterol and beta-sitosterol in bile salt micelles.

PubMed

Matsuoka, Keisuke; Hirosawa, Takashi; Honda, Chikako; Endo, Kazutoyo; Moroi, Yoshikiyo; Shibata, Osamu

2007-07-01

Differences in the preferential solubilization of cholesterol and competitive solubilizates (beta-sitosterol and aromatic compounds) in bile salt micelles was systematically studied by changing the molar ratio of cholesterol to competitive solubilizates. The cholesterol solubility in a mixed binary system (cholesterol and beta-sitosterol) was almost half that of the cholesterol alone system, regardless of the excess beta-sitosterol quantity added. On the other hand, the mutual solubilities of cholesterol and pyrene were not inhibited by their presence in binary mixed crystals. Finally, the cholesterol solubility was measured by changing the alkyl chain length of n-alkylbenzenes. When tetradecylbenzene was added to the bile solution, the cholesterol solubility decreased slightly and was below the original cholesterol solubility. Based on Gibbs energy change (DeltaG degrees ) for solubilization, chemicals that inhibit cholesterol solubility in their combined crystal systems showed a larger negative DeltaG degrees value than cholesterol alone.

Dielectric relaxation and hydrogen bonding interaction in xylitol-water mixtures using time domain reflectometry

NASA Astrophysics Data System (ADS)

Rander, D. N.; Joshi, Y. S.; Kanse, K. S.; Kumbharkhane, A. C.

2016-01-01

The measurements of complex dielectric permittivity of xylitol-water mixtures have been carried out in the frequency range of 10 MHz-30 GHz using a time domain reflectometry technique. Measurements have been done at six temperatures from 0 to 25 °C and at different weight fractions of xylitol (0 < W X ≤ 0.7) in water. There are different models to explain the dielectric relaxation behaviour of binary mixtures, such as Debye, Cole-Cole or Cole-Davidson model. We have observed that the dielectric relaxation behaviour of binary mixtures of xylitol-water can be well described by Cole-Davidson model having an asymmetric distribution of relaxation times. The dielectric parameters such as static dielectric constant and relaxation time for the mixtures have been evaluated. The molecular interaction between xylitol and water molecules is discussed using the Kirkwood correlation factor ( g eff ) and thermodynamic parameter.

Negative Entropy of Life

NASA Astrophysics Data System (ADS)

Goradia, Shantilal

2015-10-01

We modify Newtonian gravity to probabilistic quantum mechanical gravity to derive strong coupling. If this approach is valid, we should be able to extend it to the physical body (life) as follows. Using Boltzmann equation, we get the entropy of the universe (137) as if its reciprocal, the fine structure constant (ALPHA), is the hidden candidate representing the negative entropy of the universe which is indicative of the binary information as its basis (http://www.arXiv.org/pdf/physics0210040v5). Since ALPHA relates to cosmology, it must relate to molecular biology too, with the binary system as the fundamental source of information for the nucleotides of the DNA as implicit in the book by the author: ``Quantum Consciousness - The Road to Reality.'' We debate claims of anthropic principle based on the negligible variation of ALPHA and throw light on thermodynamics. We question constancy of G in multiple ways.

Solubility of Naproxen in Polyethylene Glycol 200 + Water Mixtures at Various Temperatures

PubMed Central

Panahi-Azar, Vahid; Soltanpour, Shahla; Martinez, Fleming; Jouyban, Abolghasem

2015-01-01

The solubility of naproxen in binary mixtures of polyethylene glycol 200 (PEG 200) + water at the temperature range from 298.0 K to 318.0 K were reported. The combinations of Jouyban-Acree model + van’t Hoff and Jouyban-Acree model + partial solubility parameters were used to predict the solubility of naproxen in PEG 200 + water mixtures at different temperatures. Combination of Jouyban-Acree model with van’t Hoff equation can be used to predict solubility in PEG 200 + water with only four solubility data in mono-solvents. The obtained solubility calculation errors vary from ~ 17 % up to 35 % depend on the number of required input data. Non-linear enthalpy-entropy compensation was found for naproxen in the investigated solvent system and the Jouyban−Acree model provides reasonably accurate mathematical descriptions of the thermodynamic data of naproxen in the investigated binary solvent systems. PMID:26664370

Evaluating the Effect from Constructing Binary Geothermal Power Units Based on Spent Petroleum and Gas Boreholes in the South Regions of Russia

NASA Astrophysics Data System (ADS)

Alkhasov, A. B.; Alkhasova, D. A.

2018-02-01

The article substantiates the possibility of efficiently harnessing the geothermal resources available in the North Caucasian region through constructing binary geothermal power plants (GeoTPPs) using idle petroleum and gas wells. The power capacities of GeoTPPs are evaluated, and the basic characteristics of these power plants in case of constructing them in the promising areas are determined. The overall useful GeoTPP capacity equal to approximately 330 MW can be obtained from using the entire fleet of idle wells available in these areas. Diagrams confirming the possibility of reaching the optimal flowrate of geothermal heat carrier circulating in the geothermal circulation system loop are presented. This flowrate corresponds to a binary GeoTPP's maximal useful power output. The article shows, taking the Ternair geothermal field as an example, that it is inefficient to use medium-enthalpy thermal waters for generating energy at a binary GeoTPP involving reinjection of a spent heat carrier. It is shown that good prospects can be expected from applying a hybrid geothermal and combined-cycle technology, by means of which it is possible to use lowenthalpy (80-100°C) thermal waters for generating electricity in a highly efficient manner. In accordance with such technology, geothermal heat is used in the binary GeoTPP cycle for heating low-boiling working fluid to its evaporation temperature. The working fluid is evaporated and superheated by using the heat of exhaust gases from a gas turbine power unit. Owing to combined use of the thermal water heat potential and the heat of exhaust gases from a gas turbine power plant in a hybrid process system, it becomes possible to obtain high power performance indicators of hybrid geothermal and combined-cycle power plants. This conclusion is confirmed by the results from numerical evaluations carried out as applied to the Ternair geothermal field. With the fully harnessed resource potential of the Ternair field, the total capacity of hybrid geothermal and combined-cycle power plants may reach 60 MW, a level that would make it possible to relieve a significant part of energy, environmental, economic, and social problems faced by the city of Makhachkala.

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.

SECULAR EVOLUTION OF BINARIES NEAR MASSIVE BLACK HOLES: FORMATION OF COMPACT BINARIES, MERGER/COLLISION PRODUCTS AND G2-LIKE OBJECTS

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

Prodan, Snezana; Antonini, Fabio; Perets, Hagai B., E-mail: sprodan@cita.utoronto.ca, E-mail: antonini@cita.utoronto.ca

2015-02-01

Here we discuss the evolution of binaries around massive black holes (MBHs) in nuclear stellar clusters. We focus on their secular evolution due to the perturbation by the MBHs, while simplistically accounting for their collisional evolution. Binaries with highly inclined orbits with respect to their orbits around MBHs are strongly affected by secular processes, which periodically change their eccentricities and inclinations (e.g., Kozai-Lidov cycles). During periapsis approach, dissipative processes such as tidal friction may become highly efficient, and may lead to shrinkage of a binary orbit and even to its merger. Binaries in this environment can therefore significantly change theirmore » orbital evolution due to the MBH third-body perturbative effects. Such orbital evolution may impinge on their later stellar evolution. Here we follow the secular dynamics of such binaries and its coupling to tidal evolution, as well as the stellar evolution of such binaries on longer timescales. We find that stellar binaries in the central parts of nuclear stellar clusters (NSCs) are highly likely to evolve into eccentric and/or short-period binaries, and become strongly interacting binaries either on the main sequence (at which point they may even merge), or through their later binary stellar evolution. The central parts of NSCs therefore catalyze the formation and evolution of strongly interacting binaries, and lead to the enhanced formation of blue stragglers, X-ray binaries, gravitational wave sources, and possible supernova progenitors. Induced mergers/collisions may also lead to the formation of G2-like cloud-like objects such as the one recently observed in the Galactic center.« less

Thermodynamic compensation upon binding to exosite 1 and the active site of thrombin.

PubMed

Treuheit, Nicholas A; Beach, Muneera A; Komives, Elizabeth A

2011-05-31

Several lines of experimental evidence including amide exchange and NMR suggest that ligands binding to thrombin cause reduced backbone dynamics. Binding of the covalent inhibitor dPhe-Pro-Arg chloromethyl ketone to the active site serine, as well as noncovalent binding of a fragment of the regulatory protein, thrombomodulin, to exosite 1 on the back side of the thrombin molecule both cause reduced dynamics. However, the reduced dynamics do not appear to be accompanied by significant conformational changes. In addition, binding of ligands to the active site does not change the affinity of thrombomodulin fragments binding to exosite 1; however, the thermodynamic coupling between exosite 1 and the active site has not been fully explored. We present isothermal titration calorimetry experiments that probe changes in enthalpy and entropy upon formation of binary ligand complexes. The approach relies on stringent thrombin preparation methods and on the use of dansyl-l-arginine-(3-methyl-1,5-pantanediyl)amide and a DNA aptamer as ligands with ideal thermodynamic signatures for binding to the active site and to exosite 1. Using this approach, the binding thermodynamic signatures of each ligand alone as well as the binding signatures of each ligand when the other binding site was occupied were measured. Different exosite 1 ligands with widely varied thermodynamic signatures cause a similar reduction in ΔH and a concomitantly lower entropy cost upon DAPA binding at the active site. The results suggest a general phenomenon of enthalpy-entropy compensation consistent with reduction of dynamics/increased folding of thrombin upon ligand binding to either the active site or exosite 1.

Chemical thermodynamics of ultrasound speed in solutions and liquid mixtures.

PubMed

Reis, João Carlos R; Santos, Angela F S; Lampreia, Isabel M S

2010-02-01

A comprehensive formalism is developed to treat thermodynamically speed of ultrasound data for solutions and liquid mixtures. For solutions, the apparent speed of ultrasound of a solute is introduced and proposed to take the place of empirically defined quantities. The partial speed of ultrasound of a solute is defined and related to the partial molar volume and partial molar isentropic compression. For liquid mixtures, the concept of speed of sound before mixing pure liquids is presented and used to define the change in speed of ultrasound upon ideal mixing, which is predicted to be generally a negative quantity. A new thermodynamic equation is derived linking the values for excess speed of ultrasound, excess molar volume and excess molar isentropic compression of a mixture, and its applications are discussed. Ideal and excess apparent speeds of ultrasound, as well as ideal and excess partial speeds of ultrasound, are defined for substances making up a liquid mixture. Accurate speeds of ultrasound in 31 mixtures of water with the amphiphile 2-(ethylamino)ethanol at 293.15 K are reported. These data are used to demonstrate the ability of the apparent speed of ultrasound to describe the impact of solutes on sonic properties of solutions and the advantages of analysing thermodynamic properties of binary liquid mixtures in terms of the dependence on composition of Balankina's ratios between excess and ideal values. It is concluded that the new thermodynamic functions defined for speeds of ultrasound in solutions and liquid mixtures give, at the least, equivalent information on molecular aspects to the usual functions related to the isentropic compressibility, without needing density data for this purpose.

Magnesium Nanoparticles for Hydrogen Storage: Structure, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Pasquini, L.; Brighi, M.; Montone, A.; Vittori Antisari, M.; Dam, B.; Palmisano, V.; Bonetti, E.

2012-08-01

Magnesium nanoparticles coated by a native oxide shell and decorated by palladium clusters were synthesized by the inert gas condensation technique. The kinetics and thermodynamics of hydrogen sorption were investigated by Sieverts measurements at high temperature and by optical hydrogenography close to ambient temperature. The structure and morphology of the nanoparticles were studied by electron microscopy and X-ray diffraction both in the as-prepared state and after hydrogen sorption cycles.

Exhaust Gas Energy Recovery Technology Applications

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

Wagner, Robert M; Szybist, James P

2014-01-01

Exhaust waste heat recovery systems have the potential to significantly improve vehicle fuel economy for conventional and hybrid electric powertrains spanning passenger to heavy truck applications. This chapter discusses thermodynamic considerations and three classes of energy recovery technologies which are under development for vehicle applications. More specifically, this chapter describes the state-of-the-art in exhaust WHR as well as challenges and opportunities for thermodynamic power cycles, thermoelectric devices, and turbo-compounding systems.

Dynamical evolution of a fictitious population of binary Neptune Trojans

NASA Astrophysics Data System (ADS)

Brunini, Adrián

2018-03-01

We present numerical simulations of the evolution of a synthetic population of Binary Neptune Trojans, under the influence of the solar perturbations and tidal friction (the so-called Kozai cycles and tidal friction evolution). Our model includes the dynamical influence of the four giant planets on the heliocentric orbit of the binary centre of mass. In this paper, we explore the evolution of initially tight binaries around the Neptune L4 Lagrange point. We found that the variation of the heliocentric orbital elements due to the libration around the Lagrange point introduces significant changes in the orbital evolution of the binaries. Collisional processes would not play a significant role in the dynamical evolution of Neptune Trojans. After 4.5 × 109 yr of evolution, ˜50 per cent of the synthetic systems end up separated as single objects, most of them with slow diurnal rotation rate. The final orbital distribution of the surviving binary systems is statistically similar to the one found for Kuiper Belt Binaries when collisional evolution is not included in the model. Systems composed by a primary and a small satellite are more fragile than the ones composed by components of similar sizes.

Prospects of development of highly mineralized high-temperature resources of the Tarumovskoye geothermal field

NASA Astrophysics Data System (ADS)

Alkhasov, A. B.; Alkhasova, D. A.; Ramazanov, A. Sh.; Kasparova, M. A.

2016-06-01

The promising nature of integrated processing of high-temperature geothermal brines of the Tarumovskoye geothermal field is shown. Thermal energy of a geothermal brine can be converted to the electric power at a binary geothermal power plant (GPP) based on low-boiling working substance. The thermodynamic Rankine cycles are considered which are implemented in the GPP secondary loop at different evaporation temperatures of the working substance―isobutane. Among them, the most efficient cycle from the standpoint of attaining a maximum power is the supercritical one which is close to the so-called triangular cycle with an evaporation pressure of p e = 5.0 MPa. The used low-temperature brine is supplied from the GPP to a chemical plant, where main chemical components (lithium carbonate, burnt magnesia, calcium carbonate, and sodium chloride) are extracted from it according to the developed technology of comprehensive utilization of geothermal brines of chloride-sodium type. The waste water is delivered to the geotechnological complex and other consumers. For producing valuable inorganic materials, the electric power generated at the GPP is used. Owing to this, the total self-sufficiency of production and independence from external conditions is achieved. The advantages of the proposed geotechnological complex are the full utilization of the heat potential and the extraction of main chemical components of multiparameter geothermal resources. In this case, there is no need for reverse pumping, which eliminates the significant capital costs for building injection wells and a pumping station and the operating costs for their service. A characteristic of the modern state of the field and estimated figures of the integrated processing of high-temperature brines of well no. 6 are given, from which it follows that the proposed technology has a high efficiency. The comprehensive development of the field resources will make it possible to improve the economic structure of the region and fully meet the needs of Russia in lithium carbonate and sodium chloride.

Thermodynamic and design considerations of organic Rankine cycles in combined application with a solar thermal gas turbine

NASA Astrophysics Data System (ADS)

Braun, R.; Kusterer, K.; Sugimoto, T.; Tanimura, K.; Bohn, D.

2013-12-01

Concentrated Solar Power (CSP) technologies are considered to provide a significant contribution for the electric power production in the future. Different kinds of technologies are presently in operation or under development, e.g. parabolic troughs, central receivers, solar dish systems and Fresnel reflectors. This paper takes the focus on central receiver technologies, where the solar radiation is concentrated by a field of heliostats in a receiver on the top of a tall tower. To get this CSP technology ready for the future, the system costs have to reduce significantly. The main cost driver in such kind of CSP technologies are the huge amount of heliostats. To reduce the amount of heliostats, and so the investment costs, the efficiency of the energy conversion cycle becomes an important issue. An increase in the cycle efficiency results in a decrease of the solar heliostat field and thus, in a significant cost reduction. The paper presents the results of a thermodynamic model of an Organic Rankine Cycle (ORC) for combined cycle application together with a solar thermal gas turbine. The gas turbine cycle is modeled with an additional intercooler and recuperator and is based on a typical industrial gas turbine in the 2 MW class. The gas turbine has a two stage radial compressor and a three stage axial turbine. The compressed air is preheated within a solar receiver to 950°C before entering the combustor. A hybrid operation of the gas turbine is considered. In order to achieve a further increase of the overall efficiency, the combined operation of the gas turbine and an Organic Rankine Cycle is considered. Therefore an ORC has been set up, which is thermally connected to the gas turbine cycle at two positions. The ORC can be coupled to the solar-thermal gas turbine cycle at the intercooler and after the recuperator. Thus, waste heat from different cycle positions can be transferred to the ORC for additional production of electricity. Within this investigation different working fluids and ORC conditions have been analyzed in order to evaluate the best configuration. The investigations have been performed by application of improved thermodynamic and process analysis tools, which consider the real gas behavior of the analyzed fluids. The results show that by combined operation of the solar thermal gas turbine and the ORC, the combined cycle efficiency is approximately 4%-points higher than in the solar-thermal gas turbine cycle.

Satellite radiance data assimilation for binary tropical cyclone cases over the western North Pacific

NASA Astrophysics Data System (ADS)

Choi, Yonghan; Cha, Dong-Hyun; Lee, Myong-In; Kim, Joowan; Jin, Chun-Sil; Park, Sang-Hun; Joh, Min-Su

2017-06-01

A total of three binary tropical cyclone (TC) cases over the Western North Pacific are selected to investigate the effects of satellite radiance data assimilation on analyses and forecasts of binary TCs. Two parallel cycling experiments with a 6 h interval are performed for each binary TC case, and the difference between the two experiments is whether satellite radiance observations are assimilated. Satellite radiance observations are assimilated using the Weather Research and Forecasting Data Assimilation (WRFDA)'s three-dimensional variational (3D-Var) system, which includes the observation operator, quality control procedures, and bias correction algorithm for radiance observations. On average, radiance assimilation results in slight improvements of environmental fields and track forecasts of binary TC cases, but the detailed effects vary with the case. When there is no direct interaction between binary TCs, radiance assimilation leads to better depictions of environmental fields, and finally it results in improved track forecasts. However, positive effects of radiance assimilation on track forecasts can be reduced when there exists a direct interaction between binary TCs and intensities/structures of binary TCs are not represented well. An initialization method (e.g., dynamic initialization) combined with radiance assimilation and/or more advanced DA techniques (e.g., hybrid method) can be considered to overcome these limitations.

Cost and Precision of Brownian Clocks

NASA Astrophysics Data System (ADS)

Barato, Andre C.; Seifert, Udo

2016-10-01

Brownian clocks are biomolecular networks that can count time. A paradigmatic example are proteins that go through a cycle, thus regulating some oscillatory behavior in a living system. Typically, such a cycle requires free energy often provided by ATP hydrolysis. We investigate the relation between the precision of such a clock and its thermodynamic costs. For clocks driven by a constant thermodynamic force, a given precision requires a minimal cost that diverges as the uncertainty of the clock vanishes. In marked contrast, we show that a clock driven by a periodic variation of an external protocol can achieve arbitrary precision at arbitrarily low cost. This result constitutes a fundamental difference between processes driven by a fixed thermodynamic force and those driven periodically. As a main technical tool, we map a periodically driven system with a deterministic protocol to one subject to an external protocol that changes in stochastic time intervals, which simplifies calculations significantly. In the nonequilibrium steady state of the resulting bipartite Markov process, the uncertainty of the clock can be deduced from the calculable dispersion of a corresponding current.

Analysis and optimization of three main organic Rankine cycle configurations using a set of working fluids with different thermodynamic behaviors

NASA Astrophysics Data System (ADS)

Hamdi, Basma; Mabrouk, Mohamed Tahar; Kairouani, Lakdar; Kheiri, Abdelhamid

2017-06-01

Different configurations of organic Rankine cycle (ORC) systems are potential thermodynamic concepts for power generation from low grade heat. The aim of this work is to investigate and optimize the performances of the three main ORC systems configurations: basic ORC, ORC with internal heat exchange (IHE) and regenerative ORC. The evaluation for those configurations was performed using seven working fluids with typical different thermodynamic behaviours (R245fa, R601a, R600a, R227ea, R134a, R1234ze and R1234yf). The optimization has been performed using a genetic algorithm under a comprehensive set of operative parameters such as the fluid evaporating temperature, the fraction of flow rate or the pressure at the steam extracting point in the turbine. Results show that there is no general best ORC configuration for all those fluids. However, there is a suitable configuration for each fluid. Contribution to the topical issue "Materials for Energy harvesting, conversion and storage II (ICOME 2016)", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

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.

Thermodynamic behavior of the binaries 1-butylpyridinium tetrafluoroborate with water and alkanols: their interpretation using 1H NMR spectroscopy and quantum-chemistry calculations.

PubMed

Vreekamp, Remko; Castellano, Desire; Palomar, José; Ortega, Juan; Espiau, Fernando; Fernández, Luís; Penco, Eduvigis

2011-07-14

Here we present experimental data of different properties for a set of binary mixtures composed of water or alkanols (methanol to butanol) with an ionic liquid (IL), butylpyridinium tetrafluoroborate [bpy][BF(4)]. Solubility data (x(IL),T) are presented for each of the mixtures, including water, which is found to have a small interval of compositions in IL, x(IL), with immiscibility. In each case, the upper critical solubility temperature (UCST) is determined and a correlation was observed between the UCST and the nature of the compounds in the mixtures. Miscibility curves establish the composition and temperature intervals where thermodynamic properties of the mixtures, such as enthalpies H(m)(E) and volumes V(m)(E), can be determined. Hence, at 298.15 and 318.15 K these can only be found with the first four alkanols. All mixing properties are correlated with a suitable equation ξ (x(IL),T,Y(m)(E) = 0. An analysis on the influence of the temperature in the properties is shown, likewise a comparison between the results obtained here and those of analogous mixtures, discussing the position of the -CH(3) group in the pyridinic ring. The (1)H NMR spectra are determined to analyze the molecular interactions present, especially those due to hydrogen bonds. Additional information about the molecular interactions and their influence on the mixing properties is obtained by quantum chemistry calculations. © 2011 American Chemical Society

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 9. Extensible thermodynamic constraints for pure compounds and new model developments.

PubMed

Diky, Vladimir; Chirico, Robert D; Muzny, Chris D; Kazakov, Andrei F; Kroenlein, Kenneth; Magee, Joseph W; Abdulagatov, Ilmutdin; Frenkel, Michael

2013-12-23

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported in this journal. The present article describes the background and implementation for new additions in latest release of TDE. Advances are in the areas of program architecture and quality improvement for automatic property evaluations, particularly for pure compounds. It is shown that selection of appropriate program architecture supports improvement of the quality of the on-demand property evaluations through application of a readily extensible collection of constraints. The basis and implementation for other enhancements to TDE are described briefly. Other enhancements include the following: (1) implementation of model-validity enforcement for specific equations that can provide unphysical results if unconstrained, (2) newly refined group-contribution parameters for estimation of enthalpies of formation for pure compounds containing carbon, hydrogen, and oxygen, (3) implementation of an enhanced group-contribution method (NIST-Modified UNIFAC) in TDE for improved estimation of phase-equilibrium properties for binary mixtures, (4) tools for mutual validation of ideal-gas properties derived through statistical calculations and those derived independently through combination of experimental thermodynamic results, (5) improvements in program reliability and function that stem directly from the recent redesign of the TRC-SOURCE Data Archival System for experimental property values, and (6) implementation of the Peng-Robinson equation of state for binary mixtures, which allows for critical evaluation of mixtures involving supercritical components. Planned future developments are summarized.

FAST TRACK COMMUNICATION Understanding adhesion at as-deposited interfaces from ab initio thermodynamics of deposition growth: thin-film alumina on titanium carbide

NASA Astrophysics Data System (ADS)

Rohrer, Jochen; Hyldgaard, Per

2010-12-01

We investigate the chemical composition and adhesion of chemical vapour deposited thin-film alumina on TiC using and extending a recently proposed nonequilibrium method of ab initio thermodynamics of deposition growth (AIT-DG) (Rohrer and Hyldgaard 2010 Phys. Rev. B 82 045415). A previous study of this system (Rohrer et al 2010 J. Phys.: Condens. Matter 22 015004) found that use of equilibrium thermodynamics leads to predictions of a non-binding TiC/alumina interface, despite its industrial use as a wear-resistant coating. This discrepancy between equilibrium theory and experiment is resolved by the AIT-DG method which predicts interfaces with strong adhesion. The AIT-DG method combines density functional theory calculations, rate-equation modelling of the pressure evolution of the deposition environment and thermochemical data. The AIT-DG method was previously used to predict prevalent terminations of growing or as-deposited surfaces of binary materials. Here we extend the method to predict surface and interface compositions of growing or as-deposited thin films on a substrate and find that inclusion of the nonequilibrium deposition environment has important implications for the nature of buried interfaces.

The Co-Sb-Ga System: Isoplethal Section and Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech; Chen, Sinn-wen; Chen, Wei-an; Chang, Jui-shen; Snyder, G. Jeffrey; Tang, Yinglu

2015-04-01

The Co-Sb-Ga ternary system is an important thermoelectric material system, and its phase equilibria are in need of further understanding. The CoSb3-GaSb isoplethal section is experimentally determined in this study. Phase equilibria of the ternary Co-Sb-Ga system are assessed, and the system's thermodynamic models are developed. In addition to the terminal phases and liquid phase, there are six binary intermediate phases and a ternary Co3Sb2Ga4 phase. The Ga solution in the CoSb3 compound is described by a dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model. Phase diagrams are calculated using the developed thermodynamic models, and a reaction scheme is proposed based on the calculation results. The calculated results are in good agreement with the experimentally determined phase diagrams, including the CoSb3-GaSb isoplethal section, the liquidus projection, and an isothermal section at 923 K (650 °C). The dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model gives good descriptions of both phase equilibria and thermoelectric properties of the CoSb3 phase with Ga doping.

Predicting low-temperature free energy landscapes with flat-histogram Monte Carlo methods

NASA Astrophysics Data System (ADS)

Mahynski, Nathan A.; Blanco, Marco A.; Errington, Jeffrey R.; Shen, Vincent K.

2017-02-01

We present a method for predicting the free energy landscape of fluids at low temperatures from flat-histogram grand canonical Monte Carlo simulations performed at higher ones. We illustrate our approach for both pure and multicomponent systems using two different sampling methods as a demonstration. This allows us to predict the thermodynamic behavior of systems which undergo both first order and continuous phase transitions upon cooling using simulations performed only at higher temperatures. After surveying a variety of different systems, we identify a range of temperature differences over which the extrapolation of high temperature simulations tends to quantitatively predict the thermodynamic properties of fluids at lower ones. Beyond this range, extrapolation still provides a reasonably well-informed estimate of the free energy landscape; this prediction then requires less computational effort to refine with an additional simulation at the desired temperature than reconstruction of the surface without any initial estimate. In either case, this method significantly increases the computational efficiency of these flat-histogram methods when investigating thermodynamic properties of fluids over a wide range of temperatures. For example, we demonstrate how a binary fluid phase diagram may be quantitatively predicted for many temperatures using only information obtained from a single supercritical state.

Interactions in Massive Colliding Wind Binaries

NASA Technical Reports Server (NTRS)

Corcoran, M.

2012-01-01

The most massive stars (M> 60 Solar Mass) play crucial roles in altering the chemical and thermodynamic properties of their host galaxies. Stellar mass is the fundamental stellar parameter that determines their ancillary properties and which ultimately determines the fate of these stars and their influence on their galactic environs. Unfortunately, stellar mass becomes observationally and theoretically less well constrained as it increases. Theory becomes uncertain mostly because very massive stars are prone to strong, variable mass loss which is difficult to model. Observational constraints are uncertain too. Massive stars are rare, and massive binary stars (needed for dynamical determination of mass) are rarer still: and of these systems only a fraction have suitably high orbital inclinations for direct photometric and spectroscopic radial-velocity analysis. Even in the small number of cases in which a high-inclination binary near the upper mass limit can be identified, rotational broadening and contamination of spectral line features from thick circumstellar material (either natal clouds or produced by strong stellar wind driven mass loss from one or both of he stellar components) biases the analysis. In the wilds of the upper HR diagram, we're often left with indirect and circumstantial means of determining mass, a rather unsatisfactory state of affairs.

Structure Defect Property Relationships in Binary Intermetallics

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Ding, Hong; Chen, Wei; Persson, Kristin; Canning, Andrew; Haranczyk, Maciej; Asta, Mark

2015-03-01

Ordered intermetallics are light weight materials with technologically useful high temperature properties such as creep resistance. Knowledge of constitutional and thermal defects is required to understand these properties. Vacancies and antisites are the dominant defects in the intermetallics and their concentrations and formation enthalpies could be computed by using first principles density functional theory and thermodynamic formalisms such as dilute solution method. Previously many properties of the intermetallics such as melting temperatures and formation enthalpies were statistically analyzed for large number of intermetallics using structure maps and data mining approaches. We undertook a similar exercise to establish the dependence of the defect properties in binary intermetallics on the underlying structural and chemical composition. For more than 200 binary intermetallics comprising of AB, AB2 and AB3 structures, we computed the concentrations and formation enthalpies of vacancies and antisites in a small range of stoichiometries deviating from ideal stoichiometry. The calculated defect properties were datamined to gain predictive capabilities of defect properties as well as to classify the intermetallics for their suitability in high-T applications. Supported by the US DOE under Contract No. DEAC02-05CH11231 under the Materials Project Center grant (Award No. EDCBEE).

Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

NASA Astrophysics Data System (ADS)

Lei, Qi; Bader, Roman; Kreider, Peter; Lovegrove, Keith; Lipiński, Wojciech

2017-11-01

We explore the thermodynamic efficiency of a solar-driven combined cycle power system with manganese oxide-based thermochemical energy storage system. Manganese oxide particles are reduced during the day in an oxygen-lean atmosphere obtained with a fluidized-bed reactor at temperatures in the range of 750-1600°C using concentrated solar energy. Reduced hot particles are stored and re-oxidized during night-time to achieve continuous power plant operation. The steady-state mass and energy conservation equations are solved for all system components to calculate the thermodynamic properties and mass flow rates at all state points in the system, taking into account component irreversibilities. The net power block and overall solar-to-electric energy conversion efficiencies, and the required storage volumes for solids and gases in the storage system are predicted. Preliminary results for a system with 100 MW nominal solar power input at a solar concentration ratio of 3000, designed for constant round-the-clock operation with 8 hours of on-sun and 16 hours of off-sun operation and with manganese oxide particles cycled between 750 and 1600°C yield a net power block efficiency of 60.0% and an overall energy conversion efficiency of 41.3%. Required storage tank sizes for the solids are estimated to be approx. 5-6 times smaller than those of state-of-the-art molten salt systems.

Non-equilibrium thermodynamical description of rhythmic motion patterns of active systems: a canonical-dissipative approach.

PubMed

Dotov, D G; Kim, S; Frank, T D

2015-02-01

We derive explicit expressions for the non-equilibrium thermodynamical variables of a canonical-dissipative limit cycle oscillator describing rhythmic motion patterns of active systems. These variables are statistical entropy, non-equilibrium internal energy, and non-equilibrium free energy. In particular, the expression for the non-equilibrium free energy is derived as a function of a suitable control parameter. The control parameter determines the Hopf bifurcation point of the deterministic active system and describes the effective pumping of the oscillator. In analogy to the equilibrium free energy of the Landau theory, it is shown that the non-equilibrium free energy decays as a function of the control parameter. In doing so, a similarity between certain equilibrium and non-equilibrium phase transitions is pointed out. Data from an experiment on human rhythmic movements is presented. Estimates for pumping intensity as well as the thermodynamical variables are reported. It is shown that in the experiment the non-equilibrium free energy decayed when pumping intensity was increased, which is consistent with the theory. Moreover, pumping intensities close to zero could be observed at relatively slow intended rhythmic movements. In view of the Hopf bifurcation underlying the limit cycle oscillator model, this observation suggests that the intended limit cycle movements were actually more similar to trajectories of a randomly perturbed stable focus. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

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.

Rotary Stirling-Cycle Engine And Generator

NASA Technical Reports Server (NTRS)

Chandler, Joseph A.

1990-01-01

Proposed electric-power generator comprises three motor generators coordinated by microprocessor and driven by rotary Stirling-cycle heat engine. Combination offers thermodynamic efficiency of Stirling cycle, relatively low vibration, and automatic adjustment of operating parameters to suit changing load on generator. Rotary Stirling cycle engine converts heat to power via compression and expansion of working gas between three pairs of rotary pistons on three concentric shafts in phased motion. Three motor/generators each connected to one of concentric shafts, can alternately move and be moved by pistons. Microprocessor coordinates their operation, including switching between motor and generator modes at appropriate times during each cycle.

Advantages of using a logarithmic scale in pressure-volume diagrams for Carnot and other heat engine cycles

NASA Astrophysics Data System (ADS)

Shieh, Lih-Yir; Kan, Hung-Chih

2014-04-01

We demonstrate that plotting the P-V diagram of an ideal gas Carnot cycle on a logarithmic scale results in a more intuitive approach for deriving the final form of the efficiency equation. The same approach also facilitates the derivation of the efficiency of other thermodynamic engines that employ adiabatic ideal gas processes, such as the Brayton cycle, the Otto cycle, and the Diesel engine. We finally demonstrate that logarithmic plots of isothermal and adiabatic processes help with visualization in approximating an arbitrary process in terms of an infinite number of Carnot cycles.

The Light-time Effect in the Eclipsing Binaries with Early-type Components U CrB and RW Tau

NASA Astrophysics Data System (ADS)

Khaliullina, A. I.

2018-04-01

A detailed study of the orbital-period variations of the Algol-type eclipsing binaries with earlyspectral- type primary components U CrB and RW Tau has been performed. The period variations in both systems can be described as a superposition of secular and cyclic variations of the period. A secular period increase at a rate of 2.58d × 10-7/year is observed for U CrB, which can be explained if there is a uniform flow of matter from the lower-mass to the higher-mass component, with the total angular momentum conserved. RW Tau features a secular period decrease at a rate of -8.6d × 10-7/year; this could be due to a loss of angular momentum by the binary due to magnetic braking. The cyclic orbital-period variations of U CrB and RWTau can be explained by the motion of the eclipsing binary systems along their long-period orbits. In U CrB, this implies that the eclipsing binary moves with a period of 91.3 years around a third body with mass M 3 > 1.13 M ⊙; in RW Tau, the period of the motion around the third body is 66.6 years, and the mass of the third body is M 3 > 1.24 M ⊙. It also cannot be ruled out that the variations are due to the magnetic cycles of the late-type secondaries. The residual period variations could be a superposition of variations due to non-stationary ejection of matter and effects due to magnetic cycles.

A Structural Perspective on the Dynamics of Kinesin Motors

PubMed Central

Hyeon, Changbong; Onuchic, José N.

2011-01-01

Despite significant fluctuation under thermal noise, biological machines in cells perform their tasks with exquisite precision. Using molecular simulation of a coarse-grained model and theoretical arguments, we envisaged how kinesin, a prototype of biological machines, generates force and regulates its dynamics to sustain persistent motor action. A structure-based model, which can be versatile in adapting its structure to external stresses while maintaining its native fold, was employed to account for several features of kinesin dynamics along the biochemical cycle. This analysis complements our current understandings of kinesin dynamics and connections to experiments. We propose a thermodynamic cycle for kinesin that emphasizes the mechanical and regulatory role of the neck linker and clarify issues related to the motor directionality, and the difference between the external stalling force and the internal tension responsible for the head-head coordination. The comparison between the thermodynamic cycle of kinesin and macroscopic heat engines highlights the importance of structural change as the source of work production in biomolecular machines. PMID:22261064

Approaches to Cycle Analysis and Performance Metrics

NASA Technical Reports Server (NTRS)

Parson, Daniel E.

2003-01-01

The following notes were prepared as part of an American Institute of Aeronautics and Astronautics (AIAA) sponsored short course entitled Air Breathing Pulse Detonation Engine (PDE) Technology. The course was presented in January of 2003, and again in July of 2004 at two different AIAA meetings. It was taught by seven instructors, each of whom provided information on particular areas of PDE research. These notes cover two areas. The first is titled Approaches to Cycle Analysis and Performance Metrics. Here, the various methods of cycle analysis are introduced. These range from algebraic, thermodynamic equations, to single and multi-dimensional Computational Fluid Dynamic (CFD) solutions. Also discussed are the various means by which performance is measured, and how these are applied in a device which is fundamentally unsteady. The second topic covered is titled PDE Hybrid Applications. Here the concept of coupling a PDE to a conventional turbomachinery based engine is explored. Motivation for such a configuration is provided in the form of potential thermodynamic benefits. This is accompanied by a discussion of challenges to the technology.

Chemical interactions and thermodynamic studies in aluminum alloy/molten salt systems

NASA Astrophysics Data System (ADS)

Narayanan, Ramesh

The recycling of aluminum and aluminum alloys such as Used Beverage Container (UBC) is done under a cover of molten salt flux based on (NaCl-KCl+fluorides). The reactions of aluminum alloys with molten salt fluxes have been investigated. Thermodynamic calculations are performed in the alloy/salt flux systems which allow quantitative predictions of the equilibrium compositions. There is preferential reaction of Mg in Al-Mg alloy with molten salt fluxes, especially those containing fluorides like NaF. An exchange reaction between Al-Mg alloy and molten salt flux has been demonstrated. Mg from the Al-Mg alloy transfers into the salt flux while Na from the salt flux transfers into the metal. Thermodynamic calculations indicated that the amount of Na in metal increases as the Mg content in alloy and/or NaF content in the reacting flux increases. This is an important point because small amounts of Na have a detrimental effect on the mechanical properties of the Al-Mg alloy. The reactions of Al alloys with molten salt fluxes result in the formation of bluish purple colored "streamers". It was established that the streamer is liquid alkali metal (Na and K in the case of NaCl-KCl-NaF systems) dissipating into the melt. The melts in which such streamers were observed are identified. The metal losses occurring due to reactions have been quantified, both by thermodynamic calculations and experimentally. A computer program has been developed to calculate ternary phase diagrams in molten salt systems from the constituting binary phase diagrams, based on a regular solution model. The extent of deviation of the binary systems from regular solution has been quantified. The systems investigated in which good agreement was found between the calculated and experimental phase diagrams included NaF-KF-LiF, NaCl-NaF-NaI and KNOsb3-TINOsb3-LiNOsb3. Furthermore, an insight has been provided on the interrelationship between the regular solution parameters and the topology of the phase diagram. The isotherms are flat (i.e. no skewness) when the regular solution parameters are zero. When the regular solution parameters are non-zero, the isotherms are skewed. A regular solution model is not adequate to accurately model the molten salt systems used in recycling like NaCl-KCl-LiF and NaCl-KCl-NaF.

Assisted stellar suicide in V617 Sagittarii

NASA Astrophysics Data System (ADS)

Steiner, J. E.; Oliveira, A. S.; Cieslinski, D.; Ricci, T. V.

2006-02-01

Context: .V617 Sgr is a V Sagittae star - a group of binaries thought to be the galactic counterparts of the Compact Binary Supersoft X-ray Sources - CBSS. Aims: .To check this hypothesis, we measured the time derivative of its orbital period. Methods: .Observed timings of eclipse minima spanning over 30 000 orbital cycles are presented. Results: .We found that the orbital period evolves quite rapidly: P/dot{P} = 1.1×106 years. This is consistent with the idea that V617 Sgr is a wind driven accretion supersoft source. As the binary system evolves with a time-scale of about one million years, which is extremely short for a low mass evolved binary, it is likely that the system will soon end either by having its secondary completely evaporated or by the primary exploding as a supernova of type Ia. Conclusions: .

Dynamics of rotationally fissioned asteroids: Source of observed small asteroid systems

NASA Astrophysics Data System (ADS)

Jacobson, Seth A.; Scheeres, Daniel J.

2011-07-01

We present a model of near-Earth asteroid (NEA) rotational fission and ensuing dynamics that describes the creation of synchronous binaries and all other observed NEA systems including: doubly synchronous binaries, high- e binaries, ternary systems, and contact binaries. Our model only presupposes the Yarkovsky-O'Keefe-Radzievskii-Paddack (YORP) effect, "rubble pile" asteroid geophysics, and gravitational interactions. The YORP effect torques a "rubble pile" asteroid until the asteroid reaches its fission spin limit and the components enter orbit about each other (Scheeres, D.J. [2007]. Icarus 189, 370-385). Non-spherical gravitational potentials couple the spin states to the orbit state and chaotically drive the system towards the observed asteroid classes along two evolutionary tracks primarily distinguished by mass ratio. Related to this is a new binary process termed secondary fission - the secondary asteroid of the binary system is rotationally accelerated via gravitational torques until it fissions, thus creating a chaotic ternary system. The initially chaotic binary can be stabilized to create a synchronous binary by components of the fissioned secondary asteroid impacting the primary asteroid, solar gravitational perturbations, and mutual body tides. These results emphasize the importance of the initial component size distribution and configuration within the parent asteroid. NEAs may go through multiple binary cycles and many YORP-induced rotational fissions during their approximately 10 Myr lifetime in the inner Solar System. Rotational fission and the ensuing dynamics are responsible for all NEA systems including the most commonly observed synchronous binaries.

The COBAIN (COntact Binary Atmospheres with INterpolation) Code for Radiative Transfer

NASA Astrophysics Data System (ADS)

Kochoska, Angela; Prša, Andrej; Horvat, Martin

2018-01-01

Standard binary star modeling codes make use of pre-existing solutions of the radiative transfer equation in stellar atmospheres. The various model atmospheres available today are consistently computed for single stars, under different assumptions - plane-parallel or spherical atmosphere approximation, local thermodynamical equilibrium (LTE) or non-LTE (NLTE), etc. However, they are nonetheless being applied to contact binary atmospheres by populating the surface corresponding to each component separately and neglecting any mixing that would typically occur at the contact boundary. In addition, single stellar atmosphere models do not take into account irradiance from a companion star, which can pose a serious problem when modeling close binaries. 1D atmosphere models are also solved under the assumption of an atmosphere in hydrodynamical equilibrium, which is not necessarily the case for contact atmospheres, as the potentially different densities and temperatures can give rise to flows that play a key role in the heat and radiation transfer.To resolve the issue of erroneous modeling of contact binary atmospheres using single star atmosphere tables, we have developed a generalized radiative transfer code for computation of the normal emergent intensity of a stellar surface, given its geometry and internal structure. The code uses a regular mesh of equipotential surfaces in a discrete set of spherical coordinates, which are then used to interpolate the values of the structural quantites (density, temperature, opacity) in any given point inside the mesh. The radiaitive transfer equation is numerically integrated in a set of directions spanning the unit sphere around each point and iterated until the intensity values for all directions and all mesh points converge within a given tolerance. We have found that this approach, albeit computationally expensive, is the only one that can reproduce the intensity distribution of the non-symmetric contact binary atmosphere and can be used with any existing or new model of the structure of contact binaries. We present results on several test objects and future prospects of the implementation in state-of-the-art binary star modeling software.

Endoreversible quantum heat engines in the linear response regime.

PubMed

Wang, Honghui; He, Jizhou; Wang, Jianhui

2017-07-01

We analyze general models of quantum heat engines operating a cycle of two adiabatic and two isothermal processes. We use the quantum master equation for a system to describe heat transfer current during a thermodynamic process in contact with a heat reservoir, with no use of phenomenological thermal conduction. We apply the endoreversibility description to such engine models working in the linear response regime and derive expressions of the efficiency and the power. By analyzing the entropy production rate along a single cycle, we identify the thermodynamic flux and force that a linear relation connects. From maximizing the power output, we find that such heat engines satisfy the tight-coupling condition and the efficiency at maximum power agrees with the Curzon-Ahlborn efficiency known as the upper bound in the linear response regime.

IO-MFA and Thermodynamic Approach for Metal Recycling

NASA Astrophysics Data System (ADS)

Nakajima, Kenichi; Matsubae, Kazuyo; Kondo, Yasushi; Nakamura, Shinichiro; Nagasaka, Tetsuya

Recently, the issue of sustainable resource management has been increasingly recognized. In order to increase resource efficiency, Castro et al. (2004) pointed out an importance to understand the interconnections between the materials' processing routes and their thermodynamic constraints, and discussed losses due to contaminations during recycling. One of the dominant solutions to avoid such losses or contaminants is knowledge about the substance flows in material cycles. Material flow analysis (MFA) is a powerful tool to understand the resource consumption and material cycle in the national economy. Some advanced MFA studies discussed the complex web of metal flows and their linkages (Nakamura et al. 2007, 2008). Discussions on the limitations of impurity removal and the recoverability of elements in the recycling of EoL metal products, however, have been insufficient even in conventional MFA studies.

Global linear-irreversible principle for optimization in finite-time thermodynamics

NASA Astrophysics Data System (ADS)

Johal, Ramandeep S.

2018-03-01

There is intense effort into understanding the universal properties of finite-time models of thermal machines —at optimal performance— such as efficiency at maximum power, coefficient of performance at maximum cooling power, and other such criteria. In this letter, a global principle consistent with linear irreversible thermodynamics is proposed for the whole cycle —without considering details of irreversibilities in the individual steps of the cycle. This helps to express the total duration of the cycle as τ \\propto {\\bar{Q}^2}/{Δ_\\text{tot}S} , where \\bar{Q} models the effective heat transferred through the machine during the cycle, and Δ_ \\text{tot} S is the total entropy generated. By taking \\bar{Q} in the form of simple algebraic means (such as arithmetic and geometric means) over the heats exchanged by the reservoirs, the present approach is able to predict various standard expressions for figures of merit at optimal performance, as well as the bounds respected by them. It simplifies the optimization procedure to a one-parameter optimization, and provides a fresh perspective on the issue of universality at optimal performance, for small difference in reservoir temperatures. As an illustration, we compare the performance of a partially optimized four-step endoreversible cycle with the present approach.

Renewable hydrogen production via thermochemical/electrochemical coupling

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

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

Massive binaries in R136 using Hubble

NASA Astrophysics Data System (ADS)

Caballero-Nieves, Saida; Crowther, Paul; Bostroem, K. Azalee; Maíz Apellániz, Jesus

2014-09-01

We have undertaken a complete HST/STIS spectroscopic survey of R136, the young, central dense starburst cluster of the LMC 30 Doradus nebula, which hosts the most massive stars currently known. Our CCD datasets, comprising 17 adjacent 0.2"×52" long slits, were split across Cycles 19 and 20 to allow us to search for spectroscopic binaries. We will present the results of our survey, including a comparison with the massive-star population in the wider 30 Doradus region from the VLT Flames Tarantula survey. We will also describe upcoming HST/FGS observations, which will probe intermediate-separation binaries in R136, and discuss this cluster in the context of unresolved young extragalactic star clusters.

Regulated dc-to-dc converter for voltage step-up or step-down with input-output isolation

NASA Technical Reports Server (NTRS)

Feng, S. Y.; Wilson, T. G. (Inventor)

1973-01-01

A closed loop regulated dc-to-dc converter employing an unregulated two winding inductive energy storage converter is provided by using a magnetically coupled multivibrator acting as duty cycle generator to drive the converter. The multivibrator is comprised of two transistor switches and a saturable transformer. The output of the converter is compared with a reference in a comparator which transmits a binary zero until the output exceeds the reference. When the output exceeds the reference, the binary output of the comparator drives transistor switches to turn the multivibrator off. The multivibrator is unbalanced so that a predetermined transistor will always turn on first when the binary feedback signal becomes zero.

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

Clark, Corrie E.; Harto, Christopher B.; Schroeder, Jenna N.

This report is the third in a series of reports sponsored by the U.S. Department of Energy Geothermal Technologies Program in which a range of water-related issues surrounding geothermal power production are evaluated. The first report made an initial attempt at quantifying the life cycle fresh water requirements of geothermal power-generating systems and explored operational and environmental concerns related to the geochemical composition of geothermal fluids. The initial analysis of life cycle fresh water consumption of geothermal power-generating systems identified that operational water requirements consumed the vast majority of water across the life cycle. However, it relied upon limited operationalmore » water consumption data and did not account for belowground operational losses for enhanced geothermal systems (EGSs). A second report presented an initial assessment of fresh water demand for future growth in utility-scale geothermal power generation. The current analysis builds upon this work to improve life cycle fresh water consumption estimates and incorporates regional water availability into the resource assessment to improve the identification of areas where future growth in geothermal electricity generation may encounter water challenges. This report is divided into nine chapters. Chapter 1 gives the background of the project and its purpose, which is to assess the water consumption of geothermal technologies and identify areas where water availability may present a challenge to utility-scale geothermal development. Water consumption refers to the water that is withdrawn from a resource such as a river, lake, or nongeothermal aquifer that is not returned to that resource. The geothermal electricity generation technologies evaluated in this study include conventional hydrothermal flash and binary systems, as well as EGSs that rely on engineering a productive reservoir where heat exists, but where water availability or permeability may be limited. Chapter 2 describes the approach and methods for this work and identifies the four power plant scenarios evaluated: a 20-MW EGS binary plant, a 50-MW EGS binary plant, a 10-MW hydrothermal binary plant, and a 50-MW hydrothermal flash plant. The methods focus on (1) the collection of data to improve estimation of EGS stimulation volumes, aboveground operational consumption for all geothermal technologies, and belowground operational consumption for EGS; and (2) the mapping of the geothermal and water resources of the western United States to assist in the identification of potential water challenges to geothermal growth. Chapters 3 and 4 present the water requirements for the power plant life cycle. Chapter 3 presents the results of the current data collection effort, and Chapter 4 presents the normalized volume of fresh water consumed at each life cycle stage per lifetime energy output for the power plant scenarios evaluated. Over the life cycle of a geothermal power plant, from construction through 30 years of operation, the majority of water is consumed by plant operations. For the EGS binary scenarios, where dry cooling was assumed, belowground operational water loss is the greatest contributor depending upon the physical and operational conditions of the reservoir. Total life cycle water consumption requirements for air-cooled EGS binary scenarios vary between 0.22 and 1.85 gal/kWh, depending upon the extent of belowground operational water consumption. The air-cooled hydrothermal binary and flash plants experience far less fresh water consumption over the life cycle, at 0.04 gal/kWh. Fresh water requirements associated with air- cooled binary operations are primarily from aboveground water needs, including dust control, maintenance, and domestic use. Although wet-cooled hydrothermal flash systems require water for cooling, these plants generally rely upon the geofluid, fluid from the geothermal reservoir, which typically has high salinity and total dissolved solids concentration and is much warmer than normal groundwater sources, for their cooling water needs; thus, while there is considerable geofluid loss at 2.7 gal/kWh, fresh water consumption during operations is similar to that of aircooled binary systems. Chapter 5 presents the assessment of water demand for future growth in deployment of utility-scale geothermal power generation. The approach combines the life cycle analysis of geothermal water consumption with a geothermal supply curve according to resource type, levelized cost of electricity (LCOE), and potential growth scenarios. A total of 17 growth scenarios were evaluated. In general, the scenarios that assumed lower costs for EGSs as a result of learning and technological improvements resulted in greater geothermal potential, but also significantly greater water demand due to the higher water consumption by EGSs. It was shown, however, that this effect could be largely mitigated if nonpotable water sources were used for belowground operational water demands. The geographical areas that showed the highest water demand for most growth scenarios were southern and northern California, as well as most of Nevada. In addition to water demand by geothermal power production, Chapter 5 includes data on water availability for geothermal development areas. A qualitative analysis is included that identifies some of the basins where the limited availability of water is most likely to affect the development of geothermal resources. The data indicate that water availability is fairly limited, especially under drought conditions, in most of the areas with significant near- and medium-term geothermal potential. Southern California was found to have the greatest potential for water-related challenges with its combination of high geothermal potential and limited water availability. The results of this work are summarized in Chapter 6. Overall, this work highlights the importance of utilizing dry cooling systems for binary and EGS systems and minimizing fresh water consumption throughout the life cycle of geothermal power development. The large resource base for EGSs represents a major opportunity for the geothermal industry; however, depending upon geology, these systems can require large quantities of makeup water due to belowground reservoir losses. Identifying potential sources of compatible degraded or low-quality water for use for makeup injection for EGS and flash systems represents an important opportunity to reduce the impacts of geothermal development on fresh water resources. The importance of identifying alternative water sources for geothermal systems is heightened by the fact that a large fraction of the geothermal resource is located in areas already experiencing water stress. Chapter 7 is a glossary of the technical terms used in the report, and Chapters 8 and 9 provide references and a bibliography, respectively.« less

Gaussian Mean Field Lattice Gas

NASA Astrophysics Data System (ADS)

Scoppola, Benedetto; Troiani, Alessio

2018-03-01

We study rigorously a lattice gas version of the Sherrington-Kirckpatrick spin glass model. In discrete optimization literature this problem is known as unconstrained binary quadratic programming and it belongs to the class NP-hard. We prove that the fluctuations of the ground state energy tend to vanish in the thermodynamic limit, and we give a lower bound of such ground state energy. Then we present a heuristic algorithm, based on a probabilistic cellular automaton, which seems to be able to find configurations with energy very close to the minimum, even for quite large instances.

Liquid-gas phase transition in asymmetric nuclear matter at finite temperature

NASA Astrophysics Data System (ADS)

Maruyama, Toshiki; Tatsumi, Toshitaka; Chiba, Satoshi

2010-03-01

Liquid-gas phase transition is discussed in warm asymmetric nuclear matter. Some peculiar features are figured out from the viewpoint of the basic thermodynamics about the phase equilibrium. We treat the mixed phase of the binary system based on the Gibbs conditions. When the Coulomb interaction is included, the mixed phase is no more uniform and the sequence of the pasta structures appears. Comparing the results with those given by the simple bulk calculation without the Coulomb interaction, we extract specific features of the pasta structures at finite temperature.

Algorithmic complexity of real financial markets

NASA Astrophysics Data System (ADS)

Mansilla, R.

2001-12-01

A new approach to the understanding of complex behavior of financial markets index using tools from thermodynamics and statistical physics is developed. Physical complexity, a quantity rooted in the Kolmogorov-Chaitin theory is applied to binary sequences built up from real time series of financial markets indexes. The study is based on NASDAQ and Mexican IPC data. Different behaviors of this quantity are shown when applied to the intervals of series placed before crashes and to intervals when no financial turbulence is observed. The connection between our results and the efficient market hypothesis is discussed.

Thermodynamics of the complex formation of copper(II) with L-phenylalanine in aqueous ethanol solutions

NASA Astrophysics Data System (ADS)

Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.

2013-05-01

Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.

Application of regular associated solution model to the liquidus curves of the Sn-Te and Sn-SnS systems

NASA Astrophysics Data System (ADS)

Eric, H.

1982-12-01

The liquidus curves of the Sn-Te and Sn-SnS systems were evaluated by the regular associated solution model (RAS). The main assumption of this theory is the existence of species A, B and associated complexes AB in the liquid phase. Thermodynamic properties of the binary A-B system are derived by ternary regular solution equations. Calculations based on this model for the Sn-Te and Sn-SnS systems are in agreement with published data.

Crystallization of pure anhydrous polymorphs of carbamazepine by solution enhanced dispersion with supercritical fluids (SEDS).

PubMed

Edwards, A D; Shekunov, B Y; Kordikowski, A; Forbes, R T; York, P

2001-08-01

Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDS). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDS process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. alpha-Carbamazepine was crystallized at high supersaturations and low temperatures, beta-carbamazepine crystallized from a methanol-carbon dioxide phase split, and gamma-carbamazepine crystallized via nucleation at high temperatures and low supersaturation. Copyright 2001 Wiley-Liss, Inc.

Survey of Current and Next Generation Space Power Technologies

DTIC Science & Technology

2006-06-26

different thermodynamic cycles, such as the Brayton, Rankine, and Stirling cycles, alkali metal thermal electric converters ( AMTEC ) and thermionic...efficiencies @ 1700K. The primary issue with this system is the integration of the converter technology into the nuclear reactor core. AMTEC (static...Alkali metal thermal to electric converters ( AMTECs ) are thermally powered electrochemical concentration cells that convert heat energy directly to DC

Dynamical diagnostics of the SST annual cycle in the eastern equatorial Pacific: part I a linear coupled framework

NASA Astrophysics Data System (ADS)

Chen, Ying-Ying; Jin, Fei-Fei

2018-03-01

The eastern equatorial Pacific has a pronounced westward propagating SST annual cycle resulting from ocean-atmosphere interactions with equatorial semiannual solar forcing and off-equatorial annual solar forcing conveyed to the equator. In this two-part paper, a simple linear coupled framework is proposed to quantify the internal dynamics and external forcing for a better understanding of the linear part of the dynamics annual cycle. It is shown that an essential internal dynamical factor is the SST damping rate which measures the coupled stability in a similar way as the Bjerknes instability index for the El Niño-Southern Oscillation. It comprises three major negative terms (dynamic damping due to the Ekman pumping feedback, mean circulation advection, and thermodynamic feedback) and two positive terms (thermocline feedback and zonal advection). Another dynamical factor is the westward-propagation speed that is mainly determined by the thermodynamic feedback, the Ekman pumping feedback, and the mean circulation. The external forcing is measured by the annual and semiannual forcing factors. These linear internal and external factors, which can be estimated from data, determine the amplitude of the annual cycle.

World Geothermal Congress WGC-2015

NASA Astrophysics Data System (ADS)

Tomarov, G. V.; Shipkov, A. A.

2016-08-01

This article discusses materials and results of the World Geothermal Congress that was held in Melbourne (Australia) from April 19 to April 25, 2015. Information on the extent and technological features of utilization of geothermal resources for heat supply and power production, as well as in other economic areas, is given. A stable growth in the capacity and number of geothermal power systems that is determined by ecological cleanliness, economic efficiency, and the highest (among renewable energy sources) indicators of installed capacity utilization is shown. It was noted that combined schemes of geothermal power plants (GPPs), such as turbine units of different type (binary units, units with one or two separation pressures, etc.), have become more frequently used to increase the efficiency of utilization of geothermal heat carrier. Actual data determining room heating systems with the total worldwide capacity of nearly 50000 MW thermal (MWt) as the most currently significant segment of consumption of geothermal waters are given. In addition, geothermal resources are also utilized in soil pumps, balneological and sports basins, greenhouse complexes, and other manufactures. It was noted that geological studies were carried out in more than 40 countries, with the development of methods of simulation of tanks for the existing and new geothermal fields. Trends of development and the role of geothermal power engineering in the energy supply of many countries are shown. It was shown that prospects for the development of geothermal power generation are significantly associated with utilization of low-temperature geothermal sources in binary power generating units, as well as with the increase in installed capacity of operating geothermal power plants (GPPs) without drilling additional wells, i.e., by using waste geothermal heat carrier in binary-cycle or combined-cycle power plants. The article provides data on a pilot binary power unit at Pauzhetka GPP and on a promising Russian geothermal project to increase the installed capacity of Mutnovsk GPP (whose current capacity is 50.0 (2 × 25.0) MW of electric power) by 25% by constructing a combined binary-cycle power generating unit on the basis of waste separate utilization.

Thermodynamics of H-bonding in alcohols and water. The mobile order theory as opposed to the classical multicomponent order theories

NASA Astrophysics Data System (ADS)

Huyskens, P.; Kapuku, F.; Colemonts-Vandevyvere, C.

1990-09-01

In liquids the partners of H bonds constantly change. As a consequence the entities observed by IR spectroscopy are not the same as those considered for thermodynamic properties. For the latter, the H-bonds are shared by all the molecules. The thermodynamic "monomeric fraction", γ, the time fraction during which an alcohol molecule is vaporizable, is the square root of the spectroscopic monomeric fraction, and is the fraction of molecules which, during a time interval of 10 -14 s, have their hydroxylic proton and their lone pairs free. The classical thermodynamic treatments of Mecke and Prigogine consider the spectroscopic entities as real thermodynamic entities. Opposed to this, the mobile order theory considers all the formal molecules as equal but with a reduction of the entropy due to the fact that during a fraction 1-γ of the time, the OH proton follows a neighbouring oxygen atom on its journey through the liquid. Mobile order theory and classic multicomponent treatment lead, in binary mixtures of the associated substance A with the inert substance S, to expressions of the chemical potentials μ A and μ S that are fundamentally different. However, the differences become very important only when the molar volumes overlineVS and overlineVA differ by a factor larger than 2. As a consequence the equations of the classic theory can still fit the experimental vapour pressure data of mixtures of liquid alcohols and liquid alkanes. However, the solubilities of solid alkanes in water for which overlineVS > 3 overlineVA are only correctly predicted by the mobile order theory.

Thermodynamic compensation upon binding to exosite 1 and the active site of thrombin

PubMed Central

Treuheit, Nicholas A.; Beach, Muneera A.; Komives, Elizabeth A.

2011-01-01

Several lines of experimental evidence including amide exchange and NMR suggest that ligands binding to thrombin cause reduced backbone dynamics. Binding of the covalent inhibitor dPhe-Pro-Arg chloromethylketone to the active site serine, as well as non-covalent binding of a fragment of the regulatory protein, thrombomodulin, to exosite 1 on the back side of the thrombin molecule both cause reduced dynamics. However, the reduced dynamics do not appear to be accompanied by significant conformational changes. In addition, binding of ligands to the active site does not change the affinity of thrombomodulin fragments binding to exosite 1, however, the thermodynamic coupling between exosite 1 and the active site has not been fully explored. We present isothermal titration calorimetry experiments that probe changes in enthalpy and entropy upon formation of binary ligand complexes. The approach relies on stringent thrombin preparation methods and on the use of dansyl-L-arginine-(3-methyl-1,5-pantanediyl) amide and a DNA aptamer as ligands with ideal thermodynamic signatures for binding to the active site and to exosite 1. Using this approach, the binding thermodynamic signatures of each ligand alone as well as the binding signatures of each ligand when the other binding site was occupied were measured. Different exosite 1 ligands with widely varied thermodynamic signatures cause the same reduction in ΔH and a concomitantly lower entropy cost upon DAPA binding at the active site. The results suggest a general phenomenon of enthalpy-entropy compensation consistent with reduction of dynamics/increased folding of thrombin upon ligand binding to either the active site or to exosite 1. PMID:21526769

r -process nucleosynthesis from matter ejected in binary neutron star mergers [On r -process nucleosynthesis from matter ejected in binary neutron star mergers

DOE PAGES

Bovard, Luke; Martin, Dirk; Guercilena, Federico; ...

2017-12-05

Here, when binary systems of neutron stars merge, a very small fraction of their rest mass is ejected, either dynamically or secularly. This material is neutron-rich and its nucleosynthesis provides the astrophysical site for the production of heavy elements in the Universe, together with a kilonova signal confirming neutron-star mergers as the origin of short gamma-ray bursts. We perform full general-relativistic simulations of binary neutron-star mergers employing three different nuclear-physics equations of state (EOSs), considering both equal- and unequal-mass configurations, and adopting a leakage scheme to account for neutrino radiative losses. Using a combination of techniques, we carry out anmore » extensive and systematic study of the hydrodynamical, thermodynamical, and geometrical properties of the matter ejected dynamically, employing the WinNet nuclear-reaction network to recover the relative abundances of heavy elements produced by each configurations. Among the results obtained, three are particularly important. First, we find that, within the sample considered here, both the properties of the dynamical ejecta and the nucleosynthesis yields are robust against variations of the EOS and masses. Second, using a conservative but robust criterion for unbound matter, we find that the amount of ejected mass is ≲10 –3 M⊙, hence at least one order of magnitude smaller than what normally assumed in modelling kilonova signals. Finally, using a simplified and gray-opacity model we assess the observability of the infrared kilonova emission finding, that for all binaries the luminosity peaks around ~1/2 day in the H-band, reaching a maximum magnitude of –13, and decreasing rapidly after one day.« less

r -process nucleosynthesis from matter ejected in binary neutron star mergers [On r -process nucleosynthesis from matter ejected in binary neutron star mergers

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

Bovard, Luke; Martin, Dirk; Guercilena, Federico

Here, when binary systems of neutron stars merge, a very small fraction of their rest mass is ejected, either dynamically or secularly. This material is neutron-rich and its nucleosynthesis provides the astrophysical site for the production of heavy elements in the Universe, together with a kilonova signal confirming neutron-star mergers as the origin of short gamma-ray bursts. We perform full general-relativistic simulations of binary neutron-star mergers employing three different nuclear-physics equations of state (EOSs), considering both equal- and unequal-mass configurations, and adopting a leakage scheme to account for neutrino radiative losses. Using a combination of techniques, we carry out anmore » extensive and systematic study of the hydrodynamical, thermodynamical, and geometrical properties of the matter ejected dynamically, employing the WinNet nuclear-reaction network to recover the relative abundances of heavy elements produced by each configurations. Among the results obtained, three are particularly important. First, we find that, within the sample considered here, both the properties of the dynamical ejecta and the nucleosynthesis yields are robust against variations of the EOS and masses. Second, using a conservative but robust criterion for unbound matter, we find that the amount of ejected mass is ≲10 –3 M⊙, hence at least one order of magnitude smaller than what normally assumed in modelling kilonova signals. Finally, using a simplified and gray-opacity model we assess the observability of the infrared kilonova emission finding, that for all binaries the luminosity peaks around ~1/2 day in the H-band, reaching a maximum magnitude of –13, and decreasing rapidly after one day.« less

Experimental study of elliptical jet from sub to supercritical conditions

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

Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in

2014-04-15

The jet mixing at supercritical conditions involves fluid dynamics as well as thermodynamic phenomena. All the jet mixing studies at critical conditions to the present date have focused only on axisymmetric jets. When the liquid jet is injected into supercritical environment, the thermodynamic transition could be well understood by considering one of the important fluid properties such as surface tension since it decides the existence of distinct boundary between the liquid and gaseous phase. It is well known that an elliptical liquid jet undergoes axis-switching phenomena under atmospheric conditions due to the presence of surface tension. The experimental investigations weremore » carried out with low speed elliptical jet under supercritical condition. Investigation of the binary component system with fluoroketone jet and N{sub 2} gas as environment shows that the surface tension force dominates for a large downstream distance, indicating delayed thermodynamic transition. The increase in pressure to critical state at supercritical temperature is found to expedite the thermodynamic transition. The ligament like structures has been observed rather than droplets for supercritical pressures. However, for the single component system with fluoroketone jet and fluoroketone environment shows that the jet disintegrates into droplets as it is subjected to the chamber conditions even for the subcritical pressures and no axis switching phenomenon is observed. For a single component system, as the pressure is increased to critical state, the liquid jet exhibits gas-gas like mixing behavior and that too without exhibiting axis-switching behavior.« less

Identifying functional thermodynamics in autonomous Maxwellian ratchets

NASA Astrophysics Data System (ADS)

Boyd, Alexander B.; Mandal, Dibyendu; Crutchfield, James P.

2016-02-01

We introduce a family of Maxwellian Demons for which correlations among information bearing degrees of freedom can be calculated exactly and in compact analytical form. This allows one to precisely determine Demon functional thermodynamic operating regimes, when previous methods either misclassify or simply fail due to approximations they invoke. This reveals that these Demons are more functional than previous candidates. They too behave either as engines, lifting a mass against gravity by extracting energy from a single heat reservoir, or as Landauer erasers, consuming external work to remove information from a sequence of binary symbols by decreasing their individual uncertainty. Going beyond these, our Demon exhibits a new functionality that erases bits not by simply decreasing individual-symbol uncertainty, but by increasing inter-bit correlations (that is, by adding temporal order) while increasing single-symbol uncertainty. In all cases, but especially in the new erasure regime, exactly accounting for informational correlations leads to tight bounds on Demon performance, expressed as a refined Second Law of thermodynamics that relies on the Kolmogorov-Sinai entropy for dynamical processes and not on changes purely in system configurational entropy, as previously employed. We rigorously derive the refined Second Law under minimal assumptions and so it applies quite broadly—for Demons with and without memory and input sequences that are correlated or not. We note that general Maxwellian Demons readily violate previously proposed, alternative such bounds, while the current bound still holds. As such, it broadly describes the minimal energetic cost of any computation by a thermodynamic system.

Picosecond solvation dynamics—A potential viewer of DMSO—Water binary mixtures

NASA Astrophysics Data System (ADS)

Banik, Debasis; Kundu, Niloy; Kuchlyan, Jagannath; Roy, Arpita; Banerjee, Chiranjib; Ghosh, Surajit; Sarkar, Nilmoni

2015-02-01

In this work, we have investigated the composition dependent anomalous behavior of dimethyl sulfoxide (DMSO)-water binary mixture by collecting the ultrafast solvent relaxation response around a well known solvation probe Coumarin 480 (C480) by using a femtosecond fluorescence up-conversion spectrometer. Recent molecular dynamics simulations have predicted two anomalous regions of DMSO-water binary mixture. Particularly, these studies encourage us to investigate the anomalies from experimental background. DMSO-water binary mixture has repeatedly given evidences of its dual anomalous nature in front of our systematic investigation through steady-state and time-resolved measurements. We have calculated average solvation times of C480 by two individual well-known methods, among them first one is spectral-reconstruction method and another one is single-wavelength measurement method. The results of both the methods roughly indicate that solvation time of C480 reaches maxima in the mole fraction of DMSO XD = 0.12-0.17 and XD = 0.27-0.35, respectively. Among them, the second region (XD = 0.27-0.35) is very common as most of the thermodynamic properties exhibit deviation in this range. Most probably, the anomalous solvation trend in this region is fully guided by the shear viscosity of the medium. However, the first region is the most interesting one. In this region due to formation of strongly hydrogen bonded 1DMSO:2H2O complexes, hydration around the probe C480 decreases, as a result of which solvation time increases.

The Kirkwood-Buff theory of solutions and the local composition of liquid mixtures.

PubMed

Shulgin, Ivan L; Ruckenstein, Eli

2006-06-29

The present paper is devoted to the local composition of liquid mixtures calculated in the framework of the Kirkwood-Buff theory of solutions. A new method is suggested to calculate the excess (or deficit) number of various molecules around a selected (central) molecule in binary and multicomponent liquid mixtures in terms of measurable macroscopic thermodynamic quantities, such as the derivatives of the chemical potentials with respect to concentrations, the isothermal compressibility, and the partial molar volumes. This method accounts for an inaccessible volume due to the presence of a central molecule and is applied to binary and ternary mixtures. For the ideal binary mixture it is shown that because of the difference in the volumes of the pure components there is an excess (or deficit) number of different molecules around a central molecule. The excess (or deficit) becomes zero when the components of the ideal binary mixture have the same volume. The new method is also applied to methanol + water and 2-propanol + water mixtures. In the case of the 2-propanol + water mixture, the new method, in contrast to the other ones, indicates that clusters dominated by 2-propanol disappear at high alcohol mole fractions, in agreement with experimental observations. Finally, it is shown that the application of the new procedure to the ternary mixture water/protein/cosolvent at infinite dilution of the protein led to almost the same results as the methods involving a reference state.

Perfluorooctane sulfonate adsorption on powder activated carbon: Effect of phosphate (P) competition, pH, and temperature.

PubMed

Qian, Jin; Shen, Mengmeng; Wang, Peifang; Wang, Chao; Li, Kun; Liu, Jingjing; Lu, Bianhe; Tian, Xin

2017-09-01

Powdered activated carbon (PAC), as an adsorbent, was applied to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Laboratory batch experiments were performed to investigate the influences of phosphate (P) competition, temperature, and pH for PFOS adsorption onto PAC. The results showed that higher temperature favored PFOS adsorption in single and binary systems. The kinetic data fitted very well to the pseudo second-order kinetic model. Thermodynamically, the endothermic enthalpy of the PFOS adsorption in single and binary systems were 125.07 and 21.25 kJ mol -1 , respectively. The entropy of the PFOS adsorption in single and binary systems were 0.479 and 0.092 kJ mol -1  K -1 , respectively. And the Gibbs constants were negative. These results indicated that the adsorption processes were spontaneous. The adsorption isotherms of PFOS agreed well with the Langmuir model. In the single system, PFOS adsorption decreased with increased pH value. The difference in the amount of PFOS adsorption between the single and binary systems increased at higher pH. Frustrated total internal reflection (FTIR) demonstrated that P competition increased the hydrophilicity of the PAC and the electrostatic repulsion between PFOS and PAC, then the PFOS adsorption amount decreased. It also demonstrated that, at higher temperature, increased PFOS adsorption was mainly due to the higher diffusion rate of PFOS molecules and greater number of active sites opened on the PAC surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

A vigorous activity cycle mimicking a planetary system in HD 200466

NASA Astrophysics Data System (ADS)

Carolo, E.; Desidera, S.; Gratton, R.; Martinez Fiorenzano, A. F.; Marzari, F.; Endl, M.; Mesa, D.; Barbieri, M.; Cecconi, M.; Claudi, R. U.; Cosentino, R.; Scuderi, S.

2014-07-01

Stellar activity can be a source of radial velocity (RV) noise and can reproduce periodic RV variations similar to those produced by an exoplanet. We present the vigorous activity cycle in the primary of the visual binary HD 200466, a system made of two almost identical solar-type stars with an apparent separation of 4.6 arcsec at a distance of 44 ± 2 pc. High precision RV over more than a decade, adaptive optics (AO) images, and abundances have been obtained for both components. A linear trend in the RV is found for the secondary. We assumed that it is due to the binary orbit and once coupled with the astrometric data, it strongly constrains the orbital solution of the binary at high eccentricities (e ~ 0.85) and quite small periastron of ~21 AU. If this orbital motion is subtracted from the primary radial velocity curve, a highly significant (false alarm probability <0.1%) period of about 1300 d is obtained, suggesting in a first analysis the presence of a giant planet, but it turned out to be due to the stellar activity cycle. Since our spectra do not include the Ca II resonance lines, we measured a chromospheric activity indicator based on the Hα line to study the correlation between activity cycles and long-term activity variations. While the bisector analysis of the line profile does not show a clear indication of activity, the correlation between the Hα line indicator and the RV measurements identify the presence of a strong activity cycle. Based on observations made with the Italian Telescopio Nazionale Galileo (TNG) operated on the island of La Palma by the Fundación Galileo Galilei of the Istituto Nazionale di Astrofisica (INAF) at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofísica de Canarias.Tables 5 and 6 are available in electronic form at http://www.aanda.org

Thermodynamic framework for the ground state of a simple quantum system

NASA Astrophysics Data System (ADS)

Souza, Andre M. C.; Nobre, Fernando D.

2017-01-01

The ground state of a two-level system (associated with probabilities p and 1 -p , respectively) defined by a general Hamiltonian H ̂=Ĥ0+λ V ̂ is studied. The simple case characterized by λ =0 , whose Hamiltonian Ĥ0 is represented by a diagonal matrix, is well established and solvable within Boltzmann-Gibbs statistical mechanics; in particular, it follows the third law of thermodynamics, presenting zero entropy (SBG=0 ) at zero temperature (T =0 ). Herein it is shown that the introduction of a perturbation λ V ̂ (λ >0 ) in the Hamiltonian may lead to a nontrivial ground state, characterized by an entropy S [p ] (with S [p ] ≠SBG[p ] ), if the Hermitian operator V ̂ is represented by a 2 ×2 matrix, defined by nonzero off-diagonal elements V12=V21=-z , where z is a real positive number. Hence, this new term in the Hamiltonian, presenting V12≠0 , may produce physically significant changes in the ground state, and especially, it allows for the introduction of an effective temperature θ (θ ∝λ z ), which is shown to be a parameter conjugated to the entropy S . Based on this, one introduces an infinitesimal heatlike quantity, δ Q =θ d S , leading to a consistent thermodynamic framework, and by proposing an infinitesimal form for the first law, a Carnot cycle and thermodynamic potentials are obtained. All results found are very similar to those of usual thermodynamics, through the identification T ↔θ , and particularly the form for the efficiency of the proposed Carnot Cycle. Moreover, S also follows a behavior typical of a third law, i.e., S →0 , when θ →0 .

Thermodynamic framework for the ground state of a simple quantum system.

PubMed

Souza, Andre M C; Nobre, Fernando D

2017-01-01

The ground state of a two-level system (associated with probabilities p and 1-p, respectively) defined by a general Hamiltonian H[over ̂]=H[over ̂]_{0}+λV[over ̂] is studied. The simple case characterized by λ=0, whose Hamiltonian H[over ̂]_{0} is represented by a diagonal matrix, is well established and solvable within Boltzmann-Gibbs statistical mechanics; in particular, it follows the third law of thermodynamics, presenting zero entropy (S_{BG}=0) at zero temperature (T=0). Herein it is shown that the introduction of a perturbation λV[over ̂] (λ>0) in the Hamiltonian may lead to a nontrivial ground state, characterized by an entropy S[p] (with S[p]≠S_{BG}[p]), if the Hermitian operator V[over ̂] is represented by a 2×2 matrix, defined by nonzero off-diagonal elements V_{12}=V_{21}=-z, where z is a real positive number. Hence, this new term in the Hamiltonian, presenting V_{12}≠0, may produce physically significant changes in the ground state, and especially, it allows for the introduction of an effective temperature θ (θ∝λz), which is shown to be a parameter conjugated to the entropy S. Based on this, one introduces an infinitesimal heatlike quantity, δQ=θdS, leading to a consistent thermodynamic framework, and by proposing an infinitesimal form for the first law, a Carnot cycle and thermodynamic potentials are obtained. All results found are very similar to those of usual thermodynamics, through the identification T↔θ, and particularly the form for the efficiency of the proposed Carnot Cycle. Moreover, S also follows a behavior typical of a third law, i.e., S→0, when θ→0.

APPLICATION OF GAS DYNAMICAL FRICTION FOR PLANETESIMALS. II. EVOLUTION OF BINARY PLANETESIMALS

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

Grishin, Evgeni; Perets, Hagai B.

2016-04-01

One of the first stages of planet formation is the growth of small planetesimals and their accumulation into large planetesimals and planetary embryos. This early stage occurs long before the dispersal of most of the gas from the protoplanetary disk. At this stage gas–planetesimal interactions play a key role in the dynamical evolution of single intermediate-mass planetesimals (m{sub p} ∼ 10{sup 21}–10{sup 25} g) through gas dynamical friction (GDF). A significant fraction of all solar system planetesimals (asteroids and Kuiper-belt objects) are known to be binary planetesimals (BPs). Here, we explore the effects of GDF on the evolution of BPs embedded inmore » a gaseous disk using an N-body code with a fiducial external force accounting for GDF. We find that GDF can induce binary mergers on timescales shorter than the disk lifetime for masses above m{sub p} ≳ 10{sup 22} g at 1 au, independent of the binary initial separation and eccentricity. Such mergers can affect the structure of merger-formed planetesimals, and the GDF-induced binary inspiral can play a role in the evolution of the planetesimal disk. In addition, binaries on eccentric orbits around the star may evolve in the supersonic regime, where the torque reverses and the binary expands, which would enhance the cross section for planetesimal encounters with the binary. Highly inclined binaries with small mass ratios, evolve due to the combined effects of Kozai–Lidov (KL) cycles with GDF which lead to chaotic evolution. Prograde binaries go through semi-regular KL evolution, while retrograde binaries frequently flip their inclination and ∼50% of them are destroyed.« less

Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

NASA Astrophysics Data System (ADS)

Qian, Hong; Kjelstrup, Signe; Kolomeisky, Anatoly B.; Bedeaux, Dick

2016-04-01

Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

Solution for a bipartite Euclidean traveling-salesman problem in one dimension

NASA Astrophysics Data System (ADS)

Caracciolo, Sergio; Di Gioacchino, Andrea; Gherardi, Marco; Malatesta, Enrico M.

2018-05-01

The traveling-salesman problem is one of the most studied combinatorial optimization problems, because of the simplicity in its statement and the difficulty in its solution. We characterize the optimal cycle for every convex and increasing cost function when the points are thrown independently and with an identical probability distribution in a compact interval. We compute the average optimal cost for every number of points when the distance function is the square of the Euclidean distance. We also show that the average optimal cost is not a self-averaging quantity by explicitly computing the variance of its distribution in the thermodynamic limit. Moreover, we prove that the cost of the optimal cycle is not smaller than twice the cost of the optimal assignment of the same set of points. Interestingly, this bound is saturated in the thermodynamic limit.

Solution for a bipartite Euclidean traveling-salesman problem in one dimension.

PubMed

Caracciolo, Sergio; Di Gioacchino, Andrea; Gherardi, Marco; Malatesta, Enrico M

2018-05-01

The traveling-salesman problem is one of the most studied combinatorial optimization problems, because of the simplicity in its statement and the difficulty in its solution. We characterize the optimal cycle for every convex and increasing cost function when the points are thrown independently and with an identical probability distribution in a compact interval. We compute the average optimal cost for every number of points when the distance function is the square of the Euclidean distance. We also show that the average optimal cost is not a self-averaging quantity by explicitly computing the variance of its distribution in the thermodynamic limit. Moreover, we prove that the cost of the optimal cycle is not smaller than twice the cost of the optimal assignment of the same set of points. Interestingly, this bound is saturated in the thermodynamic limit.

Quantum-mechanical engines working with an ideal gas with a finite number of particles confined in a power-law trap

NASA Astrophysics Data System (ADS)

Wang, Jianhui; Ma, Yongli; He, Jizhou

2015-07-01

Based on quantum thermodynamic processes, we make a quantum-mechanical (QM) extension of the typical heat engine cycles, such as the Carnot, Brayton, Otto, Diesel cycles, etc., with no introduction of the concept of temperature. When these QM engine cycles are implemented by an ideal gas confined in an arbitrary power-law trap, a relation between the quantum adiabatic exponent and trap exponent is found. The differences and similarities between the efficiency of a given QM engine cycle and its classical counterpart are revealed and discussed.

Comment on "Similarity between quantum mechanics and thermodynamics: Entropy, temperature, and Carnot cycle".

PubMed

González-Díaz, L A; Díaz-Solórzano, S

2015-05-01

In the paper by Abe and Okuyama [Phys. Rev. E 83, 021121 (2011)], the quantum Carnot cycle of a simple two-state model of a particle confined in a one-dimensional infinite potential well is discussed. It is claimed that the state at the beginning of the quantum Carnot cycle is pure. After that, it is apparently transmuted to a mixed state if Clausius equality is imposed. We prove that this statement is incorrect. In particular, we prove that the state at the beginning of the cycle is mixed due to the process of measuring energy.

In situ monitoring of atomic layer controlled pore reduction in alumina tubular membranes using sequential surface reactions

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

Berland, B.S.; Gartland, I.P.; Ott, A.W.

1998-12-01

The pore diameter in alumina tubular membranes with an initial diameter of 50 {angstrom} was systematically reduced using the atomic layer controlled deposition of Al{sub 2}O{sub 3}. The Al{sub 2}O{sub 3} was deposited using sequential exposures of Al(CH{sub 3}){sub 3} (trimethylaluminum, TMA) and H{sub 2}O in an ABAB... binary reaction sequence. The pore diameter reduction was monitored using in situ N{sub 2} and Ar conductance measurements. The conductance, C = Q/{Delta}P, was measured using a mass flow controller to define a constant gas throughput, Q, and a pair of capacitance manometers to monitor the transmembrane pressure drop, {Delta}P. Conductance measurementsmore » were periodically obtained at 298 K as a function of AB binary reaction cycles. These conductance measurements were consistent with a pore diameter reduction from 50 {angstrom} to {approximately}5--10 {angstrom} at a rate of {approximately}2.5 {angstrom} for each AB cycle. Conductance measurements were also performed during the Al{sub 2}O{sub 3} deposition at 500 K after each half-reaction in the binary reaction sequence. These in situ conductance measurements demonstrate that the pore diameters in mesoporous membranes can be reduced to molecular dimensions with atomic layer control using sequential surface reactions. Poe diameters can be tailored for specific applications by varying the number of AB cycles and changing the nature of the terminating surface functional groups.« less

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

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

PubMed

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

2017-08-01

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

Modeling of Antarctic Sea Ice in a General Circulation Model.

NASA Astrophysics Data System (ADS)

Wu, Xingren; Simmonds, Ian; Budd, W. F.

1997-04-01

A dynamic-thermodynamic sea ice model is developed and coupled with the Melbourne University general circulation model to simulate the seasonal cycle of the Antarctic sea ice distribution. The model is efficient, rapid to compute, and useful for a range of climate studies. The thermodynamic part of the sea ice model is similar to that developed by Parkinson and Washington, the dynamics contain a simplified ice rheology that resists compression. The thermodynamics is based on energy conservation at the top surface of the ice/snow, the ice/water interface, and the open water area to determine the ice formation, accretion, and ablation. A lead parameterization is introduced with an effective partitioning scheme for freezing between and under the ice floes. The dynamic calculation determines the motion of ice, which is forced with the atmospheric wind, taking account of ice resistance and rafting. The simulated sea ice distribution compares reasonably well with observations. The seasonal cycle of ice extent is well simulated in phase as well as in magnitude. Simulated sea ice thickness and concentration are also in good agreement with observations over most regions and serve to indicate the importance of advection and ocean drift in the determination of the sea ice distribution.

Binary Hierarchical Porous Graphene/Pyrolytic Carbon Nanocomposite Matrix Loaded with Sulfur as a High-Performance Li-S Battery Cathode.

PubMed

Zhang, Hang; Gao, Qiuming; Qian, Weiwei; Xiao, Hong; Li, Zeyu; Ma, Li; Tian, Xuehui

2018-06-06

A N,O-codoped hierarchical porous nanocomposite consisting of binary reduced graphene oxide and pyrolytic carbon (rGO/PC) from chitosan is fabricated. The optimized rGO/PC possesses micropores with size distribution concentrated around 1.1 nm and plenty of meso/macropores. The Brunauer-Emmett-Teller specific surface area is 480.8 m 2 g -1 , and it possesses impressively large pore volume of 2.14 cm 3 g -1 . On the basis of the synergistic effects of the following main factors: (i) the confined space effect in the hierarchical porous binary carbonaceous matrix; (ii) the anchor effects by strong chemical bonds with codoped N and O atoms; and (iii) the good flexibility and conductivity of rGO, the rGO/PC/S holding 75 wt % S exhibits high performance as Li-S battery cathode. Specific capacity of 1625 mA h g -1 can be delivered at 0.1 C (1 C = 1675 mA g -1 ), whereas 848 mA h g -1 can be maintained after 300 cycles at 1 C. Even at high rate of 5 C, 412 mA h g -1 can be restrained after 1000 cycles.

An Atlas of O-C Diagrams of Eclipsing Binary Stars

NASA Astrophysics Data System (ADS)

Kreiner, Jerzy M.; Kim, Chun-Hwey; Nha, Il-Seong

The Atlas contains data for 1,138 eclipsing binaries represented by 91,798 minima timings, collected from the usual international and local journals, observatory publications and unpublished minima. Among this source material there is a considerable representation of amateur astronomers. Some timings were found in the card-index catalogue of the Astronomical Observatory of the Jagiellonian University, Cracow. Stars were included in the Atlas provided that they satisfied 3 criteria: (1) at least 20 minima had been times; (2) these minima spanned at least 2,500 cycles; and (3) the 2,500 cycles represented no fewer than 40 years. Some additional stars not strictly satisfying these criteria were also included if useful information was available. For each star, the Atlas contains the (O-C) diagram calculated by the authors and a table of general information containing: binary characteristics; assorted catalogue numbers; the statistics of the collected minima timings; the light elements (light ephemeris); comments and literature references. All of the data and diagrams in the Atlas are also available in electronic form on the Internet at http://www.as.ap.krakow.pl/o- c".

Length requirements for numerical-relativity waveforms

NASA Astrophysics Data System (ADS)

Hannam, Mark; Husa, Sascha; Ohme, Frank; Ajith, P.

2010-12-01

One way to produce complete inspiral-merger-ringdown gravitational waveforms from black-hole-binary systems is to connect post-Newtonian (PN) and numerical-relativity (NR) results to create “hybrid” waveforms. Hybrid waveforms are central to the construction of some phenomenological models for gravitational-wave (GW) search templates, and for tests of GW search pipelines. The dominant error source in hybrid waveforms arises from the PN contribution, and can be reduced by increasing the number of NR GW cycles that are included in the hybrid. Hybrid waveforms are considered sufficiently accurate for GW detection if their mismatch error is below 3% (i.e., a fitting factor above 0.97). We address the question of the length requirements of NR waveforms such that the final hybrid waveforms meet this requirement, considering nonspinning binaries with q=M2/M1∈[1,4] and equal-mass binaries with χ=Si/Mi2∈[-0.5,0.5]. We conclude that, for the cases we study, simulations must contain between three (in the equal-mass nonspinning case) and ten (the χ=0.5 case) orbits before merger, but there is also evidence that these are the regions of parameter space for which the least number of cycles will be needed.

Thermodynamic constraints on fluctuation phenomena

NASA Astrophysics Data System (ADS)

Maroney, O. J. E.

2009-12-01

The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

Thermodynamic constraints on fluctuation phenomena.

PubMed

Maroney, O J E

2009-12-01

The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

Microstructural modeling of fatigue fracture of shape memory alloys at thermomechanical cyclic loading

NASA Astrophysics Data System (ADS)

Belyaev, Fedor S.; Evard, Margarita E.; Volkov, Aleksandr E.

2018-05-01

A microstructural model of shape memory alloys (SMA) describing their deformation and fatigue fracture is presented. A new criterion of fracture has been developed which takes into account the effect of hydrostatic pressure, deformation defects and material damage. It is shown that the model can describe the fatigue fracture of SMA under various thermomechanical cycling regimes. Results of calculating the number of cycles to failure at thermocycling under a constant stress, at symmetric two-sided cyclic deformation, at straining-unloading cycles, at cycling in the regime of the thermodynamic cycles of a SMA working body in the hard (strain controlled) and soft (stress controlled) working cycles, is studied. Results of calculating the number of cycles to failure are presented for different parameters of these cycles.

Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

PubMed

Grasso, E J; Oliveira, R G; Maggio, B

2016-02-15

The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning. Copyright © 2015 Elsevier Inc. All rights reserved.

Study on Colloid Vibration Current in Aqueous Solution of Binary Surfactant Mixtures: Effects of Counterions and Hydrophobic Chains.

PubMed

Takata, Youichi; Hyono, Atsushi; Ohshima, Hiroyuki

2016-11-01

In order to elucidate an electroacoustic phenomenon of mixed micelles in an aqueous solution, we measured the colloid vibration current (CVI) in aqueous solutions of binary surfactant mixtures. Based on the thermodynamic treatment of critical micelle concentration (cmc) values determined by conductivity measurements, it was expected that dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) molecules would mix ideally in the micelle. However, the micelle composition as evaluated from the CVI measurement, based on the linear dependence of the CVI value on the micelle composition, differed from the aforementioned ideality. Considering these observations, we concluded that the CVI measurement was more sensitive to the counterion distribution near the micelle surface, whereas the thermodynamically determined micelle composition included the counterions more loosely bound in the diffuse double layer due to the electroneutrality condition included in its assumption. On the other hand, the phase diagram illustrating micelle formation in the lithium dodecyl sulfate (LiDS) - lithium perfluorooctane sulfonate (LiFOS) mixture system showed a heteroazeotropic point arising from the stronger interactions between homologous surfactants than between heterologous ones. Although the concentration dependence of CVI values was expected to drastically change at a heteroazeotropic point due to the enormous variation in the density of the micelle core, the results showed a monotonous change, which suggests that the density of the micelle core varies continuously. By taking the partial molar volume of fluorocarbon compounds in the hydrocarbon compounds into account, the density of the micelle core was affected by the size of the micelle as well as its constituents.

Thermodynamic and Mechanical Analysis of a Thermomagnetic Rotary Engine

NASA Astrophysics Data System (ADS)

Fajar, D. M.; Khotimah, S. N.; Khairurrijal

2016-08-01

A heat engine in magnetic system had three thermodynamic coordinates: magnetic intensity ℋ, total magnetization ℳ, and temperature T, where the first two of them are respectively analogous to that of gaseous system: pressure P and volume V. Consequently, Carnot cycle that constitutes the principle of a heat engine in gaseous system is also valid on that in magnetic system. A thermomagnetic rotary engine is one model of it that was designed in the form of a ferromagnetic wheel that can rotates because of magnetization change at Curie temperature. The study is aimed to describe the thermodynamic and mechanical analysis of a thermomagnetic rotary engine and calculate the efficiencies. In thermodynamic view, the ideal processes are isothermal demagnetization, adiabatic demagnetization, isothermal magnetization, and adiabatic magnetization. The values of thermodynamic efficiency depend on temperature difference between hot and cold reservoir. In mechanical view, a rotational work is determined through calculation of moment of inertia and average angular speed. The value of mechanical efficiency is calculated from ratio between rotational work and heat received by system. The study also obtains exergetic efficiency that states the performance quality of the engine.

On ternary species mixing and combustion in isotropic turbulence at high pressure

NASA Astrophysics Data System (ADS)

Lou, Hong; Miller, Richard S.

2004-05-01

Effects of Soret and Dufour cross-diffusion, whereby both concentration and thermal diffusion occur in the presence of mass fraction, temperature, and pressure gradients, are investigated in the context of both binary and ternary species mixing and combustion in isotropic turbulence at large pressure. The compressible flow formulation is based on a cubic real-gas state equation, and includes generalized forms for heat and mass diffusion derived from nonequilibrium thermodynamics and fluctuation theory. A previously derived formulation of the generalized binary species heat and mass fluxes is first extended to the case of ternary species, and appropriate treatment of the thermal and mass diffusion factors is described. Direct numerical simulations (DNS) are then conducted for both binary and ternary species mixing and combustion in stationary isotropic turbulence. Mean flow temperatures and pressures of =700 K and =45 atm are considered to ensure that all species mixtures remain in the supercritical state such that phase changes do not occur. DNS of ternary species systems undergoing both pure mixing and a simple chemical reaction of the form O2+N2→2NO are then conducted. It is shown that stationary scalar states previously observed for binary mixing persist for the ternary species problem as well; however, the production and magnitude of the scalar variance is found to be altered for the intermediate molecular weight species as compared to the binary species case. The intermediate molecular weight species produces a substantially smaller scalar variance than the remaining species for all flows considered. For combustion of nonstoichiometric mixtures, a binary species mixture, characterized by stationary scalar states, results at long times after the lean reactant is depleted. The form of this final scalar distribution is observed to be similar to that found in the binary flow situation. A series of lower resolution simulations for a variety of species is then used to show the dependence of the stationary scalar variance on the turbulence Reynolds number, turbulence Mach number, species molecular weight ratio, and relative proportion of two species present in the flow after completion of combustion.

Off-design performance of a chemical looping combustion (CLC) combined cycle: effects of ambient temperature

NASA Astrophysics Data System (ADS)

Chi, Jinling; Wang, Bo; Zhang, Shijie; Xiao, Yunhan

2010-02-01

The present work investigates the influence of ambient temperature on the steady-state off-design thermodynamic performance of a chemical looping combustion (CLC) combined cycle. A sensitivity analysis of the CLC reactor system was conducted, which shows that the parameters that influence the temperatures of the CLC reactors most are the flow rate and temperature of air entering the air reactor. For the ambient temperature variation, three off-design control strategies have been assumed and compared: 1) without any Inlet Guide Vane (IGV) control, 2) IGV control to maintain air reactor temperature and 3) IGV control to maintain constant fuel reactor temperature, aside from fuel flow rate adjusting. Results indicate that, compared with the conventional combined cycle, due to the requirement of pressure balance at outlet of the two CLC reactors, CLC combined cycle shows completely different off-design thermodynamic characteristics regardless of the control strategy adopted. For the first control strategy, temperatures of the two CLC reactors both rise obviously as ambient temperature increases. IGV control adopted by the second and the third strategy has the effect to maintain one of the two reactors' temperatures at design condition when ambient temperature is above design point. Compare with the second strategy, the third would induce more severe decrease of efficiency and output power of the CLC combined cycle.

Theoretical investigation of the structural stabilities, optoelectronic properties and thermodynamic characteristics of GaPxSb1-x ternary alloys

NASA Astrophysics Data System (ADS)

Oumelaz, F.; Nemiri, O.; Boumaza, A.; Ghemid, S.; Meradji, H.; Bin Omran, S.; El Haj Hassan, F.; Rai, D. P.; Khenata, R.

2018-06-01

In this theoretical study, we have investigated the structural, phase transition, electronic, thermodynamic and optical properties of GaPxSb1-x ternary alloys. Our calculations are performed with the WIEN2k code based on density functional theory using the full-potential linearized augmented plane wave method. For the electron exchange-correlation potential, a generalized gradient approximation within Wu-Cohen scheme is considered. The recently developed Tran-Blaha modified Becke-Johnson potential has also been used to improve the underestimated band gap. The structural properties, including the lattice constants, the bulk moduli and their pressure derivatives are in very good agreement with the available experimental data and theoretical results. Several structural phase transitions were studied here to establish the stable structure and to predict the phase transition under hydrostatic pressure. The computed transition pressure (Pt) of the material of our interest from the zinc blende (B3) to the rock salt (B1) phase has been determined and found to agree well with the experimental and theoretical data. The calculated band structure shows that GaSb binary compound and the ternary alloys are direct band gap semiconductors. Optical parameters such as the dielectric constants and the refractive indices are calculated and analyzed. The thermodynamic results are also interpreted and analyzed.

Insight into the Am-O Phase Equilibria: A Thermodynamic Study Coupling High-Temperature XRD and CALPHAD Modeling.

PubMed

Epifano, Enrica; Guéneau, Christine; Belin, Renaud C; Vauchy, Romain; Lebreton, Florent; Richaud, Jean-Christophe; Joly, Alexis; Valot, Christophe; Martin, Philippe M

2017-07-03

In the frame of minor actinide transmutation, americium can be diluted in UO 2 and (U, Pu)O 2 fuels burned in fast neutron reactors. The first mandatory step to foresee the influence of Am on the in-reactor behavior of transmutation targets or fuel is to have fundamental knowledge of the Am-O binary system and, in particular, of the AmO 2-x phase. In this study, we coupled HT-XRD (high-temperature X-ray diffraction) experiments with CALPHAD thermodynamic modeling to provide new insights into the structural properties and phase equilibria in the AmO 2-x -AmO 1.61+x -Am 2 O 3 domain. Because of this approach, we were able for the first time to assess the relationships between temperature, lattice parameter, and hypostoichiometry for fcc AmO 2-x . We showed the presence of a hyperstoichiometric existence domain for the bcc AmO 1.61+x phase and the absence of a miscibility gap in the fcc AmO 2-x phase, contrary to previous representations of the phase diagram. Finally, with the new experimental data, a new CALPHAD thermodynamic model of the Am-O system was developed, and an improved version of the phase diagram is presented.

Thermodynamically consistent Langevin dynamics with spatially correlated noise predicting frictionless regime and transient attraction effect

NASA Astrophysics Data System (ADS)

Majka, M.; Góra, P. F.

2016-10-01

While the origins of temporal correlations in Langevin dynamics have been thoroughly researched, the understanding of spatially correlated noise (SCN) is rather incomplete. In particular, very little is known about the relation between friction and SCN. In this article, starting from the microscopic, deterministic model, we derive the analytical formula for the spatial correlation function in the particle-bath interactions. This expression shows that SCN is the inherent component of binary mixtures, originating from the effective (entropic) interactions. Further, employing this spatial correlation function, we postulate the thermodynamically consistent Langevin equation driven by the Gaussian SCN and calculate the adequate fluctuation-dissipation relation. The thermodynamical consistency is achieved by introducing the spatially variant friction coefficient, which can be also derived analytically. This coefficient exhibits a number of intriguing properties, e.g., the singular behavior for certain types of interactions. Eventually, we apply this new theory to the system of two charged particles in the presence of counter-ions. Such particles interact via the screened-charge Yukawa potential and the inclusion of SCN leads to the emergence of the anomalous frictionless regime. In this regime the particles can experience active propulsion leading to the transient attraction effect. This effect suggests a nonequilibrium mechanism facilitating the molecular binding of the like-charged particles.

Molecular investigation on the binding of Cd(II) by the binary mixtures of montmorillonite with two bacterial species

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

Du, Huihui; Qu, ChenChen; Liu, Jing

Bacteria and phyllosilicate commonly coexist in the natural environment, producing various bacteria–clay complexes that are capable of immobilizing heavy metals, such as cadmium, via adsorption. However, the molecular binding mechanisms of heavy metals on these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive B. subtilis, Gram-negative P. putida and their binary mixtures with montmorillonite (Mont) using the Cd K-edge x-ray absorption spectroscopy (XAS) and isothermal titration calorimetry (ITC). We observed a lower adsorptive capacity for P. putida than B. subtilis, whereas P. putida–Mont and B. subtilis–Mont mixtures showed nearly identical Cd adsorption behaviors. EXAFS fitsmore » and ITC measurements demonstrated more phosphoryl binding of Cd in P. putida. The decreased coordination of C atoms around Cd and the reduced adsorption enthalpies and entropies for the binary mixtures compared to that for individual bacteria suggested that the bidentate Cd-carboxyl complexes in pure bacteria systems were probably transformed into monodentate complexes that acted as ionic bridging structure between bacteria and motmorillonite. This study clarified the binding mechanism of Cd at the bacteria–phyllosilicate interfaces from a molecular and thermodynamic view, which has an environmental significance for predicting the chemical behavior of trace elements in complex mineral–organic systems.« less

Simultaneous adsorption of Cu2+ and Acid fuchsin (AF) from aqueous solutions by CMC/bentonite composite.

PubMed

Gong, Ning; Liu, Yanping; Huang, Ruihua

2018-04-21

Carboxymethyl-chitosan (CMC)/bentonite composite was prepared by the method of membrane-forming, and characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques. The simultaneous adsorption of Cu 2+ and Acid fuchsin (AF) applying CMC/bentonite composite as an adsorbent in single or binary systems was investigated. The adsorption study was conducted systematically by varying the ratio of CMC to bentonite, adsorbent dosage, initial pH value, initial Cu 2+ (or AF) concentration, contact time and the interaction of two components in binary solutions. The results showed that the presence of Cu 2+ hindered the adsorption of AF, while the presence of AF almost had no influence on the adsorption of Cu 2+ in binary systems. The adsorption data of Cu 2+ and AF were both suitable for Langmuir isotherm model, and the maximum adsorption capacities of CMC/bentonite composite, according to the Langmuir isotherm model were 81.4 mg/g for Cu 2+ and 253.2 mg/g for AF at 298 K. The pseudo-second-order model could better describe the adsorption process of Cu 2+ and AF. Thermodynamic constant values illustrated that the adsorption of Cu 2+ was endothermic, while the adsorption process of AF was exothermic. Copyright © 2018. Published by Elsevier B.V.

Properties of binary transition-metal arsenides (TAs)

NASA Astrophysics Data System (ADS)

Saparov, Bayrammurad; Mitchell, Jonathan E.; Sefat, Athena S.

2012-08-01

We present thermodynamic and transport properties of transition-metal (T) arsenides, TAs, with T = Sc to Ni (3d), Zr, Nb, Ru (4d), Hf and Ta (5d). Characterization of these binaries is carried out with powder x-ray diffraction, temperature- and field-dependent magnetization and resistivity, temperature-dependent heat capacity, Seebeck coefficient, and thermal conductivity. All binaries show metallic behavior except TaAs and RuAs. TaAs, NbAs, ScAs and ZrAs are diamagnetic, while CoAs, VAs, TiAs, NiAs and RuAs show approximately Pauli paramagnetic behavior. FeAs and CrAs undergo antiferromagnetic ordering below TN ≈ 71 K and TN ≈ 260 K, respectively. MnAs is a ferromagnet below TC ≈ 317 K and undergoes hexagonal-orthorhombic-hexagonal transitions at TS ≈ 317 K and 384 K, respectively. For TAs, Seebeck coefficients vary between + 40 and - 40 μV K-1 in the 2-300 K range, whereas thermal conductivity values stay below 18 W m-1 K-1. The Sommerfeld coefficients γ are less than 10 mJ K-2 mol-1. At room temperature with application of 8 T magnetic field, large positive magnetoresistance is found for TaAs (˜25%), MnAs (˜90%) and NbAs (˜75%).

Body centered cubic magnesium niobium hydride with facile room temperature absorption and four weight percent reversible capacity.

PubMed

Tan, XueHai; Wang, Liya; Holt, Chris M B; Zahiri, Beniamin; Eikerling, Michael H; Mitlin, David

2012-08-21

We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic destabilization relative to the baseline -77 kJ mol(-1) H(2) for rutile MgH(2). The hydrogenation cycling kinetics are remarkable. At room temperature and 1 bar hydrogen it takes 30 minutes to absorb a 1.5 μm thick film at sorption cycle 1, and 1 minute at cycle 5. Reversible desorption is achieved in about 60 minutes at 175 °C. Using ab initio calculations we have examined the thermodynamic stability of metallic alloys with hexagonal close packed (hcp) versus bcc crystal structure. Moreover we have analyzed the formation energies of the alloy hydrides that are bcc, rutile or fluorite.

Computer Program for the Design and Off-Design Performance of Turbojet and Turbofan Engine Cycles

NASA Technical Reports Server (NTRS)

Morris, S. J.

1978-01-01

The rapid computer program is designed to be run in a stand-alone mode or operated within a larger program. The computation is based on a simplified one-dimensional gas turbine cycle. Each component in the engine is modeled thermo-dynamically. The component efficiencies used in the thermodynamic modeling are scaled for the off-design conditions from input design point values using empirical trends which are included in the computer code. The engine cycle program is capable of producing reasonable engine performance prediction with a minimum of computer execute time. The current computer execute time on the IBM 360/67 for one Mach number, one altitude, and one power setting is about 0.1 seconds. about 0.1 seconds. The principal assumption used in the calculation is that the compressor is operated along a line of maximum adiabatic efficiency on the compressor map. The fluid properties are computed for the combustion mixture, but dissociation is not included. The procedure included in the program is only for the combustion of JP-4, methane, or hydrogen.

A practical approximation algorithm for solving massive instances of hybridization number for binary and nonbinary trees.

PubMed

van Iersel, Leo; Kelk, Steven; Lekić, Nela; Scornavacca, Celine

2014-05-05

Reticulate events play an important role in determining evolutionary relationships. The problem of computing the minimum number of such events to explain discordance between two phylogenetic trees is a hard computational problem. Even for binary trees, exact solvers struggle to solve instances with reticulation number larger than 40-50. Here we present CycleKiller and NonbinaryCycleKiller, the first methods to produce solutions verifiably close to optimality for instances with hundreds or even thousands of reticulations. Using simulations, we demonstrate that these algorithms run quickly for large and difficult instances, producing solutions that are very close to optimality. As a spin-off from our simulations we also present TerminusEst, which is the fastest exact method currently available that can handle nonbinary trees: this is used to measure the accuracy of the NonbinaryCycleKiller algorithm. All three methods are based on extensions of previous theoretical work (SIDMA 26(4):1635-1656, TCBB 10(1):18-25, SIDMA 28(1):49-66) and are publicly available. We also apply our methods to real data.

Structure, dynamics, and thermodynamics of a family of potentials with tunable softness

NASA Astrophysics Data System (ADS)

Shi, Zane; Debenedetti, Pablo G.; Stillinger, Frank H.; Ginart, Paul

2011-08-01

We investigate numerically the structure, thermodynamics, and relaxation behavior of a family of (n, 6) Lennard-Jones-like glass-forming binary mixtures interacting via pair potentials with variable softness, fixed well depth, and fixed well depth location. These constraints give rise to progressively more negative attractive tails upon softening, for separations greater than the potential energy minimum. Over the range of conditions examined, we find only modest dependence of structure on softness. In contrast, decreasing the repulsive exponent from n = 12 to n = 7 causes the diffusivity to increase by as much as two orders of magnitude at fixed temperature and density, and produces mechanically stable packings (inherent structures) with cohesive energies that are, on average, ˜1.7 well depths per particle larger than for the corresponding Lennard-Jones (n = 12) case. The softer liquids have markedly higher entropies and lower Kauzmann temperatures than their Lennard-Jones (n = 12) counterparts, and they remain diffusive down to appreciably lower temperatures. We find that softening leads to a modest increase in fragility.

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

Stiegler, Thomas; Sadus, Richard J., E-mail: rsadus@swin.edu.au

General methods for combining interactions between particles characterised by non-identical intermolecular potentials are investigated. The combination methods are tested by performing molecular dynamics simulations to determine the pressure, energy, isochoric and isobaric heat capacities, thermal expansion coefficient, isothermal compressibility, Joule-Thomson coefficient, and speed of sound of 10-5 + 12-6 Mie potential binary mixtures. In addition to the two non-identical Mie potentials, mixtures are also studied with non-identical intermolecular parameters. The combination methods are compared with results obtained by simply averaging the Mie exponents. When either the energy or size parameters are non-identical, very significant differences emerge in the thermodynamic propertiesmore » predicted by the alternative combination methods. The isobaric heat capacity is the thermodynamic property that is most affected by the relative magnitude of the intermolecular potential parameters and the method for combining non-identical potentials. Either the arithmetic or geometric combination of potentials provides a simple and effective way of performing simulations involving mixtures of components characterised by non-identical intermolecular potentials, which is independent of their functional form.« less

Dissolution thermodynamics and solubility of silymarin in PEG 400-water mixtures at different temperatures.

PubMed

Shakeel, Faiyaz; Anwer, Md Khalid

2015-01-01

An isothermal method was used to measure the solubility of silymarin in binary polyethylene glycol 400 (PEG 400) + water co-solvent mixtures at temperatures T = 298.15-333.15 K and pressure p = 0.1 MPa. Apelblat and Yalkowsky models were used to correlate experimental solubility data. The mole fraction solubility of silymarin was found to increase with increasing the temperature and mass fraction of PEG 400 in co-solvent mixtures. The root mean square deviations were observed in the range of 0.48-5.32% and 1.50-9.65% for the Apelblat equation and Yalkowsky model, respectively. The highest and lowest mole fraction solubility of silymarin was observed in pure PEG 400 (0.243 at 298.15 K) and water (1.46 × 10(-5) at 298.15 K). Finally, thermodynamic parameters were determined by Van't Hoff and Krug analysis, which indicated an endothermic and spontaneous dissolution of silymarin in all co-solvent mixtures.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

PubMed

El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands

PubMed Central

El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

Diffuse-interface model for rapid phase transformations in nonequilibrium systems.

PubMed

Galenko, Peter; Jou, David

2005-04-01

A thermodynamic approach to rapid phase transformations within a diffuse interface in a binary system is developed. Assuming an extended set of independent thermodynamic variables formed by the union of the classic set of slow variables and the space of fast variables, we introduce finiteness of the heat and solute diffusive propagation at the finite speed of the interface advancing. To describe transformations within the diffuse interface, we use the phase-field model which allows us to follow steep but smooth changes of phase within the width of the diffuse interface. Governing equations of the phase-field model are derived for the hyperbolic model, a model with memory, and a model of nonlinear evolution of transformation within the diffuse interface. The consistency of the model is proved by the verification of the validity of the condition of positive entropy production and by outcomes of the fluctuation-dissipation theorem. A comparison with existing sharp-interface and diffuse-interface versions of the model is given.

Fluoride salts and container materials for thermal energy storage applications in the temperature range 973 to 1400 K

NASA Technical Reports Server (NTRS)

Misra, Ajay K.; Whittenberger, J. Daniel

1987-01-01

Multicomponent fluoride salt mixtures were characterized for use as latent heat of fusion heat storage materials in advanced solar dynamic space power systems with operating temperatures in the range of 973 to 1400 K. The melting points and eutectic composition for many systems with published phase diagrams were verified, and several new eutectic compositions were identified. Additionally, the heats of fusion of several binary and ternary eutectics and congruently melting intermediate compounds were measured by differential scanning calorimetry. The extent of corrosion of various metals by fluoride melts was estimated from thermodynamic considerations, and equilibrium conditions inside a containment vessel were calculated as functions of the initial moisture content of the salt and free volume above the molten salt. Preliminary experimental data on the corrosion of commercial, high-temperature alloys in LiF-19.5CaF2 and NaF-27CaF2-36MgF2 melts are presented and compared to the thermodynamic predictions.

Fluoride salts and container materials for thermal energy storage applications in the temperature range 973 - 1400 K

NASA Technical Reports Server (NTRS)

Misra, Ajay K.; Whittenberger, J. Daniel

1987-01-01

Multicomponent fluoride salt mixtures were characterized for use as latent heat of fusion heat storage materials in advanced solar dynamic space power systems with operating temperatures in the range of 973 to 1400 K. The melting points and eutectic composition for many systems with published phase diagrams were verified, and several new eutectic compositions were identified. Additionally, the heats of fusion of several binary and ternary eutectics and congruently melting intermediate compounds were measured by differential scanning calorimetry. The extent of corrosion of various metals by fluoride melts was estimated from thermodynamic considerations, and equilibrium conditions inside a containment vessel were calculated as functions of the initial moisture content of the salt and free volume above the molten salt. Preliminary experimental data on the corrosion of commercial, high-temperature alloys in LiF-19.5CaF2 and NaF-27CaF2-36MgF2 melts are presented and compared to the thermodynamic predictions.

Thermodynamic and acoustical properties of mixtures p-anisaldehyde—alkanols (C1-C4)—2-methyl-1-propanol at 303.15 K

NASA Astrophysics Data System (ADS)

Saini, Balwinder; Kumar, Ashwani; Rani, Ruby; Bamezai, Rajinder K.

2016-07-01

The density, viscosity and speed of sound of pure p-anisaldehyde and some alkanols, for example, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, and the binary mixtures of p-anisaldehyde with these alkanols were measured over the entire composition range at 303.15 K. From the experimental data, various thermodynamic parameters such as excess molar volume ( V E), excess Gibbs free energy of activation (Δ G*E), and deviation parameters like viscosity (Δη), speed of sound (Δ u), isentropic compressibility (Δκs), are calculated. The excess as well as deviation parameters are fitted to Redlich—Kister equation. Additionally, the viscosity data for the systems has been used to correlate the application of empirical relation given by Grunberg and Nissan, Katti and Chaudhari, and Hind et al. The results are discussed in terms of specific interactions present in the mixtures.

Irreversible opinion spreading on scale-free networks

NASA Astrophysics Data System (ADS)

Candia, Julián

2007-02-01

We study the dynamical and critical behavior of a model for irreversible opinion spreading on Barabási-Albert (BA) scale-free networks by performing extensive Monte Carlo simulations. The opinion spreading within an inhomogeneous society is investigated by means of the magnetic Eden model, a nonequilibrium kinetic model for the growth of binary mixtures in contact with a thermal bath. The deposition dynamics, which is studied as a function of the degree of the occupied sites, shows evidence for the leading role played by hubs in the growth process. Systems of finite size grow either ordered or disordered, depending on the temperature. By means of standard finite-size scaling procedures, the effective order-disorder phase transitions are found to persist in the thermodynamic limit. This critical behavior, however, is absent in related equilibrium spin systems such as the Ising model on BA scale-free networks, which in the thermodynamic limit only displays a ferromagnetic phase. The dependence of these results on the degree exponent is also discussed for the case of uncorrelated scale-free networks.

Consideration of some dilute-solution phenomena based on an expression for the Gibbs free energy

NASA Astrophysics Data System (ADS)

Jonah, D. A.

1986-07-01

Rigorous expressions based on the Lennard-Jones (6 12) potential, are presented for the Gibbs and Helmholtz free energy of a dilute mixture. These expressions give the free energy of the mixture in terms of the thermodynamic properties of the pure solvent, thereby providing a convenient means of correlating dilute mixture behavior with that of the pure solvent. Expressions for the following dilute binary solution properties are derived: Henry's constant, limiting activity coefficients with their derivatives, solid solubilities in supercritical gases, and mixed second virial coefficients. The Henry's constant expression suggests a linear temperature dependence; application to solubility data for various gases in methane and water shows a good agreement between theory and experiment. In the thermodynamic modeling of supercritical fluid extraction, we have demonstrated how to predict new solubility-pressure isotherms from a given isotherm, with encouraging results. The mixed second virial coefficient expression has also been applied to experimental data; the agreement with theory is good.

Thermodynamic Analysis for the Refining Ability of Salt Flux for Aluminum Recycling

PubMed Central

Hiraki, Takehito; Miki, Takahiro; Nakajima, Kenichi; Matsubae, Kazuyo; Nakamura, Shinichiro; Nagasaka, Tetsuya

2014-01-01

The removability of impurities during the aluminum remelting process by oxidation was previously investigated by our research group. In the present work, alternative impurity removal with chlorination has been evaluated by thermodynamic analysis. For 43 different elements, equilibrium distribution ratios among metal, chloride flux and oxide slag phases in the aluminum remelting process were calculated by assuming the binary systems of aluminum and an impurity element. It was found that the removability of impurities isn’t significantly affected by process parameters such as chloride partial pressure, temperature and flux composition. It was shown that Ho, Dy, Li, La, Mg, Gd, Ce, Yb, Ca and Sr can be potentially eliminated into flux by chlorination from the remelted aluminum. Chlorination and oxidation are not effective to remove other impurities from the melting aluminum, due to the limited parameters which can be controlled during the remelting process. It follows that a proper management of aluminum scrap such as sorting based on the composition of the products is important for sustainable aluminum recycling. PMID:28788144

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

Phase Stability and Electronic Structure of Prospective Sb-Based Mixed Sulfide and Iodide 3D Perovskite (CH3NH3)SbSI2.

PubMed

Li, Tianyang; Wang, Xiaoming; Yan, Yanfa; Mitzi, David B

2018-06-29

Lead-free antimony-based mixed sulfide and iodide perovskite phases have recently been reported to be synthesized experimentally and to exhibit reasonable photovoltaic performance. Through a combination of experimental validation and computational analysis, we show no evidence of the formation of the mixed sulfide and iodide perovskite phase, MASbSI 2 (MA = CH 3 NH 3 + ), and instead that the main products are a mixture of the binary and ternary compounds (Sb 2 S 3 and MA 3 Sb 2 I 9 ). Density functional theory calculations also indicate that such a mixed sulfide and iodide perovskite phase should be thermodynamically less stable compared with binary/ternary anion-segregated secondary phases and less likely to be synthesized under equilibrium conditions. Additionally, band structure calculations show that this mixed sulfide and iodide phase, if possible to synthesize (e.g., under nonequilibrium conditions), should have a suitable direct band gap for photovoltaic application.

Separation of non-racemic mixtures of enantiomers: an essential part of optical resolution.

PubMed

Faigl, Ferenc; Fogassy, Elemér; Nógrádi, Mihály; Pálovics, Emese; Schindler, József

2010-03-07

Non-racemic enantiomeric mixtures form homochiral and heterochiral aggregates in melt or suspension, during adsorption or recrystallization, and these diastereomeric associations determine the distribution of the enantiomers between the solid and other (liquid or vapour) phases. That distribution depends on the stability order of the homo- and heterochiral aggregates (conglomerate or racemate formation). Therefore, there is a correlation between the binary melting point phase diagrams and the experimental ee(I)vs. ee(0) curves (ee(I) refers to the crystallized enantiomeric mixtures, ee(0) is the composition of the starting ones). Accordingly, distribution of the enantiomeric mixtures between two phases is characteristic and usually significant enrichment can be achieved. There are two exceptions: no enrichment could be observed under thermodynamically controlled conditions when the starting enantiomer composition corresponded to the eutectic composition, or when the method used was unsuitable for separation. In several cases, when kinetic control governed the crystallization, the character of the ee(0)-ee(I) curve did not correlate with the melting point binary phase diagram.

Boussinesq approximation of the Cahn-Hilliard-Navier-Stokes equations.

PubMed

Vorobev, Anatoliy

2010-11-01

We use the Cahn-Hilliard approach to model the slow dissolution dynamics of binary mixtures. An important peculiarity of the Cahn-Hilliard-Navier-Stokes equations is the necessity to use the full continuity equation even for a binary mixture of two incompressible liquids due to dependence of mixture density on concentration. The quasicompressibility of the governing equations brings a short time-scale (quasiacoustic) process that may not affect the slow dynamics but may significantly complicate the numerical treatment. Using the multiple-scale method we separate the physical processes occurring on different time scales and, ultimately, derive the equations with the filtered-out quasiacoustics. The derived equations represent the Boussinesq approximation of the Cahn-Hilliard-Navier-Stokes equations. This approximation can be further employed as a universal theoretical model for an analysis of slow thermodynamic and hydrodynamic evolution of the multiphase systems with strongly evolving and diffusing interfacial boundaries, i.e., for the processes involving dissolution/nucleation, evaporation/condensation, solidification/melting, polymerization, etc.

Metal ion-improved complexation countercurrent chromatography for enantioseparation of dihydroflavone enantiomers.

PubMed

Han, Chao; Wang, Wenli; Xue, Guimin; Xu, Dingqiao; Zhu, Tianyu; Wang, Shanshan; Cai, Pei; Luo, Jianguang; Kong, Lingyi

2018-01-12

Cu(II) ion was selected as an additive to improve the enantioseparation efficiency of three dihydroflavone enantiomers in high-speed counter-current chromatography (HSCCC), using hydroxypropyl-β-cyclodextrin (HP-β-CyD) as the chiral selector. The influences of important parameters, including the metal ion, the concentrations of HP-β-CyD and the Cu(II) ion, and the sample size were investigated. Under optimal conditions, three dihydroflavone enantiomers, including (±)-hesperetin, (±)-naringenin, and (±)-farrerol, were successfully enantioseparated. The chiral recognition mechanism was investigated. The enantioseparation was attributed to the different thermodynamic stabilities of the binary complexes of HP-β-CyD and (±)-hesperetin, and Cu(II) ion could enhance this difference by forming ternary complexes with the binary complexes. This Cu(II) ion-improved complexation HSCCC system exhibited improved performance for chiral separation, and therefore it has great application potential in the preparative enantioseparation of other compounds with similar skeletons. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluoride salts as phase change materials for thermal energy storage in the temperature range 1000-1400 K

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1988-01-01

Eutectic compositions and congruently melting intermediate compounds in binary and ternary fluoride salt systems were characterized for potential use as latent heat of fusion phase change materials to store thermal energy in the temperature range 1000-1400 K. The melting points and eutectic compositions for many systems with published phase diagrams were experimentally verified and new eutectic compositions having melting points between 1000 and 1400 K were identified. Heats of fusion of several binary and ternary eutectics and congruently melting compounds were experimentally measured by differential scanning calorimetry. For a few systems in which heats of mixing in the melts have been measured, heats of fusion of the eutectics were calculated from thermodynamic considerations and good agreement was obtained between the measured and calculated values. Several combinations of salts with high heats of fusion per unit mass (greater than 0.7 kJ/g) have been identified for possible use as phase change materials in advanced solar dynamic space power applications.

The Cu-Li-Sn Phase Diagram: Isopleths, Liquidus Projection and Reaction Scheme

PubMed Central

Flandorfer, Hans

2016-01-01

The Cu-Li-Sn phase diagram was constructed based on XRD and DTA data of 60 different alloy compositions. Eight ternary phases and 14 binary solid phases form 44 invariant ternary reactions, which are illustrated by a Scheil-Schulz reaction scheme and a liquidus projection. Phase equilibria as a function of concentration and temperature are shown along nine isopleths. This report together with an earlier publication of our group provides for the first time comprehensive investigations of phase equilibria and respective phase diagrams. Most of the phase equilibria could be established based on our experimental results. Only in the Li-rich part where many binary and ternary compounds are present estimations had to be done which are all indicated by dashed lines. A stable ternary miscibility gap could be found which was predicted by modelling the liquid ternary phase in a recent work. The phase diagrams are a crucial input for material databases and thermodynamic optimizations regarding new anode materials for high-power Li-ion batteries. PMID:27788175

The coal-fired gas turbine locomotive - A new look

NASA Technical Reports Server (NTRS)

Liddle, S. G.; Bonzo, B. B.; Purohit, G. P.

1983-01-01

Advances in turbomachine technology and novel methods of coal combustion may have made possible the development of a competitive coal fired gas turbine locomotive engine. Of the combustor, thermodynamic cycle, and turbine combinations presently assessed, an external combustion closed cycle regenerative gas turbine with a fluidized bed coal combustor is judged to be the best suited for locomotive requirements. Some merit is also discerned in external combustion open cycle regenerative systems and internal combustion open cycle regenerative gas turbine systems employing a coal gasifier. The choice of an open or closed cycle depends on the selection of a working fluid and the relative advantages of loop pressurization, with air being the most attractive closed cycle working fluid on the basis of cost.

Some single-piston closed-cycle machines and Peter Tailer's thermal lag engine

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

West, C.D.

1993-01-01

Peter Tailer has devised, built, and operated a beautifully simple engine with a closed working gas cycle, external heating, and only a single piston. The aim of this paper is to cast some light on the possible modes of operation for his machine. The methods develops to analyze certain aspects of Stirling cycle engines, and especially the thermodynamic losses incurred in systems that are neither perfectly isothermal nor perfectly adiabatic, can be applied to Tailer's system. The results identify two idealized cycles fr such machines; relate those cycles to a single piston, ported cylinder machine proposed earlier; and offer amore » possible explanation for the success of the thermal lag engine.« less

Closed-cycle gas dynamic laser design investigation

NASA Technical Reports Server (NTRS)

Ketch, G. W.; Young, W. E.

1977-01-01

A conceptual design study was made of a closed cycle gas-dynamic laser to provide definition of the major components in the laser loop. The system potential application is for long range power transmission by way of high power laser beams to provide satellite propulsion energy for orbit changing or station keeping. A parametric cycle optimization was conducted to establish the thermodynamic requirements for the system components. A conceptual design was conducted of the closed cycle system and the individual components to define physical characteristics and establish the system size and weight. Technology confirmation experimental demonstration programs were outlined to develop, evaluate, and demonstrate the technology base needed for this closed cycle GDL system.

Oxide reduction during triggered-lightning fulgurite formation

NASA Astrophysics Data System (ADS)

Jones, B. E.; Jones, K. S.; Rambo, K. J.; Rakov, V. A.; Jerald, J.; Uman, M. A.

2005-03-01

In this study triggered-lightning induced fulgurites were formed in 99.9% pure binary oxides of manganese (MnO) and nickel (NiO) in order to study oxide reduction mechanisms. The fulgurite formation process involved packing the oxide in PVC holders and using the standard rocket-and-wire technique to trigger a lightning strike through the oxide at the International Center for Lightning Research and Testing in Camp Blanding, Florida. These two oxides were chosen from the thermodynamic extrapolation of the oxide stability using the Ellingham Diagram. This diagram indicates that NiO is significantly less stable than MnO. Fulgurites from the pure oxides were analyzed in a scanning electron microscope (SEM); secondary electron images, backscattered images and energy dispersive spectroscopy (EDS) were used to determine the microstructure and composition of the fulgurites. SEM/EDS analysis of the NiO and MnO prior to fulgurite formation confirmed they were pure binary oxides with no metallic contamination. After fulgurite formation, it was found that the nickel oxide fulgurite contained metallic nickel particles; the manganese oxide fulgurite showed no metallic phase formation. Transmission electron microscopy (TEM) examination confirmed that the MnO was a pure oxide with no sign of metallic phase formation. However, TEM results of the NiO showed that approximately 50% of the NiO was reduced to metallic face-centered cubic Ni. The Ni and NiO were observed to be coherent with the [1 0 0]Ni//[1 0 0]NiO and [1 1 0]Ni//[1 1 0]NiO. These results are consistent with the aforementioned thermodynamic stability calculations and show that the presence of carbonaceous material or mixtures of oxides is not necessary for oxide reduction during fulgurite formation. These studies do not rule out the possibility that electrolysis plays a role in oxide reduction. However, these fulgurites were made simultaneously during the same lightning strike and therefore were subjected to the same electrical current, and thus it is proposed the thermodynamic stability of the oxide must play a role in oxide reduction.

Isentropic expansion and related thermodynamic properties of non-ionic amphiphile-water mixtures.

PubMed

Reis, João Carlos R; Douhéret, Gérard; Davis, Michael I; Fjellanger, Inger Johanne; Høiland, Harald

2008-01-28

A concise thermodynamic formalism is developed for the molar isentropic thermal expansion, ES,m = ( partial differential Vm/ partial differential T)(Sm,x), and the ideal and excess quantities for the molar, apparent molar and partial molar isentropic expansions of binary liquid mixtures. Ultrasound speeds were determined by means of the pulse-echo-overlap method in aqueous mixtures of 2-methylpropan-2-ol at 298.15 K over the entire composition range. These data complement selected extensive literature data on density, isobaric heat capacity and ultrasound speed for 9 amphiphile (methanol, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-2-ol, ethane-1,2-diol, 2-methoxyethanol, 2-ethoxyethanol or 2-butoxyethanol)-water binary systems, which form the basis of tables listing molar and excess molar isobaric expansions and heat capacities, and molar and excess molar isentropic compressions and expansions at 298.15 K and at 65 fixed mole fractions spanning the entire composition range and fine-grained in the water-rich region. The dependence on composition of these 9 systems is graphically depicted for the excess molar isobaric and isentropic expansions and for the excess partial molar isobaric and isentropic expansions of the amphiphile. The analysis shows that isentropic thermal expansion properties give a much stronger response to amphiphile-water molecular interactions than do their isobaric counterparts. Depending on the pair property-system, the maximum excess molar isentropic value is generally twenty- to a hundred-fold greater than the corresponding maximum isobaric value, and occurs at a lower mole fraction of the amphiphile. Values at infinite dilution of the 9 amphiphiles in water are given for the excess partial molar isobaric heat capacity, isentropic compression, isobaric expansion and isentropic expansion. These values are interpreted in terms of the changes occurring when amphiphile molecules cluster into an oligomeric form. Present results are discussed from theoretical and experimental thermodynamic viewpoints. It is concluded that isentropic thermal expansion properties constitute a new distinct resource for revealing particular features and trends in complex mixing processes, and that analyses using these new properties compare favourably with conventional approaches.

Structure, thermodynamics, and solubility in tetromino fluids.

PubMed

Barnes, Brian C; Siderius, Daniel W; Gelb, Lev D

2009-06-16

To better understand the self-assembly of small molecules and nanoparticles adsorbed at interfaces, we have performed extensive Monte Carlo simulations of a simple lattice model based on the seven hard "tetrominoes", connected shapes that occupy four lattice sites. The equations of state of the pure fluids and all of the binary mixtures are determined over a wide range of density, and a large selection of multicomponent mixtures are also studied at selected conditions. Calculations are performed in the grand canonical ensemble and are analogous to real systems in which molecules or nanoparticles reversibly adsorb to a surface or interface from a bulk reservoir. The model studied is athermal; objects in these simulations avoid overlap but otherwise do not interact. As a result, all of the behavior observed is entropically driven. The one-component fluids all exhibit marked self-ordering tendencies at higher densities, with quite complex structures formed in some cases. Significant clustering of objects with the same rotational state (orientation) is also observed in some of the pure fluids. In all of the binary mixtures, the two species are fully miscible at large scales, but exhibit strong species-specific clustering (segregation) at small scales. This behavior persists in multicomponent mixtures; even in seven-component mixtures of all the shapes there is significant association between objects of the same shape. To better understand these phenomena, we calculate the second virial coefficients of the tetrominoes and related quantities, extract thermodynamic volume of mixing data from the simulations of binary mixtures, and determine Henry's law solubilities for each shape in a variety of solvents. The overall picture obtained is one in which complementarity of both the shapes of individual objects and the characteristic structures of different fluids are important in determining the overall behavior of a fluid of a given composition, with sometimes counterintuitive results. Finally, we note that no sharp phase transitions are observed but that this appears to be due to the small size of the objects considered. It is likely that complex phase behavior may be found in systems of larger polyominoes.

Mixed ligand complex formation of 2-aminobenzamide with Cu(II) in the presence of some amino acids: Synthesis, structural, biological, pH-metric, spectrophotometric and thermodynamic studies

NASA Astrophysics Data System (ADS)

Dharmaraja, Jeyaprakash; Esakkidurai, Thirugnanasamy; Subbaraj, Paramasivam; Shobana, Sutha

2013-10-01

Mixed ligand Cu(II) complexes of 2-aminobenzamide (2AB) and amino acids viz., glycine (gly), L-alanine (ala), L-valine (val) and L-phenylalanine (phe) have been synthesised and characterized by various physico-chemical and spectral techniques. The calculated g-tensor values for Cu(II) complexes at 77 K and 300 K, show the distorted octahedral geometry which has been confirmed from the absorption studies. Consequently, the thermal studies illustrate that the loss of water and acetate molecules in the initial stage which are followed by the decomposition of organic residues. The powder X-ray diffraction and SEM analysis reflect that all the complexes have well-defined crystallinity nature with homogeneous morphology. The binding activities of CT DNA with CuAB complexes have been examined by absorption studies. Further, the oxidative cleavage interactions of 2-aminobenzamide and CuAB complexes with DNA were studied by gel electrophoresis method in H2O2 medium. Also, the complex formation of Cu(II) involving 2-aminobenzamide and amino acids were carried out by a combined pH-metric and spectrophotometric techniques in 50% (v/v) water-ethanol mixture at 300, 310, 320 and 330 ± 0.1 K with I = 0.15 mol dm-3 (NaClO4). In solution, CuAB and CuAB2 species has been detected and the binding modes of 2-aminobenzamide and amino acids in both binary and mixed ligand complexes are same. The calculated stabilization value of Δ log K, log X and log X' indicates higher stabilities for the mixed ligand complexes rather than their binary species. The thermodynamic parameters like ΔG, ΔH and ΔS have been determined from temperature dependence of the stability constant. In vitro biological activities of 2-aminobenzamide, CuA and CuAB complexes show remarkable activities against some bacterial and fungal strains. The percentage distribution of various binary and mixed ligand species in solution at dissimilar pH intervals were also evaluated.

Carbon-Carbon Recuperators in Closed-Brayton-Cycle Nuclear Space Power Systems: A Feasibility Assessment

NASA Technical Reports Server (NTRS)

Barrett, Michael J.; Johnson, Paul K.

2004-01-01

The feasibility of using carbon-carbon recuperators in closed-Brayton-cycle (CBC) nuclear space power conversion systems (PCS) was assessed. Recuperator performance expectations were forecast based on projected thermodynamic cycle state values for a planetary mission. Resulting thermal performance, mass and volume for a plate-fin carbon-carbon recuperator were estimated and quantitatively compared with values for a conventional offset-strip-fin metallic design. Material compatibility issues regarding carbon-carbon surfaces exposed to the working fluid in the CBC PCS were also discussed.

Optimization of Turbine Engine Cycle Analysis with Analytic Derivatives

NASA Technical Reports Server (NTRS)

Hearn, Tristan; Hendricks, Eric; Chin, Jeffrey; Gray, Justin; Moore, Kenneth T.

2016-01-01

A new engine cycle analysis tool, called Pycycle, was recently built using the OpenMDAO framework. This tool uses equilibrium chemistry based thermodynamics, and provides analytic derivatives. This allows for stable and efficient use of gradient-based optimization and sensitivity analysis methods on engine cycle models, without requiring the use of finite difference derivative approximation methods. To demonstrate this, a gradient-based design optimization was performed on a multi-point turbofan engine model. Results demonstrate very favorable performance compared to an optimization of an identical model using finite-difference approximated derivatives.

Optimal Power and Efficiency of Quantum Thermoacoustic Micro-cycle Working in 1D Harmonic Trap

NASA Astrophysics Data System (ADS)

E, Qing; Wu, Feng; Yin, Yong; Liu, XiaoWei

2017-10-01

Thermoacoustic engines (including heat engines and refrigerators) are energy conversion devices without moving part. They have great potential in aviation, new energy utilization, power technology, refrigerating and cryogenics. The thermoacoustic parcels, which compose the working fluid of a thermoacoustic engine, oscillate within the sound channel with a temperature gradient. The thermodynamic foundation of a thermoacoustic engine is the thermoacoustic micro-cycle (TAMC). In this paper, the theory of quantum mechanics is applied to the study of the actual thermoacoustic micro-cycle for the first time. A quantum mechanics model of the TAMC working in a 1D harmonic trap, which is named as a quantum thermoacoustic micro-cycle (QTAMC), is established. The QTAMC is composed of two constant force processes connected by two straight line processes. Analytic expressions of the power output and the efficiency for QTAMC have been derived. The effects of the trap width and the temperature amplitude on the power output and the thermal efficiency have been discussed. Some optimal characteristic curves of power output versus efficiency are plotted, and then the optimization region of QTAMC is given in this paper. The results obtained here not only enrich the thermoacoustic theory but also expand the application of quantum thermodynamics.

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.

Thermodynamics of non-Markovian reservoirs and heat engines

NASA Astrophysics Data System (ADS)

Thomas, George; Siddharth, Nana; Banerjee, Subhashish; Ghosh, Sibasish

2018-06-01

We show that non-Markovian effects of the reservoirs can be used as a resource to extract work from an Otto cycle. The state transformation under non-Markovian dynamics is achieved via a two-step process, namely an isothermal process using a Markovian reservoir followed by an adiabatic process. From second law of thermodynamics, we show that the maximum amount of extractable work from the state prepared under the non-Markovian dynamics quantifies a lower bound of non-Markovianity. We illustrate our ideas with an explicit example of non-Markovian evolution.

Using compression calorimetry to characterize powder compaction behavior of pharmaceutical materials.

PubMed

Buckner, Ira S; Friedman, Ross A; Wurster, Dale Eric

2010-02-01

The process by which pharmaceutical powders are compressed into cohesive compacts or tablets has been studied using a compression calorimeter. Relating the various thermodynamic results to relevant physical processes has been emphasized. Work, heat, and internal energy change values have been determined with the compression calorimeter for common pharmaceutical materials. A framework of equations has been proposed relating the physical processes of friction, reversible deformation, irreversible deformation, and inter-particle bonding to the compression calorimetry values. The results indicate that irreversible deformation dominated many of the thermodynamic values, especially the net internal energy change following the compression-decompression cycle. The relationships between the net work and the net heat from the complete cycle were very clear indicators of predominating deformation mechanisms. Likewise, the ratio of energy stored as internal energy to the initial work input distinguished the materials according to their brittle or plastic deformation tendencies. (c) 2009 Wiley-Liss, Inc. and the American Pharmacists Association.